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121.
Boruah A Rao IN Nandy JP Kumar SK Kunwar AC Iqbal J 《The Journal of organic chemistry》2003,68(12):5006-5008
A cis-proline derived cyclic mimic of a type VI beta-turn is synthesized via a ring-closing metathesis reaction. The solution NMR conformational study indicates that the major conformer of the cyclic peptide adopts a type VIa beta-turn in CDCl(3) and a type VIb beta-turn in DMSO-d(6). 相似文献
122.
The polarographic behaviour of uranium and tellurium has been studied in the presence of increasing concentration of complex forming agent viz. ?-caprolactam at pH 4.4 for U(VI) and at pH 10.0 for Te(IV) at μ=0.1 M KNO3. In both cases the waves have been found to be diffusion controlled and irreversible. The values of kinetic parameters (σπa and K°f,h) have been calculated as a function of the ligand concentration. Method is suitable for the quantitative determination of these metals individually and simultaneously with the effect of diverse ions. 相似文献
123.
Hydrated copper (II) perchlorate (in acetonitrile) has been used for the direct visual and potentiometric determination of ascorbic acid in acetic acid-acetonitrile media. Diphenylamine and diphenylbenzidine are suitable indicators. A bright platinum wire is used as indicator electrode and a modified calomel or an antimony electrode as reference electrode for the potentiometric titration. Ascorbic acid is oxidized to dehydroascorbic acid. The proposed method is simple, accurate and reliable. The reverse titration also works well. 相似文献
124.
Kar S Chanda N Mobin SM Urbanos FA Niemeyer M Puranik VG Jimenez-Aparicio R Lahiri GK 《Inorganic chemistry》2005,44(5):1571-1579
The reaction of cis-Ru(acac)2(CH3CN)2 (acac = acetylacetonate) with 2,2'-dipyridylamine (L) in ethanolic medium resulted in facile one-pot synthesis of stable [(acac)2RuIII(L)]ClO4 ([1]ClO4), trans-[(acac)2RuII(L)2] (2), trans-[(acac)2RuIII)L)2]ClO4 ([2]ClO4), and cis-[(acac)2RuII(L)2] (3). The bivalent congener 1 was generated via electrochemical reduction of [1]ClO4. Although in [1]+ the dipyridylamine ligand (L) is bonded to the metal ion in usual bidentate fashion, in 2/[2]+ and 3, the unusual monodentate binding mode of L has been preferentially stabilized. Moreover, in 2/[2]+ and 3, two such monodentate L's have been oriented in the trans- and cis-configurations, respectively. The binding mode of L and the isomeric geometries of the complexes were established by their single-crystal X-ray structures. The redox stability of the Ru(II) state follows the order 1 < 2 < 3. In contrast to the magnetic moment obtained for [1]ClO4, mu = 1.84 muB at 298 K, typical for low-spin Ru(III) species, the compound [2]ClO4 exhibited an anomalous magnetic moment of 2.71 muB at 300 K in the solid state. The variable-temperature magnetic measurements showed a pronounced decrease of the magnetic moment with the temperature, and that dropped to 1.59 muB at 3 K. The experimental data can be fitted satisfactorily using eq 2 that considered nonquenched spin-orbit coupling and Weiss constant in addition to the temperature-independent paramagnetism. [1]ClO4 and [2]ClO4 displayed rhombic and axial EPR spectra, respectively, in both the solid and the solution states at 77 K. 相似文献
125.
Shrawan Kumar 《Communications in Mathematical Physics》1986,106(2):177-181
We give a necessary topological condition on a cohomology class of any Lie group, modelled on a Fréchet space, to be representable by a bi-invariant form on. As a corollary, we show that if for somed>0, then there exists a cohomology class in which cannot be represented by any bi-invariant form. In particular, we conclude that there are many cohomology generators, in general, in the case of gauge groups and also Kac-Moody groups which cannot be represented by bi-invariant forms, although, very often, they are representable by left invariant forms. 相似文献
126.
Sokoloff MD Anjos JC Appel JA Bracker SB Browder TE Cremaldi LM Elliott JR Escobar CO Estabrooks P Gibney MC Hartner GF Karchin PE Kumar BR Losty MJ Luste GJ Mantsch PM Martin JF McHugh S Menary SR Morrison RJ Nash T Ong P Pinfold J Purohit MV Raab JR Santoro AF Sidhu JS Sliwa K Souza MH Spalding WJ Streetman ME Stundia AB Witherell MS 《Physical review letters》1986,57(24):3003-3006
127.
