02558nas a2200229 4500008004100000022001400041245008900055210006900144260007100213300001400284490000700298520173600305100002302041700001802064700001802082700001902100700002002119700001702139700002202156700002702178856012302205 2014 eng d a0897-475600aSoft colloidal scaffolds capable of elastic recovery after large compressive strains0 aSoft colloidal scaffolds capable of elastic recovery after large a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcSEP a5161-51680 v263 a

Assemblies of inorganic or glassy particles are typically brittle and cannot sustain even moderate deformations. This restricts the use of such materials to applications where they do not experience significant loading or deformation. Here, we demonstrate a general strategy to create centimeter-size macroporous monoliths, composed primarily (>90 wt %) of colloidal particles, that recover elastically after compression to about one-tenth their original size. We employ ice templating of an aqueous dispersion of particles, polymer, and cross-linker such that cross-linking happens in the frozen state. This method yields elastic composite scaffolds for starting materials ranging from nanoparticles to micron-sized dispersions of inorganics or glassy lattices. The mechanical response of the monoliths is also qualitatively independent of polymer type, molecular weight, and even cross-linking chemistry. Our results suggest that the monolith mechanical properties arise from the formation of a unique hybrid microstructure, generated by cross-linking the polymer during ice templating. Particles that comprise the scaffold walls are connected by a cross-linked polymeric mesh. This microstructure results in soft monoliths, with moduli similar to O (10(4) Pa), despite the very high particle content in their walls. A remarkable consequence of this microstructure is that the monolith mechanical response is entropic in origin: the modulus of these scaffolds increases with temperature over a range of 140 K. We show that interparticle connections formed by cross-linking during ice templating determine the monolith modulus and also allow relative motion between connected particles, resulting in entropic elasticity.

1 aRajamanickam, Raja1 aKumar, Sushma1 aKumar, Deepak1 aGhosh, Shankar1 aKim, Jong, Chul1 aTae, Giyoong1 aGupta, Sayam, Sen1 aKumaraswamy, Guruswamy uhttps://library.ncl.res.in/content/soft-colloidal-scaffolds-capable-elastic-recovery-after-large-compressive-strains-001360nas a2200157 4500008004100000245008600041210006900127260000800196300001600204490000700220520080100227100001801028700001601046700002601062856011401088 2016 eng d00aN-2 activation on Al metal clusters: catalyzing role of BN-doped graphene support0 aN2 activation on Al metal clusters catalyzing role of BNdoped gr cOCT a27721-277270 v183 aThe successful sustenance of life demands an ambient abiotic process for N-2 activation and dissociation. The Bosch-Haber process remains the only abiotic and synthetic means for N-2 activation and its fixation. Metal nanoclusters have been recently reported for activating molecular nitrogen. Interestingly, the metal clusters explored so far for N-2 activation are free clusters and, hence, are practically not applicable by experimental chemists. Using density functional theory (DFT) based methodology, we propose a potential catalytic system for di-nitrogen activation, viz. supported Al clusters. Al clusters supported on BN doped graphene sheets are seen to activate N-2 molecule with a red shift in the N-N stretching frequency up to 874 cm(-1) with activation barriers as low as 1.14 eV.1 aKumar, Deepak1 aPal, Sourav1 aKrishnamurty, Sailaja uhttps://library.ncl.res.in/content/n-2-activation-al-metal-clusters-catalyzing-role-bn-doped-graphene-support02241nas a2200193 4500008004100000022001400041245018100055210006900236260000900305300001200314490000600326520148200332100002301814700001801837700002401855700001601879700002401895856012801919 2016 eng d a2196-735000aStrategic Preparation of Efficient and Durable NiCo Alloy Supported N-Doped Porous Graphene as an Oxygen Evolution Electrocatalyst: A Theoretical and Experimental Investigation0 aStrategic Preparation of Efficient and Durable NiCo Alloy Suppor cOCT  a16005320 v33 a

