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

Breaking the Pt electron symmetry and OH spillover towards ptir active center for performance modulation in direct ammonia fuel cell - Barik, Sidharth; Kharabe, Geeta Pandurang; Samal, Pragnya Paramita; Urkude, Rajashri R.; Kumar, Sachin; Yoyakki, Athira; Vinod, C. P.; Krishnamurty, Sailaja; Kurungot, Sreekumar (Small, 2024)
The growing interest in low-temperature direct ammonia fuel cells (DAFCs) arises from the utilization of a carbon-neutral ammonia source; however, DAFCs encounter significant electrode overpotentials due to the substantial energy barrier of the *NH2 to *NH dehydrogenation, compounded by the facile deactivation by *N on the Pt surface. In this work, a unique catalyst, Pt4Ir@AlOOH/NGr i.e., Pt4Ir/ANGr, is introduced composed of PtIr alloy nanoparticles controllably decorated on the pseudo-boehmite phase of AlOOH-supported nitrogen-doped reduced graphene (AlOOH/NGr) composite, synthesized via the polyol reduction method. The detailed studies on the structural and electronic properties of the catalyst by XAS and VB-XPS reveal the possible electronic modulations. The optimized Pt4Ir/ANGr composition exhibits a significantly improved onset potential and mass activity for AOR. The DFT study confirms the OHad species spillover by AlOOH and Pt4Ir (100) facilitates the conversion of the *NH2 to *NH with minimal energy barriers. Finally, testing of DAFC at the system level using a membrane electrode assembly (MEA) with Pt4Ir/ANGr as the anode catalyst, demonstrating the suitability of the catalyst for its practical applications. This study thus uncovers the potential of the Pt4Ir catalyst in synergy with ANGr, largely addressing the challenges in hydrogen transportation, storage, and safety within DAFCs. In this article, a versatile catalyst, Pt4Ir/ANGr, is introduced composed of PtIr alloy nanoparticles decorated on AlOOH/NGr composite. The AlOOH provides an -OH-rich surface conducive to the facile adsorption and decoration of the PtIr alloy nanoparticles and OHad species spillover from AlOOH to the Pt4Ir active center during AOR, further validating the higher experimental activity obtained in Pt4Ir/ANGr. image
Keywords: ammonia oxidation reaction (AOR); d-band center; density functional theory (DFT) study; direct ammonia fuel cells; hydroxyl spillover effect; XAS analysis

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.

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

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

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

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

Comparative proteomics of sugarcane smut fungus- Sporisorium scitamineum unravels dynamic proteomic alterations during the dimorphic transition - Kumaravel, Nalayeni; Ebinezer, Leonard Barnabas; Ashwin, N. M. R.; Franchin, Cinzia; Battisti, Ilaria; Carletti, Paolo; Sundar, Amalraj Ramesh; Masi, Antonio; Malathi, Palaniyandi; Viswanathan, Rasappa; Arrigoni, Giorgio (Journal of Proteomics, 2024)
Life cycle of the dimorphic sugarcane smut fungi, Sporisorium scitamineum , involves recognition and mating of compatible saprophytic yeast -like haploid sporidia (MAT -1 and MAT -2) that upon fusion, develop into infective dikaryotic mycelia. Although the dimorphic transition is intrinsically linked with the pathogenicity and virulence of S. scitamineum , it has never been studied using a proteomic approach. In the present study, an iTRAQ-based comparative proteomic analysis of three distinct stages was carried out. The stages were: the dimorphic transition period - haploid sporidial stage (MAT -1 and MAT -2); the transition phase (24 h post co -culturing (hpc)) and the dikaryotic mycelial stage (48 hpc). Functional categorization of differentially abundant proteins showed that the most altered biological processes were energy production, primary metabolism, especially, carbohydrate, amino acid, fatty acid, followed by translation, post -translation and protein turnover. Several differentially abundant proteins (DAPs), especially in the dikaryotic mycelial stage were predicted as effectors. Taken together, key molecular mechanisms underpinning the dimorphic transition in S. scitamineum at the proteome level were highlighted. The catalogue of stage -specific and dimorphic transition -associated -proteins and potential effectors identified herein represents a list of potential candidates for defective mutant screening to elucidate their functional role in the dimorphic transition and pathogenicity in S. scitamineum . Biological significance: Being the first comparative proteomics analysis of S. scitamineum , this study comprehensively examined three pivotal life cycle stages of the pathogen: the non-pathogenic haploid phase, the transition phase, and the pathogenic dikaryotic mycelial stage. While previous studies have reported the sugarcane and S. scitamineum interactions, this study endeavored to specifically identify the proteins responsible for pathogenicity. By analyzing the proteomic alterations between the haploid and dikaryotic mycelial phases, the study revealed significant changes in metabolic pathway -associated proteins linked to energy production, notably oxidative phosphorylation, and the citrate cycle. Furthermore, this study successfully identified key metabolic pathways that undergo reprogramming during the transition from the non-pathogenic to the pathogenic stage. The study also deciphered the underlying mechanisms driving the morphological and physiological alterations crucial for the S. scitamineum virulence. By studying its life cycle stages, identifying the key metabolic pathways and stage -specific proteins, it provides unprecedented insights into the pathogenicity and potential avenues for intervention. As proteomics continues to advance, such studies pave the way for a deeper understanding of plantpathogen interactions and the development of innovative strategies to mitigate the impact of devastating pathogens like S. scitamineum.
Keywords: dimorphism; fungi; iTRAQ; Smut; Sugarcane; Virulence

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

Continuous flow synthesis of hierarchical low silica X zeolite - Adarsh, V. K.; Shrotri, Aadesh R.; Birje, Amit R.; Nandanwar, Sachin U. (Materials Today Communications, 2024)
Zeolites, renowned for their versatile applications in catalysis, adsorption, and ion exchange, have long been synthesized using conventional batch processes. However, the inherent limitations of these methods, such as resource-intensive conditions and inconsistent product quality, underscore the need for a sustainable and efficient approach. In this study, a continuous flow synthesis process was established for the synthesis of industrially important low silica X (LSX) zeolite using a tubular reactor. The synthesis gel was subjected to aging for 5 days at room temperature to facilitate nucleation and crystal growth combined with the fast-heating rate in a tubular reactor at 363 K & 1.1 atm., which in turn produces LSX after 40 min. The synthesized product was confirmed by the XRD, FE-SEM, EDS, XRF, TEM, and N2 adsorption-desorption; the data was compared with the LSX sample synthesized by batch process. The result implies that LSX prepared by continuous flow has a pure phase of LSX with the hierarchical structure, which provides better adsorption capacity of CO2 at 298 K up to 20 bar. Due to continuous flow synthesis, the crystallization time was reduced and faster kinetics which may be helpful for scale-up the process for LSX synthesis.
Keywords: Adsorption; Carbon dioxide; continuous flow; Low silica X; Tubular reactor; zeolites

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

De novo structure prediction of meteorin and meteorin-like protein for identification of domains, functional receptor binding regions, and their high-risk missense variants - Shankar, S. Shiva; Banarjee, Reema; Jathar, Swaraj M.; Rajesh, S.; Ramasamy, Sureshkumar; Kulkarni, Mahesh J. (Journal of Biomolecular Structure & Dynamics, 2024)
Meteorin (Metrn) and Meteorin-like (Metrnl) are homologous secreted proteins involved in neural development and metabolic regulation. In this study, we have performed de novo structure prediction and analysis of both Metrn and Metrnl using Alphafold2 (AF2) and RoseTTAfold (RF). Based on the domain and structural homology analysis of the predicted structures, we have identified that these proteins are composed of two functional domains, a CUB domain and an NTR domain, connected by a hinge/loop region. We have identified the receptor binding regions of Metrn and Metrnl using the machine-learning tools ScanNet and Masif. These were further validated by docking Metrnl with its reported KIT receptor, thus establishing the role of each domain in the receptor interaction. Also, we have studied the effect of non-synonymous SNPs on the structure and function of these proteins using an array of bioinformatics tools and selected 16 missense variants in Metrn and 10 in Metrnl that can affect the protein stability. This is the first study to comprehensively characterize the functional domains of Metrn and Metrnl at their structural level and identify the functional domains, and protein binding regions. This study also highlights the interaction mechanism of the KIT receptor and Metrnl. The predicted deleterious SNPs will allow further understanding of the role of these variants in modulating the plasma levels of these proteins in disease conditions such as diabetes.
Keywords: domains; Meteorin; meteorin-like; missense variants; protein-protein interactions; structure prediction

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

Depolymerization of waste polyethylene to linear alkenes via sequential dehydrogenation and metathesis - Khopade, Kishor V.; Rajput, Nikhita S.; Rangappa, Raghavendrakumar; Barsu, Nagaraju; Chikkali, Samir H. (Green Chemistry, 2024)
Polyethylene (PE) is the most abundantly sourced plastic and significant efforts are needed for its end-of-life management. The deconstruction of PE is an uphill task and requires the breaking of highly stable C-C bonds. Here we demonstrate that PE can be deconstructed to value-added dodecene, along with other long-chain alkenes. The PCP-iridium complex catalyzes the dehydrogenation of commercial and post-consumer polyethylene waste to produce dehydrogenated polyethylene (DHP) with 0.5-1.0% unsaturation. The DHP was subjected to an ethylene cross-metathesis reaction in the presence of suitable catalysts. Through meticulous optimization of reaction parameters, 63% selectivity toward dodecene, with 26% overall yield, was achieved. The practical significance of our method has been demonstrated by subjecting post-consumer plastic waste to dehydrogenation followed by ethylene metathesis to produce dodecene as a major product, together with long-chain alkenes. The PE deconstruction has been confirmed by recording molar mass before and after depolymerization using high-temperature gel permeation chromatography. The existence of dodecene has been unambiguously ascertained using GC, GC-MS, NMR, and IR spectroscopy. Thus, these results demonstrate the conversion of waste PE to value-added dodecene and long-chain alkenes under mild reaction conditions.

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, synthesis, anti-inflammatory evaluation and in silico molecular docking of novel furan-based derivatives as potential TNF-α production inhibitors - Bhoge, Satish; Singh, Prabal Pratap; Das, Deepak; Ali, Yakub; Dhulap, Abhijeet (Letters in Drug Design & Discovery, 2024)
Introduction Inflammation is the first response and an alarming signal for the onset of chronic disease. Most of the anti-inflammatory drugs available in the market are reported to have undesirable gastrointestinal toxicities. Therefore, it is of urgent significance to develop anti-inflammatory drugs with low toxicity and good efficacy.Methods We created a targeted scaffold based on a literature review by combining the different structural characteristics of furan and benzyl amides into a single pharmacophore. A series of eighteen furan-based derivatives (1-18) were designed, synthesized for in vitro and in vivo anti-inflammatory activity. The characterization of synthesized compounds was elucidated by techniques like 1H-NMR, 13C-NMR, FT-IR and MS.Results The synthetic compounds were examined through molecular docking studies on TNF-alpha for probable binding mode and interactions with hydrophilic and hydrophobic pocket of TNF-alpha in comparison to standard drug (Indomethacin).Conclusion When compared to the standard treatment, compounds 18, 15 and 9 displayed a remarkable inhibitory effect on the production of TNF-alpha and in vivo inflammatory activity with no damage to stomach and reduction of LPO. The compounds 18, 15 and 9 might be a good consideration for potential anti-inflammatory agents.
Keywords: analgesic; Anti-inflammatory; Furan-based derivatives; Lipid peroxidation; TNF-alpha; ulcerogenic

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

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

Development of an in silico platform (TRIPinRNA) for the identification of novel RNA intramolecular triple helices and their validation using biophysical techniques - Rakheja, Isha; Bharti, Vishal; Sahana, S.; Das, Prosad Kumar; Ranjan, Gyan; Kumar, Ajit; Jain, Niyati; Maiti, Souvik (Biochemistry, 2024)
There are surprisingly few RNA intramolecular triple helices known in the human transcriptome. The structure has been most well-studied as a stability-element at the 3 ` end of lncRNAs such as MALAT1 and NEAT1, but the intrigue remains whether it is indeed as rare as it is understood to be or just waiting for a closer look from a new vantage point. TRIPinRNA, our Python-based in silico platform, allows for a comprehensive sequence-pattern search for potential triplex formation in the human transcriptome-noncoding as well as coding. Using this tool, we report the putative occurrence of homopyrimidine type (canonical) triple helices as well as heteropurine-pyrimidine strand type (noncanonical) triple helices in the human transcriptome and validate the formation of both types of triplexes using biophysical approaches. We find that the occurrence of triplex structures has a strong correlation with local GC content, which might be influencing their formation. By employing a search that encompasses both canonical and noncanonical triplex structures across the human transcriptome, this study enriches the understanding of RNA biology. Lastly, TRIPinRNA can be utilized in finding triplex structures for any organism with an annotated transcriptome.

