全文获取类型
收费全文 | 7552篇 |
免费 | 263篇 |
国内免费 | 641篇 |
专业分类
化学 | 7347篇 |
晶体学 | 64篇 |
力学 | 78篇 |
综合类 | 20篇 |
数学 | 566篇 |
物理学 | 381篇 |
出版年
2024年 | 7篇 |
2023年 | 52篇 |
2022年 | 103篇 |
2021年 | 173篇 |
2020年 | 156篇 |
2019年 | 185篇 |
2018年 | 153篇 |
2017年 | 185篇 |
2016年 | 176篇 |
2015年 | 154篇 |
2014年 | 203篇 |
2013年 | 654篇 |
2012年 | 293篇 |
2011年 | 263篇 |
2010年 | 211篇 |
2009年 | 278篇 |
2008年 | 314篇 |
2007年 | 333篇 |
2006年 | 309篇 |
2005年 | 309篇 |
2004年 | 309篇 |
2003年 | 289篇 |
2002年 | 1797篇 |
2001年 | 244篇 |
2000年 | 172篇 |
1999年 | 142篇 |
1998年 | 107篇 |
1997年 | 116篇 |
1996年 | 106篇 |
1995年 | 117篇 |
1994年 | 86篇 |
1993年 | 80篇 |
1992年 | 74篇 |
1991年 | 48篇 |
1990年 | 33篇 |
1989年 | 23篇 |
1988年 | 36篇 |
1987年 | 33篇 |
1986年 | 19篇 |
1985年 | 21篇 |
1984年 | 26篇 |
1983年 | 6篇 |
1982年 | 15篇 |
1981年 | 9篇 |
1980年 | 13篇 |
1979年 | 6篇 |
1978年 | 8篇 |
1977年 | 2篇 |
1973年 | 3篇 |
1966年 | 1篇 |
排序方式: 共有8456条查询结果,搜索用时 360 毫秒
51.
The N-benzoyl-l-tyrosine ethyl ester (BTEE) anchored in cyclodextrin (β and β-methyl CD) serves as an excellent substrate for subtilisin
Carlsberg catalysis. The rate of hydrolysis was found to be approximately twofold higher than that of the methanolic substrate.
The Kmapp and Vmax values for the CD anchored substrates were significantly higher than the methanol-solubilized BTEE. 相似文献
52.
A. Shapiro 《Journal of Optimization Theory and Applications》1990,66(3):477-487
Various definitions of directional derivatives in topological vector spaces are compared. Directional derivatives in the sense of Gâteaux, Fréchet, and Hadamard are singled out from the general framework of -directional differentiability. It is pointed out that, in the case of finite-dimensional spaces and locally Lipschitz mappings, all these concepts of directional differentiability are equivalent. The chain rule for directional derivatives of a composite mapping is discussed. 相似文献
53.
近几年,随着对主客体化学研究的深入,杯芳烃的功能化修饰成为该领域的研究热点[1-6]。本文以邻、间、对氨基苯甲酸和杯[6]芳烃为原料,经重氮化 偶联反应合成了新型有色邻、间、对羧基苯偶氮基杯[6]芳烃,产物的结构经IR,1HNMR和元素分析表征;并研究了它们生色原理和光谱性能。结果表明它们是一类新型指示剂和具有新型配位空腔的主体分子。合成路线如下:图1 邻、间、对羧基苯偶氮基杯[6]芳烃的合成Fig.1 Fig1:Synthesisofp (o,m,p carboxylbenzeneazo)calix[6]arenes1 实验部分1 1 仪器与试剂Nicolet 460型傅里叶红外光谱仪(KBr… 相似文献
54.
本文拟定的纸色谱法是以苯-乙酸乙酯-甲醇-乙酸(9:2:1:1)作展开剂,将血卟啉衍生物(HPD)分离为五部份,分别测定各部份浸取液的荧光发射光谱,作为一种对血卟啉衍生物组份作对比鉴定的参考方法。采用Ward的高效液相色谱程序对比研究结果表明,国产与美国产HPD的组份近似,均以血卟啉为主要组份,而前者血卟啉的含量较高;二者还均含有羟乙基乙烯基衍生物和羟基乙酸酯,初步研究了血卟啉衍生物在甲醇-水溶剂系统中的高效液相色谱行为,进一步将血卟啉衍生物分离为九部份,有利于单一组份研究。 相似文献
55.
