全文获取类型
收费全文 | 22180篇 |
免费 | 1983篇 |
国内免费 | 4380篇 |
专业分类
化学 | 12629篇 |
晶体学 | 207篇 |
力学 | 773篇 |
综合类 | 162篇 |
数学 | 339篇 |
物理学 | 3048篇 |
综合类 | 11385篇 |
出版年
2024年 | 142篇 |
2023年 | 429篇 |
2022年 | 849篇 |
2021年 | 790篇 |
2020年 | 804篇 |
2019年 | 667篇 |
2018年 | 592篇 |
2017年 | 719篇 |
2016年 | 845篇 |
2015年 | 857篇 |
2014年 | 1067篇 |
2013年 | 1383篇 |
2012年 | 1276篇 |
2011年 | 1336篇 |
2010年 | 1105篇 |
2009年 | 1315篇 |
2008年 | 1259篇 |
2007年 | 1489篇 |
2006年 | 1387篇 |
2005年 | 1321篇 |
2004年 | 1192篇 |
2003年 | 958篇 |
2002年 | 848篇 |
2001年 | 703篇 |
2000年 | 729篇 |
1999年 | 621篇 |
1998年 | 545篇 |
1997年 | 498篇 |
1996年 | 434篇 |
1995年 | 395篇 |
1994年 | 338篇 |
1993年 | 328篇 |
1992年 | 290篇 |
1991年 | 203篇 |
1990年 | 189篇 |
1989年 | 173篇 |
1988年 | 161篇 |
1987年 | 101篇 |
1986年 | 51篇 |
1985年 | 42篇 |
1984年 | 27篇 |
1983年 | 19篇 |
1982年 | 20篇 |
1981年 | 15篇 |
1980年 | 7篇 |
1979年 | 10篇 |
1977年 | 2篇 |
1971年 | 1篇 |
1957年 | 4篇 |
1955年 | 5篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
31.
This paper is devoted to a detailed theoretical study of an ion pair SN2 reaction LiNCO+CH3F in the gas phase and in solution at the level of MP2(full)/6-31+G**//HF/6-31+G**. Two possible reaction mechanisms, inversion and retention, are discussed. There are eight possible reaction pathways. The inversion mechanism is more favorable no matter in the gas phase or in solution based on analyses of the transition structures. Methyl isocyanate should form preferentially in the gas phase and more stable methyl cyanate is the main product in solution. The retardation of the reaction in solvents was attributed to the difference in solvation in the separated reactants and in the transition state. 相似文献
32.
We present all-atom molecular dynamics simulations ofn-hexane on the basal plane of graphite at monolayer and multilayer coverages. In keeping with experimental data, we find the
presence of ordered adsorbed layers both at single monolayer coverage and when the adsorbed layer coexists with excess liquid
adsorbate. Using a simulation method that does not impose any particular periodicity on the adsorbed layer, we quantitatively
compare our results to the results of neutron diffraction experiments and find a structural transition from a uniaxially incommensurate
lattice to a fully commensurate structure on increasing the coverage from a monolayer to a multilayer. The zig-zag backbone
planes of all the alkane molecules lie parallel to the graphite surface at the multilayer coverage, while a few molecules
are observed to attain the perpendicular orientation at monolayer coverage.
Dedicated to Professor C N R Rao on his 70th birthday 相似文献
33.
Marcelino Maneiro Manuel R. Bermejo M. Isabel Fernndez Ana M. Gonzlez‐Noya Alexei M. Tyryshkin Robin G. Pritchard 《无机化学与普通化学杂志》2003,629(2):285-290
A new MnIII‐Schiff base complex, [MnL(OH2)](ClO4) ( 1 ) (H2L = N, N′‐bis‐(3‐Br‐5‐Cl‐salicylidene)‐1, 2‐diimino‐2‐methylethane), an inorganic model of the catalytic center (OEC, Oxygen Evolving Complex) in photosystem II (PSII), has been synthesized and characterized by elemental analysis, IR and EPR spectroscopy, mass spectrometry, magnetic susceptibility measurement and the study of its redox properties by cyclic and normal pulse voltammetry. This complex mimics reactivity (showing a relevant photolytic activity), and also some structural characteristics (parallel‐mode MnIII EPR signal from partially assembled OEC cluster) of the natural OEC. The complex 1 was found to rearrange in solution into a crystallographically solved square‐pyramidal complex, [MnLL′] ( 2 ) (HL′ = 6‐bromo‐4‐chloro‐2‐cyanophenol), through a process, which probably liberates radical species (detected by EPR), and provokes a C—N bond cleavage in the ligand. A photo‐radical mechanism is discussed to explain this rearrangement. 相似文献
34.
