Review of recent progress in electrospinning-derived freestanding and binder-free electrodes for supercapacitors - Joshi, Bhavana; Samuel, Edmund; Kim, Yong-il; Yarin, Alexander L.; Swihart, Mark T.; Yoon, Sam S. (Coordination Chemistry Reviews, 2022)
The versatile electrospinning technique is scalable and suitable to fabricate highly conducting freestanding carbon nanofiber composite electrodes for energy storage devices. Freestanding/flexible electrodes hold enormous potential for use in wearable electronic devices. Carbon-yielding polymers and the optimal use of sacrificial polymers, metal oxides, and sulfides retain the flexibility and enhance the surface area and pseudocapacitance of electrodes. Both as-prepared electrospun fibers and carbonized nanofibers are compatible with surface decoration via various chemical and electrochemical routes. Metal oxides/sulfides with various morphologies, such as nanocones and nanosheets, can be grown on the carbon nanofibers or on the as-prepared electrospun fibers using chemical synthesis methods such as electro-deposition, hydrothermal processes, and chemical impregnation to enhance the pseudocapacitance of the electrodes. Similarly, the deposition of metal organic frameworks on as-prepared electrospun fibers embellishes these fibers with nanostructures of specific morphologies such as dodecahedral and spindle-shaped structures. Under optimal conditions, these morphologies do not hamper the flexibility of the fibers, and binders are not required to retain them or maintain the electrode integrity. The engineering of electrodes with various morphologies and process parameters is presented systematically. Electrospinning-derived electrodes that have demonstrated significant electrochemical performance are highlighted and critically analyzed, and the energy storage mechanisms of these supercapacitors are described in detail. (C) 2022 Elsevier B.V. All rights reserved.
Keywords: Carbon nanofibers; Co-axial; composites; core-shell; electrospinning; Flexible; Porous; supercapacitor

Review on non-noble metal catalysts for glycerol hydrodeoxygenation to 1,2-propanediol with and without external hydrogen - Mane, Rasika; Jeon, Yukwon; Rode, Chandrashekhar (Green Chemistry, 2022)
The depleting petroleum oil resources, political embargos, and global warming dilemma have made it mandatory to develop alternative green technologies for energy and chemical production. Glycerol is one of the top-12 building block chemicals that can be mainly obtained as a coproduct of biodiesel production. The value addition of glycerol is only possible through its conversion to commodity and fine chemicals. Glycerol hydrogenolysis is one of the crucial pathways to produce several value-added products, among which 1,2-propanediol (1,2-PDO), 1,3-propanediol (1,3-PDO), ethylene glycol (EG) and 1-and/or 2-propanols are hydrogenolysis products. Selective glycerol hydrogenolysis to the desired product 1,2-PDO is only possible through the catalyst having an optimum combination of acid/base and metal sites (metallic and mixed oxides). The present review mainly focuses on the critical assessment of the influence of different supports, catalyst preparation methods, and/or pretreatment on structural, and electronic properties and simultaneously on the activity and product selectivity of non-noble metal catalysts. The role of reaction parameters in this industrially important reaction on catalyst performance will also be presented. A rigorous survey of patented literature on non-noble metal-catalyzed glycerol hydrogenolysis to 1,2-PDO is also discussed. Further, the review covers recent progress on non-noble metal-catalyzed autogenous glycerol hydrogenolysis through glycerol aqueous phase reforming (APR) and/or catalytic transfer hydrogenolysis (CTH), to overcome the cost and handling issues of external hydrogen. Finally, techno-economic analysis is also presented which compares the glycerol hydrogenolysis with and without external hydrogen with the conventional process of 1,2-PDO production. This analysis indicated that CTH and glycerol hydrogenolysis under ambient hydrogen pressure have the potential for commercialization, however catalyst stability and elimination of co-product formation at higher glycerol concentration need to be considered critically.

Role of facet in the competitive pathway of ethylene epoxidation - Nair, Aathira; Kenge, Nivedita; Joshi, Kavita (Surface Science, 2022)
Ethylene epoxide (EtO) is used as raw material for a broad range of products from pharmaceuticals and plastics to paints and adhesives. Although the reaction of ethylene interacting with preadsorbed oxygen on Ag surface is known for decades, the underlying mechanism of EtO formation is not completely understood. Successful investigation of oxametallacycle (OMC) intermediate common to selective as well as non-selective pathways has ensured at least 50% selectivity. The current study brings out the electronic signatures of distinct conformers of OMC stabilised on two different facets of Ag viz. (100) and (111). There are subtle differences between OMC conformers observed on these two facets with near-eclipsed on Ag(100) and near-staggered on Ag(111). A detailed analysis of Ag-O, C-O, C-C, and Ag-C interactions along with projected Density of States (pDOS) and projected Crystal Orbital Hamilton Population (pCOHP) imply towards ring closure on Ag(100) and hydrogen transfer on Ag(111). Finally, our understanding based on electronic and structural signatures are backed up by activation barriers computed through NEB calculations. Activation barrier for EtO is lower on (100) as compared to (111) facet. Thus, our study sheds light on how these differences between OMC affect the selectivity towards EtO.
Keywords: Ag(100); Ag(111); DFT; epoxidation; Ethylene Oxide (EtO); OMC

Rongalite as a sulfone source: sulfonylation of para-quinone methides and alkyl/allyl halides - Kale, Someshwar B.; Jori, Popat K.; Das, Utpal (Chemistry-an Asian Journal, 2022)
A one-pot three-component reaction using p-quinone methides, rongalite and alkyl/allyl halides has been described. The corresponding unsymmetrical sulfones were obtained in good yields under mild reaction conditions in the absence of any metal, base or any other additive.
Keywords: Alkyl halides; diaryl methine; p-Quinone methide; rongalite; sulfonylation

Silk fibroin and recombinant elastin blend nano-coatings for implantable medical devices - Joseph, Emmanuel; Kane, Kartiki; Parekh, Nimisha; Nisal, Anuya; Janorkar, V. Amol (Materials Today Communications, 2022)
Silicone breast implants are conventionally used to reconstruct the shape and size of the breast in breast cancer patients. However, rate of failure of implants due to formation of capsular contracture is significantly high. Recent studies have shown that coating the surface of the implant with a biocompatible polymer can mitigate this risk. Here, we have modified the surface of implant using a biocompatible natural biopolymer silk fibroin (SF). Further, we have developed formulations of SF with a recombinantly produced elastin-like-peptide (ELP) and compared their performance with a known anti-fouling hydrophilic polymer - polyethylene oxide (PEO). Microscopic and spectroscopic characterization confirm the formation of uniform coatings. These coatings have been also characterized for their ability to resists crack formation. Further, the coatings have been evaluated for their biological performance. Our studies show that addition of 25 wt% of ELP to SF significantly enhances the crack resistance for the coatings. In addition, SF/ELP coatings reduce the adsorption of blood plasma proteins by more than 80 %. Preliminary analysis shows that the SF/ELP blend coatings are non-cytotoxic and support adhesion, growth and proliferation of fibroblast cells. The study therefore demonstrates that SF/ELP coatings have the potential to mitigate the risk of breast implant failure.
Keywords: Blood plasma; Crack resistance; Protein adsorption; Recombinant elastin; Silk fibroin

Silver-catalyzed [3 + 3]-annulation cascade of alkynyl alcohols and α,β-unsaturated ketones for the regioselective assembly of chromanes - Nakate, Ashwini K.; Thorat, Sagar S.; Jain, Shailja; Rama Krishna, Gamidi; Vanka, Kumar; Kontham, Ravindar (Organic Chemistry Frontiers, 2022)
An unprecedented Ag(i)-catalyzed [3 + 3]-annulation of alkynyl alcohols (5-hexyn-1-ols) and α,β-unsaturated ketones is reported to construct simple to complex chromanes. This transformation begins with hydroalkoxylation of alkynol through C–C triple bond activation to give cyclic-enol ether, followed by intermolecular 1,4-addition and intramolecular 1,2-addition of enol ethers onto the enone and oxidative aromatization or Grob-type elimination steps. Facile reaction conditions, broad substrate scope, good to excellent yields, and atom economy are the salient features of this protocol. Isolation of the active pyran-tethered cyclohexadiene reaction intermediate, additional supporting experiments, and DFT calculations strongly support the experimental findings and corroborate our proposed mechanism.

Small molecule quercetin binds MALAT1 triplex and modulates its cellular function - Rakheja, Isha; Ansari, Asgar Hussain; Ray, Arjun; Joshi, Dheeraj Chandra; Maiti, Souvi (Molecular Therapy-Nucleic Acids, 2022)
The triple-helix structure at the 30 end of metastasis-associated lung adenocarcinoma transcript 1 (MALAT1), a long non -cod-ing RNA, has been considered to be a target for modulating the oncogenic functions of MALAT1. This study examines the binding of quercetin-a known triplex binding molecule-to the MALAT1 triplex. By employing UV-visible spectroscopy, circular dichroism spectroscopy, and isothermal titration calo-rimetry, we observed that quercetin binds to the MALAT1 triplex with a stoichiometry of 1:1 and Kd of 495 +/- 61 nM, along with a negative change in free energy, indicating a spontaneous interaction. Employing real-time PCR measurements, we observed around 50% downregulation of MALAT1 transcript levels in MCF7 cells, and fluorescence in situ hybridization (FISH) experiments showed concomitantly reduced levels of MALAT1 in nuclear speckles. This interaction is likely a result of a direct interaction between the molecule and the RNA, as indicated by a transcription-stop experiment. Further, tran-scriptome-wide analysis of alternative splicing changes induced by quercetin revealed modulation of MALAT1 downstream genes. Collectively, our study shows that quercetin strongly binds to the MALAT1 triplex and modulates its functions. It can thus be used as a scaffold for further development of ther-apeutics or as a chemical tool to understand MALAT1 func-tions.

Statistical optimization of media for enhancing intracellular lipid content in Yarrowia lipolytica NCIM 3589 grown on waste cooking oil for biodiesel production - Jagtap, Shubhangi Ramling; RaviKumar, Ameeta; Raut, Gouri; Kumar, V. Ravi (Journal of the American Oil Chemists Society, 2022)

Steroidal alkaloids defence metabolism and plant growth are modulated by the joint action of gibberellin and jasmonate signalling - Panda, Sayantan; Jozwiak, Adam; Sonawane, Prashant D.; Szymanski, Jedrzej; Kazachkova, Yana; Vainer, Andrii; Kilambi, Himabindu Vasuki; Almekias-Siegl, Efrat; Dikaya, Varvara; Bocobza, Samuel; Shohat, Hagai; Meir, Sagit; et al. (New Phytologist, 2022)
Steroidal glycoalkaloids (SGAs) are protective metabolites constitutively produced by Solanaceae species. Genes and enzymes generating the vast structural diversity of SGAs have been largely identified. Yet, mechanisms of hormone pathways coordinating defence (jasmonate; JA) and growth (gibberellin; GA) controlling SGAs metabolism remain unclear. We used tomato to decipher the hormonal regulation of SGAs metabolism during growth vs defence tradeoff. This was performed by genetic and biochemical characterisation of different JA and GA pathways components, coupled with in vitro experiments to elucidate the crosstalk between these hormone pathways mediating SGAs metabolism. We discovered that reduced active JA results in decreased SGA production, while low levels of GA or its receptor led to elevated SGA accumulation. We showed that MYC1 and MYC2 transcription factors mediate the JA/GA crosstalk by transcriptional activation of SGA biosynthesis and GA catabolism genes. Furthermore, MYC1 and MYC2 transcriptionally regulate the GA signalling suppressor DELLA that by itself interferes in JA-mediated SGA control by modulating MYC activity through protein-protein interaction. Chemical and fungal pathogen treatments reinforced the concept of JA/GA crosstalk during SGA metabolism. These findings revealed the mechanism of JA/GA interplay in SGA biosynthesis to balance the cost of chemical defence with growth.
Keywords: alpha-tomatine; defence; gibberellin (GA); growth; jasmonate (JA); steroidal glycoalkaloids (SGAs); Tomato

Studies toward the total synthesis of (+)-neopeltolide using N-heterocyclic carbene-catalyzed oxo-acyloxylation/reductive oxa-Michael addition strategy - Reddi, Rambabu N.; Sudalai, Arumugam; Jo, Changbum (Bulletin of the Korean Chemical Society, 2022)
This article describes a concise synthesis of two important fragments (tetrahydropyran [THP] and ketone moieties) of the cytotoxic macrolide (+)-neopeltolide in 10 long linear steps in enantiomerically pure form. Asymmetric Keck allylation to install the required C11 and C13 stereocenters, N-heterocyclic carbene (NHC)-catalyzed oxoacyloxylation to functionalize alkenes, and reductive oxa-Michael addition to construct 2,6-difunctionalized THP unit intramolecularly are the important steps in synthetic efforts. Finally, Keck asymmetric allylation and Lewis acid-catalyzed diastereoselective allylation of the aldehyde were sequentially employed to establish the stereocenters at C11 and C13 positions, respectively.
Keywords: (+)-neopeltolide; Keck allylation; Macrolide; NHC-catalyzed oxoacyloxylation; reductive oxa-Michael addition

Subcritical water hydrolysis of N-acetyl-D-glucosamine: hydrolysis mechanism, reaction pathways and optimization for selective production of 5-HMF and levulinic acid - Kulkarni, Sphurti Prakash; Dure, Shital N.; Joshi, Sunil S.; V. Pandare, Kiran; Mali, Nilesh A. (Carbohydrate Research, 2022)
In this study, the subcritical water hydrolysis of N-acetyl-D-glucosamine (NAG), a monomer of abundant renewable marine biopolymer chitin, for production of value-added chemicals is investigated. The enhanced ionization of water at subcritical conditions (200 degrees C; 50-100 bar), provides enough acidity for deacetylation of NAG resulting in 80% yield of acetic acid along with traces of formic acid, lactic acid, glucose, fructose, 5hydroxymethylfurfural (5-HMF),etc. The significant humin formation indicates that the self-condensation and polymerisation of 5-HMF is favored in water at subcritical conditions. A catalyst p-toluenesulfonic acid (p-TsOH) was employed to selectively convert NAG to levulinic acid (LA) via ring opening of 5-HMF previously formed during hydrolysis. The maximum yield of 27.13 +/- 1% and 53.46 +/- 1% of 5-HMF and LA, respectively, was obtained at process conditions optimized using Box-Behnken design coupled with response surface methodology. Subcritical water enables greener conversion of NAG to platform chemicals wherein the selective production can be achieved by tuning the process conditions.
Keywords: 5-Hydroxymethylfurfural; chitin; Glucosamine; levulinic acid; Response surface methodology; Subcritical water

