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   3830篇
  免费   569篇
  国内免费   551篇
化学   3012篇
晶体学   61篇
力学   178篇
综合类   49篇
数学   496篇
物理学   1154篇
  2024年   7篇
  2023年   38篇
  2022年   77篇
  2021年   89篇
  2020年   115篇
  2019年   148篇
  2018年   123篇
  2017年   96篇
  2016年   186篇
  2015年   199篇
  2014年   224篇
  2013年   260篇
  2012年   284篇
  2011年   305篇
  2010年   243篇
  2009年   230篇
  2008年   306篇
  2007年   267篇
  2006年   241篇
  2005年   208篇
  2004年   184篇
  2003年   198篇
  2002年   238篇
  2001年   193篇
  2000年   115篇
  1999年   87篇
  1998年   52篇
  1997年   30篇
  1996年   26篇
  1995年   18篇
  1994年   15篇
  1993年   18篇
  1992年   12篇
  1991年   9篇
  1990年   4篇
  1989年   4篇
  1988年   10篇
  1987年   5篇
  1986年   5篇
  1985年   17篇
  1984年   9篇
  1982年   4篇
  1980年   6篇
  1979年   4篇
  1977年   4篇
  1975年   3篇
  1974年   3篇
  1973年   4篇
  1972年   3篇
  1936年   5篇
排序方式: 共有4950条查询结果,搜索用时 0 毫秒
91.
A simple and economical CE method has been developed for the analysis of four model basic proteins by employing N‐methyl‐2‐pyrrolidonium methyl sulfonate ionic liquid (IL) as the dynamic coating material based on the interaction of both between electrostatic attraction and hydrogen bond, and between the organic cations of IL and the inner surface of bare fused‐silica capillary. The N‐methyl‐2‐pyrrolidonium‐based IL modified capillary not only generated a stable suppressed electroosmotic flow, but also effectively eliminated the wall adsorption of proteins. Several important parameters such as the IL concentration, pH values, and concentrations of the background electrolyte were optimized to improve the separation of basic proteins. Consequently, under the optimum separation conditions, a satisfied separation of basic proteins including lysozyme, cytochrome c, ribonuclease A, and α‐chymotrypsinogen A with theoretical plates ranging from 2.09 × 105 to 4.48 × 105 plates/m had been accomplished within 15 min. The proposed method first illustrated the effect of hydrogen bond between coating material and inner capillary surface on the coating, which should be a new strategy to design and select more effective coating materials to form more stable coatings in CE.  相似文献   
92.
The brominated flame retardants hexabromocyclododecane (HBCD) and tetrabromobisphenol A (TBBPA) are high-production-volume chemicals. In recent years, their presence has been reported in sediment and biota from the marine environment. In this study, an analytical method was developed for the simultaneous determination of HBCD, TBBPA, and the possible metabolite dimethyl-TBBPA. The method was applied in a preliminary screening of egg, liver, and adipose tissue of marine biota from Greenland and the Faroe Islands. α-HBCD was detected in 35 of 36 analysed samples from the Arctic, indicating a ubiquitous presence of α-HBCD in the environment. β- and γ-HBCD were found in 10 and 14 samples, respectively. TBBPA and dimethyl-TBBPA were not detected in any of the samples indicating limited or no transport of these compounds to remote areas.  相似文献   
93.
Chiral N-[1-benzyl-2-hydroxyethyl]-3-[2-oxo-pyrrole]propionamide (C16H22N2O3) was obtained unexpectedly from the reaction of oxazoline involving pyrrolidone with copper acetate monohydrate, and the structure was characterized by NMR, IR, elemental analysis, and X-ray analysis.  相似文献   
94.
95.
Two‐dimensional (2D) copper‐based ternary and quaternary semiconductors are promising building blocks for the construction of efficient solution‐processed photovoltaic devices at low cost. However, the facile synthesis of such 2D nanoplates with well‐defined shape and uniform size remains a challenge. Reported herein is a universal template‐mediated method for preparing copper‐based ternary and quaternary chalcogenide nanoplates, that is, CuInS2, CuInxGa1−xS2, and Cu2ZnSnS4, by using a pre‐synthesized CuS nanoplate as the starting template. The various synthesized nanoplates are monophasic with uniform thickness and lateral size. As a proof of concept, the Cu2ZnSnS4 nanoplates were immobilized on a Mo/glass substrate and used as semiconductor photoelectrode, thus showing stable photoelectrochemical response. The method is general and provides future opportunities for fabrication of cost‐effective photovoltaic devices based on 2D semiconductors.  相似文献   
96.
