Novel sulfonic acid functionalized silica supported isonicotinic acid catalyst for conversion of 2-methylfuran to diesel fuel precursors - Tarade, Komal P.; Kamble, Sanjay P.; Rode, Chandrashekhar V. (Catalysis Letters, 2024)
Polyfuranic compounds produced after carbon up-gradation of 2-methylfuran by acid catalyzed C-C bond forming reactions when undergo hydro-deoxygenation produce diesel fuel. Herein, we prepared a simple and novel silica supported sulfonic acid functionalized isonicotinic acid SO3H-INA@SiO2 catalyst by treating isonicotinic acid with chlorosulphonic acid followed by heterogenization on silica. This heterogeneous solid acid catalyst was explored for the solvent free conversion of 2-methylfuran to diesel fuel precursors of C-15 and C-20 units via tandem ring opening followed by condensation sequence. Under optimized reaction conditions, SO3H-INA@SiO2 was able to convert, 2-methylfuran completely into condensation products such as 5,5-bis(5-methylfuran-2-yl)pentan-2-one (1) and 2,4,4-tris(5-methylfuran-2-yl)pentan-1-ol (2) with 19% and 67% yields, respectively. The heterogeneous SO3H-INA@SiO2 catalyst was successfully recycled up to six consecutive runs without loss of its activity. The SO3H-INA@SiO2 catalyst offered superior activity as compared to the commercially available -SO3H functionalized resins. Superior activity of the prepared catalyst could be attributed for its higher acidity, smaller particle size and high surface area. Structure of the prepared catalyst was confirmed by FTIR and solid state NMR. Total acidity of the prepared catalyst was determined by acid-base titration.
Keywords: 2-Methylfuran; Diesel fuel; heterogeneous catalyst; Ionic solid; solid acid

N-SO3H functionalised brønsted acidic ionic liquid catalysed sequential one-pot synthesis of 2-amino-3-cyanopyridines via claisen-schmidt condensation under solvent-free condition - Das, Sukanya; Paul, Subham; Kashyap, Niharika; Saikia, Pinku; Borah, Ruli (Chemistryselect, 2024)
This work presents a simple approach for the synthesis of 2-amino-3-cyanopyridines via a one pot two-step sequential route catalysed by direct N–SO3H functionalised Br & oslash;nsted acidic ionic liquids (BAILs). Herein, catalytic activities of four BAILs namely ([TSPi][Cl](2), [DSIM][TFA], [EDSIM][TFA] and [DBDSA][TFA]) were explored and among them [TSPi][Cl](2) was found to be the most efficient reusable homogeneous catalyst. This process involves the ionic liquid catalysed in situ generation of chalcones from Claisen-Schmidt condensation between aromatic aldehydes and acetophenone/4-Cl acetophenone, followed by multicomponent reaction (MCR) with malononitrile and ammonium acetate using the same IL catalyst to selectively produce 2-amino-3-cyanopyridine derivatives in a solvent-free medium at 80 degrees C within 30-60 minutes in high yields (96-86 %). This amalgamation of MCR with ionic liquids and solvent-free conditions makes the present work more compliant with the protocols of Green Chemistry.
Keywords: 2-amino-3-cyanopyridines; Bronsted acidic ionic liquids; chalcones; Multicomponent reaction; One-pot approach

N-terminal domain of polypyrimidine-tract binding protein is a dynamic folding platform for adaptive RNA recognition - Damberger, Fred F.; Krepl, Miroslav; Arora, Rajika; Beusch, Irene; Maris, Christophe; Dorn, Georg; Sponer, Jiri; Ravindranathan, Sapna; Allain, Frederic H-T (NUCLEIC ACIDS RESEARCH, 2024)
Keywords: CHEMICAL-SHIFT ANISOTROPY; NMR; ROTATING-FRAME RELAXATION; TIME-SCALE DYNAMICS

Ocimum kilimandscharicum 4CL11 negatively regulates adventitious root development via accumulation of flavonoid glycosides - Lavhale, Santosh G.; Kondhare, Kirtikumar R.; Sinthadurai, Veenothini S.; Barvkar, Vitthal T.; Kale, Rutuja S.; Joshi, Rakesh S.; Giri, Ashok P. (Plant Journal, 2024)
4-Coumarate-CoA Ligase (4CL) is an important enzyme in the phenylpropanoid biosynthesis pathway. Multiple 4CLs are identified in Ocimum species; however, their in planta functions remain enigmatic. In this study, we independently overexpressed three Ok4CL isoforms from Ocimum kilimandscharicum (Ok4CL7, -11, and -15) in Nicotiana benthamiana. Interestingly, Ok4CL11 overexpression (OE) caused a rootless or reduced root growth phenotype, whereas overexpression of Ok4CL15 produced normal adventitious root (AR) growth. Ok4CL11 overexpression in N. benthamiana resulted in upregulation of genes involved in flavonoid biosynthesis and associated glycosyltransferases accompanied by accumulation of specific flavonoid-glycosides (kaempferol-3-rhamnoside, kaempferol-3,7-O-bis-alpha-l-rhamnoside [K3,7R], and quercetin-3-O-rutinoside) that possibly reduced auxin levels in plants, and such effects were not seen for Ok4CL7 and -15. Docking analysis suggested that auxin transporters (PINs/LAXs) have higher binding affinity to these specific flavonoid-glycosides, and thus could disrupt auxin transport/signaling, which cumulatively resulted in a rootless phenotype. Reduced auxin levels, increased K3,7R in the middle and basal stem sections, and grafting experiments (intra and inter-species) indicated a disruption of auxin transport by K3,7R and its negative effect on AR development. Supplementation of flavonoids and the specific glycosides accumulated by Ok4CL11-OE to the wild-type N. benthamiana explants delayed the AR emergence and also inhibited AR growth. While overexpression of all three Ok4CLs increased lignin accumulation, flavonoids, and their specific glycosides were accumulated only in Ok4CL11-OE lines. In summary, our study reveals unique indirect function of Ok4CL11 to increase specific flavonoids and their glycosides, which are negative regulators of root growth, likely involved in inhibition of auxin transport and signaling.
Keywords: 4-Coumarate-CoA ligase; 7-O-bis-alpha-l-rhamnoside; adventitious root; auxin transport; Flavonoids; kaempferol-3; Ocimum kilimandscharicum; quercetin-3-O-rutinoside; rootless

One-pot catalytic conversion of sucrose to 1,2-propanediol over titania supported Ni-Ce metal catalyst under milder reaction conditions - Sreekantan, Sreejith; Sreedharan, Sarath; Kirali, Arun Arunima Balachandran; Yadav, Parmeshwar; Marimuthu, Banu (Biomass Conversion and Biorefinery, 2024)
The increased energy demand and decreasing fossil resources have driven the research community to look into a sustainable, green process to meet the energy demands. India being one of the top producers of sugarcane derived sucrose, and conversion of surplus sucrose to value chemicals is always an advantage. 5%Ni-15%Ce/TiO2 catalyst is found to produce high yield of 1,2-PDO (similar to 74%) under very mild reaction condition of 180 degrees C, 30 bar H-2 for 3-h reaction time. The characterization of the catalyst by using various physicochemical methods indicates the synergy between Ni-Ce bimetal which enhances the selective production of glycol. The low temperature and pressure requirement and the advantage of being the one-pot process will always attract the future scope of commercialization.
Keywords: Glycol; Low pressure; Low temperature; Ni-Ce catalyst; Sucrose; titania

One-pot synthesis of pyrazoles from sulfonyl hydrazides and alkynyl ketones using environmentally benign sulfonium iodate (I) reagent - Mishra, Akanksha; Talukdar, Mrinal; Krishna, Gamidi Rama; Begari, Eeshwaraiah (ChemistrySelect, 2024)
Pyrazole is an omnipresent moiety in many natural products and pharmaceutically active compounds. Here, we have developed a simple and dynamic method for one-pot synthesis of substituted pyrazoles through the intramolecular cyclization of hydrazides and alkynyl ketones, using a novel sulfonium saltbased iodate (& Iukcy;) reagent system. This method has the advantage that it proceeds in a one-pot, without isolating a less stable hydrazone intermediate. Hypervalent iodine-based reagents are an environmentally benign and greener option to toxic metal oxidants; they have an extensive application in metal-catalyst-free reactions, and this reaction proceeds in less time with high yields.
Keywords: Deprotonation; One-pot reaction; Oxidative iodination; Pyrazole; S(N)2-type cyclization

Organocatalytic route to the enantioselective synthesis of syn/ anti-α-hydrazino-γ-fluoro alcohols - Khonde, Nilesh S.; Said, Madhukar S.; Danve, Shivam S.; Kumar, Pradeep (Tetrahedron Letters, 2024)
A general organocatalytic method has been developed for the asymmetric synthesis of alpha-hydrazino-gamma-fluoro alcohols, a precursor to syn/anti-1,3-fluoro amines. The strategy employs alpha-fluorination catalyzed by prolinederived catalyst, (S)-alpha,alpha-bis[3,5-bis(trifluoromethyl)phenyl]-2-pyrrolidinemetha nol trimethylsilyl ether followed by Horner-Wadsworth-Emmons (HWE) olefination of aldehydes, and proline-catalyzed alpha-amination as the key steps. The title compounds showed excellent diastereoselectivity (up to 99:1) and enantioselectivity (up to 99 %).
Keywords: alpha-Amination; alpha-Fluorination; diastereoselectivity; Enantioselectivity; HWE olefination; organocatalyst

Organocatalyzed [4+2] cycloaddition of α,β-unsaturated ketones and isatylidene malononitrile: accessing spiro[3-arylcyclohexanone]oxindole derivatives - Patil, Baliram R.; Nichinde, Chandrakant B.; Chaudhari, Suryakant S.; Krishna, Gamidi Rama; Kinage, Anil K. (RSC Advances, 2024)
Herein, we developed a series of compounds featuring spiro[3-arylcyclohexanone]oxindoles through Barbas [4 + 2] cycloaddition reactions between isatylidene malononitrile and alpha,beta-unsaturated ketones using l-proline as an organocatalyst. The reported methodology offers many advantages such as mild reaction conditions, diverse substrate scope with high yields, easy reaction setup, and use of easily synthesizable starting materials. An l-proline catalyzed-Barbas-[4 + 2]-cycloaddition reaction is reported for the synthesis of spiro[3-arylcyclohexanone]oxindole derivatives. The method can tolerate a diverse substrate scope with high yields.

Oxidative and selective C-C cleavage of glycerol to glycolaldehyde with atom-like Cu on Cu-TiO2: photocatalytic water reduction with concurrent glycerol oxidation in sunlight - Bajpai, Himanshu; Nivedhitha, Thazhath R.; Dais, Elsa; Kanungo, Subhashree S.; Gopinath, Chinnakonda S. (Journal of Catalysis, 2024)
Concurrent consumption of electrons and holes for the conversion of a biomass component to value added products represents a highly efficient and sustainable approach towards utilizing renewable energy, but difficult to achieve. The integration of hydrogen production with glycerol oxidation presents a novel and sustainable approach towards achieving a circular economy. In the current study, integration of atom-like Cu-clusters onto TiO2 substrate has been achieved using a facile photo-deposition technique (TC-PDO). Also, novel synthetic approaches have been employed to augment the surface coverage of Cu on TiO2 with atom-like clusters of Cu, either by borohydride treatment on TiO2 followed by Cu-deposition (TC-200) or oxygen-vacancy creation by UV illumination followed by Cu-deposition (TC-PDO). Increased dispersion and enhanced electronic integration of Cu with TiO2 lead to a corresponding increase in the efficiency of photocatalytic hydrogen evolution (13.8 mmol/h.g for TC-PDO at pH 9). Several atom-like Cu integrated with each TiO2 particle acts as photocatalytic reactor, and the same enhances electron-hole separation as well as activity. Sustainable aspect was also studied for TC-PDO up to 25 h at pH 9. Concurrently, glycerol oxidation displays the highest selectivity to C2 product (glycolaldehyde with 70 %) with a C-C cleavage. The investigation of this process holds significant potential for the extensive and simultaneous exploitation of electrons and holes in order to achieve water splitting and glycerol oxidation towards selective value-added products formation.
Keywords: C -C Cleavage; Glycerol; nanotechnology; Photo -deposition; solar energy conversion

PANI-grafted boron, nitrogen co-doped carbon fiber: An outstanding, high-performance supercapacitor electrode - Nayan, Rajiv; Sinha, Shubhra; Dixit, Vaibhav; Satnami, Manmohan L.; Ghosh, Kallol K.; Pervez, Shamsh; Deb, Manas Kanti; Shrivas, Kamlesh; Rai, Manish K.; Yenchalwar, Sandeep G.; Wasnik, Kundan; Jadkar, Sandesh R.; et al. (JOURNAL OF ENERGY STORAGE, 2024)
Keywords: Composite; polyaniline; Solid-state supercapacitor

Photocatalytic CO2 reduction to syngas using nickel phosphide-loaded CdS under visible light irradiation - Yadav, Poonam; Kumar, Santosh; Velankanni, Nandhakumar; Kuehne, Thomas D.; Gosavi, Suresh; Raghupathy, Ramya Kormath Madam; Bhosale, Reshma; Held, Georg; Shelke, Manjusha; Ogale, Satishchandra (Journal of Physics-Energy, 2024)
Photocatalytic CO2 reduction is a sustainable pathway to produce syngas (H-2 + CO), which is a key feedstock for the production of several important liquid fuels on the industrial scale. However, achieving an appropriate tunable ratio of H-2:CO in syngas for commercial purposes is a challenging task. In this work, we present a low-cost and non-noble metal, phosphide-based co-catalyst-Ni2P-loaded cadmium sulfide (CdS) photocatalyst system, for photocatalytic CO2 reduction. As a co-catalyst, Ni2P fosters an efficient charge separation of photoexcited charges generated in the CdS production of syngas. In total, 3 wt.% Ni2P/CdS exhibited exceptional performance of 50.6 mu mol g(-1) h(-1) in the CO evolution rate and 115 mu mol g(-1) h(-1) in the H-2 evolution rate, with a syngas composition varying from 2 to 4 in the H-2:CO ratio. Furthermore, first-principles density functional theory calculations were performed to study the surface energetics of the catalyst system and the results are found to be consistent with our experimental findings. Indeed, they establish that the composite favors CO2 photoreduction into syngas more efficiently than pure surfaces.
Keywords: CdS; CO2 reduction; Photocatalysis; Syngas; transition metal phosphides

Photocatalytic regeneration of reactive cofactors with inP quantum dots for the continuous chemical synthesis - Chakraborty, Indra Narayan; Jain, Vanshika; Roy, Pradyut; Kumar, Pawan; Vinod, Chathakudath P.; Pillai, Pramod P. (ACS Catalysis, 2024)
The shuttling of redox-active nicotinamide cofactors between the light and dark cycles is the key to the continuous production of biomass in photosynthesis. The replication of such processes in artificial photosynthetic systems demands fast photoregeneration as well as simultaneous integration of these nicotinamide cofactors into the dark cycle. Here, we report the design of an artificial photosynthetic system for the continuous production of butanol via the constant photoregeneration and consumption of nicotinamide cofactors, powered by an indium phosphide quantum dot (InP QD) photocatalyst and alcohol dehydrogenase (ADH) enzyme, respectively. A strong electrostatic attraction between the oppositely charged InP QDs and electron mediators significantly enhanced the charge extraction and utilization processes, enabling a fast (similar to 30 min, with a turn over frequency of similar to 1333 h(-1)), quantitative (>99%), and selective photoregeneration of enzymatically active nicotinamide cofactors in the light cycle. These photoregenerated nicotinamide cofactors were further coupled in the dark cycle to trigger the ADH oxidoreductase enzyme for the production of butanol, via sequential as well as simultaneous light-dark cycles. The amount of butanol produced under simultaneous light-dark cycles was higher than the stoichiometric limit, proving the constant regeneration and consumption of nicotinamide cofactors in light and dark cycles, respectively. Thus, a proper design and integration of the InP QD-based photocatalytic cycle with the enzymatic cycle led to the effective electron shuttling between light and dark cycles, as seen in photosynthesis.
Keywords: artificial photosynthesis; biologicalcofactors; charge transfer; indiumphosphide; Photocatalysis; quantum dots

Phytic acid customized hydrogel polymer electrolyte and prussian blue analogue cathode material for rechargeable zinc metal hydrogel batteries - Dilwale, Swati; Puthiyaveetil, Priyanka Pandinhare; Babu, Athira; Kurungot, Sreekumar (Small, 2024)
Zinc anode deterioration in aqueous electrolytes, and Zn dendrite growth is a major concern in the operation of aqueous rechargeable Zn metal batteries (AZMBs). To tackle this, the replacement of aqueous electrolytes with a zinc hydrogel polymer electrolyte (ZHPE) is presented in this study. This method involves structural modifications of the ZHPE by phytic acid through an ultraviolet (UV) light-induced photopolymerization process. The high membrane flexibility, high ionic conductivity (0.085 S cm-1), improved zinc corrosion overpotential, and enhanced electrochemical stability value of approximate to 2.3 V versus Zn|Zn2+ show the great potential of ZHPE as an ideal gel electrolyte for rechargeable zinc metal hydrogel batteries (ZMHBs). This is the first time that the dominating effect of chelation of phytic acid with M2+ center over H-bonding with water is described to tune the gel electrolyte properties for battery applications. The ZHPE shows ultra-high stability over 360 h with a capacity of 0.50 mAh cm-2 with dendrite-free plating/stripping in Zn||Zn symmetric cell. The fabrication of the ZMHB with a high-voltage zinc hexacyanoferrate (ZHF) cathode shows a high-average voltage of approximate to 1.6 V and a comparable capacity output of 63 mAh g-1 at 0.10 A g-1 of the current rate validating the potential application of ZHPE. A novel phytic acid (PA) modulated zinc hydrogel polymer electrolyte (ZHPE) as an efficient electrolyte and separator for rechargeable Zn-metal hydrogel batteries (ZMHB) is designed. The zincophilic, and hydrogen bonding characteristics of ZHPE help in regulating uniform dendrite-free Zn-deposition over the Zn anode surface. ZHPE in combination with the developed high-voltage zinc hexacyanoferrate (ZHF) cathode performs as an efficient ZMHB. image
Keywords: high voltage cathode; high-conducting gel polymer electrolyte; phytic acid; rechargeable Zn-metal hydrogel batteries; Zn hydrogel polymer electrolyte

Polymer nanocomposites with UiO-derived zirconia fillers for energy generation and pressure-sensing devices: the role of crystal structure and surface characteristics - Mukherjee, Gargi; Verma, Ankur; Madhu, Arjun Hari; Prasad, Bhagavatula L. V.; Karumuthil, Subash Cherumannil (ACS Applied Nano Materials, 2024)
Piezoelectric energy harvesting and pressure sensing using polymer nanocomposites have opened up promising avenues in the field of flexible electronics. Herein, the influence of varying crystal structures of zirconia nanoparticles on a piezoelectric energy-generating zirconia-poly(vinylidene difluoride) (PVDF) composite is investigated, and the fabrication of a security alert pavement unit using the material with an optimized composition is demonstrated. More specifically, two metal-organic frameworks, UiO-66 and UiO-67, were employed to synthesize four different types of zirconia nanoparticles with precise control of the monoclinic and tetragonal phases. Polymer nanocomposite with monoclinic zirconia nanoparticles derived from UiO-66 (ZrO2-66m) performed better than other derivatives with 61% enhancement in the beta phase with respect to pure PVDF. It was hypothesized that the stable crystalline structure of the monoclinic phase might act as a better nucleating agent, and among monoclinic derivatives, ZrO2-66m was found to be more hydrophobic, probably enabling a better interaction with PVDF. Subsequently, a prototype device with a PVDF-ZrO2-66m (P/66m) film was made and tested for its energy generation. The maximum output voltage generated by the device under an irregular biomechanical hand tapping force of 8-9 N was 80 V, while the maximum open circuit current was found to be 65 mu A. The prototype displayed a power of 2162.24 mu W at a load resistance of 1 M Omega. A laboratory scale demonstration was executed with the prototype as an energy-generating and security alert pavement unit. A wireless, Bluetooth-based security alert system supported by an Android application was developed and demonstrated as a promising application with the fabricated prototype. The results and demonstrations validate that the PVDF-monoclinic ZrO2 nanoparticle nanocomposites will be an excellent value addition for flexible, durable energy generation and pressure-sensing applications.
Keywords: energy generation and pressure sensing; piezoelectric materials; PVDF/ZrO2 polymernanocomposite; self-powered devices; wearable electronics

Polymeric PEI/PEG coated optical fiber fabry-perot interferometer for CO2 detection - Pawar, Dnyandeo; Lo Presti, Daniela; Lemma, Enrico D.; Rainer, Alberto; Kumar, Ajay; Kanawade, Rajesh; Silvestri, Sergio; Schena, Emiliano; Massaroni, Carlo (IEEE Sensors Journal, 2024)
Monitoring carbon dioxide (CO2) gas is essential for numerous applications, but the detection of CO2 in miniaturized devices presents significant challenges. In this study, a polyethyleneimine/poly(ethylene glycol) (PEI/PEG) coated optical fiber Fabry-Perot interferometer (FPI) and its charge transfer process toward CO2 are investigated. Scanning electron microscopy and Fourier transform infrared spectroscopy were used to analyze the surface morphology and vibration bands of the PEI/PEG composite. The PEI/PEG composite Fabry-Perot (FP) cavity of length similar to 13 mu m is coated at the distal end of the single-mode fiber using a dip coating technique. A highly sensitive optical and low-cost FPI probe fabrication has displayed a linear sensitivity of 17.10 nm/% in the range of 0.31%-1.25% CO2 gas. The response and recovery times of the sensor are in a few tens of seconds. The enhanced performance of the sensor is primarily due to the protonation and charge transfer between CO2 gas molecules and PEI/PEG composite. Due to low-cost fabrication and high sensitivity, this FPI sensor can be used in a range of potential applications in bioprocessing, healthcare, and environmental monitoring.
Keywords: dip coating; Fresnel's reflection; Interference; monitoring; Optical fiber sensors; Optical fibers; polymer composite; Polymers; refractive index; sensitivity; Sensor phenomena and characterization; sensors; swelling; Temperature sensors

Poly(d,l-lactide-co-glycolide) surface-anchored biotin-loaded irinotecan nanoparticles for active targeting of colon cancer - Giram, Prabhanjan S.; Nimma, Ramakrishna; Bulbule, Anuradha; Yadav, Amit Singh; Gorain, Mahadeo; Radharani, Nalukurthi Naga Venkata; Kundu, Gopal C.; Garnaik, Baijayantimala (ACS Omega, 2024)
A poly-(d,l-lactide-co-glycolide) (PLGA) copolymer was synthesized using the ring-opening polymerization of d,l-lactide and glycolide monomers in the presence of zinc proline complex in bulk through the green route and was well characterized using attenuated total reflectance-Fourier transform infrared, H-1 and C-13 nuclear magnetic resonance, gel permeation chromatography, differential scanning calorimetry, X-ray diffraction, matrix-assisted laser desorption/ionization time-of-flight, etc. Furthermore, PLGA-conjugated biotin (PLGA-B) was synthesized using the synthesized PLGA and was employed to fabricate nanoparticles for irinotecan (Ir) delivery. These nanoparticles (PLGA-NP-Ir and PLGA-B-NP-Ir) were tested for physicochemical and biological characteristics. PLGA-B-NP-Ir exhibited a stronger cellular uptake and anticancer activity as compared to PLGA-NP-Ir in CT-26 cancer cells (log p < 0.05). The accumulation and retention of fluorescence-labeled nanoparticles were observed to be better in CT-26-inoculated solid tumors in Balb/c mice. The PLGA-B-NP-Ir-treated group inhibited tumor growth significantly more (log p < 0.001) than the untreated control, PLGA-NP-Ir, and Ir-treated groups. Furthermore, no body weight loss, hematological, and blood biochemical tests demonstrated the nanocarriers' nontoxic nature. This work presents the use of safe PLGA and the demonstration of a proof-of-concept of biotin surface attached PLGA nanoparticle-mediated active targeted Ir administration to combat colon cancer. To treat colon cancer, PLGA-B-NP-Ir performed better due to specific active tumor targeting and greater cellular uptake due to biotin.

Polyvalent interaction and confinement to suppress polysulfide dissolution and improve electrocatalysis - Bharathkumar, H. J.; Shivankar, Bhavana R.; Krishnamurty, Sailaja; Chen, Dehong; Caruso, Rachel A.; Krishnamoorthy, Kothandam (CATALYSIS SCIENCE & TECHNOLOGY, 2024)
Keywords: cathode material; HIGH-CAPACITY; Particles; SULFUR CATHODE

Proteome dataset of Candida albicans (ATCC10231) opaque cell - Zore, Gajanan; Abdulghani, Mazen; Kodgire, Santosh; Kazi, Rubina; Shelar, Amruta; Patil, Rajendra (BMC Research Notes, 2024)
<h3 class="c-article__sub-heading" data-test="abstract-sub-heading" style="margin: 0px 0px 8px; box-sizing: inherit; font-size: 1.5rem; font-family: -apple-system, BlinkMacSystemFont, "Segoe UI", Roboto, Oxygen-Sans, Ubuntu, Cantarell, "Helvetica Neue", sans-serif; line-height: 1.24; font-weight: 400;"> Objectives Candida albicans, a polymorphic yeast, is one of the most common, opportunistic fungal pathogens of humans. Among the different morphological forms, opaque form is one of the least-studied ones. This opaque phenotype is essential for mating and is also reported to be involved in colonizing the gastrointestinal tract. Considering the significance of the clinical and sexual reproduction of C. albicans, we have investigated the morphophysiological modulations in opaque form using a proteomic approach. <h3 class="c-article__sub-heading" data-test="abstract-sub-heading" style="margin: 24px 0px 8px; box-sizing: inherit; font-size: 1.5rem; font-family: -apple-system, BlinkMacSystemFont, "Segoe UI", Roboto, Oxygen-Sans, Ubuntu, Cantarell, "Helvetica Neue", sans-serif; line-height: 1.24; font-weight: 400;"> Data description In the current investigation, we have used Micro-Liquid Chromatography-Mass Spectrometry (LC-MS/MS) analysis to create a protein profile for opaque-specific proteins. Whole-cell proteins from C. albicans (ATCC10231) cells that had been cultured for seven days on synthetic complete dextrose (SCD) medium in both as an opaque (test) and as a white (control) form cells were extracted, digested, and identified using LC-MS/MS. This information is meant to serve the scientific community and represents the proteome profile (SWATH Spectral Libraries) of C. albicans opaque form.

Quasi-molecular hydrogen storage capacity of graphene quantum dots: A dispersion corrected DFT study - Khadilkar, Pranav; Samudre, Nikhil S.; Krishnamurty, Sailaja (Journal of Energy Storage, 2024)
Efficient storage of hydrogen, green fuel with the highest energy density, remains a pressing challenge. Among the several materials investigated for their potential hydrogen storage, 2D materials, like graphene, have advantages such as mechanical strength and large surface area but fail to store hydrogen reversibly. In this context, the present computational experiment demonstrates the potential of Graphene Quantum Dots (GQDs) with 24, 40 and 42 carbon atoms for their hydrogen storage capacity in quasi-molecular mode. Factors such as edge terminations, heteroatom doping, and anchoring of metal atoms are evaluated as a function of their storage capacity. The study clearly demonstrates an enhanced storage capacity of quantum dots, particularly, when a single Ti adatom is anchored on a 24 carbon atom GQD with a storage weight % of 2.24 % w/w. The storage weight % is further noted to increase as a function of the number of Ti atoms anchored on the GQD with the highest hydrogen storage weight % of 6.1 % w/w. Importantly, the adsorption of hydrogen molecule on the Ti atom is through a quasi-molecular mode and is driven by Kubas interaction. This type of interactions makes GQDs as viable storage materials at room temperature. Secondly, the work demonstrates that GQDs offer higher storage capacities of hydrogen molecules as compared to their 2D counterparts viz., graphene sheets, making them attractive candidates to be explored experimentally.
Keywords: Density functional theory; graphene quantum dots; Hydrogen storage; Kubas interaction; Quasi -molecular adsorption; Ti adatom

Rational design of zero-dimensional manganese(II) halide hybrids with suppressed melting temperatures - Singh, Shivangi; Marayathungal, Jumana Hasin; Das, Deep Kumar; Khan, Akram Aadil; Bakthavatsalam, Rangarajan; Hathwar, Venkatesha R.; Kundu, Janardan (JOURNAL OF PHYSICAL CHEMISTRY C, 2024)
Keywords: ORGANIC-INORGANIC PEROVSKITES; TRANSITION

Rational monomer design for the synthesis of conjugated polymers by direct heteroarylation polymerization - Kakde, Navnath R.; Sharma, Himanshu; Dalvi, Nitin V.; Vanka, Kumar; Asha, S. K (ACS Polymers Au, 2024)
This study focuses on the design concepts that contribute to the C–H activation in bithiophene-flanked monomers incorporating naphthalene diimide (NDI), perylene diimide (PDI), and fluorene (FLU) and their polymerization by direct heteroarylation. Density functional theory (DFT) calculations reveal distinct energy requirements for C–H bond abstraction, which is dictated by the electron-withdrawing strength of the central aromatic core flanked by bithiophene. These provide insights into the reactivity of each monomer for C–H bond activation. Proton NMR spectroscopic experimental results confirm the favorable energetic profiles predicted by DFT, with NDI- and PDI-flanked monomers exhibiting lower energy requirements than fluorene-flanked monomers. Successful polymer synthesis is demonstrated for NDI and PDI, while the fluorene-flanked monomer shows challenges due to its higher energy demands.

Reaction kinetics for catalytic hydrogenation of quinoline to decahydroquinoline as liquid organic hydrogen carrier - Bagwan, Farahanaz M.; Kinage, Anil K.; Vasireddy, Satyam Naidu (International Journal of Hydrogen Energy, 2024)
The catalytic hydrogenation of quinoline to decahydroquinoline (DHQ) formation is studied for various parameters such as temperature, hydrogen pressure, reaction time, solvents, reactant-to-solvent ratio, and catalyst loading over 5%Pd loaded on alumina (Pd/Al2O3) to obtain optimal reaction conditions. The hydrogen uptake of quinoline in the liquid phase reaction using isopropylalcohol (IPA) is studied in an autoclave reactor. The optimum reaction parameters of 50 bar H2 pressure and 175oC with reactant to solvent ratio of 1:9 for reaction time of 5 h are observed. The effect of IPA solvent showed that hydrogen uptake of 6.91 wt% with complete hydrogenation of quinoline and DHQ yield of more than 99% is observed. The reaction kinetic model is developed for a simplified reaction mechanism and is simulated using the Markov Chain Monte Carlo (MCMC) simulation tool to predict the rate constants and the experimental observations are validated with the model predictions. The activation energy for quinoline hydrogenation to py-THQ formation is estimated to be 136.57 kJ/mol. It is envisaged that quinoline hydrogenation to pz-THQ is the rate-limiting step in the DHQ formation.
Keywords: Decahydroquinoline (DHQ); Hydrogen uptake; Liquid organic hydrogen carrier (LOHC); Markov chain Monte Carlo (MCMC) simulation; Thermal screening unit (TSU); tool

Ready access to [5,6,5]-Trioxa-spiro and fused ketals via ag-catalyzed cascade annulation of 4-pentyn-1-ols and aldehydes - Vinodkumar, Ramavath; Nakate, Ashwini K.; Gamidi, Rama Krishna; Kontham, Ravindar (Organic Letters, 2024)
In this study, we unveil the versatility of 4-pentyn-1-ols as carbonyl surrogates for the unprecedented synthesis of diverse oxygen heterocycles, including [5,6,5]-bis-spiroketals (trioxadispiroketals) and [5,6,5]-furano-spiroketals related to bioactive natural products. These reactions commence with the pi-activation-induced intramolecular hydroalkoxylation of 4-pentyn-1-ols, yielding cyclic enol ethers, which undergo subsequent three-component annulation with aldehydes in a [2+2+1+1] fashion, resulting in the formation of [5,6,5]-bis-spiroketals. Notably, the distinctive steric features of alkynyl alcohols, particularly those with a secondary or tertiary alcohol functionality, dictate divergent reaction pathways, leading to the formation of [5,6,5]-furano-spiroketals.

Reconstituting the microstructural properties and ionic conductivity of copper - doped yttria-stabilized zirconia via mechanochemical synthesis for intermediate-temperature solid oxide fuel cell applications - Momin, Naeemakhtar; Manjanna, J.; Kobayashi, Satoru; Aruna, S. T.; Kumar, S. Senthil; Ahmad, Tokeer; Nayaka, G. P.; Mubeen, B.; Sabale, Sandip; Kangralkari, Mrunal V.; Keri, Rangappa S. (CERAMICS INTERNATIONAL, 2024)
Keywords: ELECTRICAL-PROPERTIES; OPTICAL-PROPERTIES; THERMAL-STABILITY; TRANSITION-METAL

Reduced graphene oxide/tungsten oxide (rGO/WO3): a versatile nanocomposite for enhanced detection of acetone - Patil, Abhijeet P.; Gaikwad, Mayur A.; Nadargi, Jyoti D.; Shaikh, Hamid; Alam, Mohammad Asif; Tamboli, Mohaseen S.; Kim, Jin Hyeok; Mulla, Imtiaz S.; Suryavanshi, Sharad S. (Journal of Materials Science-Materials In Electronics, 2024)
In this study, we report a straightforward method for synthesizing semi-cubical nanostructures of tungsten trioxide (WO3) loaded with reduced graphene oxide (rGO) via a hydrothermal approach. Furthermore, the systematic investigations were made towards the improved gas sensing capabilities of these nanostructures for acetone. The use of semi-cubical rGO/WO3 nanostructures demonstrate the provision of efficient gas diffusion routes via a meticulously arranged mesoporous framework. Hence, it leads to a significant improvement in the sensing response towards acetone. The analysis of the sensing capabilities demonstrates that the response of the sensor is influenced by variations in operating temperature and gas concentration. It is seen that the inclusion of rGO not only enhances the sensing response but also gives quick response and recovery, which are measured to be 12 and 33 s, respectively. The WO3 sensor loaded with 0.1 wt% rGO demonstrates a discerning reaction to acetone, exhibiting a high response of 93.60% than that of the unmodified WO3 sensor (76.30%). The gas sensing properties are explained through the role of rGO and the structural and morphological properties of the developed nanostructures.

Relaxation of the 2a1 ionized water dimer: an interplay of intermolecular Coulombic decay (ICD) and proton transfer processes - Kumar, Ravi; Ghosh, Aryya; Vaval, Nayana (Journal of Chemical Physics, 2024)
This article investigates the relaxation dynamics of the ionized 2a(1) state of a water molecule within a water dimer. The study was motivated by findings from two previous pieces of research that focused on the relaxation behaviors of the inner-valence ionized water dimer. The present study discloses an observation indicating that water dimers display specific fragmentation patterns following inner-valence ionization, depending on the position of the vacancy. Vacancies were created in the 2a(1) state of the proton-donating water molecule (PDWM) and proton-accepting water molecule (PAWM). Utilizing Born-Oppenheimer molecular dynamics simulations, the propagation of the 2a(1) ionized state was carried out for both scenarios. The results revealed proton transfer occurred when the vacancy resided in the PDWM, accompanied by the closing of decay channels for O-H bond distance (RO-H) > 1.187 & Aring; (matching Richter et al.'s findings). Conversely, when vacancy was on PAWM, we observed no closing of decay channels (aligning with Jahnke et al.'s findings). This difference translates to distinct fragmentation pathways. In PDWM cases, 2a(1) state ionization leads to H3O+ -OH center dot formation. In contrast, PAWM vacancies result in decay pathways leading to H2O+-H(2)O(+ )products.

