全文获取类型
收费全文 | 1127篇 |
免费 | 54篇 |
国内免费 | 1篇 |
专业分类
化学 | 992篇 |
晶体学 | 4篇 |
力学 | 9篇 |
数学 | 73篇 |
物理学 | 104篇 |
出版年
2023年 | 6篇 |
2022年 | 12篇 |
2021年 | 21篇 |
2020年 | 28篇 |
2019年 | 16篇 |
2018年 | 14篇 |
2017年 | 11篇 |
2016年 | 37篇 |
2015年 | 22篇 |
2014年 | 44篇 |
2013年 | 46篇 |
2012年 | 82篇 |
2011年 | 82篇 |
2010年 | 57篇 |
2009年 | 34篇 |
2008年 | 56篇 |
2007年 | 61篇 |
2006年 | 49篇 |
2005年 | 60篇 |
2004年 | 44篇 |
2003年 | 34篇 |
2002年 | 49篇 |
2001年 | 12篇 |
2000年 | 8篇 |
1999年 | 13篇 |
1998年 | 11篇 |
1997年 | 9篇 |
1996年 | 5篇 |
1995年 | 11篇 |
1994年 | 10篇 |
1993年 | 5篇 |
1991年 | 5篇 |
1990年 | 7篇 |
1989年 | 5篇 |
1987年 | 10篇 |
1985年 | 12篇 |
1984年 | 15篇 |
1982年 | 11篇 |
1980年 | 9篇 |
1978年 | 10篇 |
1977年 | 9篇 |
1976年 | 12篇 |
1975年 | 7篇 |
1973年 | 9篇 |
1962年 | 6篇 |
1947年 | 6篇 |
1937年 | 4篇 |
1935年 | 5篇 |
1928年 | 5篇 |
1920年 | 4篇 |
排序方式: 共有1182条查询结果,搜索用时 203 毫秒
21.
Elisabeth Egholm JacobsenErik van Hellemond Anders Riise MoenLucia Camino Vazquez Prado Thorleif Anthonsen 《Tetrahedron letters》2003,44(46):8453-8455
In esterifications of secondary alcohols catalyzed by immobilized lipase B from Candida antarctica (Novozym 435) the E-values decreased during the reaction. Hydrolysis of the corresponding butanoates showed the opposite effect. When an enantiopure (R)-alcohol, related but different, was added to the transesterification reaction, the E-value was significantly enhanced. 相似文献
22.
Reactivities of homogeneous series of ethylenic compounds R1CHCH21, trans R1CHCHMe 2, R1MeCCH23 and R1CHCMe24 have been measured in methanol at 25°C (R1 Me, Et, n-Pr, -CH2C6H5-CH2OCOCH3, -CH2Cl). The criterion developed to decide between a bridged and a carbonium ion-like transition state is based on an internal comparison of the series and avoids resorting to external structural scales. Even in the case of alkenes 3 and 4 which are very dissymmetric with respect to polarity, the sensitivity to polar effects remains constant and the transition state behaves like a symmetric entity; only a slight secondary effect, attributed to hyperconjugation, is detectable. 相似文献
23.
To screen for organic pigments, like fringelites or porphyrins, in sediments and fossil specimen, a simple diffuse reflectance UV-vis spectroscopic determination was developed. In contrast to common inorganic pigments, like Fe2O3, these pigments exhibit well-structured characteristic absorption peaks which allow their recognition. This method was then used to identify fringelite H in a non-crinoidSolenopora species from the Jurassic. Reflectance FTIR spectroscopy proved not to be useful for this purpose. 相似文献
24.
A nonradioactive method was employed to detect different cell membrane antigens on human polymorphonuclear granulocytes, monocytes and platelets. We compared the reactivity of one monoclonal antibody, N1III10, assumed to be FcγRII-specific by functional assays, with other well-characterized monoclonal antibodies and human sera. Intact cells were incubated with biotin N-hydroxysulfosuccinimide ester which preferentially reacts with lysine residues in polypeptides. Biotin-labeled cells were lysed and the antigen was isolated from the cell lysate by immunoprecipitation with the antibody bound to Protein A-Sepharose. The precipitates were separated by sodium dodecyl sulfate-polyacrylamide gel electrophoresis, transferred onto nitrocellulose membrane, and visualized by a streptavidin-alkaline phosphatase system with a suitable substrate. Using this biotin-labeling system we could show that N1III10 detects a 40 kDa antigen on monocytes and platelets, comparable to that expected of FcγRII monoclonal antibodies. 相似文献
25.
