Asymmetric synthesis of inositol derivatives - Patil, Nivedita T.; Sarkar, Nitai; Mysore, S. Shashidhar; Gonnade, Rajesh G. (Tetrahedron, 2024)
Both the enantiomers of racemic 4- O -tosyl-6- O -benzyl- myo -inositol-1,3,5-orthoformate ( 2 ) were isolated by preferential crystallization and used to synthesize several enantiomeric myo -inositol derivatives - natural ononitol, natural laminitol, precursors for myo -inositol phosphates and an oxabicyclo [2.2.1] heptane derivative. This work demonstrates the potential of the enantiomeric tosylates D2 and L2 to serve as versatile starting materials for the absolute asymmetric synthesis of inositol derivatives and other natural products from symmetric myo -inositol since no optically active molecular entity was required for the resolution of 2.
Keywords: Asymmetric synthesis; Carbohydrate; Cyclitol; Inositol; Natural product

Base controlled rongalite-mediated reductive aldol/cyclization and dimerization of isatylidene malononitriles/cyanoacetates - Chaudhari, Suryakant S.; Nichinde, Chandrakant B.; Patil, Baliram R.; Girase, Amardipsing S.; Rama Krishna, Gamidi; Kinage, Anil K. (Organic and biomolecular chemistry, 2024)
In this study, we developed a novel methodology involving a base-controlled, rongalite-mediated reductive/aldol reaction, followed by cyclization of isatylidene malononitriles/cyanoacetates, resulting in the synthesis of spiro[2,3-dihydrofuran-3,3 `-oxindole]. Additionally, we have disclosed a rongalite-mediated dimerization process for isatylidene malononitriles, yielding dispiro[cyclopent-3 `-ene]bisoxindole. The utilization of rongalite in this reaction serves a dual purpose, acting both as a reducing agent and a C1 synthon. The developed approach has several advantages like a simple reaction setup, a wide substrate scope, requiring less time, using water as a green solvent, no metal or catalyst is required and products can be easily isolated via filtration with excellent yields under mild reaction conditions. A novel methodology was developed for the synthesis of spiro[2,3-dihydrofuran-3,3 `-oxindole] and dispiro[cyclopent-3 `-ene]bisoxindole under mild reaction conditions using inexpensive reagents.

Biexciton emission in CsPbBr3 nanocrystals: polar facet matters - Titus, Timi; Vishnu, E. Krishnan; Garai, Arghyadeep; Dutta, Sumit Kumar; Sandeep, Kuttysankaran; Shelke, Ankita; Ajithkumar, Thalasseril G.; Shaji, Anil; Pradhan, Narayan; Thomas, K. George (Nano Letters, 2024)
The metal halide perovskite nanocrystals exhibit a remarkable tolerance to midgap defect states, resulting in high photoluminescence quantum yields. However, the potential of these nanocrystals for applications in display devices is hindered by the suppression of biexcitonic emission due to various Auger recombination processes. By adopting single-particle photoluminescence spectroscopy, herein, we establish that the biexcitonic quantum efficiency increases with the increase in the number of facets on cesium lead bromide perovskite nanocrystals, progressing from cube to rhombic dodecahedron to rhombicuboctahedron nanostructures. The observed enhancement is attributed mainly to an increase in their surface polarity as the number of facets increases, which reduces the Coulomb interaction of charge carriers, thereby suppressing Auger recombination. Moreover, Auger recombination rate constants obtained from the time-gated photon correlation studies exhibited a discernible decrease as the number of facets increased. These findings underscore the significance of facet engineering in fine-tuning biexciton emission in metal halide perovskite nanocrystals.
Keywords: Auger recombination; biexciton emission; Cs-133 MAS NMR spectroscopy; Perovskites; time-gatedphoton correlation

Biocatalysis enables the scalable conversion of biobased furans into various furfurylamines - Giri, Pritam; Lim, Seonga; Khobragade, Taresh P.; Pagar, Amol D.; Patil, Mahesh D.; Sarak, Sharad; Jeon, Hyunwoo; Joo, Sangwoo; Goh, Younghwan; Jung, Seohee; Jang, Yu-Jeong; Choi, Seung Beom; et al. (NATURE COMMUNICATIONS, 2024)
Keywords: Biomass; OMEGA-TRANSAMINASE; OXIDASE; Reductive amination; SPECIFICITY

Biocompatible PVAc-g--PLLA acrylate polymers for DLP 3D printing with tunable mechanical properties - Pal, Shibam; Gavhane, Utreshwar Arjun; Asha, S. K. (ACS APPLIED MATERIALS & INTERFACES, 2024)
Keywords: acid; copolymers; polymerization; TACONIC ANHYDRIDE

Bismuth ferrite based acetone gas sensor: evaluation of graphene oxide loading - Ghadage, Pandurang; Shinde, K. P.; Nadargi, Digambar; Nadargi, Jyoti; Shaikh, Hamid; Alam, Mohammad Asif; Mulla, Imtiaz; Tamboli, Mohaseen S.; Park, J. S.; Suryavanshi, Sharad (RSC Advances, 2024)
We report a BiFeO3/graphene oxide (BFO/GO) perovskite, synthesized using a CTAB-functionalized glycine combustion route, as a potential material for acetone gas sensing applications. The physicochemical properties of the developed perovskite were analysed using XRD, FE-SEM, TEM, HRTEM, EDAX and XPS. The gas sensing performance was analysed for various test gases, including ethanol, acetone, propanol, ammonia, nitric acid, hydrogen sulphide and trimethylamine at a concentration of 500 ppm. Among the test gases, the developed BFO showed the best selectivity towards acetone, with a response of 61% at an operating temperature of 250 degrees C. All the GO-loaded BFO samples showed an improved gas sensing performance compared with pristine BFO in terms of sensitivity, the response/recovery times, the transient response curves and the stability. The 1 wt% GO-loaded BiFeO3 sensor showed the highest sensitivity of 89% towards acetone (500 ppm) at an operating temperature of 250 degrees C. These results show that the developed perovskites have significant potential for use in acetone gas sensing applications. CTAB-functionalized glycine combustion yields BiFeO3/graphene oxide (BFO/GO) perovskite for acetone gas detection.

Bridging the gap: an investigation of biosurfactants-polymer systems - Abhyankar, Isha; Hirlekar, Swarali; Prabhune, Asmita; Nisal, Anuya (Current Opinion in Colloid & Interface Science, 2024)
Biosurfactants (BSs) have been extensively researched due to their potential applications in various fields, including textiles, cosmetics, pharmaceuticals, agriculture, and oil remediation. These BSs possess a diverse range of physical, chemical, and biological properties. In recent years, researchers have combined these biosurfactants with both natural and synthetic polymers, resulting in the development of advanced material systems that exhibit a unique combination of properties. This review focuses on highlighting the recent advancements in these biosurfactant-polymer material systems and identifies existing gaps in the literature. The combination of biosurfactants with polymers has led to the formation of interpenetrated hydrogels, films, chemically modified surfaces, vesicles, functionalized nanofiber nonwoven mats, nano-formulations, and nano-assemblies. Some studies have also investigated the interactions between biosurfactants and polymer molecules. In most cases, non-specific, non-covalent interactions, such as electrostatic interactions, hydrogen bonding, and hydrophobic interactions have been found to govern the properties of these systems. Moreover, promising results have been achieved through the covalent modification of polymer surfaces, followed by functionalization using biosurfactant molecules. The literature demonstrates that these advanced materials could find applications in various fields, including drug delivery, bioremediation, biomedical materials, and as antimicrobial agents. These findings indicate the promising potential of biosurfactant-polymer systems for future advancements in these areas.

Calcination temperature impacting the structure and activity of CuAl catalyst in aqueous glycerol hydrogenolysis to 1,2-propanediol - Mane, Rasika; Potdar, Aparna; Jeon, Yukwon; Rode, Chandrashekhar (Topics in Catalysis, 2024)
This study investigated the impact of calcination temperature on the structural properties of CuAl catalyst which was found to be a robust nano-structured catalyst calcined directly without ramping at 400 °C and performed exceedingly well for aqueous phase hydrogenolysis of glycerol. Various samples of CuAl catalysts were prepared by co-precipitation at Cu: Al molar ratio 1:1 and were calcined at different temperatures (300–1000 °C). The obtained catalysts were reduced at 200 °C before their activity testing for glycerol hydrogenolysis reaction. To correlate the structure-activity, the catalysts were thoroughly characterized by XRD, XPS, BET, TEM, H2-TPR, NH3-TPD, and pyridine FTIR. It was observed that with an increase in calcination temperature from 300 to 700 °C, the glycerol conversion also increased from 47 to 55% with 93% selectivity to 1,2-PDO. The better performance of these catalysts was mainly related to the predominant presence of Brønsted acid sites, an appropriate ratio of the Cu0 to CuAl2O4 + CuO (0.33) and CuAl2O4 to CuO phases (0.35), the existence of Cu2O phase and the smaller Cu0 particle size. It was shown that altering the ramping rate for the calcination temperature of 400 °C impacted the catalytic activity. The CuAl-400 (DC) (direct calcined) catalyst exhibited a maximum glycerol conversion of 60%.

Catalytic cycloisomerization-oxidative cyclization reaction sequence of enyne diesters derived from 2-propargyloxyarylaldehydes - Prajapati, Karmdeo; Saini, Manoj Kumar; Gonnade, Rajesh G.; Basak, Ashok K. (Organic Letters, 2024)
Enyne diesters derived from 2-propargyloxyarylaldehydes are converted into 2-oxopyranochromenes via In(OTf)3-catalyzed cycloisomerization and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ)-mediated oxidative cyclization reaction sequence in one pot. The process possesses broad substrate scope and good functional group compatibility and generates various 4-(hetero)aryl-substituted 2-oxopyranochromenes in 32-79% yields (over two steps). 2-Oxopyranochromenes undergo selective decarboxylation under Krapcho conditions. When treated with aliphatic secondary amines in DMF, 2-oxopyranochromenes undergo decarboxylative amination at ambient temperature to generate 2-amino-substituted functionalized chromenes in good yields.

Catechol- and phenolic hydroxyl-functionalized partially bio-based (Co) poly(ether sulfone)s with multifarious applicability - Wale, Apparav K.; Jagtap, Ashish S.; Pandey, Priyanshi R.; Dastager, Syed G.; Shelke, Manjusha V.; Ambade, Ashootosh V.; Wadgaonkar, Prakash P. (European Polymer Journal, 2024)
A largely bio-based new bisphenol, namely, 4,4 `-((3,4-dimethoxyphenyl)methylene)-bis(2-methoxyphenol) (DMBM) was synthesized by the reaction of veratraldehyde with guaiacol. DMBM and varying compositions of DMBM and bisphenol A were polycondensed with bis(4-fluorophenyl) sulfone to afford reasonably high molecular weight film-forming (co)poly(ether sulfone)s possessing built-in methoxyl groups. T10 and Tg values of (co)poly(ether sulfone)s were in the range 382-478 degrees C and 171-187 degrees C, respectively indicating their good thermal stability and the values decreased with increase in mol % incorporation of DMBM. The methoxyl groups present in (co)poly (ether sulfone)s were quantitatively de-blocked resulting in the formation of corresponding polymers possessing pendant catechol moieties and free phenolic hydroxyl groups. By virtue of the presence of these functional moieties, (co)poly(ether sulfone)s are amenable for post-polymerization modifications, and exhibited properties such as antimicrobial (23 mm against Staphylococcus aureus and 18 mm against Escherichia coli)), antioxidant (72 % scavenger of free radicals), adhesive (2.24 MPa lap shear strength) and usefulness as redox-active agent in zinc-ion batteries. These data underscore the promise of DMBM as a versatile monomer of wider utility for the synthesis of functional (co)poly(ether sulfone)s capable of expanding their applicability beyond the conventional ones.
Keywords: (Co)poly(ether sulfone)s; adhesive; Antimicrobial; Antioxidant; bio-based; bisphenol; Zinc-ion batteries

Cathode|electrolyte interface engineering by a hydrogel polymer electrolyte for a 3D porous high-voltage cathode material in a quasi-solid-state zinc metal battery by in situ polymerization - Puthiyaveetil, Priyanka Pandinhare; Torris, Arun; Dilwale, Swati; Kanheerampockil, Fayis; Kurungot, Sreekumar (SMALL, 2024)
This work highlights the development of a superior cathode|electrolyte interface for the quasi solid-state rechargeable zinc metal battery (QSS-RZMB) by a novel hydrogel polymer electrolyte using an ultraviolet (UV) light-assisted in situ polymerization strategy. By integrating the cathode with a thin layer of the hydrogel polymer electrolyte, this technique produces an integrated interface that ensures quick Zn2+ ion conduction. The coexistence of nanowires for direct electron routes and the enhanced electrolyte ion infiltration and diffusion by the 3D porous flower structure with a wide open surface of the Zn-MnO electrode complements the interface formation during the in situ polymerization process. The QSS-RZMB configured with an integrated cathode (i-Zn-MnO) and the hydrogel polymer electrolyte (PHPZ-30) as the separator yields a comparable specific energy density of 214.14 Wh kg(-1) with that of its liquid counterpart (240.38 Wh kg(-1), 0.5 M Zn(CF3SO3)(2) aqueous electrolyte). Other noteworthy features of the presented QSS-RZMB system include its superior cycle life of over 1000 charge-discharge cycles and 85% capacity retention with 99% coulombic efficiency at the current density of 1.0 A g(-1), compared to only 60% capacity retention over 500 charge-discharge cycles displayed by the liquid-state system under the same operating conditions.
Keywords: cathode-electrolyte interface tuning; dendrite inhibition; epitaxial zinc deposition; hydrogel polymer electrolyte; In situ polymerization; Quasi solidstate rechargeable zinc metal battery

Chelation-assisted and steric-controlled selectivity in the Pd-catalyzed C-H/C-H oxidative coupling of indoles - Vijaykumar, Muniyappa; Pradhan, Chandini; Gonnade, Rajesh G.; Punji, Benudhar (Chemical Communications, 2024)
We report the first regioselective C2-C7 oxidative coupling of indoles using a palladium catalyst upon the strategic installation of N-pyridinyl and C3-carbonyl, which delivers 2,7-biindoles with a broad scope (25 examples; up to 93% yield). Isolation of the catalytic intermediate reveals the initial activation of the C(7)-H bond, followed by the C(2)-H bond in indoles, and the reaction proceeds via a Pd(ii)/Pd(0) pathway. This manuscript describes the first regioselective C2-C7 oxidative coupling of indoles using a palladium catalyst through the strategic installation of N-pyridinyl and C3-carbonyl, which delivers diverse biorelevant 2-7-biindoles.

Chemodivergent dehydrogenative coupling of alcohols by 3d metal catalysts - Bansal, Sadhna; Punji, Benudhar (ChemCatChem, 2024)
Chemodivergent synthesis by transition metal catalysts is a straightforward and sustainable approach to achieving valuable organic compounds. Especially, the chemodivergent dehydrogenative couplings of alcohols with organic motifs to develop various saturated and unsaturated compounds are highly environmentally benign due to the reduced waste generation. In this concept review, we presented the 3d transition metal (Mn, Fe, Co, and Ni)-catalyzed chemodivergent synthesis of imines and amines, saturated and unsaturated carbonyl/alcohol compounds, saturated and unsaturated nitriles, N-heterocycles, and N-/C-alkylated indoles. The discussed reaction commanded two or three different products with high chemoselectivity by changing specific reaction parameters, but keeping the catalyst unchanged. Generally, the acceptorless dehydrogenative coupling (ADC) provides unsaturated moieties, whereas the borrowing-hydrogen (BH) process results in saturated compounds. Text for Table of Contents: An overview of the chemodivergent dehydrogenative coupling of alcohols by the Earth-abundant transition metal catalysts is discussed. image
Keywords: 3d metals; Alcohols; chemodivergent; dehydrogenative coupling; heterocycles

Chitosan nanoparticles for single and combinatorial delivery of 5-fluorouracil and ursolic acid for hepatocellular carcinoma - Jaiswal, Neha; Pawar, Anil T.; Chaudhari, Bhushan P. (Emergent Materials, 2024)
Hepatocellular carcinoma (HCC) remains a significant global health challenge with limited therapeutic options. Chemotherapy has major limitations, leading to a paradigm shift towards nanomedicines. In this study, we aimed to synthesize single and dual drug-loaded chitosan nanoparticles (CSNPs) containing 5-fluorouracil (5-FU) and ursolic acid (UA) for spatial and controlled delivery against HCC. We synthesized CSNPs by a modified bottom-up ionic gelation method and optimized various parameters to formulate particles with smaller sizes, uniform size distribution, and high surface charge for intra-arterial infusion for HCC. The characterization techniques confirmed a monodisperse population of smaller sized particles with average sizes, as determined from transmission electron microscopy (TEM), as 45.25 ± 11.58, 105.66 ± 10.96, 176 ± 16.46, and 220 ± 21.37 nm for CSNPs, 5-FU-CSNPs, UA-CSNPs and 5FU + UA-CSNPs respectively. These formulations exhibited excellent encapsulation of the drugs, with an initial pH-dependent rapid release of 5-FU followed by a subsequent slower and sustained release, while showing pH-dependent slow and controlled release of UA. The in vitro cell viability assay established the highest anticancer potential for 5FU + UA-CSNPs, followed by 5-FU-CSNPs and UA-CSNPs, and the lowest for plain drugs in the Hep3B cell line. An increased uptake of both the drugs in CSNPs substantiated the supremacy of these formulations over the plain drugs as drug delivery agents. These findings suggest that 5FU + UA-CSNPs, a novel formulation, works as a potent therapeutic agent against HCC, supporting our hypothesis of co-loading 5-FU and UA in CSNPs can effectively manage HCC, with particle attributes fit for administration via intra-arterial infusion.

Circulatory levels of lysophosphatidylcholine species in obese adolescents: Findings from cross-sectional and prospective lipidomics analyses - Sharma, Sapna; Subrahmanyam, Yalamanchili Venkata; Ranjani, Harish; Sidra, Sidra; Parmar, Dharmeshkumar; Vadivel, Sangeetha; Kannan, Shanthini; Grallert, Harald; Usharani, Dandamudi; Anjana, Ranjit Mohan; Balasubramanyam, Muthuswamy; Mohan, Viswanathan; et al. (NUTRITION METABOLISM AND CARDIOVASCULAR DISEASES, 2024)
Keywords: Adolescent obesity; Asian Indians; biomarker; Lipidomics; Lysophosphatidyl- choline

Co-incorporated N-doped micro-meso porous carbon as an electrocatalyst for oxygen reduction reaction and Zn-air battery - Priya, Vaishna K.; Kharabe, Geeta Pandurang; Barik, Sidharth; Mohamed, A. Peer; Kurungot, Sreekumar; Hareesh, Unnikrishnan Nair Saraswathy (Energy and Fuels, 2024)
Metal-organic frameworks are considered ideal precursors for the preparation of transition-metal, heteroatom-doped carbon catalysts that are perceived to be efficient electrocatalysts for energy storage devices. Herein, we demonstrate the synthesis of ZIF-67-derived Co-incorporated N-doped porous carbon catalysts supported on high surface area microporous carbon prepared from a lotus seed shell. The combination of the two carbon catalysts in different weight ratios resulted in Co-incorporated N-doped carbon sheets with tuned surface area and porosity, enabling enhanced oxygen reduction reaction (ORR) activity in an alkaline medium. The optimized carbon catalyst ZL 600 (3:1) exhibited a half-wave potential of 0.79 V vs RHE and a limiting current density of -4.38 mA cm(-2) in 0.1 M KOH solution with higher stability and methanol tolerance. The optimized sample ZL 600 (3:1) demonstrated as a cathode in a zinc-air battery exhibited an open circuit voltage of 1.29 V with a flat discharge profile at a current rate of 10 mA cm(-2). The homemade system produced a specific capacity of 610 mAh g(-1) and a peak power density of 111 mW cm(-2), comparable to the cathode made with Pt/C. The high micro-mesoporosity, pyridinic and pyrrolic nitrogen contents, as well as enriched Co-active centers protected by carbon sheets favorably contributed to the efficient ORR mechanism.

Colocasia esculenta stems for the isolation of cellulose nanofibers: a chlorine-free method for the biomass conversion - Dominic, C. D. Midhun; Maheswary, S.; Neenu, V. K.; Sajadi, S. Mohammad; Rosa, Derval dos Santos; Begum, P. M. Sabura; Mathew, Mariya; Ajithkumar, T. G.; Parameswaranpillai, Jyotishkumar; George, Tresa Sunitha; Resmi, V. C.; Ilyas, R. A.; et al. (Biomass Conversion and Biorefinery, 2024)
The reuse of waste products is the green key to sustainability. The extraction of cellulose nanofibers from Colocasia esculenta stems is presented in the paper. The study proved that the waste biomass could be effectively re-engineered into highly valued cellulose nanofibers (CNFs). Cellulose nanofibers were extracted via a chemo-mechanical route. The pre-treatments included mild alkali hydrolysis (2% NaOH) and chlorine-free bleaching (peroxide bleaching in an alkaline medium). Cellulose I-beta structure was confirmed using C-13 solid-state nuclear magnetic resonance spectroscopy and X-ray diffraction analysis. The elemental analysis of CNFs detected the elements, carbon and oxygen. The CNFs had a crystallinity and transmittance of 71.72% and 60%, respectively. Microscopic studies verified the elimination of non-cellulosic components and the fibrous nature of CNFs. Moreover, the fiber diameter of CNFs was 20-40 nm. Thermal analysis revealed good thermal stability of 335.8 degrees C (T-50) for nanofibers. Long-term aids are numerous in eco-friendly technology. Developing an eco-design will support zero waste ideals, lowers carbon dioxide emissions, and encourages a circular economy. Owing to the merits of natural fibers, they can be adopted in various sectors including packaging, automobile, aerospace, electronics, biomedical, construction, and furniture.
Keywords: acid hydrolysis; cellulose nanofibers; Colocasia esculenta stems; High crystallinity

Concentration-dependent SILAR synthesized Di-bismuth copper oxide nano-materials electrode in asymmetric supercapacitor - Bobade, R. G.; Dabke, N. B.; Shaikh, Shoyebmohamad F.; Al-Enizi, Abdullah M.; Pandit, Bidhan; Lokhande, B. J.; Ambare, R. C. (Journal of Materials Science-Materials in Electronics, 2024)
In this study, we present a novel approach to prepare bismuth oxide deposited on copper substrate (Bi2CuO4) electrodes using a binder-free successive ionic layer adsorption and reaction (SILAR) technique, demonstrating their potential for energy storage applications. The resulting Bi2CuO4 electrode exhibits a tetragonal crystal structure with a polycrystalline nature, as confirmed by X-ray diffraction (XRD). Field emission scanning electron microscopy (FE-SEM) reveals a distinctive sphere-like structure with hydrophilic characteristics, as determined from contact angle measurements. X-ray photoelectron spectroscopy (XPS) further validates the composition of the sample. The electrochemical performance of Bi2CuO4 is remarkable, with a specific capacitance (SC) of 1795.9 F/g at 16 mA/cm(2). When used as an anode in an asymmetric solid-state device (ASSD) alongside activated carbon (AC) as the cathode, the Bi2CuO4 electrode attains a maximum energy density (SE) of 169.5 Wh/kg at 16 mA/cm(2) and a peak power density (SP) of 15.9 kW/kg at 24 mA/cm(2). In a 1 M KOH-polyvinyl alcohol (PVA) polymer solution, the Bi2CuO4//AC pencil-type cell achieves a superior SC of 94.5 F/g at 5 mV/s, retaining approximately 92% of its initial performance even after 5000 charge-discharge cycles. The resulting SE and SP are 43.1 Wh/kg and 5.2 kW/kg at 10 mA/cm(2), respectively. This research presents an efficient and straightforward synthesis method for producing high-performance pencil-type supercapacitors at a laboratory scale. Furthermore, we demonstrate the potential of a homemade pencil-type supercapacitor device (Bi2CuO4//AC) to power a light-emitting diode (LED), highlighting its practical utility in various energy storage applications.