Remarkable SO2 and H2S resistant ability on CO oxidation by unique Pd/WO3 3D hollow sphere nanocatalyst: correlating structure-activity relationships on SO2 exposure - Jeyavani, Vijayakrishnan; Kondhekar, Deepali; Bhati, Meema; Dev, Sahil; Joshi, Kavita; Devi, R. Nandini; Mukherjee, Shatabdi Porel (ACS Applied Energy Materials, 2024)
We report a simple inorganic route for synthesizing a Pd/WO3 3D hollow sphere nanocatalyst, where Pd nanoparticles are encapsulated and well distributed on porous tungsten oxide nanospheres. The synthesis protocol has advantages, as it requires no surfactant or stabilizing agent, Pd loading is easily tuned, and the as-synthesized nanomaterials can be directly used as catalysts for the CO oxidation reaction. The synthesized nanocatalyst exhibited 100% CO to CO2 conversion efficiency at 260 degrees C. In addition, the nanocatalyst demonstrated remarkable SO2 (3 ppm) tolerance during the CO oxidation reaction for prolonged SO2 sulfation of 1-21 h at 260-400 degrees C. This represents the longest SO2 exposure time reported to date based on a single metal Pd/support-based nanocatalyst. No decrement in CO conversion efficiency was observed even after SO2 (3 ppm) treatment for 21 h for the first time based on a single metal Pd-based nanocatalyst. Moreover, the synthesized nanocatalyst shows H2S (4 ppm), even in situ H2S tolerance during the CO oxidation reaction at 260 degrees C for 1-3 h and exhibited less sensitivity to prolonged and stringent sulfur exposure, with the highest H2S concentration and maximum 100% CO to CO2 conversion efficiency obtained after H2S treatment for the first time based on a Pd-based nanocatalyst to the best of our knowledge. The composition and structure of the R-Pd/WO3 nanocatalyst were not much influenced, even after the prolonged SO2 and H2S exposure during the CO oxidation reaction, as verified from spent catalyst analysis. Finally, our DFT-based model provides insights into understanding the observed sulfur resistance on Pd/WO3 by analyzing the underlying electronic structure. Therefore, our strategic synthesis methodology will open up many opportunities to select Pd/metal oxide-based nanomaterials for designing highly efficient, stable, and SO2/H2S-resistant nanocomposite catalyst.
Keywords: CO oxidation; DFT calculation; nanocatalyst; palladium (Pd); SO2 andH(2)S resistant ability; structure-activityrelationships; tungstenoxide (WO3)

Renewable synthesis of MoO3 nanosheets via low temperature phase transition for supercapacitor application - Sankar, K. N. Amba; Kesavan, Lokesh; Saha, Bikash; Jyolsnaraj, M. K.; Mohan, S.; Nandakumar, P.; Mohanta, Kallol; Kvarnstroem, Carita (SCIENTIFIC REPORTS, 2024)
Keywords: alpha-MoO3; h-MoO3; Mixed phases (h and alpha) of MoO3; Renewable green synthesis; Very low temperature phase transition

Resorcinol-Azodianiline Covalent Organic Framework Supported FeOOH Quantum Dot-Catalyzed Electrochemical Ammonia Synthesis under Ambient Conditions - Shekhar, Pragalbh; Kosugi, Kento; Singh, Himan Dev; Kushwaha, Rinku; Rase, Deepak; Matsuzaki, Takumi; Jain, Chitvan; Singh, Piyush; Singh, Yashraj; Vinod, Chathakudath Prabhakaran; Kondo, Mio; Masaoka, Shigeyuki; et al. (CHEMISTRY OF MATERIALS, 2024)
Keywords: conversion; nitrogen; Recent Progress; reduction

Role and significance of virus-bacteria interactions in disease progression - Pokhrel, Vatsala; Kuntal, Bhusan K.; Mande, Sharmila S. (Journal of Applied Microbiology, 2024)
Understanding disease pathogenesis caused by bacteria/virus, from the perspective of individual pathogen has provided meaningful insights. However, as viral and bacterial counterparts might inhabit the same infection site, it becomes crucial to consider their interactions and contributions in disease onset and progression. The objective of the review is to highlight the importance of considering both viral and bacterial agents during the course of coinfection. The review provides a unique perspective on the general theme of virus-bacteria interactions, which either lead to colocalized infections that are restricted to one anatomical niche, or systemic infections that have a systemic effect on the human host. The sequence, nature, and underlying mechanisms of certain virus-bacteria interactions have been elaborated with relevant examples from literature. It also attempts to address the various applied aspects, including diagnostic and therapeutic strategies for individual infections as well as virus-bacteria coinfections. The review aims to aid researchers in comprehending the intricate interplay between virus and bacteria in disease progression, thereby enhancing understanding of current methodologies and empowering the development of novel health care strategies to tackle coinfections.
Keywords: Bacteria; coinfections; infections; virus; virus-bacteria interactions

Role of nitrogen doping in modulating ruthenium nanocatalysts for enhanced electrochemical hydrogen evolution reaction in alkaline medium - Korampattu, Lavanya; Barik, Sidharth; Pandikassala, Ajmal; Urkude, Rajashri R.; Kurungot, Sreekumar; Dhepe, Paresh L. (Chemistry of Materials, 2024)
Nitrogen doping has become a fundamental approach to enhance the catalytic performance of carbon materials across various applications. The introduction of nitrogen creates defects and active sites, promoting the formation of small metal particles and strengthening the metal-support interaction within carbon materials. However, the challenge lies in developing sustainable and cost-effective methods for synthesizing nitrogen-doped carbon materials. In this study, we present a sustainable approach for the synthesis of ruthenium on nitrogen-doped carbon catalysts (Ru-CCP) using chitosan as a nitrogen and carbon source. Unlike traditional methods, our process avoids the use of additional nitrogen precursors and templates, streamlining the synthesis while using a renewable resource. The synthesized material exhibits an exceptional performance in the electrochemical hydrogen evolution reaction (HER) in alkaline conditions by achieving a current density of 25 mA cm(-2) at an impressively low overpotential of 46 mV, outperforming Pt/C under similar conditions. The detailed studies on structural and electronic properties of the materials using X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and transmission electron microscopy (TEM) revealed that the remarkable catalytic activity is upheld by the unique interplay between Ru delta+ and surface nitrogen moieties, notably pyridinic and pyrrolic nitrogen. Here, we demonstrate the control of particle size and electronic environment around the metal atom via the interaction of nitrogen and unravel the role of nitrogen doping in tuning the catalytic performance. In addition, this work offers insights into efficient HER catalyst design and emphasizes the potential of biomass-derived materials like chitosan in advancing clean hydrogen production for renewable energy applications.

Rongalite as a C1 source: sulfonylmethylation of indoles with aryl/alkyl hydrazides and sulfinates - Kale, Someshwar B.; Patil, Tejaswini A.; Das, Utpal (Journal of Organic Chemistry, 2024)
Herein, we present a sulfonylmethylation of indoles with aryl/alkyl hydrazides and sulfinates that provides viable access to sulfone compounds using rongalite as a C1 source. This protocol features readily available chemicals and simple operations, and the products were obtained in moderate to good yields.

Safety enhanced novel polymer electrolytes for lithium-ion battery: Anomalous output performance with long term cycling stability by doping and polymer blending - Balakrishnan, Neethu T. M.; Melepurakkal, Amrutha; Das, Akhila; Kenz, K. T. Mohammed; Subramaniam, Mohanapriya; Shelke, Manjusha; Pullanchiyodan, Abhilash; Raghavan, Prasanth (MATERIALS TODAY CHEMISTRY, 2024)
Keywords: Blend polymers; Ceramic fillers; Gel polymer electrolytes

Saturated NHC-stabilized borenium, boronium, hydride-bridged boron cations, and a bora-acyl chloride - Kundu, Gargi; Amrutha, P. R.; Tothadi, Srinu; Sen, Sakya S. (ORGANOMETALLICS, 2024)
Keywords: activation; BORINIUM; Chemistry

Scalable approach using a gC3N4 -covalent organic framework hybrid catalyst towards sustainable hydrogen production from seawater and wastewater - Asokan, Kiran; Bhagyasree, T. M.; Devasia, George; Krishnamurty, Sailaja; Solim, Sabah; Rueda, Lina; Al-Mohannadi, Dhabia M.; Al-Hashimi, Mohammed; Kakosimos, Konstantinos; Santhosh Babu, Sukumaran (CHEMICAL SCIENCE, 2024)

Scalable, interfacially synthesized, covalent-organic framework (COF)-based thin-film composite (TFC) hollow fiber membranes for organic solvent nanofiltration (OSN) - Kunjattu, Shebeeb H.; Thorat, Nitin M.; Gawas, Saroj; Kharul, Ulhas K. (ACS Applied Materials and Interfaces, 2024)
Covalent organic frameworks have great potential for energy-efficient molecular sieving-based separation. However, it remains challenging to implement COFs as an alternative membrane material due to the lack of a scalable and cost-effective fabrication mechanism. This work depicts a new method for fabricating a scalable in situ COF hollow fiber (HF) membrane by an interfacial polymerization (IP) approach at room temperature. The 2D COF film was constructed on a polyacrylonitrile HF substrate using aldehyde (1,3,5-trimethylphloroglucinol, Tp) and amine (4,4 `-azodianiline (Azo) and 4,4 `,4 `'-(1,3,5-triazine- 2,4,6-triyl) trianiline (Tta)) as precursors. The COF membrane on the PAN substrate showed 99% rejection of Direct red-80 with remarkable solvent permeance. The rejection analysis revealed that the structural aspects of the solute molecule play a major role in rejection rather than the molecular weight. We further optimized the precursor concentrations to improve the permeation performance of the resulting membrane. The durability study reveals excellent stability of the membrane toward organic solvents. This study also demonstrated the easy scalability of the membrane fabrication approach. The approach was further extrapolated to fabricate a cation-based COF membrane. These charged membranes exhibited an enhanced rejection performance. Finally, this approach can facilitate industrially challenging molecular sieving applications using COF-based membranes.
Keywords: covalent-organic framework; hollow fiber; interfacial polymerization; organic solvent nanofiltration; selective COF membrane

Scaling-up continuous production of mesoporous silica particles at kg scale: design & operational strategies - Jundale, Rajashri B.; Sonawane, Jayesh R.; Palghadmal, Anil V.; Jaiswal, Hemant Kumar; Deore, Hital S.; Kulkarni, Amol A. (Reaction Chemistry & Engineering, 2024)
This paper demonstrates a continuous flow pilot-scale production of highly porous mesoporous silica particles (MSPs) via a soft template based technique. The study presents pilot scale reactor design, fabrication and production of mesoporous silica particles with a 1 kg per day production rate. The extent of mixing and overall performance of the system were evaluated by conducting a hydrodynamic study, including the estimation of the heat transfer coefficient and dispersion number. Nanoparticle synthesis in a clogging-free manner is the key challenge in moving towards large scale production and commercial applications. This article presents a comprehensive study on the effect of key parameters for successful scaling up of the process. We have also addressed challenges faced and how these are overcome by troubleshooting the process. Different strategies were used to prevent the clogging of the reactor, which involved reactant dilution, periodic pulsation and slug flow (two phase flow). Among them, slug flow allows us to operate the reactor continuously for several hours without clogging and wall-deposition problems. It helped produce morphologically well-defined and near-monodisperse particles. With this process, the production is validated at a scale of 85 times compared to that of a laboratory system (from 22 mL to >1.5 L), enabling a production rate of 20-50 g h(-1).

Selective synthesis of renewable diesel fuel precursors via C-C condensation of biomass-derived furans using a niobium oxide nanocatalyst - Kumar, Mudavath Arun; Swapna, Bhattu; Kalbande, Pavan Narayan; Yalagandula, Lavanya; Singh, Satyapaul A.; Sudarsanam, Putla (ACS SUSTAINABLE CHEMISTRY & ENGINEERING, 2024)
Keywords: 2-Methylfuran; Catalysts; dehydration; NB2O5; RANGE ALKANES; solid acid; Valorization

Shell waste valorization to chemicals: methods and progress - Korampattu, Lavanya; Ghosh, Neha; Dhepe, Paresh L. (Green Chemistry, 2024)
In light of growing energy and resource demands, the conversion of biomass materials into diverse chemicals and fuels holds significant importance. This process enables the utilization of biomass as a valuable and renewable resource to meet these escalating needs. The current biomass valorization processes are largely based on plant-derived lignocellulosic biomass materials. Studying new genres of biomass materials and their value addition is highly desirable, and they would complement and expand the existing biorefinery system. Crustacean shell waste represents a highly potential bioresource that is composed of a set of useful chemicals, among which chitin, the amino polysaccharide, has come to the fore as a promising material for a plethora of applications. In terms of the abundance of biopolymers on Earth, cellulose is the most prevalent biopolymer, and chitin ranks as the second. The presence of biologically fixed nitrogen in the structure of chitin opens up new possibilities for making useful chemicals, notably nitrogen-containing chemicals, which are otherwise impossible to produce directly from lignocellulosic biomass. In the last two decades, several attempts have been made by researchers in this area to convert chitin and its derivatives into valuable chemicals. This review comprehensively summarizes the transformation of the chitin fraction from shell waste to various chemicals through different thermo-catalytic processes and appraises the advancements in this area. The effect of various catalytic systems on chitin biomass valorization processes and the challenges and opportunities allied to this are discussed. This review summarises the thermo-catalytic processes converting chitin from shell waste into diverse chemicals and reviews the advances, catalytic systems, and associated challenges.

Shuttle balance between lithiophilic functionalities substituted on conjugated polymers to improve lithium-ion diffusion and cycling stability of batteries - Kargude, Radhakisan; Javaregowda, Bharathkumar H.; Palani, Sathishkumar; Singh, Anup K.; Krishnamoorthy, Kothandam (Macromolecules, 2024)
Herein, we report the design and synthesis of i-Indigo and trans-1,2-di(2-thienyl)ethylene (TVT) comprising copolymers with various side chains that are used as anode-cum-binder in Li-ion batteries. The TVT disrupts the crystallinity, and the i-Indigo renders the handle for unsymmetrical substitution. Polymer P1 comprises alkyl chains on i-Indigo, whereas P2 comprises an alkyl chain and a chain with a urethane moiety as another side chain. Polymer P3 comprises i-Indigo with a urethane moiety and triethylene glycol as side chains. The i-Indigo in P4 is substituted with triethylene glycol and alkyl chains as side chains. These polymers were found to be amorphous with pi-pi stacking due to the extremely small torsional angle imparted by TVT moieties. All of these polymers showed comparable specific capacity while used as an anode in Li-ion batteries due to the presence of a common conjugated backbone. However, the battery metrics varied significantly while the current density of the batteries varied between 0.1 and 2.0 A g(-1). P1 and P2 showed a very close recovery of specific capacity at 0.1 A g(-1) before and after various current densities. However, polymers P3 and P4 did not recover from the specific capacity fading due to the presence of triethylene glycol side chain that degraded. Polymer P2 with an alkyl side chain and a chain with a urethane moiety showed stable performance over 2000 charge-discharge cycles. Contrary to this, the stability of polymers with triethylene glycol side chains decreased over 2000 charge-discharge cycles. Polymer P2 with a urethane side chain also showed improved Li-ion diffusion because the urethane moiety facilitated better Li-ion transport.

Silver nanoparticles in electrospun ethyl hydroxy ethyl cellulose-PVA Nanofiber: synthesis, characterization and wound dressing applications - Wali, Ashwini; Gorain, Mahadeo; Kundu, Gopal; Badiger, Manohar (Carbohydrate Polymer Technologies and Applications, 2024)
<span style="box-sizing: border-box; margin: 0px; padding: 0px; color: rgb(31, 31, 31); font-family: ElsevierGulliver, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif, sans-serif; font-size: 16px;">Electrospinning is a simple, cost-effective technique and a reproducible process for both synthetic and <a class="topic-link" href="https://www.sciencedirect.com/topics/materials-science/natural-polymer" style="box-sizing: border-box; margin: 0px; padding: 0px; background-color: rgba(0, 0, 0, 0); word-break: break-word; text-decoration-thickness: 1px; text-decoration-color: rgb(31, 31, 31); color: rgb(31, 31, 31); text-underline-offset: 1px;" title="Learn more about natural polymers from ScienceDirect's AI-generated Topic Pages">natural polymers. It is found to be an attractive tool for various applications in biomedical engineering, filtration, protective clothing, catalysis reactions and sensors. Non-ionic cellulose ethers namely Ethyl Hydroxy <a class="topic-link" href="https://www.sciencedirect.com/topics/agricultural-and-biological-sciences/ethyl-cellulose" style="box-sizing: border-box; margin: 0px; padding: 0px; background-color: rgba(0, 0, 0, 0); word-break: break-word; text-decoration-thickness: 1px; text-decoration-color: rgb(31, 31, 31); color: rgb(31, 31, 31); text-underline-offset: 1px;" title="Learn more about Ethyl Cellulose from ScienceDirect's AI-generated Topic Pages">Ethyl Cellulose (EHEC) is an important <a class="topic-link" href="https://www.sciencedirect.com/topics/agricultural-and-biological-sciences/polysaccharide" style="box-sizing: border-box; margin: 0px; padding: 0px; background-color: rgba(0, 0, 0, 0); word-break: break-word; text-decoration-thickness: 1px; text-decoration-color: rgb(31, 31, 31); color: rgb(31, 31, 31); text-underline-offset: 1px;" title="Learn more about polysaccharide from ScienceDirect's AI-generated Topic Pages">polysaccharide which is non-toxic, biocompatible and biodegradable and finds applications as thickening/rheology control agents in paints, cosmetics, detergents, oil recovery and also in the biomedical area. Poly (vinyl alcohol) (PVA) is a semi-crystalline <a class="topic-link" href="https://www.sciencedirect.com/topics/agricultural-and-biological-sciences/hydrophilic-polymers" style="box-sizing: border-box; margin: 0px; padding: 0px; background-color: rgba(0, 0, 0, 0); word-break: break-word; text-decoration-thickness: 1px; text-decoration-color: rgb(31, 31, 31); color: rgb(31, 31, 31); text-underline-offset: 1px;" title="Learn more about hydrophilic polymer from ScienceDirect's AI-generated Topic Pages">hydrophilic polymer which is highly biocompatible and non-toxic having good thermal and mechanical properties and also high water solubility. Silver shows powerful antimicrobial activity and is non-toxic. It has been used to cure severe burns and chronic ulcers for many decades and is extensively used as an additive in various fields like prostheses, burn treatment, catheters, vascular grafts, dental resin components, ion exchange fibers, <a class="topic-link" href="https://www.sciencedirect.com/topics/agricultural-and-biological-sciences/stainless-steel" style="box-sizing: border-box; margin: 0px; padding: 0px; background-color: rgba(0, 0, 0, 0); word-break: break-word; text-decoration-thickness: 1px; text-decoration-color: rgb(31, 31, 31); color: rgb(31, 31, 31); text-underline-offset: 1px;" title="Learn more about stainless steel from ScienceDirect's AI-generated Topic Pages">stainless steel materials, human skin and coating of <a class="topic-link" href="https://www.sciencedirect.com/topics/materials-science/medical-device" style="box-sizing: border-box; margin: 0px; padding: 0px; background-color: rgba(0, 0, 0, 0); word-break: break-word; text-decoration-thickness: 1px; text-decoration-color: rgb(31, 31, 31); color: rgb(31, 31, 31); text-underline-offset: 1px;" title="Learn more about medical devices from ScienceDirect's AI-generated Topic Pages">medical devices. In the present work, EHEC/PVA <a class="topic-link" href="https://www.sciencedirect.com/topics/materials-science/nanofiber" style="box-sizing: border-box; margin: 0px; padding: 0px; background-color: rgba(0, 0, 0, 0); word-break: break-word; text-decoration-thickness: 1px; text-decoration-color: rgb(31, 31, 31); color: rgb(31, 31, 31); text-underline-offset: 1px;" title="Learn more about nanofibers from ScienceDirect's AI-generated Topic Pages">nanofibers embedded with silver <a class="topic-link" href="https://www.sciencedirect.com/topics/chemical-engineering/nanoparticle" style="box-sizing: border-box; margin: 0px; padding: 0px; background-color: rgba(0, 0, 0, 0); word-break: break-word; text-decoration-thickness: 1px; text-decoration-color: rgb(31, 31, 31); color: rgb(31, 31, 31); text-underline-offset: 1px;" title="Learn more about nanoparticles from ScienceDirect's AI-generated Topic Pages">nanoparticles (AgNPs) are studied for their <a class="topic-link" href="https://www.sciencedirect.com/topics/pharmacology-toxicology-and-pharmaceutical-science/antibacterial-activity" style="box-sizing: border-box; margin: 0px; padding: 0px; background-color: rgba(0, 0, 0, 0); word-break: break-word; text-decoration-thickness: 1px; text-decoration-color: rgb(31, 31, 31); color: rgb(31, 31, 31); text-underline-offset: 1px;" title="Learn more about antibacterial activity from ScienceDirect's AI-generated Topic Pages">antibacterial activity using both gram positive and <a class="topic-link" href="https://www.sciencedirect.com/topics/pharmacology-toxicology-and-pharmaceutical-science/gram-negative-bacterium" style="box-sizing: border-box; margin: 0px; padding: 0px; background-color: rgba(0, 0, 0, 0); word-break: break-word; text-decoration-thickness: 1px; text-decoration-color: rgb(31, 31, 31); color: rgb(31, 31, 31); text-underline-offset: 1px;" title="Learn more about gram negative bacteria from ScienceDirect's AI-generated Topic Pages">gram negative bacteria. The <a class="topic-link" href="https://www.sciencedirect.com/topics/pharmacology-toxicology-and-pharmaceutical-science/nanofiber" style="box-sizing: border-box; margin: 0px; padding: 0px; background-color: rgba(0, 0, 0, 0); word-break: break-word; text-decoration-thickness: 1px; text-decoration-color: rgb(31, 31, 31); color: rgb(31, 31, 31); text-underline-offset: 1px;" title="Learn more about nanofibers from ScienceDirect's AI-generated Topic Pages">nanofibers show increase in <a class="topic-link" href="https://www.sciencedirect.com/topics/materials-science/tensile-property" style="box-sizing: border-box; margin: 0px; padding: 0px; background-color: rgba(0, 0, 0, 0); word-break: break-word; text-decoration-thickness: 1px; text-decoration-color: rgb(31, 31, 31); color: rgb(31, 31, 31); text-underline-offset: 1px;" title="Learn more about tensile properties from ScienceDirect's AI-generated Topic Pages">tensile properties with the addition of silver nano-particles. The <a class="topic-link" href="https://www.sciencedirect.com/topics/pharmacology-toxicology-and-pharmaceutical-science/silver-nanoparticle" style="box-sizing: border-box; margin: 0px; padding: 0px; background-color: rgba(0, 0, 0, 0); word-break: break-word; text-decoration-thickness: 1px; text-decoration-color: rgb(31, 31, 31); color: rgb(31, 31, 31); text-underline-offset: 1px;" title="Learn more about AgNPs from ScienceDirect's AI-generated Topic Pages">AgNPs embedded EHEC/PVA nanofiber mats having 0.5% AgNPs were found to enhance the <a class="topic-link" href="https://www.sciencedirect.com/topics/pharmacology-toxicology-and-pharmaceutical-science/wound-healing" style="box-sizing: border-box; margin: 0px; padding: 0px; background-color: rgba(0, 0, 0, 0); word-break: break-word; text-decoration-thickness: 1px; text-decoration-color: rgb(31, 31, 31); color: rgb(31, 31, 31); text-underline-offset: 1px;" title="Learn more about wound healing from ScienceDirect's AI-generated Topic Pages">wound healing with no scar formation in <a class="topic-link" href="https://www.sciencedirect.com/topics/pharmacology-toxicology-and-pharmaceutical-science/wistar-rat" style="box-sizing: border-box; margin: 0px; padding: 0px; background-color: rgba(0, 0, 0, 0); word-break: break-word; text-decoration-thickness: 1px; text-decoration-color: rgb(31, 31, 31); color: rgb(31, 31, 31); text-underline-offset: 1px;" title="Learn more about wistar rats from ScienceDirect's AI-generated Topic Pages">wistar rats. The biological <em style="box-sizing: border-box; margin: 0px; padding: 0px; color: rgb(31, 31, 31); font-family: ElsevierGulliver, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif, sans-serif; font-size: 16px;">in-vitro<span style="color: rgb(31, 31, 31); font-family: ElsevierGulliver, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif, sans-serif; font-size: 16px;"> and <em style="box-sizing: border-box; margin: 0px; padding: 0px; color: rgb(31, 31, 31); font-family: ElsevierGulliver, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif, sans-serif; font-size: 16px;">in-vivo<span style="box-sizing: border-box; margin: 0px; padding: 0px; color: rgb(31, 31, 31); font-family: ElsevierGulliver, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif, sans-serif; font-size: 16px;"> studies support the potential of EHEC based <a class="topic-link" href="https://www.sciencedirect.com/topics/agricultural-and-biological-sciences/nanofiber" style="box-sizing: border-box; margin: 0px; padding: 0px; background-color: rgba(0, 0, 0, 0); word-break: break-word; text-decoration-thickness: 1px; text-decoration-color: rgb(31, 31, 31); color: rgb(31, 31, 31); text-underline-offset: 1px;" title="Learn more about nanofibers from ScienceDirect's AI-generated Topic Pages">nanofibers as excellent bio-materials for the treatment of severe burns and <a class="topic-link" href="https://www.sciencedirect.com/topics/pharmacology-toxicology-and-pharmaceutical-science/wound" style="box-sizing: border-box; margin: 0px; padding: 0px; background-color: rgba(0, 0, 0, 0); word-break: break-word; text-decoration-thickness: 1px; text-decoration-color: rgb(31, 31, 31); color: rgb(31, 31, 31); text-underline-offset: 1px;" title="Learn more about wounds from ScienceDirect's AI-generated Topic Pages">wounds. To the best of our knowledge, this is the first report on the electrospinning of EHEC/PVA nanofibers for wound healing applications.

Size and morphology dependent activity of Cu clusters for CO2 activation and reduction: a first principles investigation - Amin, Seerat; Krishnamurty, Sailaja; Dar, Manzoor Ahmad; Joshi, Krati (ChemPhysChem, 2024)
Various Cu-based materials in diverse forms have been investigated as efficient catalysts for electrochemical reduction of CO2; however, they suffer from issues such as higher over potential and poor selectivity. The activity and selectivity of CO2 electro reduction have been shown to change significantly when the surface morphology (steps, kinks, and edges) of these catalysts is altered. In light of this, size and morphology dependent activity of selected copper clusters, Cun (n=2-20) have been evaluated for the activation and reduction of CO2 molecule. The phase-space of these copper clusters is rich in conformations of distinct morphologies starting from planar, 2D geometries to prolate-shaped geometries and also high-symmetry structures. The binding efficiency and the activation of CO2 are highest for medium sized clusters (n=9-17) with prolate-morphologies as compared to small or larger sized CunCO(2) clusters that are existing mainly as planar (triangular, tetragonal etc.) or highly-symmetric geometries (icosahedron, capped-icosahedron etc.), respectively. The best performing (prolate-shaped) CunCO2 conformations are quite fluxional and also they are thermally stable, as demonstrated by the molecular dynamics simulations. Furthermore, on these CunCO(2) conformations, the step-by-step hydrogenation pathways of CO2 to produce value-added products like methanol, formic acid, and methane are exceptionally favorable and energy-efficient.
Keywords: CO2 activation; CO2 hydrogenation; Copper clusters; Density Functional Theory (DFT); molecular dynamics

Steroidal scaffold decorations in Solanum alkaloid biosynthesis - Lucier, Rosalind; Kamileen, Mohamed O.; Nakamura, Yoko; Serediuk, Sofiia; Barbole, Ranjit; Wurlitzer, Jens; Kunert, Maritta; Heinicke, Sarah; O'Connor, Sarah E.; Sonawane, Prashant D. (Molecular Plant, 2024)
Steroidal glycoalkaloids (SGAs) are specialized metabolites produced by hundreds of Solanum species, including important vegetable crops such as tomato, potato, and eggplant. Although it has been known that SGAs play important roles in defense in plants and ``anti-nutritional''effects (e.g., toxicity and bitterness) to humans, many of these molecules have documented anti-cancer, anti-microbial, antiinflammatory, anti-viral, and anti-pyretic activities. Among these, a-solasonine and a-solamargine isolated from black nightshade (Solanum nigrum) are reported to have potent anti-tumor, anti-proliferative, and anti-inflammatory activities. Notably, a-solasonine and a-solamargine, along with the core steroidal aglycone solasodine, are the most widespread SGAs produced among the Solanum plants. However, it is still unknown how plants synthesize these bioactive steroidal molecules. Through comparative metabolomictranscriptome-guided approach, biosynthetic logic, combinatorial expression in Nicotiana benthamiana, and functional recombinant enzyme assays, here we report the discovery of 12 enzymes from S. nigrum that converts the starting cholesterol precursor to solasodine aglycone, and the downstream a-solasonine, a-solamargine, and malonyl-solamargine SGA products. We further identified six enzymes from cultivated eggplant that catalyze the production of a-solasonine, a-solamargine, and malonyl-solamargine SGAs from solasodine aglycone via glycosylation and atypical malonylation decorations. Our work provides the gene tool box and platform for engineering the production of high-value, steroidal bioactive molecules in heterologous hosts using synthetic biology.
Keywords: a-solamargine; Biosynthetic pathway; malonyl-solamargine; Solanum; Specialized metabolites; steroidal glycoalkaloids

Strain improvement for enhanced erythritol production by Moniliella pollinis Mutant-58 using jaggery as a cost-effective substrate - Khatape, Anil B.; Rangaswamy, Vidhya; Dastager, Syed G. (International Microbiology, 2024)
Erythritol has been produced by various microorganisms including Yarrowia, Moniliella, Aureobasidium, and Candida strains. Due to its relatively high price, erythritol sweetener is used lesser than other polyols despite having many advantages. Therefore, in this study, Moniliella pollinis strain was improved for erythritol production by chemical mutagenesis and subsequently screening for cost-effective carbon sources for the enhanced erythritol yield. M. pollinis was subjected to N-methyl N-nitro N-nitroso guanidine (NTG), ethyl methyl sulfonate (EMS), and UV mutagenesis for improved erythritol production. The fmutant strains were evaluated for enhanced erythritol production medium optimization by using different carbon substrates at the shake flask level. To enhance the production of erythritol and statistical media, optimization was carried out using a central composite design (CCD). Among 198 isolated mutants, Mutant-58 strain generated by EMS mutagenesis was selected for further assessment. The Mutant-58 strain showed significant morphological changes as compared to the parent strain. Furthermore, statistically optimized media composition resulted in the higher production of erythritol (91.2 & PLUSMN; 3.4 g/L) with a yield of 40.7 & PLUSMN; 3.4 % in shake flask experiments. The optimized medium composition for erythritol production constitutes (g/L) 225 jaggery, 4.4 yeast extract (YE), 4.4 KH2PO4, 0.31 MgSO4, and pH 5.5. The present study demonstrated strain improvement, media, and process optimization resulting in a 30% increase in the erythritol production in the Mutant-58 as compared to the parent strain. This is also the first instance where jaggery has been used as a cost-effective carbon source alternative to glucose for industrial-scale erythritol production.
Keywords: Erythritol; Fermentation; Moniliella pollinis; Mutation; Optimization; renewable resource

Structural insights into ketanserin salts with aliphatic acids and their physiochemical properties - Kenguva, Gowtham; Rout, Smruti Rekha; Shaikh, Tabrez R.; Baidya, Debjani; Shelke, Nikita; Sanphui, Palash; Dandela, Rambabu (CRYSTENGCOMM, 2024)
Keywords: PHARMACEUTICAL COCRYSTAL; SEROTONIN; SHYDROCHLOROTHIAZIDE; solubility

Structure of epoxide hydrolase 2 from Mangifera indica throws light on the substrate specificity determinants of plant epoxide hydrolases - Bhoite, Ashwini; Gaur, Neeraj K.; Palange, Megha; Kontham, Ravindar; Gupta, Vidya; Kulkarni, Kiran (Biochemical and Biophysical Research Communications, 2024)
Epoxide hydrolases (EHs) are a group of ubiquitous enzymes that catalyze hydrolysis of chemically reactive epoxides to yield corresponding dihydrodiols. Despite extensive studies on EHs from different clades, generic rules governing their substrate specificity determinants have remained elusive. Here, we present structural, biochemical and molecular dynamics simulation studies on MiEH2, a plant epoxide hydrolase from Mangifera indica. Comparative structure-function analysis of nine homologs of MiEH2, which include a few AlphaFold structural models, show that the two conserved tyrosines (MiEH2Y152 and MiEH2Y232) from the lid domain dissect substrate binding tunnel into two halves, forming substrate-binding-pocket one (BP1) and two (BP2). This compartmentalization offers diverse binding modes to their substrates, as exemplified by the binding of smaller aromatic substrates, such as styrene oxide (SO). Docking and molecular dynamics simulations reveal that the linear epoxy fatty acid substrates predominantly occupy BP1, while the aromatic substrates can bind to either BP1 or BP2. Furthermore, SO preferentially binds to BP2, by stacking against catalytically important histidine (MiEH2H297) with the conserved lid tyrosines engaging its epoxide oxygen. Residue (MiEH2L263) next to the catalytic aspartate (MiEH2D262) modulates substrate binding modes. Thus, the divergent binding modes correlate with the differential affinities of the EHs for their substrates. Furthermore, long-range dynamical coupling between the lid and core domains critically influences substrate enantioselectivity in plant EHs.
Keywords: Enantioselectivity; Epoxide hydrolase; molecular dynamics simulation; Regioselectivity; X-ray crystallography

Supercritical water hydrolysis of cellulose: State-of-the-art of green depolymerisation technique - Kulkarni, Sphurti P. (Biomass & Bioenergy, 2024)
Bio-refinery is a critical infrastructure to facilitate the fullest energy extraction from the pivotal energy resource biomass. Hydrolysis of the most abundant biomass constituent biopolymer cellulose to produce cello-oligomers and glucose is a critical step for the efficient production of various chemicals and fuels. Supercritical water hydrolysis (SCWH) of cellulose has emerged as the promising greener technology for the production of glucose and simple sugars. Glucose production by SCWH enables the process integration or cascading for the production of various biofuels, bioenergy, bio-based chemicals, and various bio-products, necessary for the impeccable success of cellulosic biomass-based bio-refinery. Starting from the unique interaction of cellulose and supercritical water, this minireview provides an insight into the various aspects of the SCWH of cellulose including mechanism, reaction pathways, product distribution, process optimization, and kinetic modelling. The batch reactors are simple reactor configurations for such high pressure and temperature; however, continuous flow reactors are essential for better control over process conditions and for an efficient process. With more understanding of reaction mechanism and product distribution, heat and mass transfer conjugation with reaction rates and design of high-pressure equipment, an efficient completely green process can be developed for cellulose and such biopolymer hydrolysis.
Keywords: Bio-refinery; cellulose; glucose; Supercritical water; Ultra-fast reactions

Supramolecular polyplexes from Janus peptide nucleic acids (bm-PNA-G5): self-assembled bm-PNA G-quadruplex and its tetraduplex with DNA - Todkari, Iranna Annappa; Chaudhary, Preeti; Kulkarni, Mahesh J.; Ganesh, Krishna N. (ORGANIC & BIOMOLECULAR CHEMISTRY, 2024)
Keywords: DOUBLE-HEADED NUCLEOTIDES; ENERGY-TRANSFER; Guanine; MAJOR GROOVE

Surface electronic properties-driven electrocatalytic nitrogen reduction on metal-conjugated porphyrin 2D-MOFs - Maibam, Ashakiran; Orhan, Ibrahim B.; Krishnamurty, Sailaja; Russo, Salvy P.; BabaRao, Ravichandar (ACS Applied Materials and Interfaces, 2024)
Two-dimensional (2D) metal organic framework (MOF) or metalloporphyrin nanosheets with a stable metal-N-4 complex unit present the metal as a single-atom catalyst dispersed in the 2D porphyrin framework. First-principles calculations on the 3d-transition metals in M-TCPP are investigated in this study for their surface-dependent electronic properties including work function and d-band center. Crystal orbital Hamiltonian population (-pCOHP) analysis highlights a higher contribution of the bonding state in the M-N bond and antibonding state in the N-N bond to be essential for N-N bond activation. A linear relationship between Delta G(max) and surface electronic properties, N-N bond strength, and Bader charge has been found to influence the rate-determining potential for nitrogen reduction reaction (NRR) in M-TCPP MOFs. 2D Ti-TCPP MOF, with a kinetic energy barrier of 1.43 eV in the final protonation step of enzymatic NRR, shows exclusive NRR selectivity over competing hydrogen reduction (HER) and nitrogenous compounds (NO and NO2). Thus, Ti-TCPP MOF with an NRR limiting potential of -0.35 V in water solvent is proposed as an attractive candidate for electrocatalytic NRR.
Keywords: Density Functional Theory (DFT); electrocatalytic nitrogen reductionreaction; kinetic energy barrier; limitingpotential; Metalloporphyrin; NRR selectivity

Surface-anchored PtNi alloy network over SiO2 (PtNi/SiO2): a versatile carbon-free cathode for proton exchange membrane fuel cells (PEMFCs) - Kumar, Sachin; Yoyakki, Athira; Kurungot, Sreekumar (ACS Applied Engineering Materials, 2024)
The large-scale commercialization of the PEMFCs is hindered due to the high cost of the Pt-based electrocatalysts (Pt/C) and the low durability associated with the oxidation of the carbon support in Pt/C. Many Pt-based carbon-free electrocatalysts have been explored, exhibiting excellent stability and activity, but the performance is further expected to be improved by developing suitable Pt alloy catalysts based on the carbon-free supports. To explore this possibility, we have developed a PtNi/SiO2 alloy system, which acts as a carbon-free electrocatalyst exhibiting enhanced activity for the oxygen reduction reaction (ORR). A half-cell study of PtNi/SiO2 (45 wt%) shows ∼4.3 times higher ORR activity compared to the state-of-the-art Pt/C (40%). The uniform distribution of the PtNi nanoparticles over SiO2 is the crucial feature of the catalyst. PtNi/SiO2 shows better durability even after 5000 cycles compared to the state-of-the-art Pt/C. The catalyst shows a negative shift in the half-wave potential (E1/2) by only 5 mV, which is lower than that of the 11 mV drop incurred by Pt/C. Considering this high activity of the PtNi/SiO2 catalyst for the ORR, we tried to explore the possibility of demonstrating a single-cell PEMFC in the MEA by pairing the catalyst as the cathode along with the Pt/C as the anode. This paired configuration of the single cell is found to be providing promising performance by delivering a current density of 960 mA/cm2 at 0.60 V and a maximum power density of 835 mW/cm2. Thus, this study outlines the possibility of developing potential alloy combinations of Pt on carbon-free substrates and then deploying them as electrodes for PEMFC applications. In the context of mitigating the carbon corrosion-related issues without compromising the intrinsic activities of the catalysts, the development of suitable alloy combinations on various carbon-free substrates is of significant technological advantages. The formation of the alloy phase along with the fine and uniform distribution of the alloy nanoparticles on the SiO2 substrate, followed by its successful deployment as the cathode of a single cell, points toward the scope of exploring material developments in this direction.

