全文获取类型
收费全文 | 1421篇 |
免费 | 153篇 |
国内免费 | 317篇 |
专业分类
化学 | 1741篇 |
晶体学 | 5篇 |
力学 | 6篇 |
综合类 | 4篇 |
数学 | 2篇 |
物理学 | 133篇 |
出版年
2024年 | 2篇 |
2023年 | 16篇 |
2022年 | 39篇 |
2021年 | 62篇 |
2020年 | 75篇 |
2019年 | 51篇 |
2018年 | 51篇 |
2017年 | 44篇 |
2016年 | 83篇 |
2015年 | 72篇 |
2014年 | 67篇 |
2013年 | 89篇 |
2012年 | 92篇 |
2011年 | 81篇 |
2010年 | 74篇 |
2009年 | 83篇 |
2008年 | 82篇 |
2007年 | 85篇 |
2006年 | 62篇 |
2005年 | 90篇 |
2004年 | 59篇 |
2003年 | 55篇 |
2002年 | 93篇 |
2001年 | 50篇 |
2000年 | 35篇 |
1999年 | 43篇 |
1998年 | 42篇 |
1997年 | 23篇 |
1996年 | 25篇 |
1995年 | 22篇 |
1994年 | 22篇 |
1993年 | 20篇 |
1992年 | 16篇 |
1991年 | 17篇 |
1990年 | 10篇 |
1989年 | 10篇 |
1988年 | 12篇 |
1987年 | 10篇 |
1986年 | 7篇 |
1985年 | 4篇 |
1984年 | 3篇 |
1983年 | 2篇 |
1982年 | 3篇 |
1981年 | 1篇 |
1980年 | 2篇 |
1979年 | 4篇 |
1977年 | 1篇 |
排序方式: 共有1891条查询结果,搜索用时 15 毫秒
21.
载铂铝交联蒙脱土的烷烃芳构化特性──Ⅰ.载铂铝交联蒙脱土对烷烃的择形芳构化作用 总被引:1,自引:0,他引:1
对比考察了Pt/KL沸石,Pt/Al2O3和载铂铝交联蒙脱土(Pt/Al-CLM)催化剂对不同碳原子数烷烃的芳构化特性.脉冲微反的评价结果表明:Pt/Al-CLM比Pt/Al2O3和Pt/KL具有较高的转化n-C8,n-C9为其对应芳烃的选择性,在转化n-C8时,产物中的间、对位二甲苯收率很高,而转化n-C9时有高的正丙苯收率.采用129Xe-NMR、XRD和孔分布测定考察了Pt/Al-CLM和Pt/KL、Pt/Al2O3之间孔结构的差异.结果表明:由于n-C8,n-C9在反应过程中其过渡态的极限尺寸与Pt/Al-CLM0.9nm左右的层间域相匹配,因而它对n-C8,n-C9具有择形芳构化作用. 相似文献
22.
23.
Takehiko Yamato Masashi Yasumatsu Yoshiyuki Saruwatari Louis Korbla Doamekpor 《Journal of inclusion phenomena and macrocyclic chemistry》1994,19(1-4):315-331
Novel macrocyclic compounds, hexahydroxy[1.0.1.0.1.0]- (2b) and octahydroxy[1.0.1.0.1.0.1.0]metacyclophane (2c) have been prepared in 50–70% yield by base-catalyzed condensation of 5,5-di-tert-butyl-2,2-dihydroxybiphenyl (1) with formaldehyde in refluxing xylene. An attempted alkylation of the flexible macrocycles2b and2c with ethyl bromoacetate in the presence of Cs2CO3 under acetonitrile reflux gave only one pure stereoisomer3 and4, respectively, while other possible isomers were not observed. The structural characterization of these products is also discussed. The two-phase solvent extraction data indicated that hexaethyl ester3 and octaethyl ester4 show strong metal affinity, comparable with that of the corresponding calix[n]arenes, and a high K+ selectivity was observed for octaethyl ester4.1H-NMR titration of hexaethyl ester3 and octaethyl ester4 with KSCN clearly demonstrate that a 11 complex is formed which is stable on the NMR time scale.This paper is dedicated to the commemorative issue on the 50th anniversary of calixarenes. 相似文献
24.
The photoprocesses of a series of N-substituted dibenz[b,f]azepines (iminostilbenes) were studied by absorption and emission spectroscopy, by laser flash photolysis, and by preparative irradiation with NMR analysis. In solutions, 2pi+2pi photodimers of N-cyano and N-acyl dibenzazepines are formed via the triplet state upon acetone- or benzophenone-sensitized energy transfer. T-T absorption spectra were measured and absorption coefficients were determined. The triplet energy transfer is equally efficient for N-alkyl dibenzazepines, which do not dimerize. Excited states of npi* character in the latter cases are discussed to rationalize the different reactivities. In spite of negligible intersystem crossing of 21 dibenzazepine derivatives, photodimers of N-acyl and N-cyano dibenzazepines are formed upon direct excitation in concentrated solutions (0.01-0.1 mol dm(-3)) as well as in the solid state. A selective anti-configuration of the photodimers was found throughout. 相似文献
25.
