全文获取类型
收费全文 | 2517篇 |
免费 | 61篇 |
国内免费 | 19篇 |
专业分类
化学 | 1395篇 |
晶体学 | 21篇 |
力学 | 68篇 |
数学 | 574篇 |
物理学 | 539篇 |
出版年
2023年 | 13篇 |
2022年 | 87篇 |
2021年 | 85篇 |
2020年 | 72篇 |
2019年 | 58篇 |
2018年 | 71篇 |
2017年 | 43篇 |
2016年 | 85篇 |
2015年 | 81篇 |
2014年 | 80篇 |
2013年 | 148篇 |
2012年 | 137篇 |
2011年 | 179篇 |
2010年 | 113篇 |
2009年 | 97篇 |
2008年 | 127篇 |
2007年 | 117篇 |
2006年 | 117篇 |
2005年 | 89篇 |
2004年 | 92篇 |
2003年 | 55篇 |
2002年 | 76篇 |
2001年 | 44篇 |
2000年 | 46篇 |
1999年 | 37篇 |
1998年 | 21篇 |
1997年 | 24篇 |
1996年 | 30篇 |
1995年 | 23篇 |
1994年 | 33篇 |
1993年 | 25篇 |
1992年 | 19篇 |
1991年 | 20篇 |
1990年 | 19篇 |
1989年 | 13篇 |
1988年 | 13篇 |
1987年 | 10篇 |
1986年 | 13篇 |
1985年 | 15篇 |
1984年 | 11篇 |
1981年 | 14篇 |
1979年 | 15篇 |
1978年 | 10篇 |
1977年 | 7篇 |
1976年 | 9篇 |
1974年 | 11篇 |
1973年 | 14篇 |
1972年 | 7篇 |
1971年 | 7篇 |
1970年 | 7篇 |
排序方式: 共有2597条查询结果,搜索用时 15 毫秒
31.
32.
JPC – Journal of Planar Chromatography – Modern TLC - A ten-component mixture of pesticides was applied to the edge of the layer in ‘frontal + elution’ mode for preliminary... 相似文献
33.
The proton chemical shift tensor of the hydroxyl proton in calcium hydroxide has been measured using multiple pulse NMR techniques. The tensor is axially symmetric with susceptibility corrected components σtT = ?9.3 ± 1 ppm and ppm relative to TMS. 792 79 相似文献
34.
Stationary phases with specific structural properties for high-throughput liquid chromatographic (LC) techniques are described. Special attention was paid to phases with special structural properties, mainly containing internal functional group (e.g. amide). Such materials are generally called "embedded phases". There are phases created in amidation process of aminopropylated silica gel, especially phases based on biological compounds, like phospholipids and cholesterol, which are called immobilized artificial membranes (IAM's). The synthesis and applications of polar embedded amide LC stationary phases were also reviewed. Methods of characterization of synthesized packing materials were presented, with general focusing on spectroscopic measurements like (13C and 29Si CP/MAS NMR and FT-IR), elemental and thermal analysis as well as chromatographic quantitative structure-retention relationships (QSRR) and extended chemometric tests. The potential applications of various dedicated stationary phases in a high-throughput LC screening procedures were also presented. 相似文献
35.
Brittain DE Gray BL Schreiber SL 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(17):5086-5093
A crossover in the ability of two distinct ruthenium-based metathesis pre-catalysts to effect the synthesis of dialkenylboronic esters in solution and on the solid-phase was observed. Specifically, while the Grubbs 2nd generation pre-catalyst 3 affords a greater degree of conversion to product than the Hoveyda-Grubbs pre-catalyst 2 in a solution-phase enyne-metathesis reaction, this trend is reversed in the solid-phase variant. Systematic investigation showed this trend to be general, regardless of variations in the homoallylic alcohol and alkynylboronic ester components of the reaction, as well as in the type of solid support employed. Experiments to determine a mechanistic hypothesis for this trend highlighted the significance of the ruthenium remaining bound to the substrate after metathetic rearrangement and found the presence of phosphine ligand to be detrimental to the success of the solid-phase reaction. Therefore, these results suggest an expanded role for phosphine-free pre-catalysts, such as 2, in challenging solid-phase metathesis reactions. 相似文献
36.