张伟强  王晨  赵玉荣  王栋  王继乾  徐海 《应用化学》2022,39(8):1190-1201
Some short peptides can spontaneously self-assemble into various nanostructures via the synergistic driving forces of non-covalent interactions. These non-covalent interactions,including electrostatic interaction,hydrogen bonding,aromatic interactions and other non-covalent interactions,are usually highly coupled together. Through rational sequence design and proper modification of short peptide molecules,the driving forces could be regulated purposively,and the nanostructures and morphologies of the self-assemblies could be controlled accordingly,and thus so as to achieve the fabrication of peptide-based supramolecular biomaterials and develop their functions. In this paper,the effects of hydrogen bonding,π-π stacking, electrostatic interaction,hydrophobic interaction,metal ion coordination and chiral center on the self-assembly behavior of peptide self-assembly have been reviewed. The driving force regulation strategies, including sequence design,pH and concentration adjustment and metal ion coordination,and the resulted nanostructures have also been discussed. We also make the outlooks on the development of peptide-based supramolecular biomaterials with specific functions in biomedicines and biocatalysis. © 2022, Science Press (China). All rights reserved.  相似文献   
97.
98.
Di  Lu  Dong  Hao  Chen  Dan Ni  Wang  Hai Ying  Liu  Hui Yan 《Transition Metal Chemistry》2021,46(1):57-63
Transition Metal Chemistry - A Cu(II) coordination polymer, [Cu2(pztrz)2(μ-CH3COO)(CH3COO)]·3H2O (1), derived from mono-substituted 1,2,4-triazole derivative 3-(pyrazinyl)-1,2,4-triazole...  相似文献   
99.
(E)‐α,β‐Unsaturated pyrazoleamides undergo facile dienolization to furnish copper(I)‐(1Z,3Z)‐dienolates as the major in the presence of a copper(I)‐(R)‐DTBM‐SEGPHOS catalyst and Et3N, which react with aldimines to afford syn‐vinylogous products as the major diastereoisomers in high regio‐ and enantioselectivities. In some cases, the diastereoselectivity is low, possibly due to the low ratio of copper(I)‐(1Z,3Z)‐dienolates to copper(I)‐(1Z,3E)‐dienolates. (Z)‐Allylcopper(I) species is proposed as effective intermediates, which may form an equilibrium with copper(I)‐(1Z,3Z)‐dienolates. Interestingly, the present methodology is a nice complement to our previous report, in which (E)‐β,γ‐unsaturated pyrazoleamides were employed as the prenucleophiles in the copper(I)‐catalyzed asymmetric vinylogous Mannich‐Type reaction and anti‐vinylogous products were obtained. In the previous reaction, copper(I)‐ (1Z,3E)‐dienolates were generated through α‐deprotonation, which might form an equilibrium with (E)‐allylcopper(I) species. Therefore, it is realized in the presence of a copper(I) catalyst that (E)‐α,β‐unsaturated pyrazoleamides lead to syn‐products and (E)‐β,γ‐unsaturated pyrazoleamides lead to anti‐products. Finally, by use of (E)‐β,γ‐unsaturated pyrazoleamide, (E)‐α,β‐unsaturated pyrazoleamide, (R)‐DTBM‐SEGPHOS, and (S)‐DTBM‐SEGPHOS, the stereodivergent synthesis of all four stereoisomers is successfully carried out. Then by following a three‐step reaction sequence, all four stereoisomers of N‐Boc‐2‐Ph‐3‐Me‐piperidine are synthesized in good yields, which potentially serve as common structure units in pharmaceutically active compounds.  相似文献   
100.
The reaction of Co(ClO4)2·6H2O with 2-hydroxy-3-methoxy-benzaldehyde and an aqueous solution of methylamine in acetonitrile/MeOH under microwave irradiation and controlled temperature/pressure leads to formation of heptanuclear cobalt cluster [Co7(mmp)6(CH3O)6]·(ClO4)2 (1) (mmp is 2-methoxy-6-methyliminomethyl-phenol anion) in only 20 min and also results in higher yields in contrast to other synthesis methods. Complex 1 displays dominant ferromagnetic interactions through μ 3-O and μ 2-O (oxidophenyl) binding modes.  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