Diastereoselective synthesis of functionalized spiroindolines via intramolecular ipso-iodocyclization/nucleophile addition cascade reactions of indole-tethered ynones - Bag, Debojyoti; Sawant, Sanghapal D. (Organic and biomolecular chemistry, 2024)
Herein, we describe a highly diastereoselective approach for synthesizing polyfunctionalized spiroindolines from indolyl-ynones involving an ipso-iodocyclization/nucleophile addition cascade. The developed strategy allows the formation of a spirocyclic core and the installation of two functional groups in a single operation. Also this strategy is accompanied by the generation of two C-C and one C-I bonds and two contiguous stereocenters.

Direct oxidation of alcohols to carboxylic acids using simple and economical Pd@Glu-HTC catalyst: practical and scalable approach towards biomass based value added chemicals - Kirdant, Swapnali P.; Bankar, Shubham R.; Jadhav, Vrushali H. (Biomass & Bioenergy, 2024)
Sustainable catalytic transformation of bio-based alcohols to high value-added fine chemicals is an important topic of research. This work described preparation of simple and economical Pd@Glu-HTC catalyst from biomass derived low cost D-glucose. Hydrothermal carbonization of glucose was carried out in first step to synthesize GluHTC support in a simpler, greener, economical and efficient manner followed by incorporation of palladium metal on surface of the catalyst in second step. The catalyst was characterized using techniques such as Fourier Transform Infrared Spectroscopy (FT-IR), Solid-state Cross-Polarization Magic Angle Spinning Carbon-13 (13C CPMAS), Energy-dispersive X-ray spectroscopy (EDAX), Powder X-ray diffraction (P-XRD), X-ray photoelectron spectroscopy (XPS), Thermogravimetric/Differential Thermal Analyzer (TG-DTA), Field emission scanning electron microscopy (FE-SEM) and High-resolution transmission electron microscopy (HR-TEM). The catalyst was evaluated for direct oxidation of alcohols to yield carboxylic acids and exhibited very good catalytic activity for wider substrate scope. Oxidation of alcohols was carried out using milder base, molecular oxygen and water as a solvent to achieve 92-99 % excellent yields. The practical utility of current strategy was also studied for gram scale synthesis of bio-based value added industrially important chemicals such as furoic acid (flavouring agent and preservative in industry), 2, 5-furan-dicarboxylic acid (monomer to 100 % fossil-free, recyclable polymer polyethylene furanoate (PEF), tetrahydro-2-furoic acid (production of many drugs) and vanillin (important product of flavor and fragrance industry). Pd@Glu-HTC catalyst was found to be reusable for four recycles and the catalytic performance was retained without any loss in its activity after four cycles.
Keywords: Bio-based chemicals; Carbonaceous catalyst; Carboxylic acid; Oxidation

Dishevelled2 activates WGEF via its interaction with a unique internal peptide motif of the GEF - Omble, Aishwarya; Mahajan, Shrutika; Bhoite, Ashwini; Kulkarni, Kiran (COMMUNICATIONS BIOLOGY, 2024)
The Wnt-planar cell polarity (Wnt-PCP) pathway is crucial in establishing cell polarity during development and tissue homoeostasis. This pathway is found to be dysregulated in many pathological conditions, including cancer and autoimmune disorders. The central event in Wnt-PCP pathway is the activation of Weak-similarity guanine nucleotide exchange factor (WGEF) by the adapter protein Dishevelled (Dvl). The PDZ domain of Dishevelled2 (Dvl2PDZ) binds and activates WGEF by releasing it from its autoinhibitory state. However, the actual Dvl2PDZ binding site of WGEF and the consequent activation mechanism of the GEF have remained elusive. Using biochemical and molecular dynamics studies, we show that a unique ``internal-PDZ binding motif'' (IPM) of WGEF mediates the WGEF-Dvl2PDZ interaction to activate the GEF. The residues at P 2 , P 0 , P -2 and P -3 positions of IPM play an important role in stabilizing the WGEFpep-Dvl2PDZ interaction. Furthermore, MD simulations of modelled Dvl2PDZ-WGEFIPM peptide complexes suggest that WGEF-Dvl2PDZ interaction may differ from the reported Dvl2PDZ-IPM interactions. Additionally, the apo structure of human Dvl2PDZ shows conformational dynamics different from its IPM peptide bound state, suggesting an induced fit mechanism for the Dvl2PDZ-peptide interaction. The current study provides a model for Dvl2 induced activation of WGEF. This study identifies a unique ``internal-PDZ binding motif'' (IPM) of WGEF that mediates its interaction with Dvl2PDZ, leading to the release of GEF from its autoinhibitory state. It further unravels the underlying mutual Dvl2-IPM recognition aspects.

Divergent synthesis of unsymmetrical Bis-heteroaryl ketones via base-promoted cascade reactions of 1,2-alkynedione-derived N-propargylic β-enaminones - Bag, Debojyoti; Saini, Sheetal; Rathod, Mahesh S.; Sawant, Sanghapal D. (JOURNAL OF ORGANIC CHEMISTRY, 2024)
Keywords: ASYMMETRIC-SYNTHESIS; heterocycles; intramolecular cyclization; pyrroles

Durable and stable bifunctional Co3O4-based nanocatalyst for oxygen reduction/evolution reactions - Chutia, Bhugendra; Chetry, Rashmi; Rao, Komateedi N.; Singh, Nittan; Sudarsanam, Putla; Bharali, Pankaj (ACS Applied Nano Materials, 2024)
The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are recognized as the core reaction processes in regenerative energy storage and conversion systems. The design of cost-effective and high-performance bifunctional ORR/OER electrocatalysts (ECs) is very important for their substantial commercialization. Herein, sponge-like Co3O4 nanoparticles anchored on carbon (Sp-Co3O4/C) are successfully fabricated by a facile two-step solvothermal strategy for ORR/OER in an alkaline electrolyte. The Sp-Co3O4/C EC exhibits promising bifunctional ORR/OER activity with ORR onset potential (E onset = 0.88 V vs RHE), half-wave potential (E (1/2) = 0.75 V), limiting current density (j = -6.60 mA cm(-2)), OER onset potential (E-onset = 1.26 V), and OER overpotential for 10% energy conversion (eta(10) = 0.38 V) in 0.1 M KOH. It demonstrates a significantly lower reversibility index (Delta E = E- j10 - E 1/2 = 0.86 V), comparable to standard Pt/C and RuO2 ECs. The superior ORR/OER performances of Sp-Co3O4/C EC can be ascribed to the synergistic contribution of a high electrochemically active surface area (48.33 m(2) g(-1)), BET surface area (131 m(2) g(-1)), the rich interfacial structure of the crystal facets (111), (220), and (311), and the abundant oxygen vacancies in the sponge-like morphology. Besides the methanol tolerance, accelerated durability and chronoamperometric test established excellent durability and stability in the electrocatalytic operation. This work offers insight into the development of high-performance ORR/OER ECs. [GRAPHICS]
Keywords: bifunctional; fuel cell; interface; oxygen evolution; oxygen reduction; Oxygen vacancy; Sp-Co3O4/C; sponge-like morphology

Durable polymer composites preparation with oxy-delignified banana fiber for automotive parts: A study on mechanical and thermal properties - Mulla, Abdul Mannan; Munagala, Chandan K.; Kesari, Aman K.; Raju, L. Yugender; Nagar, Harsha; Behara, Dilip K.; Aniya, Vineet (INDUSTRIAL CROPS AND PRODUCTS, 2024)
Keywords: Automotive parts; Banana fiber; Oxygen delignification; polypropylene; Twin-screw extruder

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

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

Effect of CTMABr/SiO2 molar ratio in synthesis of micro-mesoporous ZSM-5 composite and its application in 5-EMF (biofuel additive) formation - Manal, Prajakta N.; Niphadkar, Prashant S.; Nandanwar, Sachin U.; Bokade, Vijay V. (Environmental Progress and Sustainable Energy, 2024)
Synthesis of micro-mesoporous zeolite composite with optimum micro and mesoporosity is an emerging research area due to its wide applications, especially in bulk chemical or biomass transformations. It offers advantages in preserving zeolite crystallinity, creating mesoporosity and converting bulky molecules into valuable products. This work presents the process of preparing bimodal micro-mesoporous ZSM-5 using dual templates (CTMABr and TPABr). XRD, N2 adsorption-desorption, SEM, TEM, Si-29, and Al-27 NMR were used to analyze the two-dimensional micro-mesoporous ZSM-5. One-step synthesis of bimodal micro-mesoporous ZSM-5 features dual micro/mesoporosity by a marginal decrease in the crystallinity (71%). Micro-mesoporous ZSM-5 composite was found to be dependent on the optimum CTMABr/SiO2 molar ratio of 0.04 to 0.06. The micro-mesoporous ZSM-5 zeolite composite was evaluated for cascade synthesis of 5-EMF (methoxymethyl furfural- biofuel additive) from fructose and exhibited a five fold increase in 5-EMF yield to 24.2% as compared with parent ZSM-5 (4.6%).
Keywords: fructose; methoxymethyl furfural-biofuel additive; micro-meso composite; ZSM-5

Effect of furfural, acetic acid and 5-hydroxymethylfurfural on yeast growth and xylitol fermentation using Pichia stipitis NCIM 3497 - Bhavana, B. K.; Mudliar, Sandeep N.; Bokade, V. V.; Debnath, S. (Biomass Conversion and Biorefinery, 2024)
The valorization of C5 sugars (xylose) from hemicellulose of agro-industrial residues to xylitol, as one of the multi-products biorefinery approach, mandates the pretreatment of biomass which releases fermentable sugars along with the generation of biological inhibitors affecting xylitol fermentation. This study was therefore evaluated to understand the inhibitory kinetics of furfural, 5-hydroxymethylfurfural and acetic acid on xylitol fermentation. Xylitol fermentation was established using Pichia stipitis NCIM 3497 with xylose as a pure substrate optimized for xylitol yield and productivity of 0.48 g/g of xylose and 0.13 g/L/h, respectively. The functional relationship of yeast specific growth rate and limiting substrate (xylose) was expressed by Monod-type kinetics. The inhibition kinetics results indicated that the effect of inhibitors on xylitol fermentation was furfural > acetic acid > HMF. Furfural (500 mg/L) and acetic acid (1000 mg/L) reduced xylitol yield by 59% and 44%, respectively, with least reduction of 9.89% exhibited by HMF. The synergistic effect of 500 mg/L furfural, 500 mg/L HMF and 1000 mg/L acetic acid showed the highest reduction in xylitol yield of 67.6% as compared to the control. Kinetic studies predicted that the maximum concentration of furfural, HMF and acetic acid which inhibited P. stipitis growth was 884 mg/L, 3258 mg/L and 2922 mg/L, respectively, whereas xylitol production was completely inhibited at 1069 mg/L furfural, 3498 mg/L HMF and 3714 mg/L acetic acid. Furfural and acetic acid were found to be a competitive inhibitor, while uncompetitive inhibition was observed with HMF indicating negligible effect on xylitol fermentation.
Keywords: Acetic acid; furfural; HMF; Inhibition kinetics; Pichia stipitis; Xylitol fermentation

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

An effective, facile, and rapid synthesis of nanosized Mn3O4 using a microwave route - Yadav, Akash; Jha, Ratnesh; Bhatkar, Akash; Kamble, Aditi; Vaishnav, Vishal; Bogalera, Shivamurthy P.; Manikandan, Marimuthu; Nayaka, Girish Praveen; Umbarkar, Shubhangi; Raja, Thirumalaiswamy; Bhatte, Kushal D. (Journal of Nanoparticle Research, 2024)
Microwave-assisted one-pot, one-step, calcination-free synthesis of nanosized Mn3O4 is reported using only benzylamine and manganese acetate. Benzylamine in this protocol plays a vital role for efficient microwave synthesis. This microwave method enables the synthesis of nanosized Mn3O4 in just few hours only in a single step eliminating the need of calcinations of any intermediate. The synthesized nanosized Mn3O4 was analyzed by XRD, HRTEM, EDAX, and Raman spectroscopy. The catalytic and electrochemical properties of as-synthesized Mn3O4 were investigated. In galvanostatic charge-discharge experiments, after 800 cycles, more than 89% capacitance was retained for electrodes made by as synthesized Mn3O4 nanomaterials indicating its very good stability. In the catalytic conversion of cinnamyl alcohol to cinnamaldehyde via oxidation, using as prepared nanosized Mn3O4 as a catalyst, it displays effective catalytic properties. A probable mechanical study of its formation was also envisaged. This synthesis protocol is additive-free, occurs in a short time, is facile, is energy efficient, and eliminates the use of many chemicals. These silent features make these reported protocols economically viable and environmentally benign which adhere to the principles of Green Chemistry.
Keywords: Calcination free; Electrochemical and catalytic properties; Nanosized Mn3O4; Single-step synthesis

