全文获取类型
收费全文 | 1150篇 |
免费 | 49篇 |
国内免费 | 11篇 |
专业分类
化学 | 839篇 |
晶体学 | 6篇 |
力学 | 43篇 |
数学 | 148篇 |
物理学 | 174篇 |
出版年
2023年 | 8篇 |
2022年 | 7篇 |
2021年 | 25篇 |
2020年 | 15篇 |
2019年 | 29篇 |
2018年 | 14篇 |
2017年 | 17篇 |
2016年 | 45篇 |
2015年 | 22篇 |
2014年 | 33篇 |
2013年 | 74篇 |
2012年 | 88篇 |
2011年 | 83篇 |
2010年 | 36篇 |
2009年 | 64篇 |
2008年 | 85篇 |
2007年 | 68篇 |
2006年 | 53篇 |
2005年 | 56篇 |
2004年 | 43篇 |
2003年 | 49篇 |
2002年 | 49篇 |
2001年 | 21篇 |
2000年 | 26篇 |
1999年 | 11篇 |
1998年 | 14篇 |
1997年 | 13篇 |
1996年 | 24篇 |
1995年 | 7篇 |
1994年 | 12篇 |
1993年 | 8篇 |
1992年 | 15篇 |
1991年 | 3篇 |
1990年 | 3篇 |
1989年 | 8篇 |
1987年 | 6篇 |
1986年 | 9篇 |
1985年 | 15篇 |
1984年 | 6篇 |
1983年 | 2篇 |
1982年 | 4篇 |
1981年 | 5篇 |
1980年 | 7篇 |
1979年 | 2篇 |
1978年 | 5篇 |
1977年 | 4篇 |
1976年 | 2篇 |
1975年 | 3篇 |
1974年 | 3篇 |
1970年 | 2篇 |
排序方式: 共有1210条查询结果,搜索用时 15 毫秒
31.
32.
Rios R Jimeno C Carroll PJ Walsh PJ 《Journal of the American Chemical Society》2002,124(35):10272-10273
We have demonstrated the feasibility of the kinetic resolution of atropisomeric amides using the commercially avaliable AD-mix. To our knowledge, this methodology represents the first catalytic kinetic resolution of such compounds. Relative rates of up to 32 have been found for the kinetic resolution processes. We have also determined the barriers to rotation and half-lives of some of these amides. The half-lives range from 7 to 135 h at room temperature. 相似文献
33.
The coupling of a stopped-flow module to a diode-array spectrophotometric detector has been exploited for the simultaneous kinetic resolution of mixtures. The analytical possibilities are shown with the resolution of a mixture of two analytes (hydrazine and phenylhydrazine), yielding products with different spectral features (after reaction with p-dimethylaminobenzaldehyde), so that only the simultaneous measurement of their respective initial rates at their corresponding maximum absorption wavelengths is possible. The method allows 0.02–30 μg ml?1 hydrazine and 8–2200 μg ml?1 phenylhydrazine to be determined simultaneously. 相似文献
34.
The method is based on formation of the fluorescent condensation products with o-phthaldialdehyde; 0.5–2000 ng ml?1 histamine and 3–700 ng ml?1 spermidine can be quantified, with relative standard deviations of 2–3%. Histamine/spermidine ratios of 2.5:1–1:30 can be handled. A selectivity study is reported. 相似文献
35.
Mario H. Gutierrez Warren T. Ford 《Journal of polymer science. Part A, Polymer chemistry》1986,24(4):655-663
Glass transition temperatures have been determined for polystyrenes crosslinked with 1–10% divinylbenzene and swollen with toluene, chloroform, N,N-dimethylformamide, and tetrahydrofuran to as high as 0.7 weight fraction solvent. The Tg′s depend approximately on the weight fractions and the Tg′s of the components according to the empirical equation 1nTg = m1 1nTg1 + m2 1nTg2 of Pochan. The Tg′s of the networks swollen with toluene also fit approximately a quasithermodynamic equation of Karasz based on the Tg′s and the ΔCp′s at Tg of the components. 相似文献
36.
