全文获取类型
收费全文 | 1923篇 |
免费 | 72篇 |
国内免费 | 423篇 |
专业分类
化学 | 2285篇 |
晶体学 | 25篇 |
力学 | 8篇 |
综合类 | 16篇 |
物理学 | 84篇 |
出版年
2024年 | 3篇 |
2023年 | 8篇 |
2022年 | 34篇 |
2021年 | 33篇 |
2020年 | 35篇 |
2019年 | 39篇 |
2018年 | 46篇 |
2017年 | 67篇 |
2016年 | 65篇 |
2015年 | 53篇 |
2014年 | 89篇 |
2013年 | 238篇 |
2012年 | 91篇 |
2011年 | 98篇 |
2010年 | 103篇 |
2009年 | 115篇 |
2008年 | 113篇 |
2007年 | 120篇 |
2006年 | 120篇 |
2005年 | 135篇 |
2004年 | 107篇 |
2003年 | 104篇 |
2002年 | 71篇 |
2001年 | 69篇 |
2000年 | 57篇 |
1999年 | 73篇 |
1998年 | 47篇 |
1997年 | 49篇 |
1996年 | 45篇 |
1995年 | 40篇 |
1994年 | 28篇 |
1993年 | 28篇 |
1992年 | 26篇 |
1991年 | 16篇 |
1990年 | 6篇 |
1989年 | 9篇 |
1988年 | 8篇 |
1987年 | 4篇 |
1986年 | 3篇 |
1985年 | 5篇 |
1984年 | 5篇 |
1983年 | 1篇 |
1982年 | 4篇 |
1981年 | 1篇 |
1980年 | 6篇 |
1970年 | 1篇 |
排序方式: 共有2418条查询结果,搜索用时 125 毫秒
91.
The bis(dibutylstannylene) derivative of 1,2-cyclohexylidene-myo-inositol reacted with (S)-O-acetylmandeloyl chloride and diphosphate tetraesters to give 3,6-dimandelate and 3-phosphate, respectively. Using the stannylene methodology for the optical resolution and regioselective phosphorylation of the ketal, a concise synthesis of phosphatidylinositol with the natural configuration was accomplished. 相似文献
92.
93.
Kinetics study of thermal decomposition of epoxy resins containing flame retardant components 总被引:1,自引:0,他引:1
Qingfeng Wang 《Polymer Degradation and Stability》2006,91(8):1747-1754
Hyperbranched polyphosphate ester (HPPE) and phenolic melamine (PM) were blended in different ratios with a commercial epoxy resin to obtain a series of flame retardant resins. The thermal decomposition mechanism of their cured products in air was studied by thermogravimetric analysis and in situ Fourier-transform infrared spectroscopy. The degradation behaviours of epoxy resins containing various flame retardant components were found to be greatly changed. The incorporation of phosphorus and nitrogen compounds improved the thermal stability at elevated temperature. The kinetics of thermal decomposition was evaluated by Kissinger method, Flynn-Wall-Ozawa method and Horowitz-Metzger method. The results showed that the activation energy at lower degree of the degradation decreased by the incorporation of flame retardant components, while increased at higher degree of the degradation. 相似文献
94.
酚醛型氰酸酯与双酚A型环氧共固化反应的FTIR研究 总被引:1,自引:0,他引:1
在恒温固化条件下,通过FTIR跟踪方法,研究了酚醛型氰酸酯与双酚A型环氧共固化反应的路径及其反应机理.共固化体系的反应过程包括在150℃及其以下温度,主要发生的是氰酸酯的三嗪环化固化反应,其中三嗪环化固化反应由于环氧的加入,反应速率被极大地提高了;同时,酚醛型氰酸酯中的氨基甲酸酯类杂质与环氧发生开环聚合反应,引起环氧官能团产生弱而持续的消耗.但在此阶段,酚醛型氰酸酯与环氧之间没有化学反应发生;在180℃及其以上温度,三嗪环和环氧发生反应,异构为异氰脲酸环结构,并进一步反应生成唑啉酮环结构,由于该反应的发生,促进了环氧官能团的消耗速度,在环氧官能团的转化率-时间图中,出现倒S曲线;在三嗪环的转化率图中,出现一个极大值后再降落的曲线.反应温度的提高有利于促进酚醛型氰酸酯与环氧之间的共固化反应,特别是当反应温度为220℃时,氰酸酯官能团和环氧官能团的消耗、三嗪环和唑啉酮环的生成均以较快的速率进行,—OCN生成三嗪环的转化率可以较容易地达到1,而唑啉酮环的转化率不超过0.5. 相似文献
95.
