00793nas a2200217 4500008004100000022001400041245010500055210006900160260000800229300000900237490000700246653003400253653003200287653002100319100002600340700002300366700003100389700002600420700002000446856010900466 2014 eng d a2053-273300aAdditive induced capture of elusive polymorphs of conformationally flexible Sulfonamides/Sulfoesters0 aAdditive induced capture of elusive polymorphs of conformational cMAY aC7760 v7010aadditive induced polymorphism10aintermolecular interactions10aphase transition1 aShaikh, Samir, Rashid1 aGawade, Rupesh, L.1 aChakravarty, Debamitra, K.1 aPuranik, Vedavati, G.1 aGonnade, Rajesh uhttps://library.ncl.res.in/content/additive-induced-capture-elusive-polymorphs-conformationally-flexible01965nas a2200253 4500008004100000022001400041245013000055210006900185260009200254300001400346490000700360520098300367653002701350653002101377653002201398653001801420653003101438100002601469700001801495700003101513700002001544700002601564856012101590 2014 eng d a0095-897200aSynthesis, characterization, and crystal structure determination of palladacycles of para-substituted 2-thiobenzylazobenzenes0 aSynthesis characterization and crystal structure determination o a4 PARK SQUARE, MILTON PARK, ABINGDON OX14 4RN, OXON, ENGLANDbTAYLOR & FRANCIS LTDcJUN a1702-17140 v673 a

Bichelated neutral palladacycles (1-3), [Pd(L)Cl], were synthesized from reaction of the new potential tridentate (C,N,S) ligands, 2-thiobenzylazobenzene (L-1), 4'-methyl-2-thiobenzylazobenzene (L-2), and 4'-chloro-2-thiobenzylazobenzene (L-3) with sodium tetrachloropalladate(II), Na-2[PdCl4], in ethanol. The compounds were characterized by elemental analysis, FT-IR, H-1 NMR, UV-visible, and thermogravimetric analysis. The crystal structures of L-2 and 1-3 were determined by single-crystal X-ray diffraction. In 1-3, the geometry around palladium remains almost square planar, coordinated to carbon, nitrogen, and sulfur of the ligand forming a bichelated cyclopalladate complex. The C-H center dot center dot center dot Cl type intermolecular hydrogen bonds, weak pi center dot center dot center dot pi, C-H center dot center dot center dot pi, and van der Waals interactions are believed to be the stabilizing forces for the crystal packing of these palladacycles.

10a2-Thiobenzylazobenzene10aCNS-donor ligand10acrystal structure10aPalladacycles10aThermogravimetric analysis1 aBhattacharjee, Tirtha1 aKalita, Mukul1 aChakravarty, Debamitra, K.1 aBarman, Pranjit1 aPuranik, Vedavati, G. uhttps://library.ncl.res.in/content/synthesis-characterization-and-crystal-structure-determination-palladacycles-para01228nas a2200205 4500008004100000022001400041245008900055210006900144260011000213300001400323490000700337520040000344100001700744700002200761700003100783700002600814700003500840700002800875856011900903 2015 eng d a1477-052000aConformational modulation of peptides using beta-amino benzenesulfonic acid ((S)Ant)0 aConformational modulation of peptides using betaamino benzenesul aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcDEC a2087-20910 v133 a

This communication describes the utility of a conformationally restricted aromatic beta-amino acid (2-aminobenzenesulfonic acid, (S)Ant) inducing various folding interactions in short peptides. Sandwiching (S)Ant between diverse amino acid residues was shown to form robust folded architectures featuring a variety of H-bonded networks, suggesting its utility in inducing peptide folding.

