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

Atmospheric-pressure continuous-flow methane oxidation to methanol and acetic acid using H2O2 over the Au-Fe catalyst - Jagtap, Anuradha V.; Kumar, Pawan; Gupta, Sharad; Nagendra, Abharana; Jha, Shambhu Nath; Bhattacharyya, D.; Ajithkumar, Thalasseril G.; Vinod, C. P. (ACS SUSTAINABLE CHEMISTRY & ENGINEERING, 2024)
Keywords: CO oxidation; HIGHLY SELECTIVE OXIDATION; metal-organic frameworks

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

Bimetallic and plasmonic Ag and Cu integrated TiO2 thin films for enhanced solar hydrogen production in direct sunlight - Mani, Sunesh S.; Rajendran, Sivaraj; Arun, Pushkaran S.; Vijaykumar, Aparna; Mathew, Thomas; Gopinath, Chinnakonda S. (Energy Advances, 2024)
<div class="abstract author" id="aep-abstract-id7" style="box-sizing: border-box; margin: 0px 0px 8px; padding: 0px; color: rgb(31, 31, 31); font-family: ElsevierGulliver, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif, sans-serif; font-size: 16px;"> Plasmonic metal nanoparticle-integrated mesoporous TiO2 nanocomposites (Ag/TiO2, Cu/TiO2 and Ag–Cu/TiO2), prepared by a simple chemical reduction method, have been demonstrated to show superior activity in thin-film form for solar H2 generation in sunlight. Integration of Ag + Cu on TiO2 significantly enhances the solar H2 production due to the combined SPR effect of both metal species and the possible synergistic interaction among Cu + Ag in Ag–Cu/TiO2. TiAgCu-1 (0.75 wt% Ag and 0.25 wt% Cu on TiO2) showed the highest H2 yield of 6.67 mmol h−1 g−1 and it is 43 times higher than that of bare TiO2. The thin-film form of TiAgCu-1 shows 5 times higher solar H2 production than its powder counterpart. 1 wt% of Ag or Cu on TiO2 shows a H2 yield of 4.6 or 2 mmol h−1 g−1, respectively, which underscores the importance of combined or synergistic effects. The increase in solar H2 generation in Ag–Cu/TiO2 is attributed to factors such as the SPR effect of Cu and Ag, and strong interaction between Ag and Cu. The high photocatalytic efficiency of the TiAgCu-1 thin film is attributed to the large dispersion of metallic species with relatively high Ag/Cu surface atomic ratio, enhanced light absorption, a heterogeneous distribution of Ag and Cu species, and high double layer capacitance. The inter particle mesoporous network increases the interfacial charge transfer and reduces the mass transfer limitations. The plausible photocatalytic reaction mechanism could involve the combination of direct electron transfer from metal (Cu/Ag) to TiO2 as well as the significant field effect due to the Ag–Cu alloy, which is expected to increase the electron excitation locally. <div class="abstract graphical" id="aep-abstract-id9" style="box-sizing: border-box; margin: 0px 0px 8px; padding: 0px; color: rgb(31, 31, 31); font-family: ElsevierGulliver, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif, sans-serif; font-size: 16px;"> Plasmonic metal nanoparticle integrated mesoporous TiO2 nanocomposites (Ag/TiO2, Cu/TiO2 and Ag–Cu/TiO2), prepared by a simple chemical reduction method, have been demonstrated to show superior activity in thin-film form for solar H2 generation.

Biobased reusable nonisocyanate polyurethane hot-melt adhesives with potential chemical degradability - Ghuge, Gorakh Hiraman; Torris, Arun; Nair, Kiran Sukumaran (ACS Applied Polymer Materials, 2024)
Hot-melt adhesives (HMAs) derived from renewable resources are always attractive, as they promote less dependence on fossil resources and aid in developing environmentally friendly materials. However, developing sustainable HMAs exhibiting good adhesive performance and biodegradability remains challenging. Herein, reusable biobased HMAs with a high bio content of 88-90%, biodegradability, and tunable adhesive nature were developed as a possible alternative to conventional petroleum-based hot-melt adhesives. Moreover, the structure-property relationship of the product was investigated in detail. By tailoring the monomer composition, NIPU-40 HMA exhibited a good bonding ability with a superior adhesion strength of 6.39 MPa. To the best of our knowledge, this is the highest adhesion strength observed when bonding with an Al substrate among the biobased thermoplastic NIPU-HMAs. Impressively, NIPU-HMAs could display excellent reusability even after three bonding and debonding cycles without a significant drop in the adhesive strength and were found to exhibit good adhesion performance under wet conditions. More importantly, the NIPU-HMAs are prone to degradation under acid-catalyzed conditions. Considering their features, these biobased NIPU thermoplastic hot-melt adhesives offer an opportunity to create environmentally friendly, degradable adhesives that possess excellent adhesive strength and can be reused multiple times.
Keywords: acid degradability; biobased NIPUs; cyclic carbonates; hot meltadhesives; lap shearstrength; spiro-aromatic

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.

Boron- and oxygen-doped π-extended helical nanographene with circularly polarised thermally activated delayed fluorescence - Venugopal, Geethu; Kumar, Viksit; Jadhav, Ashok Badrinarayan; Dongre, Sangram D.; Khan, Abujunaid; Gonnade, Rajesh; Kumar, Jatish; Santhosh Babu, Sukumaran (Chemistry-A European Journal, 2024)
Helical nanographenes have garnered substantial attention owing to their finely adjustable optical and semiconducting properties. The strategic integration of both helicity and heteroatoms into the nanographene structure, facilitated by a boron-oxygen-based multiple resonance (MR) thermally activated delayed fluorescence (TADF), elevates its photophysical and chiroptical features. This signifies the introduction of an elegant category of helical nanographene that combines optical (TADF) and chiroptical (CPL) features. In this direction, we report the synthesis, optical, and chiroptical properties of boron, oxygen-doped pi-extended helical nanographene. The pi-extension induces distortion in the DOBNA-incorporated nanographene, endowing a pair of helicenes, (P)-B2NG, and (M)-B2NG exhibiting circularly polarized luminescence with glum of -2.3x10-3 and +2.5x10-3, respectively. B2NG exhibited MR-TADF with a lifetime below 5 mu s, and a reasonably high fluorescence quantum yield (50 %). Our molecular design enriches the optical and chiroptical properties of nanographenes and opens up new opportunities in multidisciplinary fields. B, O-doped pi-extended helical nanographene has been explored for its optical and chiroptical properties. The presence of helical and nanographene segments stabilize the helicity and imparts tunable optical properties. Helical nanographene display circularly polarized thermally activated delayed fluorescence. image
Keywords: circularly polarized luminescence; DOBNA; dual emission; nanographene; TADF

Breaking the inactivity of MXenes to drive Ampere-level selective oxygen evolution reaction in seawater - Gbadamasi, Sharafadeen; Loomba, Suraj; Haris, Muhammad; Khan, Muhammad Waqas; Maibam, Ashakiran; Mousavi, Seyed Mahdi; Mahmud, Sofiu; Thomsen, Lars; Tadich, Anton; BabaRao, Ravichandar; Xian, Jian; Mahmood, Nasir (MATERIALS SCIENCE & ENGINEERING R-REPORTS, 2024)
Keywords: 2D heterostructures; Metal-organic framework; Oxygen Evolution Reaction

Brønsted acid- and Ni(ii)-catalyzed C-H oxidation/rearrangement of cyclotriveratrylenes (CTVs) to cyclic and acyclic quinones as potential anti-cancer agents - Darole, Ratanamala S.; Choudhary, Shailendra Singh; Sharma, Himanshu; Mali, Bhupendra P.; Gopu, Booblan; Vanka, Kumar; Senthilkumar, Beeran (Organic and biomolecular chemistry, 2024)
This paper describes a simple and practical protocol for the direct synthesis of acyclic and cyclic quinone derivatives via an acid-promoted nickel(ii)-catalyzed inner rim C-H oxidation of cyclotriveratrylene (CTV) and its analogues. The cyclic quinone derivatives resulted from trimethoxy-cyclotriveratrylene (TCTV) through C-C bond formation via intramolecular ipso substitution followed by subsequent anionic rearrangement containing stereo-vicinal quaternary centers. The DFT calculations strongly support the experimental findings and reveal the role of Bronsted acids in the C-H bond activation of CTV. All the newly synthesized compounds were screened for their in vitro anti-cancer activity using colorimetric SRB assay analysis. Among them, compounds 3a, 3d, 3h, 4a, 4b, 4c and 4e exhibited moderate anticancer activity against A549, HCT-116, PC-3, MDA-MB-231, HEK-293 and SW620 human cancer cell lines.

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.

Cell based assay using virus-like particles to screen AM type mimics for SARS-CoV-2 neutralisation - Gaur, Neeraj Kailash; Urankar, Shreegauri; Sengupta, Durba; Chepuri, V. Ramana; Makde, Ravindra D.; Kulkarni, Kiran (BIOCHEMICAL AND BIOPHYSICAL RESEARCH COMMUNICATIONS, 2024)
Keywords: MINIPROTEINS

Characterization of the conformational hotspots of the RNA-dependent RNA polymerase complex identifies a unique structural malleability of nsp8 - Gharui, Sowmomita; Sengupta, Durba; Das, Atanu (Journal of Physical Chemistry B, 2024)
Several antiviral therapeutic approaches have been targeted toward the RNA-dependent RNA polymerase (RdRp) complex that is involved in viral genome replication. In SARS-CoV-2, although the RdRp is a multiprotein complex, the focus has been on the ligand binding catalytic core (nonstructural protein nsp12), and not the multiprotein functional dynamics. In this study, we focus on the conformational ensembles of the RdRp complex and their modulation by the presence of RNA, performing comprehensive microsecond-scale atomistic simulations of the apo- and RNA-bound complex. We delineate the differential impact of RNA on the constituent proteins, such as conformational polymorphisms, dominant segment-specific fluctuations, and the switch in dynamical crosstalk within the complex. We distinguish dynamical signatures of nsp7, nsp8, and nsp12 in the apo-state that are reduced in the presence of the RNA and appear to ``prime'' the complex for activity. Importantly, we identify a unique structural malleability of the nsp8 protein with high conformational heterogeneity in the apo state, especially at three sites (Y71 for nsp8A, and D52 and A66 for nsp8B). Our work highlights the functional implications of the polymorphism of nsp8 structures and reveals possibilities for the development of allosteric inhibitors.

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.

Chemodialysis of organic acids using ABPBI-based hollow fiber membranes - Gawas, Saroj; Alladi, Lavanya; Kharul, Ulhas K. (Journal of Membrane Science, 2024)
Organic acids are a class of essential commodity chemicals used in various industries. Their production methods are shifting from conventional chemicals to fermentation, driven by green process strategies, environmental regulations, cost feasibility, etc. Separating formed acid from the fermentation broth is a primary technological barrier. Conventional methods are complex and impose environmental issues. A promising approach, `Chemodialysis,' capable of transforming the techno-economical feasibility of acid recovery scenario by reducing the number of steps, needs further investigation. This work evaluates scalable hollow fiber membranes based on poly(2,5-benzimidazole) (ABPBI) for chemically assisted dialysis, viz., Chemodialysis. Sorption analyses of commercially significant organic acids (acetic, lactic, and glycolic acid) and nonacidic solutes (NaCl and glucose) were performed using conventional flat sheet samples to assess their role in governing permeation characteristics. The transport properties of acids in the presence of NaCl and glucose as co-solutes were analyzed using hollow fiber membranes. The high selectivity of acid over nonacidic solutes ranges from 400-22,400, coupled with high acid permeability, enhances the applicability of Chemodialysis for the separation of acids using hollow fiber membranes. The fluxes of acids (acetic, glycolic, and lactic) through dense, similar to 100 mu m thick, scalable hollow fiber membranes ranging from 10.9 to 13.12 g/m(2)h are highly appreciable.
Keywords: 5-benzimidazole); Acid separation; Chemodialysis; Hollow fiber membranes; Organic acids; Poly(2

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

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

Copper-mediated [3+2] oxidative cyclization of oxime acetate and its utility in the formal synthesis of fentiazac - Jadhao, Nitin L.; Musale, Harish B.; Gajbhiye, Jayant M.; Humne, Vivek T. (Organic and biomolecular chemistry, 2024)
A new protocol for the direct synthesis of 2-aminothiazole has been developed from oxime acetate and readily available sodium thiocyanate using a copper catalyst. The present transformation has good functional group tolerance. Various thiazoles were smoothly synthesized in good to excellent yields. The applicability of the present method has been extended to the formal synthesis of the non-steroidal and anti-inflammatory drug, fentiazac via the Sandmeyer reaction and Suzuki coupling. The direct synthesis of 2-aminothiazole has been developed from oxime acetate using a copper catalyst. The applicability of the present method is used in the formal synthesis of fentiazac.
Keywords: Biological evaluation; C-H functionalization; Vinylazides

Crystal engineering for intramolecular π-π stacking: effect of substitution of electron-donating and electron-withdrawing groups on the molecular geometry in conformationally flexible Sulfoesters and sulfonamides - Shaikh, Samir R.; Gawade, Rupesh L.; Dabke, Niteen B.; Dash, Soumya R.; Vanka, Kumar; Gonnade, Rajesh G. (CrystEngComm, 2024)
A series of 21 sulfoester and sulfonamide derivatives comprising two aromatic rings was synthesized to investigate the effect of the presence of either electron-donating (ED) or electron-withdrawing (EW) groups on the intramolecular pi-stacking assembly. The positioning of ED or EW moieties was carried out directly on one of the aromatic rings linked to the sulfonyl or sulfonamide moieties. In contrast, the other aromatic ring (phenyl or pyridine) was connected by a -CH2-CH2- spacer with the sulfonyl or sulfonamide moiety. The purpose of having an ethyl spacer between the two aromatic rings was to achieve conformational flexibility, facilitating the intramolecular pi-stacking assembly between the two aromatic rings. The use of sulfoester/sulfonamide groups allowed more conformational flexibility to attain desired orientations in solids with the interplay of the hydrogen-bonding interactions. Between the two functional groups, sulfonamides offered a more hydrogen-rich environment due to the amine moiety and may exhibit higher H-bonding propensity than the sulfoester moiety. The central idea here was to study the interplay between the hydrogen-bonding and pi & ctdot;pi interactions. The substituent groups chosen were categorized as strong electron-withdrawing (-CF3 and -CN), weak electron-withdrawing (-Cl and -Br), neutral (-H), and good electron-donating (-CH3 and -OCH3) groups. Crystal structure analysis revealed the syn conformation for all the derivatives, enabling intramolecular pi & ctdot;pi interactions between the two aromatic rings, whereas in the sulfonamide derivatives, the molecule takes either midway or anti conformations, except for one pyridine sulfonamide derivative, which showed the syn orientation but lacked intramolecular pi-stacking interactions. The absence of any conventional H-bond forming functional groups in the sulfoester derivatives may have resulted in the syn geometry facilitated by intramolecular pi-stacking interactions. Conversely, H-bond-forming functional groups in the sulfonamide derivatives could have prevented the syn conformation. The conformational analysis carried out employing density functional theory (DFT) calculations confirmed the higher stability of the syn conformation over the midway and anti orientations. The placing of electron-withdrawing and electron-donating groups at the para position of the benzene revealed sulfoesters preferably adopts a syn geometry facilitating the intramolecular pi-stacking, but sulphonamides takes midway or anti-geometry.

Cu-catalyzed multicomponent reaction of arylhydrazines with β-ketoesters and TBN: one-pot access to N 2-aryl 1,2,3-triazole-1-oxides - Mujahid, Mohammad; Vara, Vijay; Arshad, Usman; Gamidi, Rama Krishna; Muthukrishnan, M. (Journal of Organic Chemistry, 2024)
We report a copper-catalyzed one-pot, multicomponent strategy for the convenient synthesis of N 2-aryl 1,2,3-triazole-1-oxides using arylhydrazines, beta-ketoesters, and tert-butyl nitrite. This mild and simple reaction proceeds in an atom-economic manner with broad substrate scope, affording a variety of N 2-aryl 1,2,3-triazole-1-oxide derivatives. Other salient features of the reaction are good functional group tolerance, scalability, and product diversification.