Conformational enigma of TDP-43 misfolding in neurodegenerative disorders - Pillai, Meenakshi; Jha, Santosh Kumar (ACS OMEGA, 2024)
Keywords: DNA-BINDING PROTEIN; FRONTOTEMPORAL LOBAR DEGENERATION

Continuous flow synthesis of mesoporous silica particles with tunable size and structure - Jundale, Rajashri B.; Prasad, Bhagavatula L. V.; Devi, R. Nandini; Kulkarni, Amol A. (Industrial and Engineering Chemistry Research, 2024)
We have developed a continuous process to prepare mesoporous silica particles of different sizes and narrow size distribution in a tubular reactor. The method is based on the use of well-known Stober synthesis in the presence of cationic surfactant in methanol-water solvent system and trimethylbenzene as pore swelling agent to form porous silica particles. We observed that reaction parameters had enormous effects on particle size, distribution, and numerous morphological aspects. We demonstrated that these properties may be modified by adjusting the reaction temperature, base concentration, and surfactant concentration. MSPs of spherical morphology with variable size from 400 to 1000 nm produced with the surface area >600 m(2)/g and pore diameter of 2-4 nm. Large scale production is demonstrated by increasing reactor volume using 1/4 in. PTFE tubing from 20 to 163 mL, with this production of MSPs increased from 0.35 to 3 g/h. The method has been extended for high yield production at the kilogram scale using this approach, which will pave the way toward the industrialization of mesoporous silica based materials.

Copper-catalyzed regioselective C-H alkylation of phenol derivatives with unactivated alkyl chlorides: manifesting a Cu(I)/Cu(III) pathway - Verma, Suryadev K.; Punji, Benudhar (Journal of Catalysis, 2024)
The use of unactivated alkyl chlorides in regioselective C -H alkylation is a highly challenging process with diverse applications of alkylation strategy in drug discovery and agrochemistry. In this work, we report an efficient and cost-effective copper -catalyzed protocol for the coupling of unactivated alkyl chlorides with the C -H bond of phenol derivatives via 2-pyridinyl chelation assistance. The reaction shows a high level of regioselectivity, leading to an exclusive ortho alkylation and providing a broad scope with the endurance of numerous functionalities such as silyl, ether, thioether, pyrrolyl, indolyl, carbazolyl groups, including alkyl bearing fatty alcohol, nonylphenol, and vitamin E. Detailed mechanistic investigations suggest that the alkylation occurs through a two -electron oxidative addition of alkyl chloride to an active Cu(I) species. Deuterium labeling and kinetics experiments indicate a facile and reversible C -H bond activation process. Overall, the alkylation follows a Cu(I)/Cu(III) pathway involving chelation-assisted smooth C -H metalation and rate -limiting C-Cl oxidative addition of alkyl chloride.

Copper/Iron cocatalyzed depolymerization of postconsumer polycarbonate: a one-pot strategy to synthesize aryl ethers - Moyilla, Nageswararao; Padhi, Ganeshdev; Kalsi, Deepti; Barsu, Nagaraju (ACS SUSTAINABLE CHEMISTRY & ENGINEERING, 2024)
Keywords: aryl ethers; copper/iron cocatalysis; depolymerization; polycarbonates; Value-added products

CuNPs@Al2O3-cellulose composite for the ligand-free Suzuki cross-coupling reactions in batch and continuous flow process - Patil, Seema; Rajmane, Archana; Jadhav, Sanjay; Rode, Chandrashekhar; Kumbhar, Arjun (Journal of Organometallic Chemistry, 2024)
In the present work, we synthesized recyclable CuNPs@Al2O3-CELL composite from an inexpensive and commercially available synthetic reagent by a simple method. The catalyst was characterized by various techniques such as TGA (Thermogravimetric analysis), SEM (Scanning electron microscope), TEM (Transmission electron microscopy), XPS (X-ray photoelectron spectroscopy), EDS (Energy dispersive spectroscopy), and AAS (Atomic Absorption Spectroscopy). The composite was applied for the Suzuki coupling reactions in the batch and flow process. The aryl halides were easily coupled with arylboronic acids in 95 % ethanol at 78 C. We systematically investigated the role of reaction temperature, solvent, and catalyst loading, on the transient and steady-state behavior of the flow reactor through an automated flow chemistry platform. The CuNPs@Al2O3CELL catalytic particles demonstrate minimal deactivation and leaching over a continuous Suzuki coupling reaction at a 20 min nominal residence time at 100 C. Moreover, the catalyst can be recovered by simple filtration and reused at least five times with a moderate decrease in product yield. The excellent activity and stability of the catalyst have been attributed to the strong chelation of the Cu species with hydroxyl functional groups of the Al2O3-CELL composite. The catalytic system was highly efficient in Suzuki coupling of various aryl bromides with different aryl boronic acids, yielding good to excellent product yields (80-96 %) with a TON of 15.914-19.066 and TOF of 2.649-9.533 h(-1).
Keywords: Continuous flow process; CuNPs@Al2O3-CELL; ligand-free; recyclable; Suzuki coupling

Design of Bi-functional mixed oxide electrodes for selective oxidative C-C cleavage of glycerol to formate and synchronized green hydrogen production - Saha, Arindam; Murugiah, Vasantharadevi; Ranjan, Ravi; Chauhan, Inderjeet; Patra, Kshirodra Kumar; Bajpai, Himanshu; Saha, Avisekh; Gopinath, Chinnakonda S. (Sustainable Energy & Fuels, 2024)
Alkaline water electrolysis is a mature method to produce green hydrogen; however, it suffers from significantly high cost as high overpotentials are required for the oxygen evolution reaction (OER). However, the OER could be avoided altogether by replacing it with kinetically favorable oxidation of abundantly available feedstock molecules at a significantly low potential to value-added product(s) together with green hydrogen generation. This is a potential method to address the high cost of green hydrogen production while converting waste to wealth. Herein, we report green, template-free hydrothermal synthesis of an electrochemically active NiCoMn mixed oxide (NCMO) electrocatalyst with multiple sites, porous structure, large surface area, and nanoneedle (NN) morphology deposited directly over Ni foam (NF). Sustainable electrocatalytic performance was demonstrated for 120 h in 0.2 M alkaline glycerol using chronoamperometry and chronopotentiometry. Highly selective formate production demonstrated an exclusive C-C cleavage with the present catalyst system. Oxides of individual metal-ions (Ni, Co, and Mn) and their bimetallic combination (NiCo, NiMn, and CoMn) exhibited lower activity and product selectivity than the trimetallic NCMO electrocatalyst. The membrane-free two-electrode electrolyzer setup with NCMO/NF at both the anode and cathode (NCMO/NF & Vert;NCMO/NF) requires 1.63 V to accomplish 100 mA cm-2 with 0.2 M glycerol, which is 296 mV less than that of 1 M KOH solution. High faradaic efficiency was observed for hydrogen (98%) with highly selective formate (90%) production. Electrocatalytic formate generation from an alkaline glycerol solution with NCMO is an energy-efficient and promising approach that also supplies carbon-negative green H2. NiCoMn oxide nanoneedles with a cactus-like morphology are shown as bifunctional electrocatalysts that selectively oxidize glycerol to HCOOH and concurrently produce H2.

Designing of imine thiophene-ligated metal-complexes and implication in ethylene polymerization - Shaikh, Maulali H.; Ramekar, V. Rohan; Jawoor, Shailaja; Dash, Soumya R.; Birajadar, Rajkumar S.; Pawal, Sandip B.; Thenmani, Nandakumar; Vanka, Kumar; Chikkali, Samir H. (Journal of Macromolecular Science Part A-Pure and Applied Chemistry, 2024)
Polyethylene is the single largest volume polymer produced globally using Ziegler-type catalysts. Numerous modifications have been reported in search of a better catalyst that can control molecular weight, polydispersity, and branching. In our attempts to identify a suitable imine thiophene-ligated chromium complex, we examined 9 different titanium complexes computationally. The DFT investigations considered barriers for insertion, propagation, and termination by beta-H elimination or chain transfer, and identified N-(4-methoxyphenyl)-2-phenyl-1-(thiophen-2-yl)ethan-1-imine(L9) as the most suitable ligand. Subsequently, L9 was prepared in good yield (70%) by condensing 2-phenyl-1-(thiophen-2-yl)ethan-1-one with 4-methoxyaniline. Ligand L9 was treated with early transition metal precursors (Ti, Cr, Zr) to generate a homogenous catalyst. The identity of these catalysts was unambiguously ascertained using a combination of NMR, ICP, FT-IR, UV-Vis spectroscopy, and ESI-MS. The performance of L9-ligated titanium complex [Cat.1] was examined in ethylene polymerization using MMAO as a co-catalyst. Insertion of ethylene was tracked using high-pressure NMR experiments and Cat.1 was found to be active in the polymerization. Ethylene polymerization conditions were optimized to obtain high activity and molecular weight polyethylene. The chromium complex [Cat.2] outperformed the Ti and Zr-derived catalysts with the highest TOF of 6294 mol of PE/mol of Cr/h. Cat.2 produced high molecular weight, high-density polyethylene.
Keywords: Cr-complexes; DFT; high-density polyethylene; Imine thiophene ligand; Polyethylene

DNA-mediated formation of phase-separated coacervates of the nucleic acid-binding domain of TAR DNA-binding protein (TDP-43) prevents its amyloid-like misfolding - Patni, Divya; Patil, Anjali D.; Kirmire, Mona S.; Jha, Anjali; Jha, Santosh Kumar (ACS Chemical Neuroscience, 2024)
Sequestration of protein molecules and nucleic acids to stress granules is one of the most promising strategies that cells employ to protect themselves from stress. In vitro, studies suggest that the nucleic acid-binding domain of TDP-43 (TDP-43tRRM) undergoes amyloid-like aggregation to beta-sheet-rich structures in low pH stress. In contrast, we observed that the TDP-43tRRM undergoes complex coacervation in the presence of ssDNA to a dense and light phase, preventing its amyloid-like aggregation. The soluble light phase consists of monomeric native-like TDP-43tRRM. The microscopic data suggest that the dense phase consists of spherical coacervates with limited internal dynamics. We performed multiparametric analysis by employing various biophysical techniques and found that complex coacervation depends on the concentration and ratio of the participating biomolecules and is driven by multivalent interactions. The modulation of these forces due to environmental conditions or disease mutations regulates the extent of coacervation, and the weakening of interactions between TDP-43tRRM and ssDNA leads to amyloid-like aggregation of TDP-43tRRM. Our results highlight a competition among the native state, amyloid-like aggregates, and complex coacervates tuned by various environmental factors. Together, our results illuminate an alternate function of TDP-43tRRM in response to pH stress in the presence of the ssDNA.
Keywords: amyloid-likeaggregation; complex coacervation; DNA-protein interactions; Dynamics; pH stress; TDP-43

Early detection of KP.2 SARS-CoV-2 variant using wastewater-based genomic surveillance in Pune, Maharashtra, India - Rajput, Vinay; Das, Rashmita; Pramanik, Rinka; Nannaware, Kiran; Sushma, Y.; Taji, Nyabom; Rajput, Vishal; Rajkhowa, Riyakshi; Pacharne, Poonam; Shah, Priyanki; Gogate, Niharika; Sangwar, Poornima; et al. (Journal of Travel Medicine, 2024)

Effect of citral partitioning on structural and mechanical properties of lipid membranes - Saraf, Deepashri; Porte, Sudha; Sengupta, Durba (European Physical Journal-Special Topics, 2024)
Delineating the interactions of cellular metabolites with lipid membranes and their effects on membrane physical and mechanical properties constitutes a key step for comprehensively understanding their biological function. The plant metabolite-citral is widely used in biotechnological and cosmeceutical processes, but significant gaps remain in our understanding of how it affects cellular membranes that it interacts with. In this study, we unravel the molecular mechanisms underlying the interactions of citral with compositionally distinct model membranes using atomistic molecular dynamics simulations. Specifically, we investigate two distinct membrane compositions: the neutral phosphatidylcholine-phosphatidylethanolamine (DOPC:DOPE) bilayer, representing mammalian cell membranes and the anionic phosphatidylcholine-phosphatidylglycerol (DOPC:DOPG) bilayer, mimicking bacterial cell membranes. Our simulations reveal that citral molecules readily partition into both membranes without distinct composition-dependent effects. Monomeric citral molecules localize mainly at the interface of the acyl chain region of the lipids, and a few translocation events are sampled in the simulations. Interestingly, we observe small differences in lipid fluidity although the citral molecules significantly influence the rigidity of lipid bilayers, and a higher bending modulus was observed in DOPC:DOPE lipid bilayers compared to DOPC:DOPG bilayers. Further, citral partitioning induces an increased tendency for lipid demixing in DOPC:DOPE membranes, as evidenced by the decreased values of the Shannon entropy. Our work is an important step to elucidate the molecular processes that underlie the differential impact of cell metabolites on compositionally distinct lipid membranes.

Effect of covalently functionalized Indian bentonite clay on thermal, mechanical strength and morphology structure of extrusion/injection-molded nylon 6 composites - Shanmugam, Kumaresan; Rokade, Dhammaraj S.; Ingole, Pravin G.; Pol, Harshawardhan V.; Arunachalam, Saravanakumar; Bajaj, Hari C. (Polymers for Advanced Technologies, 2024)
The research and development of functional polymer composites and their production have posed significant challenges, particularly in creating high mechanical strength and thermal stability composites. In this study, we utilized a micro corotation extruder and injection molding to produce covalently functionalized Indian bentonite clay-nylon 6 high-strength nanocomposites. For comparison, two different amines, 3-aminopropyl trimethoxysilane and N-[3-(trimethoxysilyl) propyl] ethylene di-amine, were used to functionalize bentonite clay. Additionally, 3% and 5% less amino clay filler was added in the nanocomposite to manufacture the polymer composite. Analytical techniques such as Powder X-Ray Diffraction, Fourier transform infrared, thermal gravimetric analysis, and Brunauer-Emmett-Teller surface area were used to characterize the molecular orientation of amine functionalization on clay minerals. Wide-angle X-ray diffraction, atomic force microscopy, and transmission electron microscope were used to characterize the nylon 6 intercalated in amino clay nanocomposite and the polymer structure morphology. Thermogravimetric analysis and differential scanning calorimetry were used to investigate the crystalline thermal behavior of clay-nylon 6 composites. From the results, it was observed that the composition containing 5 wt.% amino clay demonstrated a significant improvement in tensile strength when compared with the composition containing 3 wt.% amino clay. The mechanical strength and the thermal behavior showed a significant improvement of similar to 200% for 5% amino clay-nylon 6 nanocomposite.
Keywords: amine-functionalized clay; bentonite clay; melt intercalation; Nanocomposite; nylon 6; thermal and mechanical properties

Effect of the presence of pinned particles on the structural parameters of a liquid and correlation between structure and dynamics at the local level - Patel, Palak; Bhattacharyya, Sarika Maitra (Journal of Chemical Physics, 2024)
Pinning particles at the equilibrium configuration of the liquid is expected not to affect the structure and any property that depends on the structure while slowing down the dynamics. This leads to a breakdown of the structure dynamics correlation. Here, we calculate two structural quantities: the pair excess entropy, S-2, and the mean field caging potential, the inverse of which is our structural order parameter (SOP). We show that when the pinned particles are treated the same way as the mobile particles, both S-2 and SOP of the mobile particles remain the same as those of the unpinned system, and the structure dynamics correlation decreases with an increase in pinning density, ``c.'' However, when we treat the pinned particles as a different species, even if we consider that the structure does not change, the expression of S-2 and SOP changes. The microscopic expressions show that the interaction between a pinned particle and a mobile particle affects S-2 and SOP more than the interaction between two mobile particles. We show that a similar effect is also present in the calculation of the excess entropy and is the primary reason for the well-known vanishing of the configurational entropy at high temperatures. We further show that, contrary to the common belief, the pinning process does change the structure. When these two effects are considered, both S-2 and SOP decrease with an increase in ``c,'' and the correlation between the structural parameters and the dynamics continues even for higher values of ``c.''

Efficient glycolysis of used PET bottles into a high-quality valuable monomer using a shape-engineered MnO nanocatalyst - Swapna, Bhattu; Singh, Nittan; Patowary, Suranjana; Bharali, Pankaj; Madras, Giridhar; Sudarsanam, Putla (CATALYSIS SCIENCE & TECHNOLOGY, 2024)
Keywords: Catalyst; kinetics; Nanorods; Oxidation; Oxides; POLY(ETHYLENE-TEREPHTHALATE); WASTE

Electrocatalytic and selective oxidation of glycerol to formate on 2D 3d-metal phosphate nanosheets and carbon-negative hydrogen generation - Chauhan, Inderjeet; Vijay, Pothoppurathu M.; Ranjan, Ravi; Patra, Kshirodra Kumar; Gopinath, Chinnakonda S. (ACS Materials Au, 2024)
In the landscape of green hydrogen production, alkaline water electrolysis is a well-established, yet not-so-cost-effective, technique due to the high overpotential requirement for the oxygen evolution reaction (OER). A low-voltage approach is proposed to overcome not only the OER challenge by favorably oxidizing abundant feedstock molecules with an earth-abundant catalyst but also to reduce the energy input required for hydrogen production. This alternative process not only generates carbon-negative green H2 but also yields concurrent value-added products (VAPs), thereby maximizing economic advantages and transforming waste into valuable resources. The essence of this study lies in a novel electrocatalyst material. In the present study, unique and two-dimensional (2D) ultrathin nanosheet phosphates featuring first-row transition metals are synthesized by a one-step solvothermal method, and evaluated for the electrocatalytic glycerol oxidation reaction (GLYOR) in an alkaline medium and simultaneous H2 production. Co3(PO4)2 (CoP), Cu3(PO4)2 (CuP), and Ni3(PO4)2 (NiP) exhibit 2D sheet morphologies, while FePO4 (FeP) displays an entirely different snowflake-like morphology. The 2D nanosheet morphology provides a large surface area and a high density of active sites. As a GLYOR catalyst, CoP ultrathin (∼5 nm) nanosheets exhibit remarkably low onset potential at 1.12 V (vs RHE), outperforming that of NiP, FeP, and CuP around 1.25 V (vs RHE). CoP displays 82% selective formate production, indicating a superior capacity for C–C cleavage and concurrent oxidation; this property could be utilized to valorize larger molecules. CoP also exhibits highly sustainable electrochemical stability for a continuous 200 h GLYOR operation, yielding 6.5 L of H2 production with a 4 cm2 electrode and 98 ± 0.5% Faradaic efficiency. The present study advances our understanding of efficient GLYOR catalysts and underscores the potential of sustainable and economically viable green hydrogen production methodologies.

Electrocatalytic glycerol conversion: a low-voltage pathway to efficient carbon-negative green hydrogen and value-added chemical production - Chauhan, Inderjeet; Bajpai, Himanshu; Ray, Bishakha; Kolekar, Sadhu K.; Datar, Suwarna; Patra, Kshirodra Kumar; Gopinath, Chinnakonda S. (ACS Applied Materials and Interfaces, 2024)
Electrochemical glycerol oxidation reaction (GLYOR) could be a promising way to use the abundantly available glycerol for production of value-added chemicals and fuels. Completely avoiding the oxygen evolution reaction (OER) with GLYOR is an evolving strategy to reduce the overall cell potential and generate value-added chemicals and fuels on both the anode and cathode. We demonstrate the morphology-controlled palladium nanocrystals, afforded by colloidal chemistry, and their established morphology-dependent GLYOR performance. Although it is known that controlling the morphology of an electrocatalyst can modulate the activity and selectivity of the products, still it is a relatively underexplored area for many reactions, including GLYOR. Among nanocube (Pd-NC), truncated octahedron (Pd-TO), spherical and polycrystalline (Pd-PC) morphologies, the Pd-NC electrocatalyst deposited on a Ni foam exhibits the highest glycerol conversion (85%) along with 42% glyceric acid selectivity at a low applied potential of 0.6 V (vs reversible hydrogen electrode (RHE)) in 0.1 M glycerol and 1 M KOH at ambient temperature. Owing to the much favorable thermodynamics of GLYOR on the Pd-NC surface, the assembled electrolyzer requires an electricity input of only similar to 3.7 kWh/m(3) of H-2 at a current density of 100 mA/cm(2), in contrast to the requirement of >= 5 kWh/m(3) of H-2 with an alkaline/PEM electrolyzer. Sustainability has been successfully demonstrated at 10 and 50 mA/cm(2) and up to 120 h with GLYOR in water and simulated seawater.
Keywords: electrocatalysis; Glycerol; green hydrogen; nanocube; Palladium; SDG

Electrodeposited Co-Mn-Sn multicomponent alloy as an efficient electrocatalyst for hydrogen evolution reaction - Chandran, M. Athira; Karumuthil, Subash Cherumannil; Singh, Ashutosh K.; Prasad, Bhagavatula L. V. (International Journal of Hydrogen Energy, 2024)
Despite having exciting material characteristics, the potential of multi-component alloys (MCAs) as electrocatalysts has not been fully realized. In this work, efficient binary and ternary MCA electrocatalysts containing inexpensive metals like Co, Mn and Sn have been prepared via the electrodeposition process. When tested for hydrogen evolution reaction (HER) in an alkaline medium, ternary Co-Mn-Sn alloy displayed enhanced activity with the lowest overpotential of 136 mV, a Tafel slope of 111 mV dec 1 and a very low charge transfer resistance, making it superior to the binary alloys (Co-Mn and Co-Sn), or the single metal catalysts (Co, Mn and Sn). The ternary alloy also displayed high electro-chemical and structural stability, making it a viable electrocatalyst for the hydrogen economy.(c) 2023 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Keywords: Clean energy; electrocatalysis; Electrodeposition; hydrogen evolution reaction; Multi-component alloy; Non-platinum group metals