Surface alteration driven bi-functional catalytic activity of alkali niobate-N doped graphene composite for exalted oxygen electrochemistry - Suman Kumari Jhajharia; Shashaank Gupta; Zinoy Manappadan; Kaliaperumal Selvaraj; Myoor K. Padmanabhan; Roop L. Mahajan (Applied Surface Science, 2022)
In this work, we establish that surface reconstruction, oxygen vacancies —specifically those located on the catalyst surface, and high crystallinity can be effective in tuning the catalytic activity of perovskite oxides. We report a high-performance electrocatalyst with an orthorhombic perovskite structure (NaNbO3), having an anisotropic surface layer and high crystallinity that exhibits superior activity and durability for the bi-functional oxygen electrochemistry compared to that of a similar perovskite composition with an isotropic surface layer and low crystallinity. The improvement in the electrocatalytic activity for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is mainly attributed to the formation of an easy diffusion path on the surface layer due to the ionic movements, enhanced intrinsic activity of the catalytic sites resulting from the higher crystallinity, high oxygen vacancies and a large electrochemically active surface area. The sole key parameter in achieving all the acquired characteristics is the annealing temperature. We believe that the straightforward method of bringing the desired combination of properties by just tweaking the annealing temperature is handy and energy-efficient, and hence easily adoptable.
Keywords: Bi-functionality; N-doped graphene; Oxygen Evolution Reaction; oxygen reduction reaction; perovskite; Surface reconstruction

Sustainable composite of SnFe2O4 conversion alloying anode for lithium-ion storage - Yadav, Poonam; Parte, Golu; Malik, Wahid; Sabri, Ylias M.; Jones, Lathe A.; Shelke, V. Manjusha (Sustainable Energy & Fuels, 2022)
The development of high-performance, low-cost electrodes using sustainable materials for Li-ion batteries is of vital importance in view of their increasing demand for use in electronics and electric vehicles, as we transition from non-renewable energy resources. Challenges associated with commercial graphite anode materials include relatively low capacity, the use of high-temperature synthesis, Li dendrite formation, and limited rate capability. In this study, we present a tin ferrite SnFe2O4 (SFO) conversion alloying material (CAM), and its synergistic composite with a scalable and low-cost waste-derived carbon (WDC), which was prepared by low-temperature pyrolysis of a waste material sustainably. The combination of SFO with the WDC in the composite boosts the conductivity, diffusion kinetics, stability, and reversibility, and accommodates volume expansion upon cycling. The first charge capacity obtained for WDC, SFO, and SFO-WDC is 595, 1269, and 1331 mA h g(-1), respectively at 100 mA g(-1) in a Li-ion half-cell. In a full cell fabricated with LFP, a stable capacity of 80 mA h g(-1) at 100 mA g(-1) could be obtained, and the corresponding energy density for the SFO-WDCIILFP full cell is 300 W h kg(-1). Kinetic studies revealed that capacitance-controlled charge storage is dominant so the capacity was higher in the composite. This composite system addresses both the low capacity issue of the carbon anode and stability issues of CAMs while being compatible for use with current Li-ion battery technology.

Synthesis and characterization of partially biobased aromatic (Co)polycarbonates containing biphenylene units and pendant pentadecyl chains - Ichake, Amol B.; Nagane, Samadhan S.; Jadhav, Uday A.; Torris, Arun; Grau, Etienne; Cramail, Henri; Wadgaonkar, Prakash P. (Macromolecular Chemistry and Physics, 2022)
2-Pentadecyl-[1,1''-biphenyl]-4,4''-diol (PBD) is synthesized starting from cashew nut shell liquid-a by-product of cashew processing industry. A new series of partially biobased aromatic (co)polycarbonates possessing biphenylene units and pendant pentadecyl chains is synthesized by solution polycondensation of PBD or varying compositions of PBD and bisphenol-A with triphosgene in dry dichloromethane. Inherent viscosities and number average molecular weights of (co)polycarbonates are in the range 0.51-1.24 dL g(-1) and 18 x 10(3)- 43.4 x 10(3) g mol(-1), respectively indicating the formation of reasonably high molecular weight polymers. Flexible, transparent, and free-standing films of (co)polycarbonates can be cast from chloroform solution. (Co)polycarbonates are characterized using Fourier transform infrared spectroscopy (FTIR), H-1 NMR, C-13 NMR spectroscopy, X-ray diffraction (XRD), differential scanning calorimetry, and thermogravimetric analysis. T-10 and T-g values of (co)polycarbonates are in the range 417-433 and 8-147 degrees C, respectively. It is demonstrated that the T-g values can be tuned by incorporation of appropriate mol% of PBD as a comonomer in Bisphenol-A-based copolycarbonates. The lowering of the T-g values of (co)polycarbonates can be attributed primarily to the packing disruptive effect of flexible pentadecyl chains. Furthermore, the effect of incorporation of PBD as a comonomer on water contact angle values of (co)polycarbonates is evaluated.
Keywords: aromatic polycarbonates; biobased bisphenol; Cashew nut shell liquid; pentadecyl chain; Renewable resources

Synthesis, characterization and post-modification of aromatic (Co)polyesters possessing pendant maleimide groups - Jadhav, Uday A.; Nagane, Samadhan S.; Wadgaonkar, Prakash P. (High Performance Polymers, 2022)
A new series of (co)polyesters possessing pendent maleimide groups was synthesized by low temperature solution polycondensation of 4, 4’-(5-maleimidopentane-2, 2-diyl) diphenol (BPA-MA) with isophthalic acid chloride (IPC), terephthalic acid chloride (TPC) and a mixture of TPC and IPC (50:50 mol %). Copolyesters were also synthesized by polycondensation of varying compositions of BPA-MA and bisphenol-A (BPA) with IPC. The chemical structures and compositions of (co)polyesters were confirmed by NMR spectroscopy. Inherent viscosity values and number-average molecular weights of (co)polyesters were in the range 0.50–0.76 dL/g and 17,700-32,100 g/mol, respectively, indicating the formation of reasonably high molecular weight polymers. (Co)polyesters were readily soluble in common organic solvents and could be cast into tough, transparent and flexible films from chloroform solutions. (Co)polyesters exhibited 10% weight loss and glass transition temperatures in the range 464–468 and 142–178°C, respectively. A representative copolyester possessing pendant maleimide groups was chemically modified via metal-free azide-maleimide 1,3-dipolar cycloaddition click reaction with two azido compounds, namely, (azidomethyl)benzene (Bz-N3) and 1-(azidomethyl)-pyrene (Py-N3) to yield corresponding modified copolyesters in a quantitative manner.

Synthesis of new thiazole and pyrazole clubbed 1,2,3-triazol derivatives as potential antimycobacterial and antibacterial agents - Jagadale, Shivaji M.; Abhale, Yogita K.; Pawar, Hari R.; Shinde, Abhijit; Bobade, Vivek D.; Chavan, Abhijit P.; Sarkar, Dhiman; Mhaske, Pravin C. (Polycyclic Aromatic Compounds, 2022)
New series of 4-methyl-2-(4-substituted phenyl)-5-(4-((4-(4-substituted phenyl)-1H-1,2,3-triazol-1-yl)methyl)-1-phenyl-1H-pyrazol-3-yl)thiazole, 6a-t and 4-(1,3-diphenyl-1H-pyrazol-4-yl)-1-((1,3-diphenyl-1H-pyrazol-4-yl)methyl )-1H-1,2,3-triazole, 11a-o derivatives have been synthesized by applying copper-catalyzed [3 + 2] cycloaddition reaction. The newly synthesized 1,3-thiazolyl-pyrazolyl-1,2,3-triazole (6a-t) and bis-pyrazolyl-1,2,3-triazole (11a-o) derivatives were screened for in vitro antimycobacterial activity against M. Tuberculosis H37Ra dormant and active and antibacterial activity against four pathogenic bacteria, E. coli (NCIM 2576), P. flurescence (NCIM 2059), S. aureus (NCIM 2602) and B. subtilis (NCIM 2162). Compounds 6a, 6f, 6j, 11e and 11m showed good activity against M tuberculosis H37Ra Active strain, also compounds 6g, 6h, 11f, 11n and 11o showed good activity against M tuberculosis H37Ra Dormant strain. Compounds 6b, 6i, 6l, 6o, 6r, 11k, 11l and 11m showed good activity against B. subtilis with IC50 1.99-2.96 mu g/mL. The antibacterial activity of thiazolyl-pyrazolyl-1,2,3-triazole and bis-pyrazolyl-1,2,3-triazole derivatives suggested that, these derivatives could lead to new compounds for treatment against bacterial infection.
Keywords: 123-Triazole; antibacterial activity; antimycobacterial activity; Pyrazole; Thiazole

Tailoring the properties of Ni(111)/graphone interfaces by intercalation of Al and Na: a DFT study - Archana, Ramakrishnan; Joshi, Niharika; Raja, Thirumalaiswamy (C-Journal of Carbon, 2022)
With the incredible discovery of graphene (Gr), all of the properties studied to date suggest that it has promising applications in the development of semiconductor, spintronic, insulating, and polymer materials. However, efforts are still underway to fully understand the nature of metal–graphone(GrH) interaction in order to offer better scope for tuning the electronic and magnetic properties, which can be performed by intercalation of atoms via metal support on graphene. We chose metal atoms belonging to the s and p blocks, namely Na and Al, respectively, as the intercalating atoms. Herein, the maximum coverage of a monolayer of Na and Al was comparatively studied on a Ni(111) surface. Significant changes in the magnetic and electronic properties at the Ni(111)/graphone interface were observed upon intercalation. Of the two intercalating metal atoms, Na proved to be more effective, such that the magnetic properties of the surface Ni were only slightly decreased, and the graphone also showed better magnetic properties than in the absence of Na.

Thermal and crystallization behaviour of polyphenylene sulfide in engineering polymer blends with HDPE - Nadkarni, V. M.; Shingankuli, V. L.; Jog, J. P. (International Polymer Processing, 2022)
The thermal and crystallization behaviour of polyphenylene sulfide (PPS) in its blends with high density polyethylene (HDPE) is reported. Three grades of HDPE ranging in MFI from 0.4 to 52 were used in the investigation. The effect of composition and molecular weight of HDPE on the crystallization process and morphology of PPS in the blends has been investigated by the technique of Differential Scanning Calorimetry (DSC). In the blends, PPS crystallizes in presence of molten HDPE. It is observed that the morphology of PPS in terms of crystallite size and crystallite size distribution in the blends is significantly affected by blending with HDPE. The temperature onset of melting was found to increase with increasing HDPE content and the melting peak width was found to decrease with increasing HDPE content. This indicates a larger crystallite size and a narrower crystallite size distribution of PPS in blends. The effect is more pronounced in HDPE-rich compositions. The extent of the variation in the temperature onset of melting and peak width were comparable for all the grades of HDPE. The degree of crystallinity of PPS in the blends is reduced significantly (55-70%) in HDPE-rich blends. Therefore, it is concluded that the crystallization of PPS is affected by the presence of HDPE melt. The crystallization scans of PPS in the blends, obtained in the cooling mode, did not show any evidence of accelerated nucleation. On the other hand, a marginal reduction in the temperature onset of crystallization was observed. The temperature range of crystallization of PPS in the blends was found to be less for all compositions except for 90/10 (PPS/HDPE). In summary it is concluded that blending of HDPE with PPS influences the crystal growth of PPS significantly although the effect on its homogeneous nucleation is also considerable. As a result, the morphology of PPS crystallized in blends is different from that of the homopolymer. The changes in the morphology of PPS are not sensitive to the molecular weight of HDPE probably because of the high temperature of PPS crystallization relative to the melting point of HDPE.

Total synthesis of 12, 13-dibenzyl-banistenoside B and analogs - Patil, Suhag S.; Jachak, Gorakhnath R.; Krishna, Gamidi Rama; Argade, Narshinha P.; Reddy, D. Srinivasa (European Journal of Organic Chemistry, 2022)
Banistenosides A and B possessing a unique ``azepino(1,2-a)tetrahydro-beta-carboline'' carbon framework were isolated from the stem of Banisteriopsis caapi and showed MAO-A inhibition. Herein, we report the total synthesis of dibenzyl derivative of the untouched natural product in the last two decades, Banistenoside B. The key steps involve construction of 6.5.6.7 tetracyclic core using Pictet-Spengler reaction and intramolecular amide coupling. The stereoselective glycation was achieved through Hotha's protocol using gold catalyst, and silver triflate in the late stage of synthesis. The stereochemistry of most of the essential compounds were confirmed by X-ray crystallography.
Keywords: Au-catalyst; Multiple steps total synthesis; Natural products; Pictet-Spengler reaction; Wittig reaction

Transcriptional and translational perturbation in abiotic stress induced physiological activities and metabolic pathway networks in spongy tissue disorder of mango fruit - Oak, Pranjali; Jha, Vineet; Deshpande, Ashish; Tanpure, Rahul; Dawkar, Vishal; Mundhe, Swapnil; Ghuge, Sandeep; Prabhudesai, Shrikant; Krishanpal, Anamika; Jere, Abhay; Giri, Ashok; Gupta, Vidya (Postharvest Biology and Technology, 2022)
Spongy tissue formation is economically the most detrimental but agriculturally less focused physiological disorder in mango. `Alphonso' cultivar is highly prone to oxidative stress induced spongy tissue disorder impacting biochemical and metabolic profile, thereby affecting pulp quality and nutritional value of the fruit. In the present study, comparative analysis of spongy and healthy mesocarp tissues of `Alphonso' mango by transcriptomics using Illumina sequencing and proteomics using LC-MS approaches, respectively identified and quantified many genes and proteins in the metabolic pathways responsible for the spongy tissue development. The table green and the mid ripe stages of `Alphonso' fruit ripening were evaluated by the transcriptomic study and outcomes were validated using proteomic investigations for all the four ripening stages. Colossal amount of data including 30,582 transcripts, 10,800 gene ontologies and 387 putative proteins was generated from this analysis. Current multi-omics exploration revealed the development of abiotic stress (mainly oxidative stress) induced perturbations in various metabolic pathways and their interconnections, leading to the spongy tissue formation in mango. This further unfolded the altered cell wall degradation, ethylene and flavonoid biosynthesis, fruit ripening and flavor formation, thus hampering the fruit specific characteristics in mango with spongy tissue disorder.
Keywords: Oxidative stress; Proteome; spongy tissue disorder; Transcriptome; ` Alphonso ` mango

