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   1220篇
  免费   75篇
  国内免费   4篇
化学   1044篇
晶体学   13篇
力学   20篇
数学   55篇
物理学   167篇
  2023年   16篇
  2022年   20篇
  2021年   27篇
  2020年   30篇
  2019年   26篇
  2018年   38篇
  2017年   19篇
  2016年   55篇
  2015年   41篇
  2014年   66篇
  2013年   71篇
  2012年   106篇
  2011年   149篇
  2010年   70篇
  2009年   64篇
  2008年   94篇
  2007年   73篇
  2006年   66篇
  2005年   53篇
  2004年   54篇
  2003年   49篇
  2002年   30篇
  2001年   16篇
  2000年   10篇
  1999年   6篇
  1998年   8篇
  1997年   3篇
  1996年   5篇
  1995年   6篇
  1994年   4篇
  1993年   3篇
  1992年   2篇
  1991年   3篇
  1990年   4篇
  1989年   1篇
  1988年   1篇
  1987年   1篇
  1986年   2篇
  1985年   2篇
  1984年   3篇
  1983年   1篇
  1973年   1篇
排序方式: 共有1299条查询结果,搜索用时 15 毫秒
91.
The hexapyrrole-α,ω-dicarbaldehydes 1 a and 1 b were metallated with CuII, NiII, and PdII to give bimetallic complexes where a pair of 3 N+O four-coordinate metal planes are helically distorted and the central 2,2′-bipyrrole subunit adopts a cis or trans conformation. X-ray crystallographic analysis of the bisCu complex revealed a closed form with a cis-2,2′-bipyrrole subunit and an open form with a trans-2,2′-bipyrrole subunit. The bisPd complexes took a closed form both in the solid state and in solution. They are regarded as single helicates of two turns and the energy barrier for the interchange between an M helix and a P helix was remarkably influenced by the bulky 3,3′-substituent of the central 2,2′-bipyrrole subunit. Although the bisNi complexes adopt a closed form in the solid state, they exist as a homohelical open C2-symmetric form or a heterohelical open Ci-symmetric form in solution. A theoretical study suggested that the closed form of 1 a Pd was stabilized by the Pd–Pd interaction. Compound 1 a Pd was reversibly oxidized by one electron at 0.14 V versus ferrocene/ferrocenium (Fc/Fc+) and this oxidized species showed Vis/NIR absorption bands at λ=767 and 1408 nm.  相似文献   
92.
We herein demonstrate that the amide base generated in situ from CsF and N(TMS)3 catalyzes the deprotonative coupling reactions of terminal alkynes with polyfluoroarenes, wherein mono- and dialkynylations occur efficiently for penta- and hexafluorobenzenes, respectively. Tetraalkynylated products could also be synthesized from dialkynylated compounds.  相似文献   
93.
The development and use of a multiple-activation catalyst with ion-paired Lewis acid and Brønsted acid in an asymmetric aza-Diels–Alder reaction of simple dienes (non-Danishefsky-type electron-rich dienes) was achieved by utilizing the [FeBr2]+[FeBr4] combination prepared in situ from FeBr3 and chiral phosphoric acid. Synergistic effects of the highly active ion-paired Lewis acid [FeBr2]+[FeBr4] and a chiral Brønsted acid are important for promoting the reaction with high turnover frequency and high enantioselectivity. The multiple-activation catalyst system was confirmed using synchrotron-based X-ray absorption fine structure measurements, and theoretical studies. This study reveals that the developed catalyst promoted the reaction not only by the interaction offered by the ion-paired Lewis acid and the Brønsted acid but also noncovalent interactions.  相似文献   
94.
Porous particle superstructures of about 15 nm diameter, consisting of ultrasmall nanoparticles of iridium and iridium dioxide, are prepared through the reduction of sodium hexachloridoiridate(+IV) with sodium citrate/sodium borohydride in water. The water-dispersible porous particles contain about 20 wt % poly(N-vinylpyrrolidone) (PVP), which was added for colloidal stabilization. High-resolution transmission electron microscopy confirms the presence of both iridium and iridium dioxide primary particles (1–2 nm) in each porous superstructure. The internal porosity (≈58 vol%) is demonstrated by electron tomography. In situ transmission electron microscopy up to 1000 °C under oxygen, nitrogen, argon/hydrogen (all at 1 bar), and vacuum shows that the porous particles undergo sintering and subsequent compaction upon heating, a process that starts at around 250 °C and is completed at around 800 °C. Finally, well-crystalline iridium dioxide is obtained under all four environments. The catalytic activity of the as-prepared porous superstructures in electrochemical water splitting (oxygen evolution reaction; OER) is reduced considerably upon heating owing to sintering of the pores and loss of internal surface area.  相似文献   
95.
