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101.
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
102.
The catalytic activity of Chromobacterium viscosum lipase (CV-lipase) was estimated across varying surfactant tail lengths (C-10-C-18) in water-in-oil (w/o) microemulsions of cationic surfactants containing four different hydroxyethyl-substituted head groups. An attempt to find a correlation, if any, between the activity of interfacially solubilized lipase and the varying surfactant tails was made for the first time in micellar enzymology. The second-order rate constant, k2, in lipase-catalyzed hydrolysis of p-nitrophenyl-n-hexanoate at pH 6.0 and 25 degrees C shows an improvement in enzyme activity (approximately 30-140%) across different head groups of amphiphiles with increasing tail lengths in varying solution compositions. Improvement of enzyme activity is prominent in ascending from C-10 to C-14/C-16, depending on the nature of polar head group. The hydrolytic activity of lipase in different surfactant (50 mM)/water/isooctane/n-hexanol with varying z= [alcohol]/[surfactant] (6.4 or 4.8) was amplified by 25-250% with increment in surfactant tail length in comparison with widely used cationic w/o microemulsions having solution compositions (z=16). As a notable outcome of this research, we found w/o microemulsions of 25 mM tetradecyltrimethylammonium bromide/water/isooctane/n-hexanol (z=8) producing the highest ever activity of lipase in any w/o microemulsions. 相似文献
103.
Kumar S Sharma D Ghosh G Kabir-ud-Din 《Langmuir : the ACS journal of surfaces and colloids》2005,21(21):9446-9450
Hydrophobic interactions control the morphologies of both surfactant aggregates and proteins. Globular proteins "denature" upon addition of excess amounts of denaturants such as urea. Understanding the microscopic basis of the urea effect on proteins or supramolecular aggregates such as micelles has always been a debated issue. Inspired by this need, the effect of urea (U), thiourea (TU), monomethylurea (MMU), dimethylurea(DMU), tetramethylurea (TMU), dimethylthiourea (DMTU), and tetramethylthiourea (TMTU) on the structural transition (spherical micelles to rod-shaped micelles, s --> r) in the sodium dodecylbenzenesulfonate (SDBS)-1-pentanol system has been investigated through dynamic light scattering(DLS) and viscosity measurements at 25 degrees C. 1-Pentanol, at 0.14 M, is found to promote s --> r in this system (0.2 M SDBS). The presence of the additives causes, in almost all cases, a decrease and increase in this 1-pentanol concentration depending upon the concentration and nature of the additive. These effects are explained in terms of an increased dielectric constant of the solvent medium due to the presence of additives and increased micellar hydration due to the repulsion of charged monomers caused by adsorption of the additives. Taken together, the data signal the exposure of biological assemblies to water at higher [additive], which causes a decrease in hydrophobic interactions responsible for compact structure formation (i.e., native protein). 相似文献
104.
Mandal PK Kaluarachchi KK Ogrin D Bott SG McMurray JS 《The Journal of organic chemistry》2005,70(24):10128-10131
[reaction: see text] Azabicyclo[X.Y.0]alkane amino acids are rigid dipeptide mimetics that are useful tools for structure-activity studies in peptide-based drug discovery. Herein, we report an efficient synthesis of three diastereomers of 9-tert-butoxycarbonyl-2-oxo-3-(N-tert-butoxycarbonylamino)-1-azabicyclo[4.3.0]nonane (3S,6S,9S, 3S,6R,9R, and 3S,6R,9S). Methyl N-Boc-pyroglutamate is cleaved with vinylmagnesium bromide to produce an acyclic gamma-vinyl ketone. Michael addition of N-diphenylmethyleneglycine tert-butyl ester produces the N-Boc-delta-oxo-alpha,omega-diaminoazelate intermediate, which, on hydrogenloysis, gives the fused ring system. Acidolytic deprotection followed by Fmoc-protection provided building blocks suitable for solid-phase synthesis. 相似文献
105.
The synthesis of the title spirodione, a new class of auxiliary based chiral synthon using (−)-trans-2-phenylcyclohexanol and its application to the asymmetric Diels-Alder reaction are described. Methodology for detachment of the chiral auxiliary from the cycloadduct has been developed. 相似文献
106.
