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61.
Ambujakshan KR Madhavan VS Varghese HT Panicker CY Temiz-Arpaci O Tekiner-Gulbas B Yildiz I 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2008,69(3):782-788
FT-IR spectra of 5-methyl-2-(p-methylaminophenyl)benzoxazole was recorded and analysed. The vibrational frequencies of the compound have been computed using the Hartree-Fock/6-31G* basis and compared with the experimental values. 相似文献
62.
Ali MM Aich U Varghese B Pérez S Imberty A Loganathan D 《Journal of the American Chemical Society》2008,130(26):8317-8325
The biological addition of oligosaccharide structures to asparagine residues of N-glycoproteins influences the properties and bioactivities of these macromolecules. The linkage region constituents, 2-acetamino-2-deoxy-beta-D-glucopyranose monosaccharide (GlcNAc) and L-asparagine amino acid (Asn), are conserved in the N-glycoproteins of all eukaryotes. In order to gain information about the structure and dynamics of glycosylated proteins, two chloroacetamido sugars, Glc betaNAcNHCOCH2Cl and Man betaNHCOCH2Cl, have been synthesized, and their crystal structures have been solved. Structural comparison with a series of other models and analogs gives insight about the influence of the N-acetyl group at position C2 on the conformation of the glycan-peptide linkage at C1. Interestingly, this N-acetyl group also influences the packing and network of hydrogen bonds with involvement in weak hydrogen bonds C-H...X that are of biological importance. DFT ab initio calculations performed on a series of models and analogs also confirm that the GlcNAc derivatives present different preferred conformation about the N-CO-CH2-X (chi2) torsion angle of the glycan-peptide linkage, when compared to other monosaccharide derivatives. The energy profiles that have been obtained will be useful for parametrization of molecular mechanics force-field. The conjunction of crystallographic and computational chemistry studies provides arguments for the structural effect of the N-acetyl group at C2 in establishing an extended conformation that presents the oligosaccharide away from the protein surface. 相似文献
63.
Shankar K Mor GK Prakasam HE Varghese OK Grimes CA 《Langmuir : the ACS journal of surfaces and colloids》2007,23(24):12445-12449
Films comprised of 4 microm long titanium dioxide nanotube arrays were fabricated by anodizing Ti foils in an ethylene glycol based electrolyte. A carboxylated polythiophene derivative was self-assembled onto the TiO2 nanotube arrays by immersing them in a solution of the polymer. The binding sites of the carboxylate moiety along the polymer chain provide multiple anchoring sites to the substrate, making for a stable rugged film. Backside illuminated liquid junction solar cells based on TiO2 nanotube films sensitized by the self-assembled polymeric layer showed a short-circuit current density of 5.5 mA cm-2, a 0.7 V open circuit potential, and a 0.55 fill factor yielding power conversion efficiencies of 2.1% under AM 1.5 sun. A backside illuminated single heterojunction solid state solar cell using the same self-assembled polymer was demonstrated and yielded a photocurrent density as high as 2.0 mA cm-2. When a double heterojunction was formed by infiltrating a blend of poly(3-hexylthiophene) (P3HT) and C60-methanofullerene into the self-assembled polymer coated nanotube arrays, a photocurrent as high as 6.5 mA cm-2 was obtained under AM 1.5 sun with a corresponding efficiency of 1%. The photocurrent action spectra showed a maximum incident photon-to-electron conversion efficiency (IPCE) of 53% for the liquid junction cells and 25% for the single heterojunction solid state solar cells. 相似文献
64.
S. Lakshmi K. Subramanian T. Steiner B. Varghese 《Journal of chemical crystallography》1999,29(10):1141-1143
The X-ray crystal structure of the triterpenoid piscidinol-C from the leaves of Walsura piscidia is determined. The compound, which is an apotirucallane derivative, crystallizes in the orthorhombic space group C2221 with a = 18.985(4), b = 13.092(5), c = 24.690(7) Å, and D
calc = 1.209 g cm–1 for Z = 8. 相似文献
65.
Rajnikant V. K. Gupta E.H. Kahn S. Shafi S. Hashmi Shafiullah B. Varghese Dinesh 《Crystal Research and Technology》2001,36(11):1281-1288
The crystal structure of 3b‐acetoxy‐5a‐cholestan‐6‐one‐semicarbazone (C30H51O3N3) has been determined by X‐ray diffraction methods. It crystallizes in the orthorhombic space group P212121 with cell parameters a = 11.641(1), b = 16.552(1) c = 31.181(4) Å and Z = 8. The structure has been refined to an R‐value of 0.050 for 4407 observed reflections. Two molecules in the asymmetric unit have been observed. In both the crystallographically independent molecules, all the three six‐membered rings (A, B and C ) of steroid nucleus exist in chair conformation, while the five‐ membered ring D exists in 13β distorted‐envelope in molecule‐I and 13β, 14α half‐chair conformation in molecule‐II. Three intermolecular N‐H … O hydrogen bonds have been observed. 相似文献
66.