Viscoelastic liquid from regenerated silk fibroin in the silk i conformation: a writeable and shapeable material - Kumar, Raj; Joseph, Emmanuel; Chaudhari, Atul; Nisal, Anuya; Sharma, Kamendra P. (ACS Applied Polymer Materials, 2022)
Regenerated silk fibroin (RSF) has acquired enormous attention because of its exceptional toughness, strength, and biocompatible nature. These properties make RSF a potential candidate for the fabrication of different types of materials. However, processing even a dilute aqueous solution of RSF leads to a conformational transformation from a random coil/helix-rich (silk I) to a beta-sheetrich (silk II) state. As a consequence, RSF tends to form aggregates and loses its toughness. Working in a direction to address this problem, an aqueous solution of regenerated silk fibroin has been modified with a dual layer of polyethylenimine (PEI) and a PEG-based polymer surfactant (PS). Upon freeze-drying, the RSF-polymer complex forms a solvent-free RSF bioconjugate system and exhibits a soft solid to liquid melting transition at similar to 45 degrees C. The sequential modification with PEI and PS preserves the native-like random coil conformation of RSF up to at least 8 months of storage by not allowing interchain interactions that can lead to aggregation. Rheological and small-angle X-ray scattering measurements show that the solvent-free system is viscoelastic and exhibits a higher order microstructure mediated by the packing of the PS chains, respectively. Temperature-dependent soft solid-liquid-like dual behavior offers applications in injection-based writing, compression molding, and shaping RSF bioconjugates into various types of geometries. Furthermore, the mechanical properties of the RSF bioconjugate system can be modulated by crosslinking with glutaraldehyde vapor at 50 degrees C.
Keywords: RSF liquid; RSF soft solid; silk I conformation; silk liquid; viscoelastic

Wearable fabric supercapacitors based on CNTs and polyhedral ZnO with a wide potential window - Samuel, Edmund; Joshi, Bhavana; Park, Chanwoo; Aldalbahi, Ali; El-Newehy, Mohamed; Lee, Hae-Seok; Yoon, Sam S. (International Journal of Energy Research, 2022)
Wearable electronic devices such as health monitors, sensors, and e-skin can be powered by lightweight, high-power supercapacitors. Using a binder-free and low-temperature hydrothermal method, polyhedral ZnO nanoparticles were grown on carbon nanotube (CNT)-decorated cotton fabric, which is friendly to human skin and highly wearable, inexpensive, and thus commercially viable. The concentration of the starting material, zinc acetate, was varied to optimize the electrochemical performance. The evenly spaced polyhedral ZnO facilitated efficient permeation of the electrolyte into the active material. The fabric filaments were decorated with CNTs to enhance electron transfer and the overall electrochemical processes. The symmetric cell comprised of cotton fabric decorated with ZnO polyhedron/CNT showed no discernible change in the cyclic voltammetry curves even after 500 bending cycles, demonstrating the mechanical durability of the electrode. The potential window of 1.6 V using a Na2SO4/K2SO4 aqueous dual-ion electrolyte improved the long-term electrochemical stability and increased the energy storage capacity. The capacitance retention was 94% after 5000 cycles at a current density of 1 A center dot g(-1), indicating long-term electrochemical stability. A specific capacitance of 375 F center dot g(-1) at a current density of 5 A center dot g(-1) and energy density of 33.3 Wh center dot kg(-1) at a power density of 2000 W center dot kg(-1) were recorded for the optimized electrode. Highlights Polyhedral ZnO was grown on cotton fabric using a hydrothermal process. The electrochemical performance was optimized by varying the zinc acetate concentration. The highest specific capacitance was 375 F center dot g(-1) at a current density of 5 A center dot g(-1). Under optimal conditions, the capacitance retention was 94% at N = 5000 cycles. The energy density of the electrode was as high as 33.3 Wh center dot kg(-1).
Keywords: carbon nanotube; Cotton fabric; hydrothermal process; wearable supercapacitor; ZnO polyhedron

Well-defined calcium compound catalyzes trimerization of arylisocyanates into 1,3,5-triarylisocyanurates - Kumar, Rohit; Sharma, Vishal; Jain, Shailja; Sharma, Himanshu; Vanka, Kumar; Sen, Sakya S. (ChemCatChem, 2022)
We report the synthesis of a calcium complex (2) bearing a tetradentate monoanionic ligand with a diaminoethane core and phenolate and pyridine peripheral donors. Single crystal X-ray studies on 2 revealed that LiI was also co-crystallized, leading to a four-membered ring with four different elements. 2 was found to be an efficient catalyst for the cyclotrimerization of a variety of aromatic isocyanates under mild conditions.
Keywords: calcium; Cyclotrimerization; Isocyanurates; Tetradentate ligand

Antiviral and ROS scavenging potential of Carica papaya Linn and Psidium guajava leaves extract against HIV-1 infection - Jadaun, Pratiksha; Shah, Prachibahen; Harshithkumar, R.; Said, Madhukar S.; Bhoite, Shubhangi P.; Bokuri, Sowmya; Ravindran, Selvan; Mishra, Neetu; Mukherjee, Anupam (BMC Complementary Medicine and Therapies, 2023)
Antiretroviral therapy is the only treatment option for HIV-infected patients; however, it has certain drawbacks in terms of developing multiple toxic side effects. Thus, there is a continuous need to explore safe and efficacious anti-retroviral agents. Carica papaya Linn and Psidium guajava are known for their various biological activities. In this study, we characterized the bioactive fractions of methanolic leaves extract from both plants using the High-resolution electrospray ionization mass spectrometry (HR-ESI-MS) technique, followed by the investigation of their potential as anti-HIV-1 and antioxidant agents through in vitro mechanistic assays. The anti-HIV-1 activity was examined in TZM-bl cells through luciferase gene assay against two different clades of HIV-1 strains, whereas the intracellular ROS generation was analyzed by Fluorescence-Activated Cell Sorting. Additionally, the mechanisms of action of these phyto-extracts were determined through the Time-of-addition assay. The characterization of Carica papaya Linn and Psidium guajava leaves extract through HR-ESI-MS fragmentation showed high enrichment of various alkaloids, glycosides, lipids, phenolic compounds, terpenes, and fatty acids like bioactive constituents. Both the phyto-extracts were found to be less toxic and exhibited potent antiviral activity against HIV-1 strains. Furthermore, the phyto-extracts also showed a decreased intracellular ROS in HIV-1 infected cells due to their high antioxidant potential. Overall, our study suggests the anti-HIV-1 potential of Carica papaya Linn and Psidium guajava leaves extract due to the synergistic action of multiple bioactive constituents.
Keywords: anti-HIV-1 activity; Anti-retroviral; Bioactive constituents; Carica papaya Linn; Cytotoxicity; HR-ESI-MS; Psidium guajava; reactive oxygen species

Baby step in assembling and integrating the components of an artificial photosynthesis device with forced heterojunctions towards improved efficiency - Salgaonkar, Kranti N.; Bajpai, Himanshu; Mhamane, Nitin B.; Nalajala, Naresh; Chauhan, Inderjeet; Thakkar, Kavita; Joshi, Kavita; Gopinath, Chinnakonda S. (Journal of Materials Chemistry A, 2023)
How to achieve unassisted, economical, scalable, and sustainable artificial photosynthesis for liquid fuels/products with improved solar-to-fuel efficiency (STFE) to address a carbon-neutral economy remains a big question. To a large degree, the extent of charge separation at heterojunction interfaces and charge utilization determine the STFE. Towards this, BiVO3 is assembled from ionic-precursors into TiO2 pores, and integrated structurally and electronically with TiO2 on calcination as BiVO4 quantum dots (BVQDs). BVQDs in TiO2 (BVT) pores lead to an all-inorganic system with a sub-quadrillion number of heterojunctions in a 1 cm(2) device (contains similar to 25 mu g of BiVO4 (similar to 2.5 wt%) in the nanopores of similar to 975 mu g of TiO2 (similar to 97.5 wt%)) and facilitate artificial photosynthesis. We demonstrate 31-38% STFE with a photon to chemical conversion turn over frequency (ToF(P2C)) of 2.73 s(-1) with a 1 cm(2) wireless BiVO4-TiO2 artificial leaf (BVT-AL) device for HCHO and CH3OH. The sequential nature of CO2 reduction to HCHO and then to CH3OH is evident from the reaction results. (CO2)-C-13 isotopic labeling experiments confirm that the input CO2 is the source for product formation. A large increase in the photocurrent density and incident photon-to-current efficiency (IPCE) of BVT, over 100% for the BiVO4 photoanode in visible light, demonstrates and supports efficient visible light absorption, charge separation and migration to the redox sites. A device has been demonstrated to show sustainable activity in direct sunlight, and addresses scalability from 1 to 9 cm(2). Assuming no change (50% decrease) in the STFE, a 6.74 m(2) device is expected to convert 1 (0.5) kg h(-1) CO2 into C1-oxygenates in sunlight. DFT calculations carried out with anatase TiO2 (101) and BiVO4 (121) interfaces support many of the experimental findings, including electron flow from the latter to the former, and interaction of the oxygen of TiO2 with BiVO4 and vice versa at the interface towards forced heterojunctions.

BAHD-type acyltransferase concludes the biosynthetic pathway of non-bitter glycoalkaloids in ripe tomato fruit - Sonawane, Prashant D.; Gharat, Sachin A.; Jozwiak, Adam; Barbole, Ranjit; Heinicke, Sarah; Almekias-Siegl, Efrat; Meir, Sagit; Rogachev, Ilana; O'Connor, Sarah E.; Giri, Ashok P.; Aharoni, Asaph (Nature Communications, 2023)
During tomato fruit ripening, bitter and toxic steroidal glycoalkaloids (SGAs) are converted to nonbitter and less toxic forms, but proposed acylating enzyme in pathway remain unknown. Here, authors report BAHD-type acyltransferase that catalyze acylation step in biosynthesis of non-bitter SGAs in tomato. Tomato is the highest value fruit and vegetable crop worldwide, yet produces & alpha;-tomatine, a renowned toxic and bitter-tasting anti-nutritional steroidal glycoalkaloid (SGA) involved in plant defense. A suite of modifications during tomato fruit maturation and ripening converts & alpha;-tomatine to the non-bitter and less toxic Esculeoside A. This important metabolic shift prevents bitterness and toxicity in ripe tomato fruit. While the enzymes catalyzing glycosylation and hydroxylation reactions in the Esculeoside A pathway have been resolved, the proposed acetylating step remains, to date, elusive. Here, we discovered that GAME36 (GLYCOALKALOID METABOLISM36), a BAHD-type acyltransferase catalyzes SGA-acetylation in cultivated and wild tomatoes. This finding completes the elucidation of the core Esculeoside A biosynthetic pathway in ripe tomato, allowing reconstitution of Esculeoside A production in heterologous microbial and plant hosts. The involvement of GAME36 in bitter SGA detoxification pathway points to a key role in the evolution of sweet-tasting tomato as well as in the domestication and breeding of modern cultivated tomato fruit.

Biosynthesis of gold nanoparticles by Penicillium rubens and catalytic detoxification of ochratoxin A and organic dye pollutants - Bhandari, Yogesh; Varma, Sanjana; Sawant, Amol; Beemagani, Sreelatha; Jaiswal, Neha; Chaudhari, Bhushan P.; Vamkudoth, Koteswara Rao (International Microbiology, 2023)
The environmental pollution caused by chemical dyes is a growing concern nowadays. Limitations of traditional methods opened the route for nanotechnology; owing to the versatile properties of nanomaterials, gold nanoparticles (AuNPs) became a potential strategy for different applications. In the present study, biosynthesis of gold nanoparticles (BioAuNPs) was carried out by reacting chloroauric acid (HAuCl4) with cell-free filtrate of Penicillium rubens sp. nov. NCIM 1937. The AuNPs were then characterized by UV-visible spectroscopy, HR-TEM, FTIR, and DLS analysis to further examine their efficacious biosynthesis and morphological properties including size, shape, and stability. The biogenic AuNPs are polydisperse in nature, with a mean size of 14.92 +/- 5 nm. These AuNPs exhibited promising antimicrobial activity against Escherichia coli NCIM-2065, Bacillus subtilis NCIM-2010, and Penicillium verrucosum MTCC 4935. In vitro quantitative HPLC results revealed that BioAuNPs significantly inhibited the biosynthesis of ochratoxin A (OTA). Microbial fuel cells (MFCs) are intriguing for power generation and wastewater treatment since they can directly transform chemical energy stored in organic matter to electricity by extracellular electron transfer (EET) via membrane proteins. AuNPs also showed excellent potential for dye degradation of organic pollutants, viz., methylene blue (MB), phenol red (PR), bromothymol blue (BTB), Congo red (CR), and 4-nitrophenol (4-NP). All dye removal efficiencies were estimated and fitted to pseudo-first-order processes using kinetic rate constants (Ka).The present study reveals a simple, original, and eco-friendly method for the synthesis of multifunctional biogenic AuNPs that could be effective in OTA detoxification in food products and organic pollutant removal during wastewater treatment for a sustainable environment.
Keywords: Catalytic organic dye degradation; gold nanoparticles; Ochratoxin A; Penicillium rubens; Penicillium verrucosum

Co3O4 for sustainable CO2 reduction and possible fine-tuning towards selective CO production - Ranjan, Ravi; Tekawadia, Jyoti; Jain, Ruchi; Mhamane, Nitin B.; Raja, Thirumalaiswamy; Gopinath, Chinnakonda S. (Chemical Engineering Journal, 2023)
Two main challenges involved in heterogeneous catalytic CO2 reduction are: (a) decreasing the consumption of H2 to the minimum required level with possibly the maximum CO2 conversion, and (b) concurrently enhancing the selectivity of the desired CO, at the cost of methane. Towards meeting these two challenges, Co3O4 spinel has been identified as a potential catalyst and it exhibits predominant CO selectivity > 673 K at atmospheric pressure. CO2 conversion begins > 523 K, with 100% CO selectivity observed > 673 K with CO2:H2 = 3:2. Current work shows a sustainable catalytic CO2 conversion to 100% CO selectivity with Co3O4-Nanocube (NC). Critically, CO selectivity and yield is observed to increase at the cost of methane with smaller amount of H2. 1:1 and 3:2 CO2:H2 ratio exhibits 88-100% CO selectivity with 24-32.5% CO2 conversion between 623 and 823 K. Irrespective of the input CO2:H2, ratio of CO2:H2 uptake changes from around 1:3 at 523 K to 1:1-1.5 at 823 K with concurrent production of significant methane to predominant CO, respectively. Surface electronic state changes was explored by near ambient pressure photoelectron spectroscopy, and the results suggests that Co3O4 is the active phase that promotes CO2 reduction selectively to CO. Broadening observed with the vibrational feature of the CO2 molecules at high temperature underscores the heterogeneous character of the catalyst surface, under operating conditions, due to changing electron density. By optimizing the gas hourly space velocity (GHSV), H2-lean CO2:H2 ratio, and the reaction temperature/pressure, 100% CO selectivity could be broadened to a range of operating conditions.
Keywords: Carbon neutral economy; heterogeneous catalysis; RWGS; SDG; Surface Science

