首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   16400篇
  免费   2455篇
  国内免费   1455篇
化学   18146篇
晶体学   208篇
力学   44篇
综合类   50篇
数学   15篇
物理学   1847篇
  2024年   52篇
  2023年   201篇
  2022年   611篇
  2021年   713篇
  2020年   1117篇
  2019年   801篇
  2018年   647篇
  2017年   553篇
  2016年   928篇
  2015年   877篇
  2014年   913篇
  2013年   1382篇
  2012年   1018篇
  2011年   927篇
  2010年   778篇
  2009年   789篇
  2008年   763篇
  2007年   827篇
  2006年   728篇
  2005年   685篇
  2004年   684篇
  2003年   580篇
  2002年   1205篇
  2001年   335篇
  2000年   289篇
  1999年   211篇
  1998年   254篇
  1997年   198篇
  1996年   169篇
  1995年   163篇
  1994年   125篇
  1993年   95篇
  1992年   112篇
  1991年   82篇
  1990年   84篇
  1989年   62篇
  1988年   54篇
  1987年   37篇
  1986年   32篇
  1985年   31篇
  1984年   48篇
  1983年   18篇
  1982年   28篇
  1981年   23篇
  1980年   13篇
  1979年   24篇
  1978年   10篇
  1975年   4篇
  1972年   5篇
  1969年   4篇
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
111.
In this paper, hydroxy-terminated silicone oil-butyl methacrylate-divinylbenzene (OH-TSO-BMA-DVB) copolymer was first synthesized and used as stationary phase with the aid of γ-methacryloxypropyltrimethoxylsilane (KH-570) as bridge in solid-phase microextraction (SPME) using sol–gel method and cross-linking technique. It has high extraction efficiency for both polar alcohols and fatty acids and nonpolar esters in comparison with commercial PDMS, PDMS-DVB and PA fibers. A simple and sensitive headspace SPME-gas chromatography (HS-SPME-GC) method using the novel fiber was presented for the simultaneous analysis of both polar alcohols and fatty acids and nonpolar esters in wine. To check the matrix effects, various model wine matrices, including distilled water; 11.5% ethanol/water (v/v) solution; a concentrated synthetic wine; a ‘volatile-free’ wine and a real wine were investigated in detail. Matrix effects were compensated for by using internal standard method and selecting the ‘volatile-free’ wine as working standard. The method presented in this study showed satisfactory linearity, precision, detection limits and accuracy. The recoveries obtained ranged from 85.87 to 104.2%, and the relative standard deviation values were below 9%. The results obtained indicated that the present method is a validated and accurate procedure for the simultaneous determination of both polar and nonpolar aroma compounds in wine.  相似文献   
112.
氨基酸与钠离子非共价键相互作用的电喷雾质谱研究   总被引:1,自引:0,他引:1  
实验研究中常常观察到钠离子与一些多肽或蛋白质有较强的非共价键结合能力,这种非共价键相互作用可能与生物的一些功能和活性有关。为了进一步了解这一结合作用,我们应用电喷雾质谱研究了常见的20种氨基酸与钠离子在溶液中的非共价键相互作用。实验研究中发现脯氨酸和苯丙胺酸与钠离子有较强的非共价键结合能力。  相似文献   
113.
白酒中C_9-C_(18)脂肪酸的气相色谱分析周在德,曾永昌(四川大学化学系成都610064)关键词气相色谱法,白酒,C_9-C_(18)脂肪酸。白酒中脂肪酸的含量及相互比例关系,极大地影响着白酒的色,香,味,风格 ̄([1][2])。一般采用的化学分...  相似文献   
114.
