全文获取类型
收费全文 | 121587篇 |
免费 | 14367篇 |
国内免费 | 9935篇 |
专业分类
化学 | 111959篇 |
晶体学 | 1849篇 |
力学 | 4230篇 |
综合类 | 404篇 |
数学 | 11284篇 |
物理学 | 16163篇 |
出版年
2024年 | 136篇 |
2023年 | 686篇 |
2022年 | 1810篇 |
2021年 | 1908篇 |
2020年 | 2675篇 |
2019年 | 4168篇 |
2018年 | 3862篇 |
2017年 | 4921篇 |
2016年 | 5519篇 |
2015年 | 7272篇 |
2014年 | 7434篇 |
2013年 | 11799篇 |
2012年 | 8967篇 |
2011年 | 8626篇 |
2010年 | 7214篇 |
2009年 | 7701篇 |
2008年 | 7730篇 |
2007年 | 7264篇 |
2006年 | 6551篇 |
2005年 | 6082篇 |
2004年 | 5429篇 |
2003年 | 4589篇 |
2002年 | 4895篇 |
2001年 | 3176篇 |
2000年 | 2917篇 |
1999年 | 1979篇 |
1998年 | 1276篇 |
1997年 | 1154篇 |
1996年 | 1159篇 |
1995年 | 1106篇 |
1994年 | 983篇 |
1993年 | 759篇 |
1992年 | 660篇 |
1991年 | 451篇 |
1990年 | 363篇 |
1989年 | 338篇 |
1988年 | 365篇 |
1987年 | 316篇 |
1986年 | 223篇 |
1985年 | 195篇 |
1984年 | 197篇 |
1983年 | 67篇 |
1982年 | 169篇 |
1981年 | 142篇 |
1980年 | 135篇 |
1979年 | 143篇 |
1978年 | 104篇 |
1977年 | 75篇 |
1976年 | 65篇 |
1973年 | 42篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
991.
Qingde Zhang Yisheng Tan Caihong Yang Yizhuo Han Jun Shamoto Noritatsu Tsubaki 《天然气化学杂志》2007,16(3):322-325
The attractive utilization route for one-step catalytic oxidation of dimethyl ether to dimethoxymethane was successfully carried out over the H3PW12O40(40%)/SiO2 catalyst, modified by Cs, K, Ni, and V. The Cs modification of H3PW12O40(40%)/SiO2 gave the most promising result of 20% dimethyl ether conversion and 34.8% dimethoxymethane selectivity. Dimethoxymethane could be synthe- sized via methoxy groups decomposed from dimethyl ether through the synergistic effect between the acid sites and the redox sites of Cs modified H3PW12O40(40%)/SiO2. 相似文献
992.
反相高效液相色谱法测定3种中成药中的葛根素 总被引:7,自引:0,他引:7
建立了测定小儿清感灵片、步长新脑心通胶囊和感冒清热颗粒 3种中成药中葛根素含量的反相高效液相色谱方法。采用APEXODS色谱柱 ,以醋酸铵缓冲液 (10 0mmol/L ,pH 5 0 ) 甲醇 (体积比为 75∶2 5 )的混合溶液为流动相 ,检测波长为 2 5 0nm ,流速为 0 8mL/min。葛根素在 2mg/L~ 2 0mg/L时其色谱峰面积与质量浓度的线性关系良好 (r =0 9999) ;上述 3种中成药中的葛根素含量分别为 3 48mg/g ,1 0 8mg/ g及 1 5 2mg/ g(蔗糖型 ) ;其加样回收率分别为 99 0 % ,93 4%和 97 5 %。该法简便、快速、专属性强 ,可以作为多种中药制剂中葛根素含量的测定方法。 相似文献
993.
M. J. Whitcombe A. Gilbert G. R. Mitchell 《Journal of polymer science. Part A, Polymer chemistry》1992,30(8):1681-1691
The syntheses of three methacrylate monomers with cinnamate ester side-chains and of a further monomer with a corresponding cinnamide side-chain are described. Two of the monomers, with isomeric structures, were thermotropic liquid crystals. Although the clearing points were very similar the crystal melting points differed by 8°C. One compound also exhibited a monotropic smectic phase, behavior not shown by its isomer. The other two monomers were not liquid crystalline. The monomers were polymerized by free radical polymerization, both as homopolymers and as copolymers with methyl methacrylate. In the case of one of the mesogenic ester monomers, copolymers with a cyanophenyl benzoate monomer were also prepared. Three of the four monomers formed thermotropic liquid crystalline homopolymers and the copolymers with the benzoate monomer were also liquid crystalline. The monomers were considered as photoactive components of polymeric liquid crystals. As a preliminary investigation of their photochemistry, copolymers with methyl methacrylate were prepared and irradiated in solution with a broad-band source. Under these conditions two of the materials show a facile photo-Fries rearrangement of the aryl cinnamate ester group. © 1992 John Wiley & Sons, Inc. 相似文献
994.