Sustainable bioprocess technology for producing food-flavour (+)-γ-decalactone from castor oil-derived ricinoleic acid using enzymatic activity of Candida parapsilosis: Scale-up optimization and purification using novel composite - Syed, Naziya; Singh, Suman; Chaturvedi, Shivani; Kumar, Prashant; Kumar, Deepak; Jain, Abhinav; Sharma, Praveen Kumar; Nannaware, Ashween Deepak; Chanotiya, Chandan Singh; Bhambure, Rahul; Kumar, Pankaj; Kalra, Alok; et al. (Journal of Biotechnology, 2024)
Ricinoleic acid (RA) from castor oil was employed in biotransformation of peach-flavoured gamma-decalactone (GDL), using a Candida parapsilosis strain (MTCC13027) which was isolated from waste of pineapple crown base. Using four variables-pH, cell density, amount of RA, and temperature-the biotransformation parameters were optimized using RSM and BBD. Under optimized conditions (pH 6, 10 % of microbial cells, 10 g/L RA at 28 degrees C), the conversion was maximum and resulted to 80 % (+)-GDL (4.4 g/L/120 h) yield in shake flask (500 mL). Furthermore, optimization was achieved by adjusting the aeration and agitation parameters in a 3 L bioreactor, which were then replicated in a 10 L bioreactor to accurately determine the amount of (+)-GDL. In bioreactor condition, 4.7 g/L (>85 %) of (+)-GDL is produced with 20 % and 40 % dissolved oxygen (1.0 vvm) at 150 rpm in 72 h and 66 h, respectively. Further, a new Al-Mg-Ca-Si composite column-chromatography method is developed to purify enantiospecific (+)-GDL (99.9 %). This (+)-GDL is 100 % nature-identical as validated through 14C-radio-carbon dating. Thorough chemical investigation of enantiospecific (+)-GDL is authenticated for its use as flavour. This bioflavour has been developed through a cost-effective biotechnological process in response to the demand from the food industry on commercial scale.
Keywords: (+)-gamma-Decalactone; Al-Mg-Ca-Si composite; Bioflavour; Candida parapsilosis; castor oil; Food-waste

SWATH-MS reveals that bisphenol A and its analogs regulate pathways leading to disruption in insulin signaling and fatty acid metabolism - Kulsange, Shabda E.; Sharma, Monika; Sonawane, Babasaheb; Jaiswal, Meera R.; Kulkarni, Mahesh J.; Santhakumari, B. (Food and Chemical Toxicology, 2024)
Bisphenol A (BPA) is an endocrine-disrupting chemical (EDC), associated with obesity and insulin resistance. The FDA prohibited the use of BPA-based polycarbonate resins in infant formula packaging; thus, its analogs, viz. Bisphenol S (BPS) and Bisphenol F (BPF) were considered alternatives in epoxy resins, plastics, and food cans. As these analogs might evoke a similar response, we investigated the role of Bisphenols (BPA, BPF, and BPS), on insulin signaling in CHO-HIRc-myc-GLUT4eGFP cells at environmentally relevant concentrations of 2 nM and 200 nM. Insulin signaling demonstrated that Bisphenols reduced phosphorylation of IR and AKT2, GLUT4 translocation, and glucose uptake. This was accompanied by increased oxidative stress. Furthermore, SWATHMS-based proteomics of 3T3-L1 cells demonstrated that Bisphenol-treated cells regulate proteins in insulin resistance, adipogenesis, and fatty acid metabolism pathways differently. All three Bisphenols induced differentially expressed proteins enriched similar pathways, although their abundance differed for each Bisphenol. This might be due to their varying toxicity level, structural differences, and estrogen-mimetic activity. This study has important implications in addressing health concerns related to EDCs. Given that the analogs of BPA are considered alternatives to BPA, the findings of this study suggest they are equally potent in altering fatty acid metabolism and inducing insulin resistance.
Keywords: Bisphenols; Estrogen; Lipid droplet; Mitochondrial beta-oxidation; Oxidative stress; PPAR gamma

Switchable molecular electrocatalysis - Dutt, Shifali; Kottaichamy, Alagar Raja; Dargily, Neethu Christudas; Mukhopadhyay, Sanchayita; Nayak, Bhojkumar; Devendrachari, Mruthyunjayachari Chattanhali; Vinod, Chatakudhath Prabakaran; Kotresh, Harish Makri Nimbegondi; Thotiyl, Musthafa Ottakam (CHEMICAL SCIENCE, 2024)
Keywords: CO2 reduction; COBALT PHTHALOCYANINE; NANOPOROUS GOLD; oxygen reduction

Synergistic combination of ZnCl2/Cu-BTC MOF for the photocatalytic oxidative deamination of benzylamines using CO2 under visible-light irradiation - Kumar, Amod; Bhatt, Sakshi; Samal, Pragnya Paramita; Krishnamurty, Sailaja; Jain, Suman L. (ACS Applied Engineering Materials, 2024)
This paper demonstrates the first CO2-mediated oxidative deamination of benzylamines to benzaldehydes using a combination of ZnCl2 and Cu-BTC MOF as photocatalysts in a carbon tetrachloride solvent under visible-light irradiation. Interestingly, the synergistic combination of ZnCl2 and Cu-BTC afforded the targeted oxidation of benzylamine to benzaldehyde, wherein CO2 acted as an oxidant. The individual components yielded the corresponding imine as the main product, resulting from the oxidative coupling of the benzylamine. DFT calculations and computational studies supported the proposed reaction pathways involving the formation of an intermediate imine from benzylamine via dehydrogenation followed by hydrolysis to produce benzaldehyde. This work, demonstrating the use of CO2 as an oxidant, may open up new avenues for CO2 utilization in chemical production by using sustainable light energy.

Synergistic effect of lactam and pyridine nitrogen on polysulfide chemisorption and electrocatalysis in lithium sulfur batteries - Javaregowda, Bharathkumar H.; Kargude, Radhakisan; Birajdar, Sarika; Shivankar, Bhavana; Krishnamurty, Sailaja; Jones, Lathe A.; Caruso, Rachel A.; Krishnamoorthy, Kothandam (ACS APPLIED MATERIALS & INTERFACES, 2024)
Keywords: Li-S battery; phenyl-diketopyrrolopyrrole; pyridine-diketopyrrolopyrrole

Synergistic effects of the substrate-ligand interaction in metal-organic complexes on the de-electronation kinetics of a vitamin C fuel cell - Parmar, Muskan; Mukhopadhyay, Sanchayita; Mondal, Ritwik; Nayak, Bhojkumar; Dargily, Neethu Christudas; Kotresh, Harish Makri Nimbegondi; Vinod, Chathakudath Prabhakaran; Ottakam Thotiyl, Musthafa (Dalton Transactions, 2024)
The rising demand for portable energy conversion devices has spurred the advancement of direct liquid fuel cells (DLFCs) employing fuels such as alcohol, ammonia, hydrazine, and vitamin C. In these devices, various precious metal platforms have been explored to increase the de-electronation kinetics and reduce catalyst poisoning, but with substantial cost implications. We demonstrate the crucial role of ligands in non-precious organometallic complexes in influencing the de-electronation kinetics of fuel molecules through a unique substrate-ligand synergistic interaction. This unique chemistry imparts electron deficiency at the catalytic metal center while simultaneously populating the ligand with an extensive proton charge assembly. This distinct substrate-ligand interaction enhances the DLFC performance by coulombically dragging the substrate with a distinct amplification in its de-electronation kinetics. By integrating this approach with a ferricyanide/ferrocyanide half-cell reaction, a precious metal-free vitamin C fuel cell is developed, which is capable of generating an open circuit voltage of similar to 950 mV, a peak power density of similar to 97 mW cm-2 at a peak current density of similar to 215 mA cm-2 with the performance metrics nearly 1.7 times higher than a precious metal based DLFC. This highlights the potential of the substrate-ligand synergy in the design of efficient molecular catalysts for energy conversion applications. A precious metal-free biomass fuel cell through substrate-ligand interactions.

Synthesis, crystal structure and Hirshfeld surface analysis of N-(4-methoxyphenyl)picolinamide - Burieva, Dilnoza; Torambetov, Batirbay; Bobonazarova, Sarvinoz; Abdushukurov, Anvar; Kholikov, Tursinali; Khan, Akram A; Ashurov, Jamshid; Yusufov, Mukhriddin (Acta Crystallographica Section E: Crystallographic Communications, 2024)
The synthesis, <a class="ref_lookup_yellow hideyellow" href="https://dictionary.iucr.org/Crystal_structure" style="text-decoration-line: none; color: rgb(0, 0, 0); font-family: Verdana, Arial, Helvetica, sans-serif;" target="Navigator">crystal structure, and Hirshfeld surface analysis of N-(4-methoxyphenyl)picolinamide (MPPA), C13H12N2O2, are presented. MPPA crystallizes in the monoclinic <a class="ref_lookup_yellow hideyellow" href="https://dictionary.iucr.org/Space_group" style="text-decoration-line: none; color: rgb(0, 0, 0); font-family: Verdana, Arial, Helvetica, sans-serif;" target="Navigator">space group P21/n, with a single molecule in the <a class="ref_lookup_yellow hideyellow" href="https://dictionary.iucr.org/Asymmetric_unit" style="text-decoration-line: none; color: rgb(0, 0, 0); font-family: Verdana, Arial, Helvetica, sans-serif;" target="Navigator">asymmetric unit. Structural analysis reveals that all non-hydrogen atoms are nearly coplanar, and the molecule exhibits two intramolecular hydrogen bonds that stabilize its conformation. Supramolecular features include significant intermolecular interactions, primarily C—H⋯π and various hydrogen bonds, contributing to the overall crystal cohesion, as confirmed by energy framework calculations yielding a total interaction energy of −138.3 kJ mol−1. Hirshfeld surface analysis indicates that H⋯H interactions dominate, followed by C⋯H and O⋯H interactions, highlighting the role of <a class="ref_lookup_orange hideorange" href="https://goldbook.iupac.org/V06597.html" style="text-decoration-line: none; color: rgb(0, 0, 0); font-family: Verdana, Arial, Helvetica, sans-serif;" target="Navigator">van der Waals forces and hydrogen bonding in crystal packing.

Synthesis of benzofuran-6-carboxylic acid, an intermediate of lifitegrast with low-carbon footprints - Zade, Vishal M.; Athawale, Paresh R.; Kopperi, Harishankar; Mohan, S. Venkata; Reddy, D. Srinivasa (ACS SUSTAINABLE CHEMISTRY & ENGINEERING, 2024)
Keywords: benzofuran-6-carboxylicacid; dry eye disease; life cycle; lifitegrast; process development

Synthesis of Hofmann-based metal-organic frameworks incorporating a bis-pyrazole linker for various gas separations - Matthews, Brooke L.; Harvey-Reid, Nathan C.; Jangodaz, Elnaz; Scott, Victoria-Jayne; Polson, Matthew I. J.; Maibam, Ashakiran; BabaRao, Ravichandar; Telfer, Shane G.; Kruger, Paul E. (JOURNAL OF MATERIALS CHEMISTRY A, 2024)
Keywords: acetylene; C2H2/CH4; Ni; Purification; SPIN-CROSSOVER BEHAVIOR

Synthesis of pyrazole and 1,3,4-oxadiazole derivatives of pharmaceutical potential - Kadam, Mayur; Jadhao, Nitin L.; Gajbhiye, Jayant M. (Prospects in Pharmaceutical Sciences, 2024)
Heterocyclic compounds are important molecules that serve as scaffolds or linkers for the core structure of numerous drug substances. In particular, pyrazole and 1,3,4-oxadiazole are compounds of great interest due to their comprehensive biological activities and interesting structural features. Here, we described an efficient and economical synthetic route leading to N-phenyl substituted pyrazole and 1,3,4-oxadiazole derivatives. Retrosynthetic disconnective analysis showed that the N-phenyl substituted pyrazole can be obtained from chalcone, accessible from the respective aldehyde, and acetophenone. The disubstituted 1,3,4-oxadiazole can be constructed from the respective aldehyde, which originates from pyrrole-containing compound, and formyl chloride. Based on our retrosynthetic analysis, N-phenyl substituted pyrazole was obtained by cyclization of the respective chalcone with phenylhydrazine to give pyrazoline which was in turn converted into pyrazole by oxidative aromatization. Potassium carbonate and a catalytic amount of molecular iodine were used to oxidatively cyclize semicarbazones into 1,3,4-oxadiazoles in a transition metal-free process. Novel pyrazole and 1,3,4-oxadiazoles with potential biological activity are investigated as antituberculosis, anticonvulsant, antidiabetic, anticancer, and tyrosinase inhibitory agents.

Synthesis of quinazolinone based spirocyclopropanes via [3?+?2] cycloaddition reaction: in silico anti-tubercular molecular docking studies and ADME prediction - Allaka, Bhargava Sai; Kanchrana, Madhu; Gamidi, Rama Krishna; Basavoju, Srinivas (Polycyclic Aromatic Compounds, 2024)
A highly efficient cascade annulation approach is developed for the synthesis of novel quinazolinone-based spirocyclopropanes via three-component [3 + 2] cycloaddition reaction with aldehydes, tosylhydrazide and quinazolinyl chalcones. The reaction features the formation of two C–C bonds and three stereogenic centers. A variety of highly functionalized spirocyclopropyl quinazolinones were obtained in good yields under mild reaction conditions. Furthermore, in silico anti-tubercular (anti-TB) molecular docking studies were performed for the generated compounds against three Mycobacterium tuberculosis proteins with PDBID: 1DF7, 1P44 and 4TZK. ADME prediction were evaluated for the drug like properties of the synthesized compounds.

Synthesized novel chromogenic reagent and sensor: detection and identification of dichlorvos - Gedam, Ashwin D.; Katiya, Manish M.; Dhonde, Madhukar G.; Ganorkar, Kapil S.; Thakare, Vijay J.; Mandlik, Prashant R.; Jadhao, Nitin L.; Gajbhiye, Jayant M.; Kumar, Ravi; Vaval, Nayana (Heliyon, 2024)
We developed a novel chromogenic reagent and sensor by selective approach, for the detection and identification of dichlorvos, which we tested with the thin layer chromatography method. For the first time, we reported in situ-generated glyoxal as a hydrolysis product, which then interacts with isoniazid to produce a yellow-colored cyclic compound. We used well-known spectroscopic techniques to confirm the chemical identity of the final product. We initially investigated the reaction using a variety of approaches, followed by attempts to establish the reaction mechanism using Density Functional Theory by Gaussian software.
Keywords: DFT analysis; Dichlorvos; Gloyxal; Hydrazone; Isoniazid

Synthetic layered double hydroxide on biodegradable support: an efficient adsorbent for defluoridation of water - Mayadevi, S.; Kirandas, M. D.; Manilal, A. M.; Roshini, N.; Mandal, Sujata (Indian Journal of Chemical Technology, 2024)
Fluoride concentrations in drinking water above permissible levels and incidences of fluorosis among people have been reported from many parts of the world including India. Low-cost and biodegradable adsorbents are the preferred choice for the removal of fluoride from an aqueous medium. In the present study, zinc-aluminium layered double hydroxide (LDH) supported on sugarcane bagasse (raw and acid-treated) has been synthesized, characterized, and investigated for the defluoridation of water. The SEM micrographs of the supported adsorbents show good dispersion of the LDH particles on the support material. The defluoridation capacity of the LDH is enhanced by supporting it on bagasse. The adsorption capacity of supported adsorbents increased by 3-fold than the unsupported LDH adsorbent. The adsorption data have been well fitted to the Freundlich isotherm model indicating physical and multi-layer adsorption. The maximum fluoride adsorption capacity has been found to be 8.85 mg/g with 76.3% fluoride removal when the initial fluoride concentration is 11-12 mg/L. The pseudo-second-order kinetic model has been found suitable to explain the fluoride adsorption kinetics on the supported LDH adsorbents. The present study reveals that the bagasse-supported LDH adsorbent has a high potential for defluoridation of water.
Keywords: adsorption kinetics; Fluoride adsorption; Layered double hydroxide; Sugarcane bagasse

Tailoring helical ends of π-extended [6]heterohelicenes to control optical, and electrochemical features - Kumar, Viksit; Dongre, Sangram D.; Venugopal, Geethu; Narayanan, Aswini; Babu, Sukumaran Santhosh (Chemical Communications, 2024)
The inherent helical chirality and improved pi-stacking capabilities endow helicenes with fascinating photophysical characteristics when decorated with lateral pi-extensions. Here, we report the synthesis and physicochemical characterization of expanded hetero[6]helicenes fused with thiadiazole and selenadiazole rings at the helical ends. Comparing these heterohelicenes revealed the impact of the heteroatom-embedded aromatic rings on the excited state and redox features. A small structural variation of the terminal rings from thiadiazole to selenadiazole caused a striking change in the heterohelical nanographenes. The inherent helical chirality and improved pi-stacking capabilities endow helicenes with fascinating photophysical characteristics when decorated with heteroatoms.

Total synthesis and revision of stereochemistry of a natural benzo[g]isochromene stereodiad isolated from rubia philippinensis - Choudhury, Rahul; Miriyala, Satya Ravi Teja; Resmi, K. R.; Sridhar, Balasubramanian; Kasa, S. R. Krishna Murthy; Reddy, D. Srinivasa (Organic Letters, 2024)
This study presents a total synthesis and revision of the stereochemical configuration of the conformationally flexible natural product benzo[g]isochromene stereodiad alongside its diastereomeric counterparts. The highlights of the synthesis are the TiCl4-mediated diastereoselective aldol reaction, Pd-catalyzed lactonization, and Schmidt glycosidation. Our efforts using total synthesis disclosed herein proved that a previously assigned structure required revision.

Transcriptome analysis and Structure-Based drug discovery identifies potential biofungicides for controlling Fusarium wilt in chickpea - Sahoo, Rosaleen; Kadoo, Narendra (Journal of Molecular Liquids, 2024)
Fusarium wilt caused by the fungal pathogen Fusarium oxysporum f.sp. ciceri (Foc) is a devastating chickpea disease. Foc is a soil-borne pathogen that invades plants through roots and can kill them in three to four weeks. Although Fusarium wilt can be controlled by soil solarization or fumigation with chemical fungicides, these are not always effective. Soil fumigation is also hazardous to the beneficial soil microflora, deteriorates soil health, and causes pollution. Hence, there is an urgent need to identify potent and environment-friendly biofungicides to control fungal pathogens. We employed transcriptome analysis and structure-based drug discovery approaches to identify potential biofungicides from four widely used medicinal plants: Lantana camara, Piper betel, Ricinus communis, and Azadirachta indica. Fusarium wilt-resistant and susceptible chickpea varieties were pathogeninoculated and grown under controlled conditions in a greenhouse. Transcriptome analysis was performed to identify pathogenicity-related differentially expressed genes (DEGs). Over 600 phytochemicals from the four medicinal plants and four chemical fungicides were considered for molecular docking against the predicted protein structures of the four most expressed pathogen DEGs. The phytochemicals with the best docking scores and the lowest predicted toxicity risk were considered for molecular dynamics (MD) simulation at 100 ns timescale, and 15 potential biofungicides were identified. This study paves the way for developing biofungicides with enhanced efficacy and safety to manage Fusarium wilt in chickpea.
Keywords: Antifungal molecules; Cicer arietinum; fusarium oxysporum; MD Simulation; medicinal plants; Molecular docking

Transfer semi-hydrogenation of terminal alkynes with a well-defined iron complex - Chowdhury, Deep; Goswami, Souvik; Krishna, Gamidi Rama; Mukherjee, Arup (Dalton Transaction, 2024)
The synthesis and characterization of a bis-iron(ii) complex was accomplished upon treatment of a phosphine free NNN-pincer ligand (L) with FeCl2 center dot 4H2O under ambient conditions. The deep greenish colored iron(ii) complex (Fe-1) was characterized by a single-crystal X-ray diffraction study along with IR spectroscopy, UV-Vis spectroscopy, mass spectrometry, and elemental analysis. The Fe-1 complex was tested for the transfer semi-hydrogenation of terminal alkynes to the corresponding alkenes through the dehydrogenation of dimethyl amine-borane. This procedure enables the conversion of various structurally different terminal alkynes to alkenes under mild conditions. Control experiments were performed to shed light on the possible intermediates generated during the present protocol. A bench stable iron(ii) complex with the pincer ligand backbone was synthesized and characterized. The well-defined iron complex was successfully utilized for the dehydrogenation of DMAB and subsequent transfer semi-hydrogenation of terminal alkynes.

Transient Electro-Graphitization of MOFs Affecting the Crystallization of Ruthenium Nanoclusters for Highly Efficient Hydrogen Evolution - Karim, Golam Masud; Patra, Amalika; Deb, Sujit Kumar; Upadhya, Hemanta; Das, Snehasish; Mukherjee, Priyam; Ahmad, Waleed; Barman, Narad; Thapa, Ranjit; Dambhare, V, Neha; Rath, Arup Kumar; Das, Jaysri; et al. (ADVANCED FUNCTIONAL MATERIALS, 2024)
Keywords: amorphous ruthenium; crystallization control; graphitic nanostructure

Trapping an elusive Fe(IV)-superoxo intermediate inside a self-assembled nanocage in water at room temperature - Gera, Rahul; De, Puja; Singh, Kundan K.; Jannuzzi, Sergio A. V.; Mohanty, Aisworika; Velasco, Lucia; Kumar, Pankaj; Marco, J. F.; Nagarajan, Kalaivanan; Pecharroman, Carlos; Rodriguez-Pascual, P. M.; DeBBeer, Serena; et al. (JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2024)
Keywords: CATALYTIC EPOXIDATION; DIOXYGEN ACTIVATION; NONHEME IRON; X-RAY-ABSORPTION

Triazatruxene amine donor-based visible-light-responsive unsymmetrical squaraine dyes for dye-sensitized solar cells - Ingole, Kiran Balaso; Deshmukh, Shivdeep Suresh; Verma, Tushar Singh; Krishnamurty, Sailaja; Krishnamoorthy, Kothandam; Nithyanandhan, Jayaraj (ACS Applied Energy Materials, 2024)
Optimized charge-transfer dynamics at the dye-TiO2/electrolyte interface are required for an enhanced dye-sensitized solar cell (DSSC) device performance. Such an optimized interface enhances the charge-injection, dye-regeneration, and diminished charge-recombination processes, synergistically enhancing the device efficiency. In this study, octupolar-structured sensitizers are designed to improve the interaction between the dye and the redox electrolyte for increasing the dye-regeneration process upon photoexcitation. Accordingly, a set of unsymmetrical squaraine dyes with indoline and triazatruxene amine donor-based D-A-D dyes are designed (KV1-KV3), synthesized, and sensitized with a semiconducting metal oxide (TiO2) film. The sensitizer forms a monolayer on the TiO2 surface, leading to a dye-dye interaction, which broadens the absorption spectrum. The N atom of the triazatruxene amine donor was left unsubstituted in KV1, whereas a hexyl chain was installed in KV2 and KV3 and a branched alkyl chain was installed on the core N atoms in KV3 to control the self-assembly of dyes on the TiO2 surface. Self-assembly of alkyl groups wrapped in KV1-KV3 dyes on the TiO2 surface aids surface passivation and broadens the absorption profile, improving the light-harvesting capabilities. The DSSC devices based on KV2 exhibited a high power conversion efficiency of 7.85% (V-oc = 794 mV, J(sc) = 14.76 mA/cm(2), and FF = 67%), with an onset incident photon-to-current conversion efficiency response from 680 nm.
Keywords: aggregationof dyes; Dye-sensitized solar cells; metal-free organic dyes; self-assembly of dye; squaraine dyes; triazatruxene

`Turning on' to glutathione: a rhodamine-based fluorescent chemodosimeter with nanomolar sensitivity - Badekar, Pooja S.; Deo, Harshada S.; Varma, Mokshada E.; Kulkarni, Prasad P.; Maibam, Ashakiran; Krishnamurty, Sailaja; Kumbhar, Anupa A. (ChemistrySelect, 2024)
A new colorimetric and fluorescence turn-on chemodosimeter for selective detection of GSH over Cys and Hcy with 34-fold enhancement in emission intensity is reported. Probe 1 exhibited ultra-sensitivity toward GSH with 0.125 nM detection limit and successfully displayed GSH detection in MCF-7 live cells. The mechanism of sensing is established by density functional theoretical calculations.
Keywords: Chemodosimeter; Fluorescence turn-on; GSH; MCF-7 cells; Rhodamine

Ultralight crystalline hybrid composite material for highly efficient sequestration of radioiodine - Fajal, Sahel; Mandal, Writakshi; Torris, Arun; Majumder, Dipanjan; Let, Sumanta; Sen, Arunabha; Kanheerampockil, Fayis; Shirolkar, Mandar M.; Ghosh, Sujit K. (Nature Communications, 2024)
Considering the importance of sustainable nuclear energy, effective management of radioactive nuclear waste, such as sequestration of radioiodine has inflicted a significant research attention in recent years. Despite the fact that materials have been reported for the adsorption of iodine, development of effective adsorbent with significantly improved segregation properties for widespread practical applications still remain exceedingly difficult due to lack of proper design strategies. Herein, utilizing unique hybridization synthetic strategy, a composite crystalline aerogel material has been fabricated by covalent stepping of an amino-functionalized stable cationic discrete metal-organic polyhedra with dual-pore containing imine-functionalized covalent organic framework. The ultralight hybrid composite exhibits large surface area with hierarchical macro-micro porosity and multifunctional binding sites, which collectively interact with iodine. The developed nano-adsorbent demonstrate ultrahigh vapor and aqueous-phase iodine adsorption capacities of 9.98 g.g-1 and 4.74 g.g-1, respectively, in static conditions with fast adsorption kinetics, high retention efficiency, reusability and recovery. The development of effective adsorbents of radioiodine nuclear waste remains difficult due to the lack of proper material design strategies. Here the authors report an ultralight hierarchically porous crystalline multifunctional hybrid nanocomposite for ultrafast entrapment of iodine and polyiodide species under both static and dynamic condition.

Ultra-small Au nanoclusters with tailored photoluminescence properties using modified thiol ligands: a computational and experimental demonstration - Chahande, Anurag M.; Maibam, Ashakiran; Krishnamurty, Sailaja; Devi, R. Nandini (Particle & Particle Systems Characterization, 2024)
Au nanoclusters with tailored photoluminescence can be obtained through controlled nanoparticle ligand interface chemistry. The present work reports molecular gold nanoclusters with tuneable photoluminescence emission from 600 to 700 nm using N,N `,N `'-trialkyl (11-mercaptoundecyl)ammonium chloride ligands as capping-agents. The tunability within red spectral region is regulated through specific interface chemistry between gold nanoclusters of molecular range and functional groups of the quaternary ammonium head over N,N `,N `'-trialkyl(11-mercaptoundecyl)ammonium chloride. Combined understanding obtained from the spectroscopy, microscopy, and density functional theory studies demonstrate that the functional group specific electronic interactions at the interfaces steer the emission characteristics of ``molecular'' Au nanoparticles. The study clearly identifies that bulkier functional groups, i.e., triethyl, tripropyl, tributyl, and dimethyl benzene over N+ (of thiol ligand) through their steric effects minimize the particle size giving rise to tunable photoluminescence emission in red spectral region. However, the red shift seen in the emission Au nanoclusters with N-(11-mercaptoundecyl)-N,N `-dimethylbenzenammonium chloride ligand in contradiction to particle size effect is computationally proved to be due to the delocalization of electron density from benzene aromatic ring to N+ of ammonium head leading to a reduction in the HOMO-LUMO energy gap. Fluorescence properties of water dispersible Au nanoclusters are tuned by varying the ammonium head group. Density Functional Theory studies correlate the distinction in emission when head group is phenyl to charge transfer characteristics. image
Keywords: Density functional theory; photoluminescent Au nanoclusters; surface plasmon resonance; thiol ligand

Ultrasound-assisted ionic liquid-mediated green method for synthesis of 1,3-diphenylpyrazole-based spirooxindolopyrrolizidines, their anti-tubercular activity, molecular docking study and ADME predictions - Baddepuri, Sravanthi; Gamidi, Rama Krishna; Kumari, Jyothi; Sriram, Dharmarajan; Basavoju, Srinivas (New Journal of Chemistry, 2024)
The aim of the study is to develop the synthesis of a novel series of potent anti-tubercular (anti-TB) activity of 1,3-diphenylpyrazole-based spirooxindolopyrrolizidine derivatives via an efficient green approach achieved by using an ionic liquid ([Bmim]BF4) under ultrasonication. The title compounds 4a-4ad with a general molecular formula CaHbX(0-2)NcOd (X = F/Cl/Br) were produced with high yields in shorter reaction time and well characterized by using spectral techniques; and finally single crystal X-ray diffraction method (4b). The newly synthesized compounds were evaluated for their in vitro anti-TB activity against Mycobacterium tuberculosis H37Rv strain. Among all, six compounds 4e (C36H29N5O4), 4g (C34H28N4O3), 4q (C36H28F2N4O2), 4r (C36H28ClFN4O2), 4y (C36H29BrN4O2) and 4z (C36H28BrFN4O2) exhibited significant anti-TB activity with MIC value 6.25 mu g mL-1, when compared to the standard drug ethambutol (MIC:1.56 mu g mL-1). In silico molecular docking studies were performed against M. tuberculosis enoyl-acyl carrier protein reductase inhibitor. The compounds 4o, 4p, 4y and 4aa were exhibited least binding energies -12.58, -12.61, -12.58 and -12.57 kcal mol-1, respectively. These results reveal that the produced compounds might be used for the future generation of novel anti-TB drugs. The study aims to develop and synthesis of a novel series of 1,3-diphenylpyrazole-based spirooxindolopyrrolizidine derivatives as potent anti-TB agents via an efficient green approach by using an ionic liquid ([Bmim]BF4) under ultrasonication.

Understanding in-vivo refolding of antibody fragments (Fab): Biosimilar Ranibizumab a case study - Tungekar, Aatir A.; Fulewar, Padmaja; Kumthekar, Rupali; Bhambure, Rahul (PROCESS BIOCHEMISTRY, 2024)
Keywords: CHERICHIA-COLI STRAINS; Disulfide bond formation; SOLUBLE RECOMBINANT PROTEINSES

Understanding the effects of physical properties of composite drop on its formation dynamics in presence of interfacial mass transfer - Khan, Muzammilanwar S.; Kulkarni, Amol A. (Industrial and Engineering Chemistry Research, 2024)
Dynamics of drop formation is studied in presence of interfacial mass transfer through controlled flow visualization experiments and lumped force balance based model. Experiments were conducted using eight different combinations of ternary systems, involving variations in initial composition and physical properties of drop phase over a broad range. A new image analysis method is reported to accurately measure the size of deformed, nonaxisymmetric drops. Based on flow visualization and analysis of drop shape, four modes of drop formation are identified, including (i) mass transfer free mode, (ii) interfacial instability mode (Marangoni effects), (iii) dripping, and (iv) jetting, with progressively increasing solute concentrations. Exceptions to these modes are observed for tetrahydrofuran-toluene and tetrahydrofuran-benzene mixtures, in which the drop remains in mass transfer free mode even in presence of higher solute concentrations. Model predictions of real time change in drop volume show excellent match with experimental results for all of the systems under study. The analysis of force balance implies that the interplay between (i) surface tension force and (ii) the combination of buoyancy and force due to kinetic energy controls the drop detachment time as well as the final drop volume. Therefore, for identical operating conditions, transition in drop formation time occurs from 4 s to 65 ms, depending on the density difference and interfacial tension between contacting phases. The present findings provide detailed insights into the formation dynamics of composite drops, which are commonly encountered in liquid-liquid extraction and various multiphase operations.

Unlocking the genetic and biotechnological potential of Gloriosa superba to enhance its alkaloid production - Mahajan, Yogesh A.; Shinde, Balkrishna A.; Shirke, Harshad A.; Gandra, Jawahar; Suravajhala, Prashanth; Kishor, P. B. Kavi; Kadoo, Narendra Y.; Nikam, Tukaram D. (Industrial Crops and Products, 2024)
Gloriosa superba is a medicinally important plant that produces the pharmaceutically precious colchicine molecule. Colchicine is being used for treating gout, for enhancing the production of interleukin-8 (inhibits human pancreatic cancer) and many other human ailments. Since its seeds and rhizomes (tuberous roots) are the chief sources of colchicine, pharmaceutical industries exploit the natural sources, thus demolishing its habitat. Chemo- and genetic diversity among the G. superba populations exist, but has not been exploited profitably. Scope exists for generating mutants using the chemical mutagens and also via breeding methods to generate superior varieties for commercial cultivation. Innovative methods for breaking seed dormancy and superior colchicine extraction, besides biotechnological interventions are imperative to save the biodiversity and to produce colchicine on a large scale. Biorhizomes produced in vitro hold great promise for biomanufacturing colchicine in bioreactors commercially. Since the biosynthetic pathway of colchicine is now known, isolation of the pathway genes and their heterologous overexpression or the application of synthetic biology methods needs to be explored in future for industrial manufacturing of colchicine. Advances made in the recent past in these fields of colchicine production from G. superba are critically evaluated in this review.
Keywords: Biosynthetic pathway; Colchicine; Genetic diversity; Glory lily; Metabolite elicitation; Omics approaches

Unprecedented C-F bond cleavage in perfluoronaphthalene during cobaltocene reduction - Kundu, Gargi; Pramanik, Debjit; Dash, Soumya Ranjan; Kumar, Ravi; Sangole, Mayur; Tothadi, Srinu; Ghosh, Aryya; Vanka, Kumar; Singh, Kirandeep; Sen, Sakya S. (DALTON TRANSACTIONS, 2024)

Unveiling electronic structure and magnetic properties of AFe2O4 (A = Co, Ni, Zn, and Mg): Synergizing experimentation with DFT investigation - Dhaka, Saroj; Shukla, Aarti; Garima; Poonia, Kavita; Kumar, Sudesh (Solid State Communications, 2024)
This study presents the synthesis of nano-crystalline spinel ferrites AFe2O4 (A = Co2+, Ni+2, Zn+2, and Mg+2), through the sol-gel method, yielding crystallite sizes ranging from 12 to 28 nm. The variation in IR and Raman spectra due to M-O-M bonding supports the variation in lattice parameters. The magnetization measurements revealed that CoFe2O4 has a high saturation magnetization of -55 emu/g and coercivity of -1350 Oe, while ZnFe2O4 exhibited saturation magnetization value of -8 emu/g and coercivity of -16 Oe. In addition, the electronic structure calculated using DFT, which corroborated the antiparallel alignment of Fe ions in the tetrahedral and octahedral sites, validating the measured magnetic moments. Notably, the CoFe2O4 ferrite exhibited a higher squareness ratio than other ferrites, signifying its suitability as a magnetic material for audiovideo recording.
Keywords: Density functional theory; Ferrites; Magnetic materials; X-ray diffraction

Unveiling the cell wall-targeting mechanisms and multifaceted virulence modulation by a eugenol glycoconjugate against aspergillus fumigatus: insights from in vitro and in ovo studies - Gupta, Lovely; Verma, Shalini; Goswami, Lakshmi; Kamboj, Himanshu; Sen, Pooja; Bhattacharya, Asish K.; Vijayaraghavan, Pooja (Journal of Applied Macrobiology, 2024)
Aim The primary objective of this study was to elucidate the putative cell wall-associated targets of compound 6i, a glycoconjugate of eugenol, in Aspergillus fumigatus, while also evaluating its toxicity and assessing histopathologic alterations in the liver, heart, and kidney of compound 6i-treated embryos using an in ovo model.Method To achieve this aim, compound 6i was synthesized, and a series of biochemical assays were performed to determine its impact on the fungal cell wall. Additionally, quantitative real time-PCR and liquid chromatography-mass spectrometry/mass spectrometry analyses were conducted to investigate changes in gene and protein expression profiles associated with melanin biosynthesis, conidiation, siderophore production, transcriptional regulation of beta-glucan biosynthesis, and calcineurin activity in A. fumigatus.Results The experimental findings revealed that compound 6i exhibited notable antifungal activity against A. fumigatus by perturbing cell wall integrity, hindering ergosterol, glucan, and chitin biosynthesis, and inhibiting catalase production. Moreover, relative gene expression and proteomic analyses demonstrated that compound 6i exerted both downregulatory and upregulatory effects on several crucial genes and proteins involved in the aforementioned fungal processes. Furthermore, increased expression of oxidative stress-related proteins was observed in the presence of compound 6i. Notably, the glycoconjugate of eugenol did not elicit cytotoxicity in the liver, heart, and kidney of chick embryos.Conclusion The current investigation elucidated the multifaceted mechanisms by which compound 6i exerts its antifungal effects against A. fumigatus, primarily through targeting cell wall components and signaling pathways. These findings underscore the potential of the eugenol glycoconjugate as a promising antifungal candidate, warranting further exploration and development for combating A. fumigatus infections.
Keywords: Aspergillus fumigatus; cell wall integrity; Eugenol; Glycoconjugate; Transcription regulators; Virulence

Variations in packing as a function of side chains in random copolymers and its impact on charge carrier mobility - Swain, Gitanjali; Kumar, Subramani; Samudre, Nikhil S. (Macromolecular Chemistry and Physics, 2024)
Homopolymers and alternating copolymers of conjugated molecules exhibit impressive performance in electronic devices. Despite the well-established procedures, the synthesis of alternating copolymers using three monomers is not as easy as random copolymers. Besides facile synthesis, the random copolymers can match the performance of alternating copolymers in electronic devices. Herein, random copolymers are designed and synthesized comprising thienoisoindigo (TIIG), diketopyrrolopyrrole (DPP), and thiophene. The DPP monomers installed with various side chains including branched alkyl chain, branched alkyl chain with ester functionality, linear oligo ethylene glycol, and siloxane terminated alkyl chain are incorporated into the polymers (P1, P2, P3, and P4, respectively). All the thermally stable, low bandgap random copolymers exhibited strong H-type aggregation in thin film. The relationship between thin film microstructure originating from diverse side chains and the charge transport in organic field effect transistors (OFETs) is investigated. All the random copolymers exhibited predominantly p-type charge transport and a maximum hole mobility of 2 x 10-2 cm2 V-1s-1 is observed for P3. The packing of all the polymers is examined theoretically by density functional theory (DFT) and compared with experimental values obtained from grazing incident X-ray diffraction (GIXRD). Various side chains (hydrophilic and hydrophobic) affect molecular packing of random polymers which ultimately affects its thin film morphology and semiconducting performances. Linear chains provide better interchain packing by pi-pi stacking compared to bulky branched side chains. The incorporation of heteroatoms and polar groups into the side chain further enhances the interchain interactions. image
Keywords: diketopyrrolopyrrole; organic field effect transistor; random polymer; side chain engineering; thienoisoindigo

Visible, far-red, and near-infrared active unsymmetrical squaraine dyes based on extended conjugation within the polymethine framework for dye-sensitized solar cells - Singh, Amrita; Singh, Ambarish Kumar; Dixit, Ruchi; Vanka, Kumar; Krishnamoorthy, Kothandam; Nithyanandhan, Jayaraj (ACS Applied Energy Materials, 2024)
Alkyl group wrapped visible, far-red, and NIR active unsymmetrical squaraine dyes with pi-extension in the polymethine framework-based AM4-AM7 have been designed, synthesized, and utilized as sensitizers for dye-sensitized solar cells. To extend the pi-conjugation within the polymethine framework, thiophene moieties have been incorporated between the donor and acceptor moieties. Absorption spectroscopic studies revealed that pi-extension with each -C & boxH;C- unit resulted similar to 100 nm of redshift in the charge transfer transition with the lambda(maximum) of 541, 643, 747, and 833 nm for AM4, AM5, AM6, and AM7 dyes, respectively, with the molar extinction coefficient of >10(5) M(-1)cm(-1). The pi-extended conjugation-based AM6 and AM7 dyes showed improved light-harvesting efficiency (LHE), where the AM7 dye showed an LHE of 386 nm at 60%. Electrochemical studies of AM dyes revealed that the HOMO energy level of the sensitizers has been modulated systematically. Further, pi-extension within the polymethine framework showed a dramatic effect on V-OC, J(SC), and device efficiency when move from visible active AM4 to far-red active to NIR active AM7 dyes. The DSSC efficiencies of 7.35, 5.18, 0.08, and 0.053% have been achieved with the I-/I-3(-) electrolyte (Z-50) for the AM4, AM5, AM6, and AM7 dyes, respectively. Further, AM4 dye has been cosensitized with AM5, AM6, and AM7 dyes, where AM4:AM5 (1:1) composition achieved the maximum efficiency of 8.12% with I-/I-3(-) electrolyte (Z-50) compared to the other cosensitization compositions.
Keywords: aggregation of dyes; DSSC device efficiency; light-harvesting efficiency; pi-extension; polymethine framework; squaraine dyes

Visible light-assisted ferro-photocatalytic application of bismuth ferrite nanoparticles synthesized at low temperature - Sarraf, Sonu; Kaushal, Neha; Chugh, Vibhas; Sundar, Adhiraj; Saha, Avishek; Basu, Aviru K. (Journal of Materials Science, 2024)
Polycrystalline nano-sized multiferroic bismuth ferrite was prepared by facile sole-gel method using acetic acid as a chelating agent followed by calcination at 450, 500, and 600 degrees C. Transmission electron spectroscopy and X-ray diffraction patterns revealed the crystallinity in the samples, and the crystallite size increased with calcination temperature. The calcination temperature also greatly influenced the grain size of the materials, and high calcination temperature induces a decline in the total surface area per unit mass of material. The ferroelectric polarization measurement showed a decrease in remnant polarization from 0.18 to 0.09 mu C/cm2 with an increase in temperature. The remnant polarization induced delayed recombination of charge carriers upon light illumination, and the high surface area led to the highest photocatalytic activity in 450 degrees C calcined samples. The higher photocurrent density in low-temperature calcined samples supports the visible-light photodegradation studies of Congo Red (CR) dye. A maximum of 76.6% photocatalytic activity was observed in the 450 celcius calcined bismuth ferrite samples. In summary, the higher photocatalytic efficiency in the low-temperature samples is attributable to the synergistic effect of relatively higher remnant polarization and higher surface area.