Elisabeth Eriksrud 《Journal of Electroanalytical Chemistry》1977,76(1):27-49
The title subject has been studied by galvanostatic single-pulse, chronopotentiometric and equilibrium measurements on the Zn(Hg)/Zn(II) electrode in x M KI+(1?x) M KCl (x from 0 to 1), 1 M KBr and 1 M MeCl (Me=Li, Na, K and Cs) solutions of pH 3 at 25°C. Quantitative information about the effect of specifically adsorbed halides on the rates of the Zn(II)/Zn(I) and the Zn(I)/Zn(Hg) steps is obtained separately (for the latter step mainly at potentials near ?1.0 V(SCE)), and the latter step seems to be more influenced than the former by the adsorption. An attempt is made to correlate the adsorption effect on the rate of the Zn(II)/Zn(I) step to double-layer parameters according to recent models for such effects. The extra current observed at potentials where the halides are adsorbed, seems to vary with the surface activity of the specifically adsorbed ion. The lack of any observed kinetic effect of Cs+, which is specifically adsorbed at these potentials, is possibly due to the Cs+ specific adsorption enhancing the Cl? specific adsorption and vice versa, so that the decelerating and accelerating effects by these ions may cancel each other. 相似文献
26.
27.
Meyer F Demeshko S Leibeling G Kersting B Kaifer E Pritzkow H 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(5):1518-1526
Pyrazolate-based dinucleating ligands with thioether-containing chelate arms have been used for the synthesis of a family of novel tetranuclear nickel(II) complexes [L2Ni4(N3)3(O2CR)](ClO4)2 that incorporate three azido bridges and one carboxylate (R = Me, Ph). Molecular structures have been elucidated by X-ray crystallography in four cases, revealing Ni4 cores with a unique topology in which two of the azido ligands adopt an unusual mu3-1,1,3 bridging mode. The compounds were further characterized by mass spectrometry, IR spectroscopy, and variable-temperature magnetic susceptibility measurements. Magnetic data analyses indicate a combination of significant intramolecular ferromagnetic and antiferromagnetic exchange interactions that give rise to an overall S(T) = 0 ground state. The sign and the magnitude of the individual couplings have been rationalized in the framework of the common magnetostructural correlations for end-to-end and end-on azido linkages, suggesting that these correlations also remain valid for the respective fragments of multiply bridging mu3-1,1,3 azido ligands. 相似文献
28.
29.
Elisabeth Seguin Michel Koch Evelyne Chenu Marcel Hayat 《Helvetica chimica acta》1980,63(5):1335-1346
Partial Synthesis and Oncostatic Properties of Pseudotubulosines, Analogues of Emetine and Tubulosine Pseudotubulosines, structural analogues of emetine and tubulosine, have been synthesized by either Pictet-Spengler or Bischler-Napieralski condensation from dihydrocorynantheal or corynantheidal. Spectral data, cytotoxic and oncostatic properties of these new alkaloids are described. 相似文献
30.
Ladislaus Szekeres und Elisabeth Sugár 《Fresenius' Journal of Analytical Chemistry》1960,172(1):35-38
Zusammenfassung Zur Bestimmung von Sulfit und Thiosulfat nebeneinander wird folgendes Verfahren beischrieben: In einem aliquoten Teil der zu untersuchenden Lösung wird mit elementarem Jod oxydiert, wobei die Sulfitionen zwei Äquivalente, die Thiosulfationen ein Äquivalent Jod je Mol verbrauchen. In einem zweiten aliquoten Teil der zu untersuchenden Lösung werden die Ionen mit — aus KBrO3 + KBr hergestelltem — NaOBr oxydiert; die Sulfitionen verbrauchen dabei zwei Äquivalente, die Thiosulfationen acht Äquivalente Brom je Mol. 相似文献