全文获取类型
收费全文 | 1251篇 |
免费 | 38篇 |
国内免费 | 8篇 |
专业分类
化学 | 983篇 |
晶体学 | 9篇 |
力学 | 8篇 |
数学 | 79篇 |
物理学 | 218篇 |
出版年
2023年 | 5篇 |
2022年 | 9篇 |
2021年 | 9篇 |
2020年 | 17篇 |
2019年 | 18篇 |
2018年 | 15篇 |
2017年 | 11篇 |
2016年 | 31篇 |
2015年 | 32篇 |
2014年 | 27篇 |
2013年 | 60篇 |
2012年 | 72篇 |
2011年 | 72篇 |
2010年 | 40篇 |
2009年 | 45篇 |
2008年 | 75篇 |
2007年 | 67篇 |
2006年 | 68篇 |
2005年 | 75篇 |
2004年 | 78篇 |
2003年 | 59篇 |
2002年 | 68篇 |
2001年 | 30篇 |
2000年 | 19篇 |
1999年 | 18篇 |
1998年 | 13篇 |
1997年 | 10篇 |
1996年 | 14篇 |
1995年 | 11篇 |
1994年 | 19篇 |
1993年 | 20篇 |
1992年 | 11篇 |
1991年 | 7篇 |
1990年 | 8篇 |
1989年 | 12篇 |
1988年 | 4篇 |
1987年 | 6篇 |
1986年 | 8篇 |
1985年 | 16篇 |
1984年 | 9篇 |
1983年 | 13篇 |
1982年 | 7篇 |
1981年 | 11篇 |
1980年 | 10篇 |
1979年 | 10篇 |
1978年 | 14篇 |
1977年 | 13篇 |
1976年 | 8篇 |
1975年 | 8篇 |
1974年 | 6篇 |
排序方式: 共有1297条查询结果,搜索用时 15 毫秒
21.
Onida B Borello L Busco C Ugliengo P Goto Y Inagaki S Garrone E 《The journal of physical chemistry. B》2005,109(24):11961-11966
Joint IR and computational results allow a detailed characterization of the surface properties of a mesoporous benzene-silica hybrid material with crystal-like wall structure. After outgassing at 450 degrees C, hydroxyl species mainly consist of noninteracting silanols, with both O-H and Si-O stretching modes at lower frequencies than those of SiOH in silica. Interaction with several probe molecules, followed both by experiment and calculus, shows that the aryl group in the coordination sphere of Si imparts a lesser acidity with respect to the isolated silanol in silica. In contrast, adsorption isotherms indicate that the interaction with acetone is stronger with benzene-silica than with silica: this is interpreted in terms of secondary interactions taking place between the slightly acidic CH in acetone and the electronic cloud in benzene-like rings. This suggests that both the inorganic component and the organic one play a role in dictating the surface behavior. 相似文献
22.
Resonance Raman scattering with the Q band of CuTPP shows a peculiar intensity pattern; bands due to combinations and overtones are strong, whereas the corresponding fundamentals are very weak. By a quantitative analysis of excitation profiles, this phenomenon has been fully accounted for on the basis of the vibronic theory of Raman intensities. Vibronic coupling parameters between the Q and B states of CuTPP have been obtained. 相似文献
23.
A simple and accurate titrimetric determination of calcium in the presence of larger amounts of magnesium is proposed. Calcium is extracted into a small volume of organic solvent as its glyoxal-bis(2-hydroxyanil) complex, and the calcium is titrated with EGTA. The end-point is sharp, and occurs when the red colour of the organic layer vanishes. This method has been successfully applied to the determination of calcium in sea-water with an error less than 0.1%. 相似文献
24.
Chatani N Amako K Tobisu M Asaumi T Fukumoto Y Murai S 《The Journal of organic chemistry》2003,68(4):1591-1593
The reaction of benzofuran-2,3-dione derivatives 1 with CO and alkenes (or alkynes) results in a carbonylative [2+2+1] cycloaddition in which the ester-carbonyl group is incorporated into a two-atom assembling unit to give spirolactone derivatives 2. This reaction provides the first example of an ester-carbonyl group participating in a carbonylative cycloaddition reaction. 相似文献
25.
K. Kitamura Hideyuki Mano Yoshie Shimamoto Yoshihiro Tadokoro Koji Tsuruta Shinji Kitagawa 《Analytical and bioanalytical chemistry》1997,358(4):509-513
The second-derivative spectra of chlorpromazine (CPZ) or triflupromazine (TFZ) in buffer solutions (pH 7.4) containing various amounts of BSA (the reference solutions contained the same amount of BSA) showed derivative isosbestic points. The residual background signals derived from incomplete suppression of BSA signals can be entirely eliminated in the second-derivative spectra and BSA has spectrophotometrically one kind of binding site for CPZ or TFZ. The fractions of the drugs bound to BSA were calculated from the derivative intensity differences (ΔD values) of CPZ or TFZ before and after the addition of BSA. Scatchard plot experiments suggested that the binding of the drugs to BSA could be explained as a partition like non-specific binding model. The association constants (K) of CPZ or TFZ with BSA were calculated from the ΔD values according to the non-specific binding model by a nonlinear least-squares method. The K values were almost constant for all of the drug concentrations studied, and good reproducibility was obtained. The fractions predicted by the K values were in good coincidence to the observed values. These results confirm the usefulness of the proposed derivative method which does not need any separation procedures. 相似文献
26.