COF-supported zirconium oxyhydroxide as a versatile heterogeneous catalyst for Knoevenagel condensation and nerve agent hydrolysis - Shekhar, Pragalbh; Devulapalli, Venkata Swaroopa Datta; Reji, Reshma; Singh, Himan Dev; Jose, Aleena; Singh, Piyush; Torris, Arun; Vinod, Chatakudath P.; Tokarz III, John A.; Mahle, John J.; Peterson, Gregory W.; Borguet, Eric; et al. (iScience, 2023)
A composite of catalytic Lewis acidic zirconium oxyhydroxides (8 wt %) and a covalent organic framework (COF) was synthesized. X-ray diffraction and infrared (IR) spectroscopy reveal that COF's structure is pre-served after loading with zirconium oxyhydroxides. Electron microscopy confirms a homogeneous distri-bution of nano-to sub-micron-sized zirconium clusters in the COF. 3D X-ray tomography captures the micron-sized channels connecting the well-dispersed zirconium clusters on the COF. The crystalline ZrOx(OH)(y)@COF's nanostructure was model-optimized via simulated annealing methods. Using 0.8 mol % of the catalyst yielded a turnover number of 100-120 and a turnover frequency of 160-360 h(-1) for Knoevenagel condensation in aqueous medium. Additionally, 2.2 mol % of catalyst catalyzes the hy-drolysis of dimethyl nitrophenyl phosphate, a simulant of nerve agent Soman, with a conversion rate of 37% in 180 min. The hydrolytic detoxification of the live agent Soman is also achieved. Our study unveils COF-stabilized ZrOx(OH)(y) as a new class of zirconium-based Lewis + Bronsted-acid catalysts.

Comprehensive molecular and clinical investigation of approved Anti-HCV drugs repurposing against SARS-CoV-2 infection: a glaring gap between benchside and bedside medicine - Bansode, Sneha; Singh, Pawan Kumar; Tellis, Meenakshi; Chugh, Anita; Deshmukh, Narendra; Gupta, Mahesh; Verma, Savita; Giri, Ashok; Kulkarni, Mahesh; Joshi, Rakesh; Chaudhary, Dhruva (Vaccines, 2023)
The limited availability of effective treatment against SARS-CoV-2 infection is a major challenge in managing COVID-19. This scenario has augmented the need for repurposing anti-virals for COVID-19 mitigation. In this report, the anti-SARS-CoV-2 potential of anti-HCV drugs such as daclatasvir (DCV) or ledipasvir (LDP) in combination with sofosbuvir (SOF) was evaluated. The binding mode and higher affinity of these molecules with RNA-dependent-RNA-polymerase of SARS-CoV-2 were apparent by computational analysis. In vitro anti-SARS-CoV-2 activity depicted that SOF/DCV and SOF/LDP combination has IC50 of 1.8 and 2.0 mu M, respectively, comparable to remdesivir, an approved drug for COVID-19. Furthermore, the clinical trial was conducted in 183 mild COVID-19 patients for 14 days to check the efficacy and safety of SOF/DCV and SOF/LDP compared to standard of care (SOC) in a parallel-group, hybrid, individually randomized, controlled clinical study. The primary outcomes of the study suggested no significant difference in negativity after 3, 7 and 14 days in both treatments. None of the patients displayed any worsening in the disease severity, and no mortality was observed in the study. Although, the post hoc exploratory analysis indicated significant normalization of the pulse rate showed in SOF/DCV and SOF/LDP treatment vs. SOC. The current study highlights the limitations of bench side models in predicting the clinical efficacy of drugs that are planned for repurposing.
Keywords: antiviral; COVID-19; daclatasvir; ledipasvir; SARS-CoV-2; sofosbuvir

Continuous hydrogenation of cinnamaldehyde: gas-liquid-liquid-solid helical coil reactor - Khan, Muzammil Y.; Joshi, Sunil S.; Ranade, Vivek V. (Industrial & Engineering Chemistry Research, 2023)
The advantages and challenges of using the gas-liquid-liquid-solid(GLLS) hydrogenation system are discussed in this work using the caseof selective hydrogenation of cinnamaldehyde to cinnamyl alcohol (animportant ingredient in the perfume and flavoring industry). The fourphases in this system include gas (hydrogen)-liquid (organic, reactant+ solvent)-liquid (aqueous KOH)-solid (5% Pt/C catalyst). The additionof second liquid phase, i.e., aqueous KOH significantly increasesselectivity toward cinnamyl alcohol compared to the conventional three-phasehydrogenation. The four-phase GLLS reactions were carried out andoptimized in a continuous helical coil reactor. The role of key aspectssuch as gas solubility, kinetics, flow hydrodynamics, axial dispersion,and mass transfer on the performance of a continuous GLLS reactoris presented and discussed in this work. The presented results anddiscussion will be useful for addressing conflicting demands likelong residence time, low axial dispersion, and high mass transfer.The experimental studies and results of the developed mathematicalmodel indicate that the continuous GLLS helical coil reactor outperformsthe batch operation. The production rates (kg day(-1)) of cinnamyl alcohol achieved in continuous operation were at leastdouble in comparison to batch operation, with 32% less consumptionof precious catalyst (per kg of product). The presented results will open up new opportunities for enhancing selectivity and overall performanceof hydrogenations via introducing a second immiscible liquid phaseand designing continuous tubular reactors for the same.

D-A-D-based unsymmetrical thiosquaraine dye for the dye-sensitized solar cells(dagger) - Jadhav, Avinash P.; Singh, Ambarish Kumar; Maibam, Ashakiran; Krishnamurty, Sailaja; Krishnamoorthy, Kothandam; Nithyanandhan, Jayaraj (Photochemistry and Photobiology, 2023)
In dye-sensitized solar cell, modulating the electronic properties of the sensitizer by varying the donor, pi-spacer, acceptor and anchoring groups help optimizing the structure of the dye for better device performance. Here, a donor-acceptor-donor-based unsymmetrical thiosquaraine sensitizer (SQ5S) has been designed and synthesized. Photophysical, electrochemical, theoretical and photovoltaic characterizations of SQ5S dye have been compared with its oxygen analog, SQ5. The incorporation of the sulfur atom in the acceptor unit of SQ5S dye showed an intense peak at 688 nm, which was 38 nm of red-shifted and showed the panchromatic light harvesting response with the onset of 850 nm compared with SQ5 dye. The LUMO and HOMO energy levels are well aligned with the conduction band of TiO2 and the redox potential of electrolyte for the charge injection and the dye-regeneration processes, respectively. Photovoltaic efficiency of 1.51% (V-OC 610 mV, J(SC) 3.07 mA cm(-2), ff 81%) has been achieved for SQ5S dye, whereas SQ5 showed the device performance of 5.43% (V-OC 723 mV, J(SC) 9.3 mA cm(-2), ff 80%). The decreased device performance for the dye SQ5S has been attributed to the favorable intersystem crossing process associated with the photoexcited SQ5S that reduces the driving force for the charge injection process.

Design and synthesis of photocrosslinker and light blocker based on L-Amino acid polyester and their application in solvent-free resin formulation for DLP/SLA 3D printing - Kamble, Ganesh N.; Joshi, Dheeraj Chandra; Asha, S. K. (Polymers, 2023)
Customising material design for new technological applications like additive manufacturing (AM) is a challenging yet promising approach to create a palette of materials suitable for developing eco-friendly products. LGlutamic acid and L-aspartic acid based aliphatic, photocurable polyester crosslinkers were designed and developed and incorporated into a solvent-free photocurable resin formulation with hydroxyl (ethyl)methacrylate (HEMA). Proof-of-concept 3D printing of clear and transparent objects was demonstrated using digital light processing (DLP) and Stereolithography (SLA) techniques. Resolution of the 3D printed objects could be improved by incorporating a Dansyl labelled L-glutamic acid polyester, which not only aided in modulating the viscosity of the resin formulation but could also function as a light blocker, thereby avoiding polymerization of unwanted areas while 3D printing. The curing kinetics of the photocurable formulation was analyzed using photo differential Scanning Calorimetry. Enzymatic degradability studies of 3D printed films were undertaken in PBS buffer containing esterase enzyme and compared with 3D printed samples using HEMA and a commercial crosslinker (Trimethylolpropane triacrylate (TMPTA)). Scanning electron microscopy (SEM) was used to evaluate the morphology of the 3D printed films before and after enzymatic degradation in the PBS buffer for 60 days. The 3D printed amino acid crosslinked films of HEMA presented high degree of degradation in contrast to the near total absence of any degradation in the 3D printed film crosslinked using TMPTA. The availability of new photocurable formulations that are enzymatically degradable are highly sought after for 3D printing applications.
Keywords: 3D printing; Crosslinker; L -Amino acid Polyester; Light blocker; Photocurable

Developing a feeding assay system for evaluating the insecticidal effect of phytochemicals on Helicoverpa armigera - Mohite, Sharada D.; Patil, Yogita P.; Nichit, Vikram J.; Joshi, Rakesh S. (Jove-Journal of Visualized Experiments, 2023)
Helicoverpa armigera, a lepidopteran insect, is a polyphagous pest with a worldwide distribution. This herbivorous insect is a threat to plants and agricultural productivity. In response, plants produce several phytochemicals that negatively impact the insect's growth and survival. This protocol demonstrates an obligate feeding assay method to evaluate the effect of a phytochemical (quercetin) on insect growth, development, and survival. Under controlled conditions, the neonates were maintained until the second instar on a pre-defined artificial diet. These second-instar larvae were allowed to feed on a control and quercetin-containing artificial diet for 10 days. The insects' body weight, developmental stage, frass weight, and mortality were recorded on alternate days. The change in body weight, the difference in feeding pattern, and developmental phenotypes were evaluated throughout the assay time. The described obligatory feeding assay simulates a natural mode of ingestion and can be scaled up to a large number of insects. It permits one to analyze phytochemicals' effect on the growth dynamics, developmental transition, and overall fitness of H. armigera. Furthermore, this setup can also be utilized to evaluate alterations in nutritional parameters and digestive physiology processes. This article provides a detailed methodology for feeding assay systems, which may have applications in toxicological studies, insecticidal molecule screening, and understanding chemical effects in plant-insect interactions.

Domain shuffling and site-saturation mutagenesis for the enhanced inhibitory potential of amaranthaceae α-amylase inhibitors - Rane, Ashwini S.; Nair, Vineetkumar S.; Joshi, Rakesh S.; Giri, Ashok P. (Protein Journal, 2023)
Amaranthaceae a-amylase inhibitors (AAIs) are knottin-type proteins with selective inhibitory potential against coleopteran a-amylases. Their small size and remarkable stability make them exciting molecules for protein engineering to achieve superior selectivity and efficacy. In this report, we have designed a set of AAI pro- and mature peptides chimeras. Based on in silico analysis, stable AAI chimeras having a stronger affinity with target amylases were selected for characterization. In vitro studies validated that chimera of the propeptide from Chenopodium quinoa a-AI and mature peptide from Beta vulgaris a-AI possess 3, 7.6, and 4.26 fold higher inhibition potential than parental counterparts. Importantly, recombinant AAI chimera retained specificity towards target coleopteran a-amylases. In addition, to improve the inhibitory potential of AAI, we performed in silico site-saturation mutagenesis. Computational analysis followed by experimental data showed that substituting Asparagine at the 6th position with Methionine had a remarkable increase in the specific inhibition potential of Amaranthus hypochondriacus a-AI. These results provide structural-functional insights into the vitality of AAI propeptide and a potential hotspot for mutagenesis to enhance the AAI activity. Our investigation will be a toolkit for AAI's optimization and functional differentiation for future biotechnological applications.
Keywords: & alpha; -Amylase; -Amylase inhibitors; Amaranthaceae; Coleoptera; Peptide; Pest control

Dual routes toward observation of a trans-H2/hydride complex in an iridium pincer system and hydrogenation catalytic activity - Agrawal, Nisha K.; Dash, Soumya R.; Vanka, Kumar; Jagirdar, Balaji R. (Organometallics, 2023)
The Abstraction of chloride from a six- coordinate complex, trans-[ Ir(H)(Cl)((iPr)4)(POCOP)(PPh3)] (1) [((iPr)4)(POCOP) = 2,6-bis(di-iso-propylphosphinito)benzene,kappa(3)-C6H3-1,3-[OP(Pr-i)(2 )](2)], using NaBAr4f leads to the generation of a dinitrogen complex, trans-[Ir(H)(N-2)((iPr)4)(POCOP)(PPh3)][BAr4f] (6). Addition of H-2 to [Ir(H)(N-2)((iPr)4)(POCOP)(PPh3)](+) (6) under extremely mild conditions (1 bar, 298 K) resulted in the reversible coordination of H-2 to generate the cis-[Ir(H)(eta H-2-(2))((iPr)4)(POCOP)(PPh3)](+) (cis-11) complex. The cis-[Ir(H)(eta(2)-H-2)((iPr)4)(POCOP)(PPh3)](+) complex (cis-11) isomerized to a trans isomer, trans-[Ir(H)(eta(2)-H-2)((iPr)4)(POCOP)(PPh3)](+) (trans-11), at 253 K. The isomerization process has been studied and supported by computations. Employing an alternative route, protonation of the trans-[Ir(H)(2)((iPr)4)(POCOP)(PPh3)] complex (2) at 183 K resulted in the formation of an identical, trans-[Ir(H)(eta(2)-H-2)((iPr)4)(POCOP)(PPh3)](+) complex (trans-11); upon warming the sample, the trans-H-2/hydride complex isomerized to the cis isomer above 253 K. Two independent routes to obtain trans-[Ir(H)(eta(2)-H-2)((iPr)4)(POCOP)(PPh3)](+) (trans-11) species have been established. Reaction of trans-[Ir(H)(N-2)((iPr)4)(POCOP)(PPh3)][BAr4f] (6) with C2H4 gave the cis-[Ir(H)(eta(2)-C2H4)((iPr)4)(POCOP)(PPh3)](+) complex (cis-15), which also undergoes isomerization to yield an equilibrium mixture of cis/trans-[Ir(H)(eta(2)-C2H4)((iPr)4)(POCOP)(PPh3)](+) complexes (cis-15 and trans-15) at 253 K. The trans-[Ir(H)(N-2)((iPr)4)(POCOP)(PPh3)](+) complex (6) is an excellent catalyst for hydrogenation of ethylene to ethane under very mild conditions.