Dehydrogenative coupling of alcohols with internal alkynes under nickel catalysis: an access to β-deuterated branched ketones - Subaramanian, Murugan; Gouda, Chandrakant; Roy, Triptesh Kumar; Ganesan, Sivakumar; Banerjee, Subhrashis; Vanka, Kumar; Balaraman, Ekambaram (ACS Catalysis, 2024)
In synthetic organic chemistry, unconventional strategies for advanced chemical synthesis pose interesting and challenging problems. Alcohols act as alkylating agents in the C-C and C-N bond-forming reactions via the dehydrogenative borrowing hydrogen strategy in traditional transition metal catalysis; however, as an acylating agent in the C-C bond-forming reactions is challenging and rarely reported. Here, we report the dehydrogenative coupling of benzylic alcohols with internal alkynes under nickel(II) catalysis, wherein alcohol is used as an acylating agent. This reaction system affords a wide range of alpha-branched aryl ketone derivatives with zero waste generation through the umpolung borrowing hydrogen strategy. Moreover, we have demonstrated the chemodivergent applications of the alpha-disubstituted ketones to other valuable building blocks, including large-scale synthesis of beta-deuterated branched ketones. Several spectroscopic studies, intermediate identification, and density functional theory calculations were performed to elucidate the reaction mechanism.
Keywords: Alcohols; alpha-branched aryl ketones; dehydrogenative coupling; internal alkynes; nickel catalysis; pseudoumpolung

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.

Design of human ACE2 mimic miniprotein binders that interact with RBD of SARS-CoV-2 variants of concerns - Gaur, Neeraj K.; Khakerwala, Zeenat; Makde, Ravindra D. (Journal of Biomolecular Structure & Dynamics, 2024)
The world of medicine demands from the research community solutions to the emerging problem of SARS-CoV-2 variants and other such potential global pandemics. With advantages of specificity over small molecule drugs and designability over antibodies, miniprotein therapeutics offers a unique solution to the threats of rapidly emerging SARS-CoV-2 variants. Unfortunately, most of the promising miniprotein binders are de novo designed and it is not viable to generate molecules for each new variant. Therefore in this study, we demonstrate a method for design of miniprotein mimics from the interaction interphase of human angiotensin converting enzyme 2 (ACE2). ACE2 is the natural interacting partner for the SARS-CoV-2 spike receptor binding domain (RBD) and acts as a recognition molecule for viral entry into the host cells. Starting with ACE2 N-terminal triple helix interaction interphase, we generated more than 70 miniprotein sequences. Employing Rosetta folding and docking scores we selected 10 promising miniprotein candidates amongst which 3 were found to be soluble in lab studies. Further, using molecular mechanics (MM) calculations on molecular dynamics (MD) trajectories we test interaction of miniproteins with RBD from various variants of concern (VOC). Presently, we report two key findings; miniproteins in this study are generated using less than 10 lab testing experiments, yet when tested through in-vitro experiments, they show submicro to nanomolar affinities towards SARS-CoV-2 RBD. Also in simulation studies, when compared with previously developed therapeutics, our miniproteins display remarkable ability to mimic ACE2 interphase; making them an ideal solution to the ever evolving problem of VOCs.
Keywords: ACE2 mimics; miniprotein; protein design; SARS-CoV-2; therapeutics; Variant of concern

Design, synthesis, anti-mycobacterial activity, molecular docking and ADME analysis of spiroquinoxaline-1,2,4-oxadiazoles via [3+2] cycloaddition reaction under ultrasound irradiation - Kanchrana, Madhu; Gamidi, Rama Krishna; Kumari, Jyothi; Sriram, Dharmarajan; Basavoju, Srinivas (MOLECULAR DIVERSITY, 2024)
Keywords: 2; 4-oxadiazoles; cytotoxicity activity; molecular; Mycobacterium tuberculosis; Spiroquinoxaline-1

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)

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

Electrochemical property of nanosphere-like MgO electrode synthesized via SILAR in asymmetric supercapacitor - Gaikwad, D. S.; Bobade, R. G.; Suryawanshi, V. B.; Nakate, U. T.; Shaikh, S. F.; Al-Enizi, Abdullah M.; Dabke, N. B.; Lokhande, B. J.; Ambare, Revanappa C. (Journal of Materials Science-Materials in Electronics, 2024)
In this research article, we synthesized nanospheres of MgO thin-film substrate using the successive ionic layer adsorption and reaction (SILAR) technique on stainless steel substrates. The final optimized sample was used for physical characterization. XRD revealed the cubic structure of the MgO electrode. Additionally, it was utilized for electrochemical supercapacitive characterization, including cyclic voltammetry (CV), chronopotentiometry, and electrochemical impedance spectroscopy (EIS). Results showed that MgO nanospheres exhibited a higher specific capacitance (SC) of 536.06 F/g. The maximum values of specific energy and specific power were 30.79 Wh/kg and 1420 W/kg, respectively, at 2 mA/cm2 in 1-M KOH. The EIS plot confirmed an internal resistance (Ri) of 0.86 omega, indicating good power performance and outstanding rate capability of MgO nanospheres. This material demonstrated excellent cycling capability, retaining 91.38% capacitance after 5000 CV cycles. The MgO//AC device displayed an SC of 210.21 F/g at 5 mV/s in a PVA-KOH solid-state electrolyte. With an energy density of 23.90 Wh/kg and a power density of 1.84 kW/kg, the asymmetric supercapacitor performance showed that the MgO-based electrode is suitable for use in actual device manufacturing. After 5000 CV cycles, the supercapacitor device exhibited exceptional capacitance retention of 92.93%. Thus, this research successfully demonstrated the usefulness of the simple and affordable SILAR method for synthesizing pure MgO nanostructures for application in supercapacitors.

Engineered PLGA core-lipid shell hybrid nanocarriers improve the efficacy and safety of irinotecan to combat colon cancer - Giram, Prabhanjan S.; Nimma, Ramakrishna; Bulbule, Anuradha; Yadav, Amit Singh; Gorain, Mahadeo; Radharani, Nalukurthi Naga Venkata; Kundu, Gopal C.; Garnaik, Baijayantimala (ACS BIOMATERIALS SCIENCE & ENGINEERING, 2024)
Keywords: BULK-POLYMERIZATION; Drug-delivery; LIPOSOMAL DOXORUBICIN

Engineering inhibitory repeat domains of Pin-II type proteinase inhibitors indicate their high structural-functional tolerance to mutagenesis - Barbole, Ranjit S.; Joshi, Rakesh S.; Giri, Ashok P. (Biochemical and Biophysical Research Communications, 2024)
Plant proteinase inhibitors (PIs) are critical in defending against biotic stress. Most PIs contain an inhibitory repeat domain (IRD), which serves as the functional component, displaying a high degree of sequence and structural conservation. In this study, we examined the structural and functional resilience of IRDs using a combination of computational modeling and experimental validation. We have taken an evolution-based approach to enhance the PIs effectiveness of two previously identified Capsicum annuum IRDs, IRD4 and IRD10. Through in silico site-saturation mutagenesis of IRD4 and IRD10, we identified key sites associated with enhanced PI activity for targeted mutagenesis. Binding energy predictions for a mutant IRD library, tested against target proteases, suggested that positions R11 and N32 in IRD4 and N32 and H33 in IRD10 were promising candidates for further modification to improve inhibitory potential. Subsequent experimental validation revealed that the mutant proteins IRD4_R11K and IRD4_N32S exhibited stronger chymotrypsin inhibition than the wild-type (WT) IRD4. Similarly, the mutants IRD10_N32S and IRD10_H33 N demonstrated improved trypsin inhibition relative to the WT IRD10. These findings indicate that engineered IRD variants can tolerate structural changes while maintaining or enhancing their inhibitory activity against target proteases. Overall, this study demonstrates the potential of engineering PIs to increase their structural and functional resilience, offering new opportunities for biotechnological applications.
Keywords: Capsicum annum; Inhibitory repeat domain; molecular modeling; plant proteinase inhibitors; Proteases; Saturation mutagenesis

Enhancing the Catalytic Activity of Pd Nanocrystals towards Suzuki Cross-Coupling by g-C3N4 Photosensitization - Mondal, Sanjit; Sahoo, Lipipuspa; Banoo, Maqsuma; Vaishnav, Yuvraj; Prabhakaran Vinod, Chathakudath; Gautam, Ujjal (Chemnanomat, 2024)
Developing renewable means of activating molecules over traditional catalysts for C-C bond formation is desirable for industrial applications. Herein, we report a strategy to improve the efficiency of Pd nanoparticles (NPs) for the Suzuki cross-coupling reactions by visible-light irradiation using g-C3N4 nanosheets (NSs) as photosensitizer. Pd NPs mounted on g-C3N4 become electron-rich under visible-light due to generation of excited electrons in g-C3N4 and thereby accelerate the rate-determining step. Remarkable photocatalytic activity was accomplished utilizing Pd/g-C3N4 for the Suzuki cross-coupling reaction in environmentally benign aqueous settings under room temperature conditions. The activity remarkably improves (similar to 2.5 times) upon light irradiation, yielding one of the highest known turnover frequencies (TOF) of 1858 h(-1) and confirming the photosensitizer role of g-C3N4. The TOF for coupling of aryl bromides is also significantly high (similar to 356 h(-1)). We establish that the low-energy/long-lived excitons preferencially transfer to Pd, paving a way for rational designing photocatalysts for various C-C coupling reactions.
Keywords: 2D graphitic carbon nitride; C-C cross-coupling; exciton transfer; heterogeneous photocatalyst; Photosensitization

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

Entropy-driven reversible melting and recrystallization of layered hybrid perovskites - Rajput, Parikshit Kumar; Salunkhe, Parashurama; Sarma, Manmayuri; Basu, Meghasree; Gopal, Animesh; Joshi, Aprajita; Shingote, Ajinkya Sundarnath; Saha, Surajit; Rahman, Atikur; Nag, Angshuman (SMALL, 2024)
Keywords: hybrid perovskites; photodetector; reversible melting

The ex situ exsolved exsolved Ni-Ru alloy from nickel-ruthenium co-doped SrFeO perovskite as a potential catalyst for C=C and C=O hydrogenation - Bhavisha, Meloth; Balamurugan, Sarkarainadar; Gopinath, Chinnakonda S.; Sakthivel, Ayyamperumal (SUSTAINABLE ENERGY & FUELS, 2024)
Keywords: LIQUID-PHASE HYDROGENATION; OXIDE FUEL-CELLS

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 CeO2 support morphology for the carbon dioxide hydrogenation reaction using nickel catalysts - Gupta, Sharad; Jagtap, Anuradha; Vinod, C. P. (Journal of Physical Chemistry C, 2024)
The catalytic activity and stability are examined for the hydrogenation of carbon dioxide under atmospheric pressure over 2 wt % Ni/CeO2 nanorods (2Ni-CeNRs), nanocubes (2Ni-CeNCs), and nanopolyhedra (2Ni-CeNPs). The 2Ni-CeNR catalysts display excellent catalytic activity and higher stability compared with 2Ni-CeNC and 2Ni-CeNP catalysts. A comprehensive understanding of the surface atomic and electronic structure versus activity has been derived using high-resolution electron microscopy and spectroscopy techniques. High metal dispersion, strong metal-support interaction (SMSI) effect and abundant oxygen vacancies are deduced to play a crucial role in determining the catalytic activity and selectivity of the CO2 hydrogenation reaction.

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.

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.

Fuel-influenced nanorod-to-nanosphere transformation of vanadium-doped ZnO and its performance in dye-sensitized solar cells - Kuppusamy, Sasikumar; Mohan, Theanmozhi; Gnana Kumar, G.; Gopinath, Chinnakonda S.; Saha, Arindam; Michael, Robin Jude Vimal (NEW JOURNAL OF CHEMISTRY, 2024)
Keywords: Nanoparticles; Nanowires; Photoanode; Thin-films

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

High-capacity V2N MXene for multivalent ion batteries: an Ab initio study - Saharan, Sunita; Ghanekar, Umesh; Shivankar, Bhavana R.; Meena, Shweta (Journal of Physical Chemistry C, 2024)
In this study, the electrochemical energy storage properties of V2N MXene as an electrode material for multivalent zinc (Zn2+) and calcium (Ca2+) ion rechargeable batteries have been studied using first-principles computations. Various properties like band structure, adsorption energy, diffusion kinetics, and open-circuit voltage are investigated using density functional theory. V2N MXene demonstrates metallic properties with a high structural stability and low diffusion barriers. Remarkably, Zn (976.4 mA h/g) and Ca (770.8 mA h/g)-adsorbed V2N MXene layers exhibit better storage capacity than the reported ones (517 mA h/g for zinc-intercalated CC@MnO2@Ti3C2TX and 598.63 mA h/g for calcium-intercalated V3C2/graphene). These findings make V2N MXene a highly promising cathode material for zinc and an anode material for calcium-ion batteries.

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.

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

Investigation of structural and morphological insights of nanostructured layered double hydroxides: catalytic activity in aldol condensation - Bhagat, Shailesh K.; Nagpure, Atul S.; Lanjewar, Mamata R.; Gode, Nilesh G.; Thakare, Sanjay R. (Journal of Porous Materials, 2024)
Layered double hydroxides (LDHs) materials finds extensive applications in numerous fields such as medical science, industrial sector, agriculture and food, catalysis, polymers, nanotechnology, etc. The LDHs properties (structural, textural, morphological, spectroscopic and theoretical insights) can be design for achieving required materials for particular application in scientific areas. In the current investigation, we have synthesized mesoporous nanostructured LDHs materials via microwave, sonication and stirring method. The nanostructured LDHs was scientifically characterized by various physico-chemical techniques like XRD, N2 sorption, TGA, solid state one-dimensional 27Al magic angle spinning NMR spectroscopy, XPS, Raman Spectroscopy, FT-IR, ICP-OES, Electron Microscopy (SEM, FE-SEM, TEM and HR-TEM), EDX, elemental analysis, etc. On the basis of experimental study, it can be evidently witnessed that nanostructured LDHs materials was formed with good crystalline mesoporous nature. Solid state 27Al NMR showed single and sharp 27Al NMR signal at chemical shift value of + 1.4 ppm, strongly suggesting the presence of octahedral (Oh) AlO6 coordination site in all as-synthesized LDHs. Microwave and sonication techniques furnishes regularly dispersed well-developed flower-shaped nanocrystals however, stirring method gives mostly agglomerated nano-sized platelets. The mechanistic insights for the fabrication of nanostructures LDHs via microwave, sonication and stirring process were also highlighted. The different LDHs materials were utilized in the aldol condensation reaction of furfural with acetone for understanding structure-activity correlation. Microwave and sonication methodologies can be further exploited for the synthesis of many other inorganic-organic nanocomposites materials with stable and good dispersion of nanocrystals in addition to desired morphology and catalytic activity.
Keywords: Aldol condensation; catalysis; Flower-shaped nanocrystals; layered double hydroxides; Microwave and sonication techniques; Nanostructured materials

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

Lanthanide mimicking by magnesium for oxazolidinone synthesis - Kumar, Rohit; Mahata, Biplab; Gayathridevi, S.; Raj, K. Vipin; Vanka, Kumar; Sen, Sakya S. (Chemistry- a european journal, 2024)
In the last decade, magnesium complexes have emerged as a viable alternative to transition-metal catalysts for the hydrofunctionalization of unsaturated bonds. However, their potential for advanced catalytic reactions has not been thoroughly investigated. To address this gap, we have developed a novel magnesium amide compound (3) using a PNP framework that is both bulky and flexible. Our research demonstrates that compound 3 can effectively catalyze the synthesis of biologically significant oxazolidinone derivatives. This synthesis involves a tandem reaction of hydroalkoxylation and cyclohydroamination of isocyanate using propargyl alcohol. Furthermore, we conducted comprehensive theoretical calculations to gain insights into the reaction mechanism. It is important to note that these types of transformations have not been reported for magnesium and would significantly enhance the catalytic portfolio of the 7th most abundant element. A monomeric magnesium compound was employed as a catalyst for the cascade cyclization of propargylic alcohol and isocyanate, resulting in the formation of pharmaceutically significant oxazolidinone derivatives. This transformation, previously attributed solely to transition metals or lanthanides, signifies a noteworthy advancement.image
Keywords: catalysis; Magnesium; oxazolidinone; pincer ligand; Sustainability

Lead-free Cs2AgBiCl6 double perovskite: experimental and theoretical insights into the self-trapping for optoelectronic applications - Rahane, Swati N.; Rahane, Ganesh K.; Mandal, Animesh; Jadhav, Yogesh; Godha, Akshat; Rokade, Avinash; Shah, Shruti; Hase, Yogesh; Waghmare, Ashish; Saykar, Nilesh G.; Roy, Anurag; Salgaonkar, Kranti N.; et al. (ACS Physical Chemistry Au, 2024)
Lead-free double perovskites (DPs) will emerge as viable and environmentally safe substitutes for Pb-halide perovskites, demonstrating stability and nontoxicity if their optoelectronic property is greatly improved. Doping has been experimentally validated as a powerful tool for enhancing optoelectronic properties and concurrently reducing the defect state density in DP materials. Fundamental understanding of the optical properties of DPs, particularly the self-trapped exciton (STEs) dynamics, plays a critical role in a range of optoelectronic applications. Our study investigates how Fe doping influences the structural and optical properties of Cs2AgBiCl6 DPs by understanding their STEs dynamics, which is currently lacking in the literature. A combined experimental–computational approach is employed to investigate the optoelectronic properties of pure and doped Cs2AgBiCl6 (Fe–Cs2AgBiCl6) perovskites. Successful incorporation of Fe3+ ions is confirmed by X-ray diffraction and Raman spectroscopy. Moreover, the Fe–Cs2AgBiCl6 DPs exhibit strong absorption from below 400 nm up to 700 nm, indicating sub-band gap state transitions originating from surface defects. Photoluminescence (PL) analysis demonstrates a significant enhancement in the PL intensity, attributed to an increased radiative recombination rate and higher STE density. The radiative kinetics and average lifetime are investigated by the time-resolved PL (TRPL) method; in addition, temperature-dependent PL measurements provide valuable insights into activation energy and exciton–phonon coupling strength. Our findings will not only deepen our understanding of charge carrier dynamics associated with STEs but also pave the way for the design of some promising perovskite materials for use in optoelectronics and photocatalysis.

