全文获取类型
收费全文 | 11722篇 |
免费 | 1722篇 |
国内免费 | 1743篇 |
专业分类
化学 | 12260篇 |
晶体学 | 399篇 |
力学 | 367篇 |
综合类 | 88篇 |
数学 | 158篇 |
物理学 | 1915篇 |
出版年
2024年 | 32篇 |
2023年 | 178篇 |
2022年 | 298篇 |
2021年 | 469篇 |
2020年 | 680篇 |
2019年 | 512篇 |
2018年 | 441篇 |
2017年 | 425篇 |
2016年 | 648篇 |
2015年 | 661篇 |
2014年 | 684篇 |
2013年 | 1108篇 |
2012年 | 714篇 |
2011年 | 630篇 |
2010年 | 590篇 |
2009年 | 694篇 |
2008年 | 723篇 |
2007年 | 808篇 |
2006年 | 707篇 |
2005年 | 687篇 |
2004年 | 618篇 |
2003年 | 508篇 |
2002年 | 346篇 |
2001年 | 249篇 |
2000年 | 262篇 |
1999年 | 212篇 |
1998年 | 199篇 |
1997年 | 184篇 |
1996年 | 178篇 |
1995年 | 153篇 |
1994年 | 104篇 |
1993年 | 78篇 |
1992年 | 78篇 |
1991年 | 41篇 |
1990年 | 36篇 |
1989年 | 33篇 |
1988年 | 31篇 |
1987年 | 29篇 |
1986年 | 24篇 |
1985年 | 24篇 |
1984年 | 17篇 |
1982年 | 13篇 |
1981年 | 8篇 |
1980年 | 8篇 |
1979年 | 6篇 |
1977年 | 8篇 |
1976年 | 9篇 |
1975年 | 7篇 |
1974年 | 8篇 |
1973年 | 15篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
51.
Tatiana B. Mikenas Vladimir A. Zakharov Lyudmila G. Echevskaya Mikhail A. Matsko 《Journal of polymer science. Part A, Polymer chemistry》2007,45(22):5057-5066
The effects of polymerization temperature, polymerization time, ethylene and hydrogen concentration, and effect of comonomers (hexene‐1, propylene) on the activity of supported catalyst of composition LFeCl2/MgCl2‐Al(i‐Bu)3 (L = 2,6‐bis[1‐(2,6‐dimethylphenylimino)ethyl] pyridyl) and polymer characteristics (molecular weight (MW), molecular‐weight distribution (MWD), molecular structure) have been studied. Effective activation energy of ethylene polymerization over LFeCl2/MgCl2‐Al(i‐Bu)3 has a value typical of supported Ziegler–Natta catalysts (11.9 kcal/mol). The polymerization reaction is of the first order with respect to monomer at the ethylene concentration >0.2 mol/L. Addition of small amounts of hydrogen (9–17%) significantly increases the activity; however, further increase in hydrogen concentration decreases the activity. The IRS and DSC analysis of PE indicates that catalyst LFeCl2/MgCl2‐Al(i‐Bu)3 has a very low copolymerizing ability toward propylene and hexene‐1. MW and MWD of PE produced over these catalysts depend on the polymerization time, ethylene and hexene‐1 concentration. The activation effect of hydrogen and other kinetic features of ethylene polymerization over supported catalysts based on the Fe (II) complexes are discussed. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5057–5066, 2007 相似文献
52.
53.
N-Acylalkylation of neutral and anionic N-nucleophiles with α-halocarbonyl compounds was investigated by quantum chemical methods
in terms of the density functional theory and by experimental methods for 2,3-dihydroimidazo[2,1-b]quinazolin-1(10)H-5-one, its N-anion, and simpler model structures. High reactivity of these reagents is determined primarily by stabilization
of transition states (TS) by bridge bonds involving halogen or nitrogen atoms rather than by conjugation, as has been commonly
accepted. Bridged TS are formed by both the substitution mechanism S
N
2 and the addition-elimination mechanism. α-Haloalkyl-substituted zwitterions, which are potential intermediates of stepwise
N-acylalkylation of neutral N-nucleophiles, do not exist in the isolated state, but they are rather efficiently stabilized
upon solvation. These zwitterions, as well as analogous O-anions generated from anionic N-nucleophiles, can serve as intermediates
of N-acylalkylation, as was demonstrated by localization of the corresponding TS.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1150–1164, June, 2007. 相似文献
54.
The trisilanol 1,3,5‐(HOi‐Bu2Si)3C6H3 ( 7 ), prepared in three steps from 1,3,5‐tribromobenzene via the intermediates 1,3,5‐(Hi‐Bu2Si)3C6H3 ( 8 ) and 1,3,5‐(Cli‐Bu2Si)3C6H3 ( 9 ) forms an equimolar complex with trans‐bis(4‐pyridyl)ethylene (bpe), 7 ·bpe, whose structure was investigated by X‐ray crystallography. The hydrogen‐bonded network features a number of SiO? H(H)Si and SiO? H hydrogen bridges. Evidence was found for cooperative strengthening within the sequential hydrogen bonds. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
55.