1 aPriya, Gowri1 aKotmale, Amol, S.1 aChakravarty, Debamitra, K.1 aPuranik, Vedavati, G.1 aRajamohanan, Pattuparambil, R.1 aSanjayan, Gangadhar, J. uhttps://library.ncl.res.in/content/conformational-modulation-peptides-using-beta-amino-benzenesulfonic-acid-sant-002588nas a2200217 4500008004100000022001400041245013100055210006900186260011000255300001600365490000600381520166900387100002902056700002502085700002502110700003102135700002602166700002902192700002502221856012402246 2015 eng d a2046-206900aRhodium complex with unsymmetrical vicinal diamine ligand: excellent catalyst for asymmetric transfer hydrogenation of ketones0 aRhodium complex with unsymmetrical vicinal diamine ligand excell aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcJUN a51722-517290 v53 a

New unsymmetrical vicinal diamine ligands with systematic variation in the regio and stereo positions in the amine and sulphonamide groups were synthesized from cheap starting material such as norephedrine. Catalytic Asymmetric Transfer Hydrogenation (ATH) of aromatic alkyl ketones has been investigated using transition metal complexes and new derivatives of monotosylated unsymmetrical vicinal diamine ligands using sodium formate as the hydrogen source, in water and methanol. Chiral secondary alcohols were obtained with excellent enantioselectivity (>95% ee) and conversion of ketones (>95%) with [Rh(Cp*)Cl-2](2) and ligand 4 as a catalyst. Enantioselectivity was found to be slightly higher with the use of methanol as a solvent for ATH of ketones with sodium formate as the hydrogen source compared to water as a solvent and was found to be consistent with all the ketones investigated. The reaction mixture is homogeneous in methanol unlike in water, where substrate and product are insoluble in water and form separate phase, sodium formate being soluble in water. The activity and enantioselectivity obtained for ATH of ketones using [Rh(Cp*)Cl-2](2) and unsymmetrical vicinal diamine ligand as catalyst was comparable with the C2 symmetric benchmark ligands like TsDPEN ((1R, 2R)-N-(p-tolylsulfonyl)-1,2-diphenylethylene- diamine), and TsCYDN ((1R, 2R)-N-(p-tolylsulfonyl)-1,2-cyclohexyl, diamine) under similar reaction conditions. To the best of our knowledge, this is first example of the ATH of ketones with good activity and high enantioselectivity with [Rh(Cp*)Cl-2](2) and unsymmetrical vicinal diamine ligands as catalyst systems.

1 aDeshpande, Sudhindra, H.1 aShende, Vaishali, S.1 aShingote, Savita, K.1 aChakravarty, Debamitra, K.1 aPuranik, Vedavati, G.1 aChaudhari, Raghunath, V.1 aKelkar, Ashutosh, A. uhttps://library.ncl.res.in/content/rhodium-complex-unsymmetrical-vicinal-diamine-ligand-excellent-catalyst-asymmetric-004280nas a2200277 4500008004100000022001400041245018000055210006900235260007100304300001400375490000700389520321000396100002303606700003103629700001803660700001903678700002303697700001703720700002003737700001703757700001703774700003503791700002603826700002403852856012603876 2016 eng d a1528-748300aAdditive mediated syn-anti conformational tuning at nucleation to capture elusive polymorphs: remarkable role of extended pi-stacking interactions in driving the self-assembly0 aAdditive mediated synanti conformational tuning at nucleation to a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcAPR a2416-24280 v163 a

