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   5821篇
  免费   1009篇
  国内免费   574篇
化学   3728篇
晶体学   53篇
力学   257篇
综合类   30篇
数学   791篇
物理学   2545篇
  2024年   23篇
  2023年   132篇
  2022年   200篇
  2021年   214篇
  2020年   228篇
  2019年   197篇
  2018年   182篇
  2017年   176篇
  2016年   290篇
  2015年   256篇
  2014年   319篇
  2013年   390篇
  2012年   480篇
  2011年   550篇
  2010年   336篇
  2009年   335篇
  2008年   363篇
  2007年   332篇
  2006年   319篇
  2005年   266篇
  2004年   195篇
  2003年   174篇
  2002年   194篇
  2001年   152篇
  2000年   128篇
  1999年   160篇
  1998年   134篇
  1997年   110篇
  1996年   110篇
  1995年   73篇
  1994年   53篇
  1993年   53篇
  1992年   48篇
  1991年   60篇
  1990年   31篇
  1989年   28篇
  1988年   22篇
  1987年   19篇
  1986年   22篇
  1985年   18篇
  1984年   6篇
  1983年   5篇
  1982年   5篇
  1981年   6篇
  1980年   1篇
  1979年   2篇
  1978年   4篇
  1977年   1篇
  1976年   1篇
  1957年   1篇
排序方式: 共有7404条查询结果,搜索用时 15 毫秒
991.
Metal–organic frameworks (MOFs) are promising alternative precursors for the fabrication of heteroatom‐doped carbon materials for energy storage and conversion. However, the direct pyrolysis of bulk MOFs usually gives microporous carbonaceous materials, which significantly hinder the mass transportation and the accessibility of active sites. Herein, N‐doped carbon aerogels with hierarchical micro‐, meso‐, and macropores were fabricated through one‐step pyrolysis of zeolitic imidazolate framework‐8/carboxymethylcellulose composite gel. Owing to the hierarchical porosity, high specific surface area, favorable conductivity, excellent thermal and chemical stability, the as‐prepared N‐doped carbon aerogel exhibits excellent oxygen reduction reaction (ORR) activity, long‐term durability, and good methanol tolerance in alkaline medium. This work thus provides a new way to fabricate new types of MOF‐derived carbon aerogels for various applications.  相似文献   
992.
高效液相色谱蛋白质手性固定相   总被引:4,自引:0,他引:4  
本文综述了近年文献中已报道的各种高效液相色谱蛋白质(酶)手性固定相及其在手性拆分中的应用,并阐述了蛋白质作为手性选择剂拆分机理的研究进展。  相似文献   
993.
A new zinc acetate catalyst which was prepared from modified activated carbon exhibited extreme activity towards the synthesis of vinyl acetate.The activated carbon was modified by nitric acid,vitriol and peroxyacetic acid(PAA).The effect on specific area, structure,pH and surface acidity groups of carriers by modification was discussed.Amount of carbonyl and carboxyl groups in activated carbon was increased by peroxyacetic acid treatment.The productivity of the new catalyst was 14.58%higher than that of...  相似文献   
994.
ZrO2 nanoparticles was uniformly co-deposited into a nickel matrix by electroplating of nickel from a Watts bath containing particles in suspension which were monodispersed with dispersant under DC electrodeposition condition. It was found that morphology, orientation and hardness of the nanocomposite coatings with monodispersed ZrO2 nanoparticles had lots of difference from the nanocomposite coatings with agglomerated ZrO2 nanoparticles and pure nickel coatings. Especially, the result of hardness showed that only a very low volume percent (less than 1 wt.%) of monodispered ZrO2 nanoparticles in Ni-ZrO2 nanocomposite coatings would result in higher hardness of the coatings. The hardness of Ni-ZrO2 nanocomposite coatings with monodispersed and agglomerated ZrO2 nanoparticles were 529 and 393 HV, respectively. The hardness value of the former composite coatings was over 1.3 times higher than that of the later. All these composite coatings were two-three times higher than that of pure nickel plating (207 HV) prepared under the same condition. The strengthening mechanisms of the Ni-ZrO2 nanocomposite coatings based on a combination of grain refinement strengthening from nickel matrix grain refining and dispersion strengthening from dispersion state of ZrO2 nanoparticles in the coatings.  相似文献   
995.
Well-aligned carbon nanotubes (CNTs) of high quality were synthesized by pyrolysis of phenolic resin at 800 °C in anodic alumina oxide (AAO) pores under argon protection. The innocuous source materials and safe operational conditions permit this method to synthesize well-aligned CNTs in large-scale and low cost. The formation mechanism of the synthesized CNTs is also proposed in this work by a series of visual sketches and is proved with obvious evidence. Firstly, phenolic resin nanotubes form in the template pores through the evaporation of solvent. Heat treatment then transfers these tubes into CNTs.  相似文献   
996.
