全文获取类型
收费全文 | 53245篇 |
免费 | 8500篇 |
国内免费 | 5659篇 |
专业分类
化学 | 37368篇 |
晶体学 | 641篇 |
力学 | 3075篇 |
综合类 | 328篇 |
数学 | 5956篇 |
物理学 | 20036篇 |
出版年
2024年 | 182篇 |
2023年 | 1120篇 |
2022年 | 2076篇 |
2021年 | 2214篇 |
2020年 | 2272篇 |
2019年 | 2142篇 |
2018年 | 1829篇 |
2017年 | 1776篇 |
2016年 | 2606篇 |
2015年 | 2639篇 |
2014年 | 3099篇 |
2013年 | 3954篇 |
2012年 | 4848篇 |
2011年 | 4785篇 |
2010年 | 3322篇 |
2009年 | 3112篇 |
2008年 | 3337篇 |
2007年 | 2955篇 |
2006年 | 2651篇 |
2005年 | 2276篇 |
2004年 | 1739篇 |
2003年 | 1388篇 |
2002年 | 1275篇 |
2001年 | 1018篇 |
2000年 | 895篇 |
1999年 | 1045篇 |
1998年 | 856篇 |
1997年 | 806篇 |
1996年 | 794篇 |
1995年 | 726篇 |
1994年 | 612篇 |
1993年 | 519篇 |
1992年 | 430篇 |
1991年 | 392篇 |
1990年 | 331篇 |
1989年 | 240篇 |
1988年 | 178篇 |
1987年 | 163篇 |
1986年 | 159篇 |
1985年 | 139篇 |
1984年 | 87篇 |
1983年 | 93篇 |
1982年 | 55篇 |
1981年 | 39篇 |
1980年 | 29篇 |
1979年 | 18篇 |
1977年 | 18篇 |
1976年 | 20篇 |
1975年 | 21篇 |
1972年 | 19篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
41.
42.
Alan R. Katritzky Scott A. Henderson Baozhen Yang 《Journal of heterocyclic chemistry》1998,35(5):1123-1159
Applications of benzotriazole methodology for the preparation of heterocyclic compounds are reviewed. The characteristic advantages of benzotriazole as a synthetic auxiliary are first briefly considered. This is followed by a summary of its use in ring synthesis in which the construction of small; five-membered; six-membered; and larger heterocyclic rings using benzotriazole methodology are each examined separately. Finally, consideration of the use of benzotriazole in the ring annulation - particularly benzannulation - of heterocycles. Subsequent sections deal with the introduction of substituents into aromatic heterocycles; the ring substitution of saturated heterocycles; and benzotriazole assisted modification of heterocyclic substituents. The present review supplements a recent comprehensive review of benzotriazole chemistry [1] which covers the literature through 1996. 相似文献
43.
Yang W Butler JE Russell JN Hamers RJ 《Langmuir : the ACS journal of surfaces and colloids》2004,20(16):6778-6787
We have investigated the frequency-dependent interfacial electrical properties of nanocrystalline diamond films that were covalently linked to DNA oligonucleotides and how these properties are changed upon exposure to complementary and noncomplementary DNA oligonucleotides. Frequency-dependent electrical measurements at the open-circuit potential show significant changes in impedance at frequencies of >10(4) Hz when DNA-modified diamond films are exposed to complementary DNA, with only minimal changes when exposed to noncomplementary DNA molecules. Measurements as a function of potential show that at 10(5) Hz, the impedance is dominated by the space-charge region of the diamond film. DNA molecules hybridizing at the interface induce a field effect in the diamond space-charge layer, altering the impedance of the diamond film. By identifying a range of impedances where the impedance is dominated by the diamond space-charge layer, we show that it possible to directly observe DNA hybridization, in real time and without additional labels, via simple measurement of the interfacial impedance. 相似文献
44.
在非水溶剂(二甲基亚砜(DMSO)及N,N_二甲基甲酰胺(DMF))中的伏安曲线.呈现三对电流峰,表明存在三个可逆或准可逆酞菁配体的单电子转移过程,而在水溶液中则不呈现准可逆行为,且波形改变很大.此外,还比较了四磺酸基酞菁锌的水溶液在自然光和红光(600~700nm)照射下的循环伏安曲线,其氧化还原峰的数目和峰电位基本不变,但在红光照射下比自然光照射下的峰电流明显增大. 相似文献
45.
Direct trimethylsilylation1) of phenanthrene in different molar ratio of phenanthrene/sodium/trimethylchlorosilane is reported and discussed. Instead of the aromatic silyl compounds, such as 9-trimethylsilylphenanthrene (V), the hydroaromatic silyl compounds, such as 9, 10–bis (trimethylsilyl)-9, 10-dihydrophenanthrene (I) were obtained preferentially. Structure of these compounds are characterized and discussed. These silylated products have a general trend to change their properties during long time storage in the atmosphere under exposure to light. A significant difference of chemical shifts between silylated aromatic compound (V) and silylated hydroaromatic compound (I-IV) was observed. 相似文献
46.
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
47.
Shen YH Li SH Li RT Han QB Zhao QS Liang L Sun HD Lu Y Cao P Zheng QT 《Organic letters》2004,6(10):1593-1595
Both coriatone (1). a novel highly oxygenated picrotoxane-type sesquiterpene, and corianlactone (2). with an unprecedented sesquiterpene basic skeleton, named coriane, were isolated from Coriaria nepalensis Wall. The structures of 1 and 2 were determined by analysis of their two-dimensional NMR data, and the structure of 2 was confirmed by X-ray analysis. Compounds 1 and 2 showed no remarkable inhibitory activity toward K(562) cells. They are cytotoxic with IC(50) > 50 microg/mL (cis-platinim: IC(50) = 0.49 microg/mL). 相似文献
48.
A highly effective, economical, and environmentally friendly method using of CAN as oxidant and water as solvent for oxidative coupling of N,N-dialkylarylamines was reported. 相似文献
49.
A method has been described for the direct determinations of trace cadmium using derivative atom trapping flame atomic absorption spectrometry with an improved water-cooled stainless steel trapping equipment. The characteristic concentration (gave a derivative absorbance of 0.0044) and detection limit (3sigma) of cadmium were 0.028 and 0.02 ng ml(-1) when collecting for a 1 min, respectively, which were 992 and 145-fold better than those of the conventional flame atomic absorption spectrometry. The detection limit and sensitivity of the proposed method for a 2 min collection time were 1 and 2 orders of magnitude higher than those of conventional flame atomic absorption spectrometry. The present method was applied to the determinations of cadmium in water samples with a recovery range of 91 approximately 111% and a relative standard deviation of 4.7 approximately 5.6%. 相似文献
50.