全文获取类型
收费全文 | 2685篇 |
免费 | 101篇 |
国内免费 | 1篇 |
专业分类
化学 | 1545篇 |
晶体学 | 30篇 |
力学 | 119篇 |
数学 | 578篇 |
物理学 | 515篇 |
出版年
2023年 | 24篇 |
2022年 | 27篇 |
2021年 | 26篇 |
2020年 | 64篇 |
2019年 | 76篇 |
2018年 | 83篇 |
2017年 | 69篇 |
2016年 | 131篇 |
2015年 | 91篇 |
2014年 | 120篇 |
2013年 | 359篇 |
2012年 | 130篇 |
2011年 | 135篇 |
2010年 | 99篇 |
2009年 | 95篇 |
2008年 | 125篇 |
2007年 | 95篇 |
2006年 | 102篇 |
2005年 | 57篇 |
2004年 | 73篇 |
2003年 | 55篇 |
2002年 | 51篇 |
2001年 | 55篇 |
2000年 | 35篇 |
1999年 | 40篇 |
1998年 | 35篇 |
1997年 | 33篇 |
1996年 | 36篇 |
1995年 | 24篇 |
1994年 | 28篇 |
1993年 | 23篇 |
1992年 | 12篇 |
1991年 | 12篇 |
1990年 | 14篇 |
1989年 | 10篇 |
1988年 | 17篇 |
1987年 | 13篇 |
1986年 | 12篇 |
1985年 | 30篇 |
1984年 | 18篇 |
1983年 | 14篇 |
1982年 | 13篇 |
1981年 | 23篇 |
1980年 | 24篇 |
1979年 | 14篇 |
1978年 | 13篇 |
1977年 | 14篇 |
1975年 | 13篇 |
1973年 | 7篇 |
1935年 | 7篇 |
排序方式: 共有2787条查询结果,搜索用时 15 毫秒
41.
Summary The conformation and relative configuration of [1-(2H-azirin-2-yl)alkyl]phosphonates (2) has been established by thorough investigation of some characteristic representatives of the series by1H,13C,15N, and31P NMR spectroscopy. It is shown that the chemical shift of the proton located to the phosphonate group can be used as a criterion for the discrimination and stereochemical assignment of diastereoisomers. NMR spectroscopic features of the compounds are discussed in terms of structural relationships.Dedicated to Univ.-Prof. Dr.K. Schlögl with the best wishes to his 70th birthday 相似文献
42.
In this paper we consider a class of systems described by singular integrodifferential equations. This type of systems appear, for example, in the modeling of certain aeroelastic control problems. We study these systems in frequency domain framework and show the existence of finite-dimensional stabilizing controllers. An algorithmic procedure is outlined for the construction of such controllers. In order to illustrate the numerical aspects of this algorithm, we present an example involving the classical Theodorsen model of an airfoil, which fits in the class of systems considered here.This work was supported in part by the National Science Foundation under Grants DMS-8907019 and MSS-9203418. 相似文献
43.
Binary and ternary mixtures of alpha-tocopherol (alphaT), cholesterol and dipalmitoyl phosphatidylcholine (DPPC) in the form of multilamellar liposomes have been investigated by Fourier Transform Infrared Spectroscopy (FTIR). Investigation of frequencies, bandwidths and band shapes of CH(2) stretching and scissoring bands indicate that the effect of alphaT is dominant in comparison with cholesterol and alphaT decreases the interaction of cholesterol with phospholipid membranes. 相似文献
44.
45.
We study the derivation of a Langevin equation from a microscopic basis in order to elucidate the nature of the random force. We arrive at the conclusion that the consistent interpretation of the microscopic Langevin equation in terms of a stochastic differential equation (SDE) is according to I
o rules. In addition, the random force is in general not Gaussian, and it is hence not completely characterized by its second moments. 相似文献
46.
47.
α-Aspartame (L-α-aspartyl-L-phenylalanine methyl ester) is increasingly being used in wide variety of commonly consumed food products. This structure contains ester and peptide bonds. The ester linkage may hydrolyze to produce L-α-aspartyl-L-phenylalanine or cyclohydrolyze to produce the corresponding diketopiperazine ring. This ring can open to form L-α-aspartyl-L-phenylalanine and ultimately this compound can hydrolyze to L-phenylalanine and L-aspartic acid. The pH, buffer type, concentration, the presence of water and temperature are other important factors affecting its stability. Because α-aspartame can lose its sweetness under these conditions determination of aspartame and its breakdown products is extremely important for diet foods quality. The optimum mobile phase for the chromatographic separation was found to be acetonitrile-water (20:80, ν/ν) with 5.10?3 M hexanesulfonic acid and a pH of 2.6. 相似文献
48.
