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71.
(Ss)-3-(p-Tolylsufinyl)-2-furaldimine was synthesized, and condensation of the chiral furaldimine with lithium ester enolates has been examined. The product distribution of the reaction is dependent upon reaction conditions and on the kind of the substituent placed on the esters. Disubstituted ester enolate resulted in the exclusive formation of (4R)-beta-lactam, while unsubstituted, tert-butyl ester enolate preferentially gave (3R)-beta-amino ester. With the monosubstituted ester enolates, the condensation afforded (4R)-beta-lactams and/or (3R)-beta-amino esters as major products. This method has been applied to an efficient route to chiral furyl beta-lactams. 相似文献
72.
73.
N. A. Keiko E. A. Funtikova L. G. Stepanova Yu. A. Chuvashev L. I. Larina 《Chemistry of Heterocyclic Compounds》2002,38(4):390-395
The reaction of 2-alkoxypropenals with ethane-1,2-dithiols and propane-1,3-dithiols under various conditions was studied by 1H NMR and chromato-mass spectrometry. Under kinetically controlled conditions at 20° in the absence of catalysts the addition of dithiols takes place according to the Markovnikov rule. The primary adducts are unstable and are quickly converted into the corresponding substituted 1,4-dithiacycloheptane or 1,4-dithiane. The latter in turn can be converted under the reaction conditions or at high temperature into a thiolane derivative. The reaction of 2-ethoxypropenal with a twofold excess of ethane-1,2-dithiol at 60°C in the presence of p-toluenesulfonic acid leads to 2-methyl-2,2'-bi(dithiolane) 相似文献
74.
Polypeptides with two histidines and an iron porphyrin (1H40-7H46) were synthesized with a variety of positions of a histidine. In 4H43, histidine (H43) was in the hydrophobic region of an α-helix. The other polypeptides were of slightly or substantially distorted conformation. In the pH 7.2 buffer solution, two histidines of the polypeptide coordinated the iron porphyrin regardless of their positions. Some polypeptides (1H40, 3H42, and 5H44) showed an enhanced catalytic activity in the peroxidase reaction using cumene hydroperoxide compared to that of 4H43, whereas some polypeptides (2H41 and 6H45) were ineffective catalysts. The distortion of the peptide conformation by the addition of MeOH was also effective for the peroxidase reaction. 相似文献
75.
Gunji Takahiro Toyota Kouichi Arai Kayo Abe Yoshimoto 《Journal of Sol-Gel Science and Technology》1997,10(2):139-152
Syntheses and characterization of polymetallosiloxanes by the non-hydrolysis sol-gel process using no metal alkoxides were investigated. The reaction of silicic acid (SA) with MCl4 (M = Ti, Zr) in the molar ratios SA/MCl4 = 0.5–3.0 using a tetrahydrofuran-methanol solvent formed polymetallosiloxane (PMS), which was insoluble in organic solvents regardless of the molar ratio. The PMS was isolated as esterified polymetallosiloxane by esterification with isopropyl alcohol for various periods, which were soluble in methanol, acetone, and tetrahydrofuran. The number average molecular weight was 1000–3200 for esterified polytitanosiloxane and 3400–11000 for esterified polyzirconosiloxane. Esterified polymetallosiloxanes had no melting point but decomposition point. The results of analytical data indicated that esterified polymetallosiloxane and/or polymetallosiloxane consisted of the main chain of Si–O–Si and Si–O–M linkage with the pendants of alkoxy, silanol, and chloro group. 相似文献
76.
77.
Stratum corneum (SC) lipids are of particular importance in maintaining the permeability barrier function. Although many studies have demonstrated that UVB irradiation of mammalian skin reduces barrier function, the responsible alterations in SC lipid profiles are not known. In this study, we investigated both compositional and morphological alterations in SC lipids with the development of barrier abnormalities caused by daily UVB irradiation in hairless rat skin. The UVB irradiation of suberythemal doses (0.5 minimal erythema dose) significantly increased transepidermal water loss (TEWL) relative to nonirradiated control, indicating a diminished barrier function. Under these conditions, the total amounts of major SC lipid species (ceramides, cholesterol, free fatty acids) in UVB-irradiated SC did not differ from those in nonirradiated SC. However, electron microscopic observations revealed marked abnormalities in the intercellular domains of UVB-irradiated SC, where naturally occurring intercellular multilamellar structures were often absent and leaving the area with the appearance of an empty space. Moreover, in UVB-irradiated SC, individual corneocytes often showed small amounts of intercellular deposition product with abnormal lamellar structure, where lamellar body sphingomyelinase activity was present. These observations demonstrated a partial failure of lamellar body secretion in UVB-irradiated SC and suggested that a defect in the secretion of lamellar body-derived lipids and enzymes to SC intercellular space is, at least in part, responsible for the observed abnormal intercellular structure and barrier disruption. 相似文献
78.
Tachibana Y Otsuka K Terabe S Arai A Suzuki K Nakamura S 《Journal of chromatography. A》2003,1011(1-2):181-192
A robust and simple interface for microchip electrophoresis-mass spectrometry (MCE-MS) was developed using a spray nozzle connected to the exit of the separation channel of the microchip. The spray nozzle was attached to the microchip using a polyether ether ketone screw without adhesive, thus allowing easy replaced. Sample injection and electrophoretic separation was performed by control of the voltage only. The analysis of a few basic drugs was performed using the optimized MCE-MS system. The separation was improved by using a high-viscosity separation buffer and a spray nozzle with a small bore size. This system was also applied to the separation of peptides and protein-trypsin digests. Sample adsorption was minimized by adding acetonitrile to the separation buffer when using a quartz microchip. 相似文献
79.
[reaction: see text] A stereoselective total synthesis of (+)-benzastatin E (1) is described. The synthesis involves a diastereoselective Grignard addition to 2-acylindoline 2, which is derived from commercially available (S)-2-indolinecarboxylic acid (3). The unknown absolute configuration of (+)-1 is determined as (9S,10R). 相似文献
80.
trans- and cis-1-(4-Dimethylaminophenyl)-6-(4-nitrophenyl)hex-3-ene-1,5-diynes (trans- and cis-DANE) were synthesized and their photochemical properties were studied. The absorption spectra of trans-DANE red-shifted compared with the parent compound bisphenylethynylethene (BEE) due to intramolecular charge transfer. The fluorescence spectra, Stokes shift, fluorescence lifetime, fluorescence quantum yield, and quantum yield of trans-to-cis photoisomerization of trans-DANE showed strong dependence upon the solvent polarity in the less-polar region. No fluorescence emission from trans-DANE was observed in medium-polar and polar solvents. The quantum yield of cis-to-trans isomerization was almost solvent independent. The donor-acceptor substituents shifted the equilibrium between the trans perpendicular triplet state and the trans planar triplet state to the trans triplet state, and resulted in an increase in the triplet lifetime. Comparison of the photochemical properties of trans-DANE with trans-4-dimethylamino-4'-nitrostilbene (DANS) suggests that trans-DANE is a possible fluorescent probe in the non-polar region. 相似文献