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

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

Metabolic reprogramming and signalling cross-talks in tumour-immune interaction: a system-level exploration - Shukla, Mudita; Bhowmick, Rupa; Ganguli, Piyali; Sarkar, Ram Rup (Royal Society Open Science, 2024)
Tumour-immune microenvironment (TIME) is pivotal in tumour progression and immunoediting. Within TIME, immune cells undergo metabolic adjustments impacting nutrient supply and the anti-tumour immune response. Metabolic reprogramming emerges as a promising approach to revert the immune response towards a pro-inflammatory state and conquer tumour dominance. This study proposes immunomodulatory mechanisms based on metabolic reprogramming and employs the regulatory flux balance analysis modelling approach, which integrates signalling, metabolism and regulatory processes. For the first time, a comprehensive system-level model is constructed to capture signalling and metabolic cross-talks during tumour-immune interaction and regulatory constraints are incorporated by considering the time lag between them. The model analysis identifies novel features to enhance the immune response while suppressing tumour activity. Particularly, altering the exchange of succinate and oxaloacetate between glioma and macrophage enhances the pro-inflammatory response of immune cells. Inhibition of glutamate uptake in T-cells disrupts the antioxidant mechanism of glioma and reprograms metabolism. Metabolic reprogramming through adenosine monophosphate (AMP)-activated protein kinase (AMPK), coupled with glutamate uptake inhibition, was identified as the most impactful combination to restore T-cell function. A comprehensive understanding of metabolism and gene regulation represents a favourable approach to promote immune cell recovery from tumour dominance.
Keywords: metabolic reprogramming; signalling-metabolic cross-talks; system modelling; tumour-immune interaction

Metal-organic frameworks for enhanced hydrogen generation from syngas: a density functional theory approach - Gopalsamy, Karuppasamy; Singh, Chandrodai Pratap; Krishnamurty, Sailaja; BabaRao, Ravichandar (CHEMPLUSCHEM, 2024)
Keywords: carbon capture; H-2 separation; Metal organic; Porous coordination network (PCN-250); Syngas

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

Microbial production of N-acetyl-D-glucosamine (GlcNAc) for versatile applications: biotechnological strategies for green process development - Das, Sancharini; Chowdhury, Chiranjit; Kumar, S. Pavan; Roy, Debasis; Gosavi, Suresh W.; Sen, Ramkrishna (Carbohydrate Research, 2024)
N-acetyl-D-glucosamine (GlcNAc) is a commercially important amino sugar for its wide range of applications in pharmaceutical, food, cosmetics and biofuel industries. In nature, GlcNAc is polymerised into chitin biopolymer, which is one of the major constituents of fungal cell wall and outer shells of crustaceans. Sea food processing industries generate a large volume of chitin as biopolymeric waste. Because of its high abundance, chitinaceous shellfish wastes have been exploited as one of the major precursor substrates of GlcNAc production, both in chemical and enzymatic means. Nevertheless, the current process of GlcNAc extraction from shellfish wastes generates poor turnover and attracts environmental hazards. Moreover, GlcNAc isolated from shellfish could not be prescribed to certain groups of people because of the allergic nature of shell components. Therefore, an alternative route of GlcNAc production is advocated. With the advancement of metabolic construction and synthetic biology, microbial synthesis of GlcNAc is gaining much attention nowadays. Several new and cuttingedge technologies like substrate co-utilization strategy, promoter engineering, and CRISPR interference system were proposed in this fascinating area. The study would put forward the potential application of microbial engineering in the production of important pharmaceuticals. Very recently, autotrophic fermentation of GlcNAc synthesis has been proposed. The metabolic engineering approaches would offer great promise to mitigate the issues of low yield and high production cost, which are major challenges in microbial bio-processes industries. Further process optimization, optimising metabolic flux, and efficient recovery of GlcNAc from culture broth, should be investigated in order to achieve a high product titer. The current study presents a comprehensive review on microbe-based eco-friendly green methods that would pave the way towards the development of future research directions in this field for the designing of a cost-effective fermentation process on an industrial setup.
Keywords: Genetic engineering; GlcNAc applications; Market status; Microbial bioprocess; N-acetyl-D-glucosamine; synthetic biology

Mitochondrial resilience and antioxidant defence against HIV-1: unveiling the power of Asparagus racemosus extracts and Shatavarin IV - Jadaun, Pratiksha; Harshithkumar, R.; Seniya, Chandrabhan; Gaikwad, Shraddha Y.; Bhoite, Shubhangi P.; Chandane-Tak, Madhuri; Borse, Swapnil; Chavan-Gautam, Preeti; Tillu, Girish; Mukherjee, Anupam (FRONTIERS IN MICROBIOLOGY, 2024)
Keywords: IN-SILICO; INHIBIT HIV-1

MOFite: a high-density lithiophilic and scalable metal-organic framework anode for rechargeable lithium-ion battery - Gaber, Safa; Mohammed, Abdul Khayum; Javaregowda, Bharathkumar H.; Martinez, Jose Ignacio; Sanchez, Pilar Pena; Gandara, Felipe; Krishnamoorthy, Kothandam; Shetty, Dinesh (ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2024)
Keywords: conjugated MOF; Energy storage; lithium ion battery; Metal-organic framework; scalable synthesis

Multi-dimensional impact of captopril modification on human serum albumin - Ghosh, Amrita; Jani, Vinod; Sonavane, Uddhavesh; Naphade, Anvi N.; Joshi, Rajendra; Kulkarni, Mahesh J.; Giri, Ashok P. (International Journal of Biological Macromolecules, 2024)
Captopril is a thiol drug, widely used for the management of hypertension and cardiovascular diseases. Reactive thiols are found to covalently modify the cysteines of plasma proteins and affect their structure and function. Human serum albumin (HSA) is prone to undergo modification by various low molecular weight compounds, including drugs. Cysteine34 (Cys34) in HSA has a free thiol group with antioxidant properties, considered to be the most redox-sensitive amino acid in plasma. Through mass-spectrometric analysis, we demonstrate for the first time that captopril forms a disulfide adduct at Cys34 residue and increases the protease susceptibility of HSA to trypsin. As evidenced by our biophysical and electron microscopy studies, HSA undergoes structural alteration, aggregation and morphological changes when treated with different captopril concentrations. Molecular dynamics studies further revealed the regions of secondary structural changes in HSA due to disulfide adduct formation by captopril at Cys34. It also elucidated the residues involved in the noncovalent interactions with captopril. It is envisaged that structural change in HSA may influence the efficacy of drug delivery as well as its own biological function. These findings may thus provide significant insights into the field of pharmacology intriguing further investigation into the effects of long-term captopril treatment.
Keywords: Captopril; Electron microscopy; Human serum albumin; Mass spectrometry; Molecular dynamic simulation; Spectrophotometry

Nanotrap infused ultrathin hybrid composite material for rapid and highly selective entrapment of 99TcO4- - Mandal, Writakshi; Fajal, Sahel; Majumder, Dipanjan; Sengupta, Arijit; Let, Sumanta; Urkude, Rajashri R.; Shirolkar, Mandar M.; Torris, Arun; Ghosh, Sujit K. (CHEMICAL SCIENCE, 2024)
Keywords: Adsorption; CAPTURE; EFFICIENT; Metal-organic framework; Removal; TECHNETIUM

Network motifs exhibiting a differential response to spaced and massed inputs - Sreejan, Ashley; Saxena, Priyanka; Gadgil, Chetan J. (Learning & Memory, 2024)
One characteristic of long-term memory is the existence of an inverted U-shaped response to increasing intervals between training sessions, and consequently, an optimal spacing that maximizes memory formation. Current models of this spacing effect focus on specific molecular components and their interactions. Here, we computationally study the underlying network architecture, in particular, the potential of motif dynamics in qualitatively capturing the spacing effect in a manner that is independent of the animal model, biomolecular components, and the timescales involved. We define a common training and test protocol, and computationally identify network topologies that can qualitatively replicate the experimentally observed characteristics of the spacing effect. For 41 motifs derived from fundamental network architectures such as autoregulation, feedback, and feedforward motifs, we tested their capacity to manifest the spacing effect in terms of an inverted U-shaped response curve, using different combinations of stimulation protocols, response metrics, and kinetic parameters. Our findings indicate that positive feedback motifs where the stimulus enhances conversion reaction in the loop replicate the spacing effect across all response metrics, while feedforward motifs exhibit a metric-specific spacing effect. For some parameter combinations, linear cascades of activation and conversion reactions were found sufficient to qualitatively exhibit spacing effect characteristics.

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 insights into the composition and catalytic performance of VOx-Ga/γ-Al2O3 for the oxidative dehydrogenation of propane to propene - Kandasamy, Prabu; Gawali, Sheetal; Venugopalan, Aswathy Thareparambil; Manikandan, Marimuthu; Mekala, Siva Prasad; Shelke, Ankita; Ajithkumar, Thalasseril G.; Bhatte, Kushal; Raja, Thirumalaiswamy (New Journal of Chemistry, 2024)
Oxidative dehydrogenation (ODH) of propane is a promising alternative route for propene production. In this work, we developed a series of vanadium and gallium oxides supported on gamma-Al2O3 catalysts by an incipient wetness impregnation method. Among the employed catalysts, the VGA-2 showed superior catalytic activity, and the catalyst was demonstrated for longevity in ODH of propane with a stable activity using a continuous flow fixed bed reactor at 400 degrees C. H-2-TPR and UV-visible spectra showed the presence of highly dispersed monomeric VOx species with tetrahedral coordination geometry, which influences product selectivity. The characterization results also conferred that the redox nature of vanadium (V5+ and V4+) oxide and higher V5+ content on the surface of the VGA-2 catalysts are more favourable for C-H activation. In addition, the pyridine-FTIR and Ga-71 solid-state NMR studies further substantiated the presence of Lewis acid sites and tetrahedrally coordinated Ga3+Ox species that are highly responsible for the ODHP activity, respectively. Furthermore, in situ-DRIFTS studies conferred that the propane adsorption at ambient temperature showed the formation of intermediate propoxide species with the evolution of sigma-bonds and with further increase in the temperature to 325 degrees C; the stretching vibrations of the =C-H and -C-H bonds in the propylene molecule were observed. The spent catalysts were also analyzed by thermogravimetric analysis, where the optimized catalyst (VGA-2) showed the least coke deposition.

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 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.

Novel molecular adducts of an anti-cancer drug vandetanib with enhanced solubility - Bandaru, Ravi Kumar; Giri, Lopamudra; Krishna, Gamidi Rama; Dandela, Rambabu (Crystengcomm, 2024)
The solubility, permeability, and dissolution rate of an active pharmaceutical ingredient (API) are critical factors in determining its pharmacokinetic performance in oral dosage forms. Modifying these properties can potentially enhance the drug's pharmacokinetics. Vandetanib (VDTB), classified as a class II anti-cancer drug in the biopharmaceutical classification system (BCS), suffers from low solubility (0.008 mg mL-1) and an extended pharmacokinetic half-life (19 days), necessitating the administration of high doses, which leads to undesirable side effects. To address this issue, we have employed a crystal engineering approach to enhance the solubility of VDTB. We employed the liquid-assisted grinding (LAG) method followed by the slow evaporation technique to prepare novel solid forms of VDTB by incorporating various aliphatic dicarboxylic acids, including succinic acid (SUA), adipic acid (ADA), pimelic acid (PIA), azelaic acid (AZA), and sebacic acid (SBA). These newly obtained solid forms were characterized by SC-XRD, PXRD, TGA, and DSC experiments. The crystal structure analyses revealed a proton transfer between the carboxylic acid group of aliphatic acids and the N-methyl piperidine moiety of VDTB, confirming salt/adduct formation. Additionally, all of the molecular salts were stabilized by charge-assisted N+-HMIDLINE HORIZONTAL ELLIPSISO- hydrogen bonds, while the parent VDTB crystal structure is stabilised by N-HMIDLINE HORIZONTAL ELLIPSISN interactions. Moreover, the solubility and dissolution rate of these new solid forms were assessed in a pH 7.4 phosphate buffer medium, with the results indicating that all of the solid forms, except for VDTB:SBA, exhibited higher solubility compared to pure VDTB. These findings offer promising prospects for the development of an improved VDTB formulation with enhanced pharmacokinetic properties. Successful attempt to improve the solubility and dissolution rate of Vandetanib - an anti-cancer drug, by crystal engineering approach.
Keywords: Amorfization; hydrate; Parameters; Salt; Thyroid-Cancer

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

One-pot production of liquid hydrocarbons by catalytic hydrodeoxygenation of lignocellulosic biomass using nickel loaded on zeolite-based supports - Siakpebru, Odiri K.; Uchagawkar, Anoop; Gurrala, Lakshmiprasad; Bartlett, Jared; Adamson, Piersen; Gorschak, Nicholas; Hassiba, Adam; Niphadkar, Prashant; Bokade, Vijay; Morais, Ana Rita C. (Energy & Fuels, 2024)
The synthesis of liquid hydrocarbons from lignocellulosic biomass has been achieved with notable success. However, these technologies often require multistep approaches and are energy intensive. Thus, there is a considerable economic and environmental benefit of process intensification by the synthesis of liquid hydrocarbons in a one-pot process. For the first time, we report direct conversion of raw poplar into liquid alkanes and aromatics (carbon yield of 15.6 +/- 0.6 wt %) with high selectivity toward C-7-C15 cycloalkanes (7.8 +/- 0.1 wt %) and low level of oxygenated compounds (<2.0 wt %) at 270 degrees C and 3 MPa initial H(2 )pressure for 6 h using 10% Ni/H-beta zeolite as a catalyst and cyclohexane as a solvent. The effect of temperature (250-270 degrees C), Ni loading (0-10%), and type of zeolite support (H-beta, ZSM-5, and USY) on process performance was also investigated. In addition, the 10% Ni/H-beta catalyst showed recyclability over two reactions, with a 17.6% decrease in liquid hydrocarbon yield after the first reaction. This approach has the potential to simplify the synthesis of liquid fuels from lignocellulosic biomass.