Electronic fingerprints for diverse interactions of methanol with various Zn-based systems - Mehta, Shweta; Joshi, Kavita (Surface Science, 2023)
We have investigated various Zn-based catalysts for their interaction with methanol (MeOH). MeOH is one of the most critical molecules being studied extensively, and Zn-based catalysts are widely used in many industrially relevant reactions involving MeOH. We note that the same element (Zn and O, in the present study) exhibits different catalytic activity in different environments. The changing environment is captured in the underlying electronic structure of the catalysts. In the present work, we compared the electronic structure of Zn-based systems, i.e., ZnAl2O4 and ZnO along with oxygen preadsorbed Zn (O-Zn) and metallic Zn. We demonstrate the one-to-one correlation between the pDOS of the bare facet and the outcome of that facet's interaction (i.e. either adsorption or dissociation of MeOH) with MeOH. These findings would pave the way towards the in-silico design of catalysts.
Keywords: DFT; Electronic properties; Methanol; Zn-based systems; ZnO

Electrostatic modulation of intramolecular and intermolecular interactions during the formation of an amyloid-like assembly - Pillai, Meenakshi; Das, Atanu; Jha, Santosh Kumar (Biochemistry, 2023)
The mechanism of protein aggregation can be broadly viewedas ashift from the native-state stabilizing intramolecular to the aggregated-phasesustaining intermolecular interactions. Understanding the role ofelectrostatic forces on the extent of modulation of this switch hasrecently evolved as a topic of monumental significance as proteinaggregation has lately been connected to charge modifications of anaging proteome. To decipher the distinctive role of electrostaticforces on the extremely complicated phase separation landscape, weopted for a combined in vitro-in silico approach to ascertainthe structure-dynamics-stability-aggregabilityrelationship of the functional tandem RRM domains of the ALS-relatedprotein TDP-43 (TDP-43(tRRM)), under a bivariate solutioncondition in terms of pH and salt concentration. Under acidic pH conditions,the native TDP-43(tRRM) protein creates an aggregation-proneentropically favorable partially unfolded conformational landscapedue to enthalpic destabilization caused by the protonation of theburied ionizable residues and consequent overwhelming fluctuationsof selective segments of the sequence leading to anti-correlated movementsof the two domains of the protein. The evolved fluffy ensemble witha comparatively exposed backbone then easily interacts with incomingprotein molecules in the presence of salt via typical amyloid-aggregate-likeintermolecular backbone hydrogen bonds with a considerable contributionoriginating from the dispersion forces. Subsequent exposure to excesssalt at low pH conditions expedites the aggregation process via anelectrostatic screening mechanism where salt shows preferential bindingto the positively charged side chain. The applied target observable-specificapproach complementarity unveils the hidden information landscapeof an otherwise complex process with unquestionable conviction.

Elevated level of glycated KQTALVELVK peptide of albumin is associated with the risk of diabetic nephropathy - Chaurasiya, Arvindkumar H.; Jaiswal, Meera R.; Bayatigeri, Santhakumari; Kahar, Shweta; Tiwari, Shalbha; Unnikrishnan, Ambika G.; Kulkarni, Mahesh J. (ACS Omega, 2023)
Diabetic nephropathyis a leading cause of end-stagerenal disease.Hence, early detection of diabetic nephropathy is essential to mitigatethe disease burden. Microalbuminuria, the currently used diagnosticmarker of diabetic nephropathy, is not efficient in detecting it atan early stage. Therefore, we explored the utility of glycated humanserum albumin (HSA) peptides for risk prediction of diabetic nephropathy.Three glycation-sensitive HSA peptides, namely, FKDLG-EENFK,KQTAL-VELVK, and KVPQVST-PTLVEVSR, with deoxyfructosyllysine(DFL) modification were quantified by targeted mass spectrometry (MS)in a study population comprising healthy and type II diabetes subjectswith and without nephropathy. Mass spectrometry, receiver operatingcharacteristic (ROC) curve, and correlation analysis revealed thatthe DFL-modified KQTALVELVK peptide was better than other glycatedHSA peptides and HbA(1c) for identifying diabetic nephropathy.DFL-modified KQTALVELVK could be a potential marker for risk predictionof diabetic nephropathy.

Ferroelectric polarization and iron substitution synergistically boost electrocatalytic oxygen evolution reaction in bismuth oxychloride nanosheets - Singh, Dinesh; Joshi, Bhavana; Poddar, Pankaj (Langmuir, 2023)
Ferroelectric materials have gained significant interestin variouskinds of water splitting, but the study of ferroelectric materialsfor electrocatalytic water splitting is in its infancy. Ferroelectricmaterials have spontaneous polarization below their Curie temperaturedue to dipolar alignment, which results in surface charges. In 2Dferroelectric materials, spontaneous polarization depends on thickness.Herein, we report that thickness-dependent ferroelectric polarizationin 2D nanosheets can also accelerate the oxygen evolution reaction(OER) along with the tailored active surface area of exposed crystallinefacets, which improves the electrocatalytic activity relatively. Iron-substitutedBiOCl nanosheets of varying thickness are fabricated by varying thepH using a facile coprecipitation method. The substituted iron enhancespolarization and electrochemical active sites on the surface. Thefindings in this study show that the exposed (001) facet and higherthickness of the nanosheets have high ferroelectric polarization and,in turn, superior electrocatalytic activity and remarkable stability,requiring low overpotentials (348 mV and 270 mV at 100 mA/cm(2) and 10 mA/cm(2)) in alkaline (1.0 M KOH) electrolyte. Asthe thickness of the nanosheets is decreased from 140 to 34 nm, theelectrocatalytic performance of iron-substituted BiOCl nanosheetsstarts to reduce due to the lower Coulomb-Coulomb interactionand the increasing depolarization.

G4-binding drugs, chlorpromazine and prochlorperazine, repurposed against COVID-19 infection in hamsters - Roy, Shuvra Shekhar; Sharma, Shalu; Rizvi, Zaigham Abbas; Sinha, Dipanjali; Gupta, Divya; Rophina, Mercy; Sehgal, Paras; Sadhu, Srikanth; Tripathy, Manas Ranjan; Samal, Sweety; Maiti, Souvik; Scaria, Vinod; et al. (Frontiers in Molecular Biosciences, 2023)
The COVID-19 pandemic caused by SARS-CoV-2 has caused millions of infections and deaths worldwide. Limited treatment options and the threat from emerging variants underline the need for novel and widely accessible therapeutics. G-quadruplexes (G4s) are nucleic acid secondary structures known to affect many cellular processes including viral replication and transcription. We identified heretofore not reported G4s with remarkably low mutation frequency across >5 million SARS-CoV-2 genomes. The G4 structure was targeted using FDA-approved drugs that can bind G4s - Chlorpromazine (CPZ) and Prochlorperazine (PCZ). We found significant inhibition in lung pathology and lung viral load of SARS-CoV-2 challenged hamsters when treated with CPZ or PCZ that was comparable to the widely used antiviral drug Remdesivir. In support, in vitro G4 binding, inhibition of reverse transcription from RNA isolated from COVID-infected humans, and attenuated viral replication and infectivity in Vero cell cultures were clear in case of both CPZ and PCZ. Apart from the wide accessibility of CPZ/PCZ, targeting relatively invariant nucleic acid structures poses an attractive strategy against viruses like SARS-CoV-2, which spread fast and accumulate mutations quickly.
Keywords: Conserved motif; FDA-approved drugs; G-quadruplex binding drugs; hamster model of COVID-19; RNA G-quadruplex

Green, practical & scalable approach towards the synthesis of valuable α-keto amides using a metal-free catalyst under solvent-free conditions - Bankar, Shubham R.; Ghadge, Sambhaji S.; Jadhav, Vrushali H. (New Journal of Chemistry, 2023)
alpha-Ketoamides are very important motifs as they are present in many natural products, drugs & biologically important molecules. We synthesized a very simple, cheap, eco-friendly & reusable glucose-based carbonaceous material (GCM), which showed high performance as a catalyst in the oxidative cross-dehydrogenative coupling (CDC) reaction of alpha-ketoaldehydes with amines for the synthesis of alpha-ketoamides. The GCM catalyst was also very efficient for one-pot two-step synthesis of alpha-ketoamides from alpha-ketoalcohols as well. The GCM catalyst was able to catalyze alcohol oxidation in alpha-ketoalcohols followed by CDC reaction with amines to form alpha-ketoalcohols. The reactions were found to proceed smoothly at a low temperature of 50 degrees C using a green & economical metal-free catalyst under base-free, ligand-free & solvent-free reaction conditions to get the corresponding alpha-ketoamides in good to excellent yields. The results demonstrated that the GCM catalyst showed acidic as well as superior oxidising catalytic activity due to the presence of a carboxylic acid (-COOH) and hydroxyl (-OH)-enriched carbonaceous framework, which enabled the synthesis of important alpha-ketoamide motifs. The applicability of the catalyst was also evaluated for the synthesis of an anti-HIV agent drug molecule. Greener, cheaper & eco-friendly GCM catalyst as well as catalytic process for synthesis of alpha-Keto Amides.

H-atom site exchange in an iridium trans-dihydrogen/hydride complex, trans-[Ir(H)(?2-H2)(iPr)4(POCOP)(DMAP)]+ - Agrawal, Nisha K.; Gayathridevi, S.; Dash, Soumya R.; Vanka, Kumar; Jagirdar, Balaji R. (Dalton Transactions, 2023)
Treatment of trans-[Ir(H)(N)(2)((iPr)4)(POCOP)(DMAP)][BAr4f] (2) with H-2 (1 bar) under ambient conditions (298 K) results in the formation of a trans-[Ir(H)(?(2)-H-2)((iPr)4)(POCOP)(DMAP)][BAr4f] (3) complex. Complex 3 exhibits H-atom site exchange between the bound H-2 and the hydride ligands which are mutually trans to one another. A plausible mechanism of this exchange involves metal-ligand cooperativity as studied by computations.

Histidinal-based potent antimalarial agents - Meena, Chhuttan L.; Hingamire, Tejashri; Gupta, Tanya; Deshmukh, Bhagyashree; Karmodiya, Krishanpal; Joshi, Rakesh; Shanmugam, Dhanasekaran; Sanjayan, Gangadhar J. (ChemMedChem, 2023)
Herein we report the synthesis and evaluation of peptide-histidinal conjugated drug scaffolds, which have the potential to target the hemoglobin-degrading proteases falcipain-2/3 from the human malaria parasite. Scaffolds with various substitutions were tested for antimalarial activity, and compounds 8 g, 8 h, and 15 exhibited EC50 values of similar to 0.018 mu M, similar to 0.069 mu M, and similar to 0.02 mu M, respectively. Structure-based docking studies on falcipain-2/3 proteases (PDB:2GHU and PDB:3BWK) revealed that compounds 8 g, 8 h, and 15 interact strongly with binding sites of falcipain-2/3 in a substrate-like manner. In silico ADME studies revealed that the molecules of interest showed no or minimal violations of drug-likeness parameters. Further, phenotypic assays revealed that compound 8 g and its biotinylated version inhibit hemoglobin degradation in the parasite food vacuole. The identification of falcipain-2/3 targeting potent inhibitors of the malaria parasite can serve as a starting point for the development of lead compounds as future antimalarial drug candidates.
Keywords: artemisinin; chloroquine; digestive vacuole; docking; falcipains; falciparum; P

Hydrogen from catalytic non-thermal plasma-assisted steam methane reforming reaction - Bajpai, Abhinav; Mehta, Shweta; Joshi, Kavita; Kumar, Sushant (International Journal of Hydrogen Energy, 2023)
Steam methane reforming reaction was carried out in a dielectric barrier plasma reactor. A systematic study is conducted to understand the influence of input power, flow rate, and water for the conversion, yield, and selectivity of the reaction over strategically designed catalysts. In particular, the production rate and selectivity of the products (H2, CO and C2 hydrocarbons) are monitored. CeO2 was used as packing material, mixed with oxides of manganese or copper and their combination. The optimum Cu/CeO2 catalyst illustrated the production rate of 248.7 mmolg-1h-1 and 11.25 mmolg-1h-1 for H2, and CO, respectively at specific energy input of 19.8 JL-1. DFT calculations exhibit apparent change in electronic structure of the CeO2 after inclusion of oxides of manganese and copper that enhance interaction with methane. Based on these findings, a plausible mechanism is elucidatedSteam methane reforming reaction was carried out in a dielectric barrier plasma reactor. A systematic study is conducted to understand the influence of input power, flow rate, and water for the conversion, yield, and selectivity of the reaction over strategically designed catalysts. In particular, the production rate and selectivity of the products (H2, CO and C2 hydrocarbons) are monitored. CeO2 was used as packing material, mixed with oxides of manganese or copper and their combination. The optimum Cu/CeO2 catalyst illustrated the production rate of 248.7 mmolg-1h-1 and 11.25 mmolg-1h-1 for H2, and CO, respectively at specific energy input of 19.8 JL-1. DFT calculations exhibit apparent change in electronic structure of the CeO2 after inclusion of oxides of manganese and copper that enhance interaction with methane. Based on these findings, a plausible mechanism is elucidated which can help to design catalyst for other applications in non-thermal plasma atmosphere. & COPY; 2023 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Keywords: DFT; Dielectric barrier discharge; Non-thermal plasma; selectivity; Specific energy input; Steam methane reforming