Abstract —Thymine starvation prior to 254 nm ultraviolet light (UV) exposures has been found to decrease the level of maximum photoreactivation in Escherichia coli B s-1 . The dark equilibrium level of photoreactivating enzyme-substrate complexes was determined from the levels of photoreactivation obtained with exposures to single flashes of high-intensity light. The kinetics indicate that photoreactivating enzyme concentration does not decrease as a result of thymine starvation. The UV sensitivities of normal and thymine-starved cells are found to be the same. Photoreactivation by sequential flashes shows a lesser number of total photorepairable lesions in starved cells. It is concluded that thymine starvation renders a portion of the dimers inaccessible to the photoreactivating enzyme, thus lowering the level of maximum photoreactivation. 相似文献
107.
Nandy JP Prabhakaran EN Kumar SK Kunwar AC Iqbal J 《The Journal of organic chemistry》2003,68(5):1679-1692
A novel chemo- and diastereoselective aerobic epoxidation of the N-cinnamoyl peptides catalyzed by polyaniline-supported cobalt(II) salen (PASCOS) is described. The N-cinnamoyl proline derived peptides 1 show a high pi-facial selectivity during these epoxidations. The origin of this diastereoselectivity in 1 has been attributed to (i) the propensity of the N-cinnamoyl proline amide to exist predominantly as trans rotamer in CDCl3, DMSO-d6, and CH3CN medium and (ii) existence of these peptides as organized structures (gamma- and beta-turns) due to the presence of intramolecular hydrogen bonds. An extensive solution NMR and MD simulation study on 1d and 1f indicates that the origin of the high pi-facial selectivity is due to the well-defined gamma- and beta-turns which result in the hindrance of one face of the cinnamoyl double bond in the transition state of the epoxidation reaction. 相似文献
108.
An optimized semi-automatic protocol for parallel synthesis of up to 96 peptide nucleic acids (PNA) or PNA-peptide conjugates using Boc-protection strategy has been developed using a robotic system. The approach is illustrated by synthesizing PNA and PNA-peptide libraries varying between 15 and 27 amino acid units. The peptides (NLS (nuclear localization signal) or Tat-peptide) were attached to N-terminus of the PNA. The method was found to be far superior to that based on the SPOT/Fmoc protocol by which PNA oligomers are synthesized on a modified cellulose membrane. On a 0.5 micromole scale the method typically yielded 2 mg product of 90% purity by HPLC/MALDI-TOF analysis. This approach is suitable for screening of a large number of PNA and/or peptide sequences for biochemical and biological studies. 相似文献
109.
Summary Results of spectrophotometric, conductometric and dialysis studies on the interaction of acridine orange monohydrochloride dye with sodiumdodecylsulfate (anionic), cetyltrimethylammoniumbromide (cationic) and Triton X 100 (nonionic) surfactants have been reported. The anionic surfactant, SDS has been observed to undergo both electrostatic and hydrophobic interactions with the dye cation. Aggregation of the dye molecules can be destroyed when the surfactant is in large excess, whereas, excess dye can check micellization of SD S. At a ratio of AO:SDS=1:7 and above, dye embedded mixed micelles are formed. These remain in a separate phase, probably as coacervates. At lower ratios than 1:7, aggregation of dye molecules is induced, which being complexed with SDS become stabilized as colloids. The colloid and the coacervate have been observed to be thermally stable, negatively charged materials that can be broken by salts, and cations of higher valency are more effective in this regard. An 1:3 = AO:SDS colloid has beeen found to be sufficiently large like the coacervates to pass through a membrane having cut off permeability for molecular weights 12,000 and above. All the above features of AO-SDS interaction have been observed to be absent for AO-CTAB and AO-TX 100 systems, Even hydrophobic interaction has played an insignificant role in these cases. Thus, the dye cation, the cationic and the nonionic surfactants have almost retained their self physicochemical identities in solution in the presence of each other. Electrostatic interaction is thus the primary requirement for acridine orange-surfactant (anionic) system; the hydrophobic effect is secondary and may become co-operative.With 9 figures and 2 tables 相似文献
110.
A. K. Shukla S. Saini P. Kumar J. S. P. Rai A. K. Srivastava 《Journal of polymer science. Part A, Polymer chemistry》1989,27(3):807-815
Polymerization of vinyl acetate initiated by β-picolinium p-chlorophenacylide was carried out at 30, 35, and 40°C, using conventional dilatometric technique. The initiator and the monomer exponent values were 0.80 ± 0.15 and unity, respectively. The polymerization was inhibited in the presence of hydroquinone, but was favored by nonpolar solvent and polymerization temperature. The energy of activation was 90.3 KJ mol?1. An average value of k/kt for the present system was found to be 0.37 × 10?2. The results are explained in terms of a radical mode of polymerization with degradative initiator transfer; the principal mode of termination, however, was bimolecular. 相似文献