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

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

Perturbation of fermi resonance on hydrogen-bonded > C=O: 2D IR studies of small ester probes - Sakpal, Sushil; Chakrabarty, Suranjana; Reddy, Kambham Devendra; Deshmukh, Samadhan H.; Biswas, Rajib; Bagchi, Sayan; Ghosh, Anup (Journal of Physical Chemistry B, 2024)
We utilized linear and 2D infrared spectroscopy to analyze the carbonyl stretching modes of small esters in different solvents. Particularly noteworthy were the distinct carbonyl spectral line shapes in aqueous solutions, prompting our investigation of the underlying factors responsible for these differences. Through our experimental and theoretical calculations, we identified the presence of the hydrogen-bond-induced Fermi resonance as the primary contributor to the varied line shapes of small esters in aqueous solutions. Furthermore, our findings revealed that the skeletal deformation mode plays a crucial role in the Fermi resonance for all small esters. Specifically, the first overtone band of the skeletal deformation mode intensifies when hydrogen bonds form with the carbonyl group of esters, whereas such coupling is rare in aprotic organic solvents. These spectral insights carry significant implications for the utilization of esters as infrared probes in both biological and chemical systems.

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

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

Preparation and structural characterization of disordered Na-gallosilicate zeolite with natrolite framework and itsK+ and NH4+ exchanged analogues exchanged analogues - Gavhane, Manjusha J.; Jha, R. K.; Nam, Kyung-Wan; Bhange, Deu S. (JOURNAL OF POROUS MATERIALS, 2024)

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

Reactive distillation configuration for the production of ethyl acrylate - Gore, Jayram I.; Mahajani, Sanjay M.; Mali, Nilesh A. (CHEMICAL ENGINEERING AND PROCESSING-PROCESS INTENSIFICATION, 2024)
Keywords: ACETIC-ACID; CYCLOHEXYL ACETATE; Design; Dimethyl carbonate

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

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.

Regio- and stereoselective construction of 1,3,5-triaroylcyclohexanes via KO t Bu-mediated cyclotrimerization of aryl vinyl ketones - Mahale, Sachin D.; Yadav, Vinita; Gonnade, Rajesh G.; Mhaske, Santosh B. (Journal of Organic Chemistry, 2024)
Herein, we disclose a simple one-pot method for an efficient regio- and stereoselective synthesis of 1,3,5-triaroylcyclohexanes from aryl vinyl ketones using potassium tert-butoxide. The developed protocol allows the construction of various symmetrically substituted cyclohexanes in good to excellent yields. The major product 2 also can be converted to the product 3 (all equatorial) conveniently by acid catalysis. This protocol features a good substrate scope and functional group compatibility.

Regulating the polyethylene microstructure by increasing steric crowding in naphthoxy imine-ligated Ni(II) complexes - Birajdar, Rajkumar S.; Gonnade, Rajesh G.; Chikkali, Samir H. (Polymer Chemistry, 2024)
Ligands play a prominent role in ethylene polymerization. However, it is a highly challenging task to regulate branching through ligand modifications. Here we report the synthesis of systematically sterically tailored naphthoxy imine-ligated nickel complexes (Ni1, Ni2, and Ni3), their performance in ethylene polymerization, and how the ligand steric controls branching in the resultant PE. Ni1-Ni3 were prepared in one step with an excellent yield (73-93%). The identity of these complexes was unambiguously ascertained using H-1, C-13, 2D NMR spectroscopy, mass analysis, and single-crystal X-ray diffraction. The molecular structure revealed a cis arrangement of alkyl/aryl and donor groups (C-Ni-D), which is necessary for initiating ethylene polymerization. Buried volume contours suggested Ni3 to be sterically the most bulky among the three. When exposed to ethylene, the three nickel complexes Ni1, Ni2, and Ni3 produced polyethylene with excellent activity. As predicted by buried volume calculations, dibenzhydryl-substituted Ni3 outperformed sterically less crowded Ni1 and Ni2. Careful analysis of the resultant PE disclosed that sterically less encumbered Ni1 and Ni2 produce PE with high branching (43-54 branches/1000-C atoms) density. However, the bulkiest Ni3 revealed much lower branching (28 branches/1000-C atoms) and a high TOF of 35 400 mol of PE per mol of Ni per h, along with a high molecular weight of PE (61 000 Da). The steric bulk in Ni3, most likely, reduces chain-walking and thus lowers branching in the resultant PE. As compared to the literature-reported analogous Pd1 catalyst, the Ni3 catalyst discloses high TOF, high molecular weight, and less branched, linear polyethylene.
Keywords: Catalyzed Olefin Polymerization; High-Temperature; Molecular Weight

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

Review on the recent advances in the design and structure–activity relationship of TiO2-based photocatalysts for solar hydrogen production - Mani, Sunesh S.; Rajendran, Sivaraj; Mathew, Thomas; Gopinath, Chinnakonda (Energy Advances, 2024)
The major issues that determine the efficiency of photocatalyst composite materials for solar hydrogen production, with or without a sacrificial agent, are efficient visible light harvesting properties, efficient separation of charge carriers and their utilization of redox sites, and stability. Thus, significant efforts have been devoted in the past few decades to modify the above characteristics by integrating constituent components of composites using different approaches. In the present review, we aim to summarize the recent advances, predominantly, in the area of TiO2-based photocatalyst composites for solar hydrogen production. Firstly, we present the recent progress in material integration aspects by discussing the integration of TiO2 with different categories of materials, including noble/3d metals, metal oxides/sulphides/selenides, other low bandgap semiconductors, C-based materials, and dye sensitizers. Furthermore, we discuss how material integration helps in tailoring the electronic and optical properties for activity tuning in solar H2 production. Subsequently, critical changes in the physico-chemical and electronic properties of composites with respect to their preparation methods, morphology, crystallographic facets, particle size, dopant, calcination temperature, and structure–activity relationship to solar hydrogen production are addressed in detail. Moreover, we discuss the importance of fabricating a photocatalyst in a thin film form and performing solar hydrogen production in different reactor set-ups for enhancing its photocatalytic performance, while addressing device scalability. Despite the significant advancements made in this field, solar-to-hydrogen conversion efficiency still needs to be improved to realise the practical application of solar hydrogen production. In this case, the direct conversion of water to hydrogen via overall water splitting and renewable H2 production from wastewater or biomass components by employing suitable photocatalysts are some possible ways to improve the energy efficiency, and continuous research in the above directions is highly desirable.

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.

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

Selective oxidation of biomass derived 5-hydroxymethylfurfural (HMF) to 2,5-diformylfuran (DFF) over spent dry cell battery cathode material (BCM-2) - Ghadge, Sambhaji S.; Bankar, Shubham R.; Jadhav, Vrushali H. (ACS Applied Engineering Materials, 2024)
Widespread use of batteries across the globe generates a huge amount of waste. This work is the first to report spent dry cell (Zn-Carbon) battery cathode material (BCM-2) as a heterogeneous catalyst for selective synthesis of fine chemical 2,5-diformylfuran (DFF). Cathode material was easily separated from spent batteries, and acid leached followed by calcination to obtain black powder that was denoted as BCM-2. The catalyst was characterized using various techniques such as P-XRD, EDAX, SEM, HR-TEM, TGA, XPS, and BET analysis. Superior catalytic activity was shown by the catalyst for selective formation of DFF using molecular O2 as a sole oxidant. The catalyst was found to give excellent HMF conversion of 97% with 98% high selectivity of DFF. The BCM-2 catalyst was easily recycled and reused without any significant loss in its catalytic activity. This is one of the best examples for a sustainable, cost-effective, and highly efficient catalytic system for the synthesis of the value-added chemical DFF.

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

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

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.

Size matters: computational insights into the crowning of noble gas trioxides - Dash, Soumya Ranjan; Sharma, Himanshu; Tiwari, Mrityunjay K.; Greb, Lutz; Vanka, Kumar (Inorganic Chemistry, 2024)
In pursuit of enhancing the stability of the highly explosive and shock-sensitive compound XeO3, we performed quantum chemical calculations to investigate its possible complexation with electron-rich crown ethers, including 9-crown-3, 12-crown-4, 15-crown-5, 18-crown-6, and 21-crown-7, as well as their thio analogues. Furthermore, we expanded our study to other noble gas trioxides (NgO(3)), namely, KrO3 and ArO3. The basis set superposition error (BSSE) corrected interaction energies for these adducts range from -13.0 kcal/mol to -48.2 kcal/mol, which is notably high for sigma-hole-mediated noncovalent interactions. The formation of these adducts was observed to be more favorable with the increase in the ring size of the crowns and less favorable while going from XeO3 to ArO3. A comprehensive analysis by various computational tools such as the mapping of the electrostatic potential (ESP), Wiberg bond indices (WBIs), Bader's theory of atoms-in-molecules (AIM), natural bond orbital (NBO) analysis, noncovalent interaction (NCI) plots, and energy decomposition analysis (EDA) revealed that the C-H center dot center dot center dot O interactions, as well as dispersion interactions, play a pivotal role in stabilizing adducts involving larger crowns. A noteworthy outcome of our study is the revelation of a coordination number of 9 for xenon in the complex formed between XeO3 and the thio analogue of 18-crown-6, which is higher than the largest number reported to date.

Solid-state NMR method for characterization of pharmaceutical eutectics - Hareendran, Chaithanya; Shaligram, Parth S.; Gonnade, Rajesh; Ajithkumar, T. G. (Physical Chemistry Chemical Physics, 2024)
Pharmaceutical eutectics are extremely useful for designing formulations, and currently, there are no techniques other than differential scanning calorimetry (DSC) that can confirm their formation. In this study, we demonstrate that 1H fast magic angle spinning (MAS) solid-state NMR (SSNMR) experiments can confirm the formation of eutectics by detecting their intermolecular hydrogen bonding interactions. 2D 1H-1H double quantum single quantum (DQSQ) correlation SSNMR experiment is demonstrated which can confirm the formation of pharmaceutical eutectics for which there are no techniques other than differential scanning calorimetry (DSC).

Solvent-free hydroxylation of unactivated C-H bonds in small molecules and macromolecules by a Fe complex - Chatterjee, Debasmita; Sajeevan, Amritha; Jana, Sandipan; Birajdar, Rajkumar S.; Chikkali, Samir H.; Sivaram, Swaminathan; Sen Gupta, Sayam (ACS CATALYSIS, 2024)
Keywords: Ball milling; solid-state C-H hydroxylation

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

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

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, crystal growth, physicochemical study of 1,3-dihexyl-2-me-thyl-1H-benzo[d]imidazol-3-ium bromide and in silico nonlinear optical property determination - Siddiqui, Zahir Ali; Gamidi, Rama Krishna; Sekar, Nagaiyan; More, Sandeep (Journal of Molecular Structure, 2024)
This study encompasses the synthesis and characterization of 1,3-dihexyl-2-methyl-1H-benzo[d]imidazol-3-ium bromide (DHBIB) using techniques such as NMR, IR, and HRMS. The study also explores the influence of different solvents, specifically water and acetonitrile, on the growth of single crystals. An intriguing observation is the transformation of crystal packing from orthorhombic to monoclinic when solvent conditions change, illustrating the pivotal role of the cation in controlling the crystal structure of DHBIB salts. The analysis of its electronic properties reveal a deep -lying LUMO (-3.73 eV), suggesting DHBIB's electron -accepting characteristics. Furthermore, the study records absorption maxima ( lambda max ) at 279 nm and 282 nm in various solvents, demonstrating that DHBIB lacks absorption in the visible range (400-800 nm), making it promising for non-linear optical (NLO) applications. Analysis of the natural bond orbital (NBO) stabilization energies 50.87, 42.12, and 45.33 kcal/mol along pi(C3-C4) -> pi*(C6-C8), pi(C3-C4) -> pi*(C10-C12), and pi (C10-C12) -> pi*(C6-C8) reveal a preference for intramolecular charge transfer in DHBIB. Enhanced first and second -order hyperpolarizabilities ( beta ; 13.47x10 -30 esu, gamma ; 75.36x10 - 36 esu) compared to benzimidazole and benzimidazolium salicylate salt further supports its potential for NLO applications.
Keywords: DHBIB; Hyperpolarizability; Monoclinic; NBO; Orthorhombic

Synthesis of imine-phenoxy ligated palladium complexes for norbornene homopolymerization - Birajdar, Rajkumar S.; Gupta, Poonam; Gonnade, Rajesh G.; Chikkali, Samir H. (Inorganic Chemistry, 2024)
Metal complexes with tunable ligands play a crucial role in olefin polymerization and impart control over molecular weight, crystallinity, and stereoregularity. We report the single-step synthesis of imine-phenoxy ligands in excellent yields (81-93%). The identity of electronically tuned imine-phenoxy ligands was unambiguously ascertained by using a combination of spectroscopic and analytical methods. These ligands were treated with [Pd(COD)MeCl] in the presence of 2,6-lutidine, resulting in the formation of discrete mononuclear palladium complexes Pd1-Pd4 in excellent yields. 1-2D NMR spectroscopy, mass spectrometry analysis, and single-crystal X-ray diffraction confirmed the identity of the palladium complexes. X-ray analysis revealed a distorted square planar geometry around the palladium center. Proton NMR analysis suggested that the Pd1 catalyst was deshielded, indicating electronically deficient palladium metal compared to the other complexes. Moreover, the Pd1 catalyst showed the highest buried volume percentage (%Vbur = 44.9). When exposed to norbornene, Pd1-Pd4 were found to be active and produced poly(norbornene) (PNB). High-temperature SEC analysis revealed that the electronically deficient and sterically hindered Pd1 catalyst produced the highest molecular weight polymer (PNB 37.4 kDa). Boron and aluminum-based cocatalysts were screened, and MMAO was found to outperform others with high catalytic activity (up to 63.2 x 105 g of PNB (mol Pd)-1 h-1).

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

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

Synthesis of Ti1-xWx solid solution MAX phases and derived MXenes for sodium-ion battery anodes - Ratzker, Barak; Favelukis, Bar; Baranov, Mark; Rathod, Yugal; Greenberg, Avia; Messer, Or; Goldstein, Dor A.; Upcher, Alexander; Ezersky, Vladimir; Maman, Nitzan; Biran, Ido; Natu, Varun; et al. (ADVANCED FUNCTIONAL MATERIALS, 2024)
Keywords: Behavior; CARBIDE MXENE; INTERCALATION MECHANISM; TI

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

Thermally stable P-chiral supramolecular phosphines, their self-assembly and implication in Rh-catalyzed asymmetric hydrogenation - Chandanshive, Amol C.; Gonnade, Rajesh G.; Chikkali, Samir H. (Chemistry-A European Journal, 2024)
P-chiral supramolecular phosphine ligands are crucial for asymmetric transformations, but their synthesis is tedious. We report a one-step synthesis of thermally stable P-chiral supramolecular phosphines and their performance in the asymmetric hydrogenation of functionalized alkenes. A rational designing and synthesis of (R, R)-QuinoxP* ligated palladium complex (Pd-2) in excellent yield is reported. This Pd-2 catalyzed a direct P-C coupling of 2,3-dihydro-1-H-phosphindole (A1)/1,2,3,4-tetrahydrophosphindoline (A2) with 1-(3-iodophenyl)urea (B1)/2-iodo /6-hydroxy pyridine (B2) and,produced corresponding ligands L1-L3. The P-C coupling between A1 and B2 produced 6-(2,3-dihydro-1H-phosphindol-1-yl)pyridine-2(1H)-one (L2) with an excellent enantiomeric excess of up to 99 %. L2 was found to be remarkably stable even at 150 degrees C and did not oxidize/hydrolyze for at least 24 hours in open air. Such thermal stability and an impediment to oxidation are unprecedented. L2 self-assembled and produced L2-C1 (Pt), L2-C2(Pd), and L2-C3(Rh) assemblies. The utility of the self-assembled P-chiral ligand was demonstrated in the Rh-catalyzed asymmetric hydrogenation (AH) of functionalized olefins. The L2-C3 catalyzed AH of functionalized alkenes and delivered chiral products with excellent enantioselectivity of >99 %. A small library of 16 substrates was subjected to AH using L2-C3 to produce chiral compounds with excellent conversion and ee.
Keywords: asymmetric hydrogenation; Asymmetric phosphination; P-chiral phosphine; Self-assembly; Supramolecular phosphine

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

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

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

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

Unconventional hole doping of S = ½ kagome antiferromagnet CoCu3(OH)6Cl2 - Mandal, Rimpa; Ninawe, Pranay; Ananthram, K. S.; Mhase, Akash; Gupta, Kriti; Saha, Sauvik; Ugale, Ajay; Singh, Kirandeep; Tarafder, Kartick; Ballav, Nirmalya (Advanced Physics Research, 2024)
Geometrically perfect S = ½ kagome lattices with frustrated magnetism are typically electrical insulators. Electron or hole doping is predicted to induce an exotic conducting state including superconductivity. Herein, an unconventional strategy of doping an S = ½ kagome lattice CoCu3(OH)6Cl2 is adopted – a structural analogue of a well-known quantum spin liquid (QSL) candidate herbertsmithite (ZnCu3(OH)6Cl2) – by integrating it with reduced graphene oxide (rGO) via in situ redox chemistry. Such an integration drastically enhances the electrical conductivity, resulting in the transformation of an insulator to a semiconductor, corroborating the respective density of states obtained from the density functional theory calculations. Estimation of the magnetic moments, data on the Hall-effect measurements, Bader charge analysis, and photoemission signals, altogether provide a bold signature of remote hole doping in CoCu3(OH)6Cl2 by rGO. The remote doping provides an alternative to the site doping approach to impart exotic electronic properties in spin liquid candidates, specifically, the generation of topological states like Dirac metal is envisioned.

