全文获取类型
收费全文 | 1328篇 |
免费 | 36篇 |
国内免费 | 8篇 |
专业分类
化学 | 990篇 |
晶体学 | 3篇 |
力学 | 29篇 |
数学 | 180篇 |
物理学 | 170篇 |
出版年
2023年 | 9篇 |
2022年 | 18篇 |
2021年 | 22篇 |
2020年 | 27篇 |
2019年 | 16篇 |
2018年 | 21篇 |
2017年 | 21篇 |
2016年 | 44篇 |
2015年 | 49篇 |
2014年 | 30篇 |
2013年 | 71篇 |
2012年 | 90篇 |
2011年 | 91篇 |
2010年 | 74篇 |
2009年 | 59篇 |
2008年 | 88篇 |
2007年 | 82篇 |
2006年 | 84篇 |
2005年 | 72篇 |
2004年 | 73篇 |
2003年 | 52篇 |
2002年 | 44篇 |
2001年 | 33篇 |
2000年 | 28篇 |
1999年 | 13篇 |
1998年 | 13篇 |
1997年 | 11篇 |
1996年 | 21篇 |
1995年 | 10篇 |
1994年 | 12篇 |
1993年 | 13篇 |
1992年 | 11篇 |
1991年 | 4篇 |
1990年 | 6篇 |
1989年 | 11篇 |
1988年 | 6篇 |
1987年 | 6篇 |
1986年 | 11篇 |
1985年 | 4篇 |
1984年 | 5篇 |
1983年 | 2篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1979年 | 2篇 |
1978年 | 1篇 |
1977年 | 5篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1959年 | 2篇 |
排序方式: 共有1372条查询结果,搜索用时 31 毫秒
91.
The presentation of the quantum cohomology of the moduli spaceof stable vector bundles of rank two and odd degree with fixeddeterminant over a Riemann surface of genus g > 2 is obtained.The argument avoids the use of gauge theory, providing an alternativeproof to that given by the author in Duke Math. J. 98 (1999)525540. 2000 Mathematics Subject Classification 14N35(primary); 14H60, 53D45 (secondary). 相似文献
92.
Kinetic resolution of racemic mixtures is a well-established methodology for the preparation of optically active compounds. However, excellent enantioselectivities are required to obtain them in enantiopure form, due to the decrease in ee when conversion values are close to 50%. To overcome this limitation, a parallel (asymmetric) reaction can remove the disfavored enantiomer. In this review, several examples of this strategy showing its wide range of applicability are described, as well as their mathematical treatment and some new applications in combinatorial chemistry. 相似文献
93.
Renz M Blasco T Corma A Fornés V Jensen R Nemeth L 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(20):4708-4717
Sn-Beta is used as a heterogeneous catalyst for the Baeyer-Villiger reaction with hydrogen peroxide. Cyclic ketones are transformed into the corresponding lactones, while unsaturated ketones are oxidized to the corresponding unsaturated lactones with very high chemoselectivity. The catalyst is also selective for the oxidation of aromatic aldehydes with H2O2, producing the formate ester or the corresponding hydrolyzed product, that is the alcohol. Shape-selective oxidations are observed for isomeric reactants with different molecular shapes. The catalytic Sn sites have been characterized by 119Sn MAS-NMR spectroscopy, and tetrahedral incorporation into the zeolite framework has been demonstrated. In situ IR spectroscopy and 18O labeling experiments have shown that the oxidation mechanism involves an intermediate of the Criegee type. 相似文献
94.
Racemic 1-methyl-2-oxocycloalkanecarbonitriles have been subjected to bioreduction by the fungus Mortierella isabellina NRRL 1757 through a parallel kinetic-resolution process. The u and l alcohols thus obtained (up to >99% ee) were easily separated and oxidized to the R and S ketones, respectively. The process can be then repeated so that both enantiomers of the ketone and two epimers of the alcohol can be obtained in their enantiopure forms. 相似文献
95.