Understanding the process of prenucleation clustering at supersaturating stage is of significant importance to envisage the polymorphism in crystalline materials. Preferential formation of a thermodynamically stable crystal form suggests energetically favored patterns of interactions which control molecular aggregation during nucleation. Introduction of additives during crystallization is sometimes used as a suitable strategy to obtain metastable polymorphs in cases where it is not easy to capture the same by conventional crystallization methods. Comparative analysis of energy relationships and intermolecular interactions between thermodynamically stable and metastable crystal forms provides valuable clues about the nature of growth synthons at prenucleation clustering and preferential crystallization of the thermodynamic form. Conformationally flexible sulfonamide/sulfoester derivatives constituting electron rich and electron deficient aromatic rings were synthesized to study the interplay between pi-stacking and hydrogen bonding synthons. We have identified and characterized the thermodynamically stable and metastable elusive polymorphs of aromatic sulfonamides 1 and 2 and sulfoesters 3 and 4. However, these compounds eluded polymorphism during crystallisation from various common solvents/conditions and only produced thermodynamically stable crystals forms (form I crystals). Surprisingly, exploitation of pyrazinamide as an additive in different stoichiometric ratios during crystallization gave elusive polymorphs [three for 1 (form 1II, form 1III, and form 1IV) and one each for 2 (form 2II), 3 (form 3II), and 4 (form 4II)]. Molecules in stable crystal forms of these compounds are linked via extended chains of parallel displaced pi...pi stacking interactions that seem to play a vital role in driving the self-assembly of molecules and subsequently governing the nucleation process. In contrast, molecules in metastable polymorphs are devoid of such extended pi-stacking assemblies. Interestingly, differential scanning calorimetry, hot stage microscopy, and X-ray crystallographic studies confirmed the thermal crystal-to-crystal transition of all three metastable polymorphs of 1 (form 1II, form 1III, and form 1IV) to its thermodynamically stable crystal form (form 1I). Conformational analysis of molecule 1 using density functional theory calculations also validated higher stability for syn conformation (observed in Form 1I crystals) over anti and midway conformations (seen in metastable polymorphs). Melt crystallization of form 1I crystals of 1 on the larger face (001) of delta-pyrazinamide and lattice matching analysis (GRACE) revealed that the layered arrangement of molecules of delta-pyrazinamide (on 001 face) during heterogeneous nucleation acts as a template (heteroepitaxy) to provide a preferential site for the nucleation of new metastable polymorphs by selectively inhibiting the most preferred crystal form from growing into the nucleus. Solution state one- and two-dimensional (NOESY) H-1 NMR, scanning electron microscopy, and a Cambridge Structural Database survey were conducted to substantiate the role of additives during crystallization.

1 aGawade, Rupesh, L.1 aChakravarty, Debamitra, K.1 aKotmale, Amol1 aSangtani, Ekta1 aJoshi, Pranaya, V.1 aAhmed, Awais1 aMane, Manoj, V.1 aDas, Susanta1 aVanka, Kumar1 aRajamohanan, Pattuparambil, R.1 aPuranik, Vedavati, G.1 aGonnade, Rajesh, G. uhttps://library.ncl.res.in/content/additive-mediated-syn-anti-conformational-tuning-nucleation-capture-elusive-polymorphs03043nas a2200229 4500008004100000022001400041245016600055210006900221260011000290300001400400490000600414520208700420100002302507700003102530700002402561700001702585700001602602700002402618700002602642700002202668856012302690 2016 eng d a2046-206900aComparative study of dG affinity vs. DNA methylation modulating properties of side chain derivatives of procainamide: insight into its DNA hypomethylating effect0 aComparative study of dG affinity vs DNA methylation modulating p aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcJAN a5350-53580 v63 a

Procainamide derivatives have been synthesized to investigate the role of side chains in modulating the DNA methylation level in cancer cells and gain insight into its mechanism of action. The synthesized derivatives comprised of flexible (dimethyl), constrained (pyrrolidine, piperidine, morpholine) and planar aromatic (pyridine, phenyl) side chain motifs. The affinity of procainamide and its derivatives towards the deoxyguanosine (dG) base in neutral form has been assessed by performing Differential Pulse Voltammetry (DPV) under physiological conditions. Further, molecular docking with hemimethylated CpG rich DNA acquired from an active mDNMT-1-DNA (PDB ID-4DA4) crystal structure, reveals their preferential non-covalent interaction with dG nucleobase in the intercalation cavity of the minor groove. Differential affinity of the derivatives to dG base in neutral and bound forms (DNA) is correlated with their DNA methylation modulating properties at sub-lethal concentrations. Among all the derivatives, a compound with an aromatic phenyl side chain (1) has shown a highest binding affinity for dG nucleobase in neutral form as well as for partially denatured CpG rich DNA which is attributed to the formation of p/p stacking interaction in addition to N-H/O hydrogen bonding with the pyrimidine ring of dG base. It also shows the highest cytotoxicity and global hypomethylation at a sub-lethal level in the MCF-7 cancer cell line compared to other derivatives and procainamide. A docking study has also illustrated the plausible structural basis of DNA methylation modulating a property of procainamide. Strong association of procainamide with dG bases of partially denatured CpG rich DNA via H-bonding and other non-covalent interactions may alter the active topology of DNA required by the DNA-binding regulatory proteins (e. g. DNMT-1) which is validated by a DNMT-1 inhibition assay. This systematic investigation leads to a new potent alternative to procainamide being found and gives a plausible insight into the DNA hypomethylating effect of procainamide.