Uncovering diverse reactivity of NHCs withdiazoalkane: C-H activation, C=C bond formation,and access to N-heterocyclic methylenehydrazine - Balayan, Kajal; Sharma, Himanshu; Vanka, Kumar; Gonnade, Rajesh G.; Sen, Sakya S. (Chemical Science, 2024)
N-heterocyclic carbenes (NHCs) have attracted significant attention due to their strong sigma-donating capabilities, as well as their transition-metal-like reactivity towards small molecules. However, their interaction with diazoalkanes remains understudied. In this manuscript, we explore the reactivity of a series of stable carbenes, encompassing a wide range of electronic properties, with Me3SiCHN2. 5-SIPr activates the C-H bond of Me3SiCHN2, resulting in the formation of a novel diazo derivative (1), while carbenes such as 5-IPr, 6-SIPr, and diamido carbene yield N-heterocyclic methylenehydrazine derivatives (3, 4, and 8). The reaction of Me3SiCHN2 with 5-ItBu unexpectedly leads to the formation of a triazole ring linked with the imidazole moiety via a CC double bond (6) alongside the azine product (7). Substituting the diazoalkane with diazoester consistently yields azine derivatives (9-12 and 14). Only in the case of 5-ItBu, an imidazolium salt with tetrazenide anion (13) was obtained as a side product. The reaction of 4 with HCl resulted in the desilylprotonation to form a salt, 5a, which undergoes deprotonation upon using bases such as Et3N and KHMDS to form N-heterocyclic methylene hydrazine, 5. Theoretical calculations have been conducted to elucidate the diverse mechanisms underlying product formation.

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

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

Unraveling the metal-ligand cooperativity in a phosphine-free Mn(II)-catalyzed transfer hydrogenation of nitriles to primary amines and dehydrogenation of dimethylamine borane - Chowdhury, Deep; Gupta, Kriti; Gamidi, Rama Krishna; Jindal, Garima; Mukherjee, Arup (ACS CATALYSIS, 2024)
Keywords: CATALYZED TRANSFER HYDROGENATION; STEREOSELECTIVE TRANSFER SEMIHYDROGENATION

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.

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

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

Visible-light mediated C-3 amination of quinoxalin-2(1H)-ones via electron donor-acceptor complexation - More, Devidas A.; Gayathri, P. R.; Thete, Kishor R.; Muthukrishnan, M. (Asian Journal of Organic Chemistry, 2024)
The formation of carbon-nitrogen bonds holds paramount importance in the realm of synthetic organic chemistry, finding extensive applications in the synthesis of pharmaceuticals, agrochemicals, and organic materials. Herein, we describe a novel EDA complex mediated, metal- and photocatalyst-free, visible-light-initiated direct C-3 amination of biologically important, quinoxalin-2(1H)-one moiety. The key to the success lies in the formation of a photoactivated electron donor-acceptor complex between quinoxalin-2(1H)-one and amine, which undergo subsequent electron transfer reaction to effect the desired transformation. A diverse array of 3-aminoquinoxalin-2(1H)-ones were prepared employing this process and the yields are up to 87%. This work represents a significant advancement toward a more environmentally friendly and efficient approach, characterized by mild reaction conditions and a high atom economy.
Keywords: C-3 amination; Dehydrogenative amination; EDA complex; quinoxalin-2(1H)-ones

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

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

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.

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

Aryl borane as a catalyst for dehydrative amide synthesis - Gavit, Amit Vinayak; Talekar, Sanjana S.; Mane, Manoj V.; Sawant, Dinesh Nanaji (Journal of Organic Chemistry, 2025)
Tris(pentafluorophenyl)borane B(C6F5)(3)H2O is reported as a catalyst for dehydrative amidation of carboxylic acids and amines. This protocol is applicable across a wide range of >35 substrates, including aromatic and aliphatic amines and acids, resulting in amides in <= 92% yields. The scalability of the reaction up to 10 mmol, along with the synthesis of drugs such as ibuprofen amide, moclobemide, and phenacetin, demonstrates the industrial potential of our protocol.

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.

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

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

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

Catalyst and transition-metal free 1,6-conjugate addition of azobisisobutyronitrile: access to isobutyronitrile containing diarylmethanes - Mamale, Ajay G.; Ghodake, Balaji M.; Gonnade, Rajesh G.; Bhattacharya, Asish K. (Organic & Biomolecular Chemistry, 2025)
A catalyst and transition-metal free 1,6-conjugate addition of azobisisobutyronitrile to para-quinone methides for the synthesis of isobutyronitrile containing diarylmethanes has been achieved. This protocol enables the synthesis of isobutyronitrile containing diarylmethanes in good yields and with a broad substrate scope. This is the first example wherein azobisisobutyronitrile has been used as a cyanide source for 1,6-conjugate addition under catalyst and metal-free conditions.

Catalytic hydrogenation of cinnamaldehyde over nanocrystalline nickel-doped lanthanum aluminate: synergistic effect of nickel and oxygen vacancies - Bhavisha, Meloth; Balamurugan, Sarkarainadar; Venkatesha, Naragalu J.; Gopinath, Chinnakonda S.; Sakthivel, Ayyamperumal (ChemCatChem, 2025)
Nickel-doped lanthanum aluminium perovskite, LaAl1-xNixO3-delta with x = 0, 0.1, 0.2, 0.3, 0.4,0.5, 0.6, and 0.75 (LANx), were obtained through a combustion method followed by a calcination process. The obtained LANx materials crystallized in the cubic structure by the Pm-3m (221) space group. The nanocrystalline nature of the LANx materials was confirmed by the average crystalline size determined using Debye-Scherrer formula. X-ray photoelectron spectroscopy (XPS) studies showed that nickel was present in the +2 and +3 oxidation states. The introduction of nickel resulted in distinct peaks in TPR in the temperature range of 200-600 degrees C, with an enhanced reducibility of the materials. The LANx materials were thoroughly assessed for their effectiveness in the hydrogenation of cinnamaldehyde. The maximum catalytic activity (cinnamaldehyde conversion of 98% with a hydrocinnamylalcohol selectivity 96.5%) was observed with the presence of the LAN7 catalyst at 150 degrees C for 6 h at a H2 pressure of 10 bar. The catalytic activity is maintained even after four cycles, which broadens the application scope as the material is sustainable, scalable, cost-effective, and a potential alternative to reported noble metal catalysts. The synergistic effect of nickel and oxygen vacancies in the catalyst improves the reducibility and provides a promising catalytic activity in the cinnamaldehyde hydrogenation.
Keywords: Cinnamaldehyde; Hydrocinnamylalcohol; Hydrogenation; Nickel; Perovskite oxide

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

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

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

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.

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

Coke management: unveiling the role of Ce substitution in Gd2Zr1.8Ni0.2O7-δ catalyst for dry reforming of methane - Ghodke, Seema R.; Mule, Harshada M.; Bhatkar, Akash; Devi, R. Nandini (Energy & Fuels, 2025)
The redox characteristics of cerium have become crucial elements in the carbon gasification process during methane dry reforming. This work examines the effect of cerium substitution in the Gd2Zr1.8Ni0.2O7-delta catalyst during methane dry reforming, employing a range of Ce-substituted Gd2Zr1.8-x Ni0.2Ce x O7-delta (x = 0.1, 0.2, 0.5, 0.75) catalysts synthesized via the citrate gel method. The materials crystallized in a fluorite structure, as verified by X-ray diffraction analysis and Raman spectroscopy. Enhanced reducibility of the substituted catalysts was assessed through H2-temperature-programmed reduction analysis. CO2 and O2 desorption studies along with X-ray photoelectron spectroscopy validated the enhanced basicity and generation of active oxygen and hydroxyl species. The enhanced activity and coke gasification in Gd2Zr1.6Ni0.2Ce0.2O7-delta catalyst are attributed to surface hydroxyl species, and prominent intermediate carbonate and bicarbonate species were further verified by in situ infrared spectroscopy. The high basicity of the Gd2Zr1.6Ni0.2Ce0.2O7-delta catalyst and high concentrations of oxygen vacancies (similar to 66.4%) enhances CO2 adsorption and desorption, resulting in continuous CO2 activation, leading to less carbon formation and superior activity of the catalyst. The Gd2Zr1.6Ni0.2Ce0.2O7-delta catalyst exhibits the highest CH4 and CO2 conversion rates, at 85% and 93.5%, respectively, and remains stable for 100 h. Postreaction analysis of Gd2Zr1.6Ni0.2Ce0.2O7-delta confirms structure stability and less carbon formation compared to other substituted catalysts in dry reforming of methane. This study demonstrates that the moderate concentration of Ce in the Gd2Zr1.6Ni0.2Ce0.2O7-delta catalyst exhibits balanced activity and coke gasification capacity in the dry reforming of methane for a longer duration.

Comprehensive in vitro and in silico assessment of eugenol glycoconjugates against azole and amphotericin B resistant Rhizopus spp. - Sen, Pooja; Gupta, Lovely; Chauhan, Aastha; Goswami, Lakshmi; Bhattacharya, Asish K.; Sengupta, Abhishek; Vijayaraghavan, Pooja (Molecular Biology Reports, 2025)
Background Rhizopus spp. is a major cause of mucormycosis, a severe infectious disease with high morbidity and mortality. Treatment is challenging due to rising antifungal resistance. Glycosylation is a crucial technique for enhancing the properties of phenolic compounds like eugenol. The present study aims to examine the antifungal efficacy of eugenol glycoconjugates against azole and amphotericin B-resistant Rhizopus isolates. Methods and results Out of 50 soil samples, 12 isolates belonging to Mucorales were obtained, of which 7 were identified as Rhizopus spp. via 18S ITS sequencing. Antifungal susceptibility testing (AST) revealed that all Rhizopus isolates were resistant to amphotericin B (MIC > 1 mu g/mL). Most isolates also showed resistance towards posaconazole (MIC > 1 mu g/mL) and itraconazole (MIC > 2 mu g/mL). AST of eugenol glycoconjugate (coded 6g) showed efficacy against resistant Rhizopus isolates, with MIC values ranging from 6.25 mu g/mL to 25 mu g/mL. Flow cytometry confirmed its fungicidal activity, correlating with MIC data. Compound 6g significantly reduced conidial germination within 24 h and exhibited no cytotoxicity on A549 lung cancer cells. In-silico analysis revealed a negative binding affinity of compound 6g for the spore coat protein CotH3, which could be a potential antifungal target. Conclusion Compound 6g could be an potential antifungal molecule against resistant Rhizopus spp, which requires further studies.
Keywords: Antifungals; Eugenol; Glycoconjugates; Mucormycosis; Resistance; Virulence

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

Concurrent utilization of e- and h+ for water splitting to H2 and biomass components into value-added products: sustainable solar-driven photocatalysis towards meeting SDG7, 12 and 13 - Rajendran, Sivaraj; Saju, Simi; Mathew, Thomas; Gopinath, Chinnakonda S. (Chemical Communications, 2025)
Photocatalytic water splitting is considered one of the efficient methods for producing green hydrogen. However, the sluggish oxygen evolution reaction (OER) kinetics with four electrons limits the overall efficiency of water splitting. Biomass components/biomass derivatives are renewable carbon feedstocks that are abundantly available in nature. It is prudent to make use of electrons and holes concurrently in photocatalysis for H2 production and oxidation of biomass components, respectively, due to the latter's occurrence at a lower potential (<= 1 V) than that of the OER (>1.23 V), to value-added products (VAPs); this approach makes the entire process energy-efficient and kinetically superior. This potential approach could effectively utilize the charge carriers and abundant renewable resources of water and biomass simultaneously, meeting the sustainability, energy conversion and economic goals together. Parallel utilization of the charge carriers for redox reactions also enhances the sustainability of the catalyst system employed. Interestingly, biomass component oxidation to VAPs occurs in several steps, which not only enhances hole utilization but also provides an opportunity to design better catalysts to enhance the selectivity of the target products. Carrying out such reactions under aerobic or anaerobic conditions and different pH conditions allows fine-tuning of the product selectivity. The current review provides a detailed overview of the recent developments in this emerging area with three different types of photocatalyst systems, namely, oxide-, chalcogenide-, and carbon-based materials. Among these, the oxide-based systems generally demonstrate the highest activity with sustainability, maintaining performance for several hours. While many of these systems exhibited high selectivity towards a single product, 100% selectivity to lactic acid from glycerol was observed with a BiVO4-integrated TiO2 catalyst. Finally, the challenges, opportunities and future perspectives in this thriving field are listed, and they underscore the role of a carbon-neutral economy towards achieving a potentially sustainable future.

Concurrent utilization of e− and h+ for water splitting to H2 and biomass components into value-added products: sustainable solar-driven photocatalysis towards meeting SDG7, 12 and 13 - Rajendran, Sivaraj; Saju, Simi; Mathew, Thomas; Gopinath, Chinnakonda S. (Chemical Communications, 2025)
Photocatalytic water splitting is considered one of the efficient methods for producing green hydrogen. However, the sluggish oxygen evolution reaction (OER) kinetics with four electrons limits the overall efficiency of water splitting. Biomass components/biomass derivatives are renewable carbon feedstocks that are abundantly available in nature. It is prudent to make use of electrons and holes concurrently in photocatalysis for H2 production and oxidation of biomass components, respectively, due to the latter's occurrence at a lower potential (≤1 V) than that of the OER (>1.23 V), to value-added products (VAPs); this approach makes the entire process energy-efficient and kinetically superior. This potential approach could effectively utilize the charge carriers and abundant renewable resources of water and biomass simultaneously, meeting the sustainability, energy conversion and economic goals together. Parallel utilization of the charge carriers for redox reactions also enhances the sustainability of the catalyst system employed. Interestingly, biomass component oxidation to VAPs occurs in several steps, which not only enhances hole utilization but also provides an opportunity to design better catalysts to enhance the selectivity of the target products. Carrying out such reactions under aerobic or anaerobic conditions and different pH conditions allows fine-tuning of the product selectivity. The current review provides a detailed overview of the recent developments in this emerging area with three different types of photocatalyst systems, namely, oxide-, chalcogenide-, and carbon-based materials. Among these, the oxide-based systems generally demonstrate the highest activity with sustainability, maintaining performance for several hours. While many of these systems exhibited high selectivity towards a single product, 100% selectivity to lactic acid from glycerol was observed with a BiVO4-integrated TiO2 catalyst. Finally, the challenges, opportunities and future perspectives in this thriving field are listed, and they underscore the role of a carbon-neutral economy towards achieving a potentially sustainable future.