Development of an efficient and durable water splitting electrocatalyst holds a great commitment for the future energy devices. The real application of oxygen evolution reaction (OER) catalysts mainly suffers from sluggish kinetics and high overpotential except for the Ir and Ru-based systems. However, the high cost and vulnerability of the Ir and Ru metals are the main hostiles to use them for marketization. Herein, a high-performance OER electrocatalyst consisting of NiCo alloy nanoparticles supported on high surface area N-doped porous graphene (NiCo/pNGr(75: 25)) is reported. The importance of the doped-N for achieving the uniform dispersion-cum-effective interaction of the size controlled NiCo alloy nanoparticles has been explicitly investigated by transmission electron microscopy, X-ray diffraction, X-ray photo electron spectroscopy, Raman, density functional theory (DFT) calculations, etc. The electrochemical analysis of NiCo/pNGr(75: 25) shows an overpotential of approximate to 260 mV at 10 mA cm(-2) with a smaller Tafel slope of approximate to 87 mV dec(-1) and long catalytic durability. DFT calculations are done to check the interaction between the NiCo alloy nanoparticles and the defective sites of pNGr and also with the doped-N, which could be attained for maintaining long catalytic durability. Furthermore, NiCo/pNGr(75: 25) is used as an OER catalyst to fabricate an electrolyzer, which works at very low potential of 1.5 V in 1 M KOH.

1 aSingh, Santosh, K.1 aKumar, Deepak1 aDhavale, Vishal, M.1 aPal, Sourav1 aKurungot, Sreekumar uhttps://library.ncl.res.in/content/strategic-preparation-efficient-and-durable-nico-alloy-supported-n-doped-porous-graphene01246nas a2200157 4500008004100000245009900041210006900140260000800209300001600217490000800233520065900241100001800900700002600918700001600944856012800960 2017 eng d00aDissociative adsorption of molecular hydrogen on BN-doped graphene-supported aluminum clusters0 aDissociative adsorption of molecular hydrogen on BNdoped graphen cNOV a26493-264980 v1213 aThe present work demonstrates dissociative adsorption of molecular hydrogen on supported and unsupported aluminum Wclusters (Al-n, n = 4-8, 13) using density functional theory based calculations. The studies reveal that the presence of a BN-doped graphene surface support reduces the dissociative adsorption barrier of the bond in molecular hydrogen on even atom clusters. In particular, supported Al-6 demonstrates a barrier-less dissociative adsorption toward the H-2 molecule. These results demonstrate the excellent potential of supported Al nanoparticles for hydrogen storage and also the potential of doped graphene systems are catalyzing supports.1 aKumar, Deepak1 aKrishnamurty, Sailaja1 aPal, Sourav uhttps://library.ncl.res.in/content/dissociative-adsorption-molecular-hydrogen-bn-doped-graphene-supported-aluminum-clusters01431nas a2200193 4500008004100000022001500041245012700056210006900183260000800252300001600260490000700276520071800283100001801001700002501019700002601044700002701070700001601097856012401113 2018 eng d a 1463-907600aDissociative chemisorption of hydrogen molecules on defective graphene-supported aluminium clusters: a computational study0 aDissociative chemisorption of hydrogen molecules on defective gr cNOV a26506-265120 v203 a

Using periodic density functional theory-based calculations, in the present study, we address the chemical bonding between aluminium clusters (Al-n, n = 4-8 and 13) and monovacant defective graphene. The adsorption strength of the above-mentioned aluminium clusters is fivefold (approximate to 3 to 5 eV) higher on defective graphene as compared to the earlier reported values on non-defective graphene and BN-doped graphene. The Bader charge analysis and different charge densities reveal that this adsorption is driven by significant charge transfer from the Al clusters to defective graphene. Thus, chemisorbed Al clusters demonstrate high activity towards dissociative adsorption of molecular hydrogen.