Effects of gamma irradiation on non-polar GaN films deposited on sapphire using pulsed laser deposition - Rajgoli, Tahir; Sant, Tushar; Jejurikar, Suhas M.; Hinge, Sandip; Banpurkar, Arun; Dahiwale, S. S.; Late, Datta (Applied Surface Science, 2024)
The GaN films/layers exposed to gamma-radiations is known to harvest defects and vacancies in the crystals producing donor, acceptor and recombination centers within the bandgap. Therefore it is important to investigate and study the gamma- ray irradiation effects on various physical and chemical properties of a material before any optoelectronic and/or electronic devices are being fabricated. To avoid Stark effect which is observed in most of the optoelectronic devices fabricated using GaN films grew along polar face, use of non-polar GaN films is suggested by researchers. To address such issues the article reports the investigations of physical and chemical properties of non-polar GaN films grown on polar substrate using pulsed laser deposition, which were exposed to the 60Co gamma rays varying dose values. Resistive nature against the impairment of the films caused by gamma-rays observed herewith is highly encouraging, suggesting the use of non-polar GaN films as radiations harden material suitable for fabricating new generation gamma-ray detectors. To our knowledge very limited information is available that report such investigations.
Keywords: Gallium nitride; Gamma rays; PL emission; pulsed laser deposition

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

Efficient synthesis of a monomer for bioplastic-FDCA using glucose-HTC catalyst and pinnick oxidation from HMF & fructose - Kirdant, Swapnali P. P.; Bankar, Shubham R. R.; Jadhav, Vrushali H. H. (Catalysis Letters, 2024)
An efficient solvent mediated & use of metal-free catalyst strategy was developed for synthesis of FDCA over two steps. A simple & economical glucose-hydrothermally carbonized (Glu-HTC) catalyst was prepared and evaluated for synthesis of 2,5-Diformyl furan (DFF) from fructose & 5-hydroxymethylfurfural (HMF) in the 1(st) step. DFF was then converted to FDCA using Pinnick oxidation in the 2(nd) step. DFF was obtained in 82% & 86% yields from fructose & HMF respectively whereas FDCA was obtained in 94-95% yield from DFF. FDCA was thus formed in an overall yield of 78% and 81% from fructose & HMF respectively. This strategy eliminated use of expensive noble metals for FDCA synthesis and also intermediates such as HMFCA & FFCA were not observed after the reaction as DFF was completely oxidized to FDCA.
Keywords: 2; 5-Diformyl furan (DFF); 5-Furandicarboxylic acid; Biomass; D-fructose

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

Enhanced degradation of ciprofloxacin hydrochloride using hybrid advanced oxidation process of hydrodynamic cavitation and ozonation - Bodawar, Narendra; Shetty, Rohit; Kamble, Sanjay; Kulkarni, Prashant (Chemical Engineering & Technology, 2024)
The degradation of ciprofloxacin hydrochloride (CFX), an extensively utilized antibiotic for bacterial infections, has been studied through the application of advanced oxidation processes (AOPs) including hydrodynamic cavitation (HC), ozonation (O3), the Fenton reaction, chemical oxidation, and hybrid AOPs such as HC/O3 and Fenton/O3. Among these, the hybrid combination of HC/O3 demonstrated the highest CFX degradation of 99.82 % within 180 min having an initial concentration of 1000 ppm. The optimization of the HC/O3 process was conducted by varying parameters including initial concentration, pH, ozone (O3) gas flowrate, and temperature. Throughout the degradation process, CFX underwent intermediate formation, which gradually degraded over time. The hydrodynamic cavitation (HC) in combination with ozone, referred to as the HC/ozonation process, was used for the degradation of ciprofloxacin hydrochloride present in wastewater. This process underwent optimization with respect to various reaction parameters, including the initial concentration, ozone flow rate, pH level, temperature, the influence of ions, and the specific water matrix. At these optimized conditions a degradation efficiency of 99.82 % was achieved after 180 min. image
Keywords: active pharmaceutical ingredients; Advance Oxidation Processes; Ciprofloxacin hydrochloride; Hybrid AOPs; Hydrodynamic cavitation

Enhanced disinfection efficiency using Cu vortex diode for providing safe drinking water: devising newer methodologies - Dixit, Divya; Balapure, Kshama; Bhandari, Vinay M. (Environmental Quality Management, 2024)
The present research aims to refine the hydrodynamic cavitation technique with traditional knowledgebase of Ayurveda for more efficient water disinfection and that has huge potential for implementation in real life, especially for substituting the existing chlorination method for drinking water treatment. The study incorporates use of newer copper reactor configuration, employing vortex flow for generating cavitation for the disinfection of water. Elimination of model contaminant, Escherichia coli, with initial concentration of ∼105 CFU/mL of bacteria was used for the disinfection study. Copper vortex diode with a capacity of 1 m3/h was employed as a cavitating device. The cavitation using copper vortex diode gave significantly higher disinfection, over 30%, compared that with conventional vortex diode, with aluminum as material of construction, under similar conditions. Remarkably, the addition of 0.1% betel leaf oil led to an extraordinary 260-fold increase in the rate of disinfection, requiring only a single pass to achieve complete bacteria elimination. Furthermore, a notably high synergistic index of 246.96 was achieved for the process intensification approach using the Cu vortex diode. The cost was substantially reduced by approximately three times to 0.011 $/m3 using the Cu vortex diode compared to the conventional vortex diode. The developed strategy offers significantly enhanced performance, as well as a techno-economical and sustainable solution for drinking water treatment to ensure the provision of safe drinking water. Moreover, the newer methodology can have the advantage of producing no harmful carcinogenic disinfection by-products compared to chemical disinfection processes apart from sustainable alternative to chlorination.

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

Experimental and kinetic modelling studies for the design of fixed bed methanol reactor over CuZA catalyst - Bagwan, Farahanaz M.; Dongapure, Pavan; Kulkarni, Amol A.; Vasireddy, Satyam Naidu (Chemical Engineering Research Design, 2024)
Direct conversion of CO 2 via hydrogenation to value-added chemicals is a vital approach for utilising CO 2 emitted into the atmosphere. In this paper, a critical analysis of reaction kinetic modelling studies is explored in a fixed bed reactor to improve methanol yield for different H 2 to CO 2 ratios by simulating a lab-scale reactor for adiabatic and isothermal conditions. The feed inlet temperature and pressure variations are applied to study the effect of both configurations on methanol production. The results show that the isothermal configuration yields 2.76% more methanol yield compared to the adiabatic reactor. The effect of H 2 to CO 2 molar ratios of 3, 6 and 9 on the performance of the catalyst and the influence of CO and CO 2 hydrogenation is investigated with model simulations. The overall methanol yield is increased from 19.03% to 36.41% with increase in H 2 to CO 2 molar ratio from 3 to 9. Experiments are performed using commercial copper-based catalyst for different temperatures of 210, 230 and 250 degrees C at a pressure of 40 bar for H 2 /CO 2 of 3 and GHSV of 720 h -1 as well as at optimal temperature of 250 degrees C and 50 bar with varying H 2 /CO 2 of 3, 6, 9 for 3 g and 6 g catalyst. The maximum methanol yield of 2.53% and space time yield of 13.59 mg/g cat .h is obtained at H 2 /CO 2 ratio of 9.
Keywords: CO2 conversion; CuZA catalyst; H2 toCO2 molar ratio; Kinetic modelling; Methanol

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 novel cocrystals of milrinone: a cardioprotective drug combined with nutraceuticals and an NSAID - Kenguva, Gowtham; Rekha Rout, Smruti; Shaikh, Tabrez R.; Baidya, Debjani; Shelke, Nikita; Sanphui, Palash; Dandela, Rambabu (CrystEngComm, 2024)
Milrinone is a bipyridine phosphodiesterase (PDE) inhibitor of the second generation. It's a PDE-III antagonist that raises cAMP levels to support heart function and acts as a systemic vasodilator in chronic decongested cardiovascular illness. It is categorised as class II in the Biopharmaceutics Classification System (BCS), indicating that it exhibits poor aqueous solubility and high permeability. Three new cocrystals of the cardioprotective drug milrinone (MR) with two nutraceuticals, e.g. sesamol (SES) and resveratrol (RES), and an anti-inflammatory drug, e.g. niflumic acid (NIF), were successfully synthesised using mechanochemical and solution crystallisation techniques. Thermal analysis (DSC and TGA) and diffraction tools (PXRD and SCXRD) were used to obtain structural insights into all the cocrystals. Their crystal structures indicate that the dimeric interactions in MR are preserved in the crystal structures in addition to carboxylic acid/phenol & ctdot;pyridine heterosynthons. Among the three synthesized molecular solids, MR.SES was more soluble than the native drug. The solubility of the cocrystals was correlated with polar surface contacts, the solubility of the coformer and melting points (inversely). We believe that the new MR.SES cocrystal offers a novel approach to enhance the drug's solubility, which may have a positive impact on its synergistic cardioprotective effects.

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

Exploring thermocatalytic pyrolysis to derive sustainable chemical intermediates from plastic waste; role of temperature, catalyst, and reactor conditions - Venkataraghavan, R.; Bhure, Arvind; Khan, Tufeil Sartaj; Shikare, Dipak; Devi, R. Nandini; Dhepe, Paresh Laxmikant (Journal of the Indian Institute of Science, 2024)
Plastic waste is a growing concern globally on account of the increasing use of plastic worldwide, compounded by single-use applications, poor waste collection and management practices, and its consequent leakage into the environment. In addition, plastics are derived from non-renewable fossil resources, and their growing demand is also partly responsible for greenhouse gas emissions and climate change. The aim of this paper is to explore the potential of plastic waste as a material resource, and thermocatalytic pyrolysis as a recycling process, to produce aliphatic and aromatic hydrocarbons, which are important chemical intermediates for various industries. We show that plastic pyrolysis can achieve a high yield of liquid hydrocarbons (similar to 80%) with a suitable distribution of aliphatic and aromatic compounds, by using different pyrolysis conditions and a catalyst. Specifically, this paper demonstrates the possibility of deriving two key classes of hydrocarbons, i.e., aliphatic (C10-C20 hydrocarbons) and aromatic hydrocarbons (xylene, toluene and benzene derivatives) with a yield of similar to 80% liquid hydrocarbons via catalytic pyrolysis. We also briefly discuss the challenges and opportunities, and the environmental and economic implications.