Identification of G-quadruplex structures in MALAT1 lncRNA that interact with nucleolin and nucleophosmin - Ghosh, Arpita; Pandey, Satya Prakash; Joshi, Dheeraj Chandra; Rana, Priya; Ansari, Asgar Hussain; Sundar, Jennifer Seematti; Singh, Praveen; Khan, Yasmeen; Ekka, Mary Krishna; Chakraborty, Debojyoti; Maiti, Souvik (Nucleic Acids Research, 2023)
Nuclear-retained long non-coding RNAs (lncRNAs) including MALAT1 have emerged as critical regulators of many molecular processes including transcription, alternative splicing and chromatin organization. Here, we report the presence of three conserved and thermodynamically stable RNA G-quadruplexes (rG4s) located in the 3 & PRIME; region of MALAT1. Using rG4 domain-specific RNA pull-down followed by mass spectrometry and RNA immunoprecipitation, we demonstrated that the MALAT1 rG4 structures are specifically bound by two nucleolar proteins, Nucleolin (NCL) and Nucleophosmin (NPM). Using imaging, we found that the MALAT1 rG4s facilitate the localization of both NCL and NPM to nuclear speckles, and specific G-to-A mutations that disrupt the rG4 structures compromised the localization of both NCL and NPM in speckles. In vitro biophysical studies established that a truncated version of NCL (& UDelta;NCL) binds tightly to all three rG4s. Overall, our study revealed new rG4s within MALAT1, established that they are specifically recognized by NCL and NPM, and showed that disrupting the rG4s abolished localization of these proteins to nuclear speckles

Insights into the synthesis and kinetics of silver-on-silica core-shell particles - Jundale, Rajashri B.; Bari, Atul H.; Kulkarni, Amol A. (Langmuir, 2023)
In this study, a heterogeneous nucleation and growthmodel hasbeen developed to explore the formation mechanism of silver-depositedsilica core-shell particles based on the reaction kinetics.To validate the core-shell model, the time-dependent experimentaldata were quantitatively examined and in situ reduction,nucleation, and growth rates were estimated by optimizing the concentrationprofiles of reactants and deposited silver particles. Using this model,we also attempted to predict the change in the surface area and diameterof core-shell particles. The concentration of the reducingagent, metal precursor, and reaction temperature were found to havea strong influence on the rate constants and morphology of core-shellparticles. Higher rates of nucleation and growth often produced thick,asymmetric patches that covered the entire surface, whereas lowerrates produced sparsely deposited silver particles with a sphericalshape. The result revealed that by simply tuning the process parametersand controlling the relative rates, the morphology of deposited silverparticles and the surface coverage can be controlled while retainingthe spherical shape of the core. The present study aims to offer comprehensivedata pertaining to the nucleation, growth, and coalescence processesof core-shell nanostructures which will aid in the developmentand understanding of the principles that govern the formation of nanoparticle-coatedmaterials.

Investigating the ferrimagnetic behaviour of trigonal 3C Fe7S8 nanoparticles - Jyotsna, Shubhra; Poddar, Pankaj (Bulletin of Materials Science, 2023)
The magnetic properties of trigonal 3C Fe7S8 nanoparticles, synthesized via the thermal decomposition method, are investigated using temperature-dependent zero-field cooled (ZFC) and field-cooled (FC) magnetization (M-T) curves. The M-T data, recorded at 100 and 1000 Oe, reveal magnetic ordering with high Curie transition temperature (T-C > 300 K) in the specimen. The magnetization vs. applied magnetic field (M-H) data measured in the temperature range from 7 to 300 K show that the compound exhibits ferrimagnetic ordering. The values of coercivity (H-C), saturation magnetization (M-60 kOe) and remanent magnetization (M-R) appear to increase at lower measuring temperatures. As the result of increasing M-60 kOe at lower measuring temperatures, within the temperature range of 7 to 300 K, the maximum energy product (BHmax) has the highest value of 128 kG Oe at 7 K.
Keywords: anisotropy; energy product; Fe7S8; ferrimagnetism; Pyrrhotites; trigonal phase

Lead-free solid state mechanochemical synthesis of Cs2NaBi1-XFeXCl6 double perovskite: reduces band gap and enhances optical properties - Udavant, Rohini; Thawarkar, Sachin; Rondiya, Sachin; Shelke, Ankita; Aher, Rahul; Ajithkumar, Thalasseril G.; Cross, Russell W.; Dzade, Nelson Y.; Jadkar, Sandesh (Inorganic Chemistry, 2023)
Efficient and stable lead-free halide double perovskites (DPs) have attracted great attention for the future generation of electronic devices. Herein, we have developed a doping approach to incorporate Fe3+ ions into the Cs2NaBiCl6 crystal unit and reveal a crystallographic and optoelectronic study of the Cs2NaBi1-xFexCl6 double perovskite. We report a simple solid-state mechanochemical method that has a solvent-free, one-step, green chemistry approach for the synthesis of Cs2NaBi1-xFexCl6 phosphor. The analysis of powder X-ray diffraction (XRD) data determines the contraction of the lattice due to the incorporation of Fe3+ cations, and this effect is well supported by X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FE-SEM), Raman spectroscopy, and solid-state nuclear magnetic resonance spectroscopy (ss-NMR). The band gap is reduced with increasing Fe content owing to the strong overlap of the Fe-3d orbitals with Cl-3p orbitals and shift of the valence band maxima (VBM) toward higher energies, as confirmed by ultraviolet photoelectron spectroscopy (UPS) and density functional theory (DFT) analyses. Photoluminescence (PL) studies of Cs2NaBi1-xFexCl6 phosphors exhibit a large Stokes shift, broadband emission, and increased PL intensity more than ten times for 15% of Fe content phosphor with enhancement in the average decay lifetimes (up to 38 ns) compared to pristine Cs2NaBiCl6 DP. These results indicate that the transition of dark self-trapping of excitons (STEs) into bright STEs enhances yellow emission. XRD, UV, and thermo-gravimetric analysis (TGA) confirmed that the Cs2NaB1-xFexCl6 DPs have good structural and thermal stabilities. Our findings indicate that the doping of Fe3+ cations into the Cs2NaBiCl6 lattice is a constructive strategy to enhance significantly the optoelectronic properties of these phosphors.

Made to measure squaramide COF cathode for zinc dual-ion battery with enriched storage via redox electrolyte - Kushwaha, Rinku; Jain, Chitvan; Shekhar, Pragalbh; Rase, Deepak; Illathvalappil, Rajith; Mekan, Deep; Camellus, Augastus; Vinod, Chathakudath Prabhakaran; Vaidhyanathan, Ramanathan (Advanced Energy Materials, 2023)
Aqueous rechargeable batteries are promising grid-scale energy storage devices because of their affordability, operational safety, and environmental benignity. Among these, Zn-ion batteries (ZIBs) have unfolded new horizons. Designing superior cathodes for ZIBs is crucial. Covalent organic frameworks (COFs) can be made redox active with a high storage surface. Here, for the first time, a chelating COF with redox-active ZnI2 in a ZnSO4(aq) electrolyte is combined. Including iodide harvests an approximately threefold enhancement in capacity from 208 to 690 mAh g(-1) at 1.5 A g(-1), the highest among all the COF-derived ZIBs. Remarkably, a charge-discharge curve at 1.3 V exhibits very limited dropout voltage and super-flat platform, with a remarkable capacity of 600 mAh g(-1) at 5 A g(-1) stable up to 6000 cycles, confirming that the polyiodide generation and storage are sustainable. The COF's dual-ion storage (Zn2+ and polyidode) delivers a ZIB with the highest energy density. Spectro-electrochemical measurements coupled with X-ray photoelectron spectroscopy unambiguously unveil the existence of multiple polyiodide species, with I-3(-) and IO3- ions as the prominent species. The latter gets reduced at the COF electrode under an applied potential, leaving I-3(-) as the major species stored on the COF. The prospect of COF-polyiodide((aq)) is a windfall for metal-ion batteries.
Keywords: covalent organic frameworks; flexible batteries; polyiodide; redox electrolytes; Zn ion batteries

MeGen-generation of gallium metal clusters using reinforcement learning - Modee, Rohit; Verma, Ashwini; Joshi, Kavita; Priyakumar, U. Deva (Machine Learning-Science and Technology, 2023)
The generation of low-energy 3D structures of metal clusters depends on the efficiency of the search algorithm and the accuracy of inter-atomic interaction description. In this work, we formulate the search algorithm as a reinforcement learning (RL) problem. Concisely, we propose a novel actor-critic architecture that generates low-lying isomers of metal clusters at a fraction of computational cost than conventional methods. Our RL-based search algorithm uses a previously developed DART model as a reward function to describe the inter-atomic interactions to validate predicted structures. Using the DART model as a reward function incentivizes the RL model to generate low-energy structures and helps generate valid structures. We demonstrate the advantages of our approach over conventional methods for scanning local minima on potential energy surface. Our approach not only generates isomer of gallium clusters at a minimal computational cost but also predicts isomer families that were not discovered through previous density-functional theory (DFT)-based approaches.
Keywords: gallium clusters; reinforcement learning; structure generation

MnXWO4 nanostructure-based catalysts for single-step oxidation of cyclohexane and methane to oxygenates - Prabu, Marimuthu; Manikandan, Marimuthu; Samal, Pragnya Paramita; Gurrala, Lakshmi Prasad; Mekala, Siva Prasad; Archana, Ramakrishnan; Nayak, Chandrani; Bhattacharyya, D.; Jha, S. N.; Krishnamurty, Sailaja; Raja, Thirumalaiswamy (ACS Applied Nano Materials, 2023)
Activation of the C-H bond in cyclohexane (CYH) and methane is a crucial step to obtain desirable oxygenated products using nanostructured catalyst and is a great challenge and an efficient route to mitigate the inauspicious effects of climate change. The active sites were identified using XRD, HR-TEM, SEM, N2 sorption analysis, TPR, Raman, XPS, TGA, in situ DRIFT, XAS, etc. In optimal reaction conditions, 46% of CYH was converted into adipic acid (AA) on MnxWO4 nanostructures within 6 h. The recyclability test confirmed the catalyst heterogeneity, which revealed no appreciable loss of catalytic activity even after three consecutive reactions. In situ DRIFT study reveals that CYH is oxidized to cyclohexanone and cyclohexanol (KA oil) and is further oxidized to AA via carboxylate intermediates. DFT studies disclosed that MnOx species are responsible for the C-H activation of CYH, and the Mn2+/Mn3+ redox centers play a vital role in the absorption of KA oil to form AA. Herein, we demonstrated the significant role of the ``MnOx'' species and that adequate Lewis and Bronsted acidic sites, redox centers of (Mn2+/Mn3+), and lattice oxygen are accountable for the CYH conversion toward the AA. Additionally, we have reported the oxidation of methane to methanol (146 mu mole per gram of catalyst) in the presence of water at 75 degrees C without over-oxidation products.
Keywords: Adipic Acid; C-H bond activation; Cyclohexane oxidation; methane activation; MnOx chain; Redox center

Morphology-dependent catalysis by Co3O4 nanostructures in atmospheric pressure carbon dioxide hydrogenation - Gupta, Sharad; Jain, Preeti; Jagadeesan, Dinesh; Vinod, C. P. (Journal of Physical Chemistry C, 2023)
In this work, three Co3O4 nanostructureswith different morphologies (cubes, rods, and sheets) were synthesizedusing a hydrothermal method and tested for the CO2 hydrogenationreaction. The physicochemical properties of the structured Co3O4 were well characterized by X-ray diffraction(XRD), Raman spectroscopy, field-emission scanning electron microscopy(FESEM), transmission electron microscopy (TEM), high-resolution transmissionelectron microscopy (HRTEM), hydrogen temperature-programmed reduction(H-2-TPR), and X-ray photoelectron spectroscopy (XPS) techniques.Based on the characterization, cube, rod, and sheet Co3O4 nanostructures were found to expose the (100), (110),and (112) planes, respectively. The effect of cobalt oxide morphologieswith different exposed surfaces on the activity and selectivity towardCO(2) hydrogenation reaction in a plug-flow reactor operatedbetween 200 and 400 & DEG;C under atmospheric pressure conditionswas explored. The results establish a correlation of the catalyticactivity with morphological structures in the order rods > sheets> cubes. H-2-TPR and XPS studies demonstrated that thehighreducibility of Co3O4 rod makes it an excellentcatalyst for CO2 hydrogenation.

Nanopore sequencing of RAGE gene polymorphisms and their association with type 2 diabetes - Chaurasiya, Arvindkumar H.; Khilari, Ajinkya A.; Kazi, Rubina; Jaiswal, Meera R.; Bhoite, Gouri M.; Padwal, Meghana K.; Momin, Abdulrahaman A.; Shanmugam, Dhanasekaran; Kulkarni, Mahesh J. (ACS Omega, 2023)
The receptor foradvanced glycation end products (RAGE)is a transmembraneprotein that interacts with its ligands, advanced glycation end products(AGEs). AGEs are elevated in diabetes and diabetic complications,leading to increased oxidative stress and activation of pro-inflammatorypathways facilitated by AGE-RAGE signaling. Polymorphisms inthe RAGE gene can potentially affect AGE-RAGEinteraction and its downstream signaling, which plays a crucial rolein the progression of diabetes and its complications. In this study,we used nanopore sequencing for genotyping of RAGE polymorphism and identified a maximum number of 33 polymorphisms,including two previously unreported novel mutations in a cohort ofhealthy, type 2 diabetics without nephropathy and type 2 diabeticswith nephropathy in order to identify associations. Two novel RAGE polymorphisms in the intron 8 and 3 & PRIME;UTR regionat genomic locations 32181834 and 32181132, respectively, were detectedwith a low frequency. For four previously reported polymorphisms,cross-validation by PCR-RFLP showed 99.75% concordance with nanoporesequencing. Analysis of genotype distribution and allele frequenciesrevealed that five single nucleotide polymorphisms, i.e., rs1800625,rs3131300, rs3134940, rs2070600, and rs9391855, were associated withan increased risk for type 2 diabetes.