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 β-zeolite catalysed regioselective alkylation of naphthols using alcohols for synthesis of peroxynaphthalen-2(1H)-one, Azidonaphthalen-2(1H)-one and Fluoronaphthalen-2(1H)-one derivatives - Londhe, Gokul; Bokade, Vijay; Gnanaprakasam, Boopathy (Asian Journal of Organic Chemistry, 2025)
Functionalized naphthols are prominent scaffolds in organic synthesis and materials chemistry. Herein, we demonstrated continuous flow alkylation of alpha- and beta-naphthols by using various primary and secondary benzylic alcohols in the presence of environmentally benign granular beta-zeolite as a reusable catalyst. For a variety of beta-naphthols, the respective alkylated products with good regioselectivity were obtained in high yields under mild reaction conditions. This protocol proceeded via the classical Friedel-Crafts type alkylation process and generated stable carbocations as intermediates. Applying this protocol, versatile naphthol derivatives have been synthesized using primary and secondary benzylic alcohols (50 and 44 examples in batch and continuous flow process, respectively), with good yields. Key advantages of this process includes rapid and efficient transformation, facilitates gram-scale synthesis, and generates water as the sole by-product. The most significant advantage is the continuous reusability of granular beta-zeolite, which further emphasizes the sustainability of the method. The application of alkylated naphthols for quaternary functionalization was demonstrated through peroxidation, azidation, and halogenation reactions under the continuous flow module, which yielded the respective peroxynaphthalen-2(1H)-one, azidonaphthalen-2(1H)-one and fluoronaphthalen2(1H)-one derivatives.
Keywords: continuous flow; Multigram Synthesis; Reusable beta-zeolite; Sustainable Appraoch; Transition metal free

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

Deciphering the role of metabolites and phytohormones in plant resilience to drought and herbivory - Sahu, Monika; Giri, Ashok P. (Plant Stress, 2025)
<span style="box-sizing: border-box; margin: 0px; padding: 0px; color: rgb(31, 31, 31); font-family: ElsevierGulliver, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif, sans-serif; font-size: 16px;">Climate change is expected to result in increased variability in precipitation and more frequent outbreaks of insect pests. Thus, it is important to understand how plant-environment interactions are affected by both abiotic and biotic stresses. Water is essential for plant growth, development and interactions with other organisms, including insects. This review synthesizes current studies on the impact of drought and herbivore defense mechanisms and associated metabolic changes in plants. Severe drought can enhance plant tolerance to herbivores by promoting escape strategies whereas mild or intermittent drought may benefit insects by increasing nutrient availability. We discuss how plants adjust their metabolism to mitigate the effects of combined stresses. We further highlight the role of hormonal signaling pathways, such as <a class="topic-link" href="https://www.sciencedirect.com/topics/agricultural-and-biological-sciences/abscisic-acid" style="box-sizing: border-box; margin: 0px; padding: 0px; background-color: rgba(0, 0, 0, 0); word-break: break-word; text-decoration-thickness: 1px; text-decoration-color: rgb(31, 31, 31); color: rgb(31, 31, 31); text-underline-offset: 1px;">abscisic acid, <a class="topic-link" href="https://www.sciencedirect.com/topics/biochemistry-genetics-and-molecular-biology/jasmonate" style="box-sizing: border-box; margin: 0px; padding: 0px; background-color: rgba(0, 0, 0, 0); word-break: break-word; text-decoration-thickness: 1px; text-decoration-color: rgb(31, 31, 31); color: rgb(31, 31, 31); text-underline-offset: 1px; 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;">jasmonic acid<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;">, salicylic acid and ethylene in coordinating plant responses. Research on metabolic changes accompanying hormonal crosstalk involved in managing multiple stresses is still emerging. The available evidence suggests that the outcome of drought and herbivory varies depending on factors such as stress intensity, duration, plant-herbivore species, and insect-feeding guilds. We propose open questions and anticipate further advances in molecular understanding of plant resilience to combined stresses such as drought and herbivory in the near future.

Degradation of aniline blue dye in aqueous solution using ozonation as advanced oxidation process: optimization and mechanism - Bhawsar, Aastha; Bhutada, Dinesh; Ghuge, Santosh (Journal of the Indian Chemical Society, 2025)
Aniline blue dye is widely used in various fields, including textile dyeing, biotechnological processes, and analytical chemistry research. However, its release into the environment without proper treatment can have serious adverse effects on human health and the ecosystem, emphasizing the need for effective management and remediation strategies. A limited number of studies are available in the literature employing advanced oxidation processes (AOPs) for the mineralization of aniline blue dye. Therefore, the present work explores ozonation as one of the AOPs to study the degradation aniline blue dye in aqueous solution. The experimental parameters like initial dye concentration, inlet ozone dose and initial dye solution pH were optimized in order to maximize aniline blue dye degradation efficiency. The direct and indirect degradation pathways were analyzed using tbutanol as a radical scavenger. The maximum degradation efficiency of 81.1 % was achieved at optimal experimental conditions of initial dye concentration of 250 mg/L, inlet ozone dose of 18g/h and initial dye solution pH 11 after 30 min of ozonation. The complete colour removal was observed after 15 min of ozonation at the optimized experimental conditions. The presence of radical scavenger t-butanol had no impact on colour removal efficiency indicating direct ozone molecule mechanism. However, COD removal efficiency was decreased with the addition of radical scavenger t-butanol suggesting indirect hydroxyl radical based mechanism. The experimental results suggested that ozonation is an effective and promising method for the degradation of aniline blue dye in aqueous solution, showcasing significant potential for its application in wastewater treatment.
Keywords: Aniline blue dye; Degradation mechanism; Ozonation

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 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 novel ssDNA aptamers for detection of receptor-binding domain of SARS-COV-2 - Auti, Amogh; Yadav, Pranay; Bodkhe, Rahul; Bhandari, Yogesh; Varma, Sanjana; Chaudhari, Bhushan; Rahi, Shraddha; Ghormade, Vandana; Vamkudoth, Koteswara Rao (ACS Omega, 2025)
The highly virulent and transmissible SARS-CoV-2 causes COVID-19 and poses a global public health threat. Herein cloned, expressed, and the molecular weight of the receptor-binding domain (RBD) of the SARS-CoV-2 gene encoding protein was confirmed by SDS-PAGE electrophoresis and Western blot analysis. The pivotal aim is to develop single-stranded DNA (ssDNA) aptamers for the rapid detection of SARS-COV-2 infections in humans. In this investigation, a library of nine novel ssDNA aptamers was developed by several rounds of systematic evolution of ligands by an exponential enrichment approach and assessed by an enzyme-linked aptamer assay for binding affinity against RBD antigen (Ag). An in vitro assay resulted in a varied colorimetric signal that depends on the nature of aptamer. Quantitative determination of AptRBD3, AptRBD6, and AptRBD8 aptamers exhibited excellent binding affinity against Ag in the range of 5-10 ng/mL. The putative AptRBD3, AptRBD6, and AptRBD8 aptamers were converted into peptide sequences and docked against RBD, exhibiting good binding energy of -6.8, -6.3, and -7.1 kcal/mol respectively, which were recorded. Furthermore, docking studies of ssDNA aptamers were performed using HDOCK web server to ascertain the binding mechanism and docking score perceived as -389.74, -404.28, and -390.37. Despite this, we engineered a high-affinity AptRBD3.3 aptamer that formed a single and bulged loop, which improved binding affinity, resulted in a docking score of -361.56, and exhibited sensitivity at 4 ng of Ag of SARS-CoV-2. Moreover, computational modeling of AptRBD3.3 revealed an intriguing significant binding affinity with the RBD mutant SARS-CoV-2 S-UK variant (PDB ID: 7EDG) with a docking score of -350.21. In conclusion, the AptRBD3.3 aptamer can be used for the development of lateral flow device and electrochemical sensors for rapid, low-cost, and accurate detection of COVID-19 infection in humans for point of care diagnostics.

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.

Diboron reagents in modern reduction chemistry: a versatile tool for reduction of various functional groups - Gavit, Amit Vinayak; Darandale, Nutan Rajendra; Surange, Sarthak Baburao; Sawant, Dinesh Nanaji (Advanced Synthesis & Catalysis, 2025)
Reduction of various organic functionality including aldehyde, ketone, nitro, imine, and alkyne has gained noteworthy attention due to its vast application of products in organic transformation reactions. To attempt hydrogenation several approaches have been reported by using molecular hydrogen as a reducing source. Besides, this diboron (tetrahydroxy diboron, bispinacolato diboron, neoglycolato diboron) has shown a promising and alternative approach for the reduction of the reducible functional group without using any molecular hydrogen. The ligand-free reduction approach of commercially available diboron reduces the organic compound by using water or organic solvent and metal salt making it an attractive protocol in the recent era of reduction as well as hydrogenation. Herein, we provide an extensive and collective overview of the diboron-mediated reduction approach of various organic compounds.
Keywords: diboron; H2; H2O/MeOH; Metal; reduction

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

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

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

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.

Efficient Copper-Catalyzed, One-Pot Synthesis of N2-Aryl Phosphoryl 1,2,3-Triazole 1-Oxides - Mujahid, M.; Bhavar, Akshay A.; Vara, Vijay; Gonnade, Rajesh; Muthukrishnan, M. (Asian Journal of Organic Chemistry, 2025)
A simple and facile one-pot process has been developed for the synthesis of N 2-aryl phosphoryl 1,2,3-triazole 1-oxide derivatives. This new approach utilizes simple and commercially available starting materials, operating under mild conditions. The method employs copper-catalyzed multicomponent reaction, involving the combination of arylhydrazines, beta-ketophosphonates, and tert-butyl nitrite. The developed protocol shows excellent functional group tolerance permitting an extensive range of substrate scope up to 92% isolated yield.
Keywords: Copper-catalyzed; Phosphoryl triazoles N-oxides; Phosphorylated compound; Triazole N-oxides

Efficient hydrogen liberation from autocatalytic wastewater treatment by green synthesized Ag2SeO3 nanocatalyst - Islam, Sk Najrul; Ansari, Ifra Ilyas; Gopinath, Chinnakonda S.; Ahmad, Absar (Inorganic Chemistry Communications, 2025)
Concerns about wastewater management, secure hydrogen storage, and interest in an affordable, effective, and user-friendly technique for releasing hydrogen have grown globally. Developing sustainable synthetic processes that result in industrially significant nanocatalyst to synergistically accelerate the evolution of hydrogen from wastewater treatment is extremely desirable. This work, for the first time, demonstrates the design and green fabrication of bactericidal silver selenite nanoparticles (Ag2SeO3 NPs) using the fungus Aspergillus niger for autocatalytic hydrogen production and methylene blue dye reduction by hydrolytic dehydrogenation of NaBH4. The morphology of Ag2SeO3 nanocatalysts with an average particle size of 60 nm was assessed by FETEM, while their surface chemistry, crystal structure, and optical properties were examined using XPS, XRD, and FTIR/ UV-Visible spectrophotometers, respectively. The sigmoidal trajectory of NaBH4 dehydrogenation with turnover frequencies (TOF) of 4750 mL g- 1 min- 1 suggested good autocatalytic activity of Ag2SeO3 NPs. The mechanistic study unveiled that autocatalysis was made possible by the creation of novel, active Ag co-catalyst which works synergistically with Ag2SeO3 NPs. For in-situ, real time assessment of Ag concentration during catalysis, hydrolysis of NaBH4 was carried out in the presence of methylene blue dye. The results showed that the active cocatalyst centers have a significant influence on autocatalytic hydrogen production at room temperature, reducing 98.8 % methylene blue (MB) dye in 6 min with a lesser hydrogen generation rate of 4174 mL g- 1 min- 1. The catalyst exhibited excellent stability and durability after fourth consecutive cycle, demonstrating its promise for long-term and recurring application in hydrogen liberation from autocatalytic MB dye reduction.
Keywords: Ag2SeO3 nanoparticles; Antibacterial; autocatalysis; Hydrogen generation; Wastewater treatment

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

Enhanced mid-visible light absorption and long-lived charge carriers in an electronically and structurally integrated BiVO4-TiO2 photoanode for efficient artificial photosynthesis applications - Jha, Vikas Kumar; Salgaonkar, Kranti N.; Saha, Avishek; Gopinath, Chinnakonda S.; Iyer, E. Siva Subramaniam (Nanoscale, 2025)
The ever-increasing demand for sustainable solutions for eliminating environmental pollutants, solar energy harvesting, water splitting, etc. have led to the design and development of novel materials to achieve the desired result. In this regard, structurally and electronically integrated (SEI) BiVO4-TiO2 (SEI-BVT) with abundant heterojunctions has emerged as a promising entity for efficient charge separation, which in turn enhances artificial photosynthesis (APS) activity. The present work adopted a unique synthetic strategy using SILAR to fabricate SEI-BVT from ionic precursors (Bi3+ and VO43-) into the pores of TiO2, exhibiting benchmark APS efficiency compared to the individual components. This preparation results in approximately 180 trillion uniformly distributed heterojunctions in 1 mg cm-2 of the SEI-BVT photoanode material. Charge carriers in SEI-BVT and BiVO4 are similar; however, the recombination is highly hindered when SEI-BVT heterojunctions are formed in the former. Our earlier work demonstrated 31-38% solar-to-fuel efficiency (STFE) with BiVO4-TiO2 for APS in the presence of the Pd-nanocube co-catalyst. The emphasis of the current work is to explore the dynamics of the light-induced processes in these heterojunctions to understand the interfacial charge transfer process. Femtosecond transient absorption (TA) spectroscopy has been employed to monitor the excited state dynamics. Our results show that new trap states have evolved under light illumination, which are significantly long-lived and hinder charge recombination, and consequently enhance STFE. A significantly large number of charge carriers exhibit a lifetime of >> 6 ns with visible light photons, at least up to 720 nm, which is higher than the band-gap absorption onset at 490 nm for SEI-BVT compared to bulk BiVO4. The rate of formation of charge carriers is significantly affected in the heterojunctions.

Enhancing asphalt pavement longevity through microcapsule-encapsulated rejuvenators: mechanical performance and self-healing evaluation - Gowda, Sachin; Behl, Ambika; Shanmuganathan, Kadhiravan; Gupta, Aakash (International Journal of Pavement Research and Technology, 2025)
Self-healing asphalt incorporating encapsulated rejuvenators presents a promising solution to extend pavement life by autonomously restoring binder functionality in aged or cracked regions. Calcium-alginate microcapsules encapsulating a commercially available bio-based rejuvenator available in the Indian market were synthesized (2–3 mm in diameter) and incorporated into Bituminous Concrete Grade-II asphalt mixtures at 0%, 0.5% and 1% (by aggregates weight). Capsules showed rupture strength > 18 N and thermal stability up to 200 °C. Microstructural (4D-XRM (X-ray Microscopy), Scanning Electron Microscopy (SEM), Brunauer-Emmett-Teller (BET)), chemical (Fourier Transform Infrared (FTIR), Energy-Dispersive X-ray Spectroscopy (EDAX), SARA) and mechanical (Indirect Tensile Strength (ITS), resilient modulus, dynamic creep, Semi-Circular Bending (SCB) healing) tests under unaged, short-term aged (STA) and long-term aged (LTA) conditions were performed. At 1% dosage, the Healing Index (HI) increased substantially (up to 58.03% for LTA), while volumetric, rutting and moisture resistance were not significantly affected. EDAX and SARA confirm targeted rejuvenator release under aging. These findings show that low dosages of Calcium alginate microcapsules can improve fracture recovery in aged asphalt mixtures without compromising initial performance, supporting their potential for self-healing pavements.