Krishna Gopal Dongol M. Cristina Melo e Silva Kouki Matsubara Taisuke Matsumoto Shuntaro Mataka Thies Thiemann 《无机化学与普通化学杂志》2003,629(6):945-947
The preparation of two η6‐estra‐1, 3, 5(10), 6‐tetraene tricarbonylchromium complexes 4 and 6 are described. In both cases only one stereoisomer can be isolated, in contrast to other estrane‐tricarbonylchromium complexes, where complexations are non‐stereoselective. X‐ray crystal structural analysis of 4 discloses that only the more sterically hindered β‐facial isomer is formed. It is assumed that the 6, 7‐olefinic moiety exerts a directive influence on the complexation. 相似文献
26.
Mark Salomon 《Journal of solution chemistry》1990,19(12):1225-1236
Conductivity data are used to determine thermodynamic complex formation constants for cases in which both the initial electrolyte and the complexed electrolyte form ion pairs. Using the method described in the text, the complex formation constants of Li+, Na+ and K+ with the crown ether 18-crown-6 and of Li+ with the ligand triphenylphosphine oxide in propylene carbonate have been evaluated from conductance data. The complexation of AgBr in propylene carbonate solutions of n-etrabutylammonium bromide has also been studied by the measurement of molar conductivities. The results of these studies indicate that ion pairing should not be neglected, even in high permittivity solvents such as propylene carbonate, and that the ion pair association constants correlate well with structural studies on cation-crown ether molecular conformations. 相似文献
27.
28.
Jia-you Shu Mo Zhu Yi Shu Qi-jun Liu Tong Li 《高分子科学》2006,(4):395-401
The new chelate resins, abbreviated as PNBMZs and PBBMZs based on epoxide polymer, were synthesized by polycondensation of N,N-diglycidyl-4-glycidyloxyaniline or 1,4-bis(2,3-epoxypropyl)benzene with the primary amine group of 1,3-bis(benzimidazol-2yl)propylamine (BBPAH). The ion exchangers contain 2.71-3.23 mmol of the ligand contents per gram of the resin. Batch extraction capacities were determined for the metal chloride salts in buffer solutions in the pH range from -1 to 6.0. The chelate resins were very selective for Cu^2+, Zn^2+, Cd^2+ in the presence of other divalent transition metal ions. The maximum uptake capacities of PNBMZ (synthetic molar ratio = 1:1.5) under non-competitive condition were found to be 0.94 mmol/g for Cu^2+ at pH = 2, 1.3 mmol/g for Cd^2+ at pH = 1 and 1.75 mmol/g for Zn^2+ at pH = -1 respectively. While in the case of PBBMZ, it was 1.39 mmol/g for Cd〉 at pH = 1. The metal-uptake behaviors for both of them showed strong pH dependence, and their extraction capacities increase with decreasing pH. The uptake of Cu^2+ by the resin PNBMZs at pH = 1 was found to be rather fast with t1/2 = 18 min. Metal-uptake experiments under competitive conditions also confirm that the chelate resins have a high selectivity for Cu^2+, Zn^2+, Cd^2+ and the contrary pH dependence. 相似文献
29.
Summary A theoretical treatment is presented which considers differences between the composition of the mobile phase and solvents
that are incorporated into the bonded phase via preferential sorption. Equations are derived and used to analyze retention
data for various homologs chromatographed under reversed-phase conditions using alkyl bonded phases and combinations of water-methanol,
water-acetonitrile and watertetrahydrofuran as mobile phases. In the case of water-methanol the surface phase and bulk mobile
phase compositions are similar. However, significant differences in composition between the two phases are observed when binary
combinations of water-acetonitrile and water-tetrahydrofuran are used as the cluents. 相似文献
30.
探讨了有机金属催化剂的组成及其对二氧化碳同环氧丙烷交替共聚产物结构的影响,发现二乙基锌—助剂体系的催化活性按如次顺序递降:二乙基锌—连苯三酚>二乙基锌—间苯二酚>二乙基锌—对苯二胺>二乙基锌—亚乙基脲。若用三异丁基铝代替二乙基锌同连苯三酚构成催化剂,则失去对二氧化碳同环氧丙烷交替共聚反应的活性同时,著者发现二乙基锌—二元芳胺催化体系与二乙基锌—二元酚催化体系的催化活性规律完全不同。 相似文献