Visible-light-induced radical sulfonylative-cyclization cascade of 1,6-Enynol derivatives with sulfinic acids: a sustainable approach for the synthesis of 2,3-disubstituted benzoheteroles - Haritha Kumari, Arram; Jagadesh Kumar, Jangam; Sharadha, Nunavath; Rama Krishna, Gamidi; Jannapu Reddy, Raju (CHEMSUSCHEM, 2024)
Keywords: 1; 6-Enynols; Benzofurans; Benzothiophenes; indoles; Sulfones

Water-chain mediated proton conductivity in mechanically flexible redox-active organic single crystals - Hossain, Munshi Sahid; Ghosh, Meena; Mondal, Amit; Ajmal, P.; Saha, Monochura; Reddy, C. Malla; Kurungot, Sreekumar; Bandyopadhyay, Subhajit (Journal of Materials Chemistry A, 2024)
Investigating electrochemical features of proton-conducting organic crystalline materials is relevant in developing efficient energy storage and conversion devices. However, the poor structural flexibility of the crystalline materials at the molecular level often impedes hydrogen bond reorganization of the proton carriers during proton migration, ultimately leading to low ionic conductivity. Here, we report crystals of azobenzene, functionalized with dipicolylamine at both ends (Azo-DPA), which contain an extended hydrogen-bonding network with water molecules in its structure. Interestingly, the crystals display remarkable mechanical flexibility explicitly probed by the nanoindentation technique. The mechanically flexible neutral organic crystals devoid of any acidic moieties (-COOH, -PO3H2, etc.) within the system, exhibit promising proton conductivity (1.63 x 10-4 S cm-1 at 30 degrees C under 95% relative humidity) which is almost 100 times better compared to the neutral organic systems reported to date. Mechanically flexible redox-active crystalline organic material (Azo-DPA) capable of impressive proton conduction was employed as an electrode material for the first time in an aqueous battery containing Zn2+ ions. The experimental and theoretical studies on the charge storage mechanism revealed the redox activity of the azo (-N 00000000 00000000 00000000 00000000 11111111 00000000 11111111 00000000 00000000 00000000 N-) centers involving reversible insertion/extraction of protons and Zn2+ ions. Ultimately, the electrode displayed a specific capacity similar to 49 mA h g-1 with almost 100% retention after 1400 cycles, encouraging the scope of redox-active organic crystalline materials for energy storage applications. Investigating the electrochemical features of proton-conducting flexible organic crystalline materials is crucial for the development of efficient energy storage and conversion devices.

Wide temperature enhanced sodium storage in tailored, sustainable sodiophilic biphasic N-doped carbon - Yadav, Poonam; Das, Anoushka K.; Torris, Arun; Wasnik, Kundan; Koppisetti, Heramba Venkata Sai Rama Murthy; Pol, Vilas G.; Shelke, Vilas; Shelke, Manjusha (Materials Today Chemistry, 2024)
Alternative to Li-ion batteries(LIB), Na-ion batteries (NIB) and Na metal batteries (NMB) are gaining significant attention due to their low cost, abundance, and safety. By modulating microstructural properties such as graphitization, heteroatom doping, surface-rich functional groups, and interlayer d-spacing, Na-ion storage in NIB and Na plating/striping in NMB can be ameliorated. This study reports sodiophilic N-doped polymer-derived carbon (PDC) as an anode for NIB and host for Na metal in NMB. As NIB anode, PDC provides a storage capacity of 173 mAh g- 1 at 1 A g- 1 in half-cell and 84 mAh g- 1 at 1C (1C = 128 mAhg- 1) in full-cell with Na3V2(PO4)2F3 (NVPF) cathode. As Na metal anode (NMA) host, a high columbic efficiency (C.E.) of 99.45% for over 1000 cycles at 6 mA cm- 2_4 mAh cm-2 is obtained. Furthermore, fascinating wide temperature (50 degrees C and -20 degrees C) sodiumion storage is successfully demonstrated by PDC. Advanced X-ray photoelectron spectroscopy (XPS) confirmed the formation of stable and uniform solid electrolyte interphase (SEI) composed of inorganic and organic components, X-ray microtomography confirmed uniform Na plating throughout the volume of the electrode analogous to Brunauer-Emmett-Teller (BET) surface area, Raman spectroscopy, X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM) results. A sustainable and scalable promising biphasic NIB anode and sodiophilic host for Na metal was possible due to larger d-spacing, partial graphitization, high mesoporosity, N-doping, presence of surface functional groups, better charge transfer, and diffusion properties.
Keywords: Full-cell; Low and elevated temperatures; Na metal host; Polymer-derived carbon; Sodium-ion battery; X-ray tomography

Yoga therapy attenuates the progression of diabetes - insights from proteomics and metabolomics analysis - Sonwane, Babasaheb P.; Raut, Pooja; Chitalkar, Jyotsna; Godbole, Smita; Sabnis, Shanta; Gupta, Jyoti; Santhakumari, B.; Deshpande, Mukund V.; Kulkarni, Mahesh J. (International Journal of Yoga, 2024)
<p style="box-sizing: inherit; line-height: 1.5; margin: 1.2rem 0px; color: rgb(33, 33, 33); font-family: BlinkMacSystemFont, -apple-system, "Segoe UI", Roboto, Oxygen, Ubuntu, Cantarell, "Fira Sans", "Droid Sans", "Helvetica Neue", sans-serif; font-size: 16px;"> Objective: Diabetes management remains challenging despite advancements in therapeutics, with many subjects developing complications. Yoga has been shown to aid diabetes management. This study investigates the impact of yoga therapy on diabetes progression, utilizing proteomics and metabolomics analyses to explore underlying molecular mechanisms. <p style="box-sizing: inherit; line-height: 1.5; margin: 1.2rem 0px; color: rgb(33, 33, 33); font-family: BlinkMacSystemFont, -apple-system, "Segoe UI", Roboto, Oxygen, Ubuntu, Cantarell, "Fira Sans", "Droid Sans", "Helvetica Neue", sans-serif; font-size: 16px;"> Methodology: A 3-month longitudinal study involving healthy subjects with prediabetes and diabetes was conducted. Blood glucose, glycated hemoglobin (HbA1c), lipid profile, and malondialdehyde (MDA) levels were measured before and after the yoga intervention. <p style="box-sizing: inherit; line-height: 1.5; margin: 1.2rem 0px; color: rgb(33, 33, 33); font-family: BlinkMacSystemFont, -apple-system, "Segoe UI", Roboto, Oxygen, Ubuntu, Cantarell, "Fira Sans", "Droid Sans", "Helvetica Neue", sans-serif; font-size: 16px;"> Results and conclusion: Healthy subjects showed no significant changes in blood glucose, lipid profile, HbA1c, or MDA levels. However, subjects with prediabetes and diabetes experienced positive changes, with decreases in HbA1c and MDA levels. Proteomics and metabolomics analyses provided insights into the molecular mechanisms by which yoga attenuates diabetes progression in subjects with prediabetes and diabetes. This study is a pioneering effort to understand the molecular basis of yoga's beneficial effects on diabetes management.

ZrO2 supported Cu nanoparticles for sonogashira and ullmann coupling reactions under palladium-free conditions - Patil, Seema P.; Rajmane, Archana S.; Jadhav, Sanjay N.; Rajmane, Vijaya S.; Rode, Chandrashekhar V.; Kumbhar, Arjun S. (Catalysis Letters, 2024)
Cu nanoparticles supported on ZrO2 (CuNPs@ZrO2) were synthesized using a one-step co-precipitation process, and their application in C-C coupling reactions was investigated. The catalyst was characterized using XRD, XPS, SEM, TEM, and TGA techniques. The prepared catalyst was used for the Sonogashira cross-coupling reactions of aryl bromides with phenyl-acetylene in the presence of K2CO3 in DMF at 110 degrees C, which resulted in substituted alkynes with good to excellent yields. The protocol was also extended for the Ullmann coupling reactions of aryl iodides under similar reaction conditions, yielding the desired products with good to excellent yields without homo-coupling. Interestingly, unlike other copper catalysts, the present catalyst worked under air and did not require an inert atmosphere to prevent alkyne. This catalytic system is versatile, tolerant, and significantly cheaper than the ``traditional'' Pd-catalyzed Sonogashira cross-coupling of terminal alkynes with aryl halides. The catalyst could be reused for five catalytic cycles with no significant change in the product yield. All of these characteristics make our prepared CuNPs@ZrO2 catalyst quite suitable for the gram-scale synthesis of biaryls and alkynes, with a simple workup.{GRAPHIACAL ABSTRACT
Keywords: CuNPs; Recyclability; Sonogashira coupling; Ullmann coupling; ZrO2

32nd National Congress of Parasitology, Pune: bringing together India's parasitologists - Purkayastha, Devatrisha; Pandit, Kushankur; Upadrasta, Sindhuri; Khilari, Ajinkya; Shanmugam, Dhanasekaran; Karmodiya, Krishanpal (Trends in Parasitology, 2025)
The 32nd National Congress of Parasitology (NCP) was held in person, 3-5 October 2024, at the Indian Institute of Science Education and Research Pune (IISER Pune), jointly organized by IISER Pune; the Council of Scientific and Industrial Research - National Chemical Laboratory, Pune; and Savitribai Phule Pune University (formerly University of Pune) in association with the Indian Society for Parasitology. The conference brought together around 250 attendees from across the country and abroad, including a diverse group of researchers, clinicians, industry experts, and students. The event provided a collaborative environment for exchanging research ideas relevant to the field of parasitology. The congress emphasized the concept of One Health, a holistic approach to address parasitic infections affecting humans and animals to promote overall health and well-being. In this TrendsTalk, the organizers provide an overview of the conference proceedings, which brought together India's vast and diverse parasitology community.

3D-architectured Pt-carbon electrodes for PEM fuel cells with tuned porosity and ionomer distribution-a micromanaged approach for improving activation, ohmic, and mass transport characteristics - Singh, Mayank U.; Mathew, Grigory; Kurungot, Sreekumar (ACS Applied Energy Materials, 2025)
The conventional catalyst layer in Proton Exchange Membrane Fuel Cells (PEMFCs) suffers the limitation of masked active sites, hindered proton transportation, excessive water clogging, and irregular ionomer distribution, resulting in an underutilized catalyst. To overcome these challenges, an innovative catalyst layer (CL) is constructed by aligning Vulcan carbon (VC) particles along a 3D carbon nitride interconnected network originating from a melamine sponge. This forms a robust scaffold rich in anchoring sites like sulfur and nitrogen for the Pt nanoparticle. The resultant 3D CL exhibits a doubled through-plane proton transport conductivity from 23 to 41 mS cm-1, delivering a 17.3% increase in the current density at 0.60 V compared to a conventional VC CL. This strategy enables enhanced ionomer incorporation, yielding a 19.60% enhancement in the ionomer coverage over the Pt without sacrificing the porosity, as verified by a mercury porosimeter. Kelvin probe force microscopy confirms a more uniform electron density across the 3D CL, in contrast to the traditional CL, suggesting uniform coverage. The advanced porosity and structure of the 3D CL allow the mass transport regions to shift to higher current densities, with an increase of 0.30 A cm-2 at 0.50 V compared to the VC CL. The improved ionomer coverage also demonstrates 19% lower voltage degradation at 0.80 A cm-2. Further, the impedance mapping across the entire current range graphically illustrates the 3D CL's advantage in the activation, Ohmic, and mass transport regions, showing a parabolic profile with a flattened bottom attributed to the reduced Ohmic resistance and its extension to delay the mass transport losses.
Keywords: 3D-structured catalyst layer; impedancemapping; ionomer coverage; low-temperature proton exchange membranefuel cell (LT-PEMFC); mercury porosimeter; proton resistance; triplephase boundary (TPB)

Accessing electron-deficient π-extended pyrenes via non-K-region fusion - Dongre, Sangram D.; Kumar, Viksit; Kumar, Ravi; Babu, Sukumaran Santhosh (ORGANIC LETTERS, 2025)
This study presents a new class of pyrene derivatives featuring non-K-region fusion and electron-deficient pi-extension. By strategically introducing electron-withdrawing groups at the non-K positions, the optical and redox properties of these compounds were significantly altered. For the first time, we report a non-K-region fused acceptor pyrene with an extended pi-skeleton. The detailed characterizations revealed pronounced shifts in both absorption and emission spectra, accompanied by a significant lowering of the LUMO energy levels. Our results highlight non-K region-fused pyrenes as a promising building block for next-generation organic semiconductors with tunable electronic properties.

Accessing polysubstituted 2-cyclopentenones via base-mediated annulation of β-keto esters and phenacyl bromides - Kumar, Mohit; Paul, Vincent; Gamidi, Rama Krishna; Senthilkumar, Beeran (Organic & Biomolecular Chemistry, 2025)
A transition metal-free method is demonstrated for the synthesis of polysubstituted 2-cyclopentenone compounds, which involves the direct annulation of phenacyl bromide with beta-keto esters in a single step. This process proceeds through a base-mediated SN2 nucleophilic substitution, followed by an intramolecular aldol condensation, resulting in the formation of three C-C bonds and one ring in a cascade manner. The experimental results achieved a record high yield of highly substituted diverse 2-cyclopentenone analogues, which exhibit very good structural resemblance to biologically significant natural compounds.

Achmatowicz rearrangement-enabled unified total syntheses of (+)-passifetilactones A-C - Verma, Aman Kumar; Jeddi, Dharmaraju; Kontham, Ravindar (RSC Advances, 2025)
In this manuscript, we report the enantio- and diastereoselective total synthesis of three cytotoxic 2-pyrone-derived natural products passifetilactones A-C. Our strategy leverages a unified synthetic approach that originates from simple furan-based building blocks. Key transformations include the Corey-Bakshi-Shibata (CBS) reduction to access chiral furan-derived alcohol, NBS-mediated Achmatowicz rearrangement to construct the alpha-hydroxy-delta-pyrone core, followed by a highly stereoselective, iridium-catalyzed dynamic kinetic intramolecular redox isomerization to access the delta-hydroxy-alpha-pyrone framework. This streamlined route enables efficient access to passifetilactones A, B, and C in 13, 5, and 8 steps, with overall yields of 12%, 54%, and 37%, respectively.

Advances in polymer electrolyte design strategies for highly efficient supercapacitors and Zn-based batteries - Puthiyaveetil, Priyanka Pandinhare; Babu, Athira; Kurian, Maria; Kurungot, Sreekumar (Chemical Communications, 2025)
Electrolytes play a crucial role in the performance of electrochemical energy storage systems, such as batteries and supercapacitors. Their main function is to act as a medium for ion transport between the electrodes, which is essential for the charge and discharge processes. Beyond this, the electrochemical performance of the device is strongly affected by the various properties of the electrolytes such as their ionic conductivity, chemical, thermal and electrochemical stability, chemical compatibility, etc. The intrinsic limitations of the aqueous electrolytes such as their decomposition during high voltage operations has led to the development of better electrolytes for batteries and supercapacitors. These included non-aqueous electrolytes, inorganic solid-state electrolytes, and gel polymer electrolytes. This feature article reviews the various approaches to designing a highly efficient polymer electrolyte for the targeted application along with the suitable device fabrication strategy adopted in the current literature to achieve a balanced electrochemical performance compared with a liquid electrolyte-based device.

Ag(I)-catalyzed heterocyclization/[3+2] cycloaddition of α-alkynylenones with β-enaminones: tandem access to highly substituted cyclopenta[c]furans - Vara, Vijay; Thete, Kishor R.; Panikar, Sera Deepu; Khan, Akram A.; Muthukrishnan, M. (Journal of Organic Chemistry, 2025)
A robust Ag(I)-catalyzed tandem heterocyclization/[3 + 2] cycloaddition of alpha-alkynylenones with beta-enaminones was developed, enabling efficient synthesis of cyclopenta[c]furans with good yields, operational simplicity, and broad substrate scope. In addition, it also presents an extended methodology to synthesize unsymmetrical tri(hetero)aryl methane having chromone and furan/pyrrole scaffolds by a slight modification of starting materials. Moreover, the synthesized cyclopenta[c]furans exhibit good fluorescence properties with quantum yields ranging from 0.33 to 0.53, as suggested by the photophysical studies.

AgOTf-catalyzed cascade annulation of 5-hexyn-1-ols and aldehydes: enabling the diastereoselective synthesis of [6,6,6]-trioxa-fused ketals and hexahydro-2H-chromenes - Vinodkumar, Ramavath; Nakate, Ashwini K.; Krishna, Gamidi Rama; Kontham, Ravindar (Chemical Communications, 2025)
We report the unprecedented diastereoselective synthesis of novel [6,6,6]-trioxa-fused ketals via AgOTf-catalyzed cascade annulation of 5-hexyn-1-ols (with primary or secondary hydroxyl groups) and aldehydes through a [2+2+1+1] pathway. In contrast, 5-hexyn-1-ols with tertiary hydroxyl groups yield hexahydro-2H-chromenes via a [3+1+1+1] pathway.

Air-stable double halide perovskite Cs2CuBiBr6: synthesis and memristor application - Betal, Atanu; Chetia, Anupam; Saikia, Dibyajyoti; Karmakar, Krishnendu; Bera, Ganesh; Dambhare, Neha V.; Rath, Arup K.; Sahu, Satyajit (Physical Chemistry Chemical Physics, 2025)
The excellent optical and electronic properties of halide perovskite materials have attracted researchers to investigate this particular field. However, the instability in ambient conditions and toxicity of materials like lead have given some setbacks to commercial use. To overcome these issues, perovskite-inspired materials with less toxic and excellent air-stable materials are being studied. Double perovskite materials are one of the perovskite materials. In this study, we have synthesized air-stable double perovskite Cs2CuBiBr6 using a solution process approach. The characterization of the material revealed that it has excellent crystallinity and high stability. The material shows excellent optical and electronic properties. It can be used in resistive memory devices. It shows stable current-voltage characteristics and analog switching. The ion migration through the active layer and accumulation of charge near the electrode region are the reasons behind the resistive switching.

Aldol Condensation of Furfural with Acetone by Using Mg-Al-O-t-Bu HT Catalyst and Kinetic Studies - Patil, Sneha; Kamble, Paresh; Vinod, Chathakudath Prabhakaran; Rathod, Virendra; Kantam, Mannepalli Lakshmi (Industrial & Engineering Chemistry Research, 2025)
An environment-friendly method for producing jet fuel precursors involves the aldol condensation of biomass-derived chemicals. In this study, the condensation reaction between furfural and acetone was performed using a Mg-Al-O-t-Bu hydrotalcite (HT) catalyst, achieving a furfural conversion of 99% and a selectivity of 82% toward 4-(2-furyl)-3-buten-2-one (FAc). The kinetics of the process were evaluated using a Langmuir-Hinshelwood-Hougen-Watson (LHHW) model across a range of temperatures, and the model showed an excellent fit to the experimental data. The effect of different catalysts, reaction temperatures, catalyst loadings, molar ratios, and reaction times was systematically investigated. The Mg-Al-O-t-Bu HT catalyst was extensively analyzed through techniques such as XRD, XPS, FTIR, nitrogen adsorption-desorption measurements, and CO2-TPD. The catalyst exhibited excellent stability, maintaining its performance consistently across five successive reaction cycles with no notable decline in activity. These findings highlight the industrial relevance of Mg-Al-O-t-Bu HT as a robust and recyclable solid base catalyst for biomass upgrading, with strong potential for process scale-up in renewable fuel production.

Anode|electrolyte|cathode interface engineering to develop a robust zinc metal hydrogel battery - Dilwale, Swati; Babu, Athira; Kanheerampockil, Fayis; Torris, Arun; Puthiyaveetil, Priyanka Pandinhare; Bhat, Suresh; Kurungot, Sreekumar (Journal of Materials Chemistry A, 2025)
The poor electrode-electrolyte interfaces in quasi-solid-state zinc metal batteries often hinder Zn2+ ion transport due to the poor compatibility of the gel electrolyte with the electrodes. This report proposes a dual-interface engineering strategy across the anode, cathode, and separator using a single hydrogel polymer electrolyte (HPE). The integration of vanadyl phosphate functionalized carbon nanotubes (VP/fCNT) into a commercial glass fiber (GF) separator, followed by a thin hydrogel coating and UV-light photopolymerization, resulted in a dual-interface engineered cathode-separator-electrolyte structure (VP/IC-EGF). To mitigate the dendritic growth, an artificial solid electrolyte interface was developed on Zn foil (AEI@Zn). The engineered GF (EGF) demonstrates a room-temperature conductivity of 6.5 mS cm-1 and a high electrochemical stability window of 2.4 V vs. Zn|Zn2+. The symmetric cell with AEI@Zn|EGF|AEI@Zn exhibits exceptional plating/stripping stability over 1400 h at a current density of 0.1 mA cm-2 and a capacity of 0.1 mAh cm-2. Moreover, the low-volume cell (AEI@Zn & Vert;VP/IC-EGF), featuring the dual-interface-engineered cathode-separator-electrolyte, demonstrates outstanding cycling stability with over 3000 charge-discharge cycles at a current rate of 1.0 A g-1, retaining 98-99% of its initial capacity and showing high coulombic efficiency. These findings underscore the significant impact of interface engineering on enhancing the performance of ZMBs.

Aspergillus terreus variant TB21 wet biomass optimized by in-situ transesterification for biodiesel production - Bed, Rashmi K.; Kumar, V. Ravi; RaviKumar, Ameeta (AMB Express, 2025)
The oleaginous fungus, Aspergillus terreus when subjected to random chemical mutagenesis led to isolation of TB21 variant with improved lipid content (78.1%) as compared to wild type (49.8%). The fungal wet biomass grown on sugarcane bagasse hydrolysate (SCBH) was subjected to one-step in-situ (direct) acid transesterification to optimize its conversion to biodiesel using a 2-level factorial statistical design of experiments. The process optimization revealed that wet biomass and methanol were the most significant factors and in a short reaction time period of 5 min with low methanol: wet biomass ratio (10:1) influenced FAME production Statistical optimization studies showed that TB21 exhibited a higher FAME content of 76.5 and 38.1% (w/w) from wet and dry biomass, respectively when compared to wild type (48.1 and 24.5%). FAME productivity (0.55-1 h-1) and a yield (66 gL-1) were achieved when TB21 was grown on SCBH for 120 h at 30 degrees C. The FAME profile from the wet biomass of TB21 grown on SCBH had desirable amounts of saturated (77.7%), monounsaturated (7.2%), and polyunsaturated (2.4%) methyl esters. Physico-chemical properties of TB21-derived biodiesel were determined, namely, density(0.88 g cm-3), kinematic viscosity (4.1 mm s-2), iodine value (96.82), cetane number (55.31), free fatty acid content (0.15%), total acid number (0.3 NaOH mg g-1), meeting international (ASTM D6751, EN 14214) and Indian (IS 15607) standards. Thus, the direct one-pot in situ transesterification reaction using wet biomass of variant TB21 strain showed improved production and quality of biodiesel with potential large scale application using the low-cost substrate (SCBH).
Keywords: Aspergillus Terreus; Biodiesel; In situ transesterification; Mutant; Statistical optimization; Wet biomass

Atom-economical and scalable asymmetric synthesis of daridorexant key starting material (S)-2-methylproline via the memory of chirality - Bhatt, Gaurang J.; Kumar, Shubham; Mhaske, Santosh B. (Organic Process Research & Development, 2025)
alpha-Methylproline is a key starting material (KSM) for important drugs, such as Daridorexant, Veliparib, Trofinetide, Enlicitide chloride, and Usnoflast. A practical and scalable asymmetric synthesis of (S)-2-methylproline and its derivatives has been disclosed here using a diketopiperazine intermediate-based strategy that leverages the memory of chirality. Commencing from an inexpensive starting material, l-proline, it proceeds through dimerization and alkylation, followed by hydrolysis under mild conditions, avoiding column chromatography to furnish enantiomerically pure (S)-2-methylproline.HCl, which was also converted to (S)-Boc-2-methylproline and (S)-2-methylproline methyl ester.HCl. In contrast to prior multistep approaches, which rely on expensive chiral auxiliaries and hazardous reagents, this concise three-step route offers operational simplicity, scalability, and superior stereochemical control, making it an attractive method for the synthesis of proline-derived building blocks for peptidomimetics and pharmaceutical applications.
Keywords: alpha-methylproline; atom economy; memoryof chirality; Stereoselective

Autoantibodies against Nε-carboxymethyl lysine and methylglyoxal modified albumin are associated with cardiovascular risk in type 2 diabetes - Patil, Yugendra R.; Tiwari, Shalbha; Momin, Abdulrahaman A.; Unnikrishnan, A. G.; Kulkarni, Mahesh J. (International Journal of Diabetes in Developing Countries, 2025)
{Background Albumin is an abundant plasma protein which gets modified with advanced glycation end products (AGEs) predominantly in diabetic condition. AGE modification induces immune response and autoantibodies are generated which play an important role in disease pathology. Objective This study aimed to illustrate the role of autoantibodies against N epsilon-carboxymethyl lysine (CML) and methylglyoxal (MG) modified albumin in diabetic cardiovascular complications. MethodsType-2 diabetes subjects were enrolled and further grouped into stress test positive or stress test negative based on treadmill stress test (TMT). Autoantibody titer was quantified by ELISA assay for CML-modified albumin (stress test positive
Keywords: AGE; Atherosclerosis; Diabetes; Glycation; Immune response; ROC

Bacterial nanocellulose (BNC) produced from sorbitol as a sustainable nano-filter for oil-water separation - Jagtap, Ashish; Krushnatray, Ajinkya; Dastager, Syed G. (International Journal of Biological Macromolecules, 2025)
Oil spillage is one of the serious problems for sustainable environment. Bacterial nanocellulose (BNC), a hydrophilic and highly porous material holds a promising material for oil-water separation from contaminants. In the present work, a hydrophilic BNC produced from a sorbitol as the carbon source demonstrated the unique porous symmetrical arrangement having an oleophilic property. The BNC membrane obtained showed the highest water holding capacity (WHC) of approximate to 147 gg 1 . The Brunauer-Emmett-Teller (BET) analysis of BNC revealed the unique characteristics of isothermic patterns, having macro sized pores with diameter of 121.3 nm and surface area of 40.6m2/g, which plays a vital role in separation of oil from water by allowing passage of only water through it. The separation efficiency of BNC membrane produced after 5th day of incubation has showed 99.0 % oil removal compared to 10 and 15th day incubated BNC membranes. a CFD model to investigate the possibilities of BNC membranes and clarify the dynamics of oil-water separation. The nanostructured network of BNC offers a tortuous path for oil molecules while allowing rapid permeation of water, leading to high separation selectivity and flux. Although BNC has been previously studied for oil water separation, this study provides new insights into the use of wet BNC membranes into its pristine state with sorbitol as carbon source for this application.
Keywords: bacterial nanocellulose; Macro porous; Oil-water separation; Sorbitol

Base mediated approach for the synthesis of deoxybenzoins using γ-aryl-β-ketoesters and benzoyl chlorides - Choudhary, Shailendra Singh; Darole, Ratanamala S.; Krishna, Gamidi Rama; Senthilkumar, Beeran (RSC Advances, 2025)
This study introduces a one-pot, transition metal-free strategy for synthesizing deoxybenzoins, overcoming the challenges of conventional methods. The reaction involves dual acylation of gamma-aryl beta-keto esters using K2CO3 in dioxane at 90 degrees C, followed by a concerted transformation to form deoxybenzoin. The protocol operates under mild conditions, tolerates a broad range of substrates, and produces minimal by-products, making it a practical, scalable alternative for accessing pharmaceutically relevant deoxybenzoins.

Benchmarking a dual-scale hybrid simulation framework for small globular proteins combining the CHARMM36 and Martini2 models - Yadav, Manjul; Kharche, Shalmali; Prakash, Shikha; Sengupta, Durba (Journal of Molecular Graphics & Modelling, 2025)
Multi-scale models in which varying resolutions are considered in a single molecular dynamics simulation setup are gaining importance in integrative modeling. However, combining atomistic and coarse-grain resolutions, especially for coarse-grain force fields derived from top-down approaches, have not been well explored. In this study, we have implemented and tested a dual-resolution simulation approach to model globular proteins in atomistic detail (represented by the CHARMM36 model) with the surrounding solvent in Martini2 coarse-grain detail. The hybrid scheme considered is an extension of a model implemented earlier for mainly lipid and water molecules. We have considered a set of small globular proteins and have extensively compared to atomistic benchmark simulations as well as a host of experimental observables. We show that the protein structural dynamics sampled in the hybrid scheme is robust, and the intra-protein contact maps are reproduced, despite increased fluctuations of the loop regions. A good match is observed with experimental small angle X-ray scattering (SAXS) and NMR observables, such as chemical shifts and (3)J((HN-H alpha))-coupling, with the best match obtained for the chemical shifts. However, deviations are observed in the water dynamics and protein-water interactions which we attribute to the limitation of solvent screening in the coarse-grain force field. The computational speed-up achieved is about 2-3 times compared to an all-atom system. Overall, the hybrid model is able to retain the main features of the underlying atomistic conformational landscape with a two-fold speed-up in computational cost.
Keywords: Hybrid simulations; Martini force-field; Mixed models; Multi-scale simulations

Bifunctional nanoelectrocatalyst: semi-amorphous cobalt tungstate-based nanocomposites surpassing amorphous and crystalline counterparts - Dev, Sahil; Nagappan, Sreenivasan; Kundu, Subrata; Mukherjee, Shatabdi Porel (ACS Applied Materials & Interfaces, 2025)
Electrocatalytic water splitting to hydrogen and oxygen is considered to be one of the significant routes for future renewable energy conversion. Therefore, the development of unique, efficient, and cost-effective bifunctional electrocatalysts, which can perform both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), is critical for the accessible utilization of renewable energy. The increasing overall efficiency of the water-splitting reaction is pivotal for sustainable energy conversion and hydrogen production. Herein, we present a facile solution-based synthesis route to control the crystallinity of the cobalt tungstate (CoWO4) nanomaterials to amorphous, semiamorphous, and crystalline phases and further exploit these nanomaterials as bifunctional electrocatalysts for the HER, OER, and overall electrochemical water splitting reaction. Notably, the semiamorphous cobalt tungstate nanomaterials show a remarkable surface area of approximately 150 m(2)/g, the highest reported for CoWO4-based materials, and demonstrated superior activity for both the OER and HER and outstanding stability over the amorphous and crystalline counterparts. Notably, the SemiAmp||SemiAmp electrolyzer demonstrated a better performance for overall water splitting than the commercial RuO2||Pt/C electrolyzer.
Keywords: amorphous; CoWO4; electrocatalyst; HER; Nanocomposite; OER; water splitting

Binder-free in situ interface reconstruction of NiMoO4 nanorods over Ni(OH)2 nanosheets for efficient urea oxidation - Kumar, Yogesh; Barik, Sidharth; Kharabe, Geeta Pandurang; Torris, Arun; Singh, Mayank U.; Mohan, S.; Galave, Chaitanya; Tekawadia, Jyoti; Kanawade, Rajesh; Kurungot, Sreekumar (Advanced Sustainable Systems, 2025)
Replacing the energy-intensive oxygen evolution reaction (OER) with the urea oxidation reaction (UOR) in electrochemical water splitting offers simultaneous green hydrogen production and urea-rich wastewater oxidation, enhancing energy efficiency and economic viability. In this study, a non-noble metal-based binder-free NiMoO4/Ni(OH)2/NF electrocatalyst is developed, featuring NiMoO4 nanorods anchored on Ni(OH)2 nanosheets. This unique morphology facilitates a highly active in situ reconstructed interface, delivering a current density of 134 mA cm-2 at 1.40 V (vs RHE) in 1 m KOH with 0.33 m urea, significantly outperforming its individual components. The catalyst demonstrates excellent stability over 50 h at 30 mA cm-2. When integrated into an anion exchange membrane urea electrolyser (13 cm2 area) with Pt@C/NF as the HER cathode, the system achieves 192 mA cm-2 at 1.60 V. The post-UOR studies confirm the presence of an amorphous NiMoO4-crystalline Ni(OH)2 interface, which plays a key role in enhancing the availability of the active sites to enhance the UOR performance. The improved electrochemical performance of the engineered catalyst can be ascribed to the in situ reconstructed amorphous-crystalline interface, optimal hydrophilicity, reduced charge transfer resistance, and the distinct morphology. This strategy offers a promising pathway for developing highly active electrocatalysts for energy conversion applications.
Keywords: AEM; electrolyser; OWS; tomography; UOR; wastewater

Binderless low silica X zeolite for methane separation from binary CO2/CH4 biogas stream: A comprehensive experimental and computational study - Yadav, Tushar R.; Shrotri, Aadesh R.; Kate, Pranjali N.; Devasia, George; Niphadkar, Prashant S.; Mali, Nilesh A.; Krishnamurty, Sailaja; Bokade, Vijay V.; Nandanwar, Sachin U. (Journal of Industrial and Engineering Chemistry, 2025)
This study presents the synthesis of binderless Na-LSX (B-Na-LSX) and binderless NaK-LSX (B-NaK-LSX). XRD, SEM, EDS, and N-2 physisorption were used for characterization of samples. Computational modelling of prepared sorbent was performed for the fundamental understanding of zeolite topology and adsorption behaviour. The breakthrough experiments are used to evaluate the adsorption capacities on CO2/CH4 (40/60 vol%) binary biogas stream. The results were compared with commercial Na-LSX (C-Na-LSX). The breakthrough adsorption capacity of B-Na-LSX was 3.08 mmol g(-1) and 0.29 mmol g(-1) of CO2 and CH4, respectively, at 300 K and 1 bar. CO2 sorption capacity of B-Na-LSX was similar to 11 % and similar to 17 % higher than B-NaK-LSX (2.77 mmol g(-1)) and C-Na-LSX (2.56 mmol g(-1)), respectively. DFT study reveals that the higher adsorption of CO2 over CH4 was attributed to higher charge transfer from CO2 to zeolite framework. Dual-bed six-step Pressure Swing Adsorption (PSA) was performed on B-Na-LSX at 6 bar. similar to 232 cycles were run with above 98 % of CH4 purity and similar to 74 % of recovery. The life-cycle test of sorbent was studied. It was implied that the designed sorbent is effective to produce the high purity of CH4 and can be utilized for a longer period for CH4 production.
Keywords: Binderless; Biogas; LSX zeolite; methane; PSA; Separation

Bioinspired nanochitin-based porous constructs for light-driven whole-cell biotransformations - Arumughan, Vishnu; Medipally, Hitesh; Torris, Arun; Leva, Tuukka; Grimm, Hanna C.; Tammelin, Tekla; Kourist, Robert; Kontturi, Eero (Advanced Materials, 2025)
Solid-state photosynthetic cell factories (SSPCFs) are a new production concept that leverages the innate photosynthetic abilities of microbes to drive the production of valuable chemicals. It addresses practical challenges such as high energy and water demand and improper light distribution associated with suspension-based culturing; however, these systems often face significant challenges related to mass transfer. The approach focuses on overcoming these limitations by carefully engineering the microstructure of the immobilization matrix through freeze-induced assembly of nanochitin building blocks. The use of nanochitins with optimized size distribution enabled the formation of macropores with lamellar spatial organization, which significantly improves light transmittance and distribution, crucial for maximizing the efficiency of photosynthetic reactions. The biomimetic crosslinking strategy, leveraging specific interactions between polyphosphate anions and primary amine groups featured on chitin fibers, produced mechanically robust and wet-resilient cryogels that maintained their functionality under operational conditions. Various model biotransformation reactions leading to value-added chemicals are performed in chitin-based matrix. It demonstrates superior or comparable performance to existing state-of-the-art matrices and suspension-based systems. The findings suggest that chitin-based cryogel approach holds significant promise for advancing the development of solid-state photosynthetic cell factories, offering a scalable solution to improve the efficiency and productivity of light-driven biotransformation.
Keywords: biocatalysis; light-driven biotransformation; nanochitins; porous materials

Bioinspired synthesis of bridged isochromane fused pyrazoles by a silver catalyzed cascade reaction and its application for antibacterial activity - Singh, Bhuvnesh; Tewari, Shreya; Kaur, Manleen; Sharma, Himanshu; Vanka, Kumar; Singh, Neetu; Singh, Ravi P. (JACS Au, 2025)
A stereoselective silver catalyzed one pot vinylogous aldol addition followed by a cascade [4+2] cycloaddition reaction of α-arylidene pyrazolinones to in situ generated isochromenylium ions has been developed, which provides an unprecedented bridged [2.2.2] [3.3.1] pentacyclic [5-6-6-6-6] skeleton consisting of an isochroman, chroman, and a pyrazole unit in one molecule with good to high yields as a single diastereomer. This method offers mild reaction conditions, wide substrate compatibility, excellent scalability and easy derivatization. A DFT study was carried out to clarify the reaction mechanism. It was exciting to observe that the unprecedented bridged isochromans synthesized here have shown excellent selectivity toward Gram-positive and Gram-negative bacteria. We demonstrate that while some structures are broad spectrum antibacterial there are two distinct structures that can be explored for selective activity.
Keywords: Antibacterial; Bridged [2.2.2] [3.3.1]; ROS; Stereoselective; Vinylogous aldol addition; [4+2] cycloaddition

Boosting the CO2 reduction activity of Cu double-atom catalysts through coordination environment engineering - Amin, Seerat; Krishnamurty, Sailaja; Dar, Manzoor Ahmad (Sustainable Energy & Fuels, 2025)
Double-atom catalysts (DACs) offer a reasonable and scalable route towards carbon neutrality owing to their efficient catalytic features. However, the challenges associated with the flexibility of their coordination structure usually restrict their full potential as efficient catalysts. Herein, we comprehensively examined the impact of coordination environment regulation on the CO2R activity of Cu2-DACs supported on C, N, or B co-doped graphene using ab initio simulations. We highlighted the marked role of the local coordination sphere of Cu2-DACs in modulating their structural stability and charge transfer characteristics, thereby regulating the adsorption of CO2 and various reaction characteristics. Notably, boron- and carbon-coordinated Cu2 centres (Cu2-BxCy) resulted in remarkably strong CO2 adsorption (-0.65 to -2.31 eV), attributed to their amplified electronic interactions with the CO2 molecule. The weak CO2 binding observed on the carbon-nitrogen- and nitrogen-boron-coordinated Cu2 centres (Cu2-NxCy and Cu2-NxBy) further highlighted the role of the coordination environment in facilitating the versatile binding modes of the key reaction species. The varying CO2 interactions in these systems were further comprehended and supported by a multilevel descriptor () combining both geometric and electronic parameters. This descriptor closely mirrored the DFT results, thereby accentuating its effectiveness as a predictive tool to perfectly model the CO2 interactions on these catalysts. Moreover, the dynamic behaviour in the adsorption modes led to partial breakdown of the conventional linear scaling relations between the key CO2 reduction intermediates (*COOH, *CO, and *HCO). Among the numerous types of investigated electrocatalysts, Cu2-B5C1 emerged as a highly active and selective catalyst for methanol production, with a remarkably low limiting potential of -0.54 V, surpassing the performance of several reported Cu-based systems. Besides, our findings underscored the often-overlooked yet crucial role of explicit solvation, which significantly altered both the potential-determining step and product selectivity. These outcomes emphasized the necessity of including solvation effects in realistic electrochemical modelling. Collectively, this study provides a critical mechanistic insight into better understanding the coordination effect on the CO2R and a robust design strategy for next-generation Cu-based DACs, guiding the development of highly efficient and selective catalysts for CO2 electroreduction.