CMAO Jiang-Gao 《结构化学》1998,(5)
1INTR0DUCTI0NLanthanidecarboxylatecomplexeshavebeenwidelystudiedt1iandm0starefoundtoexhibitavarietyofdimericorinfinitechainstructures.Recentstudiesinourlaboratoryhavedem0nstratedthattheprototypetertiaryaminebetaine(Me,N CHzC0z-)anditsderivativesareusefulinthegenerationoflanthanidecarb0xylate-likecomplexeswithnewstructuralfeaturesduetotheiroverallchargeneutralityandpossibleinclusionofvariouskindsofcounteranionsinthestructuret2~4i.Thelan-thanidecomplexesisolatedsofarhavebeenfoundtobemononu… 相似文献
995.
Langlet J. Claverie P. Pullman B. Piazzola D. Daudey J. P. 《Theoretical chemistry accounts》1977,46(2):105-116
The effect of water on the conformational preferences of acetylcholine has been studied within the discrete, the continuum and the combined discrete-continuum models described in parts I and II of this series. All the models lead to the conclusion that the trans-gauche form which is, following refined quantum-mechanical computations, the intrinsically preferred one and the one observed in the crystal of acetylcholine and of a number of analogues should remain also the preferred conformation in water. This result agrees with NMR studies. The results of the empirical discrete model used here compare favorably to those obtained by an ab initio super-molecule treatment. The continuum model utilized here represents a net improvement above such models utilized in other works. 相似文献
996.
A non-empirical molecular orbital method, particularly suitable for calculations on cage-like molecules, is described. The method uses as basis functions the set of free-electron functions which are the solutions of Schrödinger's equation for an electron confined between two concentric, spherical potential energy barriers. Application of the theory to the SCF calculation of the energies of the delocalized electrons in benzene and tetrasulphur tetranitride shows that the model is capable of interpreting the properties of such systems. However, it does highlight a difficulty in the calculation of excited state energies with one-centre models which appears to be largely unrecognized.Extension of the method to a consideration of all the valence electrons, using P4 as an example, reveals problems the origin of which is an inadequate treatment of the core electrons. It is suggested that these problems may best be dealt with by use of a suitable pseudo potential. 相似文献
997.
An efficient and a quick microwave‐assisted synthesis of benzimidazoles and trisubstituted imidazoles was developed. Three benzimidazoles were obtained as a result of the condensation of 1,2‐phenylenediamine with carboxylic acids and acetoacetic ester without catalyst. A series of trisubstituted imidazoles were synthesized by condensation of benzil, aromatic aldehyde and ammonium acetate in the presence of glacial acetic acid. 相似文献
998.
Concha-Graña E Turnes-Carou MI Muniategui-Lorenzo S López-Mahía P Fernández-Fernández E Prada-Rodríguez D 《Journal of chromatography. A》2004,1047(1):147-155
The scope of this work is the development of a rapid, reliable and sensitive method for the analysis of organochlorine pesticides from soils by pressurized liquid extraction (PLE). The effect of four parameters (temperature, pressure, static time and cell volume) on the extraction efficiency was studied. The great extracting power of the PLE causes the extraction of numerous interfering substances, so a more efficient purification of this extract was necessary. In this work several sorbents have also been assayed to carry out the purification of soil samples: Florisil, silica, alumina, carbon, as well as combinations of them. Finally, the proposed analytical method was validated using a certified reference soil material (CRM804-050) and the results were compared with those obtained by other extraction techniques (Soxhlet and microwave-assisted extraction). 相似文献
999.
1000.
Jian X. Gao Jian C. Wang Chong L. Song T. Liu Tian D. Hu Ya N. Xie J. Zhang G. Wang H. Yang 《Journal of solution chemistry》2006,35(1):113-119
NMR spectroscopy was used to show that the symmetry of the crown ether bis(C6) is increased by an increase of the alkali metal
cation radius. The EXAFS spectrum demonstrates that a seven oxygen atom coordinated configuration is present in the bis(C6)/Cs+/NPME system, where NPME denotes o-nitrophenylmethyl ether. The seventh oxygen in this complex, besides the six crown ether oxygens of bis(C6), may come either
from a H2O molecule or an NO3− ion. 相似文献