Maderna A Huertas R Hawthorne MF Luguya R Vicente MG 《Chemical communications (Cambridge, England)》2002,(16):1784-1785
A boron-rich, water-soluble porphyrin conjugate was synthesized by coupling of two carboranyl alcohols with 2-chlorophenoxyphosphorus dichloride, followed by conjugation to an amine-functionalized tetraphenyl-porphyrin via an amide linkage. 相似文献
96.
Escuer A Vicente R Mautner FA Goher MA Abu-Youssef MA 《Chemical communications (Cambridge, England)》2002,(1):64-65
Novel 3D topologies combining diazine and azido bridges between MnII magnetic centres have been obtained and characterised by low-temperature magnetic measurements. 相似文献
97.
Adam W García H Diedering M Martí V Olivucci M Palomares E 《Journal of the American Chemical Society》2002,124(41):12192-12199
The photochemical denitrogenation of the cyclopentene-annelated DBH-type azoalkanes 1 has been examined in solution as a function of bridgehead substitution and temperature. For all derivatives, namely, the unsubstituted 1a(H/H), monomethyl 1b(Me/H) dimethyl 1c(Me/Me), monophenyl 1d(Ph/H), and diphenyl 1e(Ph/Ph), the temperature-dependent ratio of syn and anti housanes 2 provides experimental support for a competition between the singlet (high temperature) and triplet (low temperature) reaction channels in the direct photolysis. The syn/anti ratio of the housanes 2 depends on the extent and type of bridgehead substitution; the amount of the anti diastereomer (retention) follows the order Ph > Me > H, and double substitution is more effective than single. This stereochemical memory is interpreted in terms of the mass effect (inertia) of the substituents and steric interaction (size) between the substituents at the bridgehead and the methylene bridge during the deazetation step of the transient diazenyl diradical conformations (1)DZ (exo-ax) and (1)DZ (exo-eq). These conformers are impulsively generated upon decay of the (1)(n,pi)-excited azoalkane, a trajectory assessed through computational work. The new mechanistic feature disclosed by the unprecedented anti stereoselectivity (retention) is the intervention of a puckered 1,3-cyclopentanediyl singlet diradical (1)DR as product bifurcation step, whose conformational relaxation to the planar species (loss of stereochemical memory) is encumbered by bridgehead substitution. 相似文献
98.
99.
García-Jareño JJ Giménez-Romero D Keddam M Vicente F 《The journal of physical chemistry. B》2005,109(10):4593-4598
The graphical analysis of the impedance plots is used in the study of the electrodic systems that take place through two consecutive single electron transfers. The zinc anodic dissolution is studied by using this procedure. The characteristic points easily allow us to explain and to simulate the impedance behavior of this electrodic system according to the steady-state potential and the roughness of the working electrode. The direct procedure for parametrical identification from the graphical analysis allows us to reduce the time needed for an impedance experiment. This graphical analysis is suggested for studying thin coated galvanized steels. 相似文献
100.
Effect of the platinum content on the microstructure and micropore size distribution of Pt/alumina-pillared clays 总被引:1,自引:0,他引:1
Barrera-Vargas M Valencia-Rios J Vicente MA Korili SA Gil A 《The journal of physical chemistry. B》2005,109(49):23461-23465
The aim of this work is to study the effect of the platinum content (0-1.8 wt % Pt) on the microstructure of an alumina-pillared clay. For this purpose, the nitrogen physisorption data at -196 degrees C, the micropore size distributions of the supported platinum catalysts, and the hydrogen chemisorption results at 30 degrees C have been analyzed and compared. The preparation of the catalysts has modified the textural properties of the Al-pillared clay support, giving rise to a loss of surface area and micropore volume. After reduction at 420 degrees C, the presence of dispersed metallic platinum with mean crystallite size in the 22-55 A range has been found by hydrogen adsorption. Comparison of all results reveals that the platinum species block the micropore entrances by steric hindrance to nitrogen access as the platinum content increases. 相似文献