Enhancing the crystallization kinetics and mechanical properties of poly(lactic acid) blends for 3D printing application - Kothavade, Premkumar; Yadav, Prashant; Gopal, Animesh; Pol, Harshawardhan; Kafi, Abdullah; Bateman, Stuart; Shanmuganathan, Kadhiravan (ACS Applied Polymer Materials, 2024)
3D printing of poly(lactic acid) (PLA) blends has been attempted to resolve issues such as inherent brittleness and slow crystallization rate of PLA. However, a persistent challenge remains in the form of phase separation or gradual migration of the blended soft polymer or plasticizers. To simultaneously enhance the miscibility of the blends and toughness of 3D-printed parts, a triblock copolymer PLA-PEG-PLA was synthesized and blended with PLA in varying proportions (5, 10, 15, and 20 wt %). Blending only 10-20 wt % low molecular weight PLA-PEG-PLA into PLA yielded a miscible blend that showed a 45-fold increase in elongation at break and a 23-fold enhancement in toughness over neat PLA. Scanning electron microscopy (SEM) images of fractured cross sections revealed a brittle to ductile transition in 3D-printed PLA/PLA-PEG-PLA samples. Isothermal crystallization studies and data analysis using the Avrami equation showed an enhancement in the crystal growth rate and overall rate of crystallization. The blends achieved half of their crystallinity in approximately 3 min, a significant improvement over the 9 min required by PLA alone. This underscores the efficiency of our approach. This was also evident in the spherulite growth of 3D-printed PLA and mPLA blends when examined using polarized optical microscopy (POM). To the best of our knowledge, this is the first report exploring the use of blends that include PLA and low molecular weight PLA-PEG-PLA triblock copolymers for 3D printing applications.
Keywords: Crystallization; FFF 3D printing; PLA-PEG-PLA triblock copolymer; poly(lacticacid); toughness

Establishing a new efficiency descriptor for methanol oxidation reaction and its validation with commercially available Pt-based catalysts - Deshpande, Pooja S.; Radhakrishnan, Thulasi; Prasad, Bhagavatula L. V. (Fuel Cells, 2024)
Direct methanol fuel cells (DMFCs) have received a lot of attention in recent years as promising technology for generating clean and efficient energy. In DMFC, the anode catalyst is a vital component because it is involved in the oxidation of methanol, which produces electrons that can be used as an energy source. Cyclic voltammetry (CV) is commonly used to test the characteristics of the electrode materials before they are employed in the actual fuel cell. Interestingly in the case of DMFCs CV also is a useful technique to obtain vital information about the performance and expected efficiency of the electrodes. In general, the CV of methanol electrooxidation for Pt-based catalysts has two peaks, If in the forward scan (anodic scan) and Ib in the backward scan (cathodic scan). The ratio of these two peaks (If/Ib) is the most commonly used criterion for investigating CO poisoning in catalysts. However, there is a great deal of ambiguity surrounding this criterion, owing to the genesis of Ib. Addressing this we present here a new criterion to evaluate the efficiency of the catalyst using the same CV technique. We validate this newly proposed criterion with commercial Pt/C (comm. Pt/C) and other commercially available alloy catalysts.
Keywords: catalyst poisoning; CO tolerance; direct methanol fuel cells; electrocatalysis; Methanol oxidation reaction

Exploring defect-engineered metal-organic frameworks with 1,2,4-triazolyl isophthalate and benzoate linkers - Chetry, Sibo; Lukman, Muhammad Fernadi; Bon, Volodymyr; Warias, Rico; Fuhrmann, Daniel; Moellmer, Jens; Belder, Detlev; Gopinath, Chinnakonda S.; Kaskel, Stefan; Poeppl, Andreas; Krautscheid, Harald (INORGANIC CHEMISTRY, 2024)
Keywords: Separation; spectroscopy; TRIAZOLYL

Exploring the soft pinning effect in the dynamics and the structure-dynamics correlation in multicomponent supercooled liquids - Anwar, Ehtesham; Patel, Palak; Sharma, Mohit; Bhattacharyya, Sarika Maitra (Journal of Chemical Physics, 2024)
We study multicomponent liquids by increasing the mass of 15% of the particles in a binary Kob-Andersen model. We find that the heavy particles have dual effects on the lighter particles. At higher temperatures, there is a significant decoupling of the dynamics between heavier and lighter particles, with the former resembling a pinned particle to the latter. The dynamics of the lighter particles slow down due to the excluded volume around the nearly immobile heavier particles. Conversely, at lower temperatures, there is a coupling between the dynamics of the heavier and lighter particles. The heavier particles' mass slows down the dynamics of both types of particles. This makes the soft pinning effect of the heavy particles questionable in this regime. We demonstrate that as the mass of the heavy particles increases, the coupling of the dynamics between the lighter and heavier particles weakens. Consequently, the heavier the mass of the heavy particles, the more effectively they act as soft pinning centers in both high and low-temperature regimes. A key finding is that akin to the pinned system, the self-dynamics and collective dynamics of the lighter particles decouple from each other as the mass of the heavy particles has a more pronounced impact on the latter. We analyze the structure-dynamics correlation by considering the system under the binary and modified quaternary framework, the latter describing the pinned system. Our findings indicate that whenever the heavy mass particles function as soft pinning centers, the modified quaternary framework predicts a higher correlation.

Exploring the synthesis, characterization, electrical, and magnetic behavior of crystalline Ni1-xZnxFe2O4 nanoparticles - Adsure, Kiran T.; Jagtap, Sumant B.; Newaskar, Shivkumar R.; Kore, Kiran B.; Funde, Adinath M.; Patange, Sunil M.; Late, Dattatray J. (JOURNAL OF MATERIALS SCIENCE-MATERIALS IN ELECTRONICS, 2024)
Keywords: CO; DC RESISTIVITY; DIELECTRIC-PROPERTIES; FERRITE NANOPARTICLES; Ni; Substitution; ZN

Extraction, characterization, and life cycle assessment of nanosilica from millet husk: sustainable alternative with low environmental impact - Dominic, C. D. Midhun; Rosa, Derval dos Santos; Barbosa, Rennan Felix da Silva; Anagha, O. V.; Neenu, K. V.; Begum, P. M. Sabura; Kumar, V. Aswathy; Parameswaranpillai, Jyotishkumar; Siriwong, Chomsri; Ajithkumar, T. G.; Shelke, Ankita; Pasc, Andreea (Journal of Cleaner Production, 2024)
Eco-friendly approaches for silica production are highly researched to respond increasing industrial demand for bio-nanofillers. Herein, nanosilica of 10-20 nm with mesoporosity was obtained through a mild oxalic acid pre-treatment of millet husk, followed by calcination at 700 degrees C for 2 h. Compared with commercial precipitated silica (CS) and millet husk ash (MHA) directly obtained by calcination of the husk, the pre-treated silica (MHS) had higher purity, revealed using EDX spectroscopy. Moreover, FTIR and Si-29 NMR showed a higher condensation degree in MHS with 73% of Q4 siloxane bonds vs 4% in MHA. The release of the metal and organic impurities from the husk also allows to reduce the crystallinity of MHS, and to increase the specific surface area from 82 m(2)/g in MHA to 238 m(2)/g in MHS. The type II N-2 adsorption-desorption isotherms of MHA and MHS indicate aggregates of non-porous silica particles. MHS also demonstrated remarkable thermal resilience. According to the LCA analysis, MHS has a 40% lower impact on global warming, a 38% lower impact on human carcinogenic toxicity, and a 38% lower impact on terrestrial acidification compared to rice husk nanosilica. This research thus addresses sustainability challenges by repurposing millet husks, which are readily available due to continuous millet cultivation, particularly in India. By reducing the ecological impact of husk disposal through burning, this study offers an economically viable technology for high-purity silica production, aligning with global efforts to combat climate change and promote sustainable practices.
Keywords: Life cycle assessment; Millet husk; Nanosilica; Oxalic acid

Fabrication and evaluation of a spatially resolved fiber-optic probe for diffuse reflectance measurement for noninvasive diabetic foot ulcer diagnosis perspective - Kumar, Ajay; Hattale, Gangadhar; Pawar, Dnyandeo; Kanawade, Rajesh (Optical Engineering, 2024)
Timely diagnosis and monitoring of wound progression or healing are key to improving the long-term outcome of diabetic foot ulcers (DFU). Diffuse reflectance spectroscopy (DRS) has the potential to noninvasively diagnose the DFU in real time, as it detects changes in local blood volume fraction and oxygenation state level that occur when tissue becomes diseased or ulcerated. Since foot soles have a thicker epidermis and deeper blood vessels/capillaries than other parts of the body, a spatially resolved fiber-optic probe (SRFP) is needed to detect the optimal spatially resolved diffuse reflectance (SRDR) signal from the local site of the ulcer for DFU diagnosis. Therefore, herein, an SRFP consisting of a linear array of seven 400-mu m fibers with detector-source (D-S) fiber separation (rho) ranging from 0.8 to 4.8 mm was designed, fabricated, tested, and evaluated for SRDR measurement from a standard reflectance plate of barium sulfate (BaSO4) and foot sole of 27 healthy human subjects. The variation in SRDR spectra for each detector and source fiber pair measured with BaSO4 was found to be less than 1.6%. In-vivo measurements from the foot sole demonstrate that the fabricated probe has the ability to spatially resolve and distinguish the SRDR spectra from sites, namely, the fifth metatarsal, ball of great joint, calcaneum, and great toe. Experimentally and theoretically, the detector and source fiber pair of rho=1.6 and 2.4 mm were optimal for SRDR measurements from a human foot. To evaluate and validate the performance of SRFP in a context relevant to DFU diagnosis, further SRDS measurements were performed on the solid tissue phantoms that mimic the optical properties of the normal and diabetic foot sole, and their results are statistically found different. Preliminary results suggest that developed SRFP can be explored for DRS measurement from foot ulcer patients to confirm its potential clinical applicability.
Keywords: diabetic foot ulcer; diffuse reflectance spectroscopy; foot sole; spatially resolved fiber-optic probe; tissue phantom

Facile synthesis of nanostructured Ni/NiO/N-doped graphene electrocatalysts for enhanced oxygen evolution reaction - Madampadi, Roshni; Patel, Avit Bhogilal; Vinod, C. P.; Gupta, Ritu; Jagadeesan, Dinesh (Nanoscale Advances, 2024)
Electrocatalysts containing a Ni/NiO/N-doped graphene interface have been synthesised using the ligand-assisted chemical vapor deposition technique. NiO nanoparticles were used as the substrate to grow N-doped graphene by decomposing vapours of benzene and N-containing ligands. The method was demonstrated with two nitrogen-containing ligands, namely dipyrazino[2,3-f:2 `,3 `-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile (L) and melamine (M). The structure and composition of the as-synthesized composites were characterized by XRD, Raman spectroscopy, SEM, TEM and XPS. The composite prepared using the ligand L had NiO sandwiched between Ni and N-doped graphene and showed an overpotential of 292 mV at 10 mA cm-2 and a Tafel slope of 45.41 mV dec-1 for the OER, which is comparable to the existing noble metal catalysts. The composite prepared using the ligand M had Ni encapsulated by N-doped graphene without NiO. It showed an overpotential of 390 mV at 10 mA cm-2 and a Tafel slope of 78.9 mV dec-1. The ligand-assisted CVD route demonstrates a facile route to control the microstructure of the electrocatalysts. Electrocatalysts containing a Ni/NiO/N-doped graphene interface have been synthesised using the ligand-assisted chemical vapor deposition technique.

Far-red active unsymmetrical squaraine dyes containing N-arylated indoline donors for dye sensitized solar cells - Jadhav, Avinash P.; Singh, Ambarish Kumar; Pandya, Rinu; Vanka, Kumar; Krishnamoorthy, Kothandam; Jayaraj, Nithyanandhan (Photochemistry and Photobiology, 2024)
Squaraine dyes possess sharp far-red active transition with high extinction coefficient and form aggregates on TiO2 surface. Aggregation of dyes on TiO2 has been considered as a detrimental factor for DSSC device performance, which can be controlled by appending alkyl groups to the dye structures. Hence by integrating alkylated (alkyl groups with both in-plane and out-of-plane) aryl group with indoline moiety to make it compatible with other electrolytes and for controlling the dye-aggregation, a series of squaraine acceptor-based dyes SQA4-6 have been designed and synthesized. SQA4-6 dyes showed absorption between 642 and 653 nm (lambda max), photophysical and electrochemical studies indicated that the HOMO energy levels of this sets of dyes are well aligned with the potentials of I-/I3-\$\$ {\textbackslashmathrm{I}}_3<\^>{-} \$\$ and [Co(bpy)3]2+/3+ redox shuttles for better dye regeneration process. DSSC device efficiency of 3% has been achieved for SQA5 dye with iodolyte (I-/I3-\$\$ {\textbackslashmathrm{I}}_3<\^>{-} \$\$) electrolyte in the presence of 0.3 mM of chenodeoxycholic acid (CDCA). The IPCE profile of DSSC device fabricated with SQA4-6 dyes indicated the contribution of aggregated structures for the photocurrent generation. Dye-sensitized solar cell (DSSC) device efficiency of 3% (Jsc 5.72 mA cm-2, Voc 662 mV and ff 79%) has been achieved for an unsymmetrical squaraine dye, SQA5 with iodolyte electrolyte and the incident photon to current efficiency (IPCE) profile indicates the contribution of aggregated structures for the photocurrent generation.*image
Keywords: aggregation of dye; arylation on N-atom of indoline donor; dye-sensitized solar cell; squaraine dye

Feedback driven autonomous cycles of assembly and disassembly from minimal building blocks - Reja, Antara; Jha, Sangam; Sreejan, Ashley; Pal, Sumit; Bal, Subhajit; Gadgil, Chetan; Das, Dibyendu (Nature Communications, 2024)
The construction of complex systems by simple chemicals that can display emergent network dynamics might contribute to our understanding of complex behavior from simple organic reactions. Here we design single amino acid/dipeptide-based systems that exhibit multiple periodic changes of (dis)assembly under non-equilibrium conditions in closed system, importantly in the absence of evolved biocatalysts. The two-component based building block exploits pH driven non-covalent assembly and time-delayed accelerated catalysis from self-assembled state to install orthogonal feedback loops with a single batch of reactants. Mathematical modelling of the reaction network establishes that the oscillations are transient for this network structure and helps to predict the relative contribution of the feedback loop to the ability of the system to exhibit such transient oscillation. Such autonomous systems with purely synthetic molecules are the starting point that can enable the design of active materials with emergent properties. The study of the network dynamics of complex systems formed by simple chemicals can contribute to our understanding of complex behavior from simple organic reactions. Here, built on the minimal building blocks, the authors describe a system with periodic (dis)assembly utilizing feedback loops controlled by time-delayed catalysis and pH-driven assembly.

Ferric oxide nanocatalyst: synthesis, characterization, and application in the one-pot three-component synthesis of 3,4,5-trisubstituted isoxazole derivatives - Totre, Ganesh; Shinde, Dnyaneshwar; Shirsath, Sachin; Patil, Prakash; Kulkarni, Pramod (Monatshefte Fur Chemie, 2024)
In this study, we have focused on the preparation and application of a nano-ferric oxide catalyst as a heterogeneous catalyst in the one-pot, three-component synthesis of isoxazole derivatives. The ferric oxide catalyst was synthesized using a simple precipitation method and thoroughly characterized using techniques such as FT-IR, XRD, SEM, EDX, and BET. The effectiveness of the ferric oxide catalyst as a heterogeneous catalyst was investigated in the synthesis of 3,4,5-trisubstituted isoxazole. The results of the synthesis demonstrated that the catalyst exhibited high efficiency in facilitating the three-component, one-pot synthesis of 3,4,5-trisubstituted isoxazole derivatives. The synthesis route employed in this study offers several advantages, including its simplicity, ease of workup, and environmental friendliness. Furthermore, the catalyst was successfully recovered and reused for five cycles without experiencing a significant loss in catalytic activity. This finding highlights the excellent stability and promising potential of the catalyst for organic transformations. Overall, our study showcases the successful preparation and application of the nano-ferric oxide catalyst in the synthesis of isoxazole derivatives, providing valuable insights into its catalytic performance and potential for future applications in organic chemistry.
Keywords: Ferric oxide nanoparticles; heterogeneous catalyst; Isoxazole; Multicomponent reaction

Functionalized quinolones and isoquinolones via 1,2-difunctionalization of arynes: synthesis of antagonist agent AS2717638 and floxacin key intermediates - Mahale, Sachin D.; Prasad, Anamika; Mhaske, Santosh B. (Chemical Communications, 2024)
Quinolones and isoquinolones are privileged scaffolds in synthetic/medicinal chemistry and drug discovery due to their unique chemical structures and intrinsic properties. Herein, we reveal a transition-metal-free approach for their synthesis from the reaction of dimethyl-2-((phenylamino)methylene)malonate with aryne precursors under mild conditions. The substrate scope is broad, accommodating a wide range of functional groups. The synthetic utility of the developed protocol has been demonstrated in the total synthesis of the potent antagonist agent AS2717638 and key intermediates of floxacin congeners. The gram-scale experiments illustrate its synthetic potential.

Genome sequencing and protein modeling unraveled the 2AP biosynthesis in Bacillus cereus DB25 - Dhondge, Harshal V.; Barvkar, Vitthal T.; Dastager, Syed G.; Dharne, Mahesh S.; Rajput, Vinay; Pable, Anupama A.; Henry, Robert J.; Nadaf, Altafhusain B. (International Journal of Food Microbiology, 2024)
2-Acetyl-1-pyrroline (2AP) is an important and major flavor aroma compound responsible for the fragrance of basmati rice, cheese, wine, and several other food products. Biosynthesis of 2AP in aromatic rice and a few other plant species is associated with a recessive Betaine aldehyde dehydrogenase 2 (BADH2) gene. However, the literature is scant on the relationship between the functional BADH2 gene and 2AP biosynthesis in prokaryotic systems. Therefore, in the present study, we aimed to explore the functionality of the BADH2 gene for 2AP biosynthesis in 2AP synthesizing rice rhizobacterial isolate Bacillus cereus DB25 isolated from the rhizosphere of basmati rice (Oryza sativa L.). Full-length BcBADH2 sequence was obtained through whole genome sequencing (WGS) and further confirmed through traditional PCR and Sanger sequencing. Then the functionality of the BcBADH2 gene was evaluated in-silico through bioinformatics analysis and protein docking studies and further experimentally validated through enzyme assay. The sequencing and bioinformatics analysis results revealed a full-length 1485 bp BcBADH2 coding sequence without any deletion or premature stop codons. Full-length BcBADH2 was found to encode a fully functional protein of 54.08 kDa with pI of 5.22 and showed the presence of the conserved amino acids responsible for enzyme activity. The docking studies confirmed a good affinity between the protein and its substrate whereas the presence of BcBADH2 enzyme activity confirmed the functionality of BADH2 enzyme in B. cereus DB25. In conclusion, the findings of the present study suggest that B. cereus DB25 is able to synthesize 2AP despite a functional BADH2 gene and there may be a different molecular mechanism responsible for 2AP biosynthesis in bacterial systems, unlike that found in aromatic rice and other eukaryotic plant species.
Keywords: 2-Acetyl-1-pyrroline; Basmati rice flavor; Betaine aldehyde dehydrogenase 2; Protein-ligand docking; Rhizobacteria; Whole-genome sequence

Glory of fire retardants in Li-ion batteries: could they be intrinsically safer? - Mishra, Rajat; Anne, Mounika; Das, Sayan; Chavva, Tarunikaa; Shelke, Manjusha V.; Pol, Vilas G. (Advanced Sustainable Systems, 2024)
Lithium-ion batteries (LIBs) have dramatically transformed modern energy storage, powering a wide range of devices from portable electronics to electric vehicles, yet the use of flammable liquid electrolytes raises thermal safety concerns. Researchers have investigated several ways to enhance LIB's fire resistance. Fire retarding molecules functions through cooling effects, scavenging radicals, and forming protective barriers. Incorporating fire-suppressing molecules within the LIBs aims to delay or mitigate thermal runaway scenarios, reducing the risks of fires or explosions. Achieving an optimal balance between safety and performance is a major obstacle in the design of intrinsically safer LIBs. Therefore, it is important to consider their effects on LIB's performance, long-term stability, and environmental impact. To overcome these challenges, collaborative research efforts among academia, industry, and regulatory sectors are necessary. This article reviews state-of-the-art literature associated with LIBs safety or even fire mitigation by introducing solid-state or quasi-solid-state electrolytes as well as modified liquid electrolytes. Moreover, the effectiveness of various strategies in making LIBs intrinsically safer is critically evaluated with an emphasis on fire retardants followed by shedding some light on the remaining challenges.

Green synthesis of silver and gold ultra nanocomposites from silk fibroin and their application for treatment of endodontic infections - Pramod C.; Pawar, Jayant; Mane, Deepali P.; Khadase, Ashok N.; Chaudhari, Aditya R.; Ughade, Supriya P.; Chaudhari, Ravindra D.; Agawane, Sachin B. (Emergent Materials, 2024)
The present study is designed to investigate the antibacterial efficacy of B. mori silk fibroin based silver and gold ultra bio-nanocomposites (SF-AgUNC and SF-AuUNC) against Enterococcus faecalis for endodontic disinfection. The SF-AgUNC and SF-AuUNC based irrigant solution was tested in- vitro against Enterococcus faecalis (ATCC: 29212). In this direction, SF-AgUNC and SF-AuUNC synthesized by silk fibroin are very important as they are economically cheap and easy to biosynthesize. The synthesis of SF-AgUNC and SF-AuUNC was accomplished by dissolving 1 mM silver nitrate and 0.5 mM auric chloride respectively in 10 ml of fibroin as precursors. The structural and morphological analysis was executed by UV-Vis Spectroscopy, X-ray diffraction (XRD), Fourier transform infrared spectroscopic analysis (FTIR), Field Emission Scanning Electron Microscopy (FESEM), Transmission electron microscopy (TEM), Energy-dispersive X-ray spectroscopy (EDAX) and X-ray photoelectron spectroscopy (XPS). The qualitative antimicrobial activity of SF-AgUNC and SF-AuUNC were performed against inoculum of Enterococcus faecalis containing 1⨯105 CFU/ ml. The same solutions were tested on dentine specimens inoculated with bacterial cultures and found remarkable biofilm reduction. The structural and morphological analysis reveals the formation of SF-AgUNC and SF-AuUNC having quasi-spherical morphology. The average particle size for SF-AgUNC and SF-AuUNC was same (~ 8 nm). The XRD study confirms that, both SF-AgUNC and SF-AuUNC were crystalline in nature. The bacterial growth inhibition and significant biofilm reduction was observed on dentine specimens treated with SF-AgUNC, SF-AuUNC and positive control. In antibacterial study, at 30 μg/well concentration of SF-AgUNC and SF-AuUNC, 3.13 ± 0.22 and 1.13 ± 0.22 cm of zone of inhibition was noted respectively. Moreover, growth of Enterococcus faecalis was completely inhibited at 20 μg/ml and 30 μg/ml when treated with SF-AgUNC and SF-AuUNC respectively. Hence, the present study concludes that SF-AgUNC and SF-AuUNC can be used as an effective intracanal medicament for the treatment of dental problems with no cyto toxicity.