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

Extrusion 3D printing of intrinsically fluorescent thermoplastic polyimide: revealing an undisclosed potential - Kothavade, Premkumar; Kafi, Abdullah; Dekiwadia, Chaitali; Kumar, Viksit; Sukumaran, Santhosh Babu; Shanmuganathan, Kadhiravan; Bateman, Stuart (POLYMERS, 2024)
Keywords: Additive manufacturing; functional extrusion; high-performance polymers; thermoplastic polyimide

Facile chemical synthesis of BaO:MgO nanorods for designing distinctive solid-state asymmetric supercapacitor device with activated carbon - Bobade, Rushikesh G.; Dabke, Niteen B.; Shaikh, Shoyebmohamad F.; Lokhande, Balkrushna J.; Mane, Rajaram S.; Ambare, Revanappa C. (Journal of Energy Storage, 2024)
The successive ionic layer adsorption and reaction (SILAR) technique was adapted to produce the interconnected complex network of BaO:MgO nanorods on a flexible stainless-steel (SS) substrate surface. The phase and surface morphology of the BaO:MgO electrode were examined from the X-ray diffraction and scanning electron microscopy measurements, respectively, which endowed electrochemical specific capacitance (SC) of 528.77 F/g at a 2 mV/s scan rate with great rate capability and cycling performance of 94.33 % over 5000 cyclic voltammetry cycles. Fabricated BaO:MgO//AC asymmetric solid-state supercapacitor device, using polyvinyl alcohol and potassium hydroxide gel as an electrolyte, demonstrated distinctive energy storage performance, i.e., a specific capacitance (SC) of 259.07 F/g with an energy density of 57.27 Wh/kg and a power density of 2.34 kW/kg at a current density of 4 mA/cm(2). The results demonstrated the facile method for synthesizing a spherical nanorod network of BaO:MgO and made them promising electrode materials for energy storage applications. The use of a solid-state supercapacitor device to illuminate an LED demonstrated the commercial feasibility of both the materials utilized and the design type.
Keywords: activated carbon; ASSD device; BaO:MgO; SILAR; supercapacitor

Facile microwave synthesis of Zinc Ferrite@NCDs for photocatalytic degradation of fluoroquinolone antibiotics - Kaushal, Neha; Sarraf, Sonu; Basu, Aviru Kumar; Mishra, Sunita; Saha, Avishek (Materials Chemistry and Physics, 2024)
Zinc ferrite (ZnFe2O4) composites have attracted growing interest in photocatalytic water purification. Herein, the hybrids of zinc ferrite and nitrogen-doped carbon dots (ZnF@x%NCDs) were synthesized via facile micro-wave synthesis. X-ray diffraction and Raman characterization confirm the formation of the spinel structure, and elemental composition has been analyzed by X-ray photoelectron spectroscopy. The photocatalytic activity of ZnF@x%NCDs was evaluated via the decomposition of ciprofloxacin and norfloxacin under visible light illumination. We noted that 20 % weight loading of NCDs led to the highest (similar to 79.2 %) ciprofloxacin (CIP) degradation. Diffuse reflectance measurements demonstrate the reduction of the band gap in composites ZnF@20%NCDs (1.91 eV) compared with bare ZnF (2.03 eV); moreover, the hybridization of zinc ferrites with NCDs results in enhanced photocurrent density and surface area. The effect of experimental parameters, including the role of photocatalyst dosage, pH value, and initial concentration of pollutants on the degradation of CIP, have also been investigated.
Keywords: Carbon dots; Ciprofloxacin degradation; Norfloxacin degradation; Photocatalysis; Zinc Ferrite

F-doped nickel cobalt oxide-carbon composite electrocatalysts paired with mechanically robust anion-conducting chitosan membranes for flexible and rechargeable zinc-air batteries - Kurian, Maria; Ranganath, Suresha P.; Vijayakumar, Vidyanand; Sivadasan, Sneha; Kurian, Rachna Maria; Badiger, Manohar V.; Kurungot, Sreekumar (ACS Applied Energy Materials, 2024)
High-performing, cost-effective electrocatalysts and anion-conducting polymer electrolyte membranes are essential for realizing commercially affordable zinc-air batteries (ZABs). In this context, the present work deals with the development of a bifunctional electrocatalyst and an anion-exchange quasi-solid-state electrolyte membrane (based on quaternary ammonium group-grafted chitosan) for demonstrating flexible and rechargeable ZABs. The electrocatalyst composed of NiCoO2 nanoparticles supported on a carbon framework showcased substantial advancements in its ability to catalyze both oxygen reduction and evolution reactions (ORR and OER) due to the heteroatom doping by fluorine. For instance, the optimized electrocatalyst (F-NCO-ADC-600) exhibited an onset potential of 0.96 V vs RHE with a half-wave potential of 0.83 V vs RHE for ORR, a comparable performance with the state-of-the-art Pt/C (1.0 and 0.86 V vs RHE, respectively). On a similar note, the same catalyst also displayed an overpotential of 340 mV vs RHE for OER at a current density of 20 mA cm(-2), close to that of a standard RuO2 catalyst (337 mV vs RHE). In the context of polymer electrolytes, the quaternary ammonium-group-grafted chitosan membrane depicted superior ionic conductivity, liquid electrolyte uptake, and mechanical properties, thereby proving to be an efficient anion-conducting polymer electrolyte membrane. The realistic application of the developed electrocatalyst and the polymer electrolyte membrane is demonstrated in the ZAB prototypes. The assembled rechargeable ZAB (RZAB) delivered a power density of 207 mW cm(-2) and maintained high-rate capability and cycling stability, notably in a flexible configuration (f-RZABs). Thus, this work provides a strategy for the rational design of anion-exchange membranes and bifunctional electrocatalysts for f-RZABs.
Keywords: anion-conducting polymer electrolytemembrane; F-doping; flexible and rechargeable zinc-air batteries(f-RZABs); oxygen evolution reaction(OER); oxygen reduction reaction (ORR)

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.

Fictibacillus fluitans sp. nov., isolated from freshwater pond - Yadav, Amit; Maurya, Akanksha; Bhavsar, Yash; Teware, Ruchi; Bhatt, Agrima; DaCosta, Elaine; Thorat, Vipool; Kirdat, Kiran; Dastager, Syed G. (Archives of Microbiology, 2024)
A Gram-positive, aerobic, rod-shaped, spore-forming bacterium, designated NE201(T), was isolated from a freshwater pond in Village Nerur, India. Growth was observed in the range of 15-45 degrees C temperature with optimum at 30 degrees C, pH range of 5-9 (optimum at 7.0), and at concentrations of NaCl ranging between 0 and 14% (optimum 0%, w/v). The 16S rRNA gene sequence showed the highest similarity with Fictibacillus enclensis NIO-1003(T) (JF893461) at 99.01% followed by F. rigui WPCB074(T) (EU939689) at 98.9% and F. solisalsi CGMCC 1.6854(T) (EU046268) at 98.66%. The digital DNA-DNA hybridization (dDDH) and orthoANI values for strain NE201(T) against F. enclensis NIO-1003(T) (GCA_900094955.1) were 33.7% and 87.68%, respectively. The phylogenetic analysis based on the 16S rRNA gene, 92 core genes derived from the genome, and 20 proteins involving over 20,236 amino acid positions revealed the distinct phylogenetic position of strain NE201(T) and the formation of a clearly defined monophyletic clade with F. enclensis. The strain NE201(T) showed a unique carbon utilization and assimilation pattern that differentiated it from F. enclensis NIO-1003(T). The major fatty acids were anteiso -C-15:0 (51.42%) and iso-C-15:0 (18.88%). The major polar lipids were phosphatidylglycerol (PG), phosphatidylethanolamine (PE, and diphosphatidylglycerol (DPG). The antiSMASH analyzed genome of NE201(T) highlighted its diverse biosynthetic potential, unveiling regions associated with terpene, non-ribosomal peptide synthetases (NRPS), lassopeptides, NI-siderophores, lanthipeptides (LAP), and Type 3 Polyketide Synthases (T3PKS). The overall phenotypic, genotypic, and chemotaxonomic characters strongly suggested that the strain NE201(T) represents a novel species of genus Fictibacillus for which the name Fictibacillus fluitans sp. nov. is proposed. The type strain is NE201(T) (= MCC 5285 = JCM 36474).
Keywords: Bacillus; Fictibacillus; Freshwater bacteria

Flow and clogging behavior of a mixture of particles in a silo - Bhure, Sukhada C.; Doshi, Pankaj; Orpe, Ashish V. (Physics of Fluids, 2024)
We investigated the clogging behavior observed during the flow of aspherical particles from a silo in the presence of spherical particles of different sizes and proportions using flow visualization experiments and discrete element method simulations. The size of the avalanche, essentially the tendency of clogging, exhibits non-monotonic dependence on the spherical particle volume fraction. For small enough content of spherical particles, the clogging tendency intensifies, whereas it reduces rapidly for high enough spherical particle fractions, with a minimum in between. The non-monotonic behavior is observed to persist over for different spherical particle sizes. The overall behavior is shown to arise due to competing effects between the localized total particle fraction influencing avalanche strength and mean size of the particles exiting the silo, influencing the probability of arch formation.

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

Heterogeneous acid-base organocatalyst for cascade deacetalisation-knoevenagel condensations - Chhetri, Ashis; Maibam, Ashakiran; Maniam, Subashani; BabaRao, Ravichandar; Wilson, Karen; Lee, Adam F.; Mitra, Joyee (ChemSusChem, 2024)
Multifunctional heterogeneous catalysts are an effective strategy to drive chemical cascades, with attendant time, resource and cost efficiencies by eliminating unit operations arising in normal multistep processes. Despite advances in the design of such catalysts, the fabrication of proximate, chemically antagonistic active sites remains a challenge for inorganic materials science. Hydrogen-bonded organocatalysts offer new opportunities for the molecular level design of multifunctional structures capable of stabilising antagonistic active sites. We report the catalytic application of a charge-assisted, hydrogen-bonded crystalline material, bis(melaminium)adipate (BMA), synthesised from melamine and adipic acid, which possesses proximate acid-base sites. BMA exhibits high activity for the cascade deacetalisation-Knoevenagel condensation of dimethyl acetals to form benzylidenemalononitriles under mild conditions in water; BMA is amenable to large-scale manufacture and recycling with minimal deactivation. Computational modelling of the melaminium cation in protonated BMA explains the observed catalytic reactivity, and identifies the first demethoxylation step as rate-limiting, which is in good agreement with time-dependent 1H NMR and kinetic experiments. A broad substrate scope for the cascade transformation of aromatic dimethyl acetals is demonstrated.
Keywords: Antagonistic acid-base sites; Charge-assisted hydrogen bonding; Chemical cascade; organocatalysis; Sustainable catalysis

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

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

Highly selective C-N and C-S dual functionalization of 1,3-dicarbonyl derivatives using TBHP as an oxidant - Bagad, Pooja K.; Darole, Ratanamala S.; Krishna, G. Rama; Senthilkumar, Beeran (Journal of Organic Chemistry, 2024)
A direct electrosynthesis/photocatalyst-free, atom-economical, and efficient method for the selective synthesis of (E)-3-amino-2-thiocyanato-alpha,beta-unsaturated carbonyl compounds is described through a given protocol. The present approach features the use of inexpensive ammonium thiocyanate to achieve dual functionalization of 1,3-dicarbonyl compounds using TBHP as an oxidant, providing a rapid and practical route to the selective formation of both C-N and C-S bonds via a radical process. This method offers a broad substrate scope with excellent yield and allows for further exploration of the products to construct heterocyclic compounds and other functionalities.

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

Immunogenicity of SARS-CoV-2 vaccines BBV152 (COVAXIN®) and ChAdOx1 nCoV-19 (COVISHIELD™) in seronegative and seropositive individuals in India: a multicentre, nonrandomised observational study - Asokan, Mangaiarkarasi S.; Joan, Roshni Florina; Babji, Sudhir; Dayma, Girish; Nadukkandy, Prajitha; Subrahmanyam, Vinutha; Pandey, Archana; Malagi, Girish; Arya, Pooja; Mahajan, Vibhuti; Bhavikatti, Jayateerth; Pawar, Ketakee; et al. (Lancet Regional Health - Southeast Asia, 2024)
<p style="box-sizing: inherit; line-height: 1.5; margin: 1.2rem 0px; color: rgb(33, 33, 33); font-family: BlinkMacSystemFont, -apple-system, "Segoe UI", Roboto, Oxygen, Ubuntu, Cantarell, "Fira Sans", "Droid Sans", "Helvetica Neue", sans-serif; font-size: 16px;"> Background: There are limited global data on head-to-head comparisons of vaccine platforms assessing both humoral and cellular immune responses, stratified by pre-vaccination serostatus. The COVID-19 vaccination drive for the Indian population in the age group 18-45 years began in April 2021 when seropositivity rates in the general population were rising due to the delta wave of COVID-19 pandemic during April-May 2021. <p style="box-sizing: inherit; line-height: 1.5; margin: 1.2rem 0px; color: rgb(33, 33, 33); font-family: BlinkMacSystemFont, -apple-system, "Segoe UI", Roboto, Oxygen, Ubuntu, Cantarell, "Fira Sans", "Droid Sans", "Helvetica Neue", sans-serif; font-size: 16px;"> Methods: Between June 30, 2021, and Jan 28, 2022, we enrolled 691 participants in the age group 18-45 years across four clinical sites in India. In this non-randomised and laboratory blinded study, participants received either two doses of Covaxin® (4 weeks apart) or two doses of Covishield™ (12 weeks apart) as per the national vaccination policy. The primary outcome was the seroconversion rate and the geometric mean titre (GMT) of antibodies against the SARS-CoV-2 spike and nucleocapsid proteins post two doses. The secondary outcome was the frequency of cellular immune responses pre- and post-vaccination. <p style="box-sizing: inherit; line-height: 1.5; margin: 1.2rem 0px; color: rgb(33, 33, 33); font-family: BlinkMacSystemFont, -apple-system, "Segoe UI", Roboto, Oxygen, Ubuntu, Cantarell, "Fira Sans", "Droid Sans", "Helvetica Neue", sans-serif; font-size: 16px;"> Findings: When compared to pre-vaccination baseline, both vaccines elicited statistically significant seroconversion and binding antibody levels in both seronegative and seropositive individuals. In the per-protocol cohort, Covishield™ elicited higher antibody responses than Covaxin® as measured by seroconversion rate (98.3% vs 74.4%, p < 0.0001 in seronegative individuals; 91.7% vs 66.9%, p < 0.0001 in seropositive individuals) as well as by anti-spike antibody levels against the ancestral strain (GMT 1272.1 vs 75.4 binding antibody units/ml [BAU/ml], p < 0.0001 in seronegative individuals; 2089.07 vs 585.7 BAU/ml, p < 0.0001 in seropositive individuals). As participants at all clinical sites were not recruited at the same time, site-specific immunogenicity was impacted by the timing of vaccination relative to the delta and omicron waves. Surrogate neutralising antibody responses against variants-of-concern including delta and omicron was higher in Covishield™ recipients than in Covaxin® recipients; and in seropositive than in seronegative individuals after both vaccination and asymptomatic infection (omicron variant). T cell responses are reported from only one of the four site cohorts where the vaccination schedule preceded the omicron wave. In seronegative individuals, Covishield™ elicited both CD4+ and CD8+ spike-specific cytokine-producing T cells whereas Covaxin® elicited mainly CD4+ spike-specific T cells. Neither vaccine showed significant post-vaccination expansion of spike-specific T cells in seropositive individuals.