1 aKumar, Deepak1 aGovindaraja, Thillai1 aKrishnamurty, Sailaja1 aKaliaperumal, Selvaraj1 aPal, Sourav uhttps://library.ncl.res.in/content/dissociative-chemisorption-hydrogen-molecules-defective-graphene-supported-aluminium02528nas a2200205 4500008004100000022001400041245016200055210006900217260000800286300001400294490000700308520174900315100002202064700002302086700001802109700001802127700002402145700002102169856013202190 2019 eng d a1528-748300aCrystal engineering for intramolecular pi-pi stacking: effect of sequential substitution of f on molecular geometry in conformationally flexible sulfonamides0 aCrystal engineering for intramolecular pipi stacking effect of s cOCT a5665-56780 v193 a

A small library of ten sulfonamide derivatives comprising two aromatic rings was synthesized to investigate the effect of chronological positioning of the F-atom on the intramolecular pi-stacking assembly. The sequential positioning of F atoms was carried out on one of the aromatic rings that is linked to the sulfonamide moiety directly while the other aromatic ring (phenyl or pyridine) is linked by an ethyl spacer with the sulfonamide moiety. The ethyl spacer is provided to achieve the required flexibility so that both aromatic rings can bend to acquire syn conformation facilitated pi-stacking between electron-deficient and electron-rich aromatic rings. The idea was to study the interplay between hydrogen bonding and pi-stacking synthons in the conformationally flexible sulfonamide derivatives. The solid-state conformation of all the derivatives was investigated using the single-crystal X-ray diffraction technique. Crystal structure analysis revealed that the syn conformation was achieved only in trifluoro and pentafluoro sulfonamide derivatives with benzene substitution while in all other derivatives the molecules take either midway or anti conformations. None of the sulfonamide molecules with a pyridine moiety showed syn conformation. It could be because of the involvement of the pyridine N-atom in the hydrogen bonding dimeric synthon. The molecular conformation study in solution state using 2D NOESY and HOESY NMR experiments also substantiated syn conformation in a pentafluoro sulfonamide molecule with benzene substitution. The conformational analysis carried out employing density functional theory (DFT) calculations confirmed higher stability for the syn conformation over midway and anti orientations.

1 aShaikh, Samir, R.1 aGawade, Rupesh, L.1 aKumar, Deepak1 aKotmale, Amol1 aGonnade, Rajesh, G.1 aStuerzer, Tobias uhttps://library.ncl.res.in/content/crystal-engineering-intramolecular-pi-pi-stacking-effect-sequential-substitution-f-molecular00759nas a2200205 4500008004100000022001400041245012700055210006900182260000900251300001100260490000700271100002200278700002500300700002500325700001800350700002400368700001900392700002500411856011700436 2021 eng d a0960-894X00aSynthesis and cell imaging applications of fluorescent mono/di/tri-heterocyclyl-2,6-dicyanoanilines (vol 27, pg 979, 2017)0 aSynthesis and cell imaging applications of fluorescent monoditri cJAN  a1277370 v321 aPisal, Mahesh, M.1 aAnnadate, Ritesh, A.1 aAthalye, Meghana, C.1 aKumar, Deepak1 aChavan, Subhash, P.1 aSarkar, Dhiman1 aBorate, Hanumant, B. uhttps://library.ncl.res.in/content/synthesis-and-cell-imaging-applications-fluorescent-monoditri-heterocyclyl-2602247nas a2200301 4500008004100000022001400041245013300055210006900188260000800257300001400265490000600279520122600285653001701511653002201528653002101550653002401571653002101595653002601616100002401642700002601666700002001692700002101712700001801733700001701751700002501768700002301793856012901816 2023 eng d a2574-096200aTheory-directed designing of an intrinsic-activity-modulated metal-doped copper oxide electrode for nitrate to ammonia synthesis0 aTheorydirected designing of an intrinsicactivitymodulated metald cMAY a6111-61190 v63 a