Hexagonal boron nitride quantum dots embedded on layer-by-layer films for peroxidase-assisted colorimetric detection of β-galactosidase producing pathogens - Majumdar, Sristi; Gogoi, Devipriya; Boruah, Purna K.; Thakur, Ashutosh; Sarmah, Priyakhee; Gogoi, Parishmita; Sarkar, Sanjib; Pachani, Priyakshi; Manna, Prasenjit; Saikia, Ratul; Chaturvedi, Vikash; Shelke, Manjusha V.; et al. (ACS Applied Materials and Interfaces, 2024)
Pathogen detection has become a major research area all over the world for water quality surveillance and microbial risk assessment. Therefore, designing simple and sensitive detection kits plays a key role in envisaging and evaluating the risk of disease outbreaks and providing quality healthcare settings. Herein, we have designed a facile and low-cost colorimetric sensing strategy for the selective and sensitive determination of beta-galactosidase producing pathogens. The hexagonal boron nitride quantum dots (h-BN QDs) were established as a nanozyme that showed prominent peroxidase-like activity, which catalyzes 3,3 `,5,5 `-tetramethylbenzidine (TMB) oxidation by H2O2. The h-BN QDs were embedded on a layer-by-layer assembled agarose biopolymer. The beta-galactosidase enzyme partially degrades beta-1,4 glycosidic bonds of agarose polymer, resulting in accessibility of h-BN QDs on the solid surface. This assay can be conveniently conducted and analyzed by monitoring the blue color formation due to TMB oxidation within 30 min. The nanocomposite was stable for more than 90 days and was showing TMB oxidation after incubating it with Escherichia coli (E. coli). The limit of detection was calculated to be 1.8 x 10(6) and 1.5 x 10(6) CFU/mL for E. coli and Klebsiella pneumonia (K. pneumonia), respectively. Furthermore, this novel sensing approach is an attractive platform that was successfully applied to detect E. coli in spiked water samples and other food products with good accuracy, indicating its practical applicability for the detection of pathogens in real samples.
Keywords: biopolymer; colorimetric; h-BN quantum dots; nanozyme; pathogens; Sensor

Highly electrostrictive salt cocrystal and the piezoelectric nanogenerator application of its 3D-printed polymer composite - Sahoo, Supriya; Panday, Rishukumar; Kothavade, Premkumar; Sharma, Vijay Bhan; Sowmiyanarayanan, Anirudh; Praveenkumar, Balu; Zareba, Jan K.; Kabra, Dinesh; Shanmuganathan, Kadhiravan; Boomishankar, Ramamoorthy (ACS Applied Materials and Interfaces, 2024)
Ionic cocrystals with hydrogen bonding can form exciting materials with enhanced optical and electronic properties. We present a highly moisture-stable ammonium salt cocrystal [CH3C6H4CH(CH3)NH2][CH3C6H4CH(CH3)NH3][PF6] ((p-TEA)(p-TEAH)PF6) crystallizing in the polar monoclinic C2 space group. The asymmetry in (p-TEA)(p-TEAH)PF6 was induced by its chiral substituents, while the polar order and structural stability were achieved by using the octahedral PF6- anion and the consequent formation of salt cocrystal. The ferroelectric properties of (p-TEA)(p-TEAH)PF6 were confirmed through P-E loop measurements. Piezoresponse force microscopy (PFM) enabled the visualization of its domain structure with characteristic ``butterfly'' and hysteresis loops associated with ferro- and piezoelectric properties. Notably, (p-TEA)(p-TEAH)PF6 exhibits a large electrostrictive coefficient (Q(33)) value of 2.02 m(4) C-2, higher than those found for ceramic-based materials and comparable to that of polyvinylidene difluoride. Furthermore, the composite films of (p-TEA)(p-TEAH)PF6 with polycaprolactone (PCL) polymer and its gyroid-shaped 3D-printed composite scaled-up device, 3DP-Gy, were prepared and evaluated for piezoelectric energy-harvesting functionality. A high output voltage of 22.8 V and a power density of 118.5 mu W cm(-3) have been recorded for the 3DP-Gy device. Remarkably, no loss in voltage outputs was observed for the (p-TEA)(p-TEAH)PF6 devices even after exposure to 99% relative humidity, showcasing their utility under extremely humid conditions.
Keywords: 3D printing; cocrystals; energy harvesting; ferroelectricity; Piezoelectricity

High-voltage symmetric supercapacitor electrodes via in situ synthesized multiwalled carbon nanotube-doped perylenebisimide-based donor-acceptor conjugate polymer P(PDI2OD-T2) - Wavhal, Aryan Anurath; Dilwale, Swati; Puthiyaveetil, Priyanka Pandinhare; Kakde, Navnath R.; Prakash, Medha; Kurungot, Sreekumar; Asha, S. K. (Journal of Physical Chemistry C, 2024)
This study presents the design and synthesis of a donor-acceptor pi-conjugated polymer composite P(PDI2OD-T2)/MWCNT tailored for high-voltage symmetric supercapacitor applications. The synthesis of P(PDI2OD-T2)/MWCNT was expedited by adopting a novel in situ polymerization technique that modifies the traditional Stille polymerization process. Incorporating approximately 33% by weight of multiwalled carbon nanotubes (MWCNT) into the polymer matrix, referred to as P-2, significantly enhances its conductivity, surface area, and porosity. These improvements in the material properties contribute to the superior electrochemical performance of the composites by promoting efficient electrolyte ion transport across the electrode-electrolyte interfaces. The symmetric supercapacitor devices fabricated with P-2 electrodes employing both liquid organic (LE-P-2||P-2) and quasi-solid-state gel (QSS- P-2||P-2) electrolytes demonstrate capacitance values of 85.4 and 84.2 F g(-1), respectively, at a current density of 0.25 A g(-1), while operating at a high-voltage window of 3.1 V. Moreover, these devices exhibit robust cycling stability, maintaining approximately 70% of their initial capacitance over 45,000 cycles with a coulombic efficiency of 96%. The successful demonstration of a quasi-solid-state symmetric supercapacitor underscores the potential of flexible energy storage solutions, as evidenced by a PMMA LiClO4 gel electrolyte prototype. This flexible device not only maintains structural integrity but also achieves an impressive power density of 18,600 W kg(-1) and an energy density of 112.4 Wh kg(-1), indicating its practical viability for real-world applications.

Hybrid silylene-Pd catalyst: efficient C-N cross-coupling of sterically bulky amines and chiral amines - Kaulage, Sandeep H.; Parvin, Nasrina; Khopade, Kishor V.; Khan, Shabana (Chemical Communications, 2024)
Herein, we report a catalytic system with N-heterocyclic silylene (NHSi)-phosphine-based hybrid bidentate ligands [PhC(NtBu)2SiN(PR2)(2,6-iPr2-C6H3)] and Pd(dba)2, which serves as an effective catalyst for C-N cross-coupling of a wide range of sterically bulky amines and optically active amines, which is challenging otherwise. Herein, we report a hybrid silylene-based bidentate ligand (SiNP)-Pd(0) catalytic system, which performs the C-N coupling of difficult substrates, e.g., sterically bulky amines and chiral amines.

I2-catalyzed three-component synthesis of 3-selenylated pyrazolo[1,5-a]pyrimidines - Choudhuri, Tathagata; Paul, Suvam; Sikdar, Papiya; Das, Sourav; Sawant, Sanghapal D.; Bagdi, Avik Kumar (New Journal of Chemistry, 2024)
A straightforward protocol has been developed to access 3-selenylated pyrazolo[1,5-a]pyrimidines from readily available amino pyrazoles, chalcones, and diaryl/dialkyl diselenides. This I-2-catalyzed methodology is highly useful for synthesizing a wide range of functionalized 3-(aryl/alkylselanyl)pyrazolo[1,5-a]pyrimidine derivatives. Mechanistic investigation disclosed that iodine catalysis is very important in both the cyclization process as well as in the C-H selenylation step. Moreover, the developed reaction conditions are also applicable for the cyclization of amino pyrazole with enaminone followed by C-H selenylation in one pot. The use of simple reagents and catalyst, wide substrate scope, mild and metal-free reaction conditions, and practical applicability are the attractive facets of this approach.

Immunogenicity of SARS-CoV-2 vaccines BBV152 (COVAXIN®) and ChAdOx1 nCoV-19 (COVISHIELD™) in seronegative and seropositive individuals in India: a multicentre, nonrandomised observational study - Asokan, Mangaiarkarasi S.; Joan, Roshni Florina; Babji, Sudhir; Dayma, Girish; Nadukkandy, Prajitha; Subrahmanyam, Vinutha; Pandey, Archana; Malagi, Girish; Arya, Pooja; Mahajan, Vibhuti; Bhavikatti, Jayateerth; Pawar, Ketakee; et al. (Lancet Regional Health - Southeast Asia, 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;"> Background: There are limited global data on head-to-head comparisons of vaccine platforms assessing both humoral and cellular immune responses, stratified by pre-vaccination serostatus. The COVID-19 vaccination drive for the Indian population in the age group 18-45 years began in April 2021 when seropositivity rates in the general population were rising due to the delta wave of COVID-19 pandemic during April-May 2021. <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;"> Methods: Between June 30, 2021, and Jan 28, 2022, we enrolled 691 participants in the age group 18-45 years across four clinical sites in India. In this non-randomised and laboratory blinded study, participants received either two doses of Covaxin® (4 weeks apart) or two doses of Covishield™ (12 weeks apart) as per the national vaccination policy. The primary outcome was the seroconversion rate and the geometric mean titre (GMT) of antibodies against the SARS-CoV-2 spike and nucleocapsid proteins post two doses. The secondary outcome was the frequency of cellular immune responses pre- and post-vaccination. <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;"> Findings: When compared to pre-vaccination baseline, both vaccines elicited statistically significant seroconversion and binding antibody levels in both seronegative and seropositive individuals. In the per-protocol cohort, Covishield™ elicited higher antibody responses than Covaxin® as measured by seroconversion rate (98.3% vs 74.4%, p < 0.0001 in seronegative individuals; 91.7% vs 66.9%, p < 0.0001 in seropositive individuals) as well as by anti-spike antibody levels against the ancestral strain (GMT 1272.1 vs 75.4 binding antibody units/ml [BAU/ml], p < 0.0001 in seronegative individuals; 2089.07 vs 585.7 BAU/ml, p < 0.0001 in seropositive individuals). As participants at all clinical sites were not recruited at the same time, site-specific immunogenicity was impacted by the timing of vaccination relative to the delta and omicron waves. Surrogate neutralising antibody responses against variants-of-concern including delta and omicron was higher in Covishield™ recipients than in Covaxin® recipients; and in seropositive than in seronegative individuals after both vaccination and asymptomatic infection (omicron variant). T cell responses are reported from only one of the four site cohorts where the vaccination schedule preceded the omicron wave. In seronegative individuals, Covishield™ elicited both CD4+ and CD8+ spike-specific cytokine-producing T cells whereas Covaxin® elicited mainly CD4+ spike-specific T cells. Neither vaccine showed significant post-vaccination expansion of spike-specific T cells in seropositive individuals.

Improved protein dynamics and hydration in the martini3 coarse-grain model - Kharche, Shalmali; Yadav, Manjul; Hande, Vrushali; Prakash, Shikha; Sengupta, Durba (Journal of Chemical Information and Modelling, 2024)
The Martini coarse-grain force-field has emerged as an important framework to probe cellular processes at experimentally relevant time- and length-scales. However, the recently developed version, the Martini3 force-field with the implemented Go model (Martini3Go), as well as previous variants of the Martini model have not been benchmarked and rigorously tested for globular proteins. In this study, we consider three globular proteins, ubiquitin, lysozyme, and cofilin, and compare protein dynamics and hydration with observables from experiments and all-atom simulations. We show that the Martini3Go model is able to accurately model the structural and dynamic features of small globular proteins. Overall, the structural integrity of the proteins is maintained, as validated by contact maps, radii of gyration (Rg), and SAXS profiles. The chemical shifts predicted from the ensemble sampled in the simulations are consistent with the experimental data. Further, a good match is observed in the protein-water interaction energetics, and the hydration levels of the residues are similar to atomistic simulations. However, the protein-water interaction dynamics is not accurately represented and appears to depend on the protein structural complexity, residue specificity, and water dynamics. Our work is a step toward testing and assessing the Martini3Go model and provides insights into future efforts to refine Martini models with improved solvation effects and better correspondence to the underlying all-atom systems.

In situ monitoring of competitive coformer exchange reaction by 1H MAS solid-state NMR - Hareendran, Chaithanya; Alsirawan, Bashir; Paradkar, Anant; Ajithkumar, T. G. (Molecualr Pharmaceutics, 2024)
In a competitive coformer exchange reaction, a recent topic of interest in pharmaceutical research, the coformer in a pharmaceutical cocrystal is exchanged with another coformer that is expected to form a cocrystal that is more stable. There will be a competition between coformers to form the most stable product through the formation of hydrogen bonds. This will cause destabilization of the pharmaceutical products during processing or storage. Therefore, it is important to develop a mechanistic understanding of this transformation by monitoring each and every step of the reaction, employing a technique such as H-1 nuclear magnetic resonance (NMR). In this study, an in situ monitoring of a coformer exchange reaction is carried out by H-1 magic angle spinning (MAS) solid-state NMR (SSNMR) at a spinning frequency of 60 kHz. The changes in caffeine maleic acid cocrystals on addition of glutaric acid and caffeine glutaric cocrystals on addition of maleic acid were monitored. In all of the reactions, it has been observed that caffeine glutaric acid Form I is formed. When glutaric acid was added to 2:1 caffeine maleic acid, the formation of metastable 1:1 caffeine glutaric acid Form I was observed at the start of the experiment, indicating that the centrifugal pressure is enough for the formation. The difference in the end product of the reactions with a similar reaction pathway of 1:1 and 2:1 reactant stoichiometry indicates that a complete replacement of maleic acid has occurred only in the 1:1 stoichiometry of the reactants. The polymorphic transition of caffeine glutaric acid Form II to Form I at higher temperatures was a crucial reason that triggered the exchange of glutaric acid with maleic acid in the reaction of caffeine glutaric acid and maleic acid. Our results are novel since the new reaction pathways in competitive coformer exchange reactions enabled understanding the remarkable role of stoichiometry, polymorphism, temperature, and centrifugal pressure.
Keywords: caffeine cocrystal; coformer exchange reaction; in situ monitoring; polymorphism; Solid-state NMR

In situ synthesis of metal (Bi0)-semiconductor [BiOX (X = Cl, Br, and I)] nanocomposites as a highly effective catalyst for the reduction of 4-nitrophenol to 4-aminophenol - Singh, Dinesh; Poddar, Pankaj (New Journal of Chemistry, 2024)
The reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) has been efficiently catalyzed by in situ generated Bi-0-BiOX (X = Cl, Br, I) nanocomposites in the presence of sodium borohydride (NaBH4). The hierarchical 3D arrays of precursors (BiOCl, BiOBr, and BiOI) have been synthesized by a facile co-precipitation method at ambient temperature. The metallic Bi-0 is generated in situ by partial reduction of the Bi3+ ions in BiOX (X = Cl, Br, and I) mediated by NaBH4 during the conversion of 4-NP to 4-AP. In situ generated Bi-0-BiOX shows better catalytic activity than Bi-0-BiOX composite formed by mixing individually synthesized metallic Bi-0 particles with semiconducting BiOX nanoparticles. The Bi-0-BiOI nanocomposite demonstrated higher catalytic activity (k(app) = 0.529 min(-1)) compared to Bi-0-BiOCl (k(app) = 0.095 min(-1)) and Bi-0-BiOBr (k(app) = 0.098 min(-1)) due to its efficient conversion into metallic Bi-0. The approximate percentage composition of in situ generated metallic Bi-0 on the surface of BiOCl, BiOBr, and BiOI is nearly 10, 17, and 25%, respectively. Further, the reduction of 4-NP has been completed within 24, 22, and 6 minutes by in situ generated Bi-0-BiOCl, Bi-0-BiOBr, and Bi-0-BiOI nanocomposites from BiOCl, BiOBr, and BiOI, respectively. Extensive studies have been conducted to generate a better understanding of the actual catalytic sites present on the surface of the catalysts.

Influence of deposition potential on electrodeposited bismuth-copper oxide electrodes for asymmetric supercapacitor - Bobade, Rushikesh G.; Dabke, Niteen B.; Shaikh, Shoyebmohamad F.; Al-Enizi, Abdullah M.; Pandit, Bidhan; Lokhande, Balkrishna J.; Ambare, Revanappa C. (BATTERIES & SUPERCAPS, 2024)
Keywords: Bi2CuO4; Deposition Potential; Electrodeposition; supercapacitor; thin film

Insights on prussian blue analogue cathode material engineered with polypyrrole surface protection layer for aqueous rechargeable zinc metal battery - Puthiyaveetil, Priyanka Pandinhare; Nair, Aathira; Dilwale, Swati; Kurian, Maria; Joshi, Kavita; Kurungot, Sreekumar (Small, 2024)
One of the key intricacies against using Prussian blue analogues (PBAs) in aqueous batteries is their gradual dissolution in aqueous electrolytes, resulting in inadequate cycling stability. Besides, the rate capability of PBAs is limited due to their poor electrical conductivity. To overcome these challenges, it is essential to tune the physical and chemical properties of PBAs at the nano regime without affecting the inherent charge storage properties, especially at high-voltage operating conditions. Through this work, a strategy is demonstrated to enhance the electrochemical performance of vanadium-based PBA (V-PBA) by surface engineering using a conducting polymer nano-skin (V-PBA/PPy) for aqueous zinc metal batteries. The polypyrrole (PPy) nano-skin over the V-PBA nanoparticles acts as an electron percolation path to ameliorate the poor electronic conductivity of the otherwise pristine V-PBA. Interestingly, the V-PBA with an optimized polypyrrole coating (V-PBA/PPy-2) exhibits an enhanced specific capacity (173 mAh g-1 at 0.10 A g-1) than the pristine V-PBA counterpart (80 mAh g-1) and 85% capacity retention up to 500 cycles. The DFT calculation confirms the synergistic interaction between PPy and V-PBA and the presence of PPy favors the adsorption of Zn.
Keywords: aqueous rechargeable zinc metal battery; DFT; polypyrrole coating; Prussian blue analogue; surface protection layer

Integrating 3,4-Dihydro-2H-1,4-oxazine into peptides as a modification: silver triflate-catalyzed cyclization of N-Propargyl N-Sulfonyl amino alcohols for SPPS applications - Patil, Abhijit Ramchandra; Marelli, Udaya Kiran (Organic Letters, 2024)
We present a methodology yielding 3,4-dihydro-2H-1,4-oxazine by cyclization of N-propargyl N-sulfonyl amino alcohols using silver triflate as a catalyst at ambient temperature. Additionally, we showcase the applicability of this methodology in solid phase peptide synthesis (SPPS) to introduce the oxazine heterocyclic ring into short peptides containing serine and threonine. Notably, Rink amide resin supported the on-resin formation of 3,4-dihydro-2H-1,4-oxazine, while 2-CTC resin facilitated the oxazine formation in a one-pot process involving peptide cleavage, deprotection, and subsequent C-O ring formation, thus offering a versatile method for the late-stage modification of peptides.

Interface-centric strategies in kesterite solar cells: addressing challenges, solutions, and future directions for efficient solar-harvesting technologies - Jagadish, Kusuma; Rahane, Ganesh K.; Kumar, Boddeda Sai; Borkar, Durgesh R.; Chordiya, Kalyani; Kavanagh, Sean R.; Roy, Anurag; Debnath, Tushar; Kolekar, Sadhu; Kahaly, Mousumi Upadhyay; Mali, Sawanta S.; Pal, Shovon; et al. (SMALL, 2024)
Keywords: band engineering; Defects; interface loss mechanism; kesterites; recombination control; solar energy

Intramolecular nitrone interrupted click reaction - Pothi, Tejas A.; Ramana, Chepuri V. (Organic Letters, 2024)
We document the intramolecular interception of a Cu-catalyzed azidoalkyne cycloaddition employing a suitably placed nitrone group, providing a simple route to the unprecedented spiro-polyheterocyclic scaffold. The reaction is comprised of a Cu-catalyzed [3 + 2]-cycloaddition of (2-azidoaryl)isatogen with a terminal alkyne and the intramolecular trapping of the transient Cu-triazolide intermediate with the isatogen, with a net formation of one C-C and two C-N bonds and the new heterocyclic ring being spiro-annulated.

Ionic liquid assisted green synthesis of quinoxaline based bisspirooxindoles: anticancer evaluation and molecular dynamics - Kanchrana, Madhu; Krishna, Gamidi Rama; Dey, Biswajit; Pandey, Nandita; Guru, Santosh Kumar; Sangolkar, Akanksha Ashok; Pawar, Ravinder; Basavoju, Srinivas (CHEMISTRYSELECT, 2024)
Keywords: Cycloaddition; spirooxindoles

Iron salicylaldehydate conjugated metal-organic framework for quasi solid-state supercapacitor - Mohammed, Abdul Khayum; Pandikassala, Ajmal; Sanchez, Pilar Pena; Gaber, Safa Abdullah; Canossa, Stefano; Kurian, Maria; Xavier, Gigi; He, Yao; Gandara, Felipe; Kurungot, Sreekumar; Shetty, Dinesh (CHEMICAL ENGINEERING JOURNAL, 2024)
Keywords: Carbon; conductivity; ELECTROLYTE CONCENTRATION; performance; ROBUST

Iron-catalyzed C-C and C-N bond-forming tandem amidation offering access to 3-amino-3-aminomethyl-2-oxindole frameworks - Ankade, Shidheshwar B.; Pradhan, Chandini; Samal, Pragnya Paramita; Gonnade, Rajesh G.; Krishnamurty, Sailaja; Punji, Benudhar (Advanced Synthesis & Catalysis, 2024)
An iron-catalyzed protocol for the synthesis of 3-amino-3-aminomethyl-2-oxindole heterocyclic structures is disclosed employing isatins and non-nucleophilic N-methoxybenzamides. This reaction class is associated with broad scope and tolerates numerous functionalities, such as fluoro, chloro, bromo, iodo, trifluoromethyl, nitrile, ester, ether, and alkenyl, including heteroaryl - thiophene, benzothiophene, carbazolyl, indolyl, eugenol, and polycyclic cholesterol moieties. Detailed mechanistic investigations reveal that the reaction proceeds via iron-catalyzed N-O bond cleavage in N-methoxybenzamides, generating formaldehyde and benzamide, and through the intermediacy of isatin-ketimines and N-(hydroxymethyl)benzamides. Overall, this amidation reaction involves one C-C and two C-N bond-forming tandem processes, providing a range of beta-amino-aminomethyl-oxindoles (45 examples) in up to 88% yields. image
Keywords: benzamide; iron; Isatin; tandem amidation; tetrasubstituted carbon stereocenter

Kinetic H2S/CO2 selectivity in an exceptionally sterically hindered amine membrane - Rao, Shraavya; Deng, Xuepeng; Zou, Changlong; Prasad, Babul; Han, Yang; Lin, Li-Chiang; Ho, W. S. Winston (JOURNAL OF MATERIALS CHEMISTRY A, 2024)
Keywords: Absorption; COMPOSITE MEMBRANES; GAS STREAMS; H2S; Thin-Film

Kinetic model of hydrogenation of glucose to sorbitol on a Ni/Bentonite catalyst - Pandya, Harmitkumar; Vinod, Chathakudath Prabhakaran; Rathod, Virendra; Kantam, Mannepalli Lakshmi (Industrial and Engineering Chemistry Research, 2024)
In the present work, we studied the hydrogenation of glucose to sorbitol using a nickel/bentonite catalyst. The Ni/bentonite catalyst was prepared by the wet impregnation method and characterized by different methods to understand the catalyst surface morphology, surface area, metal content, pore size, etc. Different reaction parameters such as temperature, hydrogen pressure, metal loading, catalyst loading, and agitation speed were studied to achieve a glucose conversion of 96.8% and a sorbitol selectivity of 95.3%. The reusability test was performed to examine the stability of the catalyst. The kinetic models such as the Eley-Rideal and Langmuir-Hinshelwood-Hougen-Watson models were used to study the hydrogenation of glucose and activation energy required for the reaction.

