全文获取类型
收费全文 | 504篇 |
免费 | 8篇 |
国内免费 | 85篇 |
专业分类
化学 | 545篇 |
晶体学 | 1篇 |
力学 | 2篇 |
物理学 | 49篇 |
出版年
2023年 | 9篇 |
2022年 | 5篇 |
2021年 | 12篇 |
2020年 | 5篇 |
2019年 | 4篇 |
2018年 | 13篇 |
2017年 | 8篇 |
2016年 | 11篇 |
2015年 | 14篇 |
2014年 | 14篇 |
2013年 | 53篇 |
2012年 | 29篇 |
2011年 | 35篇 |
2010年 | 28篇 |
2009年 | 45篇 |
2008年 | 51篇 |
2007年 | 43篇 |
2006年 | 25篇 |
2005年 | 20篇 |
2004年 | 32篇 |
2003年 | 19篇 |
2002年 | 14篇 |
2001年 | 12篇 |
2000年 | 8篇 |
1999年 | 10篇 |
1998年 | 7篇 |
1997年 | 11篇 |
1996年 | 7篇 |
1995年 | 5篇 |
1994年 | 6篇 |
1993年 | 7篇 |
1992年 | 8篇 |
1991年 | 6篇 |
1990年 | 4篇 |
1989年 | 6篇 |
1988年 | 4篇 |
1986年 | 2篇 |
1985年 | 1篇 |
1984年 | 2篇 |
1982年 | 1篇 |
1981年 | 1篇 |
排序方式: 共有597条查询结果,搜索用时 212 毫秒
21.
邻氨基二苯醚类重氮盐的水解及分子内缩合反应 总被引:1,自引:0,他引:1
用邻氨基二苯醚类化合物进行重氮化水解反应制备邻羟基二苯醚类化合物, 对影响氯代邻氨基二苯醚重氮盐水解反应和分子内关环反应的因素进行了系统研究, 讨论了取代基、金属及其离子催化等对两类反应的影响规律, 揭示了在金属离子催化下, 邻氨基二苯醚类化合物重氮盐发生分子内关环反应的规律, 并推测了反应机理. 相似文献
22.
连续一级反应的热动力学研究 总被引:1,自引:0,他引:1
本文把时间比法引入热动力学研究,建立了连续一级反应的热动力学研究法,并用来研究了一个连续反应体系的热动力学,验证了该方法的正确性. 相似文献
23.
Concetta De Stefano Claudia Foti Antonio Gianguzza Frank J. Millero Silvio Sammartano 《Journal of solution chemistry》1999,28(7):959-972
The hydrolysis of trimethyltin(IV) has been studied by potentiometry (H+ -glass electrode) and calorimetry in various salt media (NaNO3, NaCl, KCl, Na2SO4, and NaNO3—NaCl mixtures). The effect of ionic strength on the hydrolysis constants is accounted for by a simple Debye–Hückel type equation and by Pitzer equations. The results allow us to obtain H for hydrolysis and the temperature dependence of the Pitzer parameters. The resulting coefficients can be used to examine the speciation of (CH3)3Sn+ in multicomponent electrolyte solutions, such as natural waters, over a wide range of temperature and ionic strength. 相似文献
24.
25.
Jian‐Hua Zhao Hsuan‐Liang Liu Hsin‐Yi Lin Chih‐Hung Huang Hsu‐Wei Fang Shau‐Wei Tsai 《中国化学会会志》2007,54(4):835-842
In this study, we present the results from the semiempirical molecular orbital calculations for the acylation step in the lipase‐catalyzed ester hydrolysis. The results reveal that the lowest energy path for the formation of the tetrahedral intermediate is for the serine residue of the catalytic triad to attack the substrate, followed by coupling heavy atom movement and proton transfer. The calculations of four active site models show that the cooperation of the aspartate group and the oxyanion hole is capable of lowering the activation energy by about 16 kcalmol?1. Our results further suggest that the lipase‐catalyzed ester hydrolysis adopts the single proton transfer mechanism. 相似文献
26.
以紫外光谱法研究了青霉素G钾盐(Pen-K)在十六烷基三甲基溴化铵(CTAB)胶束体系中的水解反应, 并探讨了水解反应机理.结果表明, CTAB胶束对Pen-K的水解具有抑制作用; Pen-K在CTAB胶束体系水解时,体系pH值的变化与在水中相似, 表明H+浓度对这种抑制作用影响较小.红外光谱和微极性研究表明,部分Pen-K钾盐定位于CTAB胶束栅栏层中, 增加了其稳定性. 相似文献
27.
28.
《International journal of environmental analytical chemistry》2013,93(3):123-132
Heating a suspension of Bisphenol A diglycidyl ether (BADGE) in 20 : 80 tetrahydrofuran/water at 70°C and subsequent passage of the resulting solution through C18 columns allowed isolation and purification to > 97% of each of the two hydrolysis products 2-[4-(2,3-dihydroxypropoxy) phenyl]-2-[4-(2,3-epoxypropoxy)phenyl]propane (1HP) and 2,2-bis[4-(2,3-dihydroxypropoxy)phenyl] propane (2HP), which were characterized by UV, IR, 1H and I3C NMR spectroscopy and mass spectrometry. 相似文献
29.
The hydrolysis of bis-(nitrophenyl) phosphate (BNPP) as model for secondary phosphate esters is analyzed at six different concentrations of Eu(III) ions and four temperatures between 303 and 343 K. Eyring plots yield activation enthalpy parameters which with, e.g. [Eu 3+ ] between 0.40 and 10.0 mM drop from 130 to 74 kJ mol m 1 , respectively, with a relatively small drop in the opposing entropy contributions. The observed saturation profiles allow for the first time to evaluate the influence of j H and j S separately on the Michaelis-Menten values K M and k cat , showing that the catalytic metal-ion effects are largely due to changes in k cat and dominated by favorable j H changes. Preliminary studies of the solvent influence show a surprising difference between water mixtures with either ethanol or DMSO. With, e.g. 40% ethanol, one observes a doubling of the rate constant, with 40% DMSO an almost 10-fold rate decrease. In both cases, a linear correlation with the solvent polarity parameter E T is found. 相似文献
30.
《Journal of Coordination Chemistry》2012,65(8):1371-1380
Synthesis and characterization of zinc and cobalt phthalocyanines substituted with biphenylmethylpropionic acids, methyl-o-tolylpropionic acids, and methyl-p-tolylpropionic acids are described in this study. The new compounds have been characterized by elemental analyses, FT-IR, UV-Vis, MALDI-TOF, and 1H NMR spectroscopy. All new compounds are soluble in THF, DMF, DMSO, and dilute sodium hydroxide solution. The influence of the carboxylic acid and bulky biphenyl, ortho-methylbenzyl and para-methylbenzyl groups on the spectroscopic properties has been investigated. UV-Vis experiments suggest that the tendency of phthalocyanines to aggregate in polar solvents is significantly reduced owing to the carboxylic acid groups and bulky peripheral substituents. 相似文献