全文获取类型
收费全文 | 62332篇 |
免费 | 8653篇 |
国内免费 | 7111篇 |
专业分类
化学 | 27727篇 |
晶体学 | 1186篇 |
力学 | 11581篇 |
综合类 | 677篇 |
数学 | 16116篇 |
物理学 | 20809篇 |
出版年
2024年 | 127篇 |
2023年 | 682篇 |
2022年 | 1234篇 |
2021年 | 1927篇 |
2020年 | 2268篇 |
2019年 | 1910篇 |
2018年 | 1735篇 |
2017年 | 2177篇 |
2016年 | 2721篇 |
2015年 | 2207篇 |
2014年 | 3190篇 |
2013年 | 4912篇 |
2012年 | 3802篇 |
2011年 | 4096篇 |
2010年 | 3525篇 |
2009年 | 3959篇 |
2008年 | 3965篇 |
2007年 | 4028篇 |
2006年 | 3663篇 |
2005年 | 3304篇 |
2004年 | 2868篇 |
2003年 | 2640篇 |
2002年 | 2273篇 |
2001年 | 1925篇 |
2000年 | 1836篇 |
1999年 | 1653篇 |
1998年 | 1545篇 |
1997年 | 1239篇 |
1996年 | 1031篇 |
1995年 | 909篇 |
1994年 | 838篇 |
1993年 | 637篇 |
1992年 | 632篇 |
1991年 | 465篇 |
1990年 | 369篇 |
1989年 | 305篇 |
1988年 | 247篇 |
1987年 | 196篇 |
1986年 | 139篇 |
1985年 | 178篇 |
1984年 | 153篇 |
1983年 | 77篇 |
1982年 | 105篇 |
1981年 | 76篇 |
1980年 | 53篇 |
1979年 | 66篇 |
1978年 | 47篇 |
1977年 | 48篇 |
1976年 | 26篇 |
1957年 | 22篇 |
排序方式: 共有10000条查询结果,搜索用时 625 毫秒
991.
苯并三氮唑及其羧酸酯衍生物对铜缓蚀机理的分子动力学模拟研究 总被引:1,自引:0,他引:1
用分子动力学(MD)方法, 模拟计算了5种铜缓蚀剂[苯并三氮唑(BTA)、苯并三氮唑-5-羧酸甲酯(MBTC)、苯并三氮唑-5-羧酸丁酯(BBTC)、苯并三氮唑-5-羧酸己酯(HBTC)、苯并三氮唑-5-羧酸辛酯(OBTC)]与Cu2O晶体的相互作用. 结果发现, 中性条件下缓蚀剂分子与Cu2O晶体的结合能均大于酸性条件下的数值, 但两种条件下结合能的大小排序均为OBTC>HBTC>BBTC>MBTC>BTA. 对体系各种相互作用以及对关联函数g(r)的分析表明, 体系结合能主要由库仑作用提供, Cu2O晶体中的Cu原子与缓蚀剂分子中的N原子之间形成了配位键. 在与Cu2O(001)晶面结合过程中, BTA及其衍生物分子发生了扭曲变形, 但形变能远小于体系的非键相互作用能. 相似文献
992.
Éder Lisandro de Moraes Flores Juliano Smanioto Barin Érico Marlon de Moraes Flores Valderi Luiz Dressler 《Spectrochimica Acta Part B: Atomic Spectroscopy》2007
This work deals with the determination of fluorine by solid sampling graphite furnace molecular absorption spectrometry. The molecular absorbance of aluminum monofluoride (AlF), which is produced in the vapor phase in the presence of Al3+, is measured at 227.5 nm, a non-resonant platinum line. A conventional graphite furnace program has been used with pyrolysis and vaporization temperatures of 800 and 2300 °C, respectively. Solutions of Ba2+ and Al3+ have been used to avoid fluorine losses during the pyrolysis stage and to produce AlF in the vaporization stage, respectively. Certified coal and alumina samples were analyzed using aqueous standards for calibration. The agreement between the found concentration and the certified value, or the value obtained by another method ranged from 92 to 105%, with a relative standard deviation less than 8.5%. The limit of detection and the characteristic mass was 0.17 μg g− 1 and 205 pg, respectively. 相似文献
993.
Zhengbin Zhang Liansheng Liu Hongbin Zhao Youjun Fu Fengyun Cheng Weihong Zhao 《中国科学B辑(英文版)》1997,40(4):353-364
A new method for the study of ternary surface complexes at liquid-solid interface, theE(%) -pH curve method, was proposed. Four types ofE(%)-pH curves, namely, phenomenon of left-right shifts of S-shaped curve, V-shaped curve, monodirection shift curve and X-shaped
curve, were discovered. Correspondingly, apart from type (I) ternary surface complex
and type (II) ternary surface complex
, a new type of ternary surface complex
was discovered.
Project supported by the National Natural Science Foundation of China and the Fund of Doctoral Degree’s Spot. 相似文献
994.