Reactions of PhAsCl2 with BrMg(CH2)nMgBr (n = 4 or 5) in THF gave phenylarsacycloalkanes as colourless oily liquids which could be distilled under vacuum. Treatment of PhAs(CH2)nwith MCl2(RCN)2 (M = Pd or Pt; R = Phor Me) afforded mononuclear complexes, [MCl2{PhAs(CH2)n}2]. Reactions with [Pt2Cl2(μ‐Cl)2(PEt3)2] gave mixed‐ligand complexes, [PtCl2(PEt3){PhAs(CH2)n]. The palladium complexes adopt a trans geometry whereas the platinum complexes exist in a cis configuration. The crystal and molecular structure of [PdCl2(PhAsCH2CH2CH2CH2CH2)2] was determined by X‐ray diffraction methods. The molecule consists of a square‐planar palladium atom with trans chlorides and trans arsa ligands. The six‐membered ‘AsC5′ ring adopts a chair conformation. Copyright © 1999 John Wiley & Sons, Ltd. 相似文献
67.
Slippage of a Porphyrin Macrocycle over Threads of Varying Bulkiness: Implications for the Mechanism of Threading Polymers through a Macrocyclic Ring 下载免费PDF全文
Dr. Alexander B. C. Deutman Dr. Shaji Varghese Mohamed Moalin Dr. Johannes A. A. W. Elemans Prof. Alan E. Rowan Prof. Roeland J. M. Nolte 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(1):360-370
Threading of a polymer through a macrocyclic ring may occur directly, that is, by finding the end of the polymer chain, or by a process in which the polymer chain first folds and then threads through the macrocyclic ring in a hairpin‐like conformation. We present kinetic and thermodynamic studies on the threading of a macrocyclic porphyrin receptor ( H21 ) onto molecular threads that are blocked on one side and are open on the other side. The open side is modified by groups that vary in ease of folding and in bulkiness. Additionally, the threads contain a viologen binding site for the macrocyclic receptor, which is located close to the blocking group. The rates of threading of H21 were measured under various conditions, by recording as a function of time the quenching of the fluorescence of the porphyrin, which occurs when receptor H21 reaches the viologen binding site. The kinetic data suggest that threading is impossible if the receptor encounters an open side that is sterically encumbered in a similar way as a folded polymer chain. This indicates that threading of polymers through macrocyclic compounds through a folded chain mechanism is unlikely. 相似文献
68.
Shujiang Wang Deepanjali Gurav Dr. Oommen P. Oommen Prof. Oommen P. Varghese 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(15):5980-5985
The dynamic covalent‐coupling reaction involving α‐effect nucleophiles has revolutionized bioconjugation approaches, due to its ease and high efficiency. Key to its success is the discovery of aniline as a nucleophilic catalyst, which made this reaction feasible under physiological conditions. Aniline however, is not so effective for keto substrates. Here, we investigate the mechanism of aniline activation in the oxime reaction with aldehyde and keto substrates. We also present carboxylates as activating agents that can promote the oxime reaction with both aldehyde and keto substrates at physiological pH. This rate enhancement circumvents the influence of α‐effect by forming H‐bonds with the rate‐limiting intermediate, which drives the reaction to completion. The combination of aniline and carboxylates had a synergistic effect, resulting in a ~14–31‐fold increase in reaction rate at pD 7.4 with keto substrates. The biocompatibility and efficiency of carboxylate as an activating agent is demonstrated by performing cell‐surface oxime labeling at physiological pH using acetate, which showed promising results that were comparable with aniline. 相似文献
69.
70.
Koushik Saha Benson Joseph Rongala Ramalakshmi Dr. R. S. Anju Dr. Babu Varghese Prof. Sundargopal Ghosh 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(23):7871-7878
Thermolysis of [Cp*Ru(PPh2(CH2)PPh2)BH2(L2)] 1 (Cp*=η5‐C5Me5; L=C7H4NS2), with terminal alkynes led to the formation of η4‐σ,π‐borataallyl complexes [Cp*Ru(μ‐H)B{R‐C=CH2}(L)2] ( 2 a – c ) and η2‐vinylborane complexes [Cp*Ru(R‐C=CH2)BH(L)2] ( 3 a – c ) ( 2 a , 3 a : R=Ph; 2 b , 3 b : R=COOCH3; 2 c , 3 c : R=p‐CH3‐C6H4; L=C7H4NS2) through hydroboration reaction. Ruthenium and the HBCC unit of the vinylborane moiety in 2 a – c are linked by a unique η4‐interaction. Conversions of 1 into 3 a – c proceed through the formation of intermediates 2 a – c . Furthermore, in an attempt to expand the library of these novel complexes, chemistry of σ‐borane complex [Cp*RuCO(μ‐H)BH2L] 4 (L=C7H4NS2) was investigated with both internal and terminal alkynes. Interestingly, under photolytic conditions, 4 reacts with methyl propiolate to generate the η4‐σ,π‐borataallyl complexes [Cp*Ru(μ‐H)BH{R‐C=CH2}(L)] 5 and [Cp*Ru(μ‐H)BH{HC=CH‐R}(L)] 6 (R=COOCH3; L=C7H4NS2) by Markovnikov and anti‐Markovnikov hydroboration. In an extension, photolysis of 4 in the presence of dimethyl acetylenedicarboxylate yielded η4‐σ,π‐borataallyl complex [Cp*Ru(μ‐H)BH{R‐C=CH‐R}(L)] 7 (R=COOCH3; L=C7H4NS2). An agostic interaction was also found to be present in 2 a – c and 5 – 7 , which is rare among the borataallyl complexes. All the new compounds have been characterized in solution by IR, 1H, 11B, 13C NMR spectroscopy, mass spectrometry and the structural types were unequivocally established by crystallographic analysis of 2 b , 3 a – c and 5 – 7 . DFT calculations were performed to evaluate possible bonding and electronic structures of the new compounds. 相似文献