全文获取类型
收费全文 | 2256篇 |
免费 | 21篇 |
国内免费 | 19篇 |
专业分类
化学 | 1254篇 |
晶体学 | 81篇 |
力学 | 66篇 |
数学 | 351篇 |
物理学 | 544篇 |
出版年
2021年 | 13篇 |
2020年 | 25篇 |
2019年 | 12篇 |
2018年 | 14篇 |
2017年 | 13篇 |
2016年 | 16篇 |
2015年 | 23篇 |
2014年 | 22篇 |
2013年 | 83篇 |
2012年 | 83篇 |
2011年 | 103篇 |
2010年 | 42篇 |
2009年 | 48篇 |
2008年 | 122篇 |
2007年 | 121篇 |
2006年 | 122篇 |
2005年 | 114篇 |
2004年 | 134篇 |
2003年 | 107篇 |
2002年 | 77篇 |
2001年 | 59篇 |
2000年 | 39篇 |
1999年 | 40篇 |
1998年 | 24篇 |
1997年 | 45篇 |
1996年 | 43篇 |
1995年 | 29篇 |
1994年 | 35篇 |
1993年 | 27篇 |
1992年 | 33篇 |
1991年 | 31篇 |
1990年 | 37篇 |
1989年 | 35篇 |
1988年 | 28篇 |
1987年 | 29篇 |
1986年 | 18篇 |
1985年 | 33篇 |
1984年 | 37篇 |
1983年 | 26篇 |
1982年 | 22篇 |
1981年 | 32篇 |
1980年 | 29篇 |
1979年 | 28篇 |
1978年 | 35篇 |
1977年 | 22篇 |
1976年 | 26篇 |
1975年 | 20篇 |
1974年 | 17篇 |
1973年 | 19篇 |
1971年 | 11篇 |
排序方式: 共有2296条查询结果,搜索用时 312 毫秒
51.
52.
The reaction of 4-carbethoxy-5-chloro-1,2,3-thiadiazole () with sodium azide results in the formation of ethyl α-thiatriazolyldiazoacetate () instead of the corresponding azide (). Two plausible mechanisms for this new rearrangement are formulated. 相似文献
53.
Saracoglu N Talaz O Azizoglu A Watson WH Balci M 《The Journal of organic chemistry》2005,70(14):5403-5408
[reaction: see text] endo- and exo-2,3,4,7-tetrahydro-1H-1,4-methanobenzocycloheptene-7-carboxylic acid ethyl esters have been synthesized, and their Diels-Alder cycloaddition reactions with maleic anhydride, dimethyl acetylenedicarboxylate and singlet oxygen have been investigated. The X-ray analysis of four adducts indicated the pyramidalization of the central double bond. Density functional theory calculations on the isolated products and model compounds showed excellent agreement between the experimental and theoretical determined butterfly angles. Furthermore, it has been shown that a cyclopropyl group fused to [2.2.2] system decreases significantly the degree of the pyramidalization which is attributed to the steric interactions between the cyclopropyl group and ethano bridge of the norbornene systems. Due to the instability of the bicyclic endoperoxides, their X-ray analysis could not be carried out. DFT calculations on model compounds showed increased bending in the case of the product obtained by the addition of singlet oxygen to endo-2,3,4,7-tetrahydro-1H-1,4-methanobenzocycloheptene-7-carboxylic acid ethyl ester. 相似文献
54.
Moni Chauhan Claude Chuit Robert J. P. Corriu Catherine Rey Jean-Paul Declercq Antoine Dubourg 《Journal of organometallic chemistry》1996,510(1-2):173-179
The X-ray structure analysis of bis(8-dimethylamino-l-naphthyl)phenylphosphane (3) and of the corresponding sulphide 4 has revealed hexacoordination at phosphorus in both cases, the N … P separations being less than the sum of the van der Waal radii. Furthermore, in both cases the overall geometry corresponds to a distorted bicapped tetrahedron. The optimum geometry calculated for 4 via the
program developed by Autodesk (MM + method) suggests that the structure of the molecule is a function not only of steric requirements but also of electronic effects. 相似文献
55.
