全文获取类型
收费全文 | 55315篇 |
免费 | 3813篇 |
国内免费 | 4905篇 |
专业分类
化学 | 42948篇 |
晶体学 | 561篇 |
力学 | 998篇 |
综合类 | 695篇 |
数学 | 7339篇 |
物理学 | 11492篇 |
出版年
2023年 | 711篇 |
2022年 | 899篇 |
2021年 | 2066篇 |
2020年 | 1594篇 |
2019年 | 1584篇 |
2018年 | 1245篇 |
2017年 | 1333篇 |
2016年 | 1643篇 |
2015年 | 1670篇 |
2014年 | 2021篇 |
2013年 | 3678篇 |
2012年 | 2472篇 |
2011年 | 2705篇 |
2010年 | 2419篇 |
2009年 | 3058篇 |
2008年 | 3361篇 |
2007年 | 3490篇 |
2006年 | 2849篇 |
2005年 | 2151篇 |
2004年 | 2021篇 |
2003年 | 1817篇 |
2002年 | 4266篇 |
2001年 | 1699篇 |
2000年 | 1225篇 |
1999年 | 1039篇 |
1998年 | 1029篇 |
1997年 | 734篇 |
1996年 | 789篇 |
1995年 | 684篇 |
1994年 | 699篇 |
1993年 | 686篇 |
1992年 | 641篇 |
1991年 | 430篇 |
1990年 | 333篇 |
1989年 | 273篇 |
1988年 | 296篇 |
1987年 | 236篇 |
1986年 | 254篇 |
1985年 | 350篇 |
1984年 | 264篇 |
1983年 | 161篇 |
1982年 | 305篇 |
1981年 | 487篇 |
1980年 | 449篇 |
1979年 | 480篇 |
1978年 | 382篇 |
1977年 | 288篇 |
1976年 | 250篇 |
1974年 | 84篇 |
1973年 | 163篇 |
排序方式: 共有10000条查询结果,搜索用时 46 毫秒
911.
912.
报道了一种单颗粒微电极制备新方法, 并研究了LaNi4.7Al0.3球形单颗粒微电极的电化学行为. 相似文献
913.
接枝和交联对纳米Si02改性NR/PP共混型热塑弹性体的影响 总被引:2,自引:0,他引:2
动态硫化制备纳米二氧化硅(SiO2)改性天然橡胶,聚丙烯共混型热塑性弹性体(NR/PPTPE).研究了马来酸酐,苯乙烯,过氧化二异丙苯(MAH/St/DCP)多单体“就地”熔融接枝、交联对TPE力学性能、耐溶剂性能和耐热变形性能的影响,并用SEM分析了TPE的断面形貌.结果表明:纳米SiO2和MAH/St/DCP的最佳质量分数分别为0.03和0.0375/0.0188/0.00375时,MAH/St/DCP接枝、交联改性NR/PP/纳米SiO:TPE的力学性能、耐溶剂性能和耐热变形性能最佳.MAH/St/DCP“就地”接枝、交联通过细化交联NR分散相、改善交联NR分散的均匀性和增加两相之间的共交联,使NR与PP两相界面结合强度明显提高,NR/PPTPE的综合性能得到明显的改善. 相似文献
914.
Liu H Hu Y Yang S Guo W Lu X Zhao L 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(21):6392-6406
We report herein a comprehensive study of photoinduced reactions in complexes of Mg+ with primary (n-propyl- and isopropylamine) and secondary amines (dipropyl- and diisopropylamine) in the spectral range of 230-440 nm. Similar to the methyl- and ethylamine complexes studied previously, N-H bond activation of these complexes is very unfavorable. Instead, the C(alpha)-C, C-N, and C(alpha)-H bond-cleavage photoproducts are observed after photoexcitation of the Mg+ complexes (3(2)P<--3(2)S). For Mg+(primary amine) complexes, for example, Mg+-NH2CH2CH2CH3, and Mg+-NH2CH(CH3)2, the photoproducts resulting from C(alpha)--C rupture prevail after P(z) and charge-transfer excitations, whereas the Mg+ photofragment is predominant upon P(x,y) excitation. However, with further N-alkyl substitution, as in Mg+(secondary amine) complexes, for example, Mg+-NH(CH2CH2CH3)2 and Mg+-NH[CH(CH3)2]2, a novel intracomplex C-C coupling photoreaction dominates on P(x,y) excitation of Mg+, which is believed to arise from Mg+* insertion into the C-N bond. With P(z) and charge-transfer excitation, the Mg-R elimination photoproducts, arising from C(alpha)-C bond cleavage, predominate. The energetics and possible mechanisms of the intracomplex photoreactions are analyzed in detail with the help of extensive quantum mechanics calculations. 相似文献
915.