对实验测量的PbB4O7晶体样品的太赫兹(1012Hz)光谱、拉曼光谱以及红外—可见—紫外光谱进行了分析.在0.25—2.5THz波段介电函数随频率变化曲线ε(ν)出现共振型尖峰.四方面的分析表明PbB4O7晶体中存在软光学声子:1)介电函数随频率的变化曲线ε(ν)满足LST(Lyddane-Sachs-Teller)关系;2)在共振峰的频率附近(3.10THz)有很强的拉曼散射峰;3)吸收系数随频率的变化曲线α(ν)满足极化激元的特征;4)透过晶体的光子的色散关系ν(k)发生断开的畸变.PbB4O7晶体中存在软光学声子的意义在于,在满足产生极化激元的条件下,透过晶体的光子的频率会发生劈裂,分为升高和降低的两支,有可能利用这种原理来改变光子的频率.  相似文献   
997.
用交流阻抗、开路电位衰退及线性电位扫描等方法在0.9V(vs.Hg/Hg2SO4)和4.5mol/LH2SO4溶液中,研究了铅及Pb-Sn合金电极上所生长的阳极氧化物膜.实验结果表明,阳极膜由溶解-沉淀机理控制生长,膜中微粒间为液膜,借助液膜作为离子通道可使膜中微粒发生阳极反应,锡有利于膜中PbO微粒表层阳极氧化为PbO1+x(0相似文献   
998.
1.INTRODUCTION[()-227.3()]Endotoxinislipopolysaccharide(LPS)derivedfromthecellmembranesofgram-negativebacteria.Endotoxincancausefebrilereactionsinanimalswithsymptomsofhighfever,vasodilation,diarrheaandfetalshockwheninjectedeveninaverysmallamount[1].Iftheconcentrationofendotoxininpatients?bloodishighenoughitcancauseseveresepsis,whichisamajorcauseofdeathinpatientsandcontinuestohaveahighmortalitydespiteappropriatesurgery,potentantibiotic,andintensivesupportivetherapy[2~5].LipidAisthemaintox…  相似文献   
999.
Bioactive natural products offer multiple opportunities for the discovery of novel chemical entities with potential pharmaceutical, nutraceutical and agrochemical applications. Many new organic compounds with novel scaffolds are isolated in small quantities and established methods often fail to determine the structure and bioactivity of such novel natural products. To meet this challenge, we present here a new methodology combining RDC (residual dipolar coupling)‐based NMR spectroscopy in microtubes, with a motif‐inspired biological assessment strategy. Using only one milligram (ca. 1.5 μmol) of sample, the new protocol established the bioactivity as well as the relative and absolute configuration of vatiparol obtained from Vatica parvifolia. Vatiparol is unique in its unprecedented carbon skeleton and selective inhibitory effect on the expression of monocyte chemo‐attractant protein‐1 (MCP‐1, also known as CCL2). The plausible biosynthetic pathway of vatiparol is briefly discussed. The approach introduced here promises to be widely applicable to the determination of the structure and bioactivity of structurally unknown organic samples available in very limited amounts.  相似文献   
1000.
The long-chain alkyl derivatives of a nucleoside analogue-acyclovir were prepared in the paper. One is stearyl-glycero-succinyl-acyclovir (SGSA) with a single 18-carbon length (C18) alkyl chain. Another is dioctadecyl-aspartate-succinyl-acyclovir (DASA) with double C18 alkyl chains. They were prepared by the esterification of succinyl-acyclovir with the lipids, and sodium salts of them were also prepared. Guanine moieties and alkyl moieties bring the derivatives intermolecular hydrogen bonding and hydrophobic interaction in water separately. The forces are influenced by the number of alkyl chains and the charged state, and determine the solubility and the self-assembly behavior of the derivatives. The double alkyl-chain derivatives (DASA and DASA-Na) formed rigid Langmuir monolayers on air/water surface, while the single alkyl chain derivatives (SGSA and SGSA-Na) did not. However, cholesterol (Chol) could assist SGSA to form rigid monolayers through inserting into the alkyl chains of SGSA to mimic the second alkyl chain. SGSA self-aggregates in water were prepared by the injection method with tetrahydrofuran as solvent. Cuboid-like shape and nanoscale size demonstrated that SGSA self-aggregates were self-assembled nanoparticles. Shape, particle size, zeta potential and phase transition of the nanoparticles were characterized. And they showed an average size of 83.2 nm, a negative surface charge of -31.3-mV zeta potential and a gel-liquid crystalline phase transition of 50.38 degrees C. The formation mechanism of self-assembled nanoparticles was analyzed. Hydrophobic interaction of alkyl chains improves SGSA molecules to form bilayers, and then cuboid-like nanoparticles were obtained by layer-by-layer aggregation based on inter-bilayers hydrogen bonding. However, the charged guanine moieties make SGSA-Na lose the function of hydrogen bonding so that SGSA-Na only forms vesicles in water based on hydrophobic interaction. Strong hydrophobicity and wide-open rigid double alkyl chains