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

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

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

Europium oxide on carbon nitride for electrocatalytic glycerol oxidation coupled with hydrogen evolution reaction - Jana, Jayasmita; Sharma, Tata Sanjay Kanna; Ghanem, Mohamed A.; Choi, Won Mook; Gopinath, Chinnakonda S.; Hur, Seung Hyun (Separation and Purification Technology, 2025)
{The integration of the electrochemical glycerol oxidation reaction (GOR) with the hydrogen evolution reaction (HER) has emerged as a promising alternative to the sluggish oxygen evolution reaction (OER) in water splitting toward the development of renewable and clean energy sources. However, suitable electrodes that facilitate redox kinetics while increasing the selectivity of the desired product(s) are still required. Herein, a series of europium oxide (Eu2O3) anchored on graphitic carbon nitride (g-CN) nanoaggregates (g-CNEux
Keywords: carbon support; electrocatalysis; Glycerol; HER; Rare earth metal

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)

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

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

Feasibility study of reactive chromatography for the synthesis of 2-ethoxyethyl acetate using the amberlyst-15 catalyst - Gore, Jayram I.; Nadeem, Mohd; Mahajani, Sanjay M.; Mali, Nilesh A. (Industrial & Engineering Chemistry Research, 2025)
Reactive chromatography is a promising process intensification technology that combines reaction and separation in a single piece of equipment. In this study, the reaction kinetics and adsorption behavior of esterification of 2-ethoxyethanol (EC) with acetic acid (AcOH) using Amberlyst-15 as a catalyst are studied using batch reactions and reactive chromatography. Batch reactions are performed to study the kinetic behavior, and an appropriate kinetic model is proposed. To evaluate adsorption parameters, nonreactive separation experiments are performed in a fixed bed chromatographic reactor (FBCR), and results are compared with model predictions. Further, the MATLAB simulations are performed for reactive separation using kinetics and adsorption data, and results are validated by the experiments. Experimentally obtained breakthrough profiles of FBCR for reaction and desorption reveal the applicability of reactive chromatography for the synthesis of ethyl cellosolve.

Fermi-level equilibrium-driven trap filling in multibandgap PbS quantum dot solids enabling record voltage generation and improved carrier transport in high-performance solar cells - Dambhare, Neha V.; Biswas, Arindam; Sharma, Anjali; Shinde, Dipak Dattatray; Mitra, Anurag; Girade, Vrushali S.; Rath, Arup Kumar (ACS Energy Letters, 2025)
To leverage the unique optical properties of quantum dots (QDs) in solar cells, it is crucial to address electronic traps from unsaturated surface states of high surface area QDs. Despite advancements in surface passivation, even the best-coupled QD solids exhibit significant sub-bandgap trap states. This study introduces engineered multibandgap PbS QD solids that achieve passivation of deep traps below the conduction band through electron migration from dopant QDs. Our findings indicate that electron flow, driven by Fermi energy balancing in blend films, fills deep trap states, reducing trap density by half and shifting trap energy positions closer to the conduction band. During electrical transport, trap filling minimizes trapping and detrapping events, enhancing overall carrier mobility, despite higher-bandgap dopant QDs not contributing to carrier transport due to their unfavorable energy positions. Improved trap passivation in coupled QD solids leads to a record V oc of 725 +/- 10 meV for the 1.33 eV excitonic peak of QDs and a power conversion efficiency exceeding 14% in solar cells.

Is GCR1 the GPR157 of plants? - Gotkhindikar, Aditi; Chakravorty, David; Sengupta, Durba; Joshi, Manali; Assmann, Sarah M. (PLANT PHYSIOLOGY, 2025)

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

Gold nanorods (GNRs): a golden nano compass to navigate breast cancer by multimodal imaging approaches - Varma, Sanjana; Bamb, Aagam Lalit; Haldar, Niladri; Gajbhiye, Virendra; Amalnerkar, Dinesh; Chaudhari, Bhushan Pradosh (Journal of Biomedical Materials Research Part B-Applied Biomaterials, 2025)
The ongoing rise in the incidences of breast cancer cases has concerned medical and scientific personnel around the world. Adequate treatment of cancer predominantly relies on the pertinent diagnosis of the type of cancer as well as other molecular and cellular details at the initial stage only. Surprisingly, up till now, there is no single, self-reliant imaging modality that helps to systematically find out the anatomical and functional events taking place inside the body. This resulted in the advent of the multimodal imaging concept, which encompasses the integration of complementary imaging modalities by designing multimodal imaging probes. Gold nanorods (GNRs) are extremely popular and effective nanoparticles for multimodal bioimaging due to their unique properties. Researchers have designed varieties of stable and biocompatible GNR-based probes for targeted and nontargeted multimodal imaging of breast cancer. However, there is a lack of investigations on the in vivo fate and the toxicity of GNRs. Thus, their preclinical to clinical translation can be attained by comprehensively determining the in vivo fate and toxicity of GNRs. The review provides details about the GNRs-based nanoprobes fabricated so far for breast cancer imaging, which, by consequent studies, can be taken up to clinical usage.
Keywords: Breast cancer; Gold nanorods; imaging probes; Multimodal Imaging

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

Green 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.

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

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

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

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

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

Hydrogenation of CO2 catalyzed by thermally decomposed cobalt-containing alkaline earth metal carbonates - Gupta, Sharad; Vinod, C. P.; Poupin, Christophe; Jagadeesan, Dinesh (Energy & Fuels, 2025)
CO2 hydrogenation over Co catalysts supported on alkaline earth metal oxides was investigated. The catalysts were prepared by thermally decomposing alkaline metal carbonates CoMCO3, where M = Mg, Ca, Sr, and Ba, in H2. During the thermal activation, contingent upon the thermal stability of the precursor, it transformed into a composite of metal oxides, metals, and undecomposed metal carbonates. The thermal activation temperature, the ratio of CO2 to H2, the composition, and the basicity of the catalyst all played a significant role in influencing the conversion of CO2 and the selectivity to CH4. Among the various Co-containing alkaline earth metal carbonate precursors, CoCaCO3 activated at 400 degrees C yielded the highest steady-state CO2 conversion of 54% with a CH4 selectivity of 89.8% throughout 28 h in the reaction stream containing a 1:4 ratio of CO2 and H2. Detailed characterization showed that the CaCo-400 catalyst contained metallic Co, CaO, and undecomposed CaCO3 phases. The study assumes significance in understanding the role of the composition of catalysts in the formation of CO2 hydrogenation.

Hypersilylsilylene-supported Ni(0) toluene and Ni(II) complexes with catalytic application - Ajithkumar, V. S.; Bisai, Milan Kumar; Ghanwat, Pratiksha B.; Raj, K. Vipin; Singh, Geetika; Vanka, Kumar; Sen, Sakya S. (Organometallics, 2025)
The reaction of Ni(COD)2 with [PhC(NtBu)2SiSi(SiMe3)3] (1) in toluene results in the formation of an 18-electron silylene-Ni(0) toluene complex (2). The analogous reaction with 1,3-DFB instead of toluene affords the C-H activation followed by ring walking leading to the allylic cyclooctene adduct, the (eta 3-C8H13)Ni(II) complex (3). DFT calculations were carried out to elucidate the mechanism as well as to gain insight into why 1,3-DFB undergoes C-H bond activation instead of C-F bond activation. The use of NiCl2DME permits access to 16-electron (tetrylene)2NiCl2 (Si(4) and Ge(5)) species, and 4 was later used as a catalyst for the C-N coupling reaction.

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

An in-depth study of the Fe-Se system at the nanoscale reveals remarkable results on the electrocatalytic oxygen evolution reaction - Singh, Dinesh; Ghalawat, Monika; Poddar, Pankaj (European Journal of Inorganic Chemistry, 2025)
A catalyst for an electrocatalytic oxygen evolution reaction (OER) is a key component of the large-scale storage of renewable energy through the conversion of water into oxygen and hydrogen. Iron-based selenide materials are currently being considered as potential options for electrocatalytic oxygen evolution reaction (OER) because of their, widespread availability, low cost, and outstanding performance. In this study, we employed a thermal decomposition method to synthesize all stable phases of the Fe-Se system, including Fe7Se8, Fe3Se4, FeSe2, and FeSe. Additionally, we slurry-coated these phases onto a three-dimensional (3D) nickel foam substrate. The prepared 3D electrodes of Fe7Se8, Fe3Se4, FeSe2, and FeSe exhibit remarkably low overpotentials of 270, 276, 299, and 289 mV at a current density of 50 mA/cm2 for OER. In addition, the catalytic activity for OER is also tested on glassy carbon electrodes to compare its performance with the Ni-foam 3D substrate. The Fe7Se8 phase in the Fe-Se system exhibits the highest catalytic activity towards OER on both substrates due to variations in the Fe2+/Fe3+ ratio and the presence of Fe vacancies (cation vacancies) within the crystal lattice. Moreover, a faradaic efficiency of 98 % was exhibited by Fe7Se8 for the oxygen evolution reaction (OER).
Keywords: Iron selenide system; OER electrocatalyst; Thermal decomposition method

An integrated paradigm to understand the antibacterial and antifungal potential of bimetallic core-shell platinum silver (Pt@Ag) nanoparticles: A one health approach - Bamb, Aagam Lalit; Varma, Sanjana; Gade, Tejas Subhash; Palaskar, Shahaji; Vamkudoth, Koteswara Rao; Vyawahare, Niraj; Chaudhari, Pallavi M.; Chaudhari, Bhushan P. (Microbial Pathogenesis, 2025)
The concurrent occurrence of various microbial infections escalates the need to develop new treatments that can tackle multiple microbes and improve clinical outcomes. This study reports the synthesis and comprehensive evaluation of core-shell platinum-silver nanoparticles (Pt@AgNPs) designed to elucidate the antimicrobial effects while ensuring biocompatibility. The synthesis protocol was meticulously optimized to investigate the impact of precursor concentrations and reagent conditions. High-end characterization confirmed the formation of a welldefined core-shell structure with spherical morphology, crystalline nature, a face-centred cubic (FCC) lattice, high monodispersity, and stability, with a mean size of 20.344 +/- 4.492 nm. The antimicrobial potential of Pt@AgNPs was validated through a minimum inhibitory concentration (MIC) assay, revealing potent activity with MIC values of 15.6 mu g/mL for Pseudomonas aeruginosa and Staphylococcus aureus and 3.9 mu g/mL for Escherichia coli. Antibiofilm assay demonstrated significant inhibition of biofilm formation by P. aeruginosa at concentrations as low as 3.9 mu g/ml. The nanoparticles also exhibited notable antifungal activity, as indicated by an inhibition of 65.19 % for Aspergillus niger and 61.82 % for Fusarium verticillioides. Furthermore, hemocompatibility was noticed with the hemolysis assay, and the antioxidant properties of nanoparticles, assessed through the 2,2-diphenyl-1-picrylhydrazyl (DPPH) assay, underscored their potential to mitigate oxidative stress. This integrative study positions Pt@AgNPs as a promising platform for combating the occurrence of co-infections. The core-shell nanoparticle serves as a versatile tool in antimicrobial defence, exhibiting antibacterial, antifungal, antibiofilm, and antioxidant activity. Thus, it highlights their commercial translational potential as a next-generation antimicrobial intervention.
Keywords: Antibacterial; antibiofilm; antifungal; Antioxidant; Co-infections; Pt@Ag nanoparticles

Integrating thermal actuation and acidochromism in schiff base molecular crystals - Nag, Sayak; Bhowmik, Aritra; Mishra, Manish Kumar; Ghosh, Soumyajit (Crystal Growth & Design, 2025)
Crystalline materials capable of responding to multiple external stimuli have garnered considerable attention in recent years due to their promising potential for various applications in smart materials, sensing, and actuation. In this paper, we report the synthesis and characterization of two developed linker-based Schiff base molecular crystals, designated as 1 and 2, both of which exhibit two distinct reversible stimuli-responsive behaviors: (i) a thermal expansion-contraction response during repeated heating and cooling cycles and (ii) a reversible acidochromic color change upon sequential exposure to acidic and basic vapors. Importantly, these two reversible responses are governed by entirely distinct underlying processes. The thermal expansion-contraction behavior is driven by a martensitic phase transition, from a low-temperature phase to a high-temperature phase, which involves rapid and reversible lattice displacive rearrangements. In contrast, the acidochromic color change arises from a disruption in the electronic conjugation within the molecular framework, where the system undergoes a transformation from an A-pi-D-pi-A (acceptor-pi-donor-pi-acceptor) configuration to an A-pi-A-pi-A (acceptor-pi-acceptor-pi-acceptor) configuration upon protonation, manifested by a distinct shift in optical absorption properties. The unique combination of these two reversible phenomena-thermal expansion-contraction and acidochromic responses-within a single material system offers significant potential for advanced applications, particularly in the development of acid-sensitive sensors and thermally responsive microactuators.

Interplay between genotoxic stress and STING activation in cellular senescence and inflammatory responses - Dash, Anshurekha; Kulkarni, Akshay S.; Irshad, Faisal; Masal, Dattatraya P.; Manhas, Diksha; Nandi, Utpal; Reddy, D. Srinivasa; Goswami, Anindya (International Immunopharmacology, 2025)
STING pathway is activated by endogenous or exogenous DNA damage and is known to trigger cell-intrinsic innate immunity. In this study, we demonstrated that the Peharmaline analog NDS101781 is a potent genotoxic molecule to trigger cellular senescence via innate immune-responsive STING activation. We found NDS101781 consistently modulated the expression of DDR markers including gamma-H2AX, Rad51, PARP1, ATM and MRE11 in breast cancer cells with concomitant amplification in the hallmarks of senescence along with STING signaling mediators which is intricately involved in NDS101781-mediated senescence activation as evidenced by significant reduction in the senescent population in si-TMEM173-transfected cells. In vitro findings proclaimed that STING activation by NDS101781 is crucial for p21-mediated senescence augmentation, a process regulated by ATM and p53 via a pathway independent of cGAS. Although STING is activated by both canonical and non-canonical manner, our mechanistic findings indicated that ATM played a crucial role in early activation of NDS101781 driven STING signaling via p53 activation and stimulation of pTBK1, NF-kappa B, and p-IRF3, through a non-canonical cascade in cGAS-independent mechanism. The results also indicated that interference of canonical and non-canonical STING activation, responsible for NF-kappa B stimulation leading to IL-6 generation. Intriguingly, the inhibition of ATM diminished senescence hallmarks; however, suppression of ATM as well as p21 neutralization triggered apoptotic cascade and thus regulating the SASP factors. However, transient knockdown of p21 moderately instigated the apoptotic mediators underscoring that NDS101781 mediated senescence induction delayed programmed cell death under intact p21 conditions. Moreover, pharmacokinetics of NDS101781 confirmed its excellent half-life in a preclinical model and in vivo studies confirmed that NDS101781 significantly inhibited tumor growth in a syngeneic aggressive 4T1-p53 breast cancer model.
Keywords: ATM; IL-6; Peharmaline; Senescence; STING

Investigating the visible range photoresponse of an organic single-crystal analogue of the green fluorescent protein - Virole, Vishal; Dabke, Niteen; Verma, Sahil; Kumar, Ajay; Pandya, Rinu; Husale, Sudhir; Vanka, Kumar; Gonnade, Rajesh; Kanawade, Rajesh (Nanoscale, 2025)
The growing demand for lightweight, flexible, semi-transparent and low-cost photodetectors (PDs) in wearable electronics and optical communication systems has prompted studies to investigate organic materials as feasible alternatives to conventional inorganic PDs. However, modern organic PDs often face responsivity, detectivity, and photoresponse speed limitations, particularly in the visible range. Here, we present the photoresponse of an organic single-crystal analogue of the green fluorescent protein (GFP) chromophore photodetector, fabricated on a silicon nitride substrate. A significant increase in photocurrent was detected upon illumination with visible wavelengths (532 nm, 630 nm, and halogen light). A remarkably consistent and repeatable photoresponse was obtained during the ON and OFF illumination cycles. The device showed the dependence of photocurrent on the applied bias voltages. The measured photocurrent, responsivity, detectivity, rise time, decay time, noise equivalent power and external quantum efficiency are studied for different wavelengths. Strikingly, the fabricated device demonstrates excellent performance in the visible region compared to several conventional organic and inorganic PDs. The observed responsivity and detectivity values for the device are 98 mA W-1 and 7.94 x 108 Jones, respectively. Furthermore, the device also exhibits rapid photoresponse dynamics with a rise time of 180 ms and a decay time of 152 ms. The excellent photodetection features indicate that the single crystal GFP could serve as a versatile broadband material for future applications in optoelectronics.