Brønsted basic TMMM-hydrotrope combined catalytic system for the synthesis of diverse dihydropyranochromenes in water at ambient temperature - Rajmane, Archana; Jadhav, Aishwarya; Patil, Nita; Kumbhar, Arjun (New Journal of Chemistry, 2025)
This work describes the synthesis of a range of bioactive chromenes using a solid Br & oslash;nsted organic base called `tris(morpholinomethyl)mesitylene' (TMMM). TMMM was obtained in high yields by treating tris(bromomethyl)mesitylene (TBMM) with morpholine in the presence of K2CO3 in acetonitrile at RT. It was characterized using 1H NMR and 13C NMR spectroscopy. We developed a Br & oslash;nsted base hydrotrope combined catalytic system (BBHC) by combining TMMM and a hydrotrope (sodium p-toluene sulphonate: NaPTS) for the cascade-type Knoevenagel-Michael addition reactions of various aldehydes and malononitrile with kojic acid, 4-hydroxy coumarin, dimedone, and lawsone in water. The methodology offers diversity-oriented synthesis (DOS) of dihydropyranochromenes in high yields. The BBHC catalytic system showed at least four times recyclability without appreciable loss of its activity. TMMM is an odorless, solid organic base that can be easily handled and is resistant to air and moisture. As TMMM is a solid base, it can reduce evaporation losses, improve safety and allow its easy recovery and reuse. TMMM acts as a powerful Br & oslash;nsted base that activates reactants, while an aqueous solution of NaPTS acts as a hydrotrope that increases the solubility of organic compounds in water.

Carbohydrate-based polyester and amino acid polyester photocrosslinker and their resin formulation for 3D printing applications - Kamble, Ganesh N.; Joshi, Dheeraj Chandra; Gavhane, Utreshwar A.; Asha, S. K. (Chemistry-An Asian Journal, 2025)
Fully bio-based polyester was designed and synthesized using the carbohydrate-based diol 2,4:3,5-di-O-methylene-D-mannitol (Manx) and dimethyl ester of 2,3:4,5-di-O-methylene-galactaric acid (Galx). Photocurable resin formulations were prepared by incorporating up to 15 wt% of the carbohydrate polyester into hydroxyl ethyl methacrylate (HEMA) along with polyacrylamide crosslinker derived from L-glutamic acid. Complex 3D structures with good shape fidelity could be 3D printed using these novel polyester resin formulations. The incorporation of the carbohydrate polyester improved the glass transition temperature of the 3D-printed objects. Enzymatic erosion studies conducted using esterase enzyme revealed a higher degradation rate for the 3D-printed films containing the carbohydrate polyester. The hydrolytic degradation analysis conducted in both acidic and basic environments revealed that the 3D-printed polymer network exhibits stability and resilience in acidic conditions, while it undergoes complete degradation in basic conditions. This finding underscores the possibility of tailoring degradation processes under regulated circumstances.
Keywords: 3D printing; Amino acid; Carbohydrate polyester; Enzymatic degradation; Resin formulation

Catechin-capped silver-doped titanium dioxide nanoparticle enhanced photocatalytic toxic dye degradation - Ghosh, Sougata; Imboon, Tanawat; Layek, Rashbihari; Salunke, Gayatri; Parihar, Vijay Singh; Khumphon, Jeerawan; Webster, Thomas J.; Sutar, Santosh; Kityakarn, Sutasinne; Issro, Chaisak; Khamboonrueang, Dusadee; Thongmee, Sirikanjana (Frontiers in Chemistry, 2025)
Doping-associated surface modification is a powerful strategy to enhance the photocatalytic potential of n-type semiconductor nanomaterials. Silver (Ag) is one of the most effective dopants that can result in the retardation of the electron hole recombination-generating Schottky barrier at the TiO2 interface with a simultaneous extension of absorption to the visible region. This work presents a study on the effect of catechin, a bioactive principle polyphenol compound found in various plants, on the synthesis, Ag-doping and stabilization of TiO2 nanoparticles (TiO2NPs). The nanoparticles were irregular in shape with sizes ranging from 19 to 30 nm. Ag-TiO2NPs were fabricated using TiO2 as a precursor and 1%, 3%, and 5% AgNO3 as a doping agent. The average particle size of 1%Ag-TiO2NPs, 3%Ag-TiO2NPs, and 5%Ag-TiO2NPs was 27.3 +/- 7.5 nm, 29.8 +/- 9.6 nm, and 25.0 +/- 9.0 nm, respectively. High-resolution transmission electron microscopy (HRTEM) showed lattice fringes with an interplanar spacing of 0.23 nm corresponding to the Ag (111) plane in addition to the presence of the anatase phase of TiO2. Fourier transform infrared (FTIR) spectra exhibited a broad peak around 400-800 cm-1 that was attributed to Ti-O-Ti stretching vibrations which was slightly shifted in Ag-TiO2NPs due to changes in the local bonding environment around Ti atoms caused by interactions with Ag. Catechin loading in the TiO2NPs and Ag-TiO2NPs was between 1.55 and 3.3 wt. %. TiO2NPs, 1%Ag-TiO2NPs, 3%Ag-TiO2NPs, and 5%Ag-TiO2NPs exhibited superior photocatalytic degradation of methylene blue dye up to 78%, 87%, 91%, and 92%, respectively, and RhB dye up to 92%, 94%, 97% and 99%, respectively, with a pseudo-first-order reaction kinetics. Furthermore, its recyclability was also demonstrated for three cycles. The simplicity of fabrication and superior photocatalytic performance of TiO2 demonstrated here make this green route advantageous for environmental applications to treat dye contaminated effluent as well as for numerous other applications.
Keywords: catechin; green synthesis; methylene blue dye; Photocatalysis; Rhodamine B; silver doping; titanium dioxide nanoparticles

C=C insertion over N=C=O of allyl isocyanate into the Ge-Si bond of a germylene - Ajithkumar, V. S.; Khilari, Nripen; Ghanwat, Pratiksha B.; Koley, Debasis; Sen, Sakya S. (European Journal of Inorganic Chemistry, 2025)
Two isocyanates are reacted with the germylene, PhC(NtBu)(2)Ge-Si(SiMe3)(3) (1). Phenyl isocyanate undergoes catalytic cyclotrimerization with 1 leading to 1,3,5-triphenyl isocyanurate (2), while allyl isocyanate undergoes both cyclotrimerization and the C=C bond insertion between the Ge-Si bond. The constitution of 3 is determined by single-crystal X-ray studies. The contrasting reactivity pattern is explained by comprehensive density functional theory studies.
Keywords: Cyclotrimerization; Density functional theory; Germylene; Insertion; isocyanates

Ce[N(SiMe3)2]3(THF)3-catal yzed hydroboration of CO2, esters and epoxides with pinacolborane: selective synthesis of methanol in multigram scale - Hossain, Md Jabed; Shah, Brij Kumar; Dash, Soumya Ranjan; Vanka, Kumar; Khan, Shabana (Chemistry-A European Journal, 2025)
In this work, we have reduced CO2 with HBpin to afford borylated methanol product selectively in similar to 99 % yield using Ce[N(SiMe3)(2)](3)(THF)(3) as a catalyst. This led to multigram scale isolation of methanol obtained from CO2 reduction via the hydrolysis of borylated methanol, this establishes the potential of Ce[N(SiMe3)(2)](3)(THF)(3) as an efficient homogeneous catalyst for the bulk scale methanol synthesis. A practical application of this catalytic system was also shown by reducing CO2-containing motorbike exhaust efficiently and selectively. Further, C-O bond activation of esters and epoxides using HBpin and 1-2 mol % of Ce[N(SiMe3)(2)](3)(THF)(3) at 60 degrees C afforded the borylated alcohols in good to excellent yields, which can easily be hydrolysed to the eco-friendly corresponding alcohol. The stoichiometric experiments were performed to prove the formation of in-situ generated cerium hydride [Ce]-H as an active catalyst.
Keywords: Cerium; CO2 reduction; Epoxide; Ester; Hydroboration; Lanthanides

Characterization of a novel Tequatrovirus phage from pristine stretch of the Ganges River, India, in reducing bacterial load from sewage water - Samson, Rachel; Pawar, Ameya; Khairnar, Krishna; Dharne, Mahesh (Journal of Environmental Chemical Engineering, 2025)
Effective treatment of wastewater (WW) and its reuse is necessary to meet certain sustainable development goals and a circular economy. Escherichia coli is one of the primary contaminants in the WW, and its extra-intestinal occurrence poses a considerable threat under one health. This study is the first report of a novel broadspectrum phage (& fcy;ERS-1) isolated from a pristine stretch of the Ganges River in the biocontrol of E. coli, resistant to 3rd-and 4th generation cephalosporins and aztreonam. This is the first report of a phage from the Tequatrovirus genus to infect P. aeruginosa. The & fcy;ERS-1 could reduce the abundance of E. coli cells by 8.22 log10 CFU/mL <= 24 hrs. Additionally, phi ERS-1 disrupted the biofilm of E. coli with a reduction of 3.88 log10 CFU/mL. Further, phi ERS-1 could inhibit biofilm by multiple strains of E. coli (ATCC 8739, 25922, 43888) and multiple generaincluding E. coli ATCC 8739, Shigella boydii ATCC 9207, P. aeruginosa (ATCC 9027). The phage phi ERS-1 reduced bacterial counts in raw WW by 2 log10 CFU/mL and 4 log10 CFU/mL reduction in coliform-enriched WW in <= 24 hours. Overall, this study suggests that phi ERS-1 could be used as an effective alternative to be combined with other treatments for improving the quality of WW disposal and environmental health by reducing the bacterial load.
Keywords: Antibiofouling; Biofilm; Coliform; Ganges; Green approach; Phages; wastewater

Characterization of novel phages KPAФ1, KP149Ф1, and KP149Ф2 for lytic efficiency against clinical MDR Klebsiella pneumoniae infections - Dandekar, Shraddha S.; Thanikkal, Sinta; Londhe, Arti; Bhutada, Pankhudi; Saha, Ujjayni; Pawar, Shubhankar; Samson, Rachel; Dharne, Mahesh; Saroj, Sunil D.; Koratkar, Santosh (Microbial Pathogenesis, 2025)
Phage therapy offers a promising approach to the increasing antimicrobial resistance of Klebsiella pneumoniae. This study highlights three novel lytic bacteriophages-KPAc1, KP149c1, and KP149c2-targeting multidrugresistant (MDR) K. pneumoniae. These phages belong to the Myoviridae and Podoviridae family and demonstrate their efficacy and stability across a wide range of temperatures (up to 60 degrees C) and pH levels (pH 4 to 11). Genomic analysis reveals that they are free from virulence, toxicity, and antimicrobial resistance genes, making them promising candidates for therapeutic use. Among these phages, KPAc1 showed the highest lytic activity with a 26.15% lysis against MDR K. pneumoniae isolates. Additionally, a phage cocktail comprising all three phages improved lytic efficacy to 32.30%. This study also examined the antimicrobial resistance profiles of K. pneumoniae isolates, emphasizing the critical need for alternative treatments. By effectively targeting resistant strains, these phages offer a potential candidacy to be used as a viable alternative or a complementary antimicrobial agent to traditional antibiotics, opening up the possibility for advanced phage-based therapies. The promising results from this study pave the way for developing new treatments that could significantly improve patient care and outcomes from the growing issue of resistant bacterial infections.
Keywords: Antimicrobial resistance; Bacteriophage; MDR-Klebsiella pneumoniae; Phage cocktail; Phage therapy

Characterization of S-homocysteinylation of Human Insulin and Its Implications in Diabetes - Sheikh, Amreen B.; Jathar, Swaraj M.; Tammara, Vaishnavi; Das, Atanu; Kulkarni, Mahesh J. (Protein Journal, 2025)
Homocysteine thiolactone is a reactive thiol known for its interaction with various proteins. Nevertheless, there exists a paucity of information concerning the interaction between homocysteine thiolactone and human insulin, particularly regarding the mechanism by which homocysteine facilitates the reduction of disulfide bonds within insulin. In the present study, we have elucidated the binding sites of homocysteine to the cysteine residues (A6-B7 and A20-B19) that are implicated in the formation of intermolecular disulfide bonds in insulin through an in vitro reaction analyzed via LC-ESI MS/MS. This results in a reduction of disulfide bonds linking the A and B chains, which was corroborated by MALDI-TOF-MS and ESI-MS analysis. The secondary structure of insulin is affected by this modification, as evidenced by circular dichroism spectroscopy. In-silico studies also show that homocysteine affects the insulin structure. A glucose uptake assay conducted in Chinese hamster ovary (CHO) cells that stably express the insulin receptor revealed that HC-modified insulin is less effective in inducing glucose uptake compared to native insulin, suggesting that HC-induced structural modifications in insulin influence functional activity. This study provides insight into the HC-induced structural and functional changes in insulin and discusses the consequent implications for diabetes.
Keywords: Disulfide bonds; Homocysteinylation; insulin; Mass spectrometry

Characterization of wound-induced electrical signals and reactive oxygen species in chickpea (Cicer arietinum) - Deshpande, Shweta; Pawar, Shivani; Kumari, Archana (Plant Signaling & Behavior, 2025)
Mechanical damage to plants triggers both localized and systemic responses that activate plant defense mechanisms. Early signaling events include calcium (Ca2+) flux, reactive oxygen species (ROS), and electrical alterations. These signals coordinate downstream defense pathways, enabling plant acclimation to biotic stress. Electrical signaling following wounding/herbivory has been extensively studied in Arabidopsis; however, its dynamics in crop plants such as chickpea (Cicer arietinum) are not well understood. The pattern of the SWP in chickpea was similar to that in Arabidopsis but with a longer repolarization phase and was detectable only within the leaflets. The signals generated by damaging the leaflet were more pronounced, propagated bidirectionally and varied between herbivore-susceptible and tolerant chickpea varieties. The SWP duration is correlated with increased expression of AOS and OPR3 transcripts, which are markers of the stress hormone JA. Additionally, ROS production in wounded chickpea leaflets is associated with increased expression of ROS-generating genes. The use of DPI, an inhibitor of NADPH oxidase, which is responsible for ROS production, inhibited SWP, suggesting the crucial role of ROS in wound-induced SWP. This study provides insight into the interplay between wound-induced electrical signaling and ROS production in chickpea and proposes the measurement of electrical signals as a rapid, noninvasive approach for screening crop cultivars for pest susceptibility and tolerance.
Keywords: Chickpea; Electrical signal; Plant defense; ROS; wound

Charge transfer effect on relaxation mechanism in hydrated pyrrole-water systems following N-2s ionization - Kumar, Ravi; Bhattacharjee, Kankana; Ghosh, Aryya; Vaval, Nayana (ChemPhysChem, 2025)
This study investigates the relaxation mechanisms of pyrrole and pyrrole-water clusters (C4H5N-(H2O)n, where n=0-3 \${n = 0 - 3}\$ ) following N-2s ionization of pyrrole. Using various theoretical methods, we focus on the influence of water molecules and charge transfer on these non-radiative relaxation pathways. Our simulations included pyrrole solvated in 494 explicit water molecules equilibrated at 300 K and also employed a polarizable continuum model (PCM) to make the system more realistic and gain additional insights. In hydrated environments, the hydrogen bonding network between pyrrole and surrounding water molecules facilitates enhanced non-radiative relaxation pathways following inner valence ionization. Since these are hydrogen bonding systems, we have explored the possibility of proton transfer, which could occur in conjunction with other electronic decay processes.
Keywords: ab initio-calculations; auger decay; charge transfer; proton transfer; pyrrole

(Chiro)optical Properties of π-Extended Spiro-Double Carbo[7]helicene - Kumar, Viksit; Dongre, Sangram D.; Vandhanam, Aparna; Jadhav, Ashok Badrinarayan; Kumar, Jatish; Babu, Sukumaran Santhosh (Journal of Physical Chemistry Letters, 2025)
Helical nanographenes are a fascinating class of pi-extended chiral nanocarbons, where structural helicity imparts intrinsic chirality and unique optoelectronic properties to the rigid carbon framework. In this work, we synthesized a hexa-peri-hexabenzocoronene-based pi-extended spiro-double carbo[7]helicene. The helical distortion of the structure was unambiguously confirmed by X-ray crystallography. The optical properties were explored through UV-Vis absorption, fluorescence, and phosphorescence measurements, complemented by density functional theory (DFT) calculations. Remarkably, the pi-extended spiro-double carbo[7]helicene exhibited thermally activated delayed fluorescence (TADF) at room temperature and phosphorescence at low temperatures. Chiral HPLC successfully resolved the enantiomers into three fractions: (PP), (MM), and the meso forms (PM)/(MP), and chiroptical studies of the pure enantiomers revealed a moderately high g lum value of 1.58 x 10-3. Finally, the origin of the observed dissymmetry factors was rationalized by analyzing the transition electric dipole moments (TEDM) and transition magnetic dipole moments (TMDM) derived from time-dependent density functional theory (TD-DFT) calculations.

Chiroptical amplification of [7]-helicene nanographene by additional helical chirality - Dongre, Sangram D.; Venugopal, Geethu; Kumar, Viksit; Badrinarayan Jadhav, Ashok; Kumar, Jatish; Babu, Sukumaran Santhosh (Angewandte Chemie-International Edition, 2025)
Nanographenes have captivated scientific interest since the pioneering discovery of graphene. Recently, attention has shifted towards exploring chiral and nonplanar nanographenes, for their distinct optical, chiroptical, and electronic properties. Despite the growing acceptance of helicenes, the research on inducing helical chirality on pi-extended derivatives to boost chiroptical properties remains unattended. In our study, we introduce a new pi-extended [7]-helicene resulting from the condensation of diamines with 3,6-dibromophenanthrene-9,10-dione, complemented by two hexabenzocoronene arms in the periphery. Notably, the nanographene containing binaphtho-[1,4]diazocine, compared to the corresponding phenazine, exhibits a remarkable average 2.5, 5, and 10-fold enhancements in quantum yield, dissymmetry factor, and brightness, respectively, when measured in five different solvents. These improvements underscore the significance of the induced helical chirality by the antiaromatic binaphtho-[1,4]diazocine in influencing the chiroptical properties of the helical nanographene. Our research represents a significant stride toward unlocking the potential of pi-extended helicenes and lays the groundwork for further exploration in designing and synthesizing new chiral nanomaterials.
Keywords: circularly polarised luminescence; dissymmetry factor; helicene; nanographene; quantum yield

Chitosan-derived carbon supported ruthenium catalyst for efficient hydrogenation of levulinic acid to γ-valerolactone - Korampattu, Lavanya; Dhepe, Paresh L. (Sustainable Energy & Fuels, 2025)
The transition from fossil fuels to sustainable energy and chemical production relies heavily on efficient biomass valorization. Levulinic acid (LA), a key platform chemical from lignocellulosic biomass, serves as a versatile precursor for valuable chemicals like gamma-valerolactone (GVL), a promising green solvent, fuel additive, and polymer precursor. While ruthenium-based catalysts are effective for LA hydrogenation, conventional systems like Ru/C often suffer from metal leaching and deactivation due to weak metal-support interactions. Current approaches to improve stability, such as using nitrogen-doped carbon supports, involve complex synthesis and synthetic nitrogen precursors. Addressing these limitations, we present a facile and sustainable strategy for synthesizing a robust ruthenium catalyst by directly pyrolyzing marine biomass-derived chitosan to form a self-nitrogen-doped carbon support. This catalyst exhibited superior stability and excellent recyclability in the aqueous-phase hydrogenation of LA to GVL, surpassing conventional Ru/C while maintaining activity comparable to that of leading Ru catalysts supported on N-doped carbon. Unlike other N-doped carbon supports, our method avoids synthetic N-dopants and tedious procedures, making it inherently more sustainable. Detailed characterization via XPS and H2-TPR revealed strong metal-support interactions, facilitated by intrinsic nitrogen functionalities, effectively stabilizing the ruthenium species. This study also identifies the critical role of graphitic and pyridinic nitrogen species in controlling catalytic activity and elucidates the importance of optimizing nitrogen species and content in tailoring chitosan-derived supports. The proposed mechanism describes how Ru-N centers activate hydrogen and LA, with basic nitrogen sites aiding the dehydration step to GVL. Overall, this work features the potential of chitosan derived carbon as a sustainable and tunable support for efficient biomass hydrogenation catalysts and offers fundamental insights into the role of nitrogen doping in tailoring catalytic performance.

Clove essential oil-supported disposable in-tip cellulose paper (DICP) device for facile extraction of anesthetic drugs from postmortem samples: a white analytical toxicology (WAT) approach - Jain, Rajeev; Shivankar, Bhavana R.; Krishnamurty, Sailaja; Al-Khateeb, Lateefa A.; Sheetal, Sarah; Alharthi, Sarah (Sustainable Chemistry and Pharmacy, 2025)
A novel disposable in-tip cellulose paper (DICP) device, enhanced with clove essential oil (CEO), was developed for the extraction of four anesthetic drugs (lidocaine, prilocaine, ropivacaine, and bupivacaine) from postmortem blood and urine samples. The DICP device, equipped with 1 x 3 cm CEO-impregnated cellulose paper (CP) strips (prepared via a simple dip-coating process), is attached to a 1000 mu L micropipette. The findings from density functional theory (DFT) study reveals that CEO-impregnated cellulose demonstrates stronger and more diverse interactions with anesthetic drugs, as evidenced by more negative adsorption energy (-0.62 eV) and enhanced non-covalent interactions compared to cellulose alone. The procedure involves aspirating and dispensing diluted biological samples through the DICP device for 30 cycles, adsorbing the analytes onto the CEO-impregnated CP strips. The adsorbed analytes are subsequently eluted with 0.5 mL of ethyl acetate through 40 aspirating-dispensing cycles and analyzed by GC-MS. The method achieved limits of quantification as low as 0.01 mu g/mL, with intra-day and inter-day precisions below 10.2 % and 14.6 %, respectively, and accuracy ranging from 90.5 % to 110.7 %. Relative recoveries ranged from 66 % to 87.6 %, while matrix effects remained consistently below 11.9 %. The DICP-GC-MS method demonstrated exceptional sustainability, achieving a whiteness score of 97.2 %, underscoring its alignment with green analytical chemistry principles and operational simplicity. Applicability was demonstrated through the successful analysis of postmortem cardiac blood in a suspected anesthetic drug overdose case, highlighting its potential as a robust, high-throughput, and eco-friendly approach for routine forensic toxicological screening.
Keywords: Anesthetic drugs; Clove essential oil; Disposable in-tip cellulose paper (DICP) device; Green sample preparation; White analytical toxicology (WAT)

Cocrystals of the highly potent sickle cell anemia drug voxelotor with trimesic acid: a substantial enhancement in in vitro dissolution performance at physiological pH - Khan, Akram A.; Shaikh, Tabrez R.; George, Christy P.; Gonnade, Rajesh G. (Crystal Growth & Design, 2025)
Global Blood Therapeutic's (GBT's) Voxelotor is an investigational oral therapy for treating sickle cell anemia. It functions by increasing the affinity between hemoglobin and oxygen, thereby preventing the sickling of red blood cells and altering the disease's pathology. The US FDA has approved Voxelotor for the treatment of sickle cell anemia and granted it an orphan drug status. However, Voxelotor is classified as a BCS class II, indicating poor water solubility. The current study explores the enhancement of Voxelotor's water solubility by forming cocrystals with trimesic acid (TMA). Novel cocrystals, cocrystal solvates, and hydrates of Voxelotor (Vox) with trimesic acid (TMA) have been developed to improve their solubility. The new solids were characterized using PXRD, DSC, TGA, XPS, HSM, and single-crystal X-ray diffraction studies, and the intermolecular interactions were quantified using Hirshfeld surface analysis. Detailed crystallographic analysis revealed strong O-H center dot center dot center dot N hydrogen bonding interactions between Vox and TMA, primarily involving the COOH functional group of TMA and the pyridine or pyrazole groups of Vox. Additionally, TMA molecules participate in further hydrogen bonding-either with themselves or with solvates, including hydrates, through mono- or dimeric O-H center dot center dot center dot O H-bonding synthons. In vitro solubility studies demonstrated a significant increase in the solubility of Voxelotor in the Vox-TMA cocrystals compared to the pristine drug at physicochemical pH 4.5 and 6.8. Stability studies confirmed that the nonsolvated multicomponent crystal retains their structural integrity under nonambient conditions without undergoing polymorphic phase transitions. In contrast, the solvated crystals, including hydrates, undergo phase transitions within the temperature range of 100-130 degrees C, losing solvents and converting into one of the nonsolvated cocrystal forms. These findings suggest that the novel Vox-TMA cocrystals have the potential to enhance the therapeutic performance and clinical utility of Voxelotor.

Comprehensive genomic analysis of bipolaris sorokiniana strains: insights into genetic diversity and pathogenicity - Shukla, Anand Kumar; Sahoo, Rosaleen; Kadoo, Narendra (Plant Pathology, 2025)
Bipolaris sorokiniana is an important plant-pathogenic fungus that primarily infects cereals, such as wheat and barley, causing diseases such as spot blotch, common root rot and seedling blight. This study presents a comprehensive comparative genomic analysis of nine B. sorokiniana strains based on 16 genomic parameters, including genome completeness, virulence factors, secondary metabolite biosynthesis, effector proteins and CAZymes, to explore their genetic diversity, genome assembly quality and pathogenic potential. Genomic assemblies of the strains LK93 and ND93-1 exhibited higher N50, L50, BUSCO completeness scores and gene annotations, and were designated as high-quality. Similarly, ND90Pr and BS112 demonstrated a rich arsenal of CAZymes and effector proteins, which indicated their greater infection potential. Variability in biosynthetic gene clusters, especially the presence of isocyanide-NRPS and fungal RiPP clusters, highlights the ecological adaptability and metabolic diversity of these strains. The study also revealed distinct protein family distributions and effector protein repertoires, supporting strain-specific pathogenic strategies. Phylogenetic analyses grouped the strains into three clusters, indicating evolutionary divergence and potential ecological specialisation. The findings of the study underscore the importance of high-quality genomic data and propose LK93 and ND93-1 as more reliable reference genomes for B. sorokiniana. Integrating transcriptomics, proteomics and pathogenicity data, along with expanded strain sampling and unified assembly pipelines, can enhance understanding of the molecular basis of pathogenicity and help develop suitable disease management strategies to control this agriculturally important pathogen.
Keywords: Cochliobolus sativus; comparative genomics; effector proteins; pathogen variability; Secondary metabolites; spot blotch

Confined impinging jet reactor for high-throughput continuous flow mononitration of salicylic acid - Khan, Muzammilanwar S.; Shaikh, Tabrez R.; Kulkarni, Sphurti P.; Patil, Abhishek A.; Kulkarni, Amol A. (Organic Process Research & Development, 2025)
Novel approach is reported for highly efficient continuous mononitration of salicylic acid using confined impinging jet reactor (CIJR) with a vent. Initially, controlled semibatch reactions are optimized to achieve complete conversion and formation of mononitro products with very high selectivity for 5-nitrosalicylic acid (5-NSA). Further, the combination of computational fluid dynamics simulations and experiments is employed to optimize CIJR design and operating flow conditions, suitable to yield only mononitro products with excellent control over mixing, heat transfer, and liberation of fumes during continuous flow reaction. Detailed analysis of internal flow patterns, rate of heat generation, and concentration distribution inside the CIJR facilitated the optimization of present exothermic reaction in a safe manner. In less than a minute, complete salicylic acid (SA) conversion with good yield and better selectivity for 5-NSA is achieved using the CIJR. Safety and clogging issues are addressed effectively, even at a relatively lower mole ratio (1:5) of SA:acetic acid (AcOH). The present approach is quite scalable using the numbering-up strategy, with advantages viz. nonfouling, high throughput, and the small footprint of CIJR.
Keywords: computational fluid dynamics; confined impinging jet reactor; high-throughput synthesis; salicylic acid nitration

Conjugate addition/cyclization of propanal with isatylidene malononitriles: an efficient one-pot organocatalytic approach for the synthesis of 3′-methyl spiro[2H-pyran-3,4′-indoline] - Patil, Baliram R.; Nichinde, Chandrakant B.; Girase, Amardipsing S.; Chaudhari, Suryakant S.; Kinage, Anil K. (Organic & Biomolecular Chemistry, 2025)
The organocatalyzed one-pot Michael addition reaction of propanal to isatylidene malononitriles remains largely unexplored due to challenges in controlling the reaction and preventing side processes such as aldol condensation, self-aldolization, and 1,3-dipolar cycloaddition. In this study, we introduce a one-pot methodology for the synthesis of 3 `-alkyl spiro[2H-pyran-3,4 `-indoline] via an organocatalyzed Michael addition of simple propanal to isatylidene malononitrile derivatives, which are generated in situ from isatin derivatives and malononitrile. Subsequent reduction of the Michael adduct with NaBH4 leads to the target product with high efficiency under mild conditions. This strategy offers several advantages, including environmental sustainability, high to excellent yields, shorter reaction times, cost-effectiveness, and ease of implementation.

Continuous flow solvent-free and catalyst-free mechanochemical production of rhodamine B dyes and their derivatives - Purohit, Mukesh; Shaikh, Tabrez Rafique; Kulkarni, Amol A. (Chemical Communications, 2025)
In this communication, we have described a simple and efficient, catalyst free and solvent-free protocol for the continuous flow synthesis of rhodamine B dyes developed from 3-diethyl amino phenol and phthalic anhydride. Nearly 95% conversion was achieved within 12 min using a jacketed single screw reactor. This method is further used for the synthesis of six derivatives with 70-84% yield, which can be compared to 85% yield from a 1-hour long batch synthesis involving a catalyst.

Continuous flow synthesis of metal nanowires: protocols, engineering aspects of scale-up and applications - Sonawane, Jayesh R.; Jundale, Rajashri; Kulkarni, Amol A. (Materials Horizons, 2025)
This review comprehensively covers the translation from batch to continuous flow synthesis of metal nanowires (i.e., silver, copper, gold, and platinum nanowires) and their diverse applications across various sectors. Metal nanowires have attracted significant attention owing to their versatility and feasibility for large-scale synthesis. The efficacy of flow chemistry in nanomaterial synthesis has been extensively demonstrated over the past few decades. Continuous flow synthesis offers scalability, high throughput screening, and robust and reproducible synthesis procedures, making it a promising technology. Silver nanowires, widely used in flexible electronics, transparent conductive films, and sensors, have benefited from advancements in continuous flow synthesis aimed at achieving high aspect ratios and uniform diameters, though challenges in preventing agglomeration during large-scale production remain. Copper nanowires, considered as a cost-effective alternative to silver nanowires for conductive materials, have benefited from continuous flow synthesis methods that minimize oxidation and enhance stability, yet scaling up these processes requires precise control of reducing environments and copper ion concentration. A critical evaluation of various metal nanowire ink formulations is conducted, aiming to identify formulations that exhibit superior properties with lower metal solid content. This study delves into the intricacies of continuous flow synthesis methods for metal nanowires, emphasizing the exploration of engineering considerations essential for the design of continuous flow reactors. Furthermore, challenges associated with large-scale synthesis are addressed, highlighting the process-related issues. This review comprehensively covers the translation from batch to continuous flow synthesis of metal nanowires (i.e., silver, copper, gold, and platinum nanowires) and their diverse applications across various sectors.

Continuous flow telescopic synthesis of 3-methoxy propiophenone by the grignard reaction - Wankhede, Pranali; Kulkarni, Amol A. (Organic Process Research & Development, 2025)
The synthesis of 3-methoxypropiophenone 1, a crucial intermediate in the production of the analgesic tapentadol hydrochloride, was investigated using a multistep continuous flow process. The approach is based on the Grignard reaction. A series of continuously stirred tank reactors (CSTRs) were employed: the first reactors facilitated the continuous generation of Grignard reagents 3, which then reacted with propionitrile in the next CSTR to yield 1. This was followed by quenching, neutralization, and phase separation, conducted under varying temperatures and residence times. When compared to a 50% yield from an optimized batch synthesis protocol, a continuous flow synthesis helped achieve an 84% yield of the desired product in a much shorter reaction time. A kinetic model was developed to predict the Grignard reagent formation and product yield, revealing that the mass transfer effect is insignificant at a higher stirring rate. The approach is highly scalable for the synthesis of pharmaceutical intermediates.
Keywords: batch and continuous reaction; flow chemistry; Grignard reaction; heterogeneous kinetics

Coumarin hybrids: dual-target candidates for future antimicrobial and antitubercular therapies - Bavishi, Abhay; Vala, Hardev; Thakrar, Shailesh; Swami, Sagar; Sarkar, Dhiman; Shukla, Rushit; Kamdar, Jignesh; Shah, Anamik (Future Medicinal Chemistry, 2025)
Aims: This study aimed to synthesize, characterize, and evaluate the antimicrobial and antitubercular activities of two novel series of coumarin-based derivatives (Series 5 and Series 9), focusing on their structure-activity relationship (SAR) and molecular docking interactions with key bacterial enzymes. Materials & methods: Series 5 (5a-5j) and Series 9 (9a-9t) compounds were synthesized and characterized using spectroscopic techniques. Their antimicrobial and antitubercular activities were evaluated against Mycobacterium tuberculosis, Staphylococcus aureus, Bacillus subtilis, and E. coli. IC50 values were determined, and molecular docking studies were conducted to assess binding interactions with M. tuberculosis enoyl-ACP reductase (InhA) and E. coli DNA gyrase B. Results: Series 5 compounds exhibited moderate activity, with 5f, 5 g, 5i, and 5j showing notable inhibition. Series 9 derivatives displayed superior dual-target inhibition, with 9t, 9c, 9a, 9b, and 9p achieving >90% inhibition against S. aureus and B. subtilis. The lowest IC50 against M. tuberculosis was observed for 9c (1.50 mu g/mL), followed by 9a (2.84 mu g/mL) and 9b (2.73 mu g/mL). Molecular docking confirmed strong binding interactions, correlating with observed biological activities. Conclusions: Series 9 compounds, particularly 9t, 9c, and 9a, demonstrate high potential as dual-target antimicrobial drug candidates. Further optimization may enhance their therapeutic efficacy. [GRAPHICS]
Keywords: Antimicrobial activity; antitubercular agents; Coumarin derivatives; Molecular docking studies; structure-activity relationship (SAR); thiophene-based compounds

DABCO dicationic ionic solid supported polymer (DDIS@PS) mediated synthesis of diverse 2-amino-4H-chromenes and xanthenes: a cascade Knoevenagel-Michael approach - Rajmane, Archana; Patil, Nita; Patil, Anuradha; Kamble, Sumit; Kumbhar, Arjun (New Journal of Chemistry, 2025)
This work documented the synthesis of diverse bioactive polysubstituted 2-amino-4H-chromenes using a DABCO dicationic ionic solid (DDIS) supported on Merrifield resin (DDIS@PS) as a catalyst. The catalyst is characterized by FT-IR, SEM-EDX, and TGA analysis. The resulting PS contains supported DABCO units with free tertiary nitrogen functionality on their external surface. The catalyst effectively catalyzed cascade Knoevenagel-Michael addition reactions of various aldehydes and active methylene compounds (malononitrile and phenyl sulfonyl acetonitrile) with dimedone, yielding good to excellent results in water or ethanol at room temperature or 78 degrees C. The time required for the reaction of phenyl sulfonyl malononitrile is comparatively very high compared to malononitrile. The synthesis of bis-dimedone derivatives and 1,8-dioxo-octahydro-xanthenes was also achieved in both solvents at RT and 78 degrees C, with high yields. The catalyst demonstrated greater efficiency and maintained its activity over at least five cycles.