Magorzata A. Broda Maria Rospenk Dawid Siodak Barbara Rzeszotarska 《Journal of Molecular Structure》2005,740(1-3):17-24
The comparative studies on the association of Ac-ΔAla-NMe2 and Ac-l-Ala-NMe2 in carbon tetrachloride were performed by the analysis of their average molecular weight, dipole moments and FTIR spectra. To aid spectroscopic interpretation and gain some deeper insight into the nature of associates, the geometries of the minimum energy of the dimers of Ac-ΔAla-NMe2 and Ac-l-Ala-NMe2 were calculated by the B3LYP/6-31+G** method. The average molecular weight in the studied concentration range, for the ΔAla and l-Ala peptide, as determined by the osmometric method, did not exceed 1.5 and 1.2 of the monomeric mass, respectively. Accordingly, the percentage of the monomeric form (α) decreased as concentration was increased more significantly for the ΔAla analogue than for its saturated counterpart. In the studied concentrations, the dipole moment of the unsaturated compound decreases and that of its counterpart is almost constant. We identified a wider range of dimeric forms of Ac-ΔAla-NMe2 than those of Ac-l-Ala-NMe2. While Ac-ΔAla-NMe2 mainly forms cyclic dimers, built of open conformers H/F, specific for α,β-dehydroamino acids, Ac-l-Ala-NMe2 forms cyclic and linear dimers, characteristic for the usual amino acids. Ac-ΔAla-NMe2 has a greater tendency to associate than its saturated variant, which is the result of stronger hydrogen bonds. 相似文献
916.
灭多威的光催化降解动力学研究 总被引:19,自引:3,他引:19
研究了农药灭多威在TiO2光催化下的降解产物,反应动力学及影响降解速度的因素,灭多威在TiO2催化下10min内可被完全转换为无机物而失去毒害作用,IR研究表明,灭多威的分解产物NH^+4,SO^2-4和CO2,其分争过程中准一级反应,除铜和氯离子体低浓度时有促进作用,而高浓度为阻碍作用外,大部分阴,阳离子对降解均有不利影响。 相似文献
917.
918.
V. B. Vol'eva T. I. Prokofeva A. I. Prokofev I. S. Belostotskaya N. L. Komissarova V. V. Ershov 《Russian Chemical Bulletin》1995,44(9):1720-1724
The interaction of 3,6-di-tert-butyl-ortho-benzoquinone (1) and 3,5-di-tert-butyl-ortho-benzoquinone (2) with NH3 in water—alcohol medium and with (NH4)2CO3 in a solid phase has been studied. Redox processes with participation of a nucleophile of the medium take place for1, while2 reacts with NH3 at the carbonyl group with transformation of the quinone imide. The mechanism of redox transformation of1 has been proposed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1789–1793, September, 1995.This work was carried out with financial support from the Russian Foundation for Basic Research (Project No. 94-03-08653). 相似文献
919.
A cumulative selection procedure for choosing configuration functions for inclusion in CI calculations is described. The objective of the method is to obtain equal energy loss, relative to unselected calculations, for different states and different regions of the potential surface. Results obtained from calculations on the BH molecule indicate an overall advantage in comparison to the threshold selection procedure, particularly with regard to molecular geometry changes. 相似文献
920.
Langlet J. Claverie P. Pullman B. Piazzola D. Daudey J. P. 《Theoretical chemistry accounts》1977,46(2):105-116
The effect of water on the conformational preferences of acetylcholine has been studied within the discrete, the continuum and the combined discrete-continuum models described in parts I and II of this series. All the models lead to the conclusion that the trans-gauche form which is, following refined quantum-mechanical computations, the intrinsically preferred one and the one observed in the crystal of acetylcholine and of a number of analogues should remain also the preferred conformation in water. This result agrees with NMR studies. The results of the empirical discrete model used here compare favorably to those obtained by an ab initio super-molecule treatment. The continuum model utilized here represents a net improvement above such models utilized in other works. 相似文献