Summary A fully integrated chromatographic system was developed for the determination of leukotrienes in biological samples using
photodiode-array detection (PDAD), which eliminates time consuming manual sample handling steps. A special solid phase extraction,
(SPE) methodology for leucotriene metabolite stability was developed which increased the recoveries and eliminates the contamination
risk of biological samples. The inherent instability (autooxidation) of many of the leukotriene mediators, and the adsorption
effects onto exposed surfaces in vials and in the chromatographic system were found to be very important parameters to control
in order to circumvent high loss of sample analytes. By binding the cell supernatants to the functionalities of the SPE support
stabilised these mediators. Cell culture samples were eluted through a disposable C18 SPE column. The SPE columns were allowed to thaw and deposited in an automated sample handling unit (ASPEC XL). Desorption
of the analytes was followed by a second on-line SPE step, to eliminate remaining interfering matrix compounds. Typical recoveries
when stored at −70°C were in-between 55–97% except for (LTE4) which was found to be around 40% after 72 days of storage. Seven reversed-phase packings were studied. Selectivity factors,
as well as the separation efficiencies, were found to differ for the various C18 bonded silica stationary phases. This integrated on-line column liquid chromatographic system was applied to the determination
of leukotriene B4, leukotriene C4, leukotriene D4, leukotriene and E4 in human cell extracts using prostaglandin B2 as the internal standard. More than 1500 biological samples were analysed. Some validation data are presented for unattended
operations. 相似文献
49.
Coleman KS Bailey SR Fogden S Green ML 《Journal of the American Chemical Society》2003,125(29):8722-8723
Single-walled carbon nanotubes have been cyclopropanated under Bingel reaction conditions, and the functionalized nanotubes have been characterized by atomic force microscopy using "chemical tagging" techniques. 相似文献
50.
Ay?em Üzer 《Analytica chimica acta》2005,534(2):307-317
Contaminated land and groundwater remediation in military waste dumping sites often necessitates the use of simple, cost-effective, and rapid tests for detecting trinitrotoluene (TNT) residues in the field along with their dinitro-analogues. A simple, rapid, low-cost, and field-adaptable (on-site) colorimetric method was developed for quantifying TNT in the presence of RDX, PETN, picric acid, 2,4-DNT (dinitrotoluene), dinitrophenol, and dinitroaniline. Most commercialized methods for TNT assay-with the exception of Cold Regions Research and Engineering Laboratory of the U.S. Army (CRREL) method-use proprietary chemicals, and the color stability and intensity are highly dependent on the composition of the organic solution comprised of acetone or methanol. The developed colorimetric method is based on the extraction of TNT from water-acetone solution into an organic solvent mixture of dicyclohexylamine (DCHA)-isobutyl methyl ketone (IBMK) (10:1, v/v), filtration through a filter paper into a stoppered optical cell containing anhydrous sodium sulfate, and measurement of the absorbance of the organic extract at 531 nm after 5 min. The red-violet color of the extract was due to intermolecular charge-transfer (CT) between the electron attracting TNT and electron-donating DCHA, and the molar absorptivity for TNT in final organic solution was (1.16 ± 0.02) × 104 L mol−1 cm−1.The R.S.D. of the slope of calibration line was 0.7%. The LOD of the method in the final organic phase was 0.38 μM TNT, and LOD values expressed on the basis of original soil TNT content were 0.5, 1.3, and 1.5 ppm (μg g−1) for clay, loamy clay, and sandy soils, respectively. Unlike other spectrophotometric methods, the developed assay was basically tolerant to common cations and anions found in soil and water at 100-fold weight ratios, and to soil humic acids. Among a number of compounds that may be encountered in polynitro-explosive storage and waste reclaimation sites such as picric acid, dinitrophenol, 2,4-dinitrotoluene, dinitroaniline, RDX, PETN, and tetryl, only tetryl interfered with the developed TNT assay. Water tolerance and exploitability over a wide pH range were other superiorities over the CRREL method. The CT-complex was relatively stable, as the absorbance of the organic extract was not significantly influenced from the dilution of the water-acetone phase. Aside from the extractive-photometric procedure established for aqueous solutions, a simulated field colorimetric assay for TNT directly applicable to soil was also devised, based on direct color development in a 4:1 (v/v) acetone-dicyclohexylamine organic extract of soil at a liquid-to-solid ratio of 5 mL g−1. 相似文献