全文获取类型
收费全文 | 6634篇 |
免费 | 135篇 |
国内免费 | 14篇 |
专业分类
化学 | 4615篇 |
晶体学 | 50篇 |
力学 | 88篇 |
数学 | 973篇 |
物理学 | 1057篇 |
出版年
2021年 | 50篇 |
2020年 | 57篇 |
2019年 | 57篇 |
2016年 | 117篇 |
2015年 | 83篇 |
2014年 | 124篇 |
2013年 | 206篇 |
2012年 | 242篇 |
2011年 | 269篇 |
2010年 | 171篇 |
2009年 | 137篇 |
2008年 | 235篇 |
2007年 | 234篇 |
2006年 | 227篇 |
2005年 | 225篇 |
2004年 | 217篇 |
2003年 | 185篇 |
2002年 | 192篇 |
2001年 | 108篇 |
2000年 | 130篇 |
1999年 | 95篇 |
1998年 | 93篇 |
1997年 | 82篇 |
1996年 | 101篇 |
1995年 | 135篇 |
1994年 | 113篇 |
1993年 | 80篇 |
1992年 | 91篇 |
1991年 | 89篇 |
1990年 | 83篇 |
1989年 | 95篇 |
1988年 | 96篇 |
1987年 | 84篇 |
1986年 | 79篇 |
1985年 | 121篇 |
1984年 | 97篇 |
1983年 | 102篇 |
1982年 | 122篇 |
1981年 | 101篇 |
1980年 | 97篇 |
1979年 | 101篇 |
1978年 | 86篇 |
1977年 | 86篇 |
1976年 | 79篇 |
1975年 | 68篇 |
1974年 | 75篇 |
1973年 | 81篇 |
1972年 | 47篇 |
1971年 | 59篇 |
1970年 | 44篇 |
排序方式: 共有6783条查询结果,搜索用时 15 毫秒
61.
Gaseous Complexes NiAl2Cl8 and NiAl3Cl11 Spectral photometric measurements of equilibria which are established by reaction of solid NiCl2 with gaseous Al2Cl6 have been made. Results see ?Inhaltsübersicht”?. 相似文献
62.
Di-lithiated octamethylcyclotetrasilazane (OMCTS, 1) reacts with halosilanes in different ways. Ring contraction with formation of the isomeric cyclodisilazanes 2, 3 occurs in the reaction with chloro- and fluorotrimethylsilanes. Substitution (6) and ring contraction with formation of the isomeric six-membered ring 7 occurs with chlorodimethylsilane. 2, 3, 6 and 7 are excellent precursors of silyl-bridged, SiH-functional, four-membered ring systems (4, 5, 9–11). The mechanism of the isomerization reactions are discussed. 相似文献
63.
Me3B3N3H3Cr(CO)3 has been obtained by ring-ligand exchange starting from Et3B3N3Me3Cr(CO)3 and Me3B3N3H3. The new compound has been characterised by means of their IR, NMR, UV and mass spectroscopic data. 相似文献
64.
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
65.
Open- and closed-shell states in few-particle quantum mechanics. II. Classification of atomic states
The system developed in the first paper of this series for the classification of states as open- or closed-shed type is applied to atomic states. These may be classified in the isoelectronic limit (Z → ∞) from knowledge of the true wave function in this limit. One-matrix occupation numbers are tabulated for a number of states of the first-row atoms in the limit Z → ∞ and the states classified. A classification for finite Z is possible in the framework of the Z-dependent perturbation theory by use of a thoerem for the stability of a closed-shed with respect to small perturbations. Such a stability does not hold in general for open-shel states. 相似文献
66.
67.
Total Synthesis of (+)-D-Homoestrone 3-methyl ether A novel total synthesis of (+)-D-homoestrone 3-methyl ether ( 21 ) is described starting from (S)-8a-methyl-3,4,8,8a-tetrahydro-2H, 7H-naphthalene-1,6-dione ( 1 ) as a chiral synthon for the rings C and D. The key step involves alkylation of the derived 3 with m-methoxyphenacyl bromide ( 4 ) as an AB-building block to give the dioxo-secosteroid 5 . Hydrogenation of 5 affords the trans-decalone 11 . As by-products the epimeric cis-decalones 12 and 13 were characterized. Cyclization of 11 leads under kinetic control predominantly to the Δ9(11)-tetraene 14 . Catalytic hydrogenation of 14 and subsequent modification in ring D give the title compound 21 . It was found that 14 and also the derived Δ8-isomer 15a add hydrogen from the α-face of the molecule to an extent of about 80%. The 8α-D-homoestrone derivatives 20a and 23 as well as the 9β-isomers 19a and 22 were characterized. 相似文献
68.
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
69.
Robert Weis Marcel Kaiser Reto Brun Robert Saf Werner Seebacher 《Monatshefte für Chemie / Chemical Monthly》2006,137(10):1365-1374
Summary. 4-Aminobicyclo[2.2.2]octan-2-ones and -ols showed activity against the causative organisms of East African sleeping sickness
and Malaria tropica. Several imino derivatives of the ketones were more active. Now hydrazono analogues and 3-hydroximino
derivatives of the ketones and alcohols were synthesized. The structures of the obtained isomers were elucidated by NMR spectroscopy.
A single phenylhydrazone exhibited quite good antitrypanosomal activity in the range of already known imino analogues. 相似文献
70.
Investigation of the pharmacokinetics of celecoxib by liquid chromatography-mass spectrometry 总被引:4,自引:0,他引:4
Werner U Werner D Pahl A Mundkowski R Gillich M Brune K 《Biomedical chromatography : BMC》2002,16(1):56-60
A new method for the quantification of celecoxib in human plasma based on reversed-phase high-performance liquid chromatography (HPLC) coupled to atmospheric pressure chemical ionization (APCI) mass spectrometry (MS) after liquid-liquid extraction is presented. The method is rapid, sensitive and highly selective. The retention time of celecoxib was 2.3 min. The limit of quantification was 5 microg/L. Rofecoxib was used as internal standard. After validation, the method was used to study the pharmacokinetic profile of celecoxib following administration of a single oral dose (200 mg) in 12 healthy volunteers. Since celecoxib should be metabolized primarily by cytochrome 2C9 (CYP2C9), a poor metabolizer (PM) for this cytochrome P450 enzyme was included in the study. Pharmacokinetic characteristics (mean +/- SD) of extensive metabolizers (EM) were t(max) 2.9+/-1.2h, c(max) 842+/-280 microg/L, AUC(infinity) 6246+/-2147 microg h/L and t(1/2) 7.8+/-2.7h. The area under the curve (AUC(infinity)) for the PM was 12561 microg h/L. However, we found no noticeable increase in half life in the PM (11.5 h) after a single dose of celecoxib. 相似文献