Nanosilica from Averrhoa bilimbi juice pre-treated rice husk: preparation and characterization - Dominic, C. D. Midhun; Neenu, K. V.; Begum, P. M. Sabura; Joseph, Rani; Rosa, Derval dos Santos; Duan, Yongxin; Balan, Aiswarya; Ajithkumar, T. G.; Soumya, Mary; Shelke, Ankita; Parameswaranpillai, Jyotishkumar; Badawi, Michael (Journal of Cleaner Production, 2023)
The preparation of nanosilica from rice husk without using any concentrated mineral acids is a novel concept. This work proposes a bioleaching strategy to remove metallic impurities from rice husk for the preparation of nanosilica. Herein, nanosilica (BJRHS) was prepared by calcinating Averrhoa bilimbi juice pre-treated rice husks in a muffle furnace. The chemical and atomic structures of commercial precipitated silica (CS), rice husk ash (RHA), and BJRHS were analyzed using different analytical techniques. The optimal leaching time, calcination temperature, and calcination time were 1 h, 500 degrees C, and 6 h respectively. The particle size of BJRHS was found to be 6-12 nm, which is less than that of RHA and CS. The BET surface area of BJRHS (204 m2/g) was found to be greater than RHA (110.5 m2/g) and CS (172.1 m2/g). Mesoporous nanosilica with excellent surface area and purity was produced sustainably from rice husk which could be recommended to use in the field of catalysis, polymer technology, etc.
Keywords: Averrhoa bilimbi juice; Bioleaching; Nanosilica; rice husk

Organic field effect transistors comprising copolymers synthesized without structure-directing moieties with enhanced carrier mobility - Swain, Gitanjali; Javaregowda, Bharathkumar H.; Dambhare, Neha V.; Krishnamoorthy, Kothandam (ACS Applied Electronic Materials, 2023)
Conjugated materials are synthesized by C-C bond formation reactions. Trimethyltin and boronic acid are two widely used structure-directing moieties. While using the ethynyl moiety as a part of the monomer, additional structure-directing moieties are not needed. However, ethynylene will be part of the conjugated material. Often, the polymers with an ethynylene moiety negatively impact the polymers' properties. However, the ethynylene moiety could minimize the dihedral angle if the monomer has steric functionalities. For example, BODIPY is an attractive monomer due to its high molar extinction coefficient, partial quinoidal character, and high quantum yield. However, materials based on BODIPY exhibited poor charge carrier mobility due to steric hindrance generated by four methyl groups. Herein, we copolymerize BODIPY with ethynylene comprising i-indigo and thieno-i-indigo. The copolymer with thieno-i-indigo showed increased molecular weight and significantly reduced band gap compared to the copolymer with i-indigo. The copolymer with i-indigo showed immeasurably low hole transport mobility. On the other hand, the copolymer with thieno-i-indigo exhibited 0.003 cm2V(-1) s(-1). These measurements were made using field effect transistors. We also measured the charge carrier mobility using the space charge-limited current method. Both copolymers exhibited a mobility of 10(-3) cm(2) V-1 s(-1).
Keywords: acetylene linkage; BODIPY; field effect transistor; iso-indigo; Sonogashira coupling; thienoisoindigo

Oxidation of ethylene by Cu/TiO2: reducibility of Cu2+ in TiO2 as a possible descriptor of catalytic efficiency - Rajendran, K.; Sharma, Mandeep; Jaison, Augustine; Ankitha, Menon; Tiwari, Ankit D.; Vinod, C. P.; Jagadeesan, Dinesh (Catalysis Science & Technology, 2023)
Catalytic oxidation using non-noble metal-based catalysts is a promising approach to mitigate pollution due to VOCs in the air. In this work, mesoporous Cu/TiO2 catalysts containing different concentrations of Cu2+ (0.2, 1, 3, and 4 wt% Cu w.r.t. Ti) were synthesized using the sol-gel technique. The catalysts were characterized using inductively coupled plasma-optical emission spectrometry, XRD, Raman spectroscopy, N-2 physisorption, cyclic voltammetry, H-2-TPR and electron microscopy to understand the structure and composition. The thermal catalytic gas phase oxidation of ethylene was studied by heating a mixture of ethylene (1.5 vol%) and air (5.9 vol%) in the presence of the Cu/TiO2 samples in the temperature range of 298 to 773 K. Cu/TiO2 showed a higher catalytic activity compared to TiO2 for the thermal oxidation of ethylene, indicating a strong promotion by doped copper ions. A volcanic behaviour in the catalytic activity was observed with different concentrations of Cu doping, with 1% Cu/TiO2 showing a 99.5% ethylene conversion at 673 K and 100% selectivity to CO2. The activity of 1% Cu/TiO2 remained consistent without deactivation for 24 h. At low dopant concentrations of Cu (0.2 and 1% Cu/TiO2), the reduction of Cu2+ to Cu+ was observed. An interplay of oxygen vacancies (O-V), Cu+, Cu2+ and Ti4+ may be involved in controlling the activity. DRIFT studies indicated the formation of surface bidendate carbonate as a possible intermediate.

Parallel evolution of cannabinoid biosynthesis - Berman, Paula; de Haro, Luis Alejandro; Jozwiak, Adam; Panda, Sayantan; Pinkas, Zoe; Dong, Younghui; Cveticanin, Jelena; Barbole, Ranjit; Livne, Rotem; Scherf, Tali; Shimoni, Eyal; Levin-Zaidman, Smadar; et al. (Nature Plants, 2023)
This study reveals a cannabinoid biosynthetic pathway in Helichrysum umbraculigerum, a plant genetically distant from Cannabis, providing a potential source of new cannabinoids and metabolic engineering tools. Modulation of the endocannabinoid system is projected to have therapeutic potential in almost all human diseases. Accordingly, the high demand for novel cannabinoids stimulates the discovery of untapped sources and efficient manufacturing technologies. Here we explored Helichrysum umbraculigerum, an Asteraceae species unrelated to Cannabis sativa that produces Cannabis-type cannabinoids (for example, 4.3% cannabigerolic acid). In contrast to Cannabis, cannabinoids in H. umbraculigerum accumulate in leaves' glandular trichomes rather than in flowers. The integration of de novo whole-genome sequencing data with unambiguous chemical structure annotation, enzymatic assays and pathway reconstitution in Nicotiana benthamiana and in Saccharomyces cerevisiae has uncovered the molecular and chemical features of this plant. Apart from core biosynthetic enzymes, we reveal tailoring ones producing previously unknown cannabinoid metabolites. Orthology analyses demonstrate that cannabinoid synthesis evolved in parallel in H. umbraculigerum and Cannabis. Our discovery provides a currently unexploited source of cannabinoids and tools for engineering in heterologous hosts.

Photocatalytic setup for in situ and operando ambient-pressure X-ray photoelectron spectroscopy at MAX IV Laboratory - Klyushin, Alexander; Ghosalya, Manoj; Kokkonen, Esko; Eads, Calley; Jones, Rosemary; Nalajala, Naresh; Gopinath, Chinnakonda S.; Urpelainen, Samuli (Journal of Synchrotron Radiation, 2023)
The Ambient-Pressure X-ray Photoelectron Spectroscopy (APXPS) endstation at the SPECIES beamline at MAX IV Laboratory has been improved. The latest upgrades help in performing photo-assisted experiments under operando conditions in the mbar pressure range using gas and vapour mixtures whilst also reducing beam damage to the sample caused by X-ray irradiation. This article reports on endstation upgrades for APXPS and examples of scientific cases of in situ photocatalysis, photoreduction and photo-assisted atomic layer deposition (photo-ALD).
Keywords: APXPS; photo-ALD; Photocatalysis; solar simulator

Photoinduced CO2 and N2 reductions on plasmonically enabled gallium oxide - Ojha, Niwesh; Thakkar, Kavita; Bajpai, Abhinav; Joshi, Kavita; Kumar, Sushant (Journal of Colloid and Interface Science, 2023)
Ag-containing ZnO/ b-Ga2O3 semiconductor, which exhibit reduced bandgap, increased light absorption, and hydrophilicity, have been found to be useful for photocatalytic CO2 reduction and N2 fixation by water. The charge-separation is facilitated by the new interfaces and inherent vacancies. The Ag@GaZn demonstrated the highest photocurrent response, about 20-and 2.27-folds that of the Ga and GaZn sam-ples, respectively. CO, CH4, and H2 formed as products for photo-reduction of CO2. Ag@GaZn catalyst exhibited the highest AQY of 0.121 % at 400 nm (31.2 W/m2). Also, Ag@GaZn generated 740 lmolg-1 of NH4+ ions, which was about 18-folds higher than Ga sample. In situ DRIFTS for isotopic-labelled 13CO2 and 15N2 reaffirmed the photo-activity of as-synthesized catalysts. Density functional theory pro-vided insight into the relative affinity of different planes of heterostructures towards H2O, CO2 and N2 molecules. The structure-photoactivity rationale behind the intriguing Ag@GaZn sample offers a funda-mental insight into the role of plasmonic Ag and design principle of heterostructure with improved pho-toactivity and stability.(c) 2022 Elsevier Inc. All rights reserved.
Keywords: CO2 reduction; DRIFTS density functional theory; hydrophilicity; Photocurrent response

Quantum dot (Aun/Agn, n=3-8) capped single lipids: interactions and physicochemical properties - Maneri, Asma H. H.; Varode, Shruti Suhas; Maibam, Ashakiran; Ranjan, Priyatosh; Krishnamurty, Sailaja; Joshi, Krati (Physical Chemistry Chemical Physics, 2023)
Realizing the potential of nano-hybrid biomaterials in various applications (nanoprobes to drug delivery), special attention has been devoted towards their synthesis and development. Nonetheless, several questions pertaining to the interface chemistry between the constituent entities (biomolecules and organic/inorganic part) of these hybrids, still remain unresolved. Keeping these unsolved issues in mind, the present theoretical investigation focuses on determining the electronic/physicochemical properties and interactions within gold and silver quantum dot-capped single lipid molecules. Quantum dots of varying sizes and shapes have been chosen and then coupled with lipid molecules (1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC), 1,2-dimyristoyl-sn-glycero-3-phosphoethanolamine (DMPE), 1,2-dimyristoyl-sn-glycero-3-phosphoglycerol, sodium salt (DMPG)), at the choline/glycerol, carboxylate and phosphate site. It has been identified that Au Qds interact strongly as compared to Ag clusters. In addition to the type, the shape and size of the Qd also influences their attachment with lipids. Among various sites, the phosphate site provides a considerably stronger platform for the coupling of Qds. On the other hand, attachment at the choline site leads to significantly lower interaction energies. The trend noted in interaction energies coincides with the structure-electronic property analysis (interatomic bond distances, charge transfer, PO2- stretching frequencies), which further helps in deducing the nature of interactions. The molecular dynamics simulations performed on selected Qd-lipid complexes established that the Qd interacting with lipids at the phosphate site remains fairly stable at room temperature without undergoing fragmentation into individual components. On the other hand, at the choline site, the Qd-to-lipid coupling is unstable and therefore they experience disintegration at 300 K temperature. Additionally, a unique glycerol-to-phosphate site crossover is evidenced, which reaffirms that the phosphate site is selectively preferred by Qds for binding with lipid molecules.

Reaction pathways and kinetics of N-acetyl-d-glucosamine hydrolysis in sub- and supercritical water - Kulkarni, Sphurti P. P.; Joshi, Sunil S. S.; Kulkarni, Amol A. A. (New Journal of Chemistry, 2023)
Subcritical and supercritical water hydrolysis of N-acetyl-d-glucosamine (NAG) to value-added chemicals has been studied in detail. Experiments were carried out using a continuous flow reactor by varying temperature (250-400 degrees C), pressure (5-25 MPa) and residence time (2-60 s). A wide product distribution was obtained during the reactions, including solid, liquid and gaseous compounds, sensitive to the state of water: sub- or supercritical. Subcritical conditions promoted the formation of solid compounds, whereas gasification was favored in supercritical water. The prominent products present in the liquid fraction were glycolic acid, acetic acid, formic acid, 5-HMF and acetamide. The formation of a few distinct nitrogen-containing heterocyclic compounds was observed only in supercritical water. Following instantaneous deacetylation of NAG, several oxidation, reduction and secondary reactions occur during hydrolysis of NAG in subcritical and supercritical water. A kinetic model for the prediction of yields of acetic acid, glycolic acid and formic acid is developed. The network of reactions showed specifc deviations from conventional understanding. The current findings show that it is possible to develop a suitable process to make a set of value-added chemicals from chitinous biomass.

Recyclable Pd nanoparticles immobilized on amine functionalized LDH for the Suzuki-Miyaura cross-coupling reaction - Patil, Seema P. P.; Jadhav, Sanjay N. N.; Inamdar, Firoz A. A.; Ameen, Mohd Aatif; Rode, Chandrashekhar V. V.; Rajmane, Archana S. S.; Kumbhar, Arjun S. S. (Chemical Papers, 2023)
In the present work, we invented a Pd nanoparticle immobilized on an amine-functionalized LDH catalyst (PdNP@NH2LDH-Al-MCM-41) for cross-coupling reactions. The palladium was grafted onto the support by treating the Pd(OAc)(2) with NH2-LDH-Al-MCM-41 in acetone at room temperature. The prepared catalyst was characterized by FT-IR, SEM, TGA, TEM, and XPS techniques. The TEM characterization of the catalyst showed the uniform distribution of PdNPs with sizes ranging from 3 to 6 nm located inside the mesoporous. The Suzuki-Miyaura cross-coupling reaction was used to demonstrate the catalytic efficiency of the prepared PdNPs@NH2-LDH-Al-MCM-41 catalyst. The prepared and analyzed catalyst showed good to excellent activity in the Suzuki-Miyaura cross-coupling reaction of various aryl bromides with different aryl boronic acids in ethanol at 80 degrees C. The catalyst showed TON up to similar to 47 and TOF similar to 47 h(-1). The catalytic results exhibited that the catalyst is completely recoverable with simple filtration. The catalytic efficiency shows a slight decrease in activity for the Suzuki-Miyaura cross-coupling reactions even after five repeated recycles. TEM images of the freshly prepared and reused catalysts (after five catalytic cycles) showed palladium nanoparticles remain unchanged at the end of the reactions. [GRAPHICS] .
Keywords: LDH; PdNPs; Recyclability; Suzuki-Miyaura coupling

Regulation of trehalose metabolism in insects: from genes to the metabolite window - Tellis, Meenakshi B.; Kotkar, Hemlata M.; Joshi, Rakesh S. (Glycobiology, 2023)
Trehalose is a major circulatory sugar in the haemolymph of insects. It provides instant energy and protection against stress. Trehalose metabolism is associated with insect growth and development. The architecture and spatio-temporal expression dynamics of trehalose metabolism and transport genes are key for regulation. These genes are controlled by various transcription factors, largely linked to nutrition, insect development, and metamorphosis. Also, trehalose levels are affected by substrate affinities and modifications of enzymes involved in the pathway. A feedback mechanism involving the precursors and products can regulate trehalose metabolism. Further, the neuroendocrine system controls trehalose levels under normal and stressed conditions by producing different hormones. Hypotrehalosemic hormones work under surplus energy conditions to activate haemolymph trehalose uptake and degradation. In contrast, hypertrehalosemic hormones stimulate trehalose production in the fat body and its transport to the haemolymph. However, trehalose metabolism regulation in insects needs to be studied in detail. This review discusses aspects of trehalose synthesis, transport, and degradation dynamics in developmental transition and stress response. Unraveling the epigenetic factors, transcriptional control and chemical or genetic modulators can provide further insights into the intricate regulation of trehalose in a development- and tissue-specific manner. This molecular information about effectors and regulators of trehalose metabolism can be applied in developing diverse biotechnological applications.
Keywords: Hormone; Insect development; Metabolic regulation; Stress; trehalose

