首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   33913篇
  免费   4415篇
  国内免费   3760篇
化学   16768篇
晶体学   262篇
力学   1463篇
综合类   200篇
数学   2403篇
物理学   8219篇
综合类   12773篇
  2024年   123篇
  2023年   510篇
  2022年   905篇
  2021年   951篇
  2020年   985篇
  2019年   875篇
  2018年   789篇
  2017年   762篇
  2016年   1168篇
  2015年   1338篇
  2014年   1681篇
  2013年   1965篇
  2012年   2393篇
  2011年   2416篇
  2010年   1819篇
  2009年   1799篇
  2008年   2034篇
  2007年   1847篇
  2006年   1891篇
  2005年   1637篇
  2004年   1365篇
  2003年   1353篇
  2002年   1566篇
  2001年   1343篇
  2000年   1021篇
  1999年   1115篇
  1998年   836篇
  1997年   811篇
  1996年   756篇
  1995年   612篇
  1994年   590篇
  1993年   505篇
  1992年   474篇
  1991年   374篇
  1990年   358篇
  1989年   295篇
  1988年   272篇
  1987年   179篇
  1986年   121篇
  1985年   76篇
  1984年   46篇
  1983年   41篇
  1982年   20篇
  1981年   25篇
  1980年   11篇
  1979年   6篇
  1978年   3篇
  1976年   6篇
  1971年   3篇
  1957年   5篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
871.
The streaming potential is generated by the electrokinetic flow effect within the electrical double layer of a charged solid surface. Surface charge properties are commonly quantified in terms of the zeta potential obtained by computation with the Helmholtz-Smoluchowski (H-S) equation following experimental measurement of streaming potential. In order to estimate a rigorous zeta potential for cone-shaped microchannel, the correct H-S equation is derived by applying the Debye-Hückel approximation and the fluid velocity of diverging flow on the specified position. The present computation provides a correction ratio relative to the H-S equation for straight cylindrical channel and enables us to interpret the effects of the channel geometry and the electrostatic interaction. The correction ratio decreases with increasing of diverging angle, which implies that smaller zeta potential is generated for larger diverging angle. The increase of Debye length also reduces the correction ratio due to the overlapping of the Debye length inside of the channel. It is evident that as the diverging angle of the channel goes to nearly zero, the correction ratio converges to the previous results for straight cylindrical channel.  相似文献   
872.
Two dendritic reversible addition-fragmentation transfer (RAFT) agents with 8 and 16 terminal dithiobenzoate (DTB) groups on the surface of poly(propylene imine) (PPI) dendrimers (generation 2.0 and 3.0, respectively) were successively prepared, and they were used in the RAFT polymerization of N-isopropylacrylamide (NIPAAM). The polymerization kinetics was confirmed to pseudo-first-order behavior. The 1H NMR and GPC analyses show that the dendrimer-star den (NIPAAM)x (x = 8 or 16) prepared by RAFT method has well-defined structure, controlled molecular weight and low polydispersities (PDI < 1.3). The aqueous solution prepared from dendrimer-star PNIPAAM showed reversible changes in optical properties: transparent below a lower critical solution temperature (LCST) and opaque above the LCST.  相似文献   
873.
Nematic-isotropic interfaces exhibit novel dynamics due to anchoring of the liquid crystal molecules on the interface. The objective of this study is to demonstrate the consequences of such dynamics in the flow field created by an elongated nematic drop retracting in an isotropic matrix. This is accomplished by two-dimensional flow simulations using a diffuse-interface model. By exploring the coupling among bulk liquid crystal orientation, surface anchoring and the flow field, we show that the anchoring energy plays a fundamental role in the interfacial dynamics of nematic liquids. In particular, it gives rise to a dynamic interfacial tension that depends on the bulk orientation. Tangential gradient of the interfacial tension drives a Marangoni flow near the nematic-isotropic interface. Besides, the anchoring energy produces an additional normal force on the interface that, together with the interfacial tension, determines the movement of the interface. Consequently, a nematic drop with planar anchoring retracts more slowly than a Newtonian drop, while one with homeotropic anchoring retracts faster than a Newtonian drop. The numerical results are consistent with prior theories for interfacial rheology and experimental observations.  相似文献   
874.