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

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

Interlayer space engineering-induced pseudocapacitive zinc-ion storage in holey graphene oxide-bearing vertically oriented MoS2 nano-wall array cathode for aqueous rechargeable Zn metal batteries - Babu, Athira; Dilwale, Swati; Kurungot, Sreekumar (Small, 2024)
Transition metal dichalcogenides, particularly MoS2, are acknowledged as a promising cathode material for aqueous rechargeable zinc metal batteries (ARZMBs). Nevertheless, its lack of hydrophilicity, poor electrical conductivity, significant restacking, and restricted interlayer spacing translate into inadequate capacity and rate performance. Herein, the unique porous structure and additional functional groups present in holey graphene oxide (hGO) are taken advantage of to dictate the vertical growth pattern of oxygen-doped MoS2 nanowalls (O-MoS2/NW) over the hGO surface. Compared to conventional graphene oxide (GO), the presence of nano-pores in hGO facilitates the homogeneous dispersion of Mo precursors and provides stronger interaction sites, promoting the uniform vertical alignment of O-MoS2/NW. The synergistic interaction between O-MoS2-NW and hGO translates to enhanced electron conductivity, efficient electrolyte penetration, enhanced interlayer spacing, reduced restacking, and enhanced surface area. As a consequence of precise control of various factors that decide the overall battery performance, a high discharge capacity (227 mAh g(-1) at 100 mA g(-1)) cathode material with significantly lower charge transfer resistance (66 Omega) compared to pristine O-MoS2 (153 Omega) is developed. These findings underscore the potential of hGO as a multifunctional platform for nanoengineering high-performance cathode materials for the next generation of efficient and durable ARZMBs.
Keywords: aqueous rechargeable zinc metal battery; holey graphene oxide; hydrophilicity tuning; interlayer space engineering; oxygen-doped MoS2; transition metal dichalcogenide; vertical nanowall

Intertwining of localized (d) and delocalized (π) spins in magnetically frustrated two-dimensional metal-organic frameworks - Ugale, Ajay; Ninawe, Pranay; Jain, Anil; Sangole, Mayur; Mandal, Rimpa; Singh, Kirandeep; Ballav, Nirmalya (Inorganic Chemistry, 2024)
Two-dimensional metal-organic frameworks (2D MOFs) are emerging as a new class of multifunctional materials for diversified applications, although magnetic properties have not been widely explored. The metal ions and organic ligands in some of the 2D MOFs are arranged in the well-known Kagome lattice, leading to geometric spin frustration. Hence, such systems could be the potential candidates to exhibit an exotic quantum spin liquid (QSL) state, as was observed in Cu-3(HHTP)(2) (HHTP = hexahydroxytriphenylene), with no magnetic transition down to 38 mK. Hereto, we have investigated the spin intertwining in a bimetallic 2D MOF system, M-3(HHTP)(2) (M = Cu/Zn)(,) arising from the localized (d-electron) and delocalized (pi-electron) S = 1/2 spins from the Cu(II) ions and the HHTP radicals, respectively. The origin of the spin frustration (down to 5K) was critically examined by varying the metal composition in bimetallic systems, CuxZn3-x(HHTP)(2) (x = 1, 1.5, 2), containing both S = 1/2 and S = 0 spins. Additionally, to gain a deeper understanding, we studied the spin interaction in the pristine Zn-3(HHTP)(2) system containing only S = 0 Zn(II) ions. In view of the quantitative estimate of the localized and delocalized spins, the d-pi spin correlation appears essential in understanding the unusual magnetic and/or other physical properties of such hybrid organic-inorganic 2D crystalline solids

Investigation of cathinone analogs targeting human dopamine transporter using molecular modeling - Shivankar, Bhavana R.; Bhandare, Vishwambhar Vishnu; Joshi, Krati; Patil. Vishal S.; Dhotare, Priyanka Shrikant; Sonawane, Kailas Dasharath; Krishnamurty, Sailaja (Journal of Biomolecular Structure & Dynamics, 2024)
In a step towards understanding the structure–property relationship among Synthetic Cathinones (SCs), a combined methodology based on Density Functional Theory (DFT), Administration, Distribution, Metabolism, Excretion, and Toxicity (ADMET) predictions, docking and molecular dynamics simulations have been applied to correlate physicochemical descriptors of various SCs to their biological activity. The results from DFT and molecular docking studies correlate well with each other explaining the biological activity trends of the studied SCs. Quantum mechanical descriptors viz. polarizability, electron affinity, ionization potential, chemical hardness, electronegativity, molecular electrostatic potential, and ion interaction studies unravel the distinguishingly reactive nature of Group D (pyrrolidine substituted) and Group E (methylenedioxy and pyrrolidine substituted) compounds. According to ADMET analysis, Group D and Group E molecules have a higher probability of permeating through the blood–brain barrier. Molecular docking results indicate that Phe76, Ala77, Asp79, Val152, Tyr156, Phe320, and Phe326 constitute the binding pocket residues of hDAT in which the most active ligands MDPV, MDPBP, and MDPPP are bound. Finally, to validate the derived quantum chemical descriptors and docking results, Molecular Dynamics (MD) simulations are performed with homology-modelled hDAT (human dopamine transporter). The MD simulation results revealed that the majority of SCs remain stable within the hDAT protein’s active sites via non-bonded interactions after 100 ns long simulations. The findings from DFT, ADMET analysis, molecular docking, and molecular dynamics simulation studies complement each other suggesting that pyrrolidine-substituted SCs (Group D and E), specifically, MPBP and PVN are proven potent SCs along with MDPV, validating various experimental observations.

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

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

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)

Mechanistic modeling of size exclusion chromatography-assisted in vitro refolding of the recombinant biosimilar teriparatide (PTH-34) - Ughade, Santosh; Rana, Sunil; Nadeem, Mohd; Kumthekar, Rupali; Mahajani, Sanjay; Bhambure, Rahul (ACS Omega, 2024)
In vitro protein refolding is one of the critical unit operations in manufacturing recombinant peptides expressed using Escherichia coli as host cells. This study is focused on designing size exclusion chromatography-assisted in vitro refolding process for biosimilar recombinant parathyroid hormone. Inclusion bodies (IBs) of recombinant parathyroid hormone were solubilized at higher pH, and in vitro refolding was performed using size exclusion chromatography. In the first part of the investigation, DoE-based empirical optimization was performed to achieve a higher refolding yield for a biosimilar recombinant parathyroid hormone. The effect of solubilized inclusion body (IB) feed volume, concentration of IBs, and residence time on in vitro refolding of recombinant teriparatide was studied using the Box-Behnken design. Size exclusion chromatography (SEC)-assisted in vitro refolding was performed at 8 C-degrees at pH 10.5 by using 20 mM Tris buffer. The maximum refolding yield of 98.12% was achieved at feed volume (12.5% of CV) and 20 mg/mL inclusion body (IB) concentration with a residence time of 50 min and a purity of 66.1% based on densitometric analysis using SDS-PAGE. In the latter part of the investigation, the general rate mechanistic model framework for size exclusion chromatography was developed and validated with the experimental results. The developed model helped in the accurate prediction of the elution volumes and product yield. The developed model also helps to predict the elution performance of a scalable column a priori. Post in vitro refolding, the formation of the native peptide structure was examined using various orthogonal analytical tools to study the protein's primary, secondary, and tertiary structures. The developed hybrid process development approach is a valuable tool toachieve high-yield, scalable refolding conditions for recombinant proteins without disulfide bonds.

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

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

Modular synthesis of unsymmetrical indolyl diketones from ynediones via sequential aza-Michael addition/C-H functionalization - Naveed, Abdul; Bag, Debojyoti; Sawant, Sanghapal D. (Organic & Biomolecular Chemistry, 2024)
Herein, we disclose an efficient approach for the synthesis of unsymmetrical indolyl diketones from easily accessible 1,2-alkynediones involving a sequential aza-Michael addition/C-H Functionalization process. The two-step, one-pot strategy involves the aza-Michael addition of an aniline generating the N-aryl enaminones followed by iodine-mediated C-H functionalization.

Morphology tuning via linker modulation: metal-free covalent organic nanostructures with exceptional chemical stability for electrocatalytic water splitting - Karak, Shayan; Koner, Kalipada; Karmakar, Arun; Mohata, Shibani; Nishiyama, Yusuke; Duong, Nghia Tuan; Thomas, Neethu; Ajithkumar, Thalasseril Govindankuttykaimal; Hossain, Munshi Sahid; Bandyopadhyay, Subhajit; Kundu, Subrata; Banerjee, Rahul (Advanced Materials, 2024)
The development of synthetic routes for the formation of robust porous organic polymers (POPs) with well-defined nanoscale morphology is fundamentally significant for their practical applications. The thermodynamic characteristics that arise from reversible covalent bonding impart intrinsic chemical instability in the polymers, thereby impeding their overall potential. Herein, a unique strategy is reported to overcome the stability issue by designing robust imidazole-linked POPs via tandem reversible/irreversible bond formation. Incorporating inherent rigidity into the secondary building units leads to robust microporous polymeric nanostructures with hollow-spherical morphologies. An in-depth analysis by extensive solid-state NMR (1D and 2D) study on H-1, C-13, and N-14 nuclei elucidates the bonding and reveals the high purity of the newly designed imidazole-based POPs. The nitrogen-rich polymeric nanostructures are further used as metal-free electrocatalysts for water splitting. In particular, the rigid POPs show excellent catalytic activity toward the oxygen evolution reaction (OER) with long-term durability. Among them, the most efficient OER electrocatalyst (TAT-TFBE) requires 314 mV of overpotential to drive 10 mA cm(-2) current density, demonstrating its superiority over state-of-the-art catalysts (RuO2 and IrO2).
Keywords: bi-functional electrocatalysts; chemically robust; hollow-spherical morphologies; imidazole-linked; inherent rigidity; metal-free; water splitting

Multifunctional metabolites of Streptomyces kunmingensis BS19 from bamboo rhizosphere soil - Sangeetha, Murthy; Sasirekha, Sivakumar; Mahendran, Jaganathan; Sivarajan, Anbalmani; Radhakrishnan, Manikkam; Manigundan, Kaari; Dastager, Syed G.; Sengottuvelu, Singaravel; Balagurunathan, Ramasamy (International Microbiology, 2024)
A pigmented bioactive molecule from Streptomyces kunmingensis BS19 was isolated, characterized, and evaluated for anti-infective, antiproliferative, and wound-healing properties. The yellow–red pigment produced from the strain BS19 showed promising activity against methicillin-resistant Staphylococcus aureus (MRSA) and Mycobacterium tuberculosis. Extracellular bioactive pigment from the strain BS19 was produced by agar surface fermentation and purified through bioassay guided preparative HPLC-based purification. Based on the results of UV, FT-IR, GC–MS, 1H NMR, and 13C NMR spectral analyses, the purified pigment was identified as a chromopeptide class of molecule with phenoxazinone chromophore. Its molecular weight was determined as the chemical formula C64H90N12O16 and molecular weight 1283 g/mol. It exhibited promising antimicrobial activity against Staphylococcus aureus (ATCC 1720) and antiproliferative activity against 14 types of human cancer cell lines. It showed good in vivo wound-healing activity in the rat model. The present study explored Streptomyces kunmingensis as a newly added source for the isolation of chromopeptide antibiotics for antimicrobial, wound-healing, and anticancer applications.