Ionic liquid driven Refined functionalization of graphene oxide: An insight via combined experiments and theory - Kewat, Heera Lal; Dutta, Debangkana; Ajithkumar, T. G.; Chavda, Dhruvil; Sharma, Rahul Kumar; Tiwari, Mrityunjay K.; Sidiqi, Ubaid; Manna, Moutusi; Nigam, Sandeep; Ghosh, Pushpal (Carbon, 2025)
Functionalizing graphene and its derivative, or doping them with heteroatoms can significantly enhance their optoelectronic, photonic and bio-photonic properties; but controlled and tuneable functionalization of GO is still in their infancy. Herein, a series of functionalized graphene oxide (FGO) are synthesized solvothermally by using task specific ionic liquids (ILs) of varying alkyl chain length; 1-alkyl-3-methylimidazolium tetra fluoroborate, [Cnmim]BF4 (n = 2, 4 etc.). ILs are not only used as a solvent but also as source of fluoride ion for functionalization of GO. A drastic decrease in the oxygen containing functional groups of GO upon fluorination is evidenced by FTIR, Raman, XPS, EDX analysis and electrochemical study. Solid state 19F NMR spectroscopy indicates that, fluorination happens exclusively in edge positions, not on basal planes. Band gap of FGOs decreases along with increasing the chain length of ILs. Further, intense blue emission and high photocatalytic efficiency, using crystal violet as model dye are observed for all the FGOs under visible light. The tailored functionalization by varying alkyl chain length of IL has been rationalized by DFT calculations. It has been realized that owing to the ease of dissociation for [Cnmim]BF4 complexes with n >= 10; greater extent of fluorination/functionalization of GO has been observed. Elimination of a non-covalent interaction on increasing the alkyl chain length has been attributed for lower stability of higher chain length IL which in turn renders ease of dissociation. Easy yet controlled functionalization of GO using tuneable ILs can open a new direction in the environment friendly synthesis and applications.
Keywords: fluorination; Functionalization; graphene oxide; ionic liquids; Luminescence; Photocatalysis

Isobaric vapor-liquid-equilibrium data measurement of toluene with ethyl acetate, n-Propyl Acetate, Iso-propyl Acetate, Iso-butyl Acetate, and Iso-amyl Acetate: experiments and modeling - Sutar, Dipak S.; Mali, Nilesh A.; Ghuge, Pravin D. (Journal of Chemical and Engineering Data, 2025)
The isobaric vapor-liquid equilibrium (VLE) data of the systems (ethyl acetate + toluene), (n-propyl acetate + toluene), (iso-propyl acetate + toluene), (toluene + iso-butyl acetate), and (toluene + iso-amyl acetate) were measured under the isobaric condition at 92 kPa using a glass dynamic recirculation apparatus. The experimental VLE data was correlated by NRTL, Wilson, and UNIQUAC activity coefficient models to account for the nonideality. The binary interaction parameters of the models were obtained by regressing the experimental data using the maximum likelihood objective function. The thermodynamic consistency of the experimental data was checked by using the Van Ness test and the infinite dilution test. Extrapolating the activity coefficient at infinite dilution was done by regressing the experimental data with an extended Redlich-Kister equation. The NRTL, Wilson, and UNIQUAC models exhibited a maximum root-mean-square deviation less than unity for temperature and vapor mole fraction. Additionally, it is worth noting that no azeotrope was identified in the VLE data in this study.

Magnesium-catalyzed primary, secondary, and tertiary amide hydroboration - Mahata, Biplab; Devaraj, V.; Dash, Soumya Ranjan; Gonnade, Rajesh G.; Vanka, Kumar; Sen, Sakya S. (Inorganic Chemistry, 2025)
Catalytic hydroboration of amides is highly important because the resultant amines are commonly found in natural products, pharmaceuticals, agrochemicals, dyes, and other applications. In comparison to the conventional reduction of amides using (over)stoichiometric reductants, hydroboration of amides using magnesium compounds represents a green and sustainable approach because magnesium is both Earth abundant and environmentally benign. However, there is only one report on magnesium-catalyzed deoxygenative hydroboration of secondary and tertiary amides. Here, we describe the synthesis and structural authentication of two new magnesium compounds (1 and 2) featuring a flexible PNP ligand and the utilization of 2 as a catalyst for the pinacolborane-mediated reduction of primary, secondary, and tertiary amides to amines. The reaction scope is explored, and a mechanism is proposed based on experimental and theoretical insights.

Magnesium-ligand cooperation in breaking the O-H and C-H bonds of water and diazoalkane - Sharma, Vishal; Dash, Soumya Ranjan; Vanka, Kumar; Gonnade, Rajesh G.; Sen, Sakya S. (Organometallics, 2025)
In our previous paper, we reported that the reaction of a tridentate nacnac ligand with a pendant picolyl group, with KHMDS and MgI2, resulted in the formation of a homoleptic hexacoordinate magnesium compound. Here, we show that the analogous reaction of the ligand with CH3MgBr led to a heteroleptic magnesium bromide species (1). Attempts to generate the magnesium hydride species from 1 led to the dearomatization of the pyridine ring, and the resulting product was a magnesium hydroxide (3) presumably generated due to an adventitious amount of water. The reaction of the ligand with nBu2Mg afforded a unique dearomatized magnesium species (2) in high yield. Theoretical calculations reveal the presence of a nonbonding orbital on the magnesium, susceptible to nucleophilic attack. Indeed, the reaction of 2 with H2O/D2O cleaves the O-H/D bond via magnesium-ligand cooperation and generates a magnesium hydroxide (4 and 5). In addition, 2 reacts with Me3SiCHN2 and cleaves the C-H bond to generate another unusual, well-defined magnesium compound with a bridging isocyanide moiety (6) via migration of the SiMe3 group from the carbon to the nitrogen atom. The latter can be described as a dimer of magnesium isocyanamide. DFT calculations were performed to understand the electronic structures of the synthesized molecules.

Manganese-mediated cascade radical oxidative cyclization/1,6-conjugate addition of unsaturated oximes with p-quinone methides: facile access to β,β-diarylmethine substituted isoxazolines - Vara, Vijay; Thete, Kishor R.; Ghotekar, Ganesh S.; Muthukrishnan, M. (Chemistry-An Asian Journal, 2025)
A simple and efficient strategy for the synthesis of structurally diverse beta,beta-diarylmethine substituted isoxazoline derivatives have been developed. This approach employs a manganese-promoted oxidative cyclization coupled with a 1,6-conjugate addition of unsaturated oximes to p-quinone methides. The key features of this study include the formation of C-O and C-C bonds through intramolecular and intermolecular interactions, facilitated by in situ generated iminoxyl radicals. beta,beta-diarylmethine substituted isoxazolines, bearing a wide range of functional groups, were isolated in high yields.
Keywords: p-Quinone methide; diarylmethine substituted isoxazolines; Iminoxy radical; Manganese catalyzed

Manganese(i)-catalyzed dehydrogenative borylation of terminal alkynes - Ghanwat, Pratiksha B.; Bora, Debashree; Pandya, Rinu; Vanka, Kumar; Saha, Biswajit; Sen, Sakya S. (Dalton Transactions, 2025)
Compounds containing carbon-boron bonds serve as valuable intermediates for constructing more complex molecules by transforming these bonds into other carbon-element bonds. The catalytic dehydrogenative borylation of carbon-hydrogen bonds using HBpin presents an appealing method for synthesizing carbon-boron bonds. While this approach has been extensively explored with noble metals for various types of carbon-hydrogen bonds, its application with manganese-based catalysts remains rare. This study explores a dehydrogenative borylation process employing an Earth-abundant transition metal catalyst, FcbpyMn(CO)3Br (Mn(i)), in combination with HBpin under mild conditions. Arylalkynes featuring electron-withdrawing, electron-donating, and heteroaryl substituents yielded good to excellent results. Thorough DFT calculations were performed to understand the mechanism.

Mechanical flexibility, photosalience, and acidochromism of benzylidene indanone-based molecular crystals - Ahamed, Riyaaz; Bhowmik, Aritra; Mishra, Manish Kumar; Ghosh, Soumyajit (Crystal Growth & Design, 2025)
Molecular crystals that respond to multiple external stimuli are of great interest in smart, responsive materials in various fields. However, the integration of multiple responsive properties within the same crystal still remains a significant challenge for materials scientists due to the complex structural and electronic interactions. Previous studies on benzylidene indanone-based molecular crystals have shown only mechanical plasticity; however, we design crystals to elicit diverse responses to external stimuli, including mechanical stress, light, and acid vapor. Herein, we report two benzylidene indanone derivative-based crystals 1 and 2. Crystal 1 is mechanically brittle and exhibits light-induced photosalient splitting and jumping, attributed to [2 + 2] cycloaddition facilitated by the presence of a vinyl moiety. On the other hand, crystal 2 demonstrates anisotropic mechanical flexibility, exhibiting elasticity on one face and plasticity on alternate faces. Furthermore, crystals 1 and 2 both display reversible acidochromism in response to acid vapor. A detailed structure-property correlation has been established to elucidate the distinct mechanical responses of these molecular crystals. The development of such multistimuli-responsive smart materials holds significant potential for applications in flexible acid sensors, multifunctional responsive smart devices, and actuators, paving the way for advanced smart or intelligent molecular materials with tunable mechanical and optical properties.

Mesoporous Fe2O3-TiO2 integrated with plasmonic Ag nanoparticles for enhanced solar H2 production - Mani, Sunesh S.; Rajendran, Sivaraj; Saju, Simi; Babu, Bindhya M.; Mathew, Thomas; Gopinath, Chinnakonda S. (Chemistry-An Asian Journal, 2025)
Present work describes a sol-gel assisted one-pot synthesis of mesoporous Fe2O3-TiO2 nanocomposites (TiFe) with different Ti : Fe ratios, and fabrication of Ag-integrated with TiFe nanocomposites (TiFeAg) by a chemical reduction method and demonstrated for high solar H2 generation activity in direct sunlight. Enhanced solar H2 production is attributed to the light absorption from entire UV+Visible region of solar spectrum combined with Schottky (Ag-semiconductor) and heterojunctions (TiO2-Fe2O3), as evidenced from HRTEM and various characterization studies. TiFeAg-2 thin film (1 wt % Ag-loaded TiFe-4) displayed the highest activity with a solar H2 yield of 7.64 mmol h-1g-1, which is 48 times higher than that of bare TiO2 and 5 times higher in thin film form compared to its powder counterpart. Schottky and heterojunctions formed at the interface efficiently separate the charge carriers and increase the hydrogen production activity. The highest H2 production activity of TiFeAg-2 is partly attributed to the heterogeneous distribution of Fe3+ and metallic Ag-species with relatively high Ag/Ti surface atomic ratio. A plausible photocatalytic reaction mechanism on TiFeAg nanocomposite may involve the direct electron transfer from both Fe2O3 and TiO2 to Ag nanoparticles which are subsequently utilized for the reduction of H+ to H2.
Keywords: energy conversion; green hydrogen; Photocatalysis; Solar harvesting; water splitting

Metal deficiency tuned charge transfer in intermetallic Ni2-xSn (x =0.37-0.65) enhances selective conversion of furfural to furfuryl alcohol towards the theoretical limit - Cherevotan, Arjun; Singh, Ashutosh Kumar; Yadav, Anish; Maligal-Ganesh, Raghu V.; Raj, Jithu; Pulparambil, Anu; Goud, Devender; Vinod, Chathakudath P.; Peter, Sebastian C. (Journal of Materials Chemistry A, 2025)
Heterogeneous catalysis facilitated by intermetallic nanoparticles has recently been the subject of increased scrutiny, given the enhanced selectivity and stability they bestow on many chemical reactions compared to their monometallic components. This paper explores a series of Ni-Sn (Ni2-xSn, where x = 0.65, 0.5, 0.37) intermetallic compounds supported on a high-surface-area support, SBA-15, as catalysts for the selective hydrogenation of furfural to furfuryl alcohol. Rietveld refinements of the X-ray diffraction data show catalysts with mixed intermetallic phases that assist in the catalysis. At the same time, X-ray photoelectron spectroscopy (XPS) studies and X-ray absorption studies indicate the role played by charge transfer from Sn to Ni for the catalysis. Selectivity to the desired furfuryl alcohol in all the intermetallic samples was high (>97%), but Ni1.35Sn had a relatively lower conversion than the other intermetallic compounds.

Modulation in surface properties by Ni doping in Na2Ti3O7: effect on dry reforming of methane - Ghodke, Seema R.; Devi, R. Nandini (ACS Applied Engineering Materials, 2025)
Dry reforming of CH4 using CO2 is considered as an excellent process for converting two greenhouse gases to platform chemicals. However, the challenge is severe coking as well as sintering and consequent deactivation in the absence of steam as in the more prevalent steam reforming. Here, we present a layered Ti-based oxide with appropriate basicity to facilitate CO2 adsorption and active metal Ni incorporated in the lattice sites to minimize sintering. Ni-doped Na2Ti3O7 was synthesized using the sol–gel method and subsequently characterized and screened in dry reforming of methane. Characterization results indicate the successful formation of the monoclinic phase of Na2Ti3O7. The variant Na2Ni0.2Ti2.8O7, which contains a higher concentration of Ni, exhibited improved reducibility and basicity, as determined through H2-TPR and CO2-TPD analysis. The presence of hydroxide, carbonate, and bicarbonate species was confirmed via X-ray photoelectron spectroscopy (XPS) and diffuse reflectance infrared Fourier transformation (DRIFT) studies, leading to increased conversion of CH4 and CO2 over extended periods with the Na2Ti2.8Ni0.2O7 catalyst. Basic Ti–OH groups replenished under reaction conditions may play a vital role in reducing coke formation in this catalyst. Post-reaction characterization revealed phase transformations in low Ni content catalysts, as evidenced by X-ray diffraction (XRD) and RAMAN analysis. Additionally, the suppression of coke formation and morphological changes were assessed through thermogravimetric analysis (TGA) and field emission scanning electron microscopy (FESEM) analyses in Na2Ti2.8Ni0.2O7 catalyst, respectively. The study highlighted the significant influence of elevated Ni concentrations on phase stability and conversion efficiency in the dry reforming of methane. This also evidences the importance of defects created by appropriate doping, which modulates the surface properties facilitating coke gasification.

Moisture- responsive controlled-release herbicide system using guar gum and nano cellulose for sustainable weed management in rainfed agriculture - Prasanna, Jakku; Marimuthu, S.; Gowtham, G.; Shanmuganathan, K.; Lakshmanan, A.; Chandana, Pebbeti; Karthikeyan, S.; Somasundaram, E. (Results in Engineering, 2025)
<span style="color: rgb(31, 31, 31); font-family: ElsevierGulliver, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif, sans-serif; font-size: 16px;">Weed management poses a significant challenge in rainfed agricultural system, with chemical control being the predominant strategy due to its expeditious nature. However, the efficacy of herbicides in these systems is heavily dependent on optimal soil moisture, making the application of pre-emergence herbicides difficult due to erratic rainfall patterns. Sudden rainfall events post-sowing can result in sticky or muddy fields, complicating the application process and leading to infrequent use of pre-emergence herbicides in rainfed agriculture. To address these challenges, an innovative approach was developed involving the herbicide molecules entrapment in hydrogel matrices synthesized from biopolymers. This study focuses on the design and preparation of atrazine-loaded hydrogel using guar gum and nanocellulose, aimed at managing weeds in maize crops, which are prevalent in rainfed regions. The paper details the protocol for synthesizing the hydrogels and entrapment of atrazine, characterizing the formulations, and conducting pot validation trials to assess phytotoxicity and weed control efficacy compared to commercial atrazine application. The results demonstrated high water retention capacities and entrapment efficiency of the hydrogel for preferable application. FTIR analysis confirmed the presence of atrazine at 802 cm<span style="box-sizing: border-box; margin: 0px; padding: 0px; line-height: 0; position: relative; vertical-align: baseline; top: -0.5em; 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;">-1<span style="color: rgb(31, 31, 31); font-family: ElsevierGulliver, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif, sans-serif; font-size: 16px;"> and other excipients in the encapsulated formulations, while XRD analysis verified the presence of nanocellulose. The release pattern indicated a sustained and controlled release of atrazine from the hydrogels over 40 h in-vitro studies, compared to the complete dissolution of pure atrazine within three hours. Screening trial further validated the crop safety and improved weed control efficiency of the entrapped formulations relative to commercial atrazine. The encapsulated formulations using biopolymer-based hydrogels show promise as a viable alternative for weed management in rainfed agriculture, offering controlled herbicide release and improved application efficiency under variable moisture conditions.