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41.
42.
Aida Moreira Da Silva José Empis José J.c. Teixeira-Dias 《Journal of inclusion phenomena and macrocyclic chemistry》1999,33(1):81-97
In aqueous solution, the apparent association constant at room temperature for the 1 : 1 inclusion of S-(+)-carvone in - cyclodextrin is double of that for R-(-)-carvone, whereas, at 45 °C, both enantiomers have association constants two orders of magnitude smaller, with the S-(+) inclusion being then slightly weaker than the R-(-) encapsulation. Calculations carried out at the molecular mechanics, AM1 and STO-3G levels confirm the preferential inclusion of the S-enantiomer and provide important clues for understanding chiral discrimination by -cyclodextrin. 相似文献
43.
The intermittent simulated moving bed (I-SMB) process is a modification of the conventional SMB process that has been recently analyzed theoretically [1]. Here, we present a comparative analysis of the two processes, each operated in a six column 1-2-2-1 configuration (one column in sections 1 and 4 and two columns in sections 2 and 3) and in a four-column 1-1-1-1 configuration. Experiments are carried out on a properly modified laboratory unit to separate racemic mixtures of the enantiomers of Tröger’s base in ethanol on ChiralPak AD at a total feed concentration of 1 g/L. Simulations are carried out for the same system using the equilibrium dispersive model and a bi-Langmuir isotherm, whose parameters have been preliminarily estimated from pulse and breakthrough experiments. Experiments and simulations are fully consistent and demonstrate that the four-column I-SMB process (but not the four-column SMB process) can separate the two enantiomers at very high purity and achieve a productivity twice as large as that of the six-column I-SMB and conventional SMB processes with the same solvent consumption. 相似文献
44.
A theoretical model reproducing qualitative and quantitative characteristics of DSC traces for melting of eutectic enantiomeric
mixtures was proposed. The method for reconstruction of an idealized trace from a fragment of the real experimental melting
curve was developed. When studying a sample of intermediate enantiomeric composition, the reconstruction of the trace makes
it possible to avoid ambiguity in determination of the liquidus temperature, determine the melting temperature for an enantiopure
compound, and estimate the composition of the sample.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1288–1293, July, 2007. 相似文献
45.
46.
This work described an interesting phenomenon of the stereoselective adsorption behaviors of DNA on stable chiral surfaces which were modified with 1,2‐diphenylethylenediamine enantiomers on gold electrodes. The modification process and electrochemical characterization of the chiral surfaces were measured by cyclic voltammetry (CV). The stereoselective adsorption behaviors of DNA on the two chiral surfaces were investigated via atomic force microscopy (AFM), CV, electrochemical impedance spectroscopy (EIS) and quartz crystal microbalance (QCM). All results confirmed that (1R,2R)‐1,2‐diphenylethylenediamine modified surface had stronger interaction with DNA molecules than (1S,2S)‐1,2‐diphenylethylenediamine modified surface, and the chirality of the surfaces created an different effect on the morphology and adsorption quantity of DNA. 相似文献
47.
Chloramphenicol is a broad-spectrum antibiotic with, apart from its human medicinal use, veterinary abuse in all major food-producing animals. Chloramphenicol occurs in four stereoisomers (all para-nitro substituted) and furthermore four meta-nitro analogs of chloramphenicol exist. In this paper these are referred to as eight chloramphenicol isomers. According to EU regulations an analytical method should be able to discriminate the analyte from interfering substances that might be present in the sample, including isomers. For the first time a quantitative method for the analysis of trace levels of eight chloramphenicol isomers in urine by chiral liquid chromatography in combination with tandem mass spectrometric detection is reported. The separation of the isomers on the analytical column, the clean-up of urine and the selectivity of the monitored product ions turned out to be critical parameters. To obtain reproducible retention isocratic elution on a chiral AGP column was applied. For urine samples matrix compounds present in the final extract caused decreased retention of the isomers on the chiral stationary phase and a lack of chromatographic resolution. Therefore an extended clean-up procedure that combines solid phase extraction and liquid-liquid extraction had to be developed. The final method was fully validated and showed satisfactory performance for all isomers with decision limits (CCα) ranging from 0.005 to 0.03 μg L(-1) and within-laboratory reproducibility of all isomers below 20% at the minimum required performance limit level of 0.3 μg L(-1). 相似文献
48.
49.
Two acyl and three fluoroacyl derivatives of 32 chiral alcohols have been chromatographed on a GC column coated with octakis(2,6-di-O-n-pentyl-3-O-trifluoroacetyl)- γ-cyclodextrin. Significant differences were observed between the stereoselectivity obtained for the derivatives and that for the underivatized alcohols. Of the derivatives, only the fluoroacylated compounds were separated into enantiomers. Derivatization with fluoroacyl groups reversed the elution order for at least some of the analytes. Stereoselectivity towards simple 2- and 3-hydroxy alkanes and their fluoroacyl derivatives was highest for those alcohols with a four-carbon chain attached to the stereogenic center. For longer-chain fluoroacyl derivative groups stereoselectivity was higher for the 2- and 3-hydroxy alkanes. Differences in stereoselectivity towards alcohols with a methyl-branched alkane chain and their fluoroacyl derivatives was related to the distance between the methyl group and the hydroxyl or fluoroacyl groups. Different degrees of saturation in the carbon chain resulted in differences in stereoselectivity. Thermodynamic data calculated for a number of analytes suggest that the alcohols and trifluoroacetate derivatives are interacting with the stationary phase by similar mechanisms. The stereospecific interaction appears to have a hydrogen bonding or dipole–dipole contribution and some form of steric component, depending upon the shape and/or size of the solute. 相似文献
50.
Six chiral selectors of S-(-)-t-Leu-cyclopropylamide, S-(-)-t-Leu-cyclopentylamide, S-(-)-t-Leu-cyclohexylamide, S-(-)-t-Leu-cycloheptylamide, S-(-)-t-Leu-cyclooctylamide, S-(-)-t-Leu-cyclododecylamide have been prepared and anchored individually through amide bonding to a polydimethylsiloxane functionalized with 2,2,2-trifluoroethyl ester groups by way of nucleophilic displacement reaction. The resulting chiral polysiloxanes have been provided as stationary phases for the separation of amino acid enantiomers by capillary GC. Amino acids were derivatized into N(O)-trifluoroacetyl isopropyl esters. Especially, polydimethylsiloxane anchored with S-(-)-t-Leu-cyclooctylamide was found to be efficient for the separation of aspartic acid (Asp) enantiomers. The method was applied to the estimation of ages from the extent of Asp racemization in human dentines. 相似文献