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.

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

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

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

Novel GO hoisted SnO2-BiOBr bifunctional catalyst for the remediation of organic dyes under illumination by visible light and electrocatalytic water splitting - Dhillon, Manshu; Naskar, Abhishek; Kaushal, Neha; Bhansali, Shekhar; Saha, Avishek; Basu, Aviru Kumar (NANOSCALE, 2024)
Keywords: Chemistry; Multidisciplinary; Nanoscience & Nanotechnology

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

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

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

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

Oligo(phenyleneethynylene)s: shape-tunable building blocks for supramolecular self-assembly - Fernandez, Zulema; Sanchez, Luis; Santhosh Babu, Sukumaran; Fernandez, Gustavo (Angewandte Chemie-International Edition, 2024)
Oligo(phenyleneethynylene)s (OPEs) have attracted widespread attention due to their remarkable (opto)electronic and photophysical properties, which have enabled numerous applications. The versatile functionalization possibilities of OPEs make them unique candidates to form various shape-persistent geometries, including linear, triangular, rectangular, hexagonal and macrocyclic. However, as a result of this structural variety, it is oftentimes challenging to correlate molecular design with self-assembly properties. In this minireview, we have classified OPEs based on their molecular shapes and correlated them with their self-assembly behavior in solution. Particularly, we provide important insights into the aggregation propensity of the different molecular shapes and how to tune the association strength using various non-covalent interactions. Our classification will enable a better understanding of the structure-property correlation in OPEs, which is key to develop supramolecular functional materials.
Keywords: non-covalent interactions; Oligo(phenyleneethynylene)s; pi-conjugated systems; Self-assembly; Supramolecular Polymerizaton

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.

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

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

Performance of Li exchange hierarchical X zeolite for CO2 adsorption and H2 separation - Shrotri, Aadesh R.; Birje, Amit R.; Niphadkar, Prashant S.; V. Bokade, Vijay; Mali, Nilesh A.; Nandanwar, Sachin U. (Journal of Industrial and Engineering Chemistry, 2024)
Li exchange hierarchical X zeolite (Li-H-X) was prepared by decationization of X zeolite by NH4Cl solution followed by Li exchange and subsequent calcination. NH4-X and Li-X were prepared to compare the results of LiH-X. XRD, FE-SEM, EDS, N2 adsorption-desorption, and micro-/mesoporous volume were performed. The higher mesoporosity was confirmed in Li-H-X due to the framework dealumination during decationization. Static and dynamic sorption capacity of sorbents was evaluated to identify the performance of sorbent. The CO2 and H2 equilibrium adsorption capacity of Li-H-X was found to be 9.6 mmol g-1 and 0.78 mmol g-1, respectively, at 298 K and 20 bar, which was 25 % (CO2) and 30 % (H2) higher than Li-X. Static experimental data were validated using the Langmuir, Freundlich, and Sips models. The CO2 & H2 dynamic sorption capacity of Li-H-X sorbent for binary gas (CO2/H2, 25/75 %) was 4.145 mmol g-1 and 0.258 mmol g-1 at 303 K and 10 bar. The higher sorption capacity of Li-H-X was obtained due to large micro-/mesoporous volume of sorbent, which may allow to access unoccupied sites at higher pressure. This result reveals that micro-/mesoporous structure of zeolite adsorbs significantly higher CO2 from binary gas stream, which can use to separate pure H2 from gas stream.
Keywords: Adsorption; Carbon dioxide; Hydrogen; Microporous-mesoporous; Separation

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.

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

Photocatalytic 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

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

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

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

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

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)

Pressure swing adsorption of Li exchange hierarchical X zeolite for pure hydrogen from binary gas mixture - Shrotri, Aadesh R.; Birje, Amit R.; Nandanwar, Sachin U. (International Journal of Hydrogen Energy, 2024)
This study reports the separation of pure hydrogen (H2) employing pressure swing adsorption (PSA). The Li-X and Li-hierarchical X (Li-H-X) zeolite were prepared by an ion exchange process. The sorbents were evaluated through several experiments including, breakthrough, empty bed contact time (EBCT), single-bed, and two-bed PSA with different steps. The effect of pressure, purity, and recovery relationship was developed. The highpressure PSA study was performed at 4, 6, and 10 bar with varying feed flow rates to assess their efficacy in pure H2 separation using binary gas stream (H2/CO2, 75/25 vol.%). The breakthrough adsorption capacity of Li-H-X exhibited 3.4 mmol g-1 and 0.212 mmol g-1 of CO2 and H2, respectively. Li-H-X shows -8% higher CO2 sorption capacity than the Li-X sorbent at 1 bar and 300 K due to the large meso-microporous structure of the sorbent. The two-bed PSA purity and recovery were found higher than single-bed PSA. Using two-bed PSA, the Li-H-X achieved a 99.5% of purity, 92.9% of recovery, and 10.4 mL min-1 g-1 of productivity, which was -16% higher recovery and productivity than single-bed PSA at a flow rate of 1200 mL min-1 at 6 bar. With increasing the pressure and flow rate, the recovery of Li-H-X was enhanced up to 93.7% with 99.1%-99.9% H2 purity. The long-term PSA was run using Li-H-X sorbent for 7.5 h with 230 cycles with H2 purity between 98.5 and 99.5% at 6 bar. Interestingly, the adsorbent shows the scalability of PSA for efficient H2 separation for a binary mixture of H2/CO2.
Keywords: adsorbent; Binary gas mixture; Hydrogen purification; Li-H-X; Mesoporous zeolite; Pressure swing adsorption

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

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

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

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

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

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

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

Repurposing phytochemicals of Citrullus colocynthis against maltase-glucoamylase using molecular docking, MMGBSA, MD simulation and linear regression to identify potential anti-diabetic compounds - Sahu, Parameswar; Sahoo, Rosaleen; Sahu, Abhishek Kumar; Saluja, Sundeep Singh; Behera, Banshidhar (Journal of biomolecular structure and dynamics, 2024)
Diabetes is a common lifestyle disorder found in populations of different age groups. Maltase-glucoamylase catalyses the release of the glucose molecule in the final enzymatic reaction of starch digestion; therefore, inhibition of maltase-glucoamylase is one of the approaches in the development of therapeutics for diabetes. Citrullus colocynthis is commonly recommended in Ayurveda for the treatment of diabetes. The current study applied a structure-based drug design approach to repurpose the phytochemicals of Citrullus colocynthis to identify potential inhibitors for maltase-glucoamylase. 70 phytochemicals of Citrullus colocynthis were screened against maltase-glucoamylase and top 5 molecules 8-p-hydroxybenzylisovitexin, isoorientin, cucurbitacin B, cucurbitacin E, and cucurbitacin I with significant binding energy of -10 kcal/mol, -9.9 kcal/mol, -9.6 kcal/mol, -9.2 kcal/mol, and -7.7 kcal/mol were identified. Furthermore, MMGBSA, pharmacokinetics properties and toxicity prediction were performed on the five identified molecules and top 3 molecules were selected for molecular dynamics (MD) simulation. It was observed from the structural flexibility and dynamic behaviour of the systems that conformational changes were noticed in the complexes as compared to its native state, which suggests that the 3 molecules, namely 8-p-hydroxybenzylisovitexin, isoorientin, and cucurbitacin I of Citrullus colocynthis may act as inhibitors for maltase-glucoamylase.Communicated by Ramaswamy H. Sarma
Keywords: Citrullus colocynthis; Diabetes; linear regression; molecular dynamics simulation; phytochemicals

Robust spin liquidity in 2D metal-organic framework Cu3 (HHTP)2 with S=1/2 kagome lattice - Ninawe, Pranay; Jain, Anil; Sangole, Mayur; Anas, Mohd; Ugale, Ajay; Malik, Vivek K.; Yusuf, Seikh M.; Singh, Kirandeep; Ballav, Nirmalya (Chemistry- a european journal, 2024)
On one hand electron or hole doping of quantum spin liquid (QSL) may unlock high-temperature superconductivity and on the other hand it can disrupt the spin liquidity, giving rise to a magnetically ordered ground state. Recently, a 2D MOF, Cu-3(HHTP)(2) (HHTP - 2,3,6,7,10,11-hexahydroxytriphenylene), containing Cu(II) S = 1/2 frustrated spins in the Kagome lattice is emerging as a promising QSL candidate. Herein, we present an elegant in situ redox-chemistry strategy of anchoring Cu-3(HHTP)(2) crystallites onto diamagnetic reduced graphene oxide (rGO) sheets, resulting in the formation of electron-doped Cu-3(HHTP)(2)-rGO composite which exhibited a characteristic semiconducting behavior (5 K to 300 K) with high electrical conductivity of 70 S . m(-1) and a carrier density of similar to 1.1 x 10(18) cm(-3) at 300 K. Remarkably, no magnetic transition in the Cu-3(HHTP)(2)-rGO composite was observed down to 1.5 K endorsing the robust spin liquidity of the 2D MOF Cu-3(HHTP)(2). Specific heat capacity measurements led to the estimation of the residual entropy values of 28 % and 34 % of the theoretically expected value for the pristine Cu-3(HHTP)(2) and Cu-3(HHTP)(2)-rGO composite, establishing the presence of strong quantum fluctuations down to 1.5 K (two times smaller than the value of the exchange interaction J).
Keywords: 2D Metal-organic Framework; Electron doping; Reduced graphene oxide; Spin Liquid; Spin-frustration

Role of aromatic alcohol additives on asymmetric organocatalysis reactions: insights from theory - Banerjee, Subhrashis; Vanka, Kumar (Chemistry-an asian jounrnal, 2024)
The presence of an aromatic additive has been seen to enhance, often significantly, the enantioselectivity and yield in asymmetric organocatalysis. Considering their success across a dizzying range of organocatalysts and organic transformations, it would seem unlikely that a common principle exists for their functioning. However, the current investigations with DFT suggest a general principle: the phenolic additive sandwiches itself, through hydrogen bonding and pi & sdot;& sdot;& sdot;pi stacking, between the organocatalyst coordinated electrophile and nucleophile. This is seen for a wide range of experimentally reported systems. That such complex formation leads to enhanced stereoselectivity is then demonstrated for two cases: the cinchona alkaloid complex (BzCPD), catalysing thiocyanation (2-naphthol additive employed), as well as for L-pipecolicacid catalysing the asymmetric nitroaldol reaction with a range of nitro-substituted phenol additives. These findings, indicating that dual catalysis takes place when phenolic additives are employed, are likely to have a significant impact on the field of asymmetric organocatalysis. The current DFT based study, on a wide range of organocatalysis systems, reveals a general principle by which phenolic additives influence asymmetric organocatalysis reactions. It is shown that the phenolic additive forms a sandwich complex, through hydrogen bonding and pi & sdot;& sdot;& sdot;pi stacking interactions, with the organocatalyst coordinated electrophile and nucleophile, and enhances the enantioselectivity of the system as a result. image
Keywords: Additive; Asymmetric Organocatalysis; Cinchona Alkaloid; Density functional theory; Enantioselective Thiocyanation

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

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

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

Scanning tunneling microscopy investigation of synaptic behavior in AgInS2 quantum dots: effect of ion transport in neuromorphic applications - Betal, Atanu; Chetia, Anupam; Bera, Jayanta; Saikia, Dibyajyoti; Sharma, Ashish; Rath, Arup K.; Sahu, Satyajit (ACS Applied Nano Materials, 2024)
Scanning tunneling microscopy (STM) is a powerful technique for investigating the nanoscale properties of functional materials. Additionally, scanning tunneling spectroscopy (STS) facilitates the determination of the local density of states (LDOS) within the material. In this study, we present an exploration of the resistive switching (RS) properties and neuromorphic computing capabilities of individual AgInS2 quantum dots, utilizing STM and STS techniques. By examining the material's bandgap and its temperature dependence, we uncover a nonlinear variation below the Debye temperature and a linear trend at higher temperatures. Moreover, STS measurements demonstrate changes in the conducting states induced by localized pulses, further confirming the unique characteristics of the quantum dots. The experimental devices constructed by using these quantum dots effectively replicate the RS properties observed at the nanoscale. To assess the neuromorphic application of the devices, pulse transient measurements simulating the learning and forgetting processes were conducted. The gradual set and reset processes successfully mimic the information retention and erasure capabilities essential for neuromorphic computing. Notably, the resistive switching mechanism in these devices is attributed to localized ionic transport, which highlights the significant involvement of ionic species in the observed RS behavior. The outcomes of this study contribute to the fundamental understanding of RS properties in single AgInS2 quantum dots and offer valuable insights into their potential applications in neuromorphic computing.
Keywords: corona poling; Ion transport; neuromorphic computing; quantum dots; resistive switching; Scanning tunneling microscopy; STS

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.