The electron density distribution in potassiumbis-(carbonato)cuprate(II) has been analyzed using x-ray diffraction data from an earlier structure determination. While the
copper-ligand geometry is close to square planar the deformation density near the metal is strongly asymmetric. There are
local maxima near the copper atom along the line of the Cu-K vectors. These resemble features found in corresponding regions
in normal length metal-metal bonds. The observation is consistent with the long range nature of the Coulomb potential associated
with the potassium ion. 相似文献
56.
Watson MD Jäckel F Severin N Rabe JP Müllen K 《Journal of the American Chemical Society》2004,126(5):1402-1407
Cyclophanes with the largest-to-date polycyclic aromatic hydrocarbon (hexa-peri-hexabenzocoronene, HBC) to be entrained in such a structural motif are reported. The two disks are covalently captured by intermolecular ring-closing olefin metathesis of dienes in good yield. DSC, optical microscopy, and WAXD show the new cyclophanes to self-assemble to thermotropic columnar liquid crystal mesophases similar to monomeric analogues. Solution spectroscopic studies reveal that the two disks within a single unit lie face-to-face, with a small average lateral offset. Self-assembly into two-dimensional crystals at a solid-liquid interface was visualized by STM, and the electrical properties of single molecules were assessed by scanning tunneling spectroscopy revealing a diode-like behavior which is similar to that previously reported for single HBC disks, laying the groundwork for future electrical interrogations of dynamic molecular complexes. 相似文献
57.
Françoise Maugé Jean-Paul Gallas Jean-Claude Lavalley Guido Busca Gianguido Ramis Vincenzo Lorenzelli 《Mikrochimica acta》1988,95(1-6):57-61
In the far IR region at low molybdenum loadings, Mo-SiO2 catalysts present a pseudomolybdate or a polymolybdate species, while bulk-like MoO3 appears at loadings close to the geometrical monolayer coverage. W-SiO2 and V-SiO2 spectra show bands close to those observed on the corresponding bulk oxides.In the case of TiO2, Al2O3, ZrO2 supported catalysts, a band is observed near 1000 cm–1 which is assigned to the Mo=O stretching vibration of coordinatively unsaturated Mo
n+ ions showing a stronger interaction with the support than one observed on silica. 相似文献
58.
The photochemistry of the stereoisomeric 1,3-dimethyl-3(2-phenylethenyl)cyclohexenes has been explored Direct irradiation of the cis- and trans-β-styrylcyclohexenes leads to di-π-methane rearrangement, producing the endo- and exo-3,7-dimethyl-8-phenybicyclo[5.1.0]oct-2-enes, and cis -trans isomerization, interconverting the 1,4-diene containing substrates. Triplet sensitized photolysis of both substituted cyclohexenes leads exclusively to cis-trans isomerization. Results from low conversion direct irradiations of the cis- and trans-β-styrylcyclohexenes indicate that the singlet rearrangements are stereospecific, and lead to formation of the 8-exo and 8-endo-phenylbicyclic octenes, respectively. The relationship between di-π-methane structure and triplet reaction efficiency, and the effect of conformation on the rearrangement stereochemistry are discussed. 相似文献
59.
Paul Watson Peter Willett Valerie J. Gillet Marcel L. Verdonk 《Journal of computer-aided molecular design》2001,15(9):835-857
A knowledge-based method for calculating the similarity of functional groups is described and validated. The method is based on experimental information derived from small molecule crystal structures. These data are used in the form of scatterplots that show the likelihood of a non-bonded interaction being formed between functional group A (the `central group') and functional group B (the `contact group' or `probe'). The scatterplots are converted into three-dimensional maps that show the propensity of the probe at different positions around the central group. Here we describe how to calculate the similarity of a pair of central groups based on these maps. The similarity method is validated using bioisosteric functional group pairs identified in the Bioster database and Relibase. The Bioster database is a critical compilation of thousands of bioisosteric molecule pairs, including drugs, enzyme inhibitors and agrochemicals. Relibase is an object-oriented database containing structural data about protein-ligand interactions. The distributions of the similarities of the bioisosteric functional group pairs are compared with similarities for all the possible pairs in IsoStar, and are found to be significantly different. Enrichment factors are also calculated showing the similarity method is statistically significantly better than random in predicting bioisosteric functional group pairs. 相似文献
60.