4,4′‐hexafluoroisopropylidene‐2,2‐bis‐(phthalic acid anhydride) (1) was reacted with L ‐methionine (2) in acetic acid and the resulting N,N′–(4,4′‐hexafluoroisopropylidenediphthaloyl)‐bis‐L ‐methionine (4) was obtained in high yield. The direct polycondensation reaction of this diacid with several aromatic diols such as bisphenol A (5a), phenolphthalein (5b), 1,4‐dihydroxybenzene (5c), 4,4′‐dihydroxydiphenyl sulfide (5d), 4,6‐dihydroxypyrimidine (5e), 4,4′‐dihydroxydiphenyl sulfone (5f) and 2,4′‐dihydroxyacetophenone (5g) was carried out in a system of thionyl chloride and pyridine. Expecting that the reaction with thionyl chloride in pyridine might involve alternative intermediates different from an acyl chloride, the polycondensation at a higher temperature favorable for the reaction of the expected intermediate with nucleophiles was attempted, and a highly thermally stable poly(ester‐imide) was obtained by carrying out the reaction at 80°C. All of the above polymers were fully characterized by 1H‐NMR, 19F‐NMR FT‐IR spectroscopy, elemental analysis and specific rotation. Some structural characterization and physical properties of these optically active poly(ester‐ imide)s are reported. Copyright © 2006 John Wiley & Sons, Ltd. 相似文献
96.
A novel and green approach for the two-carbon homologation of aldehydes using amino acid catalysis has been developed and further extended to the generation of pharmaceutically active cyano-esters via four-component reactions in one-pot. 相似文献
97.
磷酰氨基酸的酯交换反应研究 总被引:1,自引:0,他引:1
本文利用^3^1P NMR , 对比研究了磷酰化组氨酸与其它磷酰化氨基酸和一级醇的磷上酯交换的反应速度,实验表明磷酰化组氨酸的反应速度最快. 由此提出了以下机理:由于咪唑环的参与,磷可以形成六配位过渡态,从而加快了反应速度. 相似文献
98.
Cocaine is transformed into hepatotoxic metabolites through oxidative pathways. For anhydroecgonine methyl ester (AEME), the main constituent in crack smoke, the oxidative metabolism has not been studied. Therefore, incubation of AEME with rat liver microsomes was performed and a metabolite of AEME, anhydroecgonine methyl ester N-oxide (AEMENO), was identified. The chemical structure of this new metabolite was confirmed by synthesis and by comparative interpretation of electrospray multiple-stage mass spectra, which were obtained in the positive ion mode. This metabolite was also detected in whole blood, serum and urine samples from crack users. The application of liquid chromatography/electrospray mass spectrometry or nanoelectrospray mass spectrometry was necessary because AEMENO is susceptible to thermal degradation during gas chromatographic/mass spectrometric analysis. This study demonstrated that AEMENO is produced by rat hepatic microsomal metabolism in vitro and is present in body fluids from crack users. 相似文献
99.
Karel Strnský Tom Jursík Antonín Vítek Jií Skoepa 《Journal of separation science》1992,15(11):730-740
A method has been developed for calculating more accurate and reproducible equivalent chain length (ECL) values of 33 straight-chain fatty acids (FA), with various positions and numbers of cis double bonds, chromatographed on DB-Wax and DB-1 columns. The dependence of ECL values on the position and the number of double bonds is described, as is a method of utilizing these relationships for the characterization of FA by gas chromatography. 相似文献
100.