La-Fe-O perovskite based gas sensors: recent advances and future challenges - Patil, Suraj S.; Babar, Bapuso M.; Nadargi, Digambar Y.; Shaikh, Faiyyaj I.; Nadargi, Jyoti D.; Sankapal, Babasaheb R.; Mulla, Imtiaz S.; Tamboli, Mohaseen S.; Truong, Nguyen Tam Nguyen; Suryavanshi, Sharad S. (ACS OMEGA, 2024)
Keywords: ASSISTED SYNTHESIS; ETHANOL SENSING CHARACTERISTICS; LAFEO3 NANOPARTICLES

Leveraging machine learning to dissect role of combinations of amino acids in modulating the effect of zinc on mammalian cell growth - Pandey, Ujjiti; Madhugiri, Indrani; Gadgil, Chetan; Gadgil, Mugdha (BIOTECHNOLOGY PROGRESS, 2024)
Keywords: Absorption; Cytotoxicity; ENTEROCYTES; HISTIDINE

Ligand isomerization driven electrocatalytic switching - Kottaichamy, Alagar Raja; Nazrulla, Mohammed Azeezulla; Parmar, Muskan; Thimmappa, Ravikumar; Devendrachari, Mruthyunjayachari Chattanahalli; Vinod, Chathakudath Prabhakaran; Volokh, Michael; Kotresh, Harish Makri Nimbegondi; Shalom, Menny; Thotiyl, Musthafa Ottakam (ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2024)
Keywords: Catalysts; CO2 reduction; O-2 REDUCTION; oxygen reduction

Ligand-free MnBr2-catalyzed chemo- and stereoselective hydroboration of terminal alkynes - Pawar, Rameshwar B.; Karmur, Mital H.; Punji, Benudhar (Chemistry-an asian jounrnal, 2024)
Developing simple and benign protocols for synthesizing alkenylboronates is crucial as they are synthetically valuable compounds in various organic transformations. In this work, we report a straightforward ligand-free protocol for synthesizing alkenylboronates via atom-economical hydroboration of alkynes with HBpin catalyzed by a manganese salt. The reaction shows a high level of chemo and regioselectivity for the terminal alkynes and exclusively produces E-selective alkenylboronates. The hydroboration scope is vast, with the resilience of a range of synthetically beneficial functionalities, such as halides, ether, alkenyl, silyl and thiophenyl groups. This reaction proceeds through the involvement of a metal-hydride intermediate. The developed alkenylboronate can be smoothly converted to useful C-C, C-N and C-I bond-forming reactions.
Keywords: alkenylboronates; alkyne; Hydroboration; manganese; stereoselectivity

LsBOS utilizes oxalyl-CoA produced by LsAAE3 to synthesize β-ODAP in grass pea - Goldsmith, Moshe; Avram, Liat; Brandis, Alexander; Mehlman, Tevie; Ben-Dor, Shifra; Peleg, Yoav; Ben-Zeev, Efrat; Barbole, Ranjit S.; Reich, Ziv (Nature Communications, 2024)

Manganese-catalyzed chemoselective direct hydrogenation of α,β-epoxy ketones and α-ketoamides at room temperature - Shabade, Anand B.; Singh, Rahul K.; Gonnade, Rajesh G.; Punji, Benudhar (Advanced Synthesis & Catalysis, 2024)
Chemoselective hydrogenation of alpha,beta-epoxy ketones and alpha-ketoamides is achieved at room temperature (25 degrees C) using 2.0 bar H-2 and a pincer-ligated Mn(I) catalyst that provides synthetically valuable alpha-hydroxy epoxides and alpha-hydroxy amides. This protocol applies to a wide range of alkyl- and aryl-substituted alpha,beta-epoxy ketones, including terpenes (alpha-ionone, nootkatone, and R-carvone)- and steroids (testosterone and progesterone)-derived epoxy ketones, and tolerates H-2 sensitive functionalities, such as halides, acetyl, nitrile, nitro, epoxide, alkenyl and alkynyl groups. Additionally, alpha-ketoamides bearing reducible functional groups, including acetyl and diazo benzene, were untouched under this protocol and selectively converted to alpha-hydroxy amides. A preliminary mechanistic study highlighted the metal-ligand cooperative H-2 activation process.
Keywords: alpha; beta-epoxy ketones; chemoselectivity; direct hydrogenation; manganese; Metal-ligand cooperation

Methanesulfonic acid-catalyzed friedel-crafts alkylation: towards sustainable synthesis of arylalkanes from donor-acceptor cyclopropane ketones - Goswami, Lakshmi; Paul, Sayantan; Mamale, Ajay G.; Gonnade, Rajesh G.; Bhattacharya, Asish K. (Asian Journal of Organic Chemistry, 2024)
We present herein Br & oslash;nsted acid-catalyzed Friedel-Crafts alkylation of phenols with Donor-Acceptor cyclopropane ketones. The presence of the 1,4-diphenyl butan-1-one and 1,3-diphenyl propane-1-one motifs in various naturally occurring biologically significant molecules inspired us to pursue the direct synthesis of these structural frameworks. Utilizing methanesulfonic acid (MeSO3H) as a catalyst, we achieved a more environmentally friendly and high-yielding synthesis, owing to its cost-effectiveness, biodegradability, transition-metal and additives free conditions. Furthermore, we have successfully extended our developed methodology to thiophenols, resulting in the production of sulfur-based butan-1-one derivatives in good yields. The presence of 1,4-diphenyl butan-1-one and 1,3-diphenyl propane-1-one motifs in various naturally occurring biologically significant molecules prompted us to develop a Br & oslash;nsted acid-catalyzed Friedel-Crafts alkylation of phenols with Donor-Acceptor cyclopropane. image
Keywords: donor-acceptor cyclopropane; Friedel-Crafts alkylation; methanesulfonic acid; Phenols; thiophenol

New binary adducts of panobinostat with different carboxylic acid based NSAIDs: structural analysis and physicochemical properties investigation - Kenguva, Gowtham; Rout, Smruti Rekha; Kar, Ananya; Giri, Lopamudra; Shaikh, Tabrez R.; Jadab, Madhusmita; Pal, Satyanarayan; Dandela, Rambabu (ChemistrySelect, 2024)
Adoption of multitarget, cost-effective fixed-dose medication combinations can help lower the pill load without increasing the risk of adverse events. In this study, three new 1:1 drug-drug binary solid forms of panobinostat (PNB) and nonsteroidal anti-inflammatory drugs (NSAIDs) were effectively synthesized by liquid-assisted grinding and slow evaporation crystallization techniques. The obtained solid forms were extensively characterized by various analytical techniques. The structural investigation revealed that all molecular adducts formed salt with a comparable R42\${\textbackslashmathrm{R}}_4<\^>2\$(10) graph set pattern created by heteromeric interactions formed between PNB and corresponding salt formers. To determine the dissolving behavior of the newly developed adducts, solubility tests were performed at various pH levels (pH 1.2 and pH 7), and the results indicated that the solubility of all forms is increased at pH 7.0, particularly PNB.NIF has a solubility of 0.195 mg/mL, which is seven times higher than the parent drug. Furthermore, PXRD was used to assess the stability of the synthesized adduct at varied temperature and humidity levels and it was found that all the adducts are stable. Based on the findings, we hope that the newly found PNB drug-drug binary adducts have possible potential to broaden the use of drug combinations without changing the chemical structures.
Keywords: Drug-drug salts; Heteromeric interactions; Hydrogen bond; Non-steroidal anti-inflammatory drugs; Panobinostat

New record of larval-pupal endoparasitoid Exorista deligata parasitising Indian Tea looper Hyposidra talaca from India - Sharma, Pooja V.; Das, Tamal; Mukherjee, Susmita; Pathan, Ejaj K.; Rahman, Azizur; Gathalkar, Ganesh B. (Phytoparasitica, 2024)
This is the first record of Exorista deligata (Pandell & eacute;, 1896) (Diptera: Tachinidae) as a parasitoid of Hyposidra talaca (Walker, 1860) (Lepidoptera: Geometridae) from India. H. talaca is a major and new emerging defoliator of the Tea plant Camellia sinensis (L) Kuntze (Theaceae). It completes multiple generations per year without diapause on C. sinensis, resulting in heavy crop loss. The field-collected larvae/pupa of H. talaca were checked for parasitoid infestations and reared until either the host or parasitoid emerged. The parasitoid was identified as E. deligata with morphological characteristics and confirmed by the mitochondrial cytochrome oxidase subunit-I (COX-CO1) gene sequencing technique. The parasitoid is infrequent with unexplored parasitic biology. It parasitises the larva and completes its lifecycle inside the developing H. talaca by entirely devouring the host. The mean percent parasitisation caused by E. deligata studied herein was 25.4% (range 5.88%-57.69%). Based on its parasitisation ability, we suggest the species could be a potential biological control agent to address the damage mitigation caused by the tea looper pest, H. talaca.
Keywords: Biocontrol; Exorista deligata; Hyposidra talaca; Invasive pest; Parasitisation

Nickel-catalyzed branch-selective C-H alkylation of indoles and azoles with alkenes: an additive- and solvent-free approach - Ankade, Shidheshwar B.; Banerjee, Shuvajit; Punji, Benudhar (European Journal of Organic Chemistry, 2024)
The development of sustainable protocols for the synthesis of alkylated heteroarenes is crucial owing to their widespread existence in medicinally relevant and bioactive natural products. Herein, we describe an efficient, additive- and solvent-free approach for the regioselective C-H alkylation of indoles and azoles with alkenes using a nickel catalyst, which proceeds through a chelation-assistance strategy. The reaction exclusively provided branched alkylated products with the compatibility of alkyl, alkoxy, fluoro, trifluoromethyl, alkene, cyano, ester, and carbonyl groups. This protocol is applicable to other heteroarenes, such as imidazoles and benzimidazoles, providing the desired alkylated products with exclusive Markovnikov selectivity. The synthetic utility and scale-up of the reaction are demonstrated, and the protocol is in concord with the principles of green chemistry. Alkylation proceeds through facile and reversible C-H nickelation and alkene insertion processes, presumably involving rate-limiting reductive elimination. A straightforward nickel-catalyzed protocol for the C-H alkylation of indoles and azoles is disclosed that proceeds under additive- and solvent-free conditions. The reaction utilizes readily available alkenes as alkylating partners and delivers Markovnikov products with tolerance of sensitive functionalities. image
Keywords: Alkylation; branch selectivity; indoles; Nickel; solvent-free synthesis

Nickel-catalyzed chemodivergent coupling of alcohols: efficient routes to access α,α-disubstituted ketones and α-substituted chalcones - Bansal, Sadhna; Punji, Benudhar (Chemistry- a european journal, 2024)
Chemodivergent (de)hydrogenative coupling of primary and secondary alcohols is achieved utilizing an inexpensive nickel catalyst, (6-OH-bpy)NiCl2. This protocol demonstrates the synthesis of branched carbonyl compounds, alpha,alpha-disubstituted ketones, and alpha-substituted chalcones via borrowing hydrogen strategy and acceptorless dehydrogenative coupling, respectively. A wide range of aryl-based secondary alcohols are coupled with various primary alcohols in this tandem dehydrogenation/hydrogenation reaction. The nickel catalyst, along with KOtBu or K2CO3, governed the selectivity for the formation of branched saturated ketones or chalcones. A preliminary mechanistic investigation confirms the reversible dehydrogenation of alcohols to carbonyls via metal-ligand cooperation (MLC) and the involvement of radical intermediates during the reaction. The chemodivergent nickel-catalyzed approach provides alpha,alpha-disubstituted ketones from aryl-substituted secondary alcohols and benzyl alcohols via the borrowing hydrogen (BH) strategy in the presence of KOtBu, whereas exclusively alpha-substituted chalcones were accomplished in the presence of mild base K2CO3 through an acceptorless dehydrogenative coupling (ADC) strategy. image
Keywords: Alcohols; dehydrogenative coupling; Metal-ligand cooperation; Nickel; substituted carbonyl compounds

Nickel-catalyzed tandem conversion of paraformaldehyde : methanol to hydrogen and formate/chemo- and stereoselective hydrogenation of alkynes under neutral conditions - Subaramanian, Murugan; Padhy, Subarna Sukanya; Gouda, Chandrakanth; Das, Tamal; Vanka, Kumar; Balaraman, Ekambaram (Catalysis Science and Technology, 2024)
The development of new catalytic protocols for clean and COx-free hydrogen generation from fundamental feedstocks is always interesting and challenging. Herein, we disclose nickel-catalyzed dihydrogen generation from a mixture of paraformaldehyde-methanol under base-free and activator-free conditions. The dihydrogen generation from this redox combination under neutral, oxidative coupling conditions has been integrated with the hydrogen transfer reactions such as chemo- and stereoselective hydrogenation of alkynes in a tandem manner. This unprecedented strategy provides diverse highly stereoselective olefins with excellent tolerance of reducible functional groups such as ether, silyl ether, aldehyde, keto, ester, nitrile, halides including bromo and iodo groups, and heteroarenes. Additionally, we demonstrated catalytic stereo-interconversion of alkenes under benign conditions. The affordable gram-scale synthesis of some important pharmaceutical bioactive molecules has further enhanced their synthetic value. A tandem dihydrogen generation from a mixture of paraformaldehyde-methanol under base-free conditions followed by semihydrogenation of alkynes is reported.

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

One-pot, easy and scalable synthesis of large-size short wave length IR emitting PbS quantum dots - Sahu, Umasharan; Prasad, Bhagavatula L. V. (Photochemistry and Photobiology, 2024)
This study presents a versatile and efficient method to synthesize large-size lead sulfide (PbS) quantum dots (QDs) that display emission in the short-wave infrared (SWIR) region, using accessible and stable diethylammonium diethyldithiocarbamate (C-2)(2)DTCA and octylammonium octyldithiocarbamate (C(8)DTCA) as sulfur sources. As these sulfur sources enable the formation of well-dispersed, large-size PbS QDs in a very convenient way, this method can further be taken up for scale-up studies. Importantly, this approach allows precise control over QD sizes, thereby enhancing their SWIR optical properties. By adjusting the hot injection temperatures and sulfur source concentrations, different synthesis routes are explored, providing flexibility for the desired QD characteristics. The results presented here offer a promising opportunity to leverage the synthesized PbS QDs in applications such as optoelectronics, sensors, and imaging technology.
Keywords: hot injection method; Optical properties; quantum dots; short wave IR emission

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.

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

Pathological mutations D169G and P112H electrostatically aggravate the amyloidogenicity of the functional domain of TDP-43 - Pillai, Meenakshi; Patil, Anjali D.; Das, Atanu; Jha, Santosh Kumar (ACS Chemical Neuroscience, 2024)
Aggregation of TDP-43 is linked to the pathogenesis of many neurodegenerative diseases, including amyotrophic lateral sclerosis (ALS). Notably, electrostatic point mutations such as D169G and P112H, located within the highly conserved functional tandem RNA recognition motif (RRM) domains of the TDP-43 protein (TDP-43tRRM), have been identified in diseased patients as well. In this study, we address how the electrostatic mutations alter both the native state stability and aggregation propensity of TDP-43tRRM. The mutants D169G and P112H show increased chemical stability compared to the TDP-43tRRM at physiological pH. However, at low pH, both the mutants undergo a conformational change to form amyloid-like fibrils, though with variable rates-the P112H mutant being substantially faster than the other two sequences (TDP-43tRRM and D169G mutant) showing comparable rates. Moreover, among the three sequences, only the P112H mutant undergoes a strong ionic strength-dependent aggregability trend. These observations signify the substantial contribution of the excess charge of the P112H mutant to its unique aggregation process. Complementary simulated observables with atomistic resolution assign the experimentally observed sequence-, pH-, and ionic strength-dependent aggregability pattern to the degree of thermal lability of the mutation site-containing RRM1 domain and its extent of dynamical anticorrelation with the RRM2 domain whose combination eventually dictate the extent of generation of aggregation-prone partially unfolded conformational ensembles. Our choice of a specific charge-modulated pathogenic mutation-based experiment-simulation-combination approach unravels the otherwise hidden residue-wise contribution to the individual steps of this extremely complicated multistep aggregation process.
Keywords: amyloid fibrils; conformational changes; disease mutations; electrostatics; Protein aggregation; stability

photoarchitectonic hydrogel for synergistic in vitro chemo–phototherapy of breast cancer - Paul, Shatabdi; Yadav, Binduma; Patil, Mahesh D.; Pujari, Anil Kumar; Singh, Umesh; Rishi, Vikas; Bhaumik, Jayeeta (Materials Advances, 2024)
Currently, combinatorial therapy has evoked interest in cancer treatment, and may promote achieving a synergistic effect using cancer medicines. Laser-assisted and pH-responsive therapies have attracted significant attention, and their combination leads to high efficiency cancer treatment. Herein, we developed a chemo–phototherapeutic hydrogel comprised of doxorubicin (DOX, a chemotherapeutic drug) and zinc phthalocyanine (ZnPc, a phototherapeutic drug) for combinatorial and synergistic treatment of breast cancer. Firstly, we have developed carbon dots (CDs, size of ∼5 nm) utilizing lignin and folic acid as biocompatible sources. Then doxorubicin was loaded on the surface of the carbon dots via conjugation (DOX@CDs). Later on, zinc phthalocyanine and acrylic acid derivatives were utilized to develop a laser-responsive hydrogel (ZnPc-PP H). Afterward, doxorubicin-conjugated carbon dots were incorporated into the photoarchitectonic hydrogel to develop a chemo–phototherapeutic drug-loaded hydrogel (DOX@CDs–ZnPc-PP H). Subsequently, the in vitro pH-triggering experiments demonstrated that the hydrogel loaded with both DOX and ZnPc could release the drugs in an acidic environment. Interestingly, in vitro assays confirmed that DOX@CDs–ZnPc-PP H could effectively target breast cancer cells (MCF-7). Furthermore, the developed chemo–phototherapeutic hydrogel exhibited non-cytotoxic behavior. Owing to laser assisted reactive oxygen species generation from ZnPc present in the hydrogel, the growth of MCF-7 cells was significantly lowered. In conclusion, all experimental outcomes indicate that the photoarchitectonic hydrogel has the potential to be applied in synergistic chemo- and photodynamic therapy of cancer.

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

Polymerized stimuli-responsive microgel hybrids of silver nanoparticles as efficient reusable catalyst for reduction reaction - Pany, Biswajit; Majumdar, Amrito Ghosh; Bhat, Suresh; Si, Satybrata; Yamanaka, Junpei; Mohanty, Priti S. (Heliyon, 2024)
We have showcased the potential of polymerized hydrogels (PGMs) with uniform -sized stimuliresponsive microgel particles as promising alternatives to prevent aggregation in solution based nanoparticle systems. In the current work, we implemented the PGM concept by embedding anionic stimuli -responsive microgels (PNIPAM-co-AAc)-silver (Ag) hybrids within a hydrogel matrix. These PGM@AgNP hybrid materials are used as catalysts for the reduction of 4-nitrophenol (4 -NP) to 4-aminophenol (4 -AP) in the presence of sodium borohydride. UV-VIS spectroscopy is used for studying catalytic activity. In the solution based system, the complete reduction of 4NP to 4 -AP took 30 minutes with pure Ag nanoparticles, 24 minutes with PNIPAM-Ag hybrid (Neutral) microgels and 15 minutes with PNIPAM-co-AAc-Ag (Anionic) hybrid microgels. In contrast PGM containing PNIPAM-co-AAc-Ag hybrids achieved full reduction in just 15 minutes, along with a 3 -minute induction period. For pure Ag nanoparticles, the first -order rate constant is found to be 0.25 min - 1, for PNIPAM-Ag hybrid (Neutral), it is 0.21 min- 1 and for PNIPAM-coAAc-Ag (Anionic), it is 0.5 min- 1 where as for PGM containing anionic microgel hybrids it is found to be 0.8 min - 1. Furthermore, the reusability of the PGM-Ag (anionic) materials for catalytic activity remains unaltered even after several washings. In summary, our study highlights the effectiveness of PGM@AgNP materials as efficient catalysts for the reduction of 4-nitrophenol to 4-aminophenol, indicating their versatile potential in various catalytic applications.
Keywords: Light scattering; Microgel-metal hybrids; Nanomaterial catalysts; PNIPAM microgels; Polymerized hydrogel matrix(PGM; Stimuli-responsive microgels

Poly(N-vinylpyrrolidone)-assisted crystal growth of zeolitic imidazolate framework (ZIF-67) and electrochemical properties of its derivatives for flexible supercapacitors - Jain, Manisha; Joshi, Bhavana; Poddar, Pankaj (Crystal Growth and Design, 2024)
A simple and explicit wet chemical method enables the room-temperature crystallization of the zeolitic imidazolate framework (ZIF-67) using cotton-cloth (CC) as a substrate; where time-dependent Avrami's kinetic studies demonstrated sluggish nucleation and fast crystal growth resulting in unprecedented morphologies-truncated cubes [synthesized without poly(N-vinylpyrrolidone); PVP], and rhombic dodecahedra (with PVP) with average sizes ranging from 500 nm to 1.41 mu m; wherein amphiphilic PVP plays a crucial function of structure directing agent by modulation of complex formation and deprotonation equilibria. To study the potential of pristine ZIF-67 (ZP0) and PVP-functionalized ZIF-67 (ZP50, ZP100, and ZP200) grown on the CC substrate for application as a flexible electrode in supercapacitors, ZP0, ZP50, ZP100, and ZP200 were annealed to form CZP0, CZP50, and CZP100, respectively. Areal capacitances of 181 and 214 mFcm(-2) were achieved at a current density of 1 mAcm(-2) and a potential window of 1.6 V for CZP0 and CZP100, respectively, and compared to the derivatives without PVP; CZP100 exhibited a superior energy density of 76.3 mu Whcm(-2) and a capacitance retention of 84.3% after 5000 cycles at a current density of 0.5 mAcm(-2).

Probing surface interactions in CdSe quantum dots with thiocyanate ligands - Deshmukh, Samadhan H.; Yadav, Sushma; Chowdhury, Tubai; Pathania, Akhil; Sapra, Sameer; Bagchi, Sayan (NANOSCALE, 2024)
Keywords: COLLOIDAL NANOCRYSTALS; STRUCTURAL DYNAMICS; Thin-films

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.