[DBUH][HSO4]-catalyzed solvent-free synthesis of 1,5-benzodiazepine derivatives: bioevaluation and in silico molecular docking study - Subhedar, Dnyaneshwar D.; Shaikh, Mubarak H.; Nagargoje, Amol A.; Sarkar, Dhiman; Khedkar, Vijay M.; Shingate, Bapurao B. (Current Organic Chemistry, 2025)
Here, we report the solvent-free one-pot multicomponent synthesis of 4-substituted-1,5-benzodiazepine derivatives from O-phenylenediamine, aromatic aldehydes, and dimedone using [DBUH][HSO4] as a catalyst in excellent yields. This process was carried out in search of a reusable, easily accessible, affordable, and efficient catalyst. 1,5-Benzodiazepines demonstrate a new family of good inhibitors with potent anti-mycobacterial properties. The most promising compounds in the present series are 4c, 4i, and 4l which showed excellent activity and inhibited the growth of both MTB H37Ra and M. bovis BCG strains with lower MICs. The most active compounds were further studied for their cytotoxicity against cell lines MCF-7, A549, HCT116, and THP-1 by MTT assays and the compounds were found to be non-toxic. The fact that none of these compounds work against either Gram-positive or Gram-negative bacteria suggests that they are only effective against MTB. The in silico docking of the molecules against mycobacterial enoyl reductase, InhA enzyme could provide well-clustered solutions and have given valuable insights into the thermodynamic elements governing the binding affinities. The findings of this investigation unmistakably point to the discovery of extremely specific and selective MTB inhibitors, which can now be investigated further in search of possible anti-tubercular drugs.
Keywords: 1; 5-benzodiazepine; Antitubercular activity; Molecular docking; multicomponent reactions; [DBUH][HSO4]

Deciphering the comprehensive microbiome of glacier-fed Ganges and functional aspects: implications for one health - Samson, Rachel; Kumar, Shubham; Dastager, Syed; Khairnar, Krishna; Dharne, Mahesh (Microbiology Spectrum, 2025)
Glacier-fed rivers are significant ecological components of the river catchments, yet their microbial diversity and the associated antimicrobial potential remain underexplored. The Ganges is a glacier-fed river of immense cultural, religious, and ecological significance that supports over 400 million people downstream, providing essential water for agriculture, industry, and daily use. Despite its importance, the microbial community composition and antimicrobial potential, across its relatively pristine origin, remain largely underexplored. One possible explanation for this could be the lower microbial load in the upstream glacier-fed region, which likely results in a reduced DNA yield, insufficient for whole-metagenome sequencing, in contrast to the more biologically diverse and nutrient-rich lower reaches. In this study, we developed an efficient DNA extraction and amplification method using low-input DNA to sequence the microbiome from sediments of the glacier-fed Ganges River in pre-monsoon and post-monsoon over 2 years. Taxonomic and functional diversity of bacterial and viral (phage) communities were analyzed, together with the seasonal variations in their composition. Significant differences in microbial communities were observed in response to seasonal shifts (P < 0.05). During the dry season, Proteobacteria and Actinobacteria were predominant, while Bacteroidetes and Firmicutes were abundant post-monsoon (P < 0.05). The microbiome harbors potential for the biosynthesis of streptomycin, phenylpropanoid, penicillin, and cephalosporins. Bacteriophages from Podoviridae, Myoviridae, and Siphoviridae showed lytic potential against putrefying and pathogenic bacteria. This first comprehensive study on the glacier-fed Ganges River highlights significant seasonal shifts in microbial diversity. The initial insights into the functional profile of the bacterial and phage diversity offer opportunities to explore various natural compounds and enzymes to tackle antimicrobial resistance under the one-health canopy.
Keywords: Bacteriophages; glacier-fed-Ganges; Microbiome; Secondary metabolites; special properties

Defect-rich CoFe-alloy with engineered carbon support for high-performance rechargeable Zn-air batteries - Kharabe, Geeta Pandurang; Barik, Sidharth; Torris, Arun; Maria, Anit; Kumar, Yogesh; Kurungot, Sreekumar (Small, 2025)
Defect-rich CoFe-alloy with engineered carbon support is synthesized as a bifunctional cathode, coupled with a modified electrode fabrication technique, for rechargeable zinc-air batteries (RZABs). The CoFe(2:1)/N-rGCNT-catalyst is synthesized by annealing graphene oxide (GO), cobalt and iron acetate, and melamine, leading to the in situ formation of CoFe alloy-encapsulated CNTs. This resulted in a unique layer-separated Fe-rich skin@CoFe alloy decorated nitrogen-doped graphene (NGr) with CoFe-encapsulated CNTs. The interplay of line defects, enhanced conductivity, and electronic modulation underpins electrocatalyst's performance. Electrochemical analysis revealed an onset potential of 955 mV vs RHE, a half-wave potential of 835 mV vs RHE for oxygen reduction reaction (ORR) and an overpotential of 340 mV for oxygen evolution reaction (OER), yielding a Delta E of 0.73 V, comparable to the reported catalysts. The 3D X-ray microtomography simulations suggest improved air permeability of CoFe(2:1)/N-rGCNT facilitates easier gas diffusion, contributing in better device performance. The RZAB with CoFe(2:1)/N-rGCNT-cathode exhibited a peak power density of 171.3 mW cm(-)2, surpassing 140.8 mW cm(-)2 obtained from a cell based on Pt/C-cathode. The Co/N-rGCNT-based battery achieved a stable discharge profile at 10 mA cm(-)2 with a specific capacity of 650 mAh g(-)(1)Zn, and in rechargeable mode, achieved 140 h of high-rate charge-discharge cycling capability.
Keywords: 3D tomography; N-doping; alloy encapsulated structure; device demonstration; grain boundaries; oxygen reduction and evolution reactions; rechargeable zinc-air battery

Depolymerization of waste polycarbonates to value-added products - Padhi, Ganeshdev; Pansare, Vaibhav Ramachandra; Bajpai, Priyam; Krishna, Gamidi Rama; Vanka, Kumar; Barsu, Nagaraju (ChemSusChem, 2025)
Additive free aminolysis method developed for the depolymerization/upcycling of polycarbonates. We report here chemical recycling of polycarbonate under ambient conditions to get its monomer bisphenol A, monoaminocarbamate and biscarbamates in 1 : 2 : 1 ratio respectively. By employing the secondary amine as the aminating reagent, facilitates the depolymerization to work under additive/catalyst free conditions. The developed method deals with depolymerization of waste polycarbonates and works even with late-stage amine derivatives such as amoxapine and desloratadine which are drugs molecules known to treat neurotic disorders and allergies respectively. The reaction can be scaled up and works with similar efficacy which depicts the efficiency of the depolymerization of wasteend-of-life polycarbonate plastic waste. The biscarbamate and bisphenol-A was further subjected for the post functionalization to obtain amides and phenol in good yields. Developed additive/catalyst free aminolysis of waste polycarbonates to carbamates and monomer BPA at ambient conditions. Variety of secondary amines were screened including the late stage amine derivatives like amoxapine and desloratadine which delivered the expected products successfully. Later the developed methodology was even applied for the different end-of-life polycarbonates with the secondary amine and achieved the depolymerization without any obstacle. Further carried out the scale up reaction and derivatization of carbamates and BPA to amide and phenol synthesis. image
Keywords: Aminolysis; carbamates; depolymerization; End-of-life; Polycarbonate

Design and synthesis of C-α-D-mannopyranoside linked mesoporous silica nanoparticles - Nechooli, Hemanth K.; Ramtenki, Vilas; Kumar, Chepuri V. Suneel; Prasad, V. B. L.; Ramana, V. Chepuri (Journal of Chemical Sciences, 2025)
Mannose functionalized mesoporous silica nanoparticles (MSNs) offer a promising approach for developing more targeted, effective, and safer cancer therapies. For many of the applications, immobilization of carbohydrates like mannose onto MSNs is a crucial aspect, and in most cases, mannose moieties are connected through O-glycosidic linkages that are susceptible to acidic/enzymatic hydrolysis. To generate a stable mannose-functionalized MSN, we designed a novel C(14)-alpha-mannosylated tetradeca-1-yne. The key steps involved in the synthesis of C-mannosylated alkyne are C1-alkynylation of tri-O-acetyl-D-glucal with 1-trimethylsilyl-tetradec-1-yne, followed by stereoselective dihydroxylation and the isomerization of the internal triple bond to a terminal position. This mannose ligand was then immobilized onto azidopropyl-functionalized SBA-15 through the Cu(I)-catalyzed azide-alkyne click (CuAAC) reaction. Various physical techniques such as low-angle powder XRD, N-2 adsorption isotherms (BET), Fourier transform infrared (FTIR), high-resolution transmission electron microscopy (HRTEM), field emission scanning electron microscopy (FE-SEM), and thermogravimetric analysis (TGA) have been employed to characterize this C-mannosyl SBA-15 silica matrix. We evaluated the binding ability of C-mannosyl SBA-15 nanoparticles by using fluorescein-labelled Con-A as a target protein.
Keywords: C-mannoside; Click reaction; mannose specific proteins; Mesoporous silica nanoparticles; Zipper reaction

A detailed study on heat of reaction and heat rate determination of nitrobenzene hydrogenation to aniline reaction using power compensation reaction calorimeter - Kumar, Rajendra; Mane, Pradip R.; Shingote, Savita K.; Mali, Nilesh A. (Process Safety Progress, 2025)
The present study reports experimental heat of reaction and heat rate data of nitrobenzene hydrogenation to aniline reaction with process parameter variation. A high-pressure isothermal power compensation reaction calorimeter was used for this work. A systematic and step-by-step procedure is also reported to determine the heat of reaction and heat rate for a highly exothermic reaction. The sensitivity of experimental molar heat of reaction (kJ/mol) and evolved heat rate (W) values for nitrobenzene hydrogenation reaction was analyzed for various important process parameters, such as temperature, pressure, substrate quantity, solvent quantity, catalyst quantity, RPM, and hydrogen feed rate. Nitrobenzene hydrogenation reactions were conducted using ethanol as solvent and 5% Pd/C as a catalyst with 55-65 degrees C temperature and 7-9 Bar absolute pressure range. More than 99.99% conversion of nitrobenzene to aniline was obtained, and no other by-products were found. The average experimental nitrobenzene hydrogenation heat of reaction of 21 different experiments was found to be -581.87 kJ/mol, and the maximum heat rate during the nitrobenzene hydrogenation reaction was found to be 16.16 W for experiments using 10 gm of nitrobenzene in solvent.
Keywords: heat of reaction; heat rate; Hydrogenation; nitrobenzene; power compensation; reaction calorimeter

Detection and variant characterization of lumpy skin disease virus from dairy cattle in India - Bajpai, Manali; Khilari, Ajinkya; Likhitkar, Bhagyashree; Musale, Pankaj; Jadhav, Santoshkumar; Dhanikachalam, Velu; Kakramkar, Payal; Bhave, Kaustubh; Swaminathan, Marimuthu; Joshi, Sachin; Shanmugam, Dhanasekaran (Virus Evolution, 2025)
The spread of a severe and often fatal form of lumpy skin disease (LSD) in cattle and water buffaloes has caused widespread mortality and morbidity of these animals in India. To track and understand the genetic changes occurring in the virus and to enable routine surveillance of the virus, multiplexed polymerase chain reaction (PCR) and sequencing methods were developed and validated in this study. Multiplexed nested PCR for LSD virus (LSDV) detection was optimized using skin lesion swabs and nasal samples collected from symptomatic and asymptomatic animals. For genotyping, overlapping PCRs to amplify the entire LSDV genome were developed and tested on field samples collected from the Maharashtra and Odisha states of India. Analysis of LSDV genomes from 41 field samples collected in 2022 and 2023 revealed the presence of highly conserved novel mutations. Phylogenetic analysis shows that a distinct genotype of LSDV has spread across India, which warrants genomic surveillance of the virus in the coming years to track the evolution and transmission of the virus. The non-invasive sample collection, detection, and genotyping methods described in this study can facilitate large-scale surveillance of LSDV in dairy animals.
Keywords: genotyping by sequencing; lumpy skin disease; multiplexed nested PCR; Oxford Nanopore technology; virus surveillance

Development and assessment of implant material sustainability in synthesized AV fistula assisting device - Raut, Abhijeet; Uddanwadikar, V. R.; Padole, P. M.; Ookalkar, D.; Kanekar, Jugal (Materials Research Express, 2025)
Arteriovenous fistula (AVF) failure remains a significant challenge in the treatment of end-stage renal disease, leading to increased morbidity and economic burden to the patients. The availability of effective devices to address AVF is still very limited globally. In view of the high failure rate of AVF during hemodialysis, development and selection of most appropriate material for AVF device is a test for the researcher. In the present research work, the mechanical and biocompatibility tests have been conducted on the implant grade silicon materials selected to develop the device before it is subjected to animal trials. The AVF assisting device is fabricated and a custom-designed in-vitro model is developed to replicate the human anatomical surroundings. The tensile strength and the elongation of the selected implant-grade silicon in the fabricated device are tested using a universal testing machine; also, the surface structure and the chemical composition are tested using scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR) respectively. The hydrophilicity and long-term performance are analyzed using a water absorption test. The biocompatibility and cytotoxicity of the material and fabricated device are determined using cell viability assay. It is observed that the silicone material used in the AVF assisting device shows strong mechanical integrity, optimum structural stability, biocompatibility and is non-cytotoxic to mammalian cell line. Thus, it can be concluded that the implant-grade silicone material is a potential candidate for the design and development of AVF assisting device due to its observed sustainability and biocompatibility.
Keywords: arteriovenous fistula (AVF) failure; AV fistula assisting device; hemodialysis; material characterization

Development of new N -4-[(7-Chloro-5-methylpyrrolo[2,1-f ] [1,2,4]triazin-4-yl)oxy]-3-fluorophenylbenzenesulfonamide analogues: exploring anticancer potential through MerTK inhibition - Sathe, Balaji Dashrath; Meenakshi, Meenakshi; Murti, Yogesh; Mane, Madhav Shivaji; Pandey, Sarvesh Kumar; Mahajan, Shriya; Rawat, Pramod; Kandhari, Harsimrat; Goel, Kapil Kumar; Dwivedi, Ashish Ranjan; Rathod, S. V. (Synlett, 2025)
Mer proto-oncogene tyrosine-protein kinase (MerTK), a part of the TAM (TYRO3, AXL, and MerTK) family, is directly correlated with metastasis and various types of cancers. The inhibition of this receptor is a promising strategy for more-effective chemotherapy. Considering the pharmacophoric features of the active domain of MerTK and the structural characteristics of the investigational drug BMS794833, we designed five new N -{4-[(7-chloro-5-methylpyrrolo[2,1- f ][1,2,4]triazin-4-yl)oxy]-3-fluorophenyl}benzenesulfonamide analogues. In cytotoxicity studies, one of the analogues displayed a significantly higher cytotoxicity than cisplatin. It showed IC50 values of 2.09, 1.96, and 3.08 mu M against A549, MCF-7, and MDA-MB-231 cancer cell lines, respectively. In drug metabolism and pharmacokinetic studies, it was the most stable analogue and displayed a moderate MerTK inhibitory potential. Molecular-docking studies were performed to corroborate the MerTK inhibition, and the same analogue achieved the most significant docking score (-12.33 kcal/mol). Docking interactions demonstrated that the imine and amine group of the 3-chloropyridine moiety of BMS794833 formed hydrogen bonds with the main chain of the ATP pocket residue Met674, while the oxygen atoms of the 4-oxo-1,4-dihydropyridine-3-carboxamide moiety established hydrogen bonds with the Lys619 and Asp741 amino acid residues of the allosteric pocket of MerTK protein. These promising results provide evidence that the N -{4-[(7-chloro-5-methylpyrrolo[2,1- f ][1,2,4]triazin-4-yl)oxy]-3-fluorophenyl}benzenesulfonamide pharmacophore can give potential insights into the development of new MerTK inhibitors.
Keywords: cancer chemotherapeutics; kinase inhibitors; metabolic studies; pyrrolotriazines; sulfonamides

Development of six-membered saturated cyclic diaminocarbenes in main-group chemistry - Kundu, Gargi; Sen, Sakya S. (Dalton Transactions, 2025)
In recent years, there has been a remarkable surge in the utilization of saturated N-heterocyclic carbenes (NHCs) as ligands in main group chemistry. While the field has predominantly focused on five-membered NHCs and cyclic alkyl(amino) carbene (CAAC) ligands, the investigation of six-membered NHCs (6-NHCs) has only just begun. Despite possessing higher nucleophilicity than their five-membered counterparts, 6-NHCs have been less explored due to their lack of structural rigidity. This feature article aims to highlight recent developments in 6-NHCs in only main group chemistry. Exciting new studies have demonstrated the activation of B-H bonds in HBpin, ring expansion from a six-membered to a seven-membered ring under ambient conditions, and the stabilization of transient units ``H-B 00000000 00000000 00000000 00000000 11111111 00000000 11111111 00000000 00000000 00000000 O'' and ``(OH)BO'', among other intriguing phenomena. A major focus of this review is on synthetic approaches for 6-NHC-stabilized main-group compounds and their unusual properties, as revealed by spectroscopic and crystallographic data. While the chemistry of 6-NHCs is still in its nascent stage, the findings presented in this feature article underscore the need for its exploration and further investigation. Furthermore, this review provides valuable insights into effective synthetic methods for creating new 6-NHCmain group (B, Al, Si, P, Zn, etc.) complexes, along with mechanistic explanations for some of these reactions. These advances hold great promise for the future development of this exciting and rapidly evolving field of N-heterocyclic carbene chemistry.

Diamondoid all-carbon porous aromatic framework host for lithium-sulfur batteries - Kumar, Viksit; Javaregowda, Bharathkumar H.; Devasia, George; Narayanan, Aswini; Krishnamurty, Sailaja; Krishnamoorthy, Kothandam; Babu, Sukumaran Santhosh (Small, 2025)
Lithium-sulfur batteries (LSBs) hold incredible potential as next-generation energy storage systems. However, practical applications of LSBs are significantly hindered by several critical challenges. For the first time, scalable all-carbon porous 3D polymers (3DPs) that do not contain heteroatoms or functional groups and do not require post-functionalization are investigated as hosts in lithium-sulfur batteries, demonstrating enhanced cycling stability and overall battery performance. The pyrene-containing 3DP exhibits 75% capacity retention after 600 cycles at 1 C and 52% capacity retention after 1300 cycles at 0.2 C, better than phenyl comprising 3DP. Furthermore, even at higher sulfur loading (4.1 mg cm(-2)) with an electrolyte/sulfur ratio of 5 mu L mg(-1), pyrene 3DP displayed a high capacity of 600 mA h g(-1) and stable performance over 250 cycles with negligible capacity fade. The defined pore structure of 3DPs prevents the migration of polysulfides through physical confinement and the large pi -clouds of 3DPs interact with the negative charge-bearing polysulfides generated in charge-discharge cycles through anion-pi interaction. In this way, The design ensures that the host 3DPs interact with neutral sulfur and anionic polysulfides, resulting in an excellent performance.
Keywords: 3D polymers; Batteries; Li-Sulfur battery; porous materials; pyrene

Discovery and biological evaluation of nitrofuranyl-pyrazolopyrimidine hybrid conjugates as potent antimicrobial agents targeting Staphylococcus aureus and methicillin-resistant S. aureus - Saini, Sapna; Reddy, G. Lakshma; Gangwar, Anjali; Kour, Harpreet; Nadre, Gajanan G.; Pandian, Ramajayan; Pal, Sunny; Nandi, Utpal; Sharma, Rashmi; Sawant, Sanghapal D. (RSC Medicinal Chemistry, 2025)
Nitrofuran and pyrazolopyrimidine-based compounds possess a broad antimicrobial spectrum including Gram-positive and Gram-negative bacteria. In the present work, a series of conjugates of these scaffolds was synthesized and evaluated for antimicrobial activity against Staphylococcus aureus and methicillin-resistant S. aureus (MRSA). Many compounds showed MIC values of <= 2 mu g ml-1, with compound 35 demonstrating excellent activity (MICs: 0.7 and 0.15 mu g ml-1 against S. aureus and MRSA, respectively) and safety up to 50 mu g ml-1 in HepG2 cells. Compound 35 also exhibited no hemolytic activity, biofilm eradication, and effectiveness against efflux-pump-overexpressing strains (NorA, TetK, MsrA) without resistance development. It showed synergistic effects with vancomycin (S. aureus) and rifampicin (MRSA). Mechanistic studies revealed that compound 35 exhibits good membrane-targeting abilities, as evidenced by DAPI/PI staining and scanning electron microscopy (SEM). In an intracellular model, it reduced bacterial load efficiently in both S. aureus and MRSA strains. With a strong in vitro profile, compound 35 demonstrated favorable oral pharmacokinetics at 30 mg kg-1 and potent in vivo anti-MRSA activity, highlighting its potential against antibiotic-resistant infections.

Divergent access to α-carbonyl-α′-vinyl sulfoxonium ylides and polysubstituted furans from β-ketosulfoxonium ylides and ynone-esters - Ingale, Sudhir R.; Sahu, Manas Ranjan; Borade, Balasaheb R.; Gamidi, Rama Krishna; Kontham, Ravindar (Journal of Organic Chemistry, 2025)
Here, we describe the synthesis of novel alpha-carbonyl-alpha `-vinyl sulfoxonium ylides under ambient, catalyst-free, and additive-free conditions, demonstrating broad substrate scope and scalability using beta-ketosulfoxonium ylides and alpha-ynone-esters. Furthermore, these ylides serve as versatile intermediates for the synthesis of highly substituted furans via Br & oslash;nsted acid (p-TsOH) catalysis at 130 degrees C. This approach offers key advantages, including wide substrate compatibility, divergent product formation from common precursors, gram-scale feasibility, and good to excellent yields.

Dopant and exfoliation induced simultaneous modification of charge density and C―C coupling sites for efficient CO2 photoreduction to ethylene - Das, Kousik; Chakraborty, Subhajit; Kediya, Siddhi; Singh, Ashutosh Kumar; Das, Risov; Mondal, Soumi; Riyaz, Mohd; Goud, Devender; Dutta, Nilutpal; Vinod, Chathakudath P.; Peter, Sebastian C. (Angewandte Chemie-International Edition, 2025)
The photochemical conversion of CO2 into C2+ products has emerged as an attractive method for synthesizing valuable chemicals and fuels using abundant solar energy. However, the challenge lies in enhancing the efficiency and selectivity of C2+ product formation. In this study, we employed a heteroatom doping strategy to optimize the photocatalytic parameters and achieve excellent efficiency and selectivity in the photocatalytic CO2 reduction to C2+ product formation. Our experimental analysis revealed that the local electronic structure of the catalyst, modified by In-doping, enables enhanced efficiency. Additionally, the incorporation of Cu facilitates the coupling of C1 intermediates, resulting in excellent selectivity towards C2+ products. The CO2 reduction performance is further enhanced through exfoliation, which increases the exposure of active sites and extends the charge carrier lifetime by reducing the charge diffusion length. We report that the rate of formation of C2H4 reached 54.3 mu molh(-1)g(-1) with an outstanding selectivity of 91% over the exfoliated CuIn-doped AgBiP2S6 catalyst. By elucidating the role of heteroatom doping and exfoliation in enhancing both the efficiency and selectivity of C2+ product formation, our study contributes to advancing the development of sustainable and efficient photocatalytic CO2 conversion technologies.
Keywords: C & horbar; C coupling; CO2 reduction; Doping; Exfoliation; Photocatalysis

Double anchoring squaraine dye with triazatruxene amine donor for dye-sensitized solar cells: sequential cosensitization for panchromatic light-harvesting - Ingole, Kiran Balaso; Siby, Jesna; Pandya, Rinu; Vanka, Kumar; Krishnamoorthy, Kothandam; Nithyanandhan, Jayaraj (Journal of Photochemistry and Photobiology A-Chemistry, 2025)
Dyes are firmly bound to a semiconducting TiO2 film using carboxylic acid anchoring groups for an efficient electron transfer from the excited state of dye to the conduction band (CB) of TiO2. Strong dye binding can be accomplished with multi-anchoring dye designs to improve photophysical characteristics, including high extinction coefficients, panchromatic absorption, post-sensitization modifications, and dark current suppression, besides enhancing the stability of the dye-TiO2 interface. Herein, a novel KV2D dye with double squaraine acceptor and double carboxylic acid anchoring groups is designed to achieve a high extinction coefficient (epsilon, 3.57 x 105M-1cm-1) and robust binding to the TiO2 film for an effective electron transfer. We systematically changed the amount of coadsorbent chenodeoxycholic acid (CDCA) to control the aggregation of dyes on the TiO2 surface that improves the power conversion efficiency (PCE, eta) for the devices based on the doubleanchoring KV2D. Out of these devices, KV2D: CDCA (1:10) based cell exhibited the best PCE of 5.26% with VOC of 754 mV, JSC of 10.41 mA/cm2, and ff of 67%. The sequential cosensitization studies were carried out with a far-red active dye to find the effect of the strong binding of the sensitizer to the TiO2 film. Interestingly, when di-anchoring, KV2D was sensitized first for 12 h and then sequentially cosensitized with far-red absorbing SQS4 for 5 h to achieve a PCE of 5.0% with VOC of 697 mV, JSC of 10.23 mA/cm2, and ff of 70% with panchromatic spectral response in IPCE upto 730 nm giving higher photocurrent generation.
Keywords: aggregation of dyes; Bulky donor unit; Double acceptor dye; Dye-sensitized solar cells; self-assembly of dye; squaraine dyes; triazatruxene

Dual inhibition of AXL and MER kinase: scope for lung and breast cancer therapeutics - Sathe, Balaji Dashrath; Kumari, Pratibha; Kumar, Hemant; Mane, Madhav Shivaji; Mudududdla, Ramesh; Baell, Jonathan; Kumar, Roshan; Singh, Shareen; Pawar, D. K.; Kommi, Damodara N.; Bushi, Ganesh; Pathak, Prateek; et al. (Bioorganic Chemistry, 2025)
Cancer cells use multiple survival pathways for continuous proliferation, survival, and growth. Recent anticancer drug discovery commonly focuses on a single target that maintains key cancer cell survival mechanisms, where typically, this is a cellular enzyme that inhibits DNA replication, inducing cell damage and apoptosis. Since drugs that act on a single target may be more susceptible to the development of resistance, the search for polypharmacotherapeutics is becoming increasingly popular to defeat drug-resistant cancer cells. Receptor tyrosine kinases (RTKs) family members, AXL and MER, have been identified as important cancer targets and found to be overexpressed and associated with various forms of cancers, such as lung and breast cancers. This review has focused on the dual inhibition of AXL and MER kinases as a strategy for treating lung and breast cancer. The roles of these two kinases in non-small cell lung cancer (NSCLC) are such that dual inhibition would be therapeutically complementary, with MER inhibition more fully blocking tumor growth while AXL inhibition encourages chemosensitivity. Hence, treatment strategies targeting both of these RTKs may be more effective and beneficial than singly targeted agents, and a dual AXL/MER inhibitor is a potential therapy for NSCLC along with breast cancer. This review highlights the preclinical and clinical development of dual AXL and MER kinase inhibitors as lung and breast cancer treatments and the prospects for their future progression.
Keywords: AXL; Breast cancer; Cancer therapy; MER; Multi-kinase inhibitors; NSCLC targeted therapy

Dual-functional LaFeO3 perovskites via auto-combustion and hydrothermal methods for gas sensing and photocatalytic dye degradation - Patil, Suraj S.; Shinde, Kiran P.; Patil, Abhijeet P.; Abbas, Muhammad Aoun; Nadargi, Jyoti D.; Mujawar, Sarfraj H.; Mulla, Imtiaz S.; Kim, K. B.; Suryavanshi, Sharad S. (Inorganic Chemistry Communications, 2025)
Integrated environmental remediation is increasingly focused on the development of multifunctional materials capable of simultaneous detection of toxic gases and wastewater treatment. Present study aims to develop dual-functional LaFeO3 perovskites for gas sensing and photocatalytic dye degradation. The nanocrystalline powders of LaFeO3 were synthesized via two distinct methods; auto-combustion (A-LFO) and hydrothermal (H-LFO). Numerous characterization techniques (e.g. XRD, SEM, EDAX, BET, TEM, and XPS) were utilized in order to study the phase, morphology, surface area and elemental composition of A-LFO and H-LFO samples. Both samples were systematically evaluated for their potential in the gas sensing and photocatalytic degradation of malachite green (MG). In results, A-LFO exhibited superior performance in both applications, compared to the H-LFO. It shows similar to 90 % sensitivity for the acetone (500 ppm) at the operating temperature of 275 degrees C and achieved similar to 78 % degradation efficiency for malachite green (MG) dye (5 ppm) within 2 h irradiation of natural sunlight. Although, H-LFO presented comparatively lower performance, both materials demonstrated good selectivity, and stability highlighting their promise as a dual-functional environmental remediation agent. By exploring the performance of the synthesized materials in these dual applications, this research established a relationship between synthesis methods, material properties, and overall performance in environmental and industrial applications, by offering a sustainable and efficient solution to complex pollution challenges.
Keywords: Dye degradation; Gas sensing; LaFeO3; Malachite Green; Perovskites

Dynamic signature of the thermodynamic transition in a novel mean field system - Anwar, Ehtesham; Nandi, Ujjwal Kumar; Patel, Palak; Kumawat, Sanket; Maitra Bhattacharyya, Sarika (Journal of Chemical Physics, 2025)
Understanding the connection between thermodynamics and dynamics in glass-forming liquids remains a central challenge in condensed matter physics. In this study, we investigate a novel model system that enables a continuous crossover from a standard three dimensional liquid to a fully connected mean field like system by introducing pseudo neighbors. These pseudo neighbors enhance the effective connectivity of the system without altering its local structure. While their presence slows down the dynamics, they influence thermodynamic properties even more significantly. In particular, the configurational entropy obtained via thermodynamic integration vanishes at a temperature much higher than the temperature where the dynamics begin to slow down, leading to a clear breakdown of the Adam-Gibbs relation. To uncover a possible dynamical signature of this thermodynamic transition, we analyze bond breakage dynamics. Unlike real-real bonds, which decay similarly in both the parent Kob-Andersen model and its mean field variant, real-pseudo bonds exhibit long lived, persistent behavior with strong temperature dependence. These bonds do not fully decay over time, leading to a finite saturation value of the bond breakage correlation function. Remarkably, we show that the number of surviving pseudo bonds can be analytically estimated and correlates directly with the thermodynamic transition temperature T-K. We propose a phenomenological relation between T-K and the number of surviving pseudo-bonds, establishing a novel link between thermodynamic and dynamic observables. Our results suggest that these persistent pseudo bonds serve as a robust dynamical signature of the thermodynamic transition, and the system might have properties analogous to those of randomly bonded ultrastable glasses.

Early and advanced glycation end product analysis from women with PCOS on metformin - Ambekar, Aditi S.; Naredi, Nikita; Malakar, Dipankar; Vashum, Y.; Misra, Pratibha; Kulkarni, Mahesh (Reproductive Biology, 2025)
In this cross-sectional study, we have analyzed advanced glycation end products (AGEs) in the plasma and follicular fluid of women with polycystic ovary syndrome (PCOS) taking metformin during in vitro fertilization (IVF) and control women undergoing IVF. Glucose, fructose, fructosamine, carboxymethyl lysine/ arginine (CML/R) proteins, and pentosidine were measured in the plasma and paired follicular fluid. Glycated proteins were characterized by mass spectrometry. Fasting serum glucose and fructosamine were comparable; however, follicular fluid glucose and fructosamine were higher in the PCOS group, and other AGEs remained unaltered. Fructose was lower in both serum and follicular fluid from the PCOS group. A positive correlation between some of these AGEs and sugars estimated was observed. Glucose and fructosamine in the follicular fluid correlated with the antral follicle count. The number of glycated peptides identified in the PCOS group by mass spectrometry was more. Glycated K75, K402 amino acid residues of albumin were detected in the PCOS group only. Additionally, some proteins involved in steroidogenesis and oocyte maturation as well as transporters, and extracellular matrix proteins, were found to be glycated in the PCOS group, which may affect their function. Elevated glucose and fructosamine in the follicular fluid of the PCOS group may contribute to abnormal folliculogenesis. The glycation of albumin should be validated in more samples to be considered as a marker for PCOS diagnosis.
Keywords: Carboxymethyl lysine; Fructosamine; fructose; glucose; Pentosidine; Polycystic ovary syndrome

Effect of cyclization and alkyl group wrapping in visible-light-active unsymmetrical squaraine dyes for dye-sensitized solar cells - Jadhav, Avinash P.; Singh, Ambarish Kumar; Shivankar, Bhavana R.; Siby, Jesna; Krishnamurty, Sailaja; Krishnamoorthy, Kothandam; Nithyanandhan, Jayaraj (ACS Applied Energy Materials, 2025)
A series of alkyl group-appended indoline- and carboxylic acid-functionalized indolenine-based visible-light-active unsymmetrical squaraine dyes, SQA7-10, were designed, synthesized, and utilized for the dye-sensitized solar cells device fabrication. The number of alkyl group has been increased systematically on the indoline moiety to control the self-assembly of dyes on TiO2 and to passivate the photoanode that helps in improving the open-circuit voltage (V-OC) by avoiding the charge recombination process. SQA7-10 dyes showed an absorption between lambda(max) 536-540 nm, with molar extinction coefficients of 1.62-2.13 x 10(5) M-1 cm(-1) in CH3CN. Further, ultraviolet-visible (UV-vis) studies on TiO2 indicated the formation of H-aggregated dyes (505-510 nm), which can be controlled by appending the alkyl groups. The energy levels of the highest occupied molecular orbital (HOMO) of these dyes are well aligned with the Nernst potentials of I-/I(3)(-)electrolyte and [Cu(tmby)(2)](+/2+) electrolytes with sufficient overpotentials required for the dye regeneration process. DSSC devices made with these dyes showed systematic enhancements of open-circuit voltage (V-OC) and device efficiency with respect to alkyl group incorporation for SQA7-10 with I-/I-3(-) electrolytes. All of the SQA dyes exhibited the device V-OC of more than 805 mV, where the introduction of alkyl groups systematically enhanced the V-OC in the order of SQA7 (805 mV) < SQA8 (829 mV) < SQA9 (843 mV) < SQA10 (862 mV) without any addition of CDCA. Within the SQA dye series, SQA10 dye has achieved the highest DSSC device efficiency of 7.52% (J(sc) of 11.16 mA/cm(2), V-oc of 862 mV, and ff of 78%) with I-/I-3(-) electrolyte, whereas use of [Cu(tmby)(2)](+/2+) redox shuttle with SQA10 showed enhanced V-oc (1080 mV) and device efficiency (8.35%). The IPCE profile for the device fabricated with SQA dyes showed good response at 480 and 560 nm, which indicates the photocurrent generation from the aggregated structures.
Keywords: aggregation of dyes; charge recombination; Dye-sensitized solar cells; indoline and indolenine donors; visible-light-activeunsymmetrical squaraine dye

Effect of doping on electrocatalytic dehydrogenation and hydrogenation of methyl decalin-methyl naphthalene system - Verma, Tushar Singh; Selvaraj, Kaliaperumal; Krishnamurty, Sailaja (Journal of Physical Chemistry C, 2025)
The hydrogen economy can benefit from the use of liquid organic hydrogen carriers (LOHCs) for cross-continent hydrogen transportation in the future. However, dehydrogenation and hydrogenation of hydrogen require catalytic systems. Current research emphasizes selective Pt/Rh doping of Fe, Co, and Ni surfaces as catalysts for the dehydrogenation and hydrogenation of the methyl naphthalene-methyl decalin LOHC system, which has more than 7% hydrogen weight capacity and meets the practical requirements established by the European Union and the United States Department of Energy. Density functional theory-based computational techniques demonstrate how the chemical modification of these surfaces with a Pt and Rh single-atom catalyst (SAC) can improve the efficiency of dehydrogenation and hydrogenation. With a sustainable method, electrochemical dehydrogenation and hydrogenation on these robust surfaces produce effective hydrogen storage for extended periods without losing hydrogen. Furthermore, optimal results for the hydrogenation of 2-methyl naphthalene on Fe-Rh SAC with path-determining step (PDS) = 0.98 eV and dehydrogenation of 1-methyl decalin on Fe-Pt SAC with PDS = 1.49 eV were obtained for the most effective active sites for the enhanced electrochemical process. This study offers new possibilities for the catalytic dehydrogenation and hydrogenation of LOHC systems by highlighting the impact of doping on transition-metal-based catalysts.