Akihiko Kanazawa Tomiki Ikeda Takeshi Endo 《Journal of polymer science. Part A, Polymer chemistry》1993,31(2):335-343
Various polymeric phosphonium salts and the corresponding low-molecular-weight model compounds were prepared and their antibacterial activities against Staphylococcus aureus and Escherichia coli were explored by the viable cell counting method in sterile distilled water. Antibacterial activity of the polymers was found to be higher than that of the corresponding model compounds, particularly against S. aureus. Furthermore, the polymeric phosphonium salt exhibited a higher activity by 2 orders of magnitude than the polymeric quaternary ammonium salt with the same structure except the cationic part. Compounds with the longest alkyl chain (octyl) studied were found to exhibit particularly high activity, and this finding may be ascribed to the contribution of the increased hydrophobicity of the compounds to the cidal activity. © 1993 John Wiley & Sons, Inc. 相似文献
995.
Julliane Diniz Yoneda Magaly Giro Albuquerque Ktia Zaccur Leal Peter R. Seidl Ralph A. Wheeler Scott E. Boesch Ricardo Bicca de Alencastro Maria Cecília B.V. de Souza Vitor F. Ferreira 《Journal of Molecular Structure》2006,778(1-3):97-103
Conformational analysis of nucleosides may have direct applications to the structure–activity relationship (SAR) studies and in the design of new drug candidates. Although conformational analysis may be accessed in many different ways, in this work it was performed using molecular dynamics (MD) simulation in order to study the dynamic behavior of a nucleoside derivative of 1,4-dihydro-4-oxoquinoline-3-carboxylic acid, synthesized by our group as a potential antiviral agent. The MD simulation was carried out during 10 ns in vacuum and in a box of water at two different temperatures (i.e., 300 and 600 K) using the AMBER force field. The in vacuum MD simulation results are in agreement with the crystallographic structure and with the DFT calculations of the nucleoside, revealing the anti conformer as the more stable one. The simulation in water, however, shows that both conformers may exist at 300 K, the temperature of the in vivo and in vitro assays, revealing that both the syn and anti conformers should be considered in a MD simulation study of the inhibitor–enzyme complex. Simulations are also in agreement with the NOE experiment, which shows that the anti conformer is the preferential one in DMSO-d6 solution at 298 K. 相似文献
996.
A global optimization strategy, based upon application of a genetic algorithm (GA), is demonstrated as an approach for determining the structures of molecules possessing significant conformational flexibility directly from gas-phase electron diffraction data. In contrast to the common approach to molecular structure determination, based on trial-and-error assessment of structures available from quantum chemical calculations, the GA approach described here does not require expensive quantum mechanical calculations or manual searching of the potential energy surface of the sample molecule, relying instead upon simple comparison between the experimental and calculated diffraction pattern derived from a proposed trial molecular structure. Structures as complex as all-trans retinal and p-coumaric acid, both important chromophores in photosensing processes, may be determined by this approach. In the examples presented here, we find that the GA approach can determine the correct conformation of a flexible molecule described by 11 independent torsion angles. We also demonstrate applications to samples comprising a mixture of two distinct molecular conformations. With these results we conclude that applications of this approach are very promising in elucidating the structures of large molecules directly from electron diffraction data. 相似文献
997.
无机胶体法制备Pt/C催化剂及其性能表征 总被引:3,自引:0,他引:3
采用无机胶体法制备用于质子交换膜燃料电池(PEMFC)的Pt/C催化剂。研究了影响PtO2胶体生成和稳定性的因素(溶液的pH值、浓度和温度条件等)以及不同还原剂浓度对Pt/C催化剂性能的影响。透射电子显微镜测试结果表明,采用经优化的工艺条件所制备的Pt/C催化剂平均粒径为3 nm,且分散性好、粒度均匀。X-射线衍射分析表明,催化剂中Pt(111)晶面的相对含量较高,有利于加速氧还原反应。单体PEMFC的电压/电流密度曲线测试表明,所制备的Pt/C催化剂具有良好的电化学性能。 相似文献
998.
999.
1000.
Xiufang Xu Guichang Wang Xuezhuang Zhao Yinming Pan Yunxiao Liang Zhenfeng Shang 《Journal of mathematical chemistry》2007,41(2):143-160
In this paper, the fuzzy symmetry of some prototypical linear molecules has been analyzed. The results show that some molecular
orbitals (MOs) are less symmetrical but some others are more symmetrical than the molecular skeleton, which the MOs correspond
to. The membership functions of space inversion for MOs are closely related to the chemical characteristics of the MOs. Sometimes,
although the symmetry of a molecular skeleton is not obvious, however that of some MO is quite obvious. The membership functions
of the fuzzy inversion symmetry depend on the choice of the position of the center of inversion. As compared to those of diatomic
molecules and linear tri-atomic molecules, the linear polyatomic molecules in which a distinctive fuzzy symmetry of space
translation may exist, and thus a significant effect on their properties can be expected. 相似文献