Purification of waste-generated biogas mixtures using covalent organic framework's high CO2 Selectivity - Paul, Ratul; Maibam, Ashakiran; Chatterjee, Rupak; Wang, Wenjing; Mukherjee, Triya; Das, Nitumani; Yellappa, Masapogu; Banerjee, Tanmay; Bhaumik, Asim; Venkata Mohan, S.; BabaRao, Ravichandar; Mondal, John (ACS APPLIED MATERIALS & INTERFACES, 2024)
Keywords: CAPTURE; CARBON-DIOXIDE; Efficiency; Energy; Hydrogen; STORAGE

Pyridazine-Based Aggregation Induced Emission Active Conjugates: Synthesis, Single Crystal XRD Analysis, and Self-Assembly Assessment - Waghchoure, Aishwarya P.; Sangale, Vijay B.; Shaligram, Parth S.; Lambud, Sushil; Pardeshi, Satish K.; Gonnade, Rajesh G.; Bandaru, Sateesh; More, Sandeep; Reddy, J. Prakasha; Bhosale, Rajesh S. (CHEMISTRYSELECT, 2024)
Keywords: AIE; Pyridazine; Self-assembly; Single crystal

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.

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.

Room temperature photocurable PEEK polymer formulations for high-performance 3D printing applications - Pal, Shibam; Gaikwad, Yogesh; Asha, S. K. (ACS Applied Engineering Materials, 2024)
Digital light processing (DLP) technology was employed to 3D print acrylate-modified poly(ether ether ketone) (PEEK). PEEK and modified PEEK (mPEEK incorporating pendant pentadecyl chain) polymers were synthesized and end-capped with urethane acrylate units. These end-modified PEEK polymers were combined with commercially available (meth)acrylic cross-linkers and photoinitiator to create photocurable resin formulations suitable for DLP 3D printing. The resulting 3D-printed parts exhibited remarkable mechanical strength, with a Young’s modulus of 2.1 GPa. This surpassed the mechanical properties of commercial acrylate resin 3D-printed parts and achieved approximately 55% of the Young’s modulus of reported commercial PEEK polymer. Notably, the thermal properties of the 3D-printed materials were impressive, including a high glass transition temperature of 140 °C and stability with only around 10% weight degradation occurring at approximately 400 °C. These innovative resins demonstrated excellent printability with high resolution, enabling the fabrication of intricate shapes, including complex dental materials by DLP 3D printing. Their versatility extends to potential applications in dentistry, automobile manufacturing, and robotics.

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

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).

Short review on the synthetic routes for the antiepileptic drug (S)-levetiracetam - Paul, Sayantan; Bhattacharya, Asish K. (Organic Process Research and Development, 2024)
Epilepsy is a chronic disorder characterized by recurrent unpredictable seizures. Levetiracetam (Keppra) was introduced by UCB for the treatment of partial onset seizures in patients above 16 years of age diagnosed with epilepsy. This review reports synthetic strategies available for the synthesis of (S)-levetiracetam and will certainly aid the quest for the development of new routes for its synthesis.
Keywords: antiepileptic drug; butyrolactam; epilepsy; levetiracetam; synthesis

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.

Simultaneously mechanically flexible, photobending, and acidochromic cyanostilbene molecular crystals - Parthasarathy, Thiyagaraj; Mishra, Manish Kumar; Bhattacharya, Biswajit; Emmerling, Franziska; Ghosh, Soumyajit (Crystal Growth & Design, 2024)
Molecular crystals that respond to multiple stimuli are gaining significant attention for their potential in smart materials like actuators and sensors. However, imparting multiple stimuli-responsive properties to a single crystal remains a major challenge. Herein, we report two cyanostilbene derivative-based crystals 1 and 2, with various responses to stimuli such as mechanical stress, light, acid vapors, etc. Both crystals 1 and 2 demonstrated mechanical flexibility and reversible acidochromism. Additionally, crystal 1 also exhibited light-induced photobending, which is ascribed to Z to E photoisomerization. Detailed structure-property correlation was established to unravel distinct mechanical responses. The development of these multitasking crystals may find applications in multitasking actuators, anticounterfeiting materials, and more.

Slowdown of solvent structural dynamics in aqueous DMF solutions - Pathania, Akhil; Bagchi, Sayan (Chemical Physics Impact, 2024)
<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 presents a comprehensive investigation into the molecular dynamics of solvation environments through an integrated approach combining Fourier-transform infrared (FTIR) spectroscopy, molecular dynamics (MD) simulations, and two-dimensional infrared (2D IR) spectroscopy. We explore the solvation of an ionic solute (ammonium thiocyanate) in various solvent systems, including N,N-dimethylformamide (DMF), water, and a 0.5 mole fraction of DMF in water, aiming to unravel the intricate interplay between solute-solvent interactions and solvent dynamics across diverse solvation environments. By integrating FTIR spectral analysis with radial distribution functions and coordination numbers obtained from MD simulations, we decipher the solvent composition around the solute molecule. Analysis of 2D IR spectra and hydrogen bond, as well as dipolar autocorrelation function from MD simulations, further elucidates the nuances of solute-solvent interactions, highlighting the impact of solvent dynamics on solvation structures. Our results reveal a significant slowdown of the solvent structural dynamics in the equimolar binary solvent mixture compared to the neat solvents. This slowdown underscores the complex relationship between solute-solvent interactions and solvent dynamics. The integration of FTIR, MD simulations, and 2D IR spectroscopy provides a unified framework for obtaining a holistic understanding of solvation dynamics, offering valuable insights into the underlying molecular mechanisms governing solute-solvent interactions in complex systems. These results pave the way for future studies to delve deeper into the molecular intricacies of solvation phenomena.

Stereodivergent sila-germylenation vs. sila-stannylenation of an internal alkyne - Ajithkumar, V. S.; Ghanwat, Pratiksha B.; Saha, Sougata; Pati, Swapan K.; Sen, Sakya S. (CHEMICAL COMMUNICATIONS, 2024)
Keywords: DIVERSE REACTIVITY; H BOND ACTIVATION; hydrides

Strategies employing transition-metal free conditions for C-C bond formation in indoles - Ghodake, Balaji M.; Paul, Sayantan; Bhattacharya, Asish K. (ChemistrySelect, 2024)
Indole motifs are omnipresent in nature and can be found in many natural products as well as pharmaceuticals. It is for this reason synthetic transformations of indole have become a topic of interest for the organic and medicinal chemist community for decades. In this review, we have emphasized the functionalization of indoles via transition-metal-free approaches. This review touches on many aspects in different sub-sections, which gives a proposition of the tactics employed for the functionalization of indoles and an overview of the road ahead. In this review, essentially transition-metal-free conditions for C-C bond formation reactions in indoles has been explored. This review describes various approaches of functionalization at the C-2, C-3, C-4 and C-7 position of indoles which comprises arylation, alkenylation, acylation, formylation, alkylation, bisindolyl and cyclization strategies. Also, strategies incorporating N-alkylation/arylation has also been covered. image
Keywords: Alkylation; Arylation; formylation; Indole; transition-metal free

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

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.

Synergistic humidity-responsive mechanical motion and proton conductivity in a cationic covalent organic framework - Das, Gobinda; Shinde, Dhanraj B.; Melapurakkal, Amrutha; Shelke, V, Manjusha; Garai, Bikash; Bazin, Philippe; Blal, Abdelhafid Ait; Benyettou, Farah; Prakasam, Thirumurugan; Halim, Rasha Abdul; Ibrahim, Fayrouzabou; Sharma, Sudhir Kumar; et al. (CHEM, 2024)
Keywords: ACTUATORS; Crystalline; DRIVEN; SOFT

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

Temperature-controlled hydrothermal synthesis of α-MnO2 nanorods for catalytic oxidation of cyclohexanone - Jha, Ratnesh Kumar; Manikandan, Marimuthu; Prabu, Marimuthu; Vineeth, Nidhi R.; Dharmalingam, Praveen; Archana, Ramakrishnan; Harsha, Murudappa; Shankar, Sonu Ram; Bhatte, Kushal; Raja, Thirumalaiswamy (CHEMPLUSCHEM, 2024)
Keywords: Adipic Acid; conversion; MANGANESE OXIDES

Thiol-ene-based degradable 3D printed network from bio resource derived monomers ethyl-lactate and isosorbide - Pal, Shibam; Asha, S. K. (European Polymer Journal, 2024)
A polymeric ene-based thiol-ene network is reported that was demonstrated for light-based 3D printing. Allyl poly (acrylate ethyl lactate) (PAEL) was synthesized starting from ethyl lactate in an efficient and scalable manner. Ethyl lactate is a biobased material obtained naturally or chemically in high yields in the form of ethyl ester of lactic acid. Isosorbide, which is also a bio based resource was converted into thiol derivative and was used along with Pentaerythritol tetrakis(3-mercaptopropionate) (PETMP) as multifunctional thiol. The polymeric nature of the ene (i.e. PAEL) imparted exceptionally high mechanical properties like Young's modulus of 1.75 GPa as well as high thermal stability with a decomposition temperature (Td,10%) exceeding 350 C for all the networks studied. The properties could also be customized by fine tuning the type and stoichiometric ratio of the thiol crosslinked employed. For instance, the Young's modulus range from 1.75 GPa to 1.03 GPa and glass transition temperature range from 44 C to 54 C could be achieved. DLP 3D printing was used to demonstrate the printability of the resins with high resolution and structural fidelity. The study also highlights the basemediated rapid hydrolytic degradation efficiency of the 3D printed parts, demonstrating the applicability of these novel polymeric ene based thiol-ene for sustainable and eco-friendly 3D printable formulations.
Keywords: 3D printing; Degradation; digital light processing; Poly (acrylate ethyl lactate); Thiol-ene

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

Tridentate NacNac tames T-shaped nickel(I) radical - Pahar, Sanjukta; Sharma, Vishal; Raj, K. Vipin; Sangole, Mayur P.; George, Christy P.; Singh, Kirandeep; Vanka, Kumar; Gonnade, Rajesh G.; Sen, Sakya S. (Chemistry- a european journal, 2024)
The reaction of a nickel(II) chloride complex containing a tridentate beta-diketiminato ligand with a picolyl group [2,6-iPr2-C6H3NC(Me)CHC(Me)NH(CH2py)]Ni(II)Cl (1)] with KSi(SiMe3)3 conveniently afforded a nickel(I) radical with a T-shaped geometry (2). The compound's metalloradical nature was confirmed through electron paramagnetic resonance (EPR) studies and its reaction with TEMPO, resulting in the formation of a highly unusual three-membered nickeloxaziridine complex (3). When reacted with disulfide and diselenide, the S-S and Se-Se bonds were cleaved, and a coupled product was formed through carbon atom of the pyridine-imine group. The nickel(I) radical activates dihydrogen at room temperature and atmospheric pressure to give the monomeric nickel hydride. A thermally stable, T-shaped, nickel(I) radical was straightforward obtained by reduction of a tridentate nacnac nickel(II) chloride with KSi(TMS)3. The metalloradical character of the compound was demonstrated by the formation of a highly unusual nickeloxaziridine complex upon addition of TEMPO. The Ni(I) species displays a rich chemistry towards activation S-S, and Se-Se bond leading to unusual C-C coupled product as well as dihydrogen activation at room temperature and atmospheric pressure to generate monomeric nickel hydride.+image
Keywords: C-C Bond formation; Hydrogen Activation; Metalloradical; Nickel; Tridentate nacnac

Tyramine-mediated hyperactivity modulates the dietary habits in Helicoverpa armigera - Patil, Yogita P.; Gawari, Shyam K.; Barvkar, Vitthal T.; Joshi, Rakesh S. (JOURNAL OF CHEMICAL ECOLOGY, 2024)
Keywords: amines; Behavior; dopamine; octopamine; RECEPTOR; sensitivity; SULFAKININ

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)

Unraveling the cooperative mechanisms in ultralow copper-loaded WC@NGC for enhanced CO2 electroreduction to acetic acid - Bagchi, Debabrata; Riyaz, Mohd; Raj, Jithu; Roy, Soumyabrata; Singh, Ashutosh Kumar; Cherevotan, Arjun; Vinod, Chathakudath P.; Peter, Sebastian C. (Chemistry of Materials, 2024)
Electrochemical CO2 reduction reaction (eCO(2)RR) has been explored on tungsten carbide (WC) nanoparticles embedded on N-doped graphitic carbon (NGC), demonstrating excellent activity toward the formation of acetic acid at an extremely lower potential. The activity has been further enhanced by loading ultralow copper sites into the catalyst system, exhibiting 80.02% Faradaic efficiency (FE) toward acetic acid at an applied potential of -0.3 V (vs RHE). Potential-dependent in situ infrared (IR), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, ex situ extended X-ray absorption fine structure (EXAFS) studies, and computational analysis confirm that synergy between uniformly dispersed Cu atoms and WC lattice plays a crucial role in the formation of acetic acid with high FE at a lower potential. It has been observed that the W atom of WC strongly chemisorbs CO2 with a significant change in the C-O bond length and the O-C-O bond angle, in contrast to weaker adsorption on Cu-based catalyst surfaces. The presence of a Cu site enhances the adsorption of CO2, thereby increasing the possibility of C-C coupling kinetically. Most importantly, hydrogen evolution predominates on the catalyst's surface at higher applied potentials (-0.5 to -1.1 V vs RHE), elucidating the mechanism underlying enhanced charge transfer between copper and WC, a phenomenon ascertained through in situ IR spectroscopy and ex situ XPS analysis

Unravelling polymorphism-driven luminescence in GFP chromophore analogues: insights into the phase transition and morphology-dependent optical waveguide properties - Dabke, Niteen B.; Raut, Yash; Mali, Bhupendra P.; Pandya, Rinu; Vanka, Kumar; Manoj, Kochunnoonny; Gonnade, Rajesh G. (Journal of Materials Chemistry C, 2024)
The advent of multi-emission organic solid-state materials in response to external stimuli has sparked the scientific community due to their potential application in developing sophisticated optoelectronic sensors and bioanalytical tools. This article presents green fluorescent protein chromophore (GFPc) analogue-based polymorphs exhibiting significantly different emissions due to various noncovalent interactions in the supramolecular environment and conformational alterations in the crystalline state. In both compounds (A and B), the polymorphs undergo monotropic thermal phase transitions that are characterized by DSC, HSM, and VT-PXRD techniques. The distinct fluorescent emission characteristics of these polymorphs demonstrated morphology-related optical waveguiding features. Specifically, the plate-type Form A1 emitted light with a 2D blue hue, while the needle-type Form A2 emitted light with a yellowish-green colour. Additionally, the impressive waveguiding capabilities of Form B1 were explored in both straight and singly/doubly bending configurations to facilitate fluorescence propagation. Consequently, there is significant interest in developing organic materials based on GFP chromophores, which exhibit low emission in solution but display multi-fluorescent emission in the solid state. These materials are promising for applications such as optoelectronic devices, security tags, live cell imaging, and fluorescent inks. Polymorphs of GFPc analogs A and B display differences in their optical waveguiding properties in 1D and 2D depending on the crystal shapes. Furthermore, Form B1 demonstrates efficient optical waveguiding capabilities even when the crystal is bent.

Unravelling the prebiotic origins of the simplest α-ketoacids in cometary ices: a computational investigation - Dash, Soumya Ranjan; Pandya, Rinu; Singh, Geetika; Sharma, Himanshu; Das, Tamal; Haldar, Hritwik; Hotha, Srinivas; Vanka, Kumar (CHEMICAL COMMUNICATIONS, 2024)
Keywords: GLYOXYLATE; Hydrocarbons; Metabolism; Precursors

Unveiling a promising active host material for sodium metal anodes through V2AlC max derivation - Wasnik, Kundan; Patrike, Apurva; Shelke, Manjusha V. (ACS Applied Energy Materials, 2024)
To address the issue of nonuniform sodium deposition, in this study, V2ZnC (named VZC), which is synthesized by substituting Zn for Al in V2AlC, is used as a host material to facilitate effective Na utilization. The key concept is to utilize Zn and its forms as an active site to trap Na, while the high mechanical strength of VZC can accommodate volume changes in the sodium metal anode during charging and discharging. VZC displayed regulated plating and stripping at a higher current and capacity of 8 mA cm-2 and 2 mAh cm(-2), respectively, with Coulombic efficiency close to 99.99%.
Keywords: electrodes; Nucleation; overpotential; sodium metal; XPS depth profiling

Unveiling different structural orderings in Fe5-xGeTe2 - Walve, Vaibhav; Parakh, Piyush; Rajput, Umashankar; Mhase, Akash S.; Singh, Kirandeep; Deshpande, Aparna (Physical Review B, 2024)
We investigate the metallic van der Waals itinerant ferromagnet Fe5-xGeTe2 5 - x GeTe 2 with atomic scale, spatially resolved low-temperature scanning tunneling microscopy (STM), and spectroscopy (STS). STM images unveil / / a new structural order 2a a x 1a a along with the known order 3a a x 3a a manifesting as nonuniform domains. STS shows spatial and energy resolved local density of states that reveal the crucial influence of Fe(1) site occupancy on the system's electronic interactions. Our magnetization measurements show magnetic anomalies at lower temperatures and identify a Curie temperature (Tc) c ) surpassing room temperature. Collectively, our results elucidate the intricate nature of Fe5-xGeTe2 5 - x GeTe 2 and underscore its potential for tunability of spintronics and high-temperature magnetic applications.

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

Valorizing biomass waste glycerol to fuel additive at room temperature using a nanostructured WO3/Nb2O5 catalyst - Putla, Suresh Babu; Subha, P.; Swapna, Bhattu; Singh, Nittan; Sudarsanam, Putla (Catalysis Communications, 2024)
We developed a nanostructured catalyst consisting of WO3 nanoparticles and Nb2O5 nanorods for efficient glycerol acetalization to produce a fuel additive (solketal) at room temperature. Particularly, the WO3/Nb2O5 nanocatalyst calcined at 400 degrees C (WO3/Nb2O5-4) contains W5+ species and optimum acid sites, which enhanced glycerol conversion (92.3%) with 95.6% of solketal selectivity at room temperature. The structure stability of the WO3/Nb2O5-4 catalyst during the reaction is showcased by hot-filtration study and XRD/XPS characterization. However, the inadequate regeneration of the Bronsted acid sites led to a gradual decrease in the recyclable activity of the WO3/Nb2O5-4 catalyst.
Keywords: Bronsted-Lewis acid sites; Fuel additive; Room-temperature glycerol acetalization; W5+species

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

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.

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.

Advanced zinc-polymer composites for marine corrosion protection and self-healing - Sharma, Sanjay; Girish, Santhosh; Nayaka, G. P.; Shiva Samhitha, S.; Pilliadugula, Rekha; Shivamurthy, B. P.; Gurumurthy, S. C.; Ruiz-Robles, Mitchel A.; Rojas, D.; Surabhi, Srivathsava (NPJ Materials Degradation, 2025)
Steel corrosion in saltwater costs over \$2.5 trillion annually. This review highlights advancements in zinc and polymer-based coatings for marine protection. It covers traditional methods and emerging technologies like nanoparticle-enhanced alloys, conducting polymers, metal organic frameworks (MOFs), and 2D materials. These offer improved resistance, self-healing, and intelligent protection with a future focus on sustainability and extended service life for marine infrastructure.

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.

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.

Altered Octopamine synthesis impairs tyrosine metabolism affecting Helicoverpa armigera vitality - Patil, Yogita P.; Wagh, Deepti S.; Barvkar, Vitthal T.; Gawari, Shyam K.; Pisalwar, Priyanka D.; Ahmed, Shadab; Joshi, Rakesh S. (Pesticide Biochemistry and Physiology, 2025)
Tyramine (1-hydroxylase (T(1H) is a key enzyme in the biosynthesis of octopamine (OA), a vital neurohormone in invertebrates. This study explores the expression patterns and functional role of Helicoverpa armigera T(1H (HaT(1H) across various tissues and developmental stages. HaT(1H expression was highest in the head and adult male stages, reflecting tissue-specific and developmental regulation. HaT(1H silencing significantly increased locomotion and decreased feeding behavior. OA supplementation in silenced insects or HaT(1H overexpression showed a contrary effect on locomotory and feeding behavior. In silico screening and inhibitory assays identified tomatidine, a tomato-derived metabolite, as a potent HaT beta H inhibitor with strong binding affinity. In vivo bioassays confirmed tomatidine's inhibitory effects, reducing feeding and increasing mortality in H. armigera. Modulation in HaT(1H expression or activity disturbs the tyrosine metabolic pathway, with altered levels of tyramine, octopamine, and dopamine. These results highlight HaT(1H as a key regulator of OA biosynthesis, influencing insect feeding, locomotion, and overall survival. The present study also introduces tomatidine as a potential candidate for insect control, given its ability to disrupt HaT beta H function. This work provides new insights into the physiological roles of HaT beta H and offers promising avenues for developing targeted pest management strategies.
Keywords: Helicoverpa armigera; Octopamine biosynthesis; Tomatidine; Tyramine (1-hydroxylase (HaT(1H); Tyrosine metabolic pathway

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.

Anomalous membrane organization by omega-6 and omega-9 fatty acids - Porte, Sudha; Pandia, Swaratmika; Joardar, Ankita; Saraf, Deepashri; Pinjari, Aadil; Chakraborty, Hirak; Sengupta, Durba (Physical Chemistry Chemical Physics, 2025)
Omega fatty acids are currently being marketed as healthy food supplements as they have been implicated in multiple pathophysiological conditions, such as reducing plaque formation of A beta peptide and inhibiting SARS-CoV-2 infection. Their mode of action has been hypothesized to be via membrane reorganization by the unsaturated acyl chains, leading to the modulation of lipid-protein cross-talk. However, the lack of molecular details led us to evaluate the molecular effect of omega-6 (linolenic acid) and omega-9 (oleic acid) fatty acids on membrane organization using a consolidated approach of fluorescence spectroscopy and all-atom molecular dynamics simulation. Our results show that the effect of these omega fatty acids is sensitive to their protonation states. Contrary to the accepted notion that chain unsaturation causes membrane disordering, both experimental and simulation results demonstrate that protonated linoleic acid promotes membrane ordering, despite having two unsaturations at the fatty acyl chain. However, protonated oleic fatty acid, with reduced unsaturation, disordered the acyl chain area of the lipid membranes. Equally surprisingly, deprotonated oleic acid orders, whereas deprotonated linoleic acid disorders, the membrane core region. Interestingly, while the lipid order parameter measurements from simulations did not capture these subtle differences, the calculated rotational autocorrelation function of a membrane dye was in line with experimentally measured apparent rotational correlation times. Our work provides a comprehensive revised molecular picture of the effect of omega fatty acids on membranes and highlights the importance of rigorous comparative approaches, as experimental and simulation studies in isolation can sometimes lead to inconsistent results.

