全文获取类型
收费全文 | 30047篇 |
免费 | 2631篇 |
国内免费 | 3914篇 |
专业分类
化学 | 8311篇 |
晶体学 | 169篇 |
力学 | 2999篇 |
综合类 | 268篇 |
数学 | 2013篇 |
物理学 | 3663篇 |
综合类 | 19169篇 |
出版年
2024年 | 146篇 |
2023年 | 486篇 |
2022年 | 815篇 |
2021年 | 858篇 |
2020年 | 907篇 |
2019年 | 729篇 |
2018年 | 698篇 |
2017年 | 911篇 |
2016年 | 1026篇 |
2015年 | 1073篇 |
2014年 | 1385篇 |
2013年 | 1693篇 |
2012年 | 1733篇 |
2011年 | 1758篇 |
2010年 | 1415篇 |
2009年 | 1621篇 |
2008年 | 1583篇 |
2007年 | 1916篇 |
2006年 | 1863篇 |
2005年 | 1723篇 |
2004年 | 1587篇 |
2003年 | 1343篇 |
2002年 | 1164篇 |
2001年 | 983篇 |
2000年 | 1011篇 |
1999年 | 821篇 |
1998年 | 711篇 |
1997年 | 663篇 |
1996年 | 615篇 |
1995年 | 509篇 |
1994年 | 478篇 |
1993年 | 411篇 |
1992年 | 397篇 |
1991年 | 287篇 |
1990年 | 301篇 |
1989年 | 256篇 |
1988年 | 231篇 |
1987年 | 162篇 |
1986年 | 84篇 |
1985年 | 56篇 |
1984年 | 41篇 |
1983年 | 23篇 |
1982年 | 37篇 |
1981年 | 17篇 |
1980年 | 5篇 |
1979年 | 6篇 |
1978年 | 8篇 |
1977年 | 8篇 |
1957年 | 16篇 |
1955年 | 6篇 |
排序方式: 共有10000条查询结果,搜索用时 453 毫秒
11.
Dr. Liat Avram Dr. Václav Havel Ronit Shusterman-Krush Dr. Mark A. Iron Dr. Moritz Zaiss Prof. Vladimír Šindelář Dr. Amnon Bar-Shir 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(7):1687-1690
The accumulated knowledge regarding molecular architectures is based on established, reliable, and accessible analytical tools that provide robust structural and functional information on assemblies. However, both the dynamicity and low population of noncovalently interacting moieties within studied molecular systems limit the efficiency and accuracy of traditional methods. Herein, the use of a saturation transfer-based NMR approach to study the dynamic binding characteristics of an anion to a series of synthetic receptors derived from bambusuril macrocycles is demonstrated. The exchange rates of BF4− are mediated by the side chains on the receptor (100 s−1<kex<5000 s−1), which play a critical role in receptor-anion binding dynamics. The signal amplification obtained with this approach allows for the identification of different types of intermolecular interactions between the receptor and the anion, something that could not have been detected by techniques hitherto used to study molecular assemblies. These findings, which are supported by a computational molecular dynamic study, demonstrate the uniqueness and added value of this NMR method. 相似文献
12.
DFT mechanistic study of the H2‐assisted chain transfer copolymerization of propylene and p‐methylstyrene catalyzed by zirconocene complex 下载免费PDF全文
Cheng‐Gen Zhang Shu‐Yuan Yu Liaoyun Zhang Huayi Li Zhi‐Xiang Wang 《Journal of polymer science. Part A, Polymer chemistry》2015,53(4):576-585
DFT computations have been performed to investigate the mechanism of H2‐assisted chain transfer strategy to functionalize polypropylene via Zr‐catalyzed copolymerization of propylene and p‐methylstyrene (pMS). The study unveils the following: (i) propylene prefers 1,2‐insertion over 2,1‐insertion both kinetically and thermodynamically, explaining the observed 1,2‐insertion regioselectivity for propylene insertion. (ii) The 2,1‐inserion of pMS is kinetically less favorable but thermodynamically more favorable than 1,2‐insertion. The observation of 2,1‐insertion pMS at the end of polymer chain is due to thermodynamic control and that the barrier difference between the two insertion modes become smaller as the chain length becomes longer. (iii) The pMS insertion results in much higher barriers for subsequent either propylene or pMS insertion, which causes deactivation of the catalytic system. (iv) Small H2 can react with the deactivated [Zr]?pMS?PPn facilely, which displace functionalized pMS?PPn chain and regenerate [Zr]? H active catalyst to continue copolymerization. The effects of counterions are also discussed. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 576–585 相似文献
13.
《Comptes Rendus Chimie》2015,18(9):993-1000
The electrochemical oxidation of N-acetyl-p-aminophenol (PAR) was investigated at a Pt electrode with the application of cyclic (CV) and differential pulse (DPV) voltammetry methods. An effect of scan rate, substrate concentration and pH on electrode reactions was determined. The parameters of substrate electro-oxidation, i.e. heterogeneous rate constant, charge transfer coefficient, and diffusion coefficient, were calculated. Our investigation's results prove the exchange of two electrons and one proton in the first step, followed by a chemical reaction. PAR electro-oxidation occurs according to an EC mechanism. 相似文献
14.