1 aGawade, Rupesh, L.1 aChakravarty, Debamitra, K.1 aDebgupta, Joyashish1 aSangtani, E.1 aNarwade, S.1 aGonnade, Rajesh, G.1 aPuranik, Vedavati, G.1 aDeobagkar, D., D. uhttps://library.ncl.res.in/content/comparative-study-dg-affinity-vs-dna-methylation-modulating-properties-side-chain-002698nas a2200289 4500008004100000022001400041245016000055210006900215260007300284300001200357490000900369520162800378653002402006653001602030653002102046653001902067653001902086653001102105100001602116700002002132700001702152700003102169700002402200700002502224700002702249856013202276 2016 eng d a0022-286000aNaphthoquinone based chemosensor 2-(2 `-aminoethylpyridine)-3-chloro-1,4-naphthoquinone: detection of metal ions, X-ray -crystal structures and DFT studies0 aNaphthoquinone based chemosensor 22 aminoethylpyridine3chloro14n aPO BOX 211, 1000 AE AMSTERDAM, NETHERLANDSbELSEVIER SCIENCE BVcJUN a132-1430 v11143 a

Naphthoquinone based Chemosensor 2; 2-(2'-aminoethylpyridine)-3-chloro-1,4-napthoquinone have been synthesized and characterized. Chemosensor 2 crystallizes in the orthorhombic space group Pbcn and shows extensive intramolecular as well as intermolecular hydrogen bonding interactions. Each molecule of Chemosensor 2 showed interaction with five neighboring molecules via C-H center dot center dot center dot N, N-H center dot center dot center dot N, C-H center dot center dot center dot Cl and C-H center dot center dot center dot O interactions. Slipped pi-pi stacking interaction was observed in adjacent quinonoid and benzenoid rings. Chemosensor abilities of Chemosensor 2 ligand have been evaluated with metal ions viz. Cu2+, Ni2+, Zn2+, Co2+, Fe3+, Mn2+, Cr3+, Hg2+, La3+ and Cd2+ in methanol, methanol-water mixture and in presence of mild base triethylamine. Stoichiometry of Chemosensor 2 with metal ions such as Cu2+, Ni2+, Zn2+ and Co2+ ions was determined by Jobs method in methanol and were found as 1:1 for Cu2+ and 2:1 for Ni2+, Zn2+ Co2+. The variation in the metal ligand ratio is observed in aqueous media for Cu2+. Chemosensor 2 can be used selectively for naked eye detection of Cu2+ ions. The association constant obtained in methanol shows the trend Cu2+>Ni2+>Co2+. Cu2+ and two (Ni-1 and Ni-2) Ni2+ complexes were synthesized. Ni-2 complex showed coordination of Chemosensor 2 ligands was through pyridine nitrogen's only. The Chemosensor 2 and its deprotonated forms in methanol, water and triethylamine were also studied by TD-DFT studies. (C) 2016 Elsevier B.V. All rights reserved.

10aAminonaphthoquinone10aChemosensor10ahydrogen bonding10aNaphthoquinone10api-pi stacking10aTD-DFT1 aPatil, Amit1 aWare, Anuja, P.1 aBhand, Sujit1 aChakravarty, Debamitra, K.1 aGonnade, Rajesh, G.1 aPingale, Subhash, S.1 aSalunke-Gawali, Sunita uhttps://library.ncl.res.in/content/naphthoquinone-based-chemosensor-2-2-aminoethylpyridine-3-chloro-14-naphthoquinone-detection