Atomic Layer Deposition Grown Titania Phases (TiO2, TiO, Ti2O) and its Influence on Water Splitting Electrocatalysis - Swaminathan, Jayashree; Palani, Parthiban; Salpekar, Devashish; Hernandez, Francisco Carlos Robles; Ashokkumar, Meiyazhagan; Ajayan, Pulickel M. (Advanced Sustainable Systems, 2025)
The systematic engineering of atoms and the precise tuning of their arrangement can unlock a range of hidden yet remarkable properties of materials. In this study, different phases of titanium oxide, including TiO2, TiO, and Ti2O, are developed using the Atomic Layer Deposition (ALD) technique. Notably, a novel TiO(2 )electride with a pbcn space group is identified, and variations in stoichiometries, such as Ti1.80O, Ti2.05O, and Ti2.30O, are observed through Rietveld analysis of the corresponding X-ray Diffraction (XRD) data. High-resolution transmission electron microscopy (HRTEM) imaging further revealed line defects such as stacking faults and edge dislocations in Ti2O. The interplay of stoichiometric defects in Ti2O electrides leads to tunable electrocatalytic behavior, enabling transitions from oxygen evolution to hydrogen evolution reactions. Importantly, using Density functional theory (DFT), Paterson analysis, and Fourier electron density mapping, the exceptional metallic properties of Ti2O are rationalized as arising from its unique spatial electron density distribution. Overall, this work underscores the significance of atomic-level structure engineering and opens the door to a new class of titanium oxide catalysts for electrochemical water splitting.
Keywords: atomic layer deposition; defect engineering; defect-rich titania; Electrocatalytic water splitting; Ti2O electrides

Atomically dispersed Co-Cu dual active sites in carbon networks as an efficient oxygen electrocatalyst - Sinha, Nibedita; Das, Chandni; Pal, Santanu; Urkude, Rajashri R.; Ahmed, Tanbir; Ghosh, Biplab; Roy, Poulomi (Dalton Transactions, 2025)
Single-atom metal-based electrocatalysts offer extended advantages by maximizing the utilization of active sites but often suffer from complex synthesis processes and low-density metal loading. The present work showcases a strategic design for integrating highly dense cobalt-copper dual atoms dispersed on a nitrogen-rich porous carbon network (CoCu-NGC). The atomically dispersed CoCu-NGC outperforms the ORR and OER activities of their single metallic counterparts (Co-NGC or Cu-NGC) and conventional noble-metal based electrocatalysts (Pt/C and RuO2). Benefitting from the electronic modulation in the dual SAC system, the CoCu-NGC displayed outstanding bifunctional performance with low Delta E values of 0.69 V in freshwater and 0.78 V in seawater, highlighting it as a potential alternative to the costly state-of-art electrocatalysts.

Atroposelective construction of biaryls enabled by a Ni(II)-catalyzed aerobic oxidation strategy - Pradhan, Chandini; Punji, Benudhar (ACS Central Science, 2025)
Enantioriched biaryls synthesis via aerobic oxidative cross-coupling of arenes involving <a class="ext-link" href="https://pubs.acs.org/doi/full/10.1021/acscentsci.4c01501" style="box-sizing: border-box; outline: none; text-decoration-line: none; color: rgb(51, 97, 184); transition: color 0.3s; font-family: Roboto, arial, sans-serif; font-size: 16px;">bioinspired oxygen activation by Ni(II).

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

Base-mediated denitrative C3-alkylation of quinoxaline derivatives - Pansare, Vaibhav Ramachandra; Barsu, Nagaraju (Organic & Biomolecular Chemistry, 2025)
We have developed a novel base-mediated method for the selective C3-alkylation of quinoxalin-2(1H)-one and N-protected quinoxalin-2(1H)-one using inexpensive, unactivated nitroalkanes. This approach tolerates a wide range of functional groups and supports the synthesis of various bioactive compounds. Gram-scale reactions demonstrate the scalability of the method. The proposed mechanism was validated by control experiments.

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

Bio-based poly(isobornyl acrylate)-b-(citronellyl methacrylate) block copolymers by PET-RAFT polymerization: thiol-ene modification and adhesion studies - Hetkale, Pragati M.; Purohit, Poorvi M.; Nair, Kiran Sukumaran; Ambade, Ashootosh V. (Journal of Macromolecular Science Part A-Pure and Applied Chemistry, 2025)
In this study, poly(isobornyl acrylate)-b-poly(citronellyl methacrylate) (PIBA-b-PCMA) block copolymers were synthesized with controlled molecular weights and low dispersity using photoinduced electron transfer-reversible addition-fragmentation chain transfer (PET-RAFT) polymerization of isobornyl acrylate (IBA) and citronellyl methacrylate (CMA), both terpene-derived monomers. A series of block copolymers was obtained by varying the chain length of PCMA block. Kinetics study of the polymerization of IBA and CMA using 4-cyano-(((dodecylthio)carbonothioyl)thio)pentanoic acid (CDTPA) as chain transfer agent showed a linear plot of ln[M]0/[M]t vs time indicating first order reaction. Distinct glass transition temperatures were observed for the individual blocks and enhanced thermal stability was seen with increasing PCMA content. Post-polymerization modification of the polymer was demonstrated using thiol-ene reaction with the vinyl group in the pendent citronellyl moiety. Adhesion performance, evaluated through lap shear test on aluminum substrates, showed that the block copolymers achieved peak shear strengths of 1.74 MPa at a 38:62 PIBA:PCMA mole ratio.
Keywords: adhesion strength; Bio-based polymers; block copolymers; PET-RAFT polymerization; Thiol-ene reaction

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.

Carbon capture from flue gases using an integrated membrane skid - Yang, Yutong; Han, Yang; Prasad, Babul; Pang, Ruizhi; Zou, Changlong; Ho, W. S. Winston (Journal of Membrane Science, 2025)
A prototype spiral-wound (SW) membrane module with a commercial-size diameter of 8 `' and a membrane area of 35 m(2) was fabricated using a new thin-film-composite facilitated transport membrane (FTM) scaled up to 21 `' in width by a continuous roll-to-roll coating process. This SW module was tested with an actual coal flue gas at the Center for Applied Energy Research (CAER) at the University of Kentucky, which exhibited an average CO2 permeance of 4269 GPU with a CO2/N-2 selectivity of 165 and remained stable for 100 h. The permeance and selectivity results are consistent with those determined from lab and scale-up flat-sheet samples. An integrated membrane skid was then constructed, where 2 SW membrane modules were arranged to form an enriching cascade. The 8 `'-diameter prototype SW module previously tested at CAER was installed as the primary CO2 capture stage, while a smaller SW module (5 `' diameter and 12 m(2) membrane area) was used to further enrich the CO2 to >95% purity. By using a simulated coal flue gas (13% CO2), the skid was operated at steady-state for 800 h with 91.0% of the CO2 removed from the flue gas, delivering 1.33 tonne/day CO2 product at 95.5% dry purity. The bench skid was then installed at the National Carbon Capture Center (NCCC), Wilsonville, AL and tested with an actual natural gas (NG) flue gas (8.6% CO2). 90-99% CO2 capture degrees were demonstrated during the parametric testing, and the skid was operated at steady state for 500 h cumulatively with 91.0% CO2 capture and >95% CO2 purity. A simulated natural gas combined cycle (NGCC) flue gas (4.3% CO2) slipstream was further provided by diluting the NG flue gas with air, and 90-99% CO2 capture degrees were also achieved with dry CO2 purities all above 95%. All these capture degrees and CO2 purities were in good agreement with their model predictions.
Keywords: Actual flue gas; carbon capture; Field trial; Integrated membrane skid; Membrane module

A carbon nanotube wrapped Na3V2(PO4)2F3 cathode with a dual cation electrolyte: enhancing high-voltage stability and cyclability in zinc-ion batteries - Pandey, Priyanshi; Shivade, Rajkiran; Deshmukh, Ashvini; Shelke, Manjusha (Nanoscale, 2025)
Aqueous zinc-ion batteries (ZIBs) offer several compelling advantages as a safer and sustainable energy storage system. Polyanion-based cathodes, characterized by their comparatively higher voltage and structural stability, are promising for ZIBs. However, challenges hinder their practical applications, such as inferior rate capability and limited cycling stability. In this study, we constructed a carbon nanotube wrapped Na3V2(PO4)2F3 (NVPF-CNT) cathode integrated with a highly concentrated dual cation electrolyte (DCE) to enhance the electrochemical performance of ZIBs by enabling a synergistic Na+ and Zn2+ co-insertion mechanism. The DCE effectively regulates the solvation structure, stabilizes the solid electrolyte interface (SEI), minimizes free water molecules, thereby widening the electrochemical window and reducing the side reactions, and inhibits cathode dissolution. Consequently, the CNT-wrapped NVPF cathode exhibits an initial reversible capacity of 131.3 mAh g-1 at 0.05 A g-1, and retains 84% of its capacity over 500 cycles at 1 A g-1, with a nominal voltage of similar to 1.5 V. This approach offers valuable insights into the potential of CNT-wrapped NVPF cathodes in combination with a DCE while providing a comprehensive framework for advancing high-performance ZIBs.

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

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 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

Chlorophobic iron hydrogen phosphite as OER-active electrocatalyst in anion exchange membrane (sea)water electrolysis - Das, Chandni; Sinha, Nibedita; Nair, Aathira; Pal, Santanu; Joshi, Kavita; Roy, Poulomi (Small, 2025)
Seawater electrolysis is recognized as a promising technology to cater to the worldwide drive for sustainable hydrogen production; however, its practical viability is often hindered by the inevitable anode corrosion arising from the electrode side reactions owing to the presence of high chloride content which eventually degrade the electrode performance eventually. Herein, the design of unprecedented ammonium iron hydrogen phosphite (FeHPhi) along with a trace amount of Cu, is reported as the unique and much desired electrode material for seawater electrolysis due to its special chloride repellant nature along with great electrocatalytic activity toward water oxidation. The [HPO3](2-) oxoanion as Lewis base in the structure effectively restricts chloride ions, while the Fe center acts as Lewis acid offering an active site for water oxidation, also well-supported theoretically. Leveraging this frustrated Lewis pair combination, the electrocatalyst achieves a high current density of 500 mA cm(-2) at 344 mV overpotential in alkaline real seawater with impressive robustness to sustain for 200 h when operated under chlorine evolution reaction dominating region (>2 V). The electrocatalyst also demonstrates superior performance in anion exchange membrane freshwater and seawater electrolysis, demonstrating its potential applicability.
Keywords: AEM electrolyzer; chloride repellant; electrocatalyst; hydrogen production; seawater oxidation

CoBr2-catalyzed straightforward synthesis of quinoxalines via dehydrogenative coupling strategy - Dubey, Shivansh; Punji, Benudhar (Chemistry-an Asian Journal, 2025)
Establishing a benign and straightforward protocol for synthesizing biorelevant and synthetically valuable quinoxaline is very important. Herein, we report a simple and efficient protocol for the sustainable synthesis of diverse quinoxaline derivatives catalyzed by cobalt salt. The reaction proceeds through the dehydrogenative coupling of alkyl and aryl ethane 1,2-diols with aryl diamines in the presence of a catalytic CoBr2/K2CO3. The usage of the greener solvent 2-MeTHF and the release of H2 and H2O as the sole byproducts make the process advantageous. The protocol led to the synthesis of diverse quinoxalines bearing synthetically useful functionalities, such as fluoro, chloro, bromo, cyano, trifluoromethyl, and ether. The reaction is presumed to proceed via the dehydrogenative-condensation pathway involving a cobalt-hydride intermediate.
Keywords: cobalt; dehydrogenative coupling; heterocycles; ligand-free process; Quinoxaline

Cocrystals of the green fluorescence protein chromophore analogue: coformer-induced switch between AIE and ACQ - Suresh, Sneha; Dabke, Niteen B.; Pandya, Rinu; Vanka, Kumar; Dutta, Madhusudan; Gonnade, Rajesh G. (Crystal Growth & Design, 2025)
Fluorescent organic solids hold great potential for advancing photonics applications. However, tuning their solid-state photoluminescent emissions remains a significant challenge. In this study, we report the synthesis and characterization of five cocrystals (two cocrystal polymorphs) derived from a pristine imidazolinone derivative (A) and the various coformer molecules, namely 1,2,4,5-tetrafluoro-3,6-diiodobenzene, 1,2,4,5-tetrafluoro-3,6-dibromobenzene, perfluoronaphthalene, and 3,4,5-trifluorobenzoic acid. The structural and optical properties of these cocrystals were examined by using single-crystal X-ray diffraction, absorption spectroscopy, photoluminescence spectroscopy, and photoluminescence decay spectroscopy. Cocrystals I, II, and III are isomorphous pairs and exhibit three-dimensional isostructurality, where the coformer molecules bridge adjacent helices of compound A, leading to aggregation-induced emission. In contrast, the cocrystal polymorphs IVA and IVB developed using coformer 3,4,5-trifluorobenzoic acid form two-dimensional sheet-like structures mediated by pi-stacking interactions between the coformers and molecule A, with interplanar distances ranging from 3.2 to 3.5 & Aring;. These stronger pi-pi interactions promote nonradiative decay pathways, resulting in reduced or quenched fluorescence and an aggregation-caused quenching effect. To gain further insights into their electronic properties, theoretical analysis including frontier molecular orbitals, time-dependent density functional theory, Hirshfeld surface analysis, molecular electrostatic potential, and noncovalent interaction plots were performed.

Comprehensive tissue specific analysis of antioxidant potential and metabolite profiling of a vulnerable therapeutic herb Ceropegia sahyadrica - Pandey, Meena; Dholakia, Bhushan B.; Saraf, Purva S.; Punekar, Sachin A.; Giri, Ashok P. (3 Biotech, 2025)
This study investigated tissue-culture of an endangered medicinal herb, Ceropegia sahyadrica, along with tissue-specific variation in antioxidant activity and GC-MS based phytochemical profiling using wild and in vitro explants. In vitro leaf explants exhibited callus induction rate of 100% in Murashige and Skoog media containing 6-benzylaminopurine (4 mu M) and 2,4-dichlorophenoxyacetic acid (2 mu M) with 5% sucrose, whereas in vitro root explant achieved 66.7% with the combination of 2 mu M 6-benzylaminopurine and 1 mu M 2,4-dichlorophenoxyacetic acid in Murashige and Skoog medium. Microtuberization was most pronounced in in vitro root explants with a maximum response of 73.3% in 1 mu M indole-3-acetic acid, 2 mu M 6-benzylaminopurine and 5% sucrose. Scanning electron microscopy imaging revealed distinct cellular organization among tissues. Further, antioxidant potential assessed through 1,1-diphenyl-2-picrylhydrazyl radical scavenging assays and estimated total phenolic content showed metabolic variation and commonality between in vitro and wild tissues. Additionally, phytochemical profiling by gas chromatography-mass spectrometry identified 201 compounds, including alkaloids, fatty acid methyl esters, flavonoids, phytosterols and other bioactive molecules with alterations in metabolite profiles between in vitro and wild tissues. These findings demonstrated that explant origin and culture condition might significantly influence metabolic responses for conservation and ensures a reliable source of bioactive compound.
Keywords: Ceropegia- Conservation; Endemic medicinal herb; GC-MS; Metabolite profiling; Tuberization

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.

Cyclopropane containing triterpenoids, cycloartenone, and cycloartenol: isolation, chemical transformations, and anticancer studies - Paul, Sayantan; Mandal, Kartik; Santra, Manas K.; Bhattacharya, Asish K. (ChemistrySelect, 2025)
Cycloartenone and cycloartenol, two plant-derived triterpenoids possessing cyclopropane ring were isolated from the latex of Artocarpus heterophyllus (jackfruit). Cycloartenol was chemically modified to synthesize dihydrocycloartenol via acetylation and deacetylation methodology followed by hydrogenation. Hydroxyl group present in the cycloartenol was also employed for the nitro benzoate formation. All the isolated and synthesized compounds were assayed against MCF7 breast cancer cell line for their anticancer properties.
Keywords: Anticancer studies; Artocarpus heterophyllus; Chemical transformations; Cycloartenol; Cycloartenone

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.

Deciphering the intricate mechanisms behind the selective oxidation of methane to C1 and C2 oxygenates over FeAu/γ-Al2O3 catalysts - Prabu, Marimuthu; Manikandan, Marimuthu; Rengam, B. Sathya Sai; Ramakrishnan, Archana; Raja, Abhishekram; Urkude, Rajashri R.; Ghosh, Biplab; Varghese, Jithin John; Raja, Thirumalaiswamy (Chemical Engineering Journal, 2025)
In this work, we demonstrate an eco-benign synthesis protocol for preparing gold nanoparticles and the role of the strong interaction between gold nanoparticles and iron oxide in FeAu/gamma-Al2O3 catalysts that render it an anionic (Au delta-) character while tailoring them in a smaller size. The multifunctional FeAu/gamma-Al2O3 catalyst selectively produces ethanol (95 % selectivity, similar to 240 mu mol(-1) cat) at a mild temperature of 75 degrees C without the addition of co-reactants during liquid phase methane oxidation with molecular oxygen. Conversely, Au/gamma-Al2O3 and Fe/gamma-Al2O3 catalysts exhibited high selectivity for CH3OH and HCHO. A high dispersion accompanied by strong electronic interaction between the Au delta–FeOx, as corroborated by diverse techniques, enables methane activation across the interface and coupling on the gold nanoparticles, which are responsible for the markedly improved formation of ethanol. Furthermore, in situ DRIFTS studies and DFT investigations point to a reaction mechanism of coupling of CH2OH and CH3 intermediates as the most likely route for ethanol formation.
Keywords: Anionic gold catalysts; Au-FeOx synergism; C-H bond activation; Ethanol; Methane oxidation; Methanol

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

Design and synthesis of PtPdNiCoMn high-entropy alloy electrocatalyst for enhanced alkaline hydrogen evolution reaction: a theoretically supported predictive design approach - Chandran, M. Athira; Dutta, Pritha; Singh, Prashant; Singh, Ashutosh K.; Prasad, Bhagavatula L. V. (Advanced Functional Materials, 2025)
Electrocatalytic hydrogen generation requires a cutting-edge, multifunctional electrocatalyst with abundant active sites to drive multielectron transfer reactions. High entropy alloys (HEA) are complex five or more-element alloy systems with high configurational entropy which makes them unique materials for next-generation electrocatalysts. Here, in this work, based on new screening guidelines for catalyst selections that combine density-functional theory calculated Gibbs formation-enthalpy with bond length and electronegativity variance, a novel HEA electrocatalyst consisting of five elements, namely, Pt, Pd, Ni, Co, and Mn is designed. By simple room temperature electrodeposition, the designed catalyst is prepared and its hydrogen evolution reaction (HER) is explored and validated through experimental and theoretical approaches. The HEA demonstrated a superior HER activity with an overpotential of 22.6 mV at -10 mA cm-2 which outperforms Pt/C commercial catalyst. No evident degradation of the material is detected even after 100 hours of continuous operation under high current density. Moreover, the HEA has shown exceptional performance in harsh electrolyte conditions such as in simulated seawater and actual seawater. Remarkably, the density-functional theory calculated small Gibbs formation-enthalpy (approximate to 0 eV) compared to Pt/C places the new HEA near the apex of Trasatti's model of Volcano plot, which is also suggestive of superior HER activity.
Keywords: DFT; electrocatalysts; Electronic Structure; HER; high-entropy alloys

Desymmetrization of myo-inositol - Patil, Nivedita T.; Patil, Madhuri T.; Gonnade, Rajesh G.; Shashidhar, Mysore S. (Carbohydrate Research, 2025)
Chemistry and biology of phosphoinositols have been intensely investigated areas of research over the last 4-5 decades due to their involvement in cellular signal transduction pathways. Efficient laboratory synthesis of enantiomeric derivatives of inositols was a central issue since they were required for the delineation of the myo-inositol cycle as well as for the total synthesis of polyol based natural products and their derivatives. This essentially meant the development of competent methods for the desymmetrization of myo-inositol leading to the preparation of enantiomeric O-substituted derivatives of myo-inositol. This was approached by: the classical resolution methods involving separable diastereomers, the chiral pool synthesis, enzyme catalysis, asymmetric catalysis and preferential crystallization of enantiomers in a racemic conglomerate. This review summarizes results obtained in author's laboratory, as well as those reported in the literature on attempts at desymmetrization of myo-inositol.
Keywords: Conglomerate; Crystallization; Cyclitol; Enantiomers; Inositol; Lipid

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 reversed-phase HPLC method for purity assessment of aryl porphyrins and their metal complexes - Ujagare, Ashish Mohan; Uzagare, Matthew C.; Ghogare, Bhausaheb N.; Gupta, Lokesh Kumar; Wadgaonkar, Prakash P.; Patil, Vishwanath R.; Donde, Kamini J. (SSC Plus, 2025)
A gradient reversed-phase HPLC method was developed for in-process monitoring of the formation of aryl porphyrins and their corresponding metallo-aryl porphyrins. The method also proved effective for determining their quantitative purity. Optimal results achieving proper peak shape and separation of peaks in the chromatogram were obtained using C8 column and gradient of acetic acid-water and acetonitrile. The detector wavelength was selected for simultaneous detection of starting materials and products for in-process analysis for conversion of aryl aldehydes to corresponding tetraaryl porphyrins at 254 nm and metallo-aryl porphyrins formation from tetraaryl porphyrin at 413 nm, respectively; while the purity of products could be determined at 413 nm. The developed method is efficient, versatile, accurate, and easy to carry out and could serve as a handy tool for the reaction monitoring and determination of purity in the processes development of synthetic porphyrins and metalloporphyrins.

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.

DLP 3D printing and characterization of PEEK-acrylate composite biomaterials for hip-joint implants - Dama, Yogiraj; Jogi, Bhagwan; Pawade, Raju; Pal, Shibam; Gaikwad, Yogesh (Obrabotka metallov - Metal Working and Material Science, 2025)
Introduction. Hip joint replacement is considered the most complex and critically important orthopedic surgical procedure compared to knee and shoulder joint replacements. Over the past few decades, there has been significant advancement in hip joint replacement technology, and various biomaterials have been substantially improved. An increasing number of hip joint replacement surgeries are now successful, assisting individuals in regaining normal daily activity and work capacity comparable to their pre-fracture state. However, the need for revision surgery, specifically for implant replacement, is still observed in active patients several years following the initial operation. This underscores the need to develop durable biomaterials and customized hip joint implants to reduce implant wear and the risk of dislocation. This research study explores a novel PEEK-in-acrylate composite biomaterial with varied weight percentages of PEEK (0 %, 5 %, and 10 %) in an acrylate-based matrix. Tests were conducted to determine its properties, biocompatibility, and 3D printability. Based on the developed material, pins (in accordance with the ASTM standard) were fabricated using 3D printing for subsequent wear rate studies. The potential use of the developed composite materials for hip-joint applications was also thoroughly investigated. The purpose of this study is to develop and investigate a new PEEK in Acrylate composite biomaterial with varied weight percentages of PEEK (0 %, 5 %, and 10 %) in an acrylate-based matrix. The research includes an assessment of the material's properties, biocompatibility, and 3D printability. Using digital light processing (DLP) 3D printing technology at room temperature, pins (in accordance with the ASTM standard) were fabricated. An experimental study of dry sliding wear resistance was conducted on the resulting samples to determine the effect of PEEK weight fraction on the wear rate and frictional performance against an SS 316 steel disk. Scanning electron microscopy (SEM) and Energy-dispersive X-ray spectroscopy (EDS) were used to analyze the surface structure and element distribution within the material. The Methods of Investigation. Digital Light Processing (DLP) 3D Printing technique was used to 3D Print the ASTM pins and Acetabular liner with different weight fraction of PEEK in acrylate. Dry sliding wear tests were carried out using a pin-on-disk tribometer. During testing, the disk rotation speed and the normal load on the pin were varied. The studies were designed to determine the influence of input parameters on the wear rate. A total of nine experiments were conducted for each PEEK weight fraction, with a sliding distance of 4 km per experiment. The load ranged from 20 to 100 N, and the sliding speed varied from 450 to 750 rpm. Surface structure and element distribution were analyzed by Energy-dispersive X-ray spectroscopy (EDS) and Scanning electron microscopy (SEM). Result and Discussion. Current study demonstrates the advantages of varying the weight fraction of PEEK in Acrylate for DLP-fabricated biomaterials. Analysis of the SEM, EDS, and wear testing results indicated that the composite with 10 wt % PEEK in Acrylate exhibited superior microstructural integrity, elemental homogeneity, and significantly improved wear resistance. The 10 wt % PEEK in Acrylate composite, fabricated via DLP 3D printing, is suitable for biomedical implant and healthcare applications
Keywords: 3D printing; Biomaterials; FDM; implant; PLA; print orientation; wear behavior

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 agonist/antagonist modulation of α9-containing nicotinic acetylcholine receptors by 2-ammoniumethyl ethers of stilbenol and stilbenol analogues - Giraudo, Alessandro; Tae, Han-Shen; Hung, Andrew; Richter, Katrin; Shivankar, Bhavana; Armano, Edoardo; Grau, Veronika; Pallavicini, Marco; Adams, David J.; Bolchi, Cristiano (Journal of Medicinal Chemistry, 2025)
2-(Cyclohexyldimethylammoniumethyl)ether of 4-stilbenol (2), and its styryl-modified analogues 21 and 22, were identified as lead compounds from a series targeting human alpha 9 alpha 10, alpha 9, and alpha 7 nicotinic acetylcholine receptors (nAChRs). Compounds 2 and 21 exhibited potent, and subtype-selective modulation of alpha 9-containing receptors, with low nanomolar IC50 values and dual agonist/antagonist activity in a concentration-dependent manner. In contrast, compound 22 acted as a selective, pure antagonist. Molecular dynamics (MD) simulations of compound 21 supported a concentration-dependent allosteric mechanism, with orthosteric binding at low concentrations and vestibular site interaction at higher levels. In a human monocytic cell line, all three compounds inhibited ATP-induced IL-1 beta release at nanomolar concentrations. These findings identify alpha 9 alpha 10-selective ligands as promising scaffolds for the development of nonopioid analgesics and immunomodulators, with favorable selectivity over alpha 7 nAChRs to minimize CNS-related side effects.

