全文获取类型
收费全文 | 1511篇 |
免费 | 34篇 |
国内免费 | 5篇 |
专业分类
化学 | 1117篇 |
晶体学 | 9篇 |
力学 | 34篇 |
综合类 | 1篇 |
数学 | 197篇 |
物理学 | 192篇 |
出版年
2023年 | 13篇 |
2022年 | 30篇 |
2021年 | 49篇 |
2020年 | 42篇 |
2019年 | 33篇 |
2018年 | 30篇 |
2017年 | 34篇 |
2016年 | 47篇 |
2015年 | 35篇 |
2014年 | 51篇 |
2013年 | 84篇 |
2012年 | 91篇 |
2011年 | 101篇 |
2010年 | 67篇 |
2009年 | 60篇 |
2008年 | 86篇 |
2007年 | 89篇 |
2006年 | 68篇 |
2005年 | 74篇 |
2004年 | 66篇 |
2003年 | 41篇 |
2002年 | 51篇 |
2001年 | 14篇 |
2000年 | 15篇 |
1999年 | 10篇 |
1998年 | 10篇 |
1997年 | 13篇 |
1996年 | 14篇 |
1995年 | 17篇 |
1994年 | 12篇 |
1993年 | 16篇 |
1992年 | 14篇 |
1991年 | 9篇 |
1990年 | 10篇 |
1989年 | 8篇 |
1988年 | 11篇 |
1987年 | 13篇 |
1985年 | 4篇 |
1983年 | 12篇 |
1982年 | 11篇 |
1981年 | 9篇 |
1980年 | 8篇 |
1979年 | 4篇 |
1978年 | 10篇 |
1977年 | 5篇 |
1976年 | 10篇 |
1975年 | 5篇 |
1974年 | 8篇 |
1970年 | 4篇 |
1955年 | 3篇 |
排序方式: 共有1550条查询结果,搜索用时 15 毫秒
11.
The hybridization in several cyclic polyacetylene compounds has been calculated by the maximum overlap method, assuming planar and non-planar geometries of the molecules. In the planar configuration the hybrids describing the molecular skeleton deviate from the corresponding bond directions. We have a few “bent” bonds, but in contrast to the situation in small rings, here the deviation angles are negative, i.e., the hybrids point toward the inside of the ring. Non-planar structures in which acetylene groups are kept in a plane and CCH2 or CH2 groups are displaced out of the plane show less deviation from the bond directions of bent bonds. Furthermore, the deviation angles decrease with an increase in the out-of-plane displacement of methylene groups. Finally, when the angle of bending of the molecules approaches 50°, the deviation vanishes, predicting a puckered conformation for the molecules. Correlation between CC stretching vibration frequencies and the corresponding CC bond overlap is discussed. 相似文献
12.
13.
We introduce generalized bond orders defined in terms of weighted Kekule valence structures. The weights were determined by the contributions of linearly independent and minimal conjugated circuits in individual Kekule valence structure. When special values for the contributions of conjugated circuits of different size are assumed, one obtains quantities that show considerable similarity to the Pauling and the Clar's bond orders. Pauling bond orders are obtained when one assumes that all conjugated circuits make equal contribution to bond orders. © 1994 John Wiley & Sons, Inc. 相似文献
14.
Paths of length two and three appear to dominate variations in isomers of alkanes when various physical and chemical molecular properties are compared. The regularities previously observed for octanes have been fully examined for the set of 35 nonane isomers C9H20. Such examinations are facilitated by construction of appropriate grid graphs with paths of length two and three, respectively, representing molecules and connecting such points along the grid axes. By ordering structures in the two-dimensional coordinate plane, various trends and regular changes in the relative magnitudes for the selected thermodynamic properties have been traced to molecular connectivity and topology. 相似文献
15.
Milan Randi 《International journal of quantum chemistry》1983,23(5):1707-1722
Many regularities in properties among structurally related compounds are known but a systematic approach to investigate all such cases is rare. A plan is outlined for a systematic study of structural regularities that is based on use of selected graph invariants as prime auxiliary quantities. In this paper carbon-13 chemical shifts in alkanes are examined. Since NMR spectra of paraffins are well understood, the example provides a useful illustration of the approach, introduces basic concepts, and illustrates the kind of the results that the graph-theoretical scheme generates. Differences and similarities between graph-theoretical viewing of the problem of structural regularities and customary direct use of additivities are discussed in some detail. 相似文献
16.
The Cu complex Cu(L)nCl (L=2-propylamine) has been found to be an advantageous catalyst for the addition of polyhalogenated compounds to chloro substituted ethenes; the 11 adducts were formed almost exclusively in up to 71% yield.
, , Cu(L)nCl (L=2-), ; 71% 11.相似文献
17.
Dillmore WS Yousaf MN Mrksich M 《Langmuir : the ACS journal of surfaces and colloids》2004,20(17):7223-7231
This work describes a chemically well defined method for patterning ligands to self-assembled monolayers (SAMs) of alkanethiolates on gold. This method begins with monolayers presenting a nitroveratryloxycarbonyl (NVOC)-protected hydroquinone which is photochemically irradiated to reveal a hydroquinone group. The resulting hydroquinone is then oxidized to the corresponding benzoquinone, providing a site for the Diels-Alder mediated immobilization of ligands. The rate constant for the photochemical deprotection is 0.032 s(-1) (with an intensity of approximately 100 mW/cm(2) between 355 and 375 nm), corresponding to a half-life of 21 s. The hydroquinone is oxidized to the benzoquinone using either electrochemical or chemical oxidation and then functionalized by reaction with a cyclopentadiene-tagged ligand. Two methods for patterning the immobilization of ligands are described. In the first, the substrate is illuminated through a mask to generate a pattern of hydroquinone groups, which are elaborated with ligands. In the second method, an optical microscope fit with a programmable translational stage is used to write patterns of deprotection which are then again elaborated with ligands. This technique is characterized by the use of well-defined chemical reactions to control the regions and densities of ligand immobilization and will be important for a range of applications that require patterned ligands for biospecific interactions. 相似文献
18.
Nada Majkić-Singh Milan Konjović Marina Stojanov Slavisa Spasić Ivan Berkeš 《Analytica chimica acta》1981,130(2):419-423
Hydrogen peroxide, the product of diamine oxidase-catalyzed putrescine or cadaverine oxidation, formed in proportion to the enzyme activity, is measured spectrophotometrically by using the above sulfonate (ABTS) and peroxidase. Only one reagent solution containing 3 mmol of putrescine or 10 mmol of cadaverine, 4 mmol of ABTS and 3000 U of peroxidase per litre of 0.2 mol l-1 Tris—0.1 mol l-1 HCl buffer pH 7.5 is needed. Absorbance changes are measured at 410 nm over the first 3 min of the reaction. This initial oxidation rate of the chromogen enables diamine oxidase activity up to 230 U l-1 to be determined. 相似文献
19.
Gutman I Vukicević D Graovac A Randić M 《Journal of chemical information and computer sciences》2004,44(2):296-299
An algebraic Kekulé structure of a benzenoid hydrocarbon is obtained from an ordinary Kekulé structure by inscribing into each hexagon the number of pi-electrons which (according to this Kekulé structure) belong to this hexagon. We show that in the case of catafusenes, there is a one-to-one correspondence between ordinary and algebraic Kekulé structures. On the other hand, in the case of perifusenes, one algebraic Kekulé structure may correspond to several ordinary Kekulé structures. 相似文献
20.