The epoxidation of cyclopentene with hydrogen peroxide catalyzed by 12-heteropolyacids of molybdenum and tungsten (H3PMo12−nWnO40, n = 1–11), 12-tungstophosphoric acid and 12-molybdophosphoric acid combined with cetylpyridinium bromide as a phase transfer reagent was carried out in acetonitrile. Among 13 heteropolyacids investigated, catalyst of H3PMo6W6O40 showed the highest activity, giving a conversion of 60% and a selectivity of 95% in the epoxidation of cyclopentene. The fresh catalysts and the catalysts under reaction condition were characterized by UV–vis, FT-IR and 31P NMR spectroscopy, which has revealed that all of the molybdotungstophosphoric acids were degraded in the presence of hydrogen peroxide to form a considerable amount of phosphorus-containing species. The active species resulted from H3PMo6W6O40 are new kinds of phosphorus-containing species, which is different from {PO4[WO(O2)2]4}3−.  相似文献   
115.
The reaction of styrene and -methylstyrene with P in aprotic polar solvents in the presence of KOH affords diorganylphosphinous acids.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1680–1681, September, 1994.  相似文献   
116.
Precision molar conductances of benzoic, o-toluic, 2,6-dimethylbenzoic, 2,3,6-trimethylbenzoic, and, o-fluorobenzoic acids have been determined in aqueous solution as a function of temperature and of concentration up to near saturation (<0.035 M). At the higher concentrations molar conductances are found to be less than anticipated for the simple dissociation of a 1-1 electrolyte. Although the deviations are only 1% or less they have been interpreted to show that these acids are dimerized in solution. The interpretation includes an assumption that the dimer ionizes to produce a triple ion. Increasing numbers of methyl groups lead to increasing dimerization. For those acids with two ortho groups the dimerization increases with increasing temperature while the other three show decreasing dimerization with increasing temperature. Temperature functions have been determined for the dimerization constants and from these functions standard changes in enthalpy, entropy, and heat capacity have been determined. Comparisons are made with dimerization studies in non-aqueous solvents. From these as well as the behavior of benzene in water it is concluded that a major factor driving the dimerization is hydrophobic interaction. To provide a limiting conductance of the triple ion needed in the dimerization calculations a conductance study was also made for o-Phenylbenzoic acid on the assumption that its anion provides an approximate model of the triple ion.  相似文献   
117.
Here we report the preparation and structural characteristics of self-assembling peptide tubelets composed of 32-membered rings formed of alternating alpha-amino acids and cis-3-aminocyclohexanecarboxylic acids. The tubelets possess a partial hydrophobic core environment, provided by the projection of the cyclohexane C2 methylene moiety into the lumen, and a Van der Waals pore diameter of about 7 A.  相似文献   
118.
聚氯乙烯接枝丙烯酸稀土的研究   总被引:5,自引:1,他引:5  
将无机稀土有机化后与聚氯乙烯(PVC)进行接枝共聚。探讨了氧化稀土与丙烯酸反应、PVC接枝丙烯酸稀土的原理和方法,并通过红外光谱、扫描电镜对接枝共聚物进行定性表征,用微量热天平对接枝共聚物的热性能进行测定。实验结果表明,经丙烯酸稀土接枝共聚后的PVC,其耐热分解性能和韧性有了明显的提高。  相似文献   
119.
Interdiffusion coefficient have been measured for 1,1,2,2-tetrabromoethane in 21 organic solvents in order to ascertain the influence of shape, size, viscosity, nature and degree of branching, of the solvent molecules on transport properties. None of the existing correlations for diffusion in binary liquid systems appear to fit all the experimental data. Steric effects due to the solvent molecules are shown to be very important in the interpretation of the diffusion process.  相似文献   
120.
Utilization of lipases for synthesis of esters of hydrophilic polyols has been investigated. The choice of a suitable solvent is crucial in this type of reaction. An interesting case is fatty acid esters from neopentylpolyols, such as trimethylolpropane, which are of great interest as high temperature lubricants. Enzymatic synthesis of trimethylolpropane tricaprylate was studied as an alternative to chemical manufacturing. Triester production occurred only if the water produced by esterification was continuously removed from the medium. In these condition, kinetics of appearance and transformation of mono-, di- and triesters were determined in order to define optimal conditions.  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号