全文获取类型
收费全文 | 8747篇 |
免费 | 270篇 |
国内免费 | 654篇 |
专业分类
化学 | 8509篇 |
晶体学 | 85篇 |
力学 | 79篇 |
综合类 | 20篇 |
数学 | 571篇 |
物理学 | 407篇 |
出版年
2024年 | 10篇 |
2023年 | 60篇 |
2022年 | 183篇 |
2021年 | 167篇 |
2020年 | 177篇 |
2019年 | 201篇 |
2018年 | 191篇 |
2017年 | 229篇 |
2016年 | 218篇 |
2015年 | 164篇 |
2014年 | 261篇 |
2013年 | 792篇 |
2012年 | 355篇 |
2011年 | 321篇 |
2010年 | 249篇 |
2009年 | 346篇 |
2008年 | 387篇 |
2007年 | 396篇 |
2006年 | 339篇 |
2005年 | 368篇 |
2004年 | 365篇 |
2003年 | 335篇 |
2002年 | 1793篇 |
2001年 | 255篇 |
2000年 | 165篇 |
1999年 | 148篇 |
1998年 | 122篇 |
1997年 | 131篇 |
1996年 | 115篇 |
1995年 | 133篇 |
1994年 | 114篇 |
1993年 | 99篇 |
1992年 | 90篇 |
1991年 | 51篇 |
1990年 | 35篇 |
1989年 | 29篇 |
1988年 | 39篇 |
1987年 | 29篇 |
1986年 | 19篇 |
1985年 | 24篇 |
1984年 | 28篇 |
1983年 | 8篇 |
1982年 | 17篇 |
1981年 | 16篇 |
1980年 | 15篇 |
1979年 | 13篇 |
1978年 | 9篇 |
1973年 | 4篇 |
1971年 | 32篇 |
1970年 | 16篇 |
排序方式: 共有9671条查询结果,搜索用时 62 毫秒
61.
利用1,4-二-(4-羧基吡啶基)丁烷(L)合成了两个新的三维配位聚合物{(CdL2)·4H2O·2ClO4}n 1和{(ZnL2)·4H2O·2ClO4}n 2。单晶X-射线结构分析表明,1和2具有相同的计量式,但其晶体属于不同的空间群(1属于P4n2,2属于P4222)。两种配合物中,每个金属离子分别由配体与四个相邻的金属离子连接,从而形成具有六重穿插的金刚石网络结构,其网络中大的空腔被高氯酸根离子和(H2O)4分子簇所占据。 相似文献
62.
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
63.
B. Turovska J. Stradins I. Turovskis A. Plotniece A. Shmidlers G. Duburs 《Chemistry of Heterocyclic Compounds》2004,40(6):753-758
A study was carried out on the electrochemical oxidation of 1,4-dihydropyridines, found as substituents in pyridinium salts, which are strong electron acceptors. The potentials for their oxidation in acetonitrile were determined. NMR spectroscopy was used to find the relative acidity of the N–H and C–H protons and the oxidation potentials were determined for the anionic products of the ionization of the N–H bond in dihydropyridine. The only product of the preparative electrolysis, in contrast to chemical oxidation, is the corresponding pyridine, namely, the oxidized dihydropyridine form. 相似文献
64.
A versatile new approach for the synthesis in three steps of 2-substituted-2,3-dihydro[1,4]dioxino[2,3-b]pyridines B via a Smiles rearrangement using easily available reagents is described. A study illustrating the influence of experimental conditions on the progress of the reaction is reported. 相似文献
65.
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
66.
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
67.
68.
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
69.
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
70.
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