The reaction of alpha,beta-unsaturated imines with CO and alkenes in the presence of Ru(3)(CO)(12) as a catalyst results in a three-component coupling reaction that gives alpha,alpha-disubstituted beta,gamma-unsaturated gamma-butyrolactams. The reaction proceeds via a two-step sequence involving the initial formation of ketone derivatives by catalytic carbonylation at the beta-olefinic C-H bonds of alpha,beta-unsaturated imines, followed by the (uncatalyzed) intramolecular nucleophilic attack of the imine nitrogen on the ketonic carbon to generate a tetrahedral intermediate, which then undergoes a 1,2-ethyl migration. The reaction of a cyclic unsaturated imine, derived from the reaction of (1R)-(-)-myrtenal with tert-butylamine, gives a beta-aminocyclopentene derivative, which is formed by an aldol-type condensation of the initially formed ketone, indicating the initial formation of ethyl ketone. 相似文献
27.
Takashi Tateno Shinji Doi Shunsuke Sato Luigi M. Ricciardi 《Journal of statistical physics》1995,78(3-4):917-935
Noise effects on phase lockings in a system consisting of a piecewise-linear van der Pol relaxation oscillator driven by a periodic input are studied. The problem of finding the period of the oscillator is reduced to the first-passage-time problem of the Ornstein-Uhlenbeck process with time-varying boundary. The probability density functions of the first-passage time are used to define the operator which governs a transition of an input phase density after one cycle of the oscillator. Phase lockings in a stochastic sense are investigated on the basis of the density evolution by the operator. 相似文献
28.
Weaver M Arisaka K Roberts D Slater W Briere RA Cheu E Harris DA Roodman A Schwingenheuer B Wah YW Winstein B Winston R Barker AR Swallow EC Bock GJ Coleman R Crisler M Enagonia J Ford R Hsiung YB Jensen DA McFarland KS Ramberg E Tschirhart R Collins EM Gollin GD Nakaya T Yamanaka T Gu P Haas P Hogan WP Kim SK Matthews JN Myung SS Schnetzer S Somalwar SV Thomson GB Zou Y 《Physical review letters》1994,72(24):3758-3761
29.
Gu P Haas P Hogan WP Kim SK Matthews JN Myung SS Schnetzer S Thomson GB Zou Y Arisaka K Roberts D Slater W Spencer MB Weaver M Briere RA Cheu E Harris DA Krolak P McFarland KS Roodman A Schwingenheuer B Somalwar SV Wah YW Winstein B Winston R Barker AR Swallow EC Bock GJ Coleman R Crisler M Enagonio J Ford R Hsiung YB Jensen DA O'Dell VR Ramberg E Tschirhart R Collins EM Gollin GD Nakaya T Yamanaka T 《Physical review letters》1996,76(23):4312-4315
30.
Harada S Kumagai N Kinoshita T Matsunaga S Shibasaki M 《Journal of the American Chemical Society》2003,125(9):2582-2590
Full details of our direct Michael addition of unmodified ketones using new asymmetric zinc catalysis are described. Et(2)Zn/(S,S)-linked-BINOL complexes were successfully applied to direct 1,4-addition reactions of hydroxyketones. The first generation Et(2)Zn/(S,S)-linked-BINOL 1 = 2/1 system was effective for 1,4-addition of 2-hydroxy-2'-methoxyacetophenone (3). Using 1 mol % of (S,S)-linked-BINOL 1 and 2 mol % of Et(2)Zn, we found that a 1,4-addition reaction of beta-unsubstituted enone proceeded smoothly at 4 degrees C to afford products in high yield (up to 90%) and enantiomeric excess (up to 95%). In the case of beta-substituted enones, however, the first generation Et(2)Zn/(S,S)-linked-BINOL 1 = 2/1 system was not at all effective. The second generation Et(2)Zn/(S,S)-linked-BINOL 1 = 4/1 with MS 3A system was developed and was effective for various beta-substituted enones to afford products in good dr, yield (up to 99%), and high enantiomeric excess (up to 99% ee). With the Et(2)Zn/1 = 4/1 systems, catalyst loading for beta-unsubstituted enone was reduced to as little as 0.01 mol % (substrate/chiral ligand = 10 000). The new system was also effective for 1,4-addition reactions of 2-hydroxy-2'-methoxypropiophenone (9) to afford chiral tert-alcohol in high enantiomeric excess (up to 96% ee). Mechanistic investigations as well as transformations of the Michael adducts into synthetically versatile intermediates are also described. 相似文献