报道从D-甘露醇出发合成手性双膦(2S,5S)-3,6-双(二苯膦)-1,4:3,6-双脱水-2,5-双去氧-L-艾杜醇,原位下BDPI与3种铑配合物作用生成手性非螯合型双膦铑催化剂,常压下对4种脱氢苯丙氨酸衍生物进行不对称催化化反主尖,对反应结果及e.e.值进行了讨论。 相似文献
56.
The reactions of γ,γ-dialkoxyallylic zirconium species with carbonyl compounds in the presence of Lewis acid are reported. The reactivity of γ,γ-dialkoxyallylic zirconium species and reaction pathway were strongly dependent on the structure and electrostatic nature of the carbonyl compounds. 相似文献
57.
Immobilized polysiloxane-anchored permethyl-β-cyclodextrin (Chirasil-Dex) with a cyclodextrin content of approximately 30 % by weight, previously employed as a versatile chiral stationary phase for the separation of enantiomers by GC, has been used for the separation of enantiomers by capillary supercritical fluid chromatography (SFC). A considerable number of racemates could be resolved, e.g. aromatic alcohols, amino alcohols (TFA derivatives), and underivatized acids. Many pharmaceutical compounds were among those analyzed, including several NSAIDs (e.g. ibuprofen and ketoprofen), a steroidal drug (nor-gestrel), a barbiturate (hexobarbital), and others. Among the racemates resolved were many which cannot be analyzed by GC owing to low volatility or decomposition at elevated temperatures. For two racemates, analysis temperature and mobile phase density were systematically varied to give constant analysis times or capacity factors k. Low temperatures (ca 60 °C) yielded the best separation in term of separation factor, α, or resolution, Rs, even though higher densities had to be used. In comparison with GC, capillary SFC was able to furnish higher separation factors and similar resolution. The applicability of capillary SFC for the analysis of mixtures of cyclodextrin derivatives, e.g. those used in the synthesis of Chirasil-Dex, was, furthermore, demonstrated. 相似文献
58.
59.
Yingjin liu Naoto Horiuchi Yoshimi Sueishi Shunzo Yamamoto 《Journal of inclusion phenomena and macrocyclic chemistry》2006,54(3-4):233-239
The kinetics of the hydride transfer reaction between Methylene Blue (MB+) and 1-benzyl-1,4-dihydronicotinamide (BNAH) were studied in 10% ethanol-90% water mixed solvents containing β- and γ-cyclodextrins (β-CD and γ-CD). The pseudo-first order rate constant shows kinetic saturation at high initial concentration of BNAH. This indicates the formation of a complex between MB+ and BNAH. The reaction was suppressed by addition of β-CD, but enhanced by addition of γ-CD. MB+ and BNAH were separately accommodated within the β-CD cavity and the cavity walls may protect the activity site of the reactants. On the other hand, in the MB+-BNAH-γ-CD system, the inclusion of the complex between MB+ and BNAH with γ-CD occurred. This effect of γ-CD can distinguish between the productive and non-productive nature of the complex. 相似文献
60.
M. G. Voronkov L. I. Larina Yu. I. Bolgova O. M. Trofimova N. F. Chernov V. A. Pestunovich 《Chemistry of Heterocyclic Compounds》2006,42(12):1585-1591
The 1H, 13C, 15N, and 29Si NMR, IR, and UV spectra of N-(1-silatranylmethyl) and N-(trimethoxysilylmethyl) derivatives of nitrogen heterocycles have
been studied. The dependence and interrelation of the chemical shifts of 29Si and 15N nuclei of the silatranyl group in the spectra of N-(1-silatranylmethyl)-substituted nitrogen heterocycles are determined
by the nature of the heterocyclic system.
__________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1857–1865, December, 2006. 相似文献