针对多层织物织造过程中,各层纬纱打纬力需保持一致以及需要减少钢筘与纱线之间摩擦的要求,提出八连杆平行打纬机构,并根据工艺要求对打纬机构进行优化。以打纬机构的主轴转动140°时,筘座在后心位置处的近似静止位移Δs最小为优化目标,通过Matlab软件分析确定设计变量,优化钢筘在后死心位置的近似停留时间。运动学仿真结果表明,优化后的打纬机构不仅保证了钢筘的打纬动程和其在后死心处的静止时间,而且增大了钢筘的惯性打纬力,有利于厚重织物的打纬。 相似文献
15.
Alkynes cycloaddition reactions are powerful tools for constructing cyclic molecules with optimal atom efficiency, but these reactions cannot proceed at ambient temperature without transition-metal catalysts. In this work, a heterobimetallic complex featuring an Nb–Fe triple bond, Nb(iPrNPMe2)3Fe–PMe3, has been evaluated as the potential catalyst for acetylene cycloaddition, using density functional theory. The calculated results show that the singlet-state (i.e. ground-state) Nb(iPrNPMe2)3Fe–PMe3 can be applied to benzene synthesis, but is not suitable for cyclobutadiene. Benzene can be obtained easily at room temperature and is the unique product on the singlet potential surface. The irradiation of infrared-red light can drive the excitation of singlet Nb(iPrNPMe2)3Fe–PMe3 to its triplet state. Both benzene and cyclobutadiene can be formed on the triplet reaction potential surface due to their low energy barriers. Therefore, Nb(iPrNPMe2)3Fe–PMe3 is a potential high reactivity heterobimetallic catalyst for the cyclotrimerization of alkynes. In the reaction process, the catalytic active site of Nb(iPrNPMe2)3Fe–PMe3 moves from niobium to iron. 相似文献
16.
采用密度泛函理论B3LYP方法,研究了锡苯和铅苯的[2+2],[4+2]及[4+4]二聚反应的微观机理和势能剖面,考察了Sn(Pb)原子上的2,4,6-三甲基苯基(Mes)取代基对反应势能剖面的影响.研究结果表明,所有反应均为协同过程,且大多数情况下,2个C—Sn(Pb)键同步形成.[2+2]和[4+2]反应在热力学和动力学上均比相应的[4+4]反应容易进行,而[4+2]反应在动力学上比相应的[2+2]反应有利.Sn(Pb)原子上的Mes取代基在热力学和动力学上均不利于反应的进行.铅苯的动力学稳定性与锡苯相当,但其热力学稳定性高于锡苯. 相似文献
17.
以焦炉上升管内壁结焦炭层块为研究对象,采用X射线荧光光谱仪(XRF)、X射线衍射仪(XRD)、傅里叶红外光谱仪(FTIR)和激光共聚焦拉曼光谱仪(Raman)对结焦炭层的元素组成,以及各结焦炭层的矿物组成、组成结构和分子结构进行测试。分析从结焦炭层块外表面向内表面过渡的各结焦炭层的差异性,揭示焦炉上升管内壁结焦机理。结果表明焦炉上升管内粉尘中Fe,S和Cr极易催化荒煤气中蒽、萘等稠环芳烃化合物成炭,在焦炉上升管内壁形成炭颗粒沉积,为焦油凝结挂壁提供载体,在荒煤气温度降至结焦温度时易结焦积碳。结焦炭层均含有芳香层结构,随着结焦炭层从外表面向内表面过渡,各结焦炭层的面层间距(d002)逐渐降低、层片直径(La)先降低后增加、层片堆砌高度(Lc)和芳香层数(N)先稳定后增加。结焦炭层石墨化过程是由结焦炭层内表面向外表面进行,主要包括其片层外缘的羧基和部分C-O结构的降解剥离,从而形成高度规整的共轭结构。结焦炭层块中C元素是以结晶碳与无定型碳的混合物形式存在。以上研究为解决焦炉上升管内壁结焦及腐蚀问题,提高换热器换热效率,有效回收焦炉荒煤气显热,降低焦化企业能耗提供实验基础和理论依据。 相似文献
18.
In this paper, we consider a viscoelastic wave equation of variable coefficients in the presence of past history with nonlinear damping and delay in the internal feedback and dynamic boundary conditions. Under suitable assumptions, we establish an explicit and general decay rate result without imposing restrictive assumption on the behavior of the relaxation function at infinity by Riemannian geometry method and Lyapunov functional method. 相似文献
19.
三门峡水库电站运行调度的优化研究 总被引:2,自引:0,他引:2
三门峡水库泥沙淤积严重,使其枢纽的各项技术指标经常变化,为其调度运行带来极大困难。为此,充分考虑三门峡水电站运行过程中的各种约束条件,分别采用动态规划和遗传算法给出了电站优化调度模型,建立了该电站的运行调度系统。经过水库1991年—2000年实际来水和控制运行的月报资料的模拟验证,结果表明,该系统可平均增加发电量约12.9%,使电站能更合理地进行管理调度。而且,通过对随机模拟的长序列入库月径流过程的模拟调度,建议了三门峡水电站具体的管理调度运行方式。 相似文献
20.
郑晓曦 《五邑大学学报(自然科学版)》2004,18(4):27-32
文中就虚拟样机四连杆机构的运动分析提出一种新的运动仿真算法,在基于场景图的虚拟样机产品模型中实现产品四连杆机构的运动仿真.其算法特点是:利用空间矢量运算原理和四连杆机构特性直接求出四连杆机构从动件的变换矩阵,再通过四连杆机构特征点构造的三角形面积变化求出从动件变换矩阵的偏离角,用偏离角补偿法校正从动件变换矩阵,实现四连杆机构的运动仿真.其算法简单,运算效率高,实现容易. 相似文献