Praveen K. Tandon Gayatri Sumita Sahgal Manish Srivastava Santosh B. Singh 《应用有机金属化学》2007,21(3):135-138
Catalytic activities of three transition metals, as iridium (III) chloride, rhodium (III) chloride and palladium (II) chloride, were compared in the oxidation of six aromatic aldehydes (benzaldehyde, p‐chloro benzaldehyde, p‐nitro benzaldehyde, m‐nitro benzaldehyde, p‐methoxy benzaldehyde and cinnamaldehyde), two hydrocarbons (viz. (anthracene and phenanthrene)) and one aromatic and one cyclic alcohol (cyclohexanol and benzyl alcohol) by 50% H2O2. The presence of traces (substrate: catalyst ratio equal to 1:62500 to 1:1961) of the chlorides of iridium(III), rhodium(III) and palladium(II) catalyze these oxidations, resulting in good to excellent yields. It was observed that in most of the cases palladium(II) chloride is the most efficient catalyst. Conditions for the highest and most economical yields were obtained. Deviation from the optimum conditions decreases the yields. Oxidation in aromatic aldehydes is selective at the aldehydeic group only and other groups remain unaffected. This new, simple and economical method, which is environmentally safe, also requires less time. Reactive species of catalysts, existing in the reaction mixture are also discussed. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
56.
A series of complexes formed between halogen-containing molecules and ammonia have been investigated by means of the atoms in molecules (AIM) approach to gain a deeper insight into halogen bonding. The existence of the halogen bond critical points (XBCP) and the values of the electron density (Pb) and Laplacian of electron density (V2pb) at the XBCP reveal the closed-shell interactions in these complexes. Integrated atomic properties such as charge, energy, polarization moment, volume of the halogen bond donor atoms, and the corresponding changes (△) upon complexation have been calculated. The present calculations have demonstrated that the halogen bond represents different AIM properties as compared to the well-documented hydrogen bond. Both the electron density and the Laplacian of electron density at the XBCP have been shown to correlate well with the interaction energy, which indicates that the topological parameters at the XBCP can be treated as a good measure of the halogen bond strength In addition, an excellent linear relationship between the interatomic distance d(X…N) and the logarithm of Pb has been established. 相似文献
57.
采用有限元方法对大型钢结构人行景观天桥进行了静力学、温度应力、动力学模态和初步的抗震能力分析,并就桥自重作用下的最大竖向位移和实际观测结果进行了比较,两者是一致的.计算结果表明:人行景观天桥在常规、温度极值改变和多遇地震荷载作用等多种工况下,现有的设计方案具有足够的强度、刚度和抗震能力. 相似文献
58.
苝二酸酐与嘧啶衍生物的氢键组装 总被引:1,自引:0,他引:1
用半经验AM1方法对苝二酸酐与嘧啶衍生物的1:1及1:2氢键复合物进行理论研究,表明随着氢键数目增多,弱相互作用能变大,主体上的供电基和客体上的吸电基有利于氢键相互作用,氢键导致电子从主体流向客体.用INDO/SCI方法计算配合物的电子光谱,表明其长波吸收峰与主体相比发生兰移,各配合物的长波吸收峰位置相差不大,与实验一致.讨论吸收峰兰移的原因并对电子跃迁进行理论指认,同时得到了配合物的双质子转移势能曲线,给出了相对于N-H键的过渡态和活化能. 相似文献
59.
Wang Yongqian Liao Xianbo Diao Hongwei Cheng Wenchao Li Guohua Chen Changyong Zhang Shibin Xu Yanyue Chen Weide Kong Guanglin 《中国科学A辑(英文版)》2002,45(10):1320-1328
A set of a-SiOx:H (0.52 <x< 1.58) films are fabricated by plasma-enhanced-chemical-vapor-deposition (PECVD) method at the substrate temperature
of 250°C. The microstructure and local bonding configurations of the films are investigated in detail using micro-Raman scattering,
X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR). It is found that the films are
structural inhomogeneous, with five phases of Si, Si2O:H, SiO:H, Si2O3:H and SiO2 that coexist. The phase of Si is composed of nonhydrogenated amorphous silicon (a-Si) clusters that are spatially isolated.
The average size of the clusters decreases with the increasing oxygen concentration x in the films. The results indicate that
the structure of the present films can be described by a multi-shell model, which suggests that a-Si cluster is surrounded
in turn by the subshells of Si2O:H, SiO:H, Si2O3:H, and SiO2. 相似文献
60.
Prof. Dr. K. Ikegami Prof. Dr. T. Sugibayashi Mr. K. Matsuo 《Archive of Applied Mechanics (Ingenieur Archiv)》1994,65(1):44-53
Summary A method of joining two metal cylindrical shafts with adhesive coupling is proposed. Two cylindrical shafts with the same diameter are connected by bonding through a cylindrical coupling with epoxy resin. The strength of the shaft joint under tensile loading and torsional loading is investigated analytically and experimentally. The stress and strain distributions of the shaft joint is analyzed by the finite element method. The analyzed strain distributions in the joint are compared with experimental values. The joint strength is predicted by applying the strength laws of shafts, coupling, adhesive layer and adhesive interface between shaft and adhesive coupling. The effects of the coupling dimension on the joint strength are examined. It is shown that the adhesive shaft joint can transfer the load by which the cylindrical shafts are plastically deformed.This paper was refined by the author, K. Ikegami, during statying at Technische Universität München under the support of Deutscher Akademischer Austauschdients. The author is grateful to Professor Lippmann of Technische Universität München who is the host professor of the support. 相似文献