Effectiveness of 3-amino-2-thiocyanato-α, β-unsaturated carbonyl compounds against chikungunya virus - Alagarasu, Kalichamy; Dhote, Radhika; Bagad, Pooja K.; Kharikar, Dwidhesh; Patil, Poonam; Roy, Diya; Shukla, Shridhar; Cherian, Sarah; Senthilkumar, Beeran; Parashar, Deepti (Future Medicinal Chemistry, 2025)
Aim Chikungunya fever (CHIKF) caused by the chikungunya virus (CHIKV) is characterized by the presence of long-term polyarthralgia in a minor proportion of the infected patients. Currently, there are no FDA-approved antivirals available. This study evaluated the anti-CHIKV potential of 16 synthetic 3-amino-2-thiocyanato-alpha, beta-unsaturated carbonyl compounds and elucidated their probable mechanisms of action. Methods Anti-CHIKV activity of 16 compounds were investigated in Vero CCL-81 cells using focus forming unit assay (FFU). Dose-dependent and time-dependent antiviral assays were performed for the effective compounds. Molecular docking was performed to find out their interactions with viral proteins. Results Five compounds showed promising anti-CHIKV activity by reducing viral titer with >1 log10 FFU/ml. Dose-dependent studies revealed that the compound 3 g was more effective in reducing the virus titer with a half-maximal inhibitory concentration (IC50) of 0.4315 mu M and a selectivity index of 35.99. Docking analyses revealed that all the compounds mainly interact with the non-structural proteins of CHIKV. Conclusions These findings demonstrate the in vitro anti-CHIKV activity of these compounds, and their possible mode of action via interference with early stages of infection and replication processes. This study warrants further preclinical and clinical evaluation to establish their safety and efficacy as novel anti-CHIKV therapeutics.
Keywords: 3-amino-2-thiocyanato-alpha; antivirals; beta-unsaturated carbonyl compounds; Chikungunya virus (CHIKV); nsP2 helicase; therapeutics

Efficient continuous catalytic process for production of bisphenol A - Dhotre, Kapil; Patil, Chetana Rupak; Tarade, Komal P.; Markandeya, Nishant; Pathak, Abhishek; Bhongale, Sunil S.; Kamble, Sanjay P. (Organic Process Research & Development, 2025)
Bisphenol A (BPA) is a versatile chemical compound that is essential for producing durable polycarbonate plastics and strong epoxy resins, which are integral to numerous everyday products. In the present study, BPA was prepared using phenol and acetone using a highly active and reusable ion-exchange resin (IER) Lewatit K1131S as the catalyst. Under optimized conditions, an acetone conversion of 84% and a BPA selectivity of 94% were achieved. The produced BPA was further purified, resulting in a 96% isolated yield with 99.5% purity. The reusability of Lewatit K1131S has been studied, and it was found that it can be reused multiple times without affecting the selectivity for BPA. The kinetics of the reaction was studied using the Langmuir-Hinshelwood model; it was found that the reaction follows pseudo-first-order kinetics, and the apparent activation energy was determined to be 12.7 kJ/mol. A continuous pilot scale process for the production of BPA using a fixed-bed reactor (packed with ion-exchange resin) has been developed. Pilot plant trials were conducted at different flow rates such as 200, 300, and 500 g/h, and a downstream processing methodology using an agitated thin film evaporator (ATFE) was employed for the BPA purification. This resulted in high throughput, producing 99.2% isolated BPA yield with 99.5% HPLC purity. Additionally, the robustness and viability of the catalyst were assessed at a flow rate of 200 g/h, producing 22.5 kg of BPA per kg of catalyst, highlighting its cost-effectiveness, stability, and resistance to deactivation, which shows its suitability for industrial-scale applications. The environmental viability of the process was further evaluated by using the E-factor and Process Mass Intensity (PMI) metrics. The estimated E-factor was 0.3118, while the corresponding PMI was 1.3935. These lower values indicate reduced waste generation, improved material efficiency, and enhanced sustainability of the process.
Keywords: bisphenolA; BPA purification; Continuous process; E-factor; ion-exchange resins (IER); PMI; process optimization; reactionkinetics

Efficient synthesis of 3,3′-Spirooxindole γ-Butyrolactone via Rongalite-mediated domino reductive aldol and spiro-lactonization reactions - Chaudhari, Suryakant S.; Nichinde, Chandrakant B.; Patil, Baliram R.; Girase, Amardipsing S.; Kinage, Anil K. (ChemistrySelect, 2025)
In this study, we develop a novel methodology involving rongalite-mediated domino reductive/aldol reaction, followed by spiro-lactonization of 2-oxoindolin-3-ylidene acetates/malonates in presence of base to synthesis of 3,3 `-spirooxindole gamma-butyrolactone. The detail study, such as effect of solvent, effect of different base and substrate has been carried out. Scale up of this methodology is also done. Sodium hydroxymethanesulfinate dihydrate (rongalite) concurrently has a dual role in this context; it acts as a reducing agent as well as C1 synthon. This approach offers several advantages, such as being metal- and catalyst-free, involving a simple reaction protocol, having a wide substrate scope, using water as a green solvent, and providing good to excellent yields of the products under mild reaction conditions.
Keywords: (+/-) Coixspirolactam A & [3; 3 `-spirooxindole gamma-butyrolactone]; Domino reductive/aldol/spiro-lactonization; Good step economy; Rongalite as reductant & C1 synthon; Water as a green solvent

Electrochemical deconstruction of waste polyvinylidene chloride (PVDC) to value-added products in batch and flow - Mishra, Subhadip; Kar, Sourav; Rangappa, Raghavendrakumar; Patil, Prashant; Kadam, Vijay; Chikkali, Samir H.; Samanta, Ramesh C. (Chemistry-A European Journal, 2025)
Chlorinated polymers have made enormous contributions to materials science and are commercially produced on a large scale. These chlorinated polymers could be recycled as chlorine sources to efficiently produce valuable chlorinated compounds owing to their facile release of HCl. Although the thermal stability of PVDC is low compared to PVC, this can be advantageous in terms of easy and fast dehydrochlorination. Herein, we report an efficient electrochemical chlorination using poly(vinylidene chloride) (PVDC) as a chlorine source that works in an undivided cell and applies to a good number of examples. This method works on commodity polymers such as waste PVDC-PVC pharma blister film, PVDC-PO multilayer food packaging, and compression molded sheets of Ixan PVDC (with heat stabilizer) with similar efficiency. Furthermore, this method also provides the dechlorination of PVDC up to 98 %, leading to unsaturated dechlorinated material. Converting PVDC into more stable unsaturated compounds, the release of harmful chlorine-containing gases during incineration can be minimized. Additionally, this method is not only restricted to batch processes but an electroflow process for PVDC dechlorination and electrosynthesis has also been demonstrated.
Keywords: chlorination; Electrochemical recycling; Electroflow-synthesis; Graphitic material; Polyvinylidene chloride

Engineered silk matrix as a substitute for acellular dermal matrix in breast reconstruction surgery - Deshpande, Rucha; Shukla, Swati; Kale, Amod; Sayyad, Raeesa; Kewale, Bhawana; Deshmukh, Narendra; Nisal, Anuya; Venugopalan, Premnath (International Journal of Biological Macromolecules, 2025)
Implant-based breast reconstruction is a common standard of care for breast cancer patients following mastectomy. To support implant weight and placement, surgeons utilize autologous tissues, acellular dermal matrices (ADMs), or synthetic meshes. While ADMs provide structural support, they present significant risks, including infection transmission and seroma. Conversely, synthetic meshes exhibit poor cellular adhesion, leading to inadequate tissue integration. To address these challenges, there is a need for a matrix that enhances tissue integration while minimizing infection risks and other complications. Silk fibroin (SF), a natural biopolymer, possesses excellent biocompatibility and mechanical properties. This study introduces a novel engineered silk matrix (ESM) as an advanced solution for soft tissue regeneration, specifically in breast reconstruction surgery. The present study establishes the safety of ESM and evaluates its potential a tissue regeneration matrix through extensive in-vitro and in-vivo analyses. In-vitro assays demonstrated superior cellular adhesion, proliferation of human mammary fibroblast cells (HMFCs), collagen deposition and angiogenesis in ESM compared to collagen matrices and ADMs. Safety assessments, conducted in accordance with ISO 10993 guidelines, confirmed noncytotoxic nature of ESM. Furthermore, subcutaneous implantation revealed no systemic toxicity or adverse tissue reactions. In-vivo studies utilizing a Yorkshire pig model of simulated breast reconstruction surgery, demonstrated superior performance of ESM over collagen matrices in tissue regeneration. The findings showed enhanced fibroblast density, increased collagen deposition, and improved vascularization. These results suggest that ESM is a safer and more effective alternative to ADMs in breast reconstruction, with the potential to revolutionize post-mastectomy care for breast cancer patients.
Keywords: Biocompatibility; Breast reconstruction; ISO 10993; Polymer; Safety; Silk protein; tissue regeneration

Enzymatic pathway for kupyaphore degradation in mycobacterium tuberculosis: mechanism of metal homeostasis and turnover - Bhosale, Rashmi S.; Chakraborty, Arnab; Wong, Tsung-Yun; Masal, Dattatraya P.; Choudhury, Rahul; Srivastava, Sonali; Reddy, D. Srinivasa; Aldrich, Courtney C.; Kamat, Siddhesh S.; Mohanty, Debasisa; Gokhale, Rajesh S. (ACS Chemical Biology, 2025)
Metallophores are essential for metal homeostasis, regulating availability, and mediating host-pathogen interactions. Kupyaphores are specialized metallophores produced by Mycobacterium tuberculosis (Mtb) that primarily chelate zinc to support bacterial survival. Elevated kupyaphore levels early in infection highlight their importance, while their rapid decline, despite increasing bacterial loads, indicates tightly regulated mechanisms of production, consumption, and degradation. However, the processes driving kupyaphore catabolism and their role in preventing zinc toxicity in Mtb remain unclear. Here, we show that covalent modification of the isonitrile moiety in kupyaphores releases zinc, triggering degradation through a sequential three-step enzymatic pathway encoded by Mtb. Isonitrile hydratase converts isonitrile groups into formamides, which are subsequently processed into amines by N-substituted formamide deformylase and ultimately oxidized to beta-ketoesters by amine oxidases. The biological significance of this pathway is underscored by the upregulation of these genes under metal-depleted and biofilm-forming conditions. Mutant Mtb strains lacking these genes exhibit impaired growth in metal-limiting environments and reduced levels of biofilm formation. Catalytic intermediates detected in Mtb cultures and infected mouse lung tissues confirm the pathway's in vivo activity. Further, genome mining reveals that similar enzymes are conserved across organisms producing isonitrile-containing metabolites, emphasizing the broader importance of this pathway. Understanding these processes could pave the way for novel therapeutic strategies targeting kupyaphore catabolism.

Essentials of Mo+6/Mo+4 and Ce+4/Ce+3 redox couples in auto-regenerated catalyst for dry methane reforming - Panda, Satyajit; Singh, Gaje; Kaishyop, Jyotishman; Gazi, Md Jahiruddin; Mule, Harshada Mahadev; Khan, Tuhin Suvra; Sharma, Ojasvi; Bordoloi, Ankur (Chemical Engineering Journal, 2025)
Biogas is a potential renewable carbon resource, and dry reforming is one of the promising routes to mitigate via generating syngas, used as a building block for the synthesis of chemicals and fuels. Coke deposition and metal sintering of the reported catalyst systems are the major challenges to developing an economically feasible dry reforming process. Molybdenum oxide is a versatile material with properties like oxygen storage, oxygen mobility, and sulphur tolerance. Here, an oxygen storage capacity enhanced catalyst has been designed by applying a mono layer molybdenum oxide on ceria-magnesia-modified alumina support using a unique chemical vapor deposition method. The Ru and Ni used as active components, and Gd as a promoter were dispersed over the modified support via a precipitation-deposition approach. The most efficient composition is found to be 4 % Ni, 0.5 % Gd, and 0.5 % Ru with Mo-promoted modified alumina with excellent stability up to 500 h for dry reforming reaction studies. Two redox cycles (Mo+6 to Mo+4 & Ce+4 to Ce+3) facilitated a significant number of oxygen vacancies, to limit surface carbon accumulation and support high catalytic stability and activity. The possible reaction pathways and stable surface intermediates were identified by using in-situ DRIFT studies, which included metal carbonyls, carboxylate species, and surface hydroxyl groups. Moreover, the DRIFT studies were supported with CH4-TPSR analysis and DFT studies evidence the formation of CHx species and subsequent oxidation. The additional advantage of the usage of molybdenum is the excellent S-tolerance capacity, which is fully scrutinized experimentally as well as theoretically.
Keywords: and Methane reforming; Coke resistant; Oxygen storage; Redox couple cycles; Sulphur tolerance

Ethyl cellulose-based controlled-release atrazine nanoformulation for effective and long-term weed management in agriculture - Gautam, Tripurari Rao; Vasmatkar, Pashupat; Gundloori, Rathna V. N.; Kadoo, Narendra (Industrial Crops and Products, 2025)
Atrazine (ATZ) is the second most widely used herbicide. However, its widespread use is hazardous to the environment. We developed ethyl cellulose-based nanoformulated atrazine (nfATZ) to achieve slow and sustained release of ATZ for long-term weed control in crops such as maize. Maize or corn is used in several industrial applications, including the production of ethanol, corn syrup, adhesives, textiles, biodegradable plastics, etc. As broadleaf weeds significantly impact maize yields, we evaluated the effects of nfATZ and conventional ATZ on tomato as a representative of broadleaf weeds. Various concentrations of ATZ and nfATZ (1-10 mg per kg of soil) were evaluated in pre-emergence, post-emergence, and re-emergence studies. Several morphological, physiological, and biochemical parameters of weeds were assessed, and the efficacy of the herbicide formulations was evaluated. nfATZ outperformed conventional ATZ even at lower concentrations with prolonged herbicidal effectiveness beyond 30 days, while the main crop remained unaffected. The weed mortality in nfATZ treatment was > 80 %, while it was 35 % - 45 % in ATZ treatment. The chlorophyll and carotenoid contents decreased by similar to 65 % in nfATZ-treated weeds, impacting their photosynthesis and overall health. ATZ and nfATZ also significantly impacted the activities of antioxidant enzymes, such as ascorbate peroxidase (similar to 57 %), superoxide dismutase (similar to 67 %), and peroxidase (similar to 77 %) in weeds. Thus, we conclude that nfATZ performed significantly better than ATZ in controlling weeds over the long term and reducing its environmental impact. Therefore, we propose nfATZ for highly effective and long-term weed control in large-scale production of industrial crops like maize.
Keywords: Controlled-release; Herbicide; Nanoformulation; Oxidative stress; Weed management; Weed mortality

Evaluating the preferential adsorption of N2 from a binary mixture of N2/O2 on extra-framework cations of zeolites: a computational and experimental study - Devasia, George; Nandanwar, Sachin U.; Krishnamurty, Sailaja (Physical Chemistry Chemical Physics, 2025)
Separation of N2 from a N2/O2 gas mixture is critical for various industrial/medical applications. Temperature/pressure swing adsorption is the top-notch industrial technology used for this separation, where zeolites are the materials used for adsorption. Zeolite X/Y with Li+ as an extra-framework cation is the best-known sorbent for N2 gas molecules. However, the present net zero emission scenario has made lithium a critical element, making it imperative to implement its alternative in various other technologies. In this context, the present work is a computational evaluation to identify a cation that can replace Li+ for preferential adsorption of N2 over O2. The DFT study, based on parameters such as selective adsorption energies of N2 over O2 and IR stretching frequencies of the adsorbed N2 and O2 molecules, identifies Mg2+, Ca2+, Sr2+, Co2+ and Zn2+ as potential cations. These cations have preferential adsorption for N2 over O2 by 10 kJ mol-1 or more. However, BOMD simulations reveal that only Mg2+, Ca2+, Co2+ and Zn2+ keep the N2 molecule bound at 300 K and the O2 molecule gets desorbed from these frameworks. The desorption temperature of N2 on Ca2+ and Zn2+ is 350 K and on Mg2+ is 400 K. These observations are corroborated by electronic charges on cations and molecular orbitals. Significantly, Ca2+ is identified to adsorb up to 2 N2 molecules, making it an ideal candidate for N2/O2 separation in place of Li+. To validate this, we have carried out an experimental study that showed a good N2 adsorption capacity of 2.1 mmol g-1 for Ca2+.

Evaluation of reaction kinetics for chemoselective hydrogenation of citral for intensification of citral intermediates using copper-based catalysts - Debtirtha, Banik; Kinage, Anil K.; Vasireddy, Satyam Naidu (Indian Chemical Engineer, 2025)
Citral intermediates’ formation kinetics is studied using non-noble metal catalyst (Cu/SiO2) to evaluate catalyst performance characteristics via chemoselective hydrogenation of citral. The catalyst is synthesised by the precipitation method and characterised using XRD, FESEM and BET surface area analyser. Hydrogenation experiments are carried out using an Autoclave reactor in the temperature range of 80–120°C, pressure range of 10–50 bar and for catalyst loadings of 0.5, 1 and 1.5 g. The intermediates product distribution comprises aldehyde and alcohol formation such as citronellal, nerol and citronellol formation. The performance of the Cu/SiO2 catalyst is evaluated using the parameters such as citral conversion, citronellol selectivity and yield as 96.96%, 95.30% and 92.30%, respectively under optimal conditions of 50 bar, 120°C and 1 g catalyst for the reaction time of 100 min. The absence of internal and external mass transfer limitations is verified using the Carberry number and Weisz-Prater modulus criterion. The intrinsic kinetics of the gas–liquid phase hydrogenation of citral is determined using the Langmuir–Hinshelwood-Hougen-Watson (LHHW) model for citral intermediates formation. The reaction kinetic parameters show that citronellol formation favours by the nerol route compared to citronellal conversion.

Expanding the Egbenema horizon: Novel species discovery in India and first complete genome assembly of the genus - Bhagat, Jayesh M.; Khilari, Ajinkya A.; Shanmugam, Dhanasekaran; Patankar, Meena (Algal Research-Biomass Biofuels and Bioproducts, 2025)
The recognition of Egbenema bharatensis, a novel species of cyanobacteria from the Northern Western Ghats, extends the ecological and phylogenetic understanding of the genus Egbenema and highlights terrestrial microbial diversity of the region. Morphological characterization revealed resemblance with other Egbenema species but was inconclusive for definitive taxonomic classification. Preliminary phylogenetic analysis based on 16S rRNA gene sequences indicated affiliation with the genus but showed less than 98 % similarity to known species, pointing toward taxonomic distinctiveness. Analysis of the 16S-ITS region further supported this differentiation, revealing unique secondary structural features. Based on these findings, we propose the isolate as a novel species within Egbenema. Whole-genome sequencing provided full resolution and functional genome annotation revealed nitrogen fixation, cobalamin biosynthesis, and stress tolerance pathways, suggesting its metabolic versatility and potential biotechnological applications. The presence of multiple toxin-antitoxin systems also reflects its adaptability to environmental fluctuation. This study also presents the first complete genome of the genus Egbenema, filling a significant gap in cyanobacterial genomic resources. These findings encourage integrative taxonomic practices and affirm the significance of exploring biodiversity hotspots for uncovering cryptic microbial diversity with ecological and industrial potential.
Keywords: 16S rRNA; Biodiversity hotspots; Cyanobacteria; Egbenema bharatensis; ITS secondary structure; Northern Western Ghats; whole-genome sequencing

Experimental investigation and lumped kinetic modeling studies for upcycling of polyolefins - Kavade, Omkar G.; Dhepe, Paresh L.; Devi, Nandini R.; Vasireddy, Satyam Naidu (Journal of the Indian Chemical Society, 2025)
The present work discusses on comparative kinetic analysis of the pyrolysis of polypropylene (PP), high-density polyethylene (HDPE), and low-density polyethylene (LDPE) using sophisticated lumped models. Unlike many previous studies that focused on single-polymer kinetic models or employed simplified reaction schemes, this study develops an enhanced multistep reaction network that explicitly considers both primary decomposition and secondary cracking pathways, thereby improving the accuracy of product distribution predictions. By integrating this detailed reaction framework with a robust nonlinear regression approach using LSQNONLIN and ODE45 solvers in MATLAB, the study achieved greater accuracy in estimating kinetic parameters than traditional curve-fitting methods. The findings reveal that HDPE exhibits the highest activation energy (222.97 kJ mol(-1)), indicating it is more thermally stable than LDPE (193.44 kJ mol(-1)) and PP (62.16 kJ mol(-1)). One of the highlights of the present work is that lower pyrolysis temperature (400 degrees C) is found to be optimum for liquid yield by reducing secondary cracking, which aligns with the sustainable fuel production principles. The study also emphasizes on the limitations of previous lumped models that overlooked wax decomposition pathways, which are crucial for optimizing the hydrocarbon distribution. Future research should investigate catalytic interventions and reactor design modifications to enhance the product selectivity and scalability. This study offers a more comprehensive kinetic framework for advancing the valorization of plastic waste through pyrolysis, aiding the development of efficient waste-to-fuel conversion strategies.
Keywords: Lumped kinetic modeling; Plastic pyrolysis; Rate constants; Reaction pathways; Secondary cracking reactions; Temperature-dependent product distributions

Exploring the electronic modulation in controlling the activity and selectivity of Ni-Au-In based catalyst in atmospheric pressure CO2 hydrogenation - Bajpai, Jyotsna P.; Gupta, Sharad; Goud, Devender; Deka, Diku Raj; V. Jagtap, Anuradha; Kumar, Pawan; Ahamed, Momin; Peter, Sebastian C.; Vinod, C. P. (Chemical Engineering Journal, 2025)
Nickel-based catalysts are widely used for the hydrogenation of CO2 but encounter stability challenges during prolonged reactions and at elevated temperatures. At atmospheric pressure, nickel primarily promotes methane formation in CO2 hydrogenation reactions. In this work, we demonstrate that the stability and activity of nickel can be significantly enhanced through gold (Au) modification. Furthermore, we achieve a near-complete selectivity switch from methane to CO by incorporating indium (In), mediated through the formation of Au-In alloy. This catalyst exhibits excellent CO2 conversion and CO selectivity at relatively lower temperatures (400 degrees C), addressing a major bottleneck in the Reverse Water-Gas Shifts (RWGS) reaction. XPS studies demonstrate an interesting electron transfer mechanism facilitated by gold, which involves the formation of electronrich Au species (Au delta-) and the development of Au-In alloys. This process improves the reducibility of nickel oxide while allowing a fraction of nickel to remain in its metallic form, managing a facile hydrogenation process and regulating the shift in selectivity from CH4 to CO.
Keywords: Alloy formation; Bimetallic catalyst; CO2 hydrogenation; RWGS; Selectivity switch; synergy; Trimetallic catalyst; XPS (X-ray photoelectron spectroscopy)

Exploring the structural and photophysical properties of tri-cation mixed halide double perovskites (Cs2AgIn0.85-XCeXBi0.15Cl6) for high-performance phosphor-based WLEDs - Ravi, Nalini; Kanapathi, Prakash; Mohan, Subramaniam; Appadurai, Tamilselvan (Dalton Transactions, 2025)
Owing to their superior optoelectronic properties, lead-free halide double perovskites (HDPs) have been extensively studied for a wide range of optoelectronic applications, especially for fabricating white light-emitting diodes (WLEDs). Considering white light emission, the HDP structure's dual octahedral configuration facilitates greater lattice distortion, thereby fostering strong electron-phonon coupling-derived self-trapped exciton (STE) emission upon photoexcitation. Herein, we propose facile fabrication of a highly feasible phosphor-converted white light LED and an intensive analysis of the structural, compositional and photophysical properties of a tri-cation mixed halide double perovskite. We chose Cs2AgIn0.85Bi0.15Cl6 as a potential candidate for electroluminescent-based white light LED devices as its composition exhibits high stability, direct-allowed transition, and a notable photoluminescence quantum yield. However, we incorporated a lanthanide ion (Ce3+) into this cubic HDP structure via tri-cation mixing at the B `' site (Cs2AgIn0.85-XCeXBi0.15Cl6) to internally disturb structural periodicity and further enhance STE emission. Initially, powder XRD revealed the lattice expansion induced by Ce3+ incorporation, while XPS and TEM verified the substitution of Ce3+ at the In3+ site. Meanwhile, compositional and optical studies established the role of Ce3+ in retaining the direct allowed transition by effectively replacing the In3+ site. Urbach energy (EU), a measure of energetic disorderness at band edges, was found to be significantly reduced, showing a value of 135 meV for the Ce-5% sample. Most significantly, PL emission studies revealed an appreciable enhancement in the PL intensity with a prolonged STE lifetime of 670 ns for Cs2AgIn0.80Ce0.05Bi0.15Cl6, indicating improved radiative recombination. Besides, excitation-dependent Pl and PLE studies revealed that the emission solely came from the STE states. Elaboratively, vibrational studies elucidated that the Ce-5% sample exhibited a restabilized elpasolite structure and enhanced lattice phonons, which ultimately helped in boosting STE emission, as proven by the Huang-Rhys factor (S = 13). Finally, an efficient and durable phosphor-converted WLED was fabricated, and its performance was assessed, revealing CIE coordinates of (0.35,0.32), a CCT of 4368 K, and an extremely high CRI (Ra) of 92. Thus, our work provides an exclusive strategy to enhance the STE emission for potential application in electroluminescent-based WLED devices.

Fabrication of a 3D iron-modified NiCo2S4 structure on nickel foam as a bifunctional electrocatalyst for overall water splitting - Singla, Gourav; Mahajan, Mani; Bhange, Siddheshwar N.; Kashyap, Varchaswal (New Journal of Chemistry, 2025)
The development of highly efficient bifunctional electrocatalysts that operate effectively in strong electrolytes, with low overpotentials at defined current densities and excellent durability, has become a central focus in research on overall water splitting. In this study, a three-dimensional (3D) sheet-wrapped wire electrocatalyst, composed of Fe-doped NiCo2S4 on nickel foam (NF), was fabricated. This material demonstrated excellent durability for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in an alkaline medium. The uniform distribution of Ni, Co, Fe, and S elements significantly enhanced the electro-catalytic performance. The incorporation of Fe improved activity, with the Fe2.5%-NiCo2S4/NF electrocatalyst achieving overpotentials of 310 mV and 260 mV for the HER and OER, respectively, at a current density of 100 mA cm-2. These results were superior to those of both bare nickel foam and NiCo2S4/NF. The 3D configuration facilitated efficient ion transport and contributed to the remarkable catalytic performance. As a water-splitting electrolyzer in an alkaline electrolyte of 1.0 M KOH, the system delivered a current density of 20 mA cm-2 at a cell voltage of 1.66 V, highlighting the effectiveness of this design strategy.

Facet dependence for solvent-modulated proton-coupled electron transfer in furfural acetalization on Pd nanostructures - Porwal, Govind; Dandekar, Pallavi; Gorai, Twinkle; Khan, Tuhin Suvra; Haider, M. Ali; Gupta, Shelaka; Vinod, C. P. (Chemical Engineering Journal, 2025)
Furfural dialkyl acetals prepared via acetalization reaction of furfural and alcohols are promising biofuels. Using defined experiments and density functional theory (DFT) simulations, the structure-dependent activity and selectivity for furfural acetalization reaction in the presence of alcohols (methanol, ethanol, propanol and butanol) as solvents was studied over well-defined supported Pd nanostructures (octahedra (111), cubes (100) and spheres (both (111) and (100)). Pd cubes supported over TiO2 in the presence of ethanol as a solvent (at 303 K and balloon pressure H-2) exhibited 78 % conversion and 100 % selectivity for furfural diethyl acetal product in a short time (similar to 180 min). In contrast, Pd octahedra (111) and Pd spheres showed low conversions (18 % and 6 %) at the same reaction conditions. Interestingly, when used as a solvent, methanol showed the highest conversion (90 %) and selectivity (100 %) for furfural acetalization over Pd cubes. DFT simulations provided mechanistic insight into the reactivity of the two different Pd facets (111) and (100) in the presence of alcohol molecules towards furfural acetalization reaction. A three-step reaction mechanism was proposed for furfural acetalization with alcohols: (i) alcohol hydroxyl-dehydrogenation (ii) hydrogenation of furfural carbonyl oxygen, and (iii) formation of hemiacetal product. For all three steps, Pd (100) exhibited low activation barriers (51.6, 26.7 and 76.2 kJ/mol) compared to Pd (111) surface (78.6, 35.8 and 92.2 kJ/mol) in the presence of ethanol. The activation barriers for the above steps were further reduced to 47.8, 23.9 and 64.6 kJ/mol on Pd (100) in the presence of methanol, explaining the experimental high reactivity aided by methanol. DFT calculations elucidated the role of the hydrogen bonding network between the solvent molecules and adsorbate, enabling proton-coupled electron transfer for accelerated reactions.
Keywords: Acetalization; DFT; facet-dependent reactivity; furfural; Furfural dialkyl acetals; solvent effect

Facile and eco-friendly synthesis of Mn2O3 nanoparticles via microwave-assisted glycerol-thermal method - Yadav, Akash; Jha, Ratnesh; Bhatkar, Akash; Gehlot, Bhavika; Kamble, Aditi; Manikandan, Marimuthu; Bhosale, Hritvik; Vaishnav, Vishal; Rathod, Rutik; Umbarkar, Shubhangi; Raja, Thirumalaiswamy; Bhatte, Kushal D. (Journal of Chemical Sciences, 2025)
Microwave-assisted efficient synthesis of nanosized manganese oxide (Mn2O3) is reported using glycerol and manganese acetate. Glycerol in this reported methodology acts as an efficient solvent for this nanomaterial synthesis under microwave radiation. This reported method enables the synthesis of nanosized Mn2O3 without further use of additives, stabilizers, and bases other than glycerol and manganese precursor. Glycerol is a renewable biomaterial derived nonvolatile and nontoxic, safe solvent. It has a high boiling point and dielectric constant, which makes it an ideal solvent for microwave synthesis. The synthesized nanosized Mn2O3 was analyzed by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. We examined the catalytic properties of as-synthesized Mn2O3 for cinnamyl alcohol oxidation to cinnamaldehyde. In this oxidation activity experiment, nanosized Mn2O3 exhibits good conversion and selectivity towards the desired product. We also made an attempt to understand the probable mechanism of nanomaterial formation and found some conclusive evidence to support it. This research methodology is facile, energy efficient, and involves minimum chemicals for synthesis. It makes this reported methodology not only economically attractive but also environmentally friendly, which aligns well with green chemistry principles.
Keywords: Glycerol; green chemistry; Nanosized Mn2O3; nanostructured catalysis

Far-red active squaraine dye-sensitized photoanode for dye-sensitized solar cells with a copper (II/I) electrolyte - Nawghare, Indrajeet S.; Deshmukh, Shivdeep Suresh; Joshi, Krati; Krishnamurty, Sailaja; Krishnamoorthy, Kothandam; Nithyanandhan, Jayaraj (Journal of Photochemistry and Photobiology A-Chemistry, 2025)
In dye-sensitized solar cells (DSSC), controlling the dye-aggregation on TiO2 and charge recombination between electrons present in TiO2 and electrolyte can be achieved by wrapping the long alkyl groups around the dye structure and further introducing bulky donor on the dye is a potential approach to enhance both the open-circuit potential and short-circuit current parameters. Additionally, bulky donor containing dye structures modulates the photophysical and electrochemical properties of the sensitizer which helps reducing the over potentials required for the dye regeneration process by utilizing a multidentate ligand containing [Cu(tme)]2+/+ and I- /I3redox electrolytes. Hagfeldt donor appended far-red NIR active unsymmetrical squaraine dye (SQ-HF) has been designed, synthesized, and characterized. SQ-HF dye showed an intense absorption at 676 nm (epsilon 1.7 x 105 M- 1cm- 1). Photophysical and electrochemical studies indicated that the LUMO and HOMO energy levels of the SQ-HF dye were suited for charge injection (from the LUMO of the dye to the conduction band of TiO2) and dyeregeneration processes, respectively. The DSSC device efficiency of 5.15 % (JSC of 10.83 mA/cm2 and VOC of 0.690 V) has been achieved for SQ-HF dye by utilizing a literature reported [Cu(tme)]2+/+ and 4.11 % (JSC of 8.74 mA/cm2 and VOC of 0.702 V) in I- /I3- redox shuttles, respectively.
Keywords: aggregation of dyes; Bulky donor; dye-sensitized solar cell; Photocurrent generation; squaraine dye

The first enantioselective total synthesis of the eremophilane-type sesquiterpenoid (-)-peniroqueforin C - Ingale, Sudhir R.; Vinodkumar, Ramavath; Kontham, Ravindar (Tetrahedron Letters, 2025)
Herein, we report the first stereoselective total synthesis of the eremophilane-type sesquiterpenoid (-)-peniroqueforin C using a chiral-pool strategy. This synthetic route features the use of readily available (S)-(+)-carvone as a chiral building block, Robinson annulation to construct the decalin system, substrate-controlled stereoselective methylation, single-step annulative construction of a tricyclic gamma-ylidene-butenolide with concomitant alkene transposition, and direct lactone-to-lactam conversion as key transformations.
Keywords: annulation reactions; Eremophilanes; Peniroqueforin C; Sesquiterpenoids; Total synthesis

Genomic insights and biotechnological potential of “Mesobacillus aurantius” strain S13: a canthaxanthin pigment-producing bacterium - Karthik, Shankar; Raman, Gurusamy; Srinivasan, Arumugam; Dastager, Syed Gulam; Wagh, Vasudev; Ayyadurai, Niraikulam (Gene Reports, 2025)
<span style="color: rgb(31, 31, 31); font-family: ElsevierGulliver, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif, sans-serif; font-size: 16px;">This study explores the discovery and characterization of pigments, from a microorganism thriving under environmentally challenging conditions. Utilizing a polyphasic taxonomic approach, we successfully isolated and identified a bacterial strain S13 within the <em style="box-sizing: border-box; margin: 0px; padding: 0px; color: rgb(31, 31, 31); font-family: ElsevierGulliver, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif, sans-serif; font-size: 16px;">Mesobacillus<span style="color: rgb(31, 31, 31); font-family: ElsevierGulliver, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif, sans-serif; font-size: 16px;"> genus and Bacillaceae family, designated as “<em style="box-sizing: border-box; margin: 0px; padding: 0px; color: rgb(31, 31, 31); font-family: ElsevierGulliver, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif, sans-serif; font-size: 16px;">Mesobacillus aurantius<span style="color: rgb(31, 31, 31); font-family: ElsevierGulliver, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif, sans-serif; font-size: 16px;">” S13. We confirmed the species based on comprehensive phenotypic, physiological, and biochemical analyses, molecular phylogenetics, DNA–DNA hybridization, average nucleotide identity, and whole-genome sequencing. The strain S13 (MTCC13141 = VKM B-3583 = NBIMCC 9084) possesses a 4.81 Mbp genome that encodes genes for pigment production. Notably, this study uses various spectroscopic methods to characterize canthaxanthin, an orange pigment and delineates its biosynthetic pathway from the genome of S13. The methylerythritol phosphate (MEP) pathway and canthaxanthin biosynthesis genes highlight the capacity of the bacterium to synthesize crucial isoprenoids and terpenoids, including canthaxanthin. This research provides a detailed account of the isolation, characterization, and taxonomic classification of “<em style="box-sizing: border-box; margin: 0px; padding: 0px; color: rgb(31, 31, 31); font-family: ElsevierGulliver, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif, sans-serif; font-size: 16px;">Mesobacillus aurantius<span style="color: rgb(31, 31, 31); font-family: ElsevierGulliver, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif, sans-serif; font-size: 16px;">” S13 and underscores the potential biotechnological applications of the bacterium in producing pharmaceuticals, biofuels, and cosmetics. Therefore, “<em style="box-sizing: border-box; margin: 0px; padding: 0px; color: rgb(31, 31, 31); font-family: ElsevierGulliver, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif, sans-serif; font-size: 16px;">Mesobacillus aurantius<span style="color: rgb(31, 31, 31); font-family: ElsevierGulliver, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif, sans-serif; font-size: 16px;">” S13 is a potentially valuable microbial resource for the industrial production of isoprenoids and pigments.

Graphitic carbon nitride supported boron quantum dots: a transition metal free alternative for di-nitrogen to ammonia reaction - Samudre, Nikhil S.; Krishnamurty, Sailaja (CHEMPHYSCHEM, 2025)
Presently, a sustainable electrochemical Nitrogen Reduction Reaction (NRR) has been essentially found to be viable on transition metal-based catalysts. However, being cost-effective and non-corrosive, metal-free catalysts present an ideal solution for a sustainable world. Herein, through a DFT-based study, we demonstrate metal-free NRR catalysts, boron quantum dots with 13 atoms as a case study and their chemically modified counterparts when anchored on graphitic carbon nitride (g-C3N4) surface. The best catalyst among the studied, a silicon-doped boron quantum dot with a cagelike structure, is found to favour the dinitrogen to ammonia reaction pathway with a low liming potential and potential rate-determining step (PDS) of -0.11 V and 0.27 eV, respectively. The present work demonstrates as to how boron quantum dots, which are reported to be experimentally synthesised, can be exploited for ammonia synthesis when supported on the surface. These catalysts effectively suppress the HER, thus establishing its suitability as an ideal catalyst. The work also represents a futuristic pathway towards a metal-free catalyst for NRR.
Keywords: Boron quantum dot; Electro-catalyst; Graphitic carbon nitride; hydrogen evolution reaction; Limiting potential; metal free catalyst; Nitrogen Reduction Reaction

Graphitic-C3N4/γ-Al2O3 composite catalyst for synthesis of 5-(Hydroxymethyl) furfural from d-Glucose - Kirdant, Swapnali P.; Ghadge, Sambhaji S.; Jadhav, Vrushali H. (Energy & Fuels, 2025)
Currently, the synthesis of 5-hydroxymethylfurfural (5-HMF), with high yields and selectivity from different renewable sources, is an important focus in the biomass conversion area. In the present study, a g-C3N4/gamma-Al2O3(1:1) composite catalyst was prepared using graphitic carbon nitride (g-C3N4) and acidic gamma-alumina (gamma-Al2O3), which was evaluated for its catalytic activity in converting sugars, mainly glucose, to 5-HMF. In the g-C3N4/gamma-Al2O3(1:1) catalyst, N-containing groups on g-C3N4 provided basicity and gamma-Al2O3 provided Lewis acidity to the catalyst. The g-C3N4/gamma-Al2O3(1:1) composite catalyst showed superior activity for 5-HMF synthesis compared to gamma-Al2O3 and g-C3N4 alone. The increased acidic and basic properties of the g-C3N4/gamma-Al2O3(1:1) catalyst significantly influenced both glucose-to-fructose isomerization and dehydration of fructose to HMF by increasing the yield of 5-HMF. In addition, the solvent DMSO:water also played an important role in the one-pot conversion of glucose to HMF by minimizing side reactions, which significantly improved the 5-HMF yield. The reaction was optimized for various solvents, temperatures, and catalyst concentrations to get a maximum yield of 91% from glucose with >99% selectivity of crude 5-HMF. Other sugars like fructose, sucrose, and lactose also provided good yields of 5-HMF. The g-C3N4/gamma-Al2O3(1:1) catalyst was stable and was effectively reused for up to four cycles.