The binding energy spectra and electron distributions in momentum space of the valence orbitals of cyclopentane (C(5)H(10)) are studied by Electron Momentum Spectroscopy (EMS) in a noncoplanar symmetric geometry. The impact energy was 1200 eV plus binding energy and energy resolution of the EMS spectrometer was 1.2 eV. The experimental momentum profiles of the outer valence orbitals are compared with the theoretical momentum distributions calculated using Hartree-Fock and density functional theory (DFT) methods. The shapes of the experimental momentum distributions are generally quite well described by both the Hartree-Fock and DFT calculations when the large and diffuse basis sets are used.  相似文献   
875.
Electron momentum distributions for outer valence orbitals of CF2Cl2 have been obtained by (e,2e) electron momentum spectroscopy at an incident energy of 1200 eV + binding energy. The experimental electron momentum profiles are compared with Hartree-Fock and density functional theory (DFT) calculations using B3LYP hybrid functional with the 6-31G and 6-311+G* basis sets. Generally, the shapes of the experimental momentum profiles are well reproduced by DFT calculations using larger basis sets 6-311 + G*. An attempt has been made to clarify the ordering of the outer valence orbitals, which have been in controversy, by comparing experimental results with B3LYP/6-311 + G* calculations.  相似文献   
876.
A new activation method has been developed for electroless copper plating on silicon wafer based on palladium chemisorption on SAMs of APTS without SnCl2 sensitization and roughening condition.A closely packed electroless copper film with strong adhesion is successfully formed by AFM observation.XPS study indicates that palladium chemisorption occurred via palladium chloride bonding to the pendant amino group of the SAMs.  相似文献   
877.
Two efficient and stereoselective methods are described for the preparation of aryl and heteroaryl ceramide analogues 2 and 3. The first route involves the addition of an aryllithium or a heteroaryllithium reagent (7a or 25a, respectively) to the L-serine-derived aldehyde 4, followed by hydrolysis of the oxazolidine, liberation of the amino group, and N-acylation. The second route, which was used to prepare arylceramide analogue 2 in eight steps and 28% overall yield starting with 3-bromobenzaldehyde, utilizes a Heck reaction to afford (E)-alpha,beta-unsaturated ester 16, then osmium-catalyzed asymmetric dihydroxylation for the introduction of the desired chirality at C-2 and C-3. Regioselective alpha-azidation of alpha-O-nosyl-beta-hydroxyester 18 with sodium azide, followed by LiAlH(4) reduction of the azido and ester groups and N-acylation, complete the synthesis of arylceramide analogue 2.  相似文献   
878.
本文用紫外可见光谱、pH滴定等方法研究了配合物[(dien)Cu(imH)](ClO4)2、[(tren)Cu(imH))(ClO4)2中Cu-imH的配位和离解作用,得到了它们的稳定常数,并探索了共存配体的影响。  相似文献   
879.
在自制的仪器上,以脉冲激光束在高真空中溅射适当的样品,产生了一系列合有1个VA族原子(N、P、As)或ⅢA族原子(B、Al)及13个以下碳原子的原子簇负离子。在实验记录的飞行时间质谱中,这些簇离子的信号强度均因其碳原子数的奇偶而发生交替变化.对实验结果的分析研究显示:这些簇离子均为直链构型.VA或ⅢA族原子位于链的一端,所有成簇原子的价键均得到满足.  相似文献   
880.
A convergent, total synthesis of epothilones B (2) and D (4) is described. The key steps are Normant coupling to establish the desired (Z)-stereochemistry at C12-C13, Wadsworth-Emmons olefination of methyl ketone 28 with the phosphonate ester 8, diastereoselective aldol condensation of aldehyde 5 with the enolate of keto acid derivatives to form the C6-C7 bond, selective deprotection of acid 52, and macrolactonization.  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号