The characteristics of the ternary complexes formed by fluoride, bromide, iodide and thiocyanate with tin(IV) and 5,7-dichloro-8-quinolinol (HCQ) have been studied. A spectrophotometric method is proposed for the determination of tin(IV) (1–20 μg ml?1), based on the extraction into chloroform of the tin/iodide/HCQ complex. Aluminium, bismuth and lead do not interfere, but antimony, copper, iron(III) and fluoride do. Copper and iron can be eliminated by preliminary extraction in the absence of iodide. 相似文献
37.
Lei Liu Wes Lee Cassandra R. Youshaw Mingbin Yuan Michael B. Geherty Peter Y. Zavalij Osvaldo Gutierrez 《Chemical science》2020,11(31):8301
A highly chemoselective iron-catalyzed three-component dicarbofunctionalization of unactivated olefins with alkyl halides (iodides and bromides) and sp2-hybridized Grignard reagents is reported. The reaction operates under fast turnover frequency and tolerates a diverse range of sp2-hybridized nucleophiles (electron-rich and electron-deficient (hetero)aryl and alkenyl Grignard reagents), alkyl halides (tertiary alkyl iodides/bromides and perfluorinated bromides), and unactivated olefins bearing diverse functional groups including tethered alkenes, ethers, protected alcohols, aldehydes, and amines to yield the desired 1,2-alkylarylated products with high regiocontrol. Further, we demonstrate that this protocol is amenable for the synthesis of new (hetero)carbocycles including tetrahydrofurans and pyrrolidines via a three-component radical cascade cyclization/arylation that forges three new C–C bonds.A highly selective iron-catalyzed three-component dicarbofunctionalization of unactivated alkenes with alkyl halides and sp2-hybridized Grignard reagents is reported. 相似文献
38.
Pericet-Camara R Papastavrou G Borkovec M 《Langmuir : the ACS journal of surfaces and colloids》2004,20(8):3264-3270
The adsorption behavior of poly(amidoamine) dendrimers to mica surfaces was investigated as a function of ionic strength and pH. The conformation and lateral distribution of the adsorbed dendrimers of generations G8 and G10 were obtained ex situ by tapping mode atomic force microscopy (AFM). The deposition kinetics of the dendrimers was found to follow a diffusion-limited process. Fractional surface coverage and pair correlation functions of the adsorbed dendrimers were obtained from the AFM images. The data are interpreted in terms of the random sequential adsorption (RSA) model, where electrostatic repulsion due to overlapping double layers is considered. Although the general trends typical for an RSA-determined process are well-reproduced, quantitative agreement is lacking at low ionic strengths. 相似文献
39.
Adahchour M Wiewel J Verdel R Vreuls RJ Brinkman UA 《Journal of chromatography. A》2005,1086(1-2):99-106
The practicability and potential of comprehensive two-dimensional gas chromatography (GC x GC) coupled to both conventional flame ionisation (FID) and time-of-flight mass spectrometric (TOF-MS) detection, were compared with those of conventional one-dimensional (1D) GC, with the determination of flavour compounds in butter as an application. For polar flavour compounds, which were collected from the aqueous fraction of butter by means of solid-phase extraction (SPE), it was found that GC x GC dramatically improves the overall separation. Consequently, quantification and preliminary identification based on the use of ordered structures, can be performed more reliably. The improvement effected by replacing 1D-GC by GC x GC is considerable also in the case of TOF-MS detection, as illustrated by the high match factors generally obtained during identification. GC x GC was also used successfully for the characterisation of volatile flavour compounds in the headspace of butter collected by solid-phase microextraction (SPME) and to study the effect of heat treatment on the composition of butter samples in more detail. 相似文献
40.
Ramon M. Barnes 《Analytical and bioanalytical chemistry》1998,361(3):246-251
This report focuses on the status, requirements, and potentials of CE-ICP-MS. The ultimate goal of a viable CE-ICP-MS system is to obtain quantitative elemental speciation information and isotopic ratio data for practical biological and environmental metal containing compounds. To make use of the CE separation features, the CE analyte must be introduced efficiently into the ICP. For practical samples, pre- and post-separation enrichment techniques probably are required. The features of electrospray ion sources that can be incorporated in CE-ICP-MS and the potential for microfabricated CE are discussed. 相似文献