Kumar D Hirao H de Visser SP Zheng J Wang D Thiel W Shaik S 《The journal of physical chemistry. B》2005,109(42):19946-19951
Density functional theory (DFT) is applied to the dark section of the catalytic cycle of the enzyme cytochrome P450, namely, the formation of the active species, Compound I (Cpd I), from the ferric-hydroperoxide species (Cpd 0) by a protonation-assisted mechanism. The chosen 96-atom model includes the key functionalities deduced from experiment: Asp(251), Thr(252), Glu(366), and the water channels that relay the protons. The DFT model calculations show that (a) Cpd I is not formed spontaneously from Cpd 0 by direct protonation, nor is the process very exothermic. The process is virtually thermoneutral and involves a significant barrier such that formation of Cpd I is not facile on this route. (b) Along the protonation pathway, there exists an intermediate, a protonated Cpd 0, which is a potent oxidant since it is a ferric complex of water oxide. Preliminary quantum mechanical/molecular mechanical calculations confirm that Cpd 0 and Cpd I are of similar energy for the chosen model and that protonated Cpd 0 may exist as an unstable intermediate. The paper also addresses the essential role of Thr(252) as a hydrogen-bond acceptor (in accord with mutation studies of the OH group to OMe). 相似文献
128.
Krishna Kumar Gollapelli Vaibhav B. Patil Allam Vinaykumar Rambabu Chegondi 《Chemical science》2021,12(4):1544
A Rh(i)-catalyzed highly stereoselective desymmetrization of 2-alkynylbenzaldehyde-tethered cyclohexadienones triggered by intramolecular Huisgen-type [3 + 2] cycloaddition has been developed. This method enables convergent construction of complex epoxy-bridged polycyclic ring systems with five contiguous stereocenters with excellent exo-selectivity and broad substrate scope. The highly atom-economical process involves 6-endo-dig cyclization of carbonyl oxygen onto an activated alkyne resulting in a highly reactive metal–benzopyrylium intermediate, which readily undergoes intramolecular [3 + 2] annulation/hydration. Asymmetric induction is also achieved for the first time in Rh(i)-catalyzed 1,3-dipolar cycloaddition using an easily accessible chiral diene as the ligand.A Rh(i)-catalyzed highly stereoselective desymmetrization of 2-alkynylbenzaldehyde-tethered cyclohexadienones triggered by intramolecular Huisgen-type [3 + 2] cycloaddition has been developed. 相似文献
129.
Designing artificial light harvesting systems with the ability to utilize the output energy for fruitful application in aqueous medium is an intriguing topic for the development of clean and sustainable energy. We report here facile synthesis of three prismatic molecular cages as imminent supramolecular optoelectronic materials via two-component coordination-driven self-assembly of a new tetra-imidazole donor (L) in combination with 180°/120° di-platinum(ii) acceptors. Self-assembly of 180° trans-Pt(ii) acceptors A1 and A2 with L leads to the formation of cages Pt4L2(1a) and Pt8L2(2a) respectively, while 120°-Pt(ii) acceptor A3 with L gives the Pt8L2(3a) metallacage. PF6− analogues (1b, 2b and 3b) of the metallacages possess a high molar extinction coefficient and large Stokes shift. 1b–3b are weakly emissive in dilute solution but showed aggregation induced emission (AIE) in a water/MeCN mixture as well as in the solid state. AIE active 2b and 3b in aqueous (90% water/MeCN mixture) medium act as donors for fabricating artificial light harvesting systems via Förster resonance energy transfer (FRET) with organic dye rhodamine-B (RhB) with high energy efficiency and good antenna effect. The metallacages 2b and 3b represent an interesting platform to fabricate new generation supramolecular aqueous light harvesting systems with high antenna effect. Finally, the harvested energy of the LHSs (2b + RhB) and (3b + RhB) was utilized successfully for efficient visible light induced photo-oxidative cross coupling cyclization of N,N-dimethylaniline (4) with a series of N-alkyl/aryl maleimides (5) in aqueous acetonitrile with dramatic enhancement in yields compared to the reactions with RhB or cages alone.Synthesis of Pt(ii) based metallacages as aggregation induced emissive supramolecular architectures for fabricating artificial light harvesting systems for cross coupling cyclization under visible light is achieved. 相似文献
130.
A. Lakshmi Sailaja K. Kishore Kumar D. V. R. Ravi Kumar C. Mohan Kumar N. M. Yugandhar G. Srinubabu 《Chromatographia》2007,65(5-6):359-361
A simple, rapid, and sensitive high-performance liquid chromatographic method for estimation of efavirenz in human plasma
has been developed and validated. Chromatography was performed with C18 analytical column and 50:50 acetonitrile–phosphate buffer (pH 3.5) as mobile phase. Compounds were monitored by UV detection
at 247 nm. The retention time for efavirenz was 6.45 min and that for the internal standard, nelfinavir, was 2.042 min. Response
was a linear over the concentration range of 0.1 μg–10 μg mL−1 in human plasma. The method was simple, specific, precise and accurate and was useful for bioequivalence and pharmacokinetic
studies of efavirenz. 相似文献