Response of cardiac pulse parameters in humans at various inclinations via 360° rotating platform for simulated microgravity perspective - Jagtap, Sagar; Kumar, Ajay; Mahale, Bhoopesh; Dixit, Jyotsana; Kalange, Ashok E.; Kanawade, Rajesh; Gangal, Shashikala; Vidyasagar, Pandit (NPJ Microgravity, 2023)
On the Earth, the human body is designed and adapted to function under uniform gravitational acceleration. However, exposure to microgravity or weightlessness as experienced by astronauts in space causes significant alterations in the functioning of the human cardiovascular system. Due to limitations in using real microgravity platforms, researchers opted for various ground-based microgravity analogs including head-down tilt (HDT) at fixed inclination. However, in the present study, an investigation of response of various cardiac parameters and their circulatory adaptation in 18 healthy male subjects was undertaken by using an indigenously developed 360 & DEG; rotating platform. Cardiac pulse was recorded from 0 & DEG; to 360 & DEG; in steps of 30 & DEG; inclination using piezoelectric pulse sensor (MLT1010) and associated cardiac parameters were analyzed. The results showed significant changes in the pulse shape while an interesting oscillating pattern was observed in associated cardiac parameters when rotated from 0 & DEG; to 360 & DEG;. The response of cardiac parameters became normal after returning to supine posture indicating the ability of the cardiovascular system to reversibly adapt to the postural changes. The observed changes in cardiac parameters at an inclination of 270 & DEG;, in particular, were found to be comparable with spaceflight studies. Based on the obtained results and the proposed extended version of fluid redistribution mechanism, we herewith hypothesize that the rotation of a subject to head down tilt inclination (270 & DEG;) along with other inclinations could represent a better microgravity analog for understanding the cumulative cardiac response of astronauts in space, particularly for short duration space missions.

Selective one pot multicomponent green synthesis of 3-[(aryl)(arylthio)methyl]-1H-indole derivatives utilizing enhanced Lewis acidic sites of Surfactant-assisted ZnO catalyst - Sangale, Vijay B. B.; Jagtap, Rohidas M. M.; Mali, Bhupendra P. P.; Gonnade, Rajesh G. G.; Pardeshi, Satish K. K. (ChemistrySelect, 2023)
Five different ZnO nanocrystallites (ZnO-1 to ZnO-5) were successfully synthesized by a surfactant-assisted hydrothermal technique using various surfactants. All the ZnO nanocrystallites are thoroughly characterized by XRD, IR, UV-DRS spectroscopy and FESEM-EDS analysis. Among the synthesized ZnO nanocrystallites, the CTAB-assisted synthesized ZnO-4 exhibited a fine disc-like morphology with a minimum crystallite size (23 nm). Subsequent to reaction optimization studies, the ZnO-4 is utilized as an efficient catalyst for one pot-three component green synthesis of 3-[(aryl)(arylthio)methyl]-1H-indoles (4a-4p) via. condensation of a variety of indoles, aromatic aldehydes and aromatic thiols at room temperature in water. The single-crystal X-ray structure of 3-[(phenyl)(phenylthio)methyl]-1H-indole (4a) is also been reported (CCDC 2170437). The Lewis acidic property of the catalyst-supported probable mechanism is well proposed subsequent to pyridine-IR studies of the ZnO catalysts. Indeed, CTAB-assisted synthesized ZnO-4 was found to be most effective and selective Lewis acid catalyst for the synthesis of a variety of 3-[(aryl)(arylthio)methyl]-1H-indole derivatives in water at ambient temperature with merits like higher yields, lower reaction time, catalyst recovery and reuse.
Keywords: 3-[(aryl)(arylthio)methyl]-1H-indole; green synthesis; Lewis acidity; Single crystal; ZnO

Shapeshifter TDP-43: molecular mechanism of structural polymorphism, aggregation, phase separation and their modulators - Doke, Abhilasha A.; Jha, Santosh Kumar (Biophysical Chemistry, 2023)
TDP-43 is a nucleic acid-binding protein that performs physiologically essential functions and is known to un-dergo phase separation and aggregation during stress. Initial observations have shown that TDP-43 forms het-erogeneous assemblies, including monomer, dimer, oligomers, aggregates, phase-separated assemblies, etc. However, the significance of each assembly of TDP-43 concerning its function, phase separation, and aggregation is poorly known. Furthermore, how different assemblies of TDP-43 are related to each other is unclear. In this review, we focus on the various assemblies of TDP-43 and discuss the plausible origin of the structural het-erogeneity of TDP-43. TDP-43 is involved in multiple physiological processes like phase separation, aggregation, prion-like seeding, and performing physiological functions. However, the molecular mechanism behind the physiological process performed by TDP-43 is not well understood. The current review discusses the plausible molecular mechanism of phase separation, aggregation, and prion-like propagation of TDP-43.
Keywords: Amyloid versus non-amyloid; Coacervation; Environmental conditions; Prion-like seeding; Structural heterogeneity; Thermodynamic and kinetic mechanism

Synthesis of N-oxyethylene substituted imidazolium-based zwitterions as a recyclable solvent for cellulose dissolution - Jadhav, Sachin; Ganvir, Vivek; Singh, Madan Kumar; Shanmuganathan, Kadhiravan (Cellulose, 2023)
Cellulose is a readily available, renewable, and natural biomaterial that has the potential to replace synthetic fibres. However, their processing to shaped materials such as fibre or film is still complex and restricted due to its insolubility in most conventional solvents. Herein, we present the synthesis and cellulose dissolution characteristics of a new class of recyclable zwitterions composed of tethered N-oxyethylene substituted imidazolium cation and alkyl carboxylate anion. Investigations on cellulose dissolution showed that increasing the alkyl chain length of carboxylate anion and introduction of oxyethylene unit on imidazolium ring led to better cellulose dissolution ability, and up to 12% (w/w) cellulose could be dissolved in aqueous zwitterions at 105 degrees C. The thermal behavior of zwitterions and their cellulose solutions was characterized by TGA and found to be more stable than the NMMO and Lyocell solutions. Rheological characterization of cellulose solutions revealed viscoelastic behavior and zero shear viscosity of 6-12% (w/w) cellulose solution in hexanoate containing aqueous zwitterion was 555 to 5900 Pa.s at 120 degrees C. The characteristics of cellulose solution indicate its potential for processing to cellulose fibre by extrusion through a tiny spinneret. Physico-chemical analysis of regenerated cellulose indicates that zwitterions cause no adverse effect on cellulose structure and morphology during dissolution. The zwitterions are recovered after the cellulose regeneration process, and the recovery was found to be 99.6% after purification using the ion-exchange method.
Keywords: Carboxylate anion; Cellulose dissolution; Oxyethylene unit; Regenerated cellulose; Rheology; zwitterions

Tale of two waves: Delineating diverse genomic and transmission landscapes driving the COVID-19 pandemic in Pune, India - Niveditha, Divya; Khan, Soumen; Khilari, Ajinkya; Nadkarni, Sanica; Bhalerao, Unnati; Kadam, Pradnya; Yadav, Ritu; Kanekar, Jugal B.; Shah, Nikita; Likhitkar, Bhagyashree; Sawant, Rutuja; Thakur, Shikha; et al. (Journal of Infection and Public Health, 2023)
Background: Modern response to pandemics, critical for effective public health measures, is shaped by the availability and integration of diverse epidemiological outbreak data. Tracking variants of concern (VOC) is integral to understanding the evolution of SARS-CoV-2 in space and time, both at the local level and global context. This potentially generates actionable information when integrated with epidemiological outbreak data.Methods: A city-wide network of researchers, clinicians, and pathology diagnostic laboratories was formed for genome surveillance of COVID-19 in Pune, India. The genomic landscapes of 10,496 sequenced samples of SARS-CoV-2 driving peaks of infection in Pune between December-2020 to March-2022, were determined. As a modern response to the pandemic, a ``band of five'' outbreak data analytics approach was used. This integrated the genomic data (Band 1) of the virus through molecular phylogenetics with key outbreak data including sample collection dates and case numbers (Band 2), demographics like age and gender (Band 3-4), and geospatial mapping (Band 5).Results: The transmission dynamics of VOCs in 10,496 sequenced samples identified B.1.617.2 (Delta) and BA(x) (Omicron formerly known as B.1.1.529) variants as drivers of the second and third peaks of infection in Pune. Spike Protein mutational profiling during pre and post-Omicron VOCs indicated differential rank ordering of high-frequency mutations in specific domains that increased the charge and binding properties of the protein. Time-resolved phylogenetic analysis of Omicron sub-lineages identified a highly divergent BA.1 from Pune in addition to recombinant X lineages, XZ, XQ, and XM. Conclusions: The band of five outbreak data analytics approach, which integrates five different types of data, highlights the importance of a strong surveillance system with high-quality meta-data for understanding the spatiotemporal evolution of the SARS-CoV-2 genome in Pune. These findings have important implica-tions for pandemic preparedness and could be critical tools for understanding and responding to future outbreaks.& COPY; 2023 Published by Elsevier Ltd on behalf of King Saud Bin Abdulaziz University for Health Sciences. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
Keywords: COVID-19; Delta; Omicron; SARS-CoV-2 genomic surveillance; Variant of concern; Whole Genome Sequencing (WGS)

Thermodynamic modulation of folding and aggregation energy landscape by DNA binding of functional domains of TDP-43 - Patni, Divya; Jha, Santosh Kumar (Biochimica Et Biophysica Acta-Proteins and Proteomics, 2023)
TDP-43 is a vital nucleic acid binding protein which forms stress-induced aberrant aggregates in around 97% cases of ALS, a fatal neurodegenerative disease. The functional tandem RRM domain of the protein (TDP-43tRRM) has been shown to undergo amyloid-like aggregation under stress in a pH-dependent fashion. However, the underlying thermodynamic and molecular basis of aggregation and how the energy landscape of folding, stability, and aggregation are coupled and modulated by nucleic acid binding is poorly understood. Here, we show that the pH stress thermodynamically destabilizes the native protein and systematically populates the unfoldedlike aggregation-prone molecules which leads to amyloid-like aggregation. We observed that specific DNA binding inhibits aggregation and populates native-like compact monomeric state even under low-pH stress as measured by circular dichroism, ANS binding, size exclusion chromatography, and transmission electron microscopy. We show that DNA-binding thermodynamically stabilizes and populates the native state even under stress and reduces the population of unfolded-like aggregation-prone molecules which leads to systematic aggregation inhibition. Our results suggest that thermodynamic modulation of the folding and aggregation energy landscape by nucleic-acid-like molecules could be a promising approach for effective therapeutic intervention in TDP-43-associated proteinopathies.
Keywords: Amyloid-like aggregation; Nucleic acid binding; RNA recognition motifs (RRMs); TDP-43; Thermodynamic stability

Trehalose transporter-like gene diversity and dynamics enhances stress response and recovery in Helicoverpa armigera - Tellis, Meenakshi B.; Chaudhari, Bhagyashri Y.; Deshpande, Shweta V.; Nikam, Sanika V.; Barvkar, Vitthal T.; Kotkar, Hemlata M.; Joshi, Rakesh S. (Gene, 2023)
Trehalose is a primary sugar and its distribution across the insect body, regulated by trehalose transporters (TRETs), is essential for sugar metabolism and energy homeostasis. The large diversity of Tret-like sugar trans-porters (ST), belonging to SLC2A transporter family, in polyphagous insects probably contributes to their extremely adaptive nature. We aim to study spatio-temporal expression dynamics and functional relevance of ST transcript variants in the lepidopteran model organism, Helicoverpa armigera. Identification of 69 putative Tret-like HaST transcript variants from databases and their digital gene expression analysis indicated tissue and development-specific expression patterns. Phylogenetic and sequence similarity network analysis of HaSTs signify evolutionary divergence, while motif and structure analysis depicted conserved signatures. In vitro gene expression validation for selected genes depicts that HaST09 and 69 are fat body and haemolymph-specific. While, HaST06, 30, 36 and 57 are developmental stage or sex-specific. HaST69 has high expression in the haemolymph of fifth instar larvae. In the presence of trehalose metabolism inhibitors and abiotic stress, HaSTs expression show dysregulation, indicating their possible association with trehalose metabolism and stress re-covery. In vivo gene silencing of HaST69 resulted in reduced trehalose accumulation in the insect body, sug-gesting its plausible role in sugar metabolism. The overall understanding of HaST diversity and expression dynamics highlights their putative roles in sugar transport during adaptation and stress recovery of insects.
Keywords: Gene expression; Helicoverpa armigera; Stress; Transporter-like; trehalose

Understanding the stability of an unprecedented Si-Be bond within quantum confinement - Maneri, Asma Harun; Krishnamurty, Sailaja; Joshi, Krati (ACS Omega, 2023)
As of today, the Si-Be bond remains underexplored in the literature, and therefore its anomalous behavior continues to be an unsolved puzzle to date. Therefore, the present study aims at evaluating the integrity of an unprecedented Si-Be bond within quantum confinement. To accomplish this, first-principles-based calculation are performed on Be-doped silicon clusters with atomic sizes 6, 7, and 10. Silicon clusters are sequentially doped with one, two, and three Be atoms, and their thermal response is registered in the temperature range of 200-1500 K, which discloses several research findings. During the course of the simulations, the clusters face various thermal events such as solid cluster phase, rapid structural metamorphosis, and fragmentation. Si-Be nanoalloy clusters are noted to be thermally stable at lower temperatures (200-700 K); however, they begins to disintegrate earlier at a temperature as low as 800 K. This lower stability is attributed to the weak nature of Si and Be heteroatomic interactions, which is corroborated from the structural and electronic property analysis of the doped clusters. In addition to this, the performance of Be-doped clusters at finite temperatures is also compared with the thermal response of two other popular systems, viz., C-and B-doped silicon clusters.