全文获取类型
收费全文 | 8285篇 |
免费 | 1209篇 |
国内免费 | 2642篇 |
专业分类
化学 | 6517篇 |
晶体学 | 148篇 |
力学 | 721篇 |
综合类 | 109篇 |
数学 | 361篇 |
物理学 | 2013篇 |
无线电 | 2267篇 |
出版年
2024年 | 68篇 |
2023年 | 261篇 |
2022年 | 483篇 |
2021年 | 467篇 |
2020年 | 473篇 |
2019年 | 337篇 |
2018年 | 270篇 |
2017年 | 360篇 |
2016年 | 443篇 |
2015年 | 384篇 |
2014年 | 470篇 |
2013年 | 630篇 |
2012年 | 519篇 |
2011年 | 563篇 |
2010年 | 487篇 |
2009年 | 548篇 |
2008年 | 593篇 |
2007年 | 557篇 |
2006年 | 500篇 |
2005年 | 459篇 |
2004年 | 443篇 |
2003年 | 386篇 |
2002年 | 312篇 |
2001年 | 253篇 |
2000年 | 294篇 |
1999年 | 193篇 |
1998年 | 227篇 |
1997年 | 187篇 |
1996年 | 156篇 |
1995年 | 150篇 |
1994年 | 143篇 |
1993年 | 121篇 |
1992年 | 109篇 |
1991年 | 59篇 |
1990年 | 48篇 |
1989年 | 38篇 |
1988年 | 41篇 |
1987年 | 22篇 |
1986年 | 9篇 |
1985年 | 14篇 |
1984年 | 16篇 |
1983年 | 14篇 |
1982年 | 12篇 |
1981年 | 4篇 |
1979年 | 4篇 |
1977年 | 2篇 |
1976年 | 1篇 |
1973年 | 1篇 |
1971年 | 1篇 |
1957年 | 4篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
31.
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
32.
Calculations and detailed first principle and thermodynamic analyses have been performed to understand the formation mechanism of K2Ti6O13 nanowires (NWs) by a hydrothermal reaction between bulk Na2Ti3O7 crystals and a KOH solution. It is found that direct ion exchange between K+ and Na+ plus H+ interactions with [TiO6] octahedra in Na2Ti3O7 promote the formation of an intermediate H2K2Ti6O14 phase. The large lattice mismatch between this intermediate phase and the bulk Na2Ti3O7 structure, and the large energy reduction associated with the formation of this intermediate phase, drive the splitting of the bulk crystal into H2K2Ti6O14 NWs. However, these NWs are not stable because of large [TiO6] octahedra distortion and are subject to a dehydration process, which results in uniform K2Ti6O13 NWs with narrowly distributed diameters of around 10 nm. 相似文献
33.
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
34.
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
35.
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
36.
Introduction In the previous studies on the oxidation reaction,peroxydisulfate was widely used as an oxidizingagent.1-5 One of the advantages of this oxidant lies in itsstability in a wide range of pH values. The reaction be-tween Fe(CN)5L3- (L=N-aromatic heterocyclic li-gands) and S2O8 2- has been proved to proceed throughan outer-sphere electron transfer mechanism.5 For a re-action [(Eq. (1)] to be under an outer-sphere mechanismthe steps involved are the formation of a reactant … 相似文献
37.
本文对激光结晶a-Si∶H SOI结构砷注入和快速退火行为作了研究.a-Si∶H激光结晶有Lp-LCR,OD,FCR-2,FCR-1四个结晶区.用剖面电镜观察了结晶区的结构.扩展电阻测量表明Lp-LCR区中有两种扩散机制,即杂质在晶粒体内扩散和沿缺陷扩散.OD区中有三种扩散形式,除有上述两种以外,还有沿缺陷的扩散.首次比较了沿晶界和缺陷的扩散速度. 相似文献
38.
The dependence of emission direction of fast electrons on the laser intensity has been investigated. The experimental results show that, at nonrelativistic laser intensities, the emission of fast electrons is mainly in the polarization plane. With the increase of the laser intensity, fast electrons emit towards the laser propagation direction from laser polarization direction. At relativistic laser intensities, fast electrons move away from the laser polarization plane, closely to the reflection direction of the incident laser beam. 相似文献
39.
在G2 (CC ,MP2 )理论水平上研究了C2 (a3 Πu)自由基与NO分子的反应 .计算了反应体系最低二重态势能面上各驻点的构型参数、振动频率和能量 ,揭示了此反应存在两种反应机理 :由NO中的O原子进攻C2 自由基形成CCON中间体的CCON机理和NO中的N进攻C2 自由基形成CCNO中间体的CCNO机理 ,分析了对应与这两种反应机理的五个可能的反应通道 ,得出了由NO中的N原子进攻3 C2 自由基 ,生成中间体CCNO自由基 ,最终得到产物CN +CO的通道是最有利的通道 . 相似文献
40.
One of the successful transformations within the field of organocatalysis, the organocatalytic asymmetric addition of nitromethane to α,β‐unsaturated aldehydes and ketones, has been studied by quantum chemical modeling. The level of accuracy of the hybrid density functional theory method B3LYP/6‐31G(d) was compared to a high level ab initio benchmark for this reaction. It is concluded that B3LYP/6‐31G(d) performs very well for this reaction type, giving good estimates of critical energies. The reaction between acrolein and nitromethane was studied in detail. The reaction mechanism revealed an intermediate oxazolidin structure, which is currently unknown. Alkyl substitution in various positions on the amine catalyst or α,β‐unsaturated carbonyl compound influences the reactivity in a predictive fashion. The iminium ion, prop‐2‐en‐iminium, is less activated towards nucleophilic attack compared to protonated acrolein. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献