Synthesis of ammonia via electrochemical reduction ofnitrate isone of the most sustainable routes both for environmental protectionas well as energy saving initiatives. However, this process is limitedto the development of high-performance free-standing catalytic electrodeswith improved selectivity and Faradaic efficiency. Herein, we reporttheory-guided designing and fabrication of free-standing non-noblemetal (Mn, Fe, and Co)-doped copper oxide (CuO) electrodes by usinga simple and scalable electrode preparation method. The density functionaltheory (DFT)-based calculations show that the doped-Co sites in theCu surface facilitate the generation and supply of H+ tothe adsorbed NO3 (-) during the reductionprocess; as a result, the Co-CuO catalyst displays higher selectivitytoward nitrate reduction. The Co-doped Cu electrode (Co-CuO)delivers a higher NH3 yield (5492 mu g cm(-2)) at a reduction potential of -0.91 V vs RHE while maintaininga Faradaic efficiency of >95%. The alloying of Co to the coppermetalnot only facilitates the proton donation to the adsorbed reactant(NO3 (-)) but also tunes the Cu d-center,resulting in the active site modulation responsible for the activationof catalysts.

10aActive sites10aammonia synthesis10aelectrocatalysis10aFaradaic efficiency10aHigh selectivity10ametal-doped electrode1 aTyagi, Nitin, Kumar1 aMahapatra, Bikash, K.1 aGhimire, Suvash1 aManna, Narugopal1 aKumar, Deepak1 aKumar, Vijay1 aMukhopadhyay, Kausik1 aSingh, Santosh, K. uhttps://library.ncl.res.in/content/theory-directed-designing-intrinsic-activity-modulated-metal-doped-copper-oxide-electrode02670nas a2200361 4500008004100000022001400041245023500055210007000290260000800360300001000368490000800378520138500386653002601771653002601797653001501823653002501838653001501863653001501878100001701893700001701910700002401927700002001951700001801971700001801989700002702007700003102034700003002065700002002095700001802115700001602133700002502149856013402174 2024 eng d a0168-165600aSustainable bioprocess technology for producing food-flavour (+)-γ-decalactone from castor oil-derived ricinoleic acid using enzymatic activity of Candida parapsilosis: Scale-up optimization and purification using novel composite0 aSustainable bioprocess technology for producing foodflavour γdec cSEP a17-300 v3933 a

Ricinoleic acid (RA) from castor oil was employed in biotransformation of peach-flavoured gamma-decalactone (GDL), using a Candida parapsilosis strain (MTCC13027) which was isolated from waste of pineapple crown base. Using four variables-pH, cell density, amount of RA, and temperature-the biotransformation parameters were optimized using RSM and BBD. Under optimized conditions (pH 6, 10 % of microbial cells, 10 g/L RA at 28 degrees C), the conversion was maximum and resulted to 80 % (+)-GDL (4.4 g/L/120 h) yield in shake flask (500 mL). Furthermore, optimization was achieved by adjusting the aeration and agitation parameters in a 3 L bioreactor, which were then replicated in a 10 L bioreactor to accurately determine the amount of (+)-GDL. In bioreactor condition, 4.7 g/L (>85 %) of (+)-GDL is produced with 20 % and 40 % dissolved oxygen (1.0 vvm) at 150 rpm in 72 h and 66 h, respectively. Further, a new Al-Mg-Ca-Si composite column-chromatography method is developed to purify enantiospecific (+)-GDL (99.9 %). This (+)-GDL is 100 % nature-identical as validated through 14C-radio-carbon dating. Thorough chemical investigation of enantiospecific (+)-GDL is authenticated for its use as flavour. This bioflavour has been developed through a cost-effective biotechnological process in response to the demand from the food industry on commercial scale.

10a(+)-gamma-Decalactone10aAl-Mg-Ca-Si composite10aBioflavour10aCandida parapsilosis10acastor oil10aFood-waste1 aSyed, Naziya1 aSingh, Suman1 aChaturvedi, Shivani1 aKumar, Prashant1 aKumar, Deepak1 aJain, Abhinav1 aSharma, Praveen, Kumar1 aNannaware, Ashween, Deepak1 aChanotiya, Chandan, Singh1 aBhambure, Rahul1 aKumar, Pankaj1 aKalra, Alok1 aRout, Prasant, Kumar uhttps://library.ncl.res.in/content/sustainable-bioprocess-technology-producing-food-flavour-%CE%B3-decalactone-castor-oil-derived