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   6270篇
  免费   491篇
  国内免费   711篇
化学   2834篇
晶体学   28篇
力学   872篇
综合类   58篇
数学   659篇
物理学   370篇
综合类   2651篇
  2024年   18篇
  2023年   89篇
  2022年   141篇
  2021年   176篇
  2020年   199篇
  2019年   197篇
  2018年   156篇
  2017年   202篇
  2016年   240篇
  2015年   218篇
  2014年   304篇
  2013年   348篇
  2012年   282篇
  2011年   357篇
  2010年   254篇
  2009年   361篇
  2008年   311篇
  2007年   401篇
  2006年   393篇
  2005年   348篇
  2004年   329篇
  2003年   346篇
  2002年   213篇
  2001年   184篇
  2000年   165篇
  1999年   157篇
  1998年   151篇
  1997年   162篇
  1996年   118篇
  1995年   124篇
  1994年   110篇
  1993年   73篇
  1992年   67篇
  1991年   62篇
  1990年   63篇
  1989年   45篇
  1988年   32篇
  1987年   24篇
  1986年   15篇
  1985年   9篇
  1984年   5篇
  1983年   3篇
  1982年   7篇
  1981年   2篇
  1979年   5篇
  1972年   3篇
  1971年   1篇
  1957年   1篇
  1955年   1篇
排序方式: 共有7472条查询结果,搜索用时 437 毫秒
991.
992.
Self-assembly of CuSO4, para-methyl-2-phenyl acetate and 1,10-phenanthroline afforded good-quality crystalline complex in quantitative yield. The complex was characterized by FTIR and UV-visible spectroscopy, electrochemistry, and powder and single-crystal XRD studies. Its structure was found to possess axially elongated octahedral symmetry with CuO4N2 chromophore. Its purity was assessed by powder XRD spectrum. Absorption study yielded a broad band corresponding to 2Eg2T2 g transition. Electrochemical solution study indicated diffusion-controlled irreversible electron transfer process corresponding to Cu(II)/Cu(I) redox couple with diffusion coefficient = 7.89(±0.1)×10?9 cm2s?1. Results of spectroscopic techniques support each other. Complex exhibited excellent DNA-binding ability through UV-visible spectroscopy and cyclic voltammetry yielding Kb values 1.399 × 104 M?1 and 5.81 × 103 M?1, respectively. The complex exhibited significant activity against bacterial strains Escherichia coli, Micrococcus luteus and Staphylococcus aureus and good activity against Bacillus subtilis. These preliminary studies impart good biological relevance on the synthesized complex.  相似文献   
993.
The reduction of TipMCl3 (Tip=2,4,6‐triisopropylphenyl) (M=Si, Ge) with KC8 in the presence of cyclic alkyl(amino) carbene (cAAC) afforded the acyclic silanylidene and germanylidene anions in the form of potassium salt [K(cAAC)MTip]2 (M=Si ( 1 ); Ge ( 2 )). The silanylidene and germanylidene anions are valence‐isoelectronic to the well‐studied phosphinidene and are a new class of acyclic anions of Group 14. Compounds 1 and 2 were isolated and well characterized by NMR and single‐crystal X‐ray structure analysis. Furthermore, the structure and bonding of compounds 1 and 2 was investigated by computational methods.  相似文献   
994.
The secondary metabolites of Xylaria cf. cubensis SWUF08-86 fungus were investigated, and the chromatographic separation of the crude extracts yielded seventeen compounds. The structure elucidation by spectroscopic analysis including 1D and 2D NMR and the comparison of these data with literature, along with HREIMS spectrometry, revealed one new amino amidine derivative (1), together with five known simple cyclic dipeptide analogs, diketopiperazines (26) and eleven other known compounds, including one hemi-cycline (10), three aromatic derivatives (1113), one sesquiterpene (14) and three sterols (1517). The isolated compounds were screened for anticancer and anti-pathogenic bacterial and fungal activities. Based on this work, Xylaria cf. cubensis SWUF08-86 has proven to be a diverse secondary metabolites producer.  相似文献   
995.
The cyclic brush polymers, due to the unique topological structure, have shown in the previous studies higher delivery efficacy than the bottlebrush analogues as carriers for drug and gene transfer. However, to the best of knowledge, the preparation of reduction‐sensitive cyclic brush polymers for drug delivery applications remains unexplored. For this purpose, a reduction‐sensitive amphiphilic cyclic brush copolymer, poly(2‐hydroxyethyl methacrylate‐g‐poly(ε‐caprolactone)‐disulfide link‐poly(oligoethyleneglycol methacrylate)) (P(HEMA‐g‐PCL‐SS‐POEGMA)) with reducible block junctions bridging the hydrophobic PCL middle layer and the hydrophilic POEGMA outer corona is designed and synthesized successfully in this study via a “grafting from” approach using sequential ring‐opening polymerization (ROP) and atom transfer free radical polymerization (ATRP) from a cyclic multimacroinitiator PHEMA. The resulting self‐assembled unimolecular core–shell–corona (CSC) micelles show sufficient salt stability and efficient destabilization in the intracellular reducing environment for a promoted drug release toward a greater therapeutic efficacy relative to the reduction‐insensitive analogues. The overall results demonstrate the reducible cyclic brush copolymers developed herein provides an elegant solution to the tradeoff between extracellular stability and intracellular high therapeutic efficacy toward efficient anticancer drug delivery.  相似文献   
996.
Consider the third order differential operator L given by and the related linear differential equation L(x)(t) + x(t) = 0. We study the relations between L, its adjoint operator, the canonical representation of L, the operator obtained by a cyclic permutation of coefficients a i , i = 1,2,3, in L and the relations between the corresponding equations.We give the commutative diagrams for such equations and show some applications (oscillation, property A).  相似文献   
997.
A simple and efficient synthesis of novel 14-membered macrocycles from a resin-bound orthogonally protected lysine residue is described. Reductive alkylation of the lysine -nitrogen introduces the first diversity element. Acylation of the resultant secondary amine with an Fmoc-amino acid introduces the second diversity element providing a resin-bound protected di-peptide precursor. Removal of the Fmoc-group is followed by acylation with a succinic anhydride to introduce the final diversity elements. Removal of the methyltrityl-group from the amino group followed by macrocyclization provides the desired macrocycles, after TFA cleavage, in excellent yield and purity.  相似文献   
998.
采用循环伏安法制备了邻苯二胺电聚合膜。研究了聚邻苯二胺(ODB)合成过程中单体浓度、扫描速率、溶液中氢离子浓度、电极材料、阴离子种类、聚合时间等对聚合电量的影响,提出了最佳聚合方案,即在0.015mol/LODB+0.4mol/LKCl+0.1mol/LHCl溶液中,以100mV·s-1的速率循环扫描50min。根据红外光谱初步推测:单体浓度低时可聚合形成类似吩嗪的桥式化学结构;而浓度高时形成1,2,4取代的链式结构。  相似文献   
999.
冲击机械的工作效率很大程度上取决于冲击机械的核心部件冲击活塞撞击所产生的应力波形.作者就冲击机械的合理加载波形,从能量传递效率和有利于工作介质变形或破坏两方面进行了研究.分析中详细考虑了工作介质类型和实际冲击加载系统的影响.研究结果表明,等波阻活塞产生的矩形波是最适合于实际冲击机械的合理加载波.  相似文献   
1000.
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