Green one-pot three component synthesis of thiazolidine-2,4-dione based bisspirooxindolo-pyrrolidines with [Bmim]BF4: their in vitro and in silico anti-TB studies - Rukyanaik, V.; Gamidi, Rama Krishna; Kumari, Jyothi; Sriram, Dharmarajan; Basavoju, Srinivas (Molecular Diversity, 2025)
A simple and effective three-component one-pot green methodology was employed for the synthesis of a new thiazolidine-2,4-dione based bisspirooxindolo-pyrrolidine derivatives using [Bmim]BF4 ionic liquid via [3 + 2] cycloaddition reaction. It is an environmentally benign, column chromatography-free, shorter reaction time, good yield and easy product isolation method. The synthesized compounds 10a-x, were thoroughly characterized by using various spectroscopic methods like FT-IR, H-1 NMR, C-13 NMR, Mass spectrometry and finally by single crystal X-ray diffraction method. In vitro anti-tubercular (anti-TB) activity studies were carried out on these synthesized compounds, and they showed good to moderate anti-TB activity against Mycobacterium tuberculosis H37Rv strain. The compound 10a exhibited good anti-TB activity, with an MIC (Minimum Inhibitory Concentration) value of 12.5 mu g/mL, and the compounds 10m, 10o and 10r showed moderate activity with an MIC value of 25.0 mu g/mL. Remaining compounds exhibited poor activity against Mycobacterium tuberculosis. Ethambutol, rifampicin and isoniazid were used as standard drugs. Furthermore, in silico molecular docking experiments on the TB protein (PDB ID: 1DF7) were carried out to understand the binding interactions, and they showed least binding energy values ranging from -8.9 to -7.2 kcal/mol.
Keywords: 4-dione based bisspirooxindolo-pyrrolidines; Anti-TB activity; green synthesis; Molecular docking; Thiazolidine-2; [3+2] cycloaddition reaction; [Bmim]BF4

Growth of Mo-doped Ni3S2 nanorods array for superior overall water splitting reaction - Sharma, Pooja; Khandare, Lina; Saha, Arindam; Chaure, Nandu B.; Yengantiwar, Ashish (International Journal of Hydrogen Energy, 2025)
Designing novel, efficient and cost-effective dual-functional electrocatalyst for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) using an alkaline electrolyte is crucial for establishing a sustainable hydrogen economy and transitioning to a society powered by renewable energy sources. In the present work, Mo-doped nickel sulfide (Mo-Ni3S2) nanorods were grown on Ni-treated nickel foam (N-NF) substrate via a two-steps hydrothermal method. Specifically, Mo-Ni3S2/N-NF surface consists of nanorods-like morphology, which provides extensive area for percolation of electrolyte, that resulting in outstanding catalytic performance. Such a well-synthesized electrode exhibited superior performance and stability for OER as compared with pristine Ni3S2/NF and bare nickel foam (NF) electrodes. In addition, Mo-Ni3S2/N-NF electrode provides good HER activity and confirms its dual-functionality in alkaline medium. Our champion Mo-Ni3S2/N-NF electrocatalyst delivers best OER overpotential of 230 mV at current density of 100 mA/cm(2). Also, it provides HER overpotential of 100.6 mV at a current density of 10 mA/cm(2). Both OER and HER are carried out in the presence of 1 M KOH alkaline electrolyte. OER stability of the best-performed Mo-Ni3S2/N-NF electrode demonstrates almost constant current density similar to 120 mA/cm(2), which retains 90% of original value after continuously tested for the duration of 22 h. The total cell voltage of 1.56 V is provided by Mo-Ni3S2/N-NF integrated system and it demonstrates a good stability for duration of 22 h. Our approach provides a new insight into developing earth-abundant, inexpensive and superior dual-functional electrocatalyst for overall water splitting reaction (WSR).
Keywords: Dual-functional electrocatalyst; HER; Mo doping; Nickel sulfide nanorods; OER; overall water splitting

Growth of structural lengthscale in Kob-Andersen binary mixtures: Role of medium range order - Kumawat, Sanket; Sharma, Mohit; Nandi, Ujjwal Kumar; Tah, Indrajit; Bhattacharyya, Sarika Maitra (Journal of Chemical Physics, 2025)
A central and extensively debated question in glass physics concerns whether a single, growing lengthscale fundamentally controls glassy dynamics, particularly in systems lacking obvious structural motifs such as the Kob-Andersen binary Lennard-Jones (KALJ) model. In this work, we investigate structural and dynamical lengthscales in supercooled liquids using the KALJ model in two compositions: 80:20 and 60:40. We compute the dynamical lengthscale from displacement-displacement correlation functions and observe a consistent growth as temperature decreases. To explore the static counterpart, we use a structural order parameter (SOP) based on the mean field caging potential. While this SOP is known to predict short time dynamics effectively, its bare correlation function reveals minimal spatial growth. Motivated by recent findings that long time dynamics reflect collective rearrangements, we perform spatial coarse-graining of the SOP and identify an optimal lengthscale L-max that maximizes structure-dynamics correlation. We show that the structural correlation length derived from SOP coarse-grained over L-max exhibits clear growth with cooling and closely tracks the dynamical lengthscale, especially for A particles in the 80:20 mixture and for both A and B particles in the 60:40 system. Our results reconcile the previously observed absence of static length growth in the KALJ model by highlighting the necessity of intermediate range structural descriptors. Furthermore, we find that the particles with larger structural length growth also correspond to species with latent crystallization tendencies, suggesting a possible link between structural order, dynamics, and incipient crystallization.

Harnessing AEM electrolyzer-level performance through strategically designing the electronic structure of electrocatalysts, enabling dynamic functional switching - Kumar, Sonu; Verma, Tushar Singh; Selvaraj, Kaliaperumal (ACS Catalysis, 2025)
The anion exchange membrane water electrolyzer (AEMWE) is a promising technology for cost-effective hydrogen production. To promote its development and adoption, targeted efforts are focused on finding non-platinum group metal (non-PGM) electrocatalysts that efficiently facilitate the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER). Nickel sulfides (NiS) are effective OER catalysts; however, they suffer due to leaching-related instability at electrolyzer stack operational conditions. We introduce a rational non-PGM design that enhances stability during the OER while excelling at the HER, showcasing molecular-level insights for a scalable AEMWE zero-gap stack device. NiS coating is applied to the Al-metal-organic framework supported by 3D porous nickel foam (NSMA), leading to charge localization at the interface, which helps in OER by requiring only 322 millivolts at 100 mA cm-2. The main innovation in the NSMA design is a controlled electroreduction process that converts the Millerite phase into Ni3S2, a catalyst (rNSMA). This transformation leads to charge delocalization at the surface and a low overpotential of -80 mV at -100 mA cm-2 for the HER. In a full cell, this catalyst duo requires an overpotential of 1.49 V, outperforming the commercial Pt/Ru catalyst pair at 1.58 V. In a scaled-up 12.96 cm2 AEM electrolyzer single-cell stack, current density rose from 398 to 1062 mA/cm2, maintained for over 100 h at high temperatures, achieving 99% Faradaic efficiency and 100% hydrogen purity. The AEM electrolyzer cell shows a good energy efficiency of 45.50 kWh/kg and a cell efficiency of 86.59%. Detailed studies, including DFT analyses, revealed that electronic structure modification enhances charge delocalization, driving its impressive performance on an industrially significant scale.
Keywords: anion exchangemembrane water electrolyzer (AEMWE); charge transfer; density functional theory(DFT); HER; nickel sulfide; OER

Harnessing DABCO ionic salts for synthesis of heterocycles via multi-component reactions - Rajmane, Archana; Narande, Poonam; Patil, Nita; Kumbhar, Arjun (Chemical Papers, 2025)
The review article discusses the advancements in synthesis and applications of acidic, basic, and neutral 1,4-diazabicyclo[2.2.2]octane (DABCO) ionic salts in multi-component reactions. Compared to imidazolium-based ionic salts, the number of DABCO-based ionic salts is significantly lower. Recently, there has been increasing focus on these salts due to their selective salt formation capabilities. A significant challenge lies in the limited availability of physical data regarding DABCO-based ionic salts; hence, most of them are not ionic liquids. While many of these salts could be reused several times with only a minimal reduction in their catalytic effectiveness, there is a significant limitation in the availability of DABCO-based salts.
Keywords: 1; 4-Diazabicyclo[2.2.2]octane; Ionic salts; Multi-component reactions; Recyclability

Harnessing microRNAs and their targets for salt stress tolerance in Pandanus odorifer - Rashmi, Deo; Barvkar, Vitthal T.; Nadaf, Altafhusain B.; Kadoo, Narendra Y. (Journal of Plant Biochemistry and Biotechnology, 2025)
Salinity poses a formidable challenge to agriculture, detrimentally impacting plant growth and the yield of several crops globally. Pandanus odorifer (Forssk.) Kuntze is a highly salt-stress resilient plant that grows naturally along the coastal regions of Asia, Southeast Asia, and Polynesia. It is frequently found as a frontier species along the sandy shores receiving constant salt sprays. MicroRNAs (miRNAs) play essential regulatory roles in growth, development, and combating various biotic and abiotic stresses. Thus, characterizing miRNAs and their targets is critical to understanding their roles in salt stress tolerance. Through a rigorous analysis based on homology, secondary structure and signatures of other miRNA genes, we identified 52 conserved nonredundant miRNAs from the P. odorifer transcriptome data. These miRNAs were diverse and belonged to 23 miRNA phylogenetic families. Several miRNAs, including pod-MIR156a, pod-MIR164d, and pod-MIR535d, demonstrated distinct expression patterns in response to salt stress. Their target genes exhibited opposing expression trends, corroborating the intricate miRNA-target relationship. Delving deeper into their influence, we discovered that these miRNAs mainly targeted transcription factors that are known for their pivotal roles in stress responses. We also detected four miRNA-star (miRNA*) sequences (the complementary strands of functional mature miRNAs), which supports the authenticity of the identified miRNAs. This study unveils the intricate regulatory mechanism through which miRNAs may reinforce salt stress tolerance in P. odorifer, providing a promising avenue for enhancing crop resilience to various stresses through miRNA-based strategies.
Keywords: Abiotic stress; microRNA; miRNA targets; Salinity tolerance; salt stress; Transcription factors

Heteroatom-synergistic effect on anchoring polysulfides in chalcone-linked nanographene covalent organic frameworks for high-performance Li―S batteries - Ranjeesh, Kayaramkodath Chandran; Javaregowda, Bharathkumar H.; Gaber, Safa; Bhauriyal, Preeti; Kumar, Sushil; Skorjanc, Tina; Finsgar, Matjaz; Heine, Thomas; Krishnamoorthy, Kothandam; Shetty, Dinesh (Advanced Science, 2025)
Lithium-sulfur (Li & horbar;S) batteries are an attractive option for future energy storage devices because they offer higher theoretical specific capacity, energy density, and cost-effectiveness than commercial lithium-ion batteries. However, the practical applications of Li & horbar;S batteries are significantly limited by the shuttle effect caused by intermediate lithium polysulfides (LiPSs) and slow redox kinetics. In this study, the molecular engineering of chalcone-linked, sp(2)-bonded nanographene-type covalent organic frameworks (COFs) as sulfur hosts is reported to enhance interactions with LiPSs, thereby effectively suppressing the shuttle effect. The developed sulfur-hosting cathode material demonstrated outstanding battery performance, surpassing most reported materials by achieving a specific capacity of 1228 mA h g(-1) at 0.5C, with 80% retention after 500 cycles and an average Coulombic Efficiency (C.E.) of 99%. Additionally, the mechanisms of sulfur immobilization, the subsequent conversion into lithium polysulfides (LiPSs), and their binding energies with COFs are investigated using density functional theory (DFT) calculations. These findings offer valuable insights into the structure-property relationships essential for developing more efficient sulfur-hosting cathodes.
Keywords: anion-pi interaction; covalent organic frameworks; lithium-sulfur battery; nanographene; polysulfide shuttle

High levels of sinigrin trigger synthesis of fatty acids in Plutella xylostella (L.) - Barve, Pranoti R.; Barvkar, Vitthal T.; Giri, Ashok P.; Kotkar, Hemlata M. (Comparative Biochemistry and Physiology D-Genomics & Proteomics, 2025)
Diamondback moth (Lepidoptera: Plutellidae; Plutella xylostella L.) is a specialist insect of the Brassicaceae family, damaging economically important crops, such as cabbage and cauliflower. Glucosinolates, also known as `mustard oil bombs' are present in all Brassicaceae members, of which sinigrin (allyl-glucosinolate or 2-propenylglucosinolate) is a major aliphatic compound. During herbivory, glucosinolates are converted to toxic isothiocyanates that deter insect pests. P. xylostella possesses glucosinolate sulfatases that desulfate them. Such a conversion renders them unfit for degradation to toxic products. Changes in the larval performance prompted us for RNA sequencing to understand probable adaptation mechanism under sinigrin stress. Differentially expressed genes were found to be related to larval cuticle proteins. Further, gene ontology and KEGG (Kyoto Encyclopedia of Genes and Genomes) analyses depict genes belonging to the categories, integral component of membrane, cellular processes and those involved in biosynthesis of fatty acids. Upregulation of cuticular genes viz. larval cuticle protein-17 (LCP-17), cuticular protein-19 (2CP-19) and ATP binding cassette transporter C7 (ABCC7), ABCC16 was validated by qRT-PCR. Liquid chromatography quadrupole time of flight mass spectrometry analysis of whole larvae feeding on sinigrin and their separated cuticle, depicted abundance of fatty acids. Changes in the topography of the larval cuticle were evident by scanning electron microscopy. Expression of PxABCH1 was corroborated to its role in the transport of cuticular lipids. Notably, molecular docking of PxABCH1 with cuticular fatty acids showed favorable binding interactions. To summarize, integrated transcriptomic and metabolomic analyses suggest that in response to a diet containing a high dose of sinigrin, P. xylostella re-programs metabolic pathways related to fatty acid biosynthesis that directly influence insect development.
Keywords: ABC transporter; Cuticle; Host metabolite; Metabolome; Plutella xylostella; Sinigrin; Transcriptome

High performance and enhanced stability of Mn-Co3V2O8 coral-like structure for supercapacitor applications - Venkatesan, Sethuraman; Rajkumar, Palanisamy; Radhika, Govindaraju; Iyer, Maalavika S.; Manigandan, Ramadoss; Rajaiah, Dhilip Kumar; Radhakrishnan, S.; Raman, Sasikumar; Marimuthu, Senthilkumaran; Kim, Jinho (ACS Applied Energy Materials, 2025)
This study explores Mn-doped Co3V2O8 as a promising electrode material for high-performance supercapacitors. Mn doping significantly enhances the electrochemical properties of Co3V2O8, resulting in improved specific capacitance and cycling stability. Structural characterization reveals a coral-like morphology that increases the active sites and facilitates efficient charge transport and ion diffusion. Electrochemical tests show an impressive specific capacitance of 2352 F g(-1) in 2 M KOH at 1 A g(-1). For the assembled MCV5//AC asymmetric supercapacitor device, it has a high capacitance retention of 87.6% and a high Coulombic efficiency of 96% over 5000 cycles. The developed asymmetric MCV5/AC supercapacitor device achieved an energy density of 45 Wh kg(-1) and a power density of 750 W kg(-1). These findings establish Mn-doped Co3V2O8 as a durable and efficient electrode material, offering valuable insights into the relationship between the morphology and electrochemical performance. This work provides a foundation for the development of advanced materials for sustainable energy storage applications
Keywords: Co3V2O8; Electrode material; Energy storage; stability; supercapacitor

Highly efficient, co-solvent assisted glycolytic depolymerization of waste polyethylene terephthalate (PET) into Bis(2-hydroxyethyl) terephthalate (BHET) monomer - Markandeya, Nishant; Solanki, Bhanupratap Singh; Ramalingam, Karthick; Kamble, Sanjay (Industrial & Engineering Chemistry Research, 2025)
Recently, growing use of plastics has led to the accumulation of waste that must be dealt with paramount priority. Among all plastic wastes, polyethylene terephthalate (PET) is the most widely used thermoplastic polyester globally because of its extensive applications in packaging, automotive manufacturing, and textile markets. Thus, there is a need to develop a sustainable and viable PET recycling process. This study presents an efficient solvothermal process for the depolymerization of PET into bis(2-hydroxyethyl) terephthalate (BHET) using co-solvent assisted glycolysis. The process uses N-methylimidazole (NMI) as a cosolvent with ethylene glycol (EG), achieving complete PET conversion and 92% BHET yield under optimized reaction conditions (180 degrees C, 45 min, PET:EG:NMI ratio of 1:7:8) without using a catalyst. The effectiveness of the cosolvent system was attributed to its polarity and H-bonding capabilities, which enhanced polymer swelling and facilitated the depolymerization. SEM analysis revealed pore formation in the NMI-treated PET, whereas FTIR studies confirmed the progressive formation of ester groups during depolymerization of PET. Kinetics studies based on different models indicated that, at higher temperatures, the surface reaction and homogeneous model proved to be rate-controlling due to the elimination of mass transfer limitations. A preliminary technoeconomic analysis and recyclability experiments further supported the scalability potential of the present study.

Highly moisture-stable ferroelectric ammonium phosphate salt showing piezoelectric energy harvesting and rotation sensing applications - Kushwaha, Vikash; Prajesh, Neetu; Gopal, Animesh; Sahoo, Supriya; Deswal, Swati; Kirana, Antonysylvester; Shanmuganathan, Kadhiravan; Zareba, Jan K.; Boomishankar, Ramamoorthy (Journal of Materials Chemistry A, 2025)
Ferroelectric phosphate-based materials are known for their biocompatibility, dipole switching, and high thermal stability. In this context, we report a novel organic ferroelectric material, diisopropylammonium bis(4-nitrophenyl) phosphate (DIPABNPP), crystallizing in the monoclinic C2 space group. DIPABNPP exhibits a high second harmonic generation (SHG) efficiency 2.5 times higher than that of potassium dihydrogen phosphate (KDP). The ferroelectric nature of DIPABNPP was confirmed by the observation of a rectangular P-E hysteresis loop, which gave a saturated polarization value of 6.82 mu C cm-2. The ferroelectric polar domains of DIPABNPP, along with the bias-dependent amplitude butterfly and phase hysteresis loops, were visualized by piezoresponse force microscopy (PFM). Furthermore, the polydimethyl siloxane (PDMS) composites of DIPABNPP enabled the fabrication of humidity-resistant piezoelectric nanogenerators (PENGs) with energy harvesting and mechanical-electrical sensing capabilities. The top-performing 10 wt% DIPABNPP-PDMS device achieved a peak output voltage of 9.5 V and a charge storage efficiency of 81.8%, successfully powering 53 LEDs. Additionally, its rapid response time of 18.5 ms enables precise rotation sensing capabilities, suggesting potential applications in motion monitoring, such as revolution per minute (RPM) counting. We also present a unique and refined method for obtaining the output work efficiency (OWE) parameter, which quantifies the ratio of harvested electrical energy to the maximum elastic energy stored in the composite device, taking into consideration several key parameters during the PENG measurements. For the 10 wt% DIPABNPP-PDMS composite, an OWE of 13.1% was achieved, highlighting both its current performance and potential for optimization. This metric provides a standardized approach for evaluating PENGs, addressing a critical gap in assessing mechanical-to-electrical energy conversion efficiency.

Hot injection assisted electronically modulated twin and grain boundary rich sub-2 nm pt3co alloy resistant to phosphate ion for PEMFCs - Singh, Mayank U.; Jadhav, Swapnil D.; Shivankar, Bhavana R.; Pandikassala, Ajmal; Kumar, Yogesh; Krishnamurty, Sailaja; Vinod, C. P.; Kurungot, Sreekumar (Small, 2025)
Modulation of the electronic d-band center, structural defects (line defects), and particle size of Pt3Co alloy electrocatalyst have huge significance in elevating its electrochemical oxygen reduction reaction activity. Deviating from traditional high-temperature strategies, the current work focuses on ripening these benefits by implying a simple economically viable hot-injection-assisted modified polyol process. A conclusive control over decrementing particle size starting from 2.7 to 1.3 nm, an increasing degree of strain (twin boundary), and shifting of the d-band center away from the Fermi level are obtained via varying the temperature to which the solution is injected. The catalyst prepared via the injection at 200 degrees C (Pt3Co(1.3 t,g-b)/fVC-200) has delivered an electrochemical surface area of 84 m(2) g(Pt)(-1) with the onset and half-wave potentials of 0.980 and 0.858 V, respectively, versus RHE and a limiting current of -6.0 mA cm(-2) with stability till 20k cycles. In the high-temperature proton exchange membrane fuel cell Pt3Co(1.3 t,g-b)/fVC-200-based cell has outperformed Pt/C rendering 600 mWcm(-2) under H-2-Air compared to 529 mWcm(-2) of Pt/C with 20% lower Pt loading and double the stability due to enhanced resistance toward phosphoric acid for accelerated voltage cycling. A similar enhancement is seen while employing the catalyst for low-temperature fuel cells.
Keywords: electrocatalyst; grain boundary; hot injection synthesis; modified polyol process; oxygen reduction reaction; proton exchange membrane fuel cell; Pt3Co alloy; twin boundary; valance band X-ray photoelectron spectroscopy

Hybrid pincer (PNN)Ni(II) complex catalyzed selective C-H alkylation of pyridones using unactivated alkyl chlorides - Verma, Suryadev K.; Samal, Pragnya Paramita; Pradhan, Chandini; Pandey, Dilip K.; Krishnamurty, Sailaja; Punji, Benudhar (ACS Catalysis, 2025)
The use of readily accessible unactivated alkyl chlorides in the alkylation reaction to install valuable alkyl and methyl motifs into privileged heterocycles is an underdeveloped area. Herein, we report the regioselective C-H alkylation of diverse pyridones employing challenging unactivated alkyl chlorides as coupling partners, enabled by a strategically developed quinolinyl-based pincer (Ph2PNNQ)Ni(II) complex. The air-stable nickel catalyst is highly effective for the selective alkylation of functionalized 2-pyridones with both primary and secondary alkyl chlorides as well as for the unexpected C6 methylation, furnishing a wide range of 6-alkyl-2-pyridone scaffolds (78 examples). Remarkably, the alkyls bearing biologically and pharmacologically significant motifs, such as pterostilbene, nonyl phenol, sesamol, estrone, vitamin E, stigmasterol, cholesterol, and diosgenin, were compatible under this catalytic approach. The insights into the mechanism suggest that the alkylation reaction follows a Ni(II)/Ni(III)/Ni(IV) pathway involving the crucial two-step, one-electron oxidative addition of alkyl chloride. Several control studies, kinetics, and EPR analyses were performed to understand the detailed reaction pathway, further supported by density functional theory calculations.
Keywords: alkyl chlorides; C-H/C-Cl activation; hybrid pincer ligand; Mechanism; Nickel; pyridones

Hydrogel electrolyte-mediated in situ Zn-anode modification and the Ru-RuO2/NGr-coated cathode for high-performance solid-state rechargeable Zn-air batteries - Kharabe, Geeta Pandurang; Verma, Tushar; Barik, Sidharth; Urkude, Rajashri R.; Ayasha, Nadeema; Ghosh, Biplab; Krishnamurty, Sailaja; Kurungot, Sreekumar (ACS Applied Materials & Interfaces, 2025)
This work aims to deal with the challenges associated with designing complementary bifunctional electrocatalysts and a separator/membrane that enables rechargeable zinc-air batteries (RZABs) with nearly solid-state operability. This solid-state RZAB was accomplished by integrating a bifunctional electrocatalyst based on Ru-RuO2 interface nanoparticles supported on nitrogen-doped (N-doped) graphene (Ru-RuO2/NGr) and a dual-doped poly(acrylic acid) hydrogel (d-PAA) electrolyte soaked in KOH with sodium stannate additive. The catalyst shows enhanced activity and stability toward the two oxygen reactions, i.e., oxygen reduction and evolution reactions (ORR and OER), with a very low potential difference (Delta E) of 0.64 V. The computational insights bring out the electronic factors contributing to the enhanced catalytic activity of Ru-RuO2/NGr based on the charge density difference (CDD) between the interfaces. The disadvantages of the existing solid-state RZABs, such as their limited lifespan brought on by passivation, dendritic growth, corrosion, and shape change, have also been taken into account. The introduction of the stannate additive to the electrolyte induced an in situ Zn-anode modification, which subsequently improved the interfacial stability of the ZABs and, hence, the battery life cycles. The experimental observations reveal that, during the charging process, the Sn nanoparticles enable the homogeneous Zn deposition on the surface of the anode. Thus, the in situ Zn-anode surface modification assisted in achieving a high-rate cycle capability, viz., the homemade catalyst-based system exhibited continuous charge-discharge cycles for 20 h at a current density of 2.0 mA cm-2, with each cycle lasting for 5 min.
Keywords: Bifunctional Electrocatalyst; Core-ShellStructure; DFT study; electrolyte additive; Hydrogel; solid-state rechargeable zinc-airbattery; X-ray absorption spectroscopy

Identification of genetic variations linked to buparvaquone resistance in Theileria annulata infecting dairy cattle in India - Musale, Pankaj; Khilari, Ajinkya; Gade, Rohini; Dhanikachalam, Velu; Jadhav, Santoshkumar; Bajpai, Manali; Turakani, Bhagya; Joshi, Akshay; Prajapati, Amar; Srivastava, Anand; Swaminathan, Marimuthu; Joshi, Sachin; et al. (Plos One, 2025)
Buparvaquone (BPQ) is used for the treatment of bovine theileriosis, a tickborne disease caused by parasites of the Theileria genus. Studies on T. annulata have linked the mechanism of BPQ resistance predominantly to genetic variations in the parasite cytochrome b (cytb) gene. In addition, cryptic mechanisms of resistance involving the parasite peptidyl-prolyl isomerase (pin1) and dihydroorotate dehydrogenase (dhodh) genes require assessment. In India, where bovine theileriosis is endemic, and BPQ is widely used for treatment, it is necessary to establish the prevalence of genetic variations linked to BPQ resistance. In this study, multiplexed PCR amplification and nanopore sequencing method was used for genotyping the complete gene loci of the three target genes. Analysis of 454 T. annulata field samples collected from seven different states of India revealed the presence of previously reported BPQ resistance associated variations S129G, A146T and P253S in cytb gene and A53P in pin1 gene. The A146T and I203V variations in cytb were found to be prevalent and mostly co-occurring, and their role in BPQ resistance needs further evaluation. This study has revealed the presence of previously reported BPQ resistance-linked mutations in cytb and pin1 genes in T. annulata infecting dairy cattle in India and establishes an Oxford nanopore sequencing method suitable for large-scale surveillance of genetic variation in Theileria parasites from field samples.

In silico designing of electrocatalysts for hydrogen evolution reaction: a focus on titanium metal-based diboride monolayers - Shivankar, Bhavana R.; Verma, Tushar Singh; Krishnamurty, Sailaja (International Journal of Hydrogen Energy, 2025)
Enhancing the efficiency of Hydrogen Evolution Reaction (HER) using chemically modified electrocatalytic titanium diboride surfaces with transition metal-based Single Atom Catalysts (SACs) is illustrated using Density Functional Theory (DFT) based methods employing solvent effects. With higher surface concentrations of nonmetal boron rather than titanium metal, these highly conductive, extremely hard, chemically, and thermally stable electrocatalysts are more cost-effective and superior to their MBene analogs. A systematic analysis of these transition metal-based SACs from the 3d, 4d, and 5d groups embedded in TiB2 monolayer for its HER activity reveals the reduction in limiting potential. As the most effective SAC for improved HER, Zn@TiB2 SAC has a limiting potential of 0.08 eV in acidic and 0.21 eV in alkaline media. The higher exchange current density of Zn@TiB2 (5.74 x 10-5 A cm-2), which exceeds most previously reported electrocatalysts, indicates exceptional HER performance. This work shows that transition metal boride electrocatalysts are economically viable for HER and pave a path for experimentalists.
Keywords: AIMD; D -band center; DFT; HER; SAC

In situ engineered triple phase boundary enhancement in 3D structured carbon supported catalyst for high-temperature PEMFC - Pandikassala, Ajmal; Jadhav, Swapnil D.; Kurian, Maria; Kurungot, Sreekumar (Journal of Materials Chemistry A, 2025)
Enhancing platinum (Pt) utilization in polymer electrolyte membrane fuel cells (PEMFCs) requires optimizing the catalyst support microstructures to expand the triple-phase boundary (TPB). A promising method has been reported here which employs a three-dimensional (3D) catalyst support with an in situ-generated ionomer interface from preadmitted monomer molecules, potentially replacing the traditional Nafion ionomers. The small-sized monomers infiltrate the catalyst's pores, and UV curing polymerizes them into an extended interfacial network within the 3D carbon support. The single-cell analysis of the membrane electrode assemblies (MEAs) in high-temperature PEMFCs (HT-PEMFCs) using phosphoric acid-doped polybenzimidazole (PBI) membranes highlights the effectiveness of this approach. The strategy helps to achieve a current density of 1.06 A cm-2 and 0.49 A cm-2 at 0.60 V in H2-O2 and H2-air feed conditions, respectively. These values represent a significant improvement over the conventional Nafion ionomer-based MEAs, which exhibit current densities of 0.87 A cm-2 and 0.40 A cm-2 under H2-O2 and H2-air feeds, respectively, when utilizing a platinum-supported carbon (Pt/C) catalyst. When Pt nanoparticles are decorated on a high-surface-area, porous 3D interconnected carbon support synthesized via the carbonization of the polydopamine-coated melamine foam (Pt/3DPDC), the conventional Nafion ionomers tend to block the nanopores in the 3D carbon supports, leading to the underutilization of the Pt active sites. In contrast, the in situ ionomer approach enabled the system to deliver 0.93 A cm-2 at 0.60 V H2-O2 feed conditions, which is significantly higher than 0.38 A cm-2 obtained with the Nafion-based ionomers under similar conditions. This approach successfully makes use of the Pt active sites present in the nanopores and tackles the issues of mass transfer and reactant distribution, both of which are essential for expanding fuel cells from single cells to stacks. The exhibited method emphasizes how crucial it is to develop process-friendly electrocatalysts and complementary electrode manufacturing techniques in order to advance the PEMFC performance through a novel scientific path.

Influence of hydrophilic/hydrophobic diols on the properties of polyurethane hydrogels: solvent-free one-pot synthesis - Divakaran, Anumon V.; Nair, Sanoop B.; Karambe, Shivani S.; Wadgaonkar, Prakash P.; Nair, Kiran Sukumaran; Badiger, Manohar V. (Journal of Materials Chemistry B, 2025)
Herein, we report the design and synthesis of bio-degradable porous polyurethane hydrogels by a green, solvent-free, one-pot technique that can withstand physiological mechanical loads and aid in tissue regeneration. The hydrophilic/hydrophobic nature of the hydrogel was tuned using diols such as polycaprolactone diol (PCL) and polycarbonate diol (PCD), in combination with polyethylene glycol (PEG, MW approximate to 4000 g mol-1), 4,4 `-methylene bis(cyclohexyl isocyanate) (H12MDI) and hexanetriol (HT), which served as crosslinking agents. The structural characterizations of the hydrogels were performed using FT-IR as well as 1H and 13C high resolution magic angle spinning nuclear magnetic resonance (HR-MAS) spectroscopy. The utilization of various diols in the synthesis of the hydrogels enabled precise control over crystallinity, pore sizes, and customization of mechanical and degradation properties. These hydrogels exhibited tensile strength in the range of 0.22-1.48 MPa, while their compressive strength varied from 0.92 to 29.3 MPa. In vitro degradation profiles in the presence and absence of the enzyme Amano lipase PS revealed that the degradation process is contingent upon the specific diol present in the hydrogel. Furthermore, preliminary in vitro biological experiments confirmed the biocompatibility of the gels, indicating their potential as suitable substrates for drug delivery applications. This diverse library of gels can be shaped into specific forms, highlighting their promising applications as scaffolds and implants in drug delivery systems and tissue engineering.

Influence of physicochemical properties of seed on template-free ferrierite synthesis and its application in oleic acid isomerization - Patil, Shrinidhi D.; Mohanty, Ananya; Kudalkar, Mahadev; Niphadkar, Prashant S.; Bhatte, Kushal D.; Bokade, Vijay V. (Journal of Chemical Sciences, 2025)
We have reported an effective, seed-assisted organic structure directing agent (OSDA) free synthesis of ferrierite (FER) zeolites. In the current study, we have observed effects of physicochemical properties of two different seeds over synthesis of FER zeolites. The physicochemical properties of seeds, such as particle size and phase purity impart significantly over crystallization time and overall synthesis duration, costs of process and crystalline nature of FER zeolites. It is noteworthy that particle size of seed mainly affects the kinetics of crystallization for concerned FER zeolites. The synthesized zeolites were well characterized by XRD, FESEM, TEM, Raman spectroscopy, 27Al and 29Si MAS NMR, EDAX and BET surface area analyser to get more insights. We also evaluated, the catalytic activity of synthesized FER zeolites in oleic acid isomerization study to derive branched-chain fatty acids formation and attempted their structure and catalytic activity relationship with respect to purity of phases in seed.
Keywords: crystallization kinetics; Ferrierite seed; oleic acid isomerization; OSDA-free synthesis

Insights into electrolyte-solvent interactions and SEI formation for sustainable sodium-ion battery operation at low temperatures - Kim, Soohwan; Mirzapure, Vinay; Atwi, Rasha; Koppisetti, Heramba V. S. R. M.; Wasnik, Kundan; Rajput, Nav Nidhi; Shelke, Manjusha; Pol, Vilas G. (Small Methods, 2025)
Sodium-ion batteries (SIBs) show promise as an alternative to lithium-ion batteries. However, they face performance challenges at ultra-low temperatures (<-40 degrees C) due to slow Na+ transfer kinetics with conventional electrolytes. This limitation restricts their use in extreme environments such as polar regions and outer space. The presented systematic study addresses this challenge by modulating and tailoring the electrolyte composition for SIBs, enabling ultra-low temperature operation down to -110 degrees C for the first time. The comprehensive molecular dynamic and density functional theory calculations combined with experimental Raman spectroscopy and nuclear magnetic resonance studies of advanced electrolytes provided a deeper mechanistic understanding of the solvation structures and their impact on electrochemical performance. By varying the solvent composition with a combination of tetrahydrofuran and 2-Methyltetrahydrofuran solvents and sodium hexafluorophosphate (NaPF6) salt, the freezing point, solubility, and Na+ solvation structure of the electrolyte is modulated and studied in detail. The extensive anion engagement in the optimized mix solvent electrolyte facilitated the formation of a stable and inorganic-rich solid electrolyte interphase layer, ensuring low overpotentials and uniform Na+ deposition, yielding superior cycling stability. As a result, the developed electrolyte enables SIBs to achieve reversible capacities of 88 mAh g(-1) at -60 degrees C and 50 mAh g(-1) at -100 degrees C. These insights may contribute to developing improved energy storage devices suitable for challenging environmental conditions.
Keywords: contact-ion pair; solid electrolyte interphase (SEI); solvation; ultra-low temperature; XPS-depth Profiling

Insights into the Chemical Durability and Structure of ZnO-Incorporated Sodium Borosilicate Glasses from Solid-State NMR - Illath, Kavya; Ananthanarayanan, Arvind; Banerjee, D.; Mishra, R. K.; Kumar, Ravi; Bhattacharya, D.; Kumar, Sanjay; Manohar, S.; Ajithkumar, T. G. (Journal of Physical Chemistry B, 2025)
ZnO-incorporated NBS glasses have been studied for their application as a matrix for nuclear waste immobilization. However, structural factors affecting chemical durability have not been established. In this study, the structural changes in NBSZn glasses across various Na2O/(B2O3 + ZnO) ratios are explored using multinuclear MAS, MQMAS NMR, and EXAFS techniques. The Na MAS and MQMAS studies reveal remarkable changes in the Na environment after ZnO incorporation, which leads to an increase in chemical durability. Based on the results from NMR and EXAFS, we rationalized the structure of this glass in terms of the modified random network (MRN) model. The glass network comprises a highly polymerized region and alkali percolation channels bordered by nonbridging oxygens from the depolymerized regions. The constriction of these percolation channels increases the chemical durability of the glass. Our findings will help in the advancement of Zn-containing NBS glasses as a promising matrix for nuclear waste immobilization.

Integrated analysis of mitochondrial ETC inhibition reveals genotype-specific heterogeneity of drug response in glioblastoma - Belekar, Madhuri; Kavatalkar, Vijendra; Yadav, Ritu; Raghunathan, Anu (Biochemical and Biophysical Research Communications, 2025)
Glioblastoma (GBM) is among the most aggressive brain cancers, driven by genetic diversity and resistance to therapy. Mitochondrial metabolism-and in particular the electron transport chain (ETC)-has emerged as both a key weakness and a source of variable drug response. To investigate this, we integrated constraint-based metabolic modeling (CBM), high-resolution drug profiling, and genomic sequencing across three GBM cell models: LN229, U87MG, and neurospheres (NSP). Modeling predicted distinct ETC vulnerabilities, which were confirmed experimentally using inhibitors against Complexes I-V. Sensitivity to rotenone varied sharply: NSP cells were most vulnerable (IC50 = 0.007 mu M), LN229 showed intermediate sensitivity (0.021 mu M), and U87MG remained highly resistant (1.816 mu M). Across inhibitors, LN229 consistently showed steep dose-response slopes, U87MG maintained flat curves, and NSP displayed selective weaknesses. By incorporating slope (m) and Instantaneous Inhibitory Potential (IIP), median-effect analysis captured dynamic drug-response behaviour's that IC50 values alone overlooked. Genomic sequencing revealed striking differences in mutational burden: U87MG and NSP carried 354 and 307 single nucleotide polymorphisms (SNPs), respectively, compared with 141 in LN229. Several non-synonymous mutations were directly linked to altered drug sensitivity, including L194S, Y50 N, and L46V in LN229; S456L, A466T, and Y629F in U87MG; and the NSP-specific R159Q. Notably, mutations near catalytic sites correlated with changes in slope and IIP, providing mechanistic insight into therapeutic response. Together, these results show how genetic variation reshapes ETC function and drug sensitivity in GBM, offering a predictive framework for mutation-informed, personalized therapy.
Keywords: Drug dose response; Electron transport chain; Glioblastoma; IC50 value; Instantaneous inhibitory potential; Mitochondrial genome

Integrated flue gas CO2 capture and conversion to formate: a sustainable approach - Kumar, Rohit; Majumder, Supriyo; Singh, Chadrodai Pratap; Samanta, Chanchal; Newalkar, Bharat L.; Krishnamurty, Sailaja; Das, Raj Kumar (ChemSusChem, 2025)
Industrial CO2 emissions, characterized by dilute streams and impurity complexity, demand energy-efficient mitigation strategies beyond conventional capture technologies. Here, an integrated CO2 capture and conversion (ICCC) system is reported employing a heterogenized iridium catalyst-hydroxyquinoline-ligated Cp*Ir-Cl immobilized on amine-functionalized silica-that directly converts CO2 from synthetic flue gas containing SOx, NOx, and O2 to formate with 100% selectivity. The catalyst delivers remarkable activity, achieving turnover numbers up to 10,286 within 16 h. Density functional theory reveals that its square pyramidal geometry, induced by the hydroxyquinoline ligand, enhances Ir-N(ring) bond strength and electronic delocalization, thereby improving hydration energy, structural robustness, and catalytic efficiency. Importantly, the catalyst system demonstrates excellent durability, maintaining full activity over five regeneration cycles. Hydrogenation in a 1 M DABCO medium, followed by thermal decomposition of the amine-formate adduct at 150 degrees C, enables efficient lean amine regeneration, allowing subsequent flue gas capture and formate production without performance loss. This closed-loop strategy delivers a sustainable, contaminant-tolerant, and recyclable CO2-to-formate platform with strong promise for scalable industrial deployment.
Keywords: CO2 capture; flue gases; integrated capture and conversions; net zero future; Recycle