本文用20%的NaOH溶液对棉纤维的预处理、醚化、接枝合成工艺进行了优化;在不同条件下,研究了咪唑季铵盐棉纤维对DOSO~-_3的吸附性能.结果表明,用NaOH预处理棉纤维后,在适当的条件下醚化棉纤维素,再用氢氧化钠作催化剂,按3 g环氧基纤维素醚与10 mL甲基咪唑配比接枝,得到白色味唑季铵盐纤维素.用咪唑季铵盐棉纤维对DOSO~-_3进行吸附,吸附率可达91.8%,吸附效果令人满意. 相似文献
35.
为了理解苯在Ru-Zn合金催化剂上的部分加氢催化机理,采用密度泛函方法对苯在Ru-Zn/Ru(0001)面上的吸附进行理论研究。计算结果表明,当苯的碳原子或者共轭双键直接位于表面Zn原子的atop位时,其吸附热较Ru(0001)面上的类似吸附状态下降约60%.Zn原子与苯环C原子之间的排斥作用导致苯环的成键轨道与表面Ru原子的价层轨道之间的空间对称性下降,从而不利于苯与合金表面的键合。当吸附位离开Zn原子时,邻近Zn原子对于苯的吸附基本没有影响。 相似文献
36.
1.INTRODUCTION[()-227.3()]Endotoxinislipopolysaccharide(LPS)derivedfromthecellmembranesofgram-negativebacteria.Endotoxincancausefebrilereactionsinanimalswithsymptomsofhighfever,vasodilation,diarrheaandfetalshockwheninjectedeveninaverysmallamount[1].Iftheconcentrationofendotoxininpatients?bloodishighenoughitcancauseseveresepsis,whichisamajorcauseofdeathinpatientsandcontinuestohaveahighmortalitydespiteappropriatesurgery,potentantibiotic,andintensivesupportivetherapy[2~5].LipidAisthemaintox… 相似文献
37.
Grishin D. F. Semyonycheva L. L. Telegina E. V. Smirnov A. S. Nevodchikov V. I. 《Russian Chemical Bulletin》2003,52(2):505-507
Organometallic compounds Cp2TiCl2, (EtC5H4)2NbCl2, and (PriC5H4)2WCl2 were assessed as additives that control polymer chain growth in the polymerization of methyl methacrylate. In the presence of compounds mentioned in amounts comparable with that of the initiator, a uniform process with no gel-effect occured and respective linear increase in the molecular weight of the polymer up to high degrees of the monomer conversion was observed. 相似文献
38.
本文从非线性自然观的视野。引用与分析了社会经济系统功能模型与效应模型。构建了系统和谐状态模型与和谐状态可信度模型,形象地说明了企业系统的和谐既是一个随机不确定状态。又是企业和谐力量与不和谐力量相互抗争干涉的过程。依据协同学原理提出了企业系统和谐演进的机制,表明企业系统的和谐发展是子系统和谐协同的过程。即子系统竞争合作的过程。文中所构建的模型,从理论上清晰地说明了企业系统和谐有序运行的机理,为如何构建和谐企业。提供了建设性的思考。 相似文献
39.
Dehydropeptides containing dehydroamino acid (ΔAA) are frequently found in natural resources with important biological activity. Herein, we report the selective synthesis of Z- and E-ΔAbu from l- and l-allo-threonine as starting materials through selenation and oxidative elimination. The detailed reaction mechanism of phosphine-assisted selenoether formation is also discussed. 相似文献
40.
Yuh-Shan Ho 《Adsorption》2004,10(2):151-158
The kinetics of four sorption systems, Cu/tree fern, Pb/tree fern, AB9/activated clay and BR18/activated clay have been studied based on the assumption of a pseudo-second order rate law. Pseudo-isotherms using the pseudo-second order kinetic expression constant have been developed to describe the four liquid-solid sorption systems. The experimental results have been analyzed using a pseudo-Langmuir and a pseudo-Redlich-Peterson isotherm. Both isotherms were found to represent the measured sorption data well. According to the evaluation using the pseudo-Langmuir equation, the monolayer sorption capacities were obtained to be 13.9, 46.6, 124 and 105 mg g–1 for copper, lead, AB9 and BR18 respectively. 相似文献