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

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.

Slowdown of solvent structural dynamics in aqueous DMF solutions - Pathania, Akhil; Bagchi, Sayan (Chemical Physics Impact, 2024)
<span style="color: rgb(31, 31, 31); font-family: ElsevierGulliver, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif, sans-serif; font-size: 16px;">This study presents a comprehensive investigation into the molecular dynamics of solvation environments through an integrated approach combining Fourier-transform infrared (FTIR) spectroscopy, molecular dynamics (MD) simulations, and two-dimensional infrared (2D IR) spectroscopy. We explore the solvation of an ionic solute (ammonium thiocyanate) in various solvent systems, including N,N-dimethylformamide (DMF), water, and a 0.5 mole fraction of DMF in water, aiming to unravel the intricate interplay between solute-solvent interactions and solvent dynamics across diverse solvation environments. By integrating FTIR spectral analysis with radial distribution functions and coordination numbers obtained from MD simulations, we decipher the solvent composition around the solute molecule. Analysis of 2D IR spectra and hydrogen bond, as well as dipolar autocorrelation function from MD simulations, further elucidates the nuances of solute-solvent interactions, highlighting the impact of solvent dynamics on solvation structures. Our results reveal a significant slowdown of the solvent structural dynamics in the equimolar binary solvent mixture compared to the neat solvents. This slowdown underscores the complex relationship between solute-solvent interactions and solvent dynamics. The integration of FTIR, MD simulations, and 2D IR spectroscopy provides a unified framework for obtaining a holistic understanding of solvation dynamics, offering valuable insights into the underlying molecular mechanisms governing solute-solvent interactions in complex systems. These results pave the way for future studies to delve deeper into the molecular intricacies of solvation phenomena.

Solution-phase ligand engineering for all-quantum-dot near-infrared light-emitting diodes - Biswas, Arindam; Mitra, Anurag; Sharma, Ashish; Shinde, Dipak Dattatray; Dambhare, V. Neha; Sharma, Anjali; Mahajan, Chandan; Rath, Arup K. (ACS Applied Nano Materials, 2024)
Strong emission over a wide near-infrared (NIR) region makes lead sulfide quantum dots (QDs) a preferred material in building NIR light-emitting diodes (NIR-LEDs) for numerous applications. Narrow-bandgap emitter QDs blended in the matrix of high-band gap QDs offer a simple yet powerful architectural platform for building high-performance NIR-LEDs. So far, the all-QD-based blend architecture has been realized using a poorly controlled solid-state ligand exchange approach. Advanced solution-phase ligand exchange, which offers greater control over surface passivation, is yet to be realized in all-QD LED device construction. We observe that the solution-phase ligand exchange from the optimized lead halide and thiol ligand combination, used in high-performing QD solar cell construction, is inefficient in realizing efficient all-QD LEDs, which could have restricted the adoption of the solution-phase ligand exchange thus far. Here, we introduce an innovative dual-ligand strategy to build all-QD-based NIR-LEDs using an advanced solution-phase ligand exchange approach. Through ligand engineering of matrix QDs, we managed to improve photoluminescence quantum yield (40%), reduce trap density (10(14) cm(-3)), and prolong carrier lifetime (832 ns). The LED devices benefit from improved electronic properties and balanced carrier injection to yield 6% EQE and 7.7% PCE, which are six times higher than those of state-of-the-art ligands.
Keywords: electroluminescence; lead sulfide; ligand passivation; light-emitting diodes; near-infrared; quantumdots

Solvation dynamics and microheterogeneity in deep eutectic solvents - Chatterjee, Srijan; Chowdhury, Tubai; Bagchi, Sayan (Journal of Physical Chemistry B, 2024)
Deep eutectic solvents have attracted considerable attention due to their unique properties and their potential to replace conventional solvents in diverse applications, such as catalysis, energy storage, and green chemistry. However, despite their broad use, the microscopic mechanisms governing solvation dynamics and the role of hydrogen bonding in deep eutectic solvents remain insufficiently understood. In this article, we present our contributions toward unravelling the micro heterogeneity within deep eutectic solvents by combining vibrational Stark spectroscopy and two-dimensional infrared spectroscopy with molecular dynamics simulations. Our findings demonstrate how the composition, constituents, and addition of water significantly influence the heterogeneous hydrogen bonding network and solvent dynamics within these systems. These insights provide valuable guidance for the design of next-generation solvents tailored to specific applications. By integrating experimental and computational approaches, this work sheds light on the intricate relationship between solvation dynamics and nanostructure in deep eutectic solvents, ultimately paving the way for innovative advances in solvent design.

Solvatochromism and side chain effects on the morphological behavior of bodipy-alt-i-Indigo copolymers - Singh, Anup Kumar; Swain, Gitanjali; Birajdar, Sarika (New Journal of Chemistry, 2024)
Among the factors that govern the self-assembly of a molecular system, side chains and solvent polarity play crucial roles in the morphological alteration of small molecules in solutions. Although the effect of side chains on the self-assembly of small molecules has been studied well, reports on their importance in the aggregation behavior of polymers are limited. Investigating whether a minor change in the side chain produce any significant impact on the morphology of the polymer in solution is of great research interest. Towards the end goal, to alter the morphology of polymers and to know the impact of the side chains on the self-assembly properties of the conjugated polymers, two BODIPY-i-Indigo alternating copolymers, P1 [poly(BDP12-alt-iI)] and P2 [poly(BDPE-alt-iI)], were synthesized, and their aggregation behavior was explored in various solvents. Both the copolymers, P1 and P2, exhibited narrow PDI values of 1.16 and 1.45, respectively. Although their cores are the same, P1 showed a thin film morphology, while P2 displayed a porous morphology (approximately 557 nm) in chloroform. On changing the solvent, P1 showed a porous morphology in a 50% THF-CHCl3 mixture. However, in P2, the pores were reduced to extremely small sizes in the 50% THF-CHCl3 mixture. This work demonstrates that even a minimal change in the side chains of copolymers and polarity differences between solvents can produce a drastic morphological effect.

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

Solvent-free organic liquids: an efficient fluid matrix for unexplored functional hybrid materials - Wakchaure, Vivek Chandrakant; Channareddy, Goudappagouda; Babu, Sukumaran Santhosh (Accounts of Chemical Research, 2024)
The invention of solvent-free organic liquids (SOLs) was serendipitous. However, the curiosity-driven research in the later stage delivered new soft materials with exciting optical, and optoelectronic properties along with appealing physical characteristics suitable for the futuristic applications. A slight change in the molecular design resulted in a drastic change in the physical state of molecules demonstrating monomer-like features in the bulk. The basic idea of core isolation has been successful in delivering new SOLs with attractive functional properties. The unique fluid matrix associated with SOLs offers a tremendous opportunity for making hybrid materials by simple mixing. The chance to study the fundamentally important electron transfer, energy transfer, charge transfer interactions, triplet-state emissions, and even detailed NMR experiments in the solvent-free neat state is the major attraction of SOLs. Usually, solvents and their polarity control such molecular properties, and in the case of SOLs, it avoids the use of solvents to study such fundamentally important properties. Besides, SOLs protect the triplet emitters and excited state processes involving triplet states from quenchers and make the analysis possible under ambient conditions. Our effort in this direction was focused on tuning the ground and excited state properties by transforming conventional organic molecules to SOLs and further value addition by preparing the hybrid SOLs. We developed a series of hybrid SOLs, exploring room-temperature phosphorescence, thermally activated delayed fluorescence, charge or energy transfer between donor and acceptor SOLs, selective explosive sensing, etc. A slight variation in the chemical structure or optoelectronic properties of the individual components imparted exciting optical features for the hybrid SOLs. It includes nonemissive charge transfer, tunable emission exciplex, room temperature phosphorescence, and thermally activated delayed fluorescence SOLs. The liquid matrix of donor SOLs accommodated varying amounts of acceptor SOLs to tune the ground and excited state features. In all examples of donor-acceptor-based hybrid SOLs, even a low amount of acceptor, such as a donor-acceptor ratio of 1000:1, can cause pronounced optical properties. Hence, the evaluation of the optical properties of SOLs, especially, in the absence of solvents is so special that it avoids the interference of solvent molecules. Still, the major drawback of SOLs remains unsolved until we report polymerizable SOLs. Although a large variety of SOLs have been reported in the literature, the long-lasting problem of surface stickiness of SOLs was resolved by polymerizable SOLs. It enabled the development of flexible, foldable, and stretchable large-area luminescent films suitable for lighting and display devices. In this Account, we summarize our work on SOLs, hybrid SOLs, polymerizable SOLs, and the application of SOLs in selective sensing of explosives. Finally, an outlook on the feasibility of luminescent polymerizable SOLs in futuristic applications is provided.

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

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

Structural basis for a two-dimensional flexible pharmaceutical solvate crystal: indomethacin methanol - Bhowmik, Aritra; Bamane, Sanjivani; Mishra, Manish Kumar (CrystEngComm, 2024)
We report the first two-dimensionally (2D) elastically bendable and twistable pharmaceutical-solvate crystal, indomethacin methanol. Its flexibility is due to interlocked packing and a structural buffer acting like isotropic interactions. For the first time, we utilized Raman spectroscopy on the two elastic faces of a bent crystal region, revealing the inhomogeneous molecular distribution in the crystal structure during bending and validating the mechanistic model of the 2D elastic crystal. We present the first 2D elastic pharmaceutical-solvate crystal and utilized Raman spectroscopy to reveal inhomogeneous lattice distribution during bending.

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

Structural origin of relaxation in dense colloidal suspensions - Sahu, Ratimanasee; Sharma, Mohit; Schall, Peter; Bhattacharyya, Sarika Maitra; Chikkadi, Vijayakumar (PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 2024)
Keywords: DEFORMATION; flow; glass-transition; ORDER; SOFT

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

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

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

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

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

Synergistic 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 and antimicrobial evaluation of novel 2'-aryl-4-aryl-2,4'-Bisthiazole and 2'-aryl-4-Pyridyl-2,4'-bisthiazole derivatives as potential antibacterial agents - Nalawade, Jitendra; Shinde, Abhijit; Abhale, Yogita K.; Nandurkar, Yogesh; Bobade, Vivek D.; Sarkar, Dhiman; Mhaske, Pravin C. (Polycyclic Aromatic Compound, 2024)
In continuation of our research work to explore bisthiazole derivatives as potential antimicrobial agents, herein we reported the synthesis of a series of novel 2'-aryl-4-aryl-2,4'-bisthiazole (7a-t) and 2'-aryl-4-pyridyl-2,4'-bisthiazole (9a-l) by cyclocondensation of 2-aryl thiazole-4-carbothioamide 5a-d with 2-bromo-1-arylethanone (6a-e) and bromo-1-(pyridin-2/3/4-yl)ethanone (8a-c), respectively. These novel candidates were evaluated in vitro for their antibacterial potential against four pathogenic bacteria, Escherichia coli (NCIM 2576), Pseudomonas flurescence (NCIM 2059), Staphylococcus aureus (NCIM 2602), and Bacillus subtilis (NCIM 2162). The synthesized compounds were also screened for their in vitro antifungal activity against Candida albicans (NCIM 3100). Among them, compounds 7b, 9d, 9 g, 9i, and 9 l exhibited excellent antibacterial activity with MIC 2.1 to 12.3 mu g/mL against all tested strains. Most of the compounds reported moderate antifungal activity. The pyridine ring-substituted bisthiazole reported good to excellent antibacterial activity as compared to phenyl ring-substituted bisthiazole. The potential antibacterial activity suggested that bisthiazole derivatives could assist in the development of lead compounds to treat microbial infections.
Keywords: 24'-bisthiazole; antibacterial activity; Antifungal activity; cyclocondensation

Synthesis and processing strategy for high-bandgap PbS quantum dots: a promising candidate for harvesting high-energy photons in solar cells - Shinde, Dipak Dattatray; Sharma, Anjali; Dambhare, Neha V.; Mahajan, Chandan; Biswas, Arindam; Mitra, Anurag; Rath, Arup K. (ACS Applied Materials & Interfaces, 2024)
The wide tunability of the energy bandgap of colloidal lead sulfide (PbS) quantum dots (QDs) has uniquely positioned them for the development of single junction and tandem solar cells. While there have been substantial advancements in moderate and narrow bandgap PbS QDs-ideal for single junction solar cells and the bottom cell in tandem solar cells, respectively; progress has been limited in high-bandgap PbS QDs that are ideally suited for the formation of the top cell in tandem solar cells. The development of appropriate high bandgap PbS QDs would be a major advancement toward realizing efficient all-QD tandem solar cells utilizing different sizes of PbS QDs. Here, we report a comprehensive approach encompassing synthetic strategy, ligand engineering, and hole transport layer (HTL) modification to implement high-bandgap PbS QDs into solar cell devices. We achieved a greater degree of size homogeneity in high-bandgap PbS QDs through the use of a growth retarding agent and a partial passivation strategy. By adjusting the ligand polarity, we successfully grow HTL over the QD film to fabricate solar cells. With the aid of an interface modifying layer, we incorporated an organic HTL for the realization of high-performance solar cells. These solar cells exhibited an impressive open-circuit voltage of 0.824 V and a power conversion efficiency of 10.7%, marking a 360% improvement over previous results.
Keywords: charge transport; lead sulfide; ligand passivation; quantum dots; solar cell

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

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

Synthesis of 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 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

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

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

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

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

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

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.