The objective of this study was to assess the effect of comprehensive exercise program widely accepted as a community-based physical intervention for the prevention of falling in the elderly persons on their controlling standing balance. Twenty-six community-dwelling elderly persons (13 males and females; 69.8 ± 2.8 years old) participated in this study. Daily exercise was comprised of walking for more than 30 min, stretching, muscle strengthening and balance exercise without exercise equipments. The intervention was continued for three months. Indicators of standing balance related to static balance, dynamic balance and postural response were measured before and after the intervention. As an effect of the intervention on static balance, the sway of center of pressure (COP) in the static stance significantly increased. In the dynamic balance, significant improvements were observed in one leg standing time, the 10-m gait time, functional reach. Additionally, the maximal movable length of COP which subjects can move voluntarily to right and left significantly increased. In the postural response, the integrated electromyography (IEMG) induced by postural response for sudden postural perturbation significantly decreased in the lower leg muscles. Since less muscular activities were sufficient to maintain posture, it was suggested that postural response was elicited more efficiently following the intervention. This study suggested that the comprehensive exercise program, which has been widely introduced as community-based interventions for the prevention of falling, have extensive effects on the control of standing balance covering static balance, dynamic balance and postural response in the elderly persons.  相似文献   
96.
Landau levels have been theoretically investigated in a two-dimensional electron gas near a quantum dot (QD) layer. By a diagrammatical method, we have formulated the self-energy for the Landau level and deduced its relation to the AC conductivity σloc(ω) in the QD layer. As an example, we have examined the density of states in the case where σloc(ω) is described by AωS(S=0.8). It is found that the Landau levels are broadened due to the interaction with the localized electrons in the QDs.  相似文献   
97.
98.
FeCl3/AgOTf-catalyzed hydroarylation of propiolic acid with electron-rich arenes such as mesitylene, tetramethylbenzene, and pentamethylbenzene in trifluoroacetic acid proceeded to give 3-arylpropenoic acids in moderate to high yields. The same reactions with anisole and 1,4-dimethoxybenzene afforded double hydroarylation products, 3,3-diarylpropionic acids.  相似文献   
99.
Lembehsterols A (1) and B (2), two novel sulfated sterols, were isolated from the marine sponge Petrosia strongylata. Both sterols showed inhibitory activity against thymidine phosphorylase, which is an enzyme related to angiogenesis in solid tumors. The structures of these sulfated sterols were established on the basis of chemical and physicochemical evidence.  相似文献   
100.
The 2:1 charge-transfer (CT) salts (1(2).FeBr(4) and 1(2).GaBr(4)) of ethylenedithiotetrathiafulvalenoquinone-1,3-dithiolemethide (1) with FeBr(4)(-) and GaBr(4)(-) counteranions were obtained as needle crystals, whose structures are almost the same as each other. The 1 molecules form a one dimensionally stacked column with alternation of their molecular axis direction, while the counteranions are aligned in parallel with the 1-stacked columns with the direction of their distorted-tetrahedral geometry maintained. The room-temperature electrical conductivities measured on the single crystals of 1(2).FeBr(4) and 1(2).GaBr(4) were 4.6 and 2.1 S cm(-1), respectively. From the temperature dependences of their electrical conductivities in both cases the electrical conducting properties were metallic between ca. 170 and 300 K, but below ca. 170 K converted to be semiconducting and continued till 5 K, although the activation energies are very small (4-10 meV). For 1(2).FeBr(4) very weak and antiferromagnetic interaction occurred between the d spins of FeBr(4)(-) ions in the temperature range of ca. 1-300 K. However, below ca. 15 K the ferromagnetic interaction was reversely preferential possibly by participation of the pi spin of 1.  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