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.

An effective alliance for successful coupling: electrochemical alcohol oxidation mediated conversion of indoles to bis(indolyl)methanes - Baravkar, Mayur D.; Prasad, Bhagavatula L. V. (Journal of Applied Electrochemistry, 2025)
Electro-organic transformation of indoles to bis(indolyl)methanes (BIMs) has been successfully achieved by combining the electrochemical alcohol oxidation reaction (AOR) with indole coupling. The fact that it is the readily available alcohols and not the traditionally used aldehydes or ketones that provide the bridging -CH2- (methylene) for this transformation makes this path extremely attractive and valuable. The formation of aldehydes as reactive intermediates during the AOR has been dexterously utilized to achieve this transformation. Most gratifyingly, the transformation also can be carried out in water-alcohol mixtures and the yields and conversions are better than the most of the previously reported chemical catalytic transformations using specially designed metal complexes. Various substituted indoles were selectively converted to their corresponding BIMs in decent yields. This strategy could further be exploited for the synthesis of different natural products, including the much sought after deuterium substituted ones (as CD3OD is readily accessible), and other important biologically active alkaloids and drug molecules, etc.
Keywords: Alcohol oxidation reaction; Bis(indolyl)methanes; Direct alcohol fuel cell; Electroorganic transformations; Vibrindole A

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

Energy-saving H2 production through H2S electrolysis accompanying solid sulfur recovery using a Ni3S2/Ni3N heterostructure as the electrocatalyst - Sinha, Nibedita; Das, Chandni; Pal, Santanu; Roy, Poulomi (ACS Applied Energy Materials, 2025)
The thermodynamically feasible electrochemical sulfion oxidation reaction (SOR) is advantageous for degrading the toxic H2S pollutant into the value-added chemical sulfur but often suffers from catalyst passivation due to blockage of electroactive sites by accumulation of solid sulfur. The strategic design of electrocatalysts with enhanced electrochemical activity and improved sulfur tolerance is thereby crucial to fully harness the benefits of the SOR. In this work, we developed nickel sulfide nanorods decorated with nickel nitride nanoparticles directly grown on conductive nickel foam as an efficient trifunctional electrocatalyst for the SOR, oxygen evolution reaction (OER), and hydrogen evolution reaction (HER). Optimized Ni3S2/Ni3N showed lower electrode potentials of 0.25, 1.487, and 0.89 V to achieve a benchmark current density of 10 mA cm(-2) for the SOR, OER, and HER, respectively. The hybrid H2S electrolysis setup employing a Ni3S2/Ni3N electrocatalyst drastically reduced the cell potential by 1.24 V compared to that of conventional water electrolysis at a current density of 200 mA cm(-2). Having said that, heterostructure formation not only enhances the activity for the SOR but also helps to avoid sulfur poisoning, enabling the electrocatalyst to sustain for 100 long hours at a high current density of 100 mA cm(-2). Consequently, the approach with the developed electrocatalyst has the ability to reduce the energy consumption by 59.22%, which can make rigorous, economically viable H-2 production driven by solar energy.
Keywords: energy-economic; H-2 production; H2S electrolysis; heterostructure; solidsulfur

Engineered silk-dressing for acceleratedwound healing: biocompatibility and efficacy studies - Deshpande, Rucha; Pillai, Lakshmi R.; Sayyad, Raeesa; Shukla, Swati; Nisal, Anuya; Venugopalan, Premnath (Macromolecular Bioscience, 2025)
Advanced wound care dressings are essential for improving clinical outcomes. The present study investigates the wound management potential of a unique dressing fabricated from silk proteins. The dressing was characterized for its physical and structural properties, including surface texture, porosity, fluid absorption capacity, and moisture vapor transmission rate. These parameters have been found to be critical for optimal wound healing. In vivo full thickness wound healing studies in a rat model validated the efficacy of the Silk-dressing compared to conventional cotton gauze and commercial polyurethane foam dressings. Histopathological analysis confirmed improved re-epithelialization, collagen deposition, angiogenesis, and formation of secondary follicles. Key advantages of Silk-dressing included non-adherence, absorption of exudate, maintenance of optimal moisture at wound site and acceleratedwound closure. Biocompatibility studies were also conducted in accordance with ISO 10993 guidelines, demonstrating no cytotoxicity, irritation, sensitization, or pyrogenicity. These findings highlight the potential of this uniquely designed Silk-dressing as a superior alternative for wound management, with a potential to improve clinical outcomes.
Keywords: Biocompatibility; biopolymer; ISO 10993; Silk protein; wound Healing

Enhanced electrocatalytic performances of NiCr layered double hydroxides by oxalate intercalation in anion exchange membrane water electrolysis - Pal, Santanu; Sinha, Nibedita; Das, Chandni; Chauhan, Inderjeet; Ahmed, Tanbir; Roy, Poulomi (ACS Applied Materials & Interfaces, 2025)
Layered double hydroxides (LDHs) have attracted much attention these days in the field of water electrolysis due to easy modulation in their layered structure and properties. Herein, NiCr-LDH has been developed, and its interlayer spacing has been considerably increased by oxalate intercalation. Such increased interlayer spacing allows easy access of hydroxides to a large number of electroactive sites and thereby boosts the electrocatalytic performances both for oxygen and hydrogen evolution reactions. Being very active toward both the electrocatalytic reactions, the oxalate-intercalated NiCr-LDH was further explored in an alkaline anion exchange membrane water electrolyzer (AEMWE), achieving 800 mA cm-2 at 1.88 V cell voltage at an operating temperature of 60 degrees C. In fact, the electrolyzer efficiency has been determined to be as high as 69.66%, and the calculated H2 production cost was found to be \$0.97 per gasoline-gallon equivalent, which is well below the targeted cost by the Department of Energy, USA. The electrocatalyst was also examined in harsh alkaline media, like highly saline or seawater, which also indicated its ability to carry out sustainable seawater electrolysis, restricting chlorides to a great extent. Interestingly, post-electrolysis characterization reveals the fact that oxalate decomposition aided carbonate formation within interlayers of NiCr-LDH, and high affinity toward hydroxides is responsible for restricting chlorides during the electrolysis process, apart from the great electrocatalytic activity.
Keywords: Anion exchange; hydrogen production; interlayerspacing; Layered double hydroxide; Sustainable; water electrolyzer

Enhanced light-matter interaction in gas nitridation-derived TiNx thin films for potential plasmonic applications - Tony, Liya; Selvam, I. Packia; Vinod, C. P.; Potty, S. N. (Journal of Materials Science, 2025)
Titanium nitride is a substitute material exhibiting improved opto-electrical characteristics suitable for plasmonic purposes with adjustable attributes. In this study, we have embraced an innovative methodology for the fabrication of titanium nitride thin coatings via the nitridation of RF magnetron-sputtered titanium metallic films for surface plasmon resonance utilisation. The augmented electrical and optical features of TiN thin coatings prepared through the nitridation procedure are reported for the first time. The metallic coatings underwent gas nitridation at diverse temperatures within the range of 450-600 degrees C. The titanium nitride phase evolution in the coatings was corroborated by x-ray diffraction and x-ray photoelectron spectroscopy examinations. The dielectric function is deduced from reflection spectra through Drude-Lorentz model fitting, and the manifestation of surface plasmon excitation in the visible region was confirmed by correlating with carrier concentration assessments and by ensuring the required negative permittivity in the region. The red shift of screened plasma wavelength was observed with the nitridation temperature, and the same is varied in the wavelength range 400-700 nm. Ultimately, surface plasmons were excited in coatings with optimised thickness using Kretschmann configuration in wavelength interrogation mode.

Enhanced oxygen electrocatalysis in zinc-air batteries via a bifunctional bimetallic organic framework - Shivade, Rajkiran D.; Pandey, Priyanshi; Shelke, Manjusha V. (Journal of Power Sources, 2025)
An efficient bifunctional oxygen electrocatalyst, a nickel-iron metal organic framework (NF-MOF) grown within three-dimensional (3D) nitrogen doped porous carbon (NPC) collectively referred as NF-MOF@NPC, is developed as high performance electrocatalyst for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). The synergistic effect of bimetallic active sites coupled with conductive nitrogen doped porous carbon matrix, provides chemical stability, abundant active sites, enhanced electron transfer, and improve catalytic activity. NFMOF@NPC exhibits OER onset potential of 1.60 V at current density of 10 mA cm- 2 with Tafel slope of 126 mV dec- 1 and ORR half wave potential of 0.81 V with electron transfer number of 3.91. A zinc-air battery fabricated using NF-MOF@NPC shows peak power density of 102 mW cm-2 and specific capacity of 741 mAh g-Z 1n. It also exhibits remarkable cycling stability for 120 h at current density of 10 mA cm- 2 highlighting its promise as alternative for conventional platinum on carbon (Pt/C) and ruthenium dioxide (RuO2) electrocatalysts demonstrating its potential for next generation energy storage devices.
Keywords: Bifunctional Electrocatalyst; Rotating disk electrode; zinc-air battery

Enhancement of mechanical and rheological properties of PA-12 through silane modification - Jadhav, V. Pravin; Mahajan, Digvijay; Patil, Prashant; Umbarkar, Shubhangi B.; Pol, Harshawardhan (Bulletin of Materials Science, 2025)
This research examines the effects of silane modifications on polyamide 12 (PA-12) to improve its mechanical and thermal properties. The study employs a reactive extrusion technique to integrate various silanes-Dynasylan (R) AMEO, Dynasylan (R) 1189, Dynasylan (R) DAMO and Dynasylan (R) VPS 4721-at different concentrations (0.25, 0.5 and 0.75%). Key findings reveal that silane modifications significantly enhance the tensile strength, impact resistance and viscoelastic behaviour of PA-12, with the Dynasylan (R) DAMO formulation achieving the highest tensile strength of 38.25 MPa vis-& agrave;-vis 8.02 MPa for PA-12. The modifications also resulted in a reduction of crystallinity by over 35%, contributing to improved toughness and impact strength. Rheological assessments indicate that the flow properties of PA-12 are positively altered, enhancing its complex viscosity and storage modulus, which are crucial for applications in automotive and aerospace industries. Thermal analysis through differential scanning calorimetry and thermogravimetric analysis confirms improved thermal stability, particularly in the 0.5% Dynasylan (R) AMEO-modified sample, exhibiting an onset temperature of 421.87 degrees C. The study emphasizes the importance of the silane type and dosage in tailoring PA-12's performance for advanced applications, suggesting future research directions to further refine silane-modification techniques for enhanced polymer performance. This research provides valuable insights into polymer-modification strategies, highlighting the potential for silane treatments to optimize the mechanical, thermal and rheological properties of PA-12 for diverse industrial applications.
Keywords: mechanical properties; Polyamide 12 (PA-12); reactive extrusion; rheological behaviour; silane modification; thermal stability

Enzymatic biodegradation of used engine oil using a novel lipase derived from renewable feedstocks - Tracy, Preetanshika; Dasgupta, Diptarka; Ashok, Patel Pratima; More, Snehal; Sarkar, Bipul; Porwal, Jyoti; Tripathi, Deependra (World Journal of Microbiology & Biotechnology, 2025)
This study introduces an eco-friendly enzymatic approach for biodegrading used engine oil, utilizing a novel lipase from the mesophilic yeast strain Pichia Caribbica. The yeast was cultured in detoxified corncob hydrolysate with used cooking oil as an inducer. OVAT study confirmed that the optimal pH and temperature for lipase production by the strain was 7.0 and 25 degrees Celsius, respectively, with lipase activity of 70 IU/mL. The enzyme effectively degraded similar to 46% of used engine oil over a period of 15 days. Gas Chromatography-Mass Spectrometry (GC-MS) and FT-IR analysis confirmed a significant reduction in hydrocarbon concentrations and the emergence of new functional groups, confirming the enzyme's ability to degrade complex hydrocarbons into less toxic derivatives. These findings highlight the lipase's potential as an effective biocatalyst for eco-friendly bioremediation of oil-contaminated environments, such as soils and aquatic systems, while also emphasizing its role in environmental management through the reuse of waste by-products in enzyme production, thus reducing the environmental impact of improper waste disposal.
Keywords: Biodegradation; Lipase; PC5703; Used cooking oil; Used engine oil

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

Evaluating sodium-ion pouch cell battery for renewable energy storage under extreme conditions - Shelke, Mehul; Boyer, Jamee M.; Mirzapure, Vinay; Pol, Vilas G. (Communications Chemistry, 2025)
A sodium-ion battery (SIB) is a sustainable energy storage technology based on abundantly available raw materials. It is a commercially viable option because of the processing similarity with Li-ion battery. Most of the energy storage studies focus on the near room temperature performance of different battery chemistries. Herein, we report the ultralow temperature performance of the SIB pouch cell. The cells fabricated using low-temperature compatible components showed significant specific energy values around 96, 74, and 46 Wh kg-1 at room temperature, -25 degrees C, and -50 degrees C, respectively. We demonstrated the battery performance under laboratory conditions as well as under actual windy and snowy environments. Such an exhibition highlights the use case of the SIB pouch cell as an emergency energy storage device in extreme weather conditions. Moreover, charging of SIB cell at -100 degrees C using polycrystalline Si solar cell is also reported, indicating the possibility of deployment for space expeditions.

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

Exploring FeSe2 and porous carbon composite as a cost-effective host for Al3+ in aqueous Aluminum ion batteries - Mirzapure, Vinay; Patrike, Apurva; Shelke, V, Manjusha (Electrochimica Acta, 2025)
Aluminum is a high-energy-density material with low cost, making rechargeable aluminum ion batteries (AIBs) a attractive alternative to alkali metal ion batteries. However, the practical development of aqueous AIBs is hindered by limited electrode. Herein, we report FeSe2-decorated porous nitrogen and sulfur-doped carbon spheres (FSPNSCS) as a cathode material for aqueous AIBs, with an emphasis on the reaction kinetics and electrochemical performance. FSPNSCS is synthesized through a hydrothermal approach, confirmed by comprehensive characterizations using X-ray Diffraction for crystalline structure validation and Scanning Electron Microscopy for analyzing composite morphology. Electrochemical properties and kinetics are probed using cyclic voltammetry and galvanostatic charge-discharge tests. Ex-situ XRD reveals a notable peak shift towards higher 2 theta values during discharge, indicating lattice contraction due to Al3+ insertion. Sulfur and nitrogen doping impart elasticity to the lattice structure, enhancing stability during cycling. Ex-situ XPS confirms Al3+ storage and minimal oxide formation, as further supported by microscopic elemental mapping with HRTEM. The FSPNSCS cathode achieves a reversible capacity of 60 mAh g- 1 at a current density of 200 mA g- 1. The system exhibits outstanding cycling stability, retaining over 90 % of its capacity at 500 mA g- 1 over 1000 cycles, highlighting its potential to advance aqueous AIBs for sustainable energy storage.
Keywords: Aqueous aluminum ion battery; cathode material; Electrochemistry; Transition metal selenide

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)

Extraction of highly crystalline and thermally stable cellulose nanofiber from Heliconia psittacorum L.f. leaves - Paul, Sharon; Joseph, Anto; Hridhya, P. D.; Badawi, Michael; Ajithkumar, T. G.; Parameswaranpillai, Jyotishkumar; Asrofi, Mochamad; Dominic, C. D. Midhun (International Journal of Biological Macromolecules, 2025)
Extracting cellulose nanofibers (CNF) from agro-waste is one of the promising and practical ways to develop sustainable nanocomposites. In this study, cellulose nanofibers were extracted from the leaves of Heliconia psittacorum for the first time. The combination of oxalic acid hydrolysis (5 wt%) and steam explosion was used for the isolation of CNF from the leaves of Heliconia psittacorum. The structural and chemical features of the prepared CNF were analyzed using various techniques, including Fourier Transform Infrared Spectroscopy (FTIR), Solid state 13C Nuclear Magnetic Resonance Spectroscopy (13C NMR), Scanning Electron Microscopy (SEM), Energy Dispersive X ray analysis (EDX), Transmission electron Microscopy (TEM), X-Ray Diffraction (XRD) and Thermogravimetric analysis (TGA). TEM micrographs reported 15 to 40 nm diameter for the nanofibers synthesized. XRD analysis reported 91 % crystallinity index for CNF, whereas that of the untreated sample was 76 %. The maximum degradation of the CNF is reported at 355 degrees C, exceeds the untreated sample (316 degrees C). The tensile strength of the CNF derived paper was found to be 23 MPa. The recovered nanocellulose can be further utilized for various applications such as the automobile industry for developing lightweight parts, biosensors, super capacitors, absorption of greenhouse gases, wastewater treatment, and packaging applications.
Keywords: biomass valorization; Nanocellulose; Waste to resource

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

From signals to sustenance: the role of biogenic amines in insect feeding behavior - Patil, Yogita P.; Joshi, Rakesh S. (Journal of Insect Behavior, 2025)
Insect feeding is a complex and finely-tuned behavior that notably impacts their physiological and metabolic processes. Chemical signals and cues, chemosensation, motor response, and physiological changes govern responses to food resources. The role of biogenic amines in regulating feeding is essential, as they significantly affect locomotory changes and nutrient assimilation. Octopamine, tyramine, dopamine, serotonin, and other biogenic amines are neuromodulators, neurotransmitters, and neurohormones. Octopamine and tyramine have contrasting effects on food-seeking and foraging behavior regulation. The interaction among biogenic amines and their respective receptors initiates diverse signaling pathways by modifying the concentrations of intracellular secondary messengers like Ca2+, AMP, and other molecules. These signal transductions regulate various physical and metabolic processes, directly influencing feeding behavior and digestive physiology. Furthermore, dopamine triggers a negative response, whereas serotonin plays a positive role in regulating feeding behavior. Biogenic amines underlie synchronized and interconnected molecular mechanisms, along with unique individual effects. It is fascinating to consider these interrelated activities and the impacts of bioamine on insect feeding behavior. In this review, we discuss the roles of insect biogenic amines and their cross-talk in insect feeding and foraging behavior.
Keywords: Biogenic amines; feeding behavior; octopamine; Signal transduction; tyramine

Germylene mediated reductive C-C and C-N coupling of an isocyanide and its device application - Gour, Kritika; Pramanik, Debjit; Dash, Soumya Ranjan; Shinde, Dipak Dattatray; Venugopal, Geethu; Vanka, Kumar; Rath, Arup K.; Sen, Sakya S. (Angewandte Chemie-International Edition, 2025)
We have demonstrated a unique reductive coupling of 4-iodophenyl isocyanide, facilitated by a perimidine-based N-heterocyclic germylene (NHGe), which yields a bis-spirogerma compound featuring simultaneous C-C and C-N bond formation. This reaction, which leads to the oxidation of germanium from +2 to +4, represents a significant departure from previously documented isocyanide-germylene interactions. The product exhibits extensive conjugation across its bicyclic C4Ge2N2 framework, conferring distinct photophysical properties, including prominent orange luminescence in both solution and solid states. The photophysical properties are supported by the TD-DFT calculations confirming an n ->pi* transition. The potential application of this compound in optoelectronic devices, particularly as a hole transport layer in PbS quantum dot solar cells, is also explored, with promising preliminary results.
Keywords: Germylene; hole transport layer; Isocyanide; reductive coupling

Green engineering of cellulose nanofibers and nanopapers from Wodyetia bifurcata fruits: a sustainable approach with emphasis on process optimization and tensile property assessment - Sankar, Sameera; Neenu, K. V.; Parameswaranpillai, Jyotishkumar; Ajithkumar, T. G.; Shelke, Ankita Ramesh; Begum, P. M. Sabura; Bipinbal, P. K.; George, Tresa Sunitha; Badawi, Michael; Dominic, Midhun (Biomass Conversion and Biorefinery, 2025)
Nanocellulose emerges as a highly promising material with versatile applications, offering solutions to environmental and sustainability challenges. This study delves into the extraction of cellulose nanofibers (CNFs) from Wodyetia bifurcata fruit pulp through mild oxalic acid hydrolysis assisted by steam explosion. To ensure environmental compatibility, chlorine-free pre-treatments were applied to eliminate non-cellulosic components. Chemical composition analysis verified the effective removal of non-cellulosic elements, validated by Fourier transform infrared spectroscopy (FTIR). Solid-state 13C nuclear magnetic resonance (13C NMR) spectroscopy confirmed the presence of type I cellulose α-polymorph in the CNF, while a crystallinity index of 60% was determined by X-ray diffraction analysis (XRD). The transmission electron microscopy (TEM) images revealed a fibrous morphology with a fiber diameter ranging from 9 to 36 nm. Dynamic light scattering (DLS) was employed to corroborate the observed fiber diameter. Mild acid hydrolysis elevated the maximum degradation temperature (Tmax) of CNF to 39 °C compared to the pristine sample. Furthermore, this research explores the application of CNFs in nanopaper development using a casting method. The resulting nanopapers exhibited a tensile strength of ~ 17 MPa and a transmittance of 25%. These nanopapers present a viable pathway toward eco-friendly products in various industries, promising to revolutionize upcoming sustainable packaging technologies.

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