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

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

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

Viscosity effects on the dynamics of diols and diol-based deep eutectic solvents - Chatterjee, Srijan; Deshmukh, Samadhan H.; Chowdhury, Tubai; Bagchi, Sayan (Photochemistry and Photobiology, 2024)
Diols, characterized by the presence of two hydroxyl groups, form extended hydrogen-bonded networks. Increasing hydrocarbon chain length is known to elevate the viscosity of diols. Given the established influence of viscosity on solvent dynamics, it becomes imperative to comprehend the impact of viscosity on the fluctuation dynamics within diols and establish connections with hydrogen bond formation and breaking dynamics. In this study, we employ two-dimensional infrared spectroscopy to investigate the viscosity dependence of the structural evolution dynamics in three diols with varying chain lengths. Complementing our experimental approach, molecular dynamics simulations are conducted to extract hydrogen bond lifetimes. Our findings reveal a linear correlation between bulk viscosity, solvent fluctuation timescales, and hydrogen bond lifetimes. Notably, the selected diols exhibit the capability to form deep eutectic solvents upon mixing with choline chloride at specific molar ratios. In contrast to molecular solvents like diols, deep eutectic solvents are characterized by the formation of heterogeneous nanodomains, comprising various intercomponent hydrogen-bonded networks. Interestingly, our observations indicate that while the fluctuation dynamics decelerate with increasing bulk viscosity in diol-based deep eutectic solvents, the relationship between viscosity and dynamics is not linear, in contrast to the observed linearity in diols. This nuanced understanding contributes to the broader comprehension of the interplay between viscosity and dynamics in both molecular and deep eutectic solvents. We investigate the impact of viscosity on structural evolution dynamics in diols with varying chain lengths. Employing two-dimensional infrared spectroscopy and molecular dynamics simulations, we explore the relationship between bulk viscosity, solvent fluctuation timescales, and hydrogen bond lifetimes. We report a linear correlation in diols between viscosity, fluctuation timescales, and hydrogen bond lifetimes. Diols also form deep eutectic solvents, characterized by heterogeneous nanodomains. While fluctuation dynamics slow down with increasing bulk viscosity in diol-based deep eutectic solvents, the relationship between viscosity and dynamics is nonlinear, contrasting with diols' linearity. This understanding enhances comprehension of viscosity-dynamics interplay in molecular and deep eutectic solvents.image
Keywords: Dynamics; Hydrogen bond; solvent; spectroscopy; viscosity

Visible light and pH-responsive star copolymer and doxorubicin-polymer conjugate micelles for combination drug delivery and bioimaging - Basutkar, Nitin B.; Surapaneni, Sai Geetika; Alam, Md. Shafi; Ambade, Ashootosh V. (Journal of macromolecular science part A- pure and applied chemistry, 2024)
Amphiphilic 3-arm star copolymer containing visible light-cleavable BODIPY group and pH-responsive imine bonds at the junction of hydrophilic poly(ethylene glycol) (PEG) and two poly(epsilon-caprolactone) (PCL) arms was synthesized by the combination of ring-opening polymerization (ROP) and click chemistry. The formation and stimuli-responsive disruption of micelles were analyzed using dynamic light scattering and transmission electron microscopy. Dual stimuli-responsive release of anticancer drugs Doxorubicin (Dox) and Camptothecin (CPT) from the micelles was studied. Micellar assemblies containing Dox conjugated to PEG-BODIPY through imine bonds were prepared and controlled release of Dox in response to visible light and pH was shown. CPT and Dox-loaded star copolymer micelles as well as CPT loaded Dox-conjugated micelles were used in cellular uptake studies on MDA-MB 231 cells, and the synergistic effect of the two stimuli on the release of the two drugs was demonstrated inside the cells. Micellar assemblies also showed excellent bioimaging properties in the cellular uptake studies. [GRAPHICS]
Keywords: BODIPY; drug conjugate; micelles; pH-responsive; visible light-responsive

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

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.

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

Additive-free, selective synthesis of N-heteroaromatics using morphology-engineered hollow CeO2 nanocatalyst - Singh, Nittan; Swapna, Bhattu; Balu, Alina Mariana; Bhatte, Kushal; Sudarsanam, Putla (ACS Sustainable Chemistry & Engineering, 2025)
We developed a highly efficient, shape-controlled CeO2 nanocatalyst for synthesizing N-heteroaromatics via an aerobic dehydrogenation approach, operating at mild reaction conditions without needing toxic acid/base additives. Different morphologies of CeO2, namely, hollow nanospheres, nanorods, and irregularly shaped nanoparticles, were synthesized, as confirmed by electron microscopy analysis. The CeO2 hollow nanosphere catalyst (CeO2-HNS) exhibited unique features, such as abundant acid-base sites, larger-sized voids, and surface oxygen vacancies. These characteristics are found to be crucial for the additive-free oxidative dehydrogenation of saturated N-heterocycles over the CeO2-HNS catalyst, resulting in 98% conversion of 1,2,3,4-tetrahydroquinoline with 100% quinoline product selectivity. The versatility of this approach was further demonstrated by the successful aerobic dehydrogenation of a broad range of saturated N-heterocycles, affording N-heteroaromatics in good to excellent yields. Furthermore, the CeO2-HNS nanocatalyst showed exceptional reusability over six cycles without requiring a regeneration step, such as high-temperature calcination treatment. The structural and morphological stability of the CeO2-HNS catalyst, along with reaction scalability and favorable green chemistry metrics, emphasized the practical viability of the CeO2-HNS catalyst for industrial applications.
Keywords: acid-base and defect sites; additive-free aerobicdehydrogenation; CeO2 hollow nanosphere catalyst; N-heteroaromatics; reusability and scalability

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

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

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

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

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

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

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

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

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

Bis-subporphyrin-like boron(iii) complexes derived from indolo[2,3-a]carbazole-based cyclic bis-BODIPYs exhibiting persistent helical chirality - Spergen, Aswini; Bal, Pranav V.; Shameem, Asif Khan Shameer; Joshy, Arun; Nambiar, Anjana P.; Andrews, Alex P.; Sabapathi, Gokulnath (Chemical Science, 2025)
Herein, we report the synthesis of 11,12-dihydroindolo[2,3-a]carbazole (InC) 1 incorporating expanded porphyrinoid 8, and its boron(iii) complexes (8BF2 and 8BF). These macrocycles exhibit a `figure-eight' conformation that exists as a pair of helical enantiomers (P,P and M,M), confirmed by X-ray crystallographic analysis. The `figure-eight' structures are stabilized by intramolecular hydrogen bonds such as NH & ctdot;N and NH & ctdot;F interactions. The synthesized macrocycles demonstrate excellent stability under ambient conditions. Further, the helically-locked structure 8BF exhibited closely held InC units with a distance of 6.17 & Aring; and enabled facile optical resolution using chiral HPLC. Circular dichroism spectroscopy of enantiopure 8BF shows the Cotton effect at 692 nm extending to the near-IR region with Delta epsilon up to 150 M-1 cm-1. The chiral induction of racemic macrocycle 8 was employed using enantiopure mandelic acids.

Caffeine vs. theophylline cocrystals: insights into structure-mechanical behavior and piezoelectricity - Bhowmik, Aritra; Bamane, Sanjivani; Saxena, Ashish Kumar; Mishra, Manish Kumar (Crystal Growth & Design, 2025)
Cocrystallization offers a versatile approach to modulate the physicochemical including mechanical properties of active pharmaceutical ingredients (APIs). In this study, we employ crystal engineering principles to design cocrystals of two structurally similar methylxanthine compounds-caffeine (CAF) and theophylline (THP)-with 3,5-dinitrosalicylic acid (DNSA) and 3,5-dinitrobenzoic acid (DNBA) as coformers. The resulting cocrystals and cocrystal polymorphs displayed diverse architectures-2D layers, corrugated sheets, and 3D interlocked structures-showing distinct deformation characteristics. Particular attention was given to the mechanical shearing of the layered structure cocrystals THP-DNBA and CAF-DNBA-I, which are critical for pharmaceutical manufacturing processes such as tablet compaction. The sheared fragmented crystal of THP-DNBA also shows plastic bending deformation. On the other hand, the CAF-DNSA, CAF-DNBA-II, and THP-DNSA cocrystals are brittle due to the absence of a flat layer structure. Our findings reveal that structural features such as flat molecular geometry, pi-stacking, and weak interlayer interactions play crucial roles in promoting plastic deformation via shearing and plastic bending. Nanoindentation studies have been performed on the major faces of all the cocrystals to quantify their mechanical properties. Notably, the CAF-DNBA-I cocrystal also exhibited piezoelectric properties. This work provides valuable insights into the structure-mechanical property relationship in pharmaceutical cocrystals and underscores the potential of cocrystallization in addressing formulation-related challenges.

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

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

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

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

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

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

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

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

The critical helping hand of water: theory shows the way to obtain elusive, granular information about kinetic asymmetry driven systems - Bajpai, Priyam; Thulasiram, Shrivatsa; Vanka, Kumar (Chemical Science, 2025)
Kinetic asymmetry is crucial in chemical systems where the selective synthesis of one product over another, or the acceleration of specific reaction(s) is necessary. However, obtaining precise information with current experimental methods about the behavior of such systems as a function of time, substrate concentration and other relevant factors, is not possible. Computational chemistry provides a powerful means to address this problem. The current study unveils a two-pronged computational approach: (i) full quantum chemical studies with density functional theory (DFT), followed by (ii) stochastic simulations with a validated Gillespie algorithm (GA) (using representative model systems where necessary), to study the behavior of a kinetic asymmetry driven unidirectional molecular motor (1-phenylpyrrole2,2 `-dicarboxylic acid) (Nature, 2022, 604 (7904), 80-85). Our approach allows us to understand what is really taking place in the system, underlining the crucial role played by water molecules in facilitating the rotation of the motor. It is seen that water lubricates the motion by increasing the rotation rate constant of the final step by, remarkably, more than ten orders of magnitude! These insights further serve to explain the efficient rotation of the very recently reported gel-embedded molecular motor (Nature, 2025, 637 (8046), 594-600), providing an upper limit for the allowed rotation barrier in such systems, and thus also casts light into the functioning of bio-molecular motors. The current work therefore provides a template for carefully and properly studying a wide variety of important, kinetic asymmetry driven systems in the future.

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

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

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

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

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

Development 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.

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

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.

Divergent synthesis of 3-formylpyrazolo[1,5-a]pyrimidines and methylene-bridged bis(pyrazolo[1,5-a]pyrimidines) using DMSO as a single carbon synthon - Sikdar, Papiya; Das, Sourav; Saini, Sheetal; Sawant, Sanghapal D.; Bagdi, Avik Kumar (Organic & Biomolecular Chemistry, 2025)
A divergent approach has been explored for synthesizing 3-formylpyrazolo[1,5-a]pyrimidines and methylene-bridged bis(pyrazolo[1,5-a]pyrimidines) using DMSO as a C1 synthon. A library of 3-formylpyrazolo[1,5-a]pyrimidines and methylene-bridged bis(pyrazolo[1,5-a]pyrimidines) has been synthesized using CuOAc and AcOH, respectively. The reaction progressed through a radical pathway. The usefulness of 3-formylpyrazolo[1,5-a]pyrimidines in synthesizing a zaleplon derivative has been demonstrated.

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

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

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

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

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

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