Kowalewski T Tsarevsky NV Matyjaszewski K 《Journal of the American Chemical Society》2002,124(36):10632-10633
Arrays of graphitic carbon nanoclusters were obtained by pyrolysis of nanoscale phase-separated block copolymers of polyacrylonitrile and poly(n-butyl acrylate). Upon heating in an inert atmosphere to temperatures ranging from approximately 400 to 1200 degrees C, polyacrylonitrile domains were converted into carbon nanoclusters, maintaining the overall shape and spacing, whereas the poly(n-butyl acrylate) phase was sacrificed. Preservation of the original nanoscale morphology of a block copolymer was possible only if pyrolysis was preceded by oxidation at temperatures of approximately 230 degrees C, in analogy with thermal stabilization of polyacrylonitrile precursor in the process used in the manufacturing of carbon fibers. Preorganization of the carbon precursor through self-assembly in block copolymers of polyacrylonitrile appears to be an attractive and robust strategy for templated synthesis of well-defined nanostructured carbon materials. 相似文献
37.
Substituted benzoic acid anions undergo decarboxylation in the medium-pressure region of an electrospray ion source yielding in most cases the correspondingly substituted phenide anions in high yield. The location of the anionic center is specified by the position of the carboxylic group. The only exceptions are compounds with substituents containing acidic hydrogen atoms, like OH and NH(2) groups. For such compounds, either an intra- or an intermolecular (mediated by the molecules of methanol or water) proton transfer from the more acidic position to the benzene ring is observed. The generated anions can be selected using the first quadrupole for studying their ion-molecule chemistry in the second quadrupole of a triple quadrupole mass spectrometer. Their reactions with CO(2), O(2), CH(3)COCH(3) and CCl(4) may serve as typical examples. The general applicability of this method for the generation of phenide anions has been confirmed on three different mass spectrometers. Experiments performed using carboxylic acids other then benzoic acid and its derivatives show that this method is not limited to phenide anions and can be used for the generation of a much wider range of carbanions in the gas phase. 相似文献
38.
An approximate kinetic‐energy functional of the generalized gradient approximation form was derived following the “conjointness conjecture” of Lee, Lee, and Parr. The functional shares the analytical form of its gradient dependency with the exchange‐energy functionals of Becke and Perdew, Burke, and Ernzerhof. The two free parameters of this functional were determined using the exact values of the kinetic energy of He and Xe atoms. A set of 12 closed‐shell atoms was used to test the accuracy of the proposed functional and more than 30 others taken from the literature. It is shown that the conjointness conjecture leads to a very good class of kinetic‐energy functionals. Moreover, the functional developed in this work is shown to be one of the most accurate despite its simple analytical form. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002 相似文献
39.
Based on an analysis of previously reported structures and a potential geometry fit with substrates, a new family of chiral dioxocyclam derivatives have been designed. The synthesis of those ligands was accomplished starting from l-proline and α-d-amino acids (converted to β-amino acids) with a key step of macrocyclization reaction of amino esters. All ligands were converted into neutral copper(II) complexes (amide groups underwent deprotonation of upon treatment of ligands with copper(II) acetate). The complexes exhibit the desired shape of their active surfaces, as proved by X-ray analysis. 相似文献
40.
Bender, O'Neil, Pearson and Schaefer (BOPS) have computed ab initio energies for 232 collinear configurations of FHH, using extensive configuration interaction. We have fitted these points using an LEPS-type function. Comparison with semi-empirical surfaces for FHH shows that the general form of these surfaces is in good accord with the ab initio findings. Evidence is presented which indicates that the BOPS ab initio surface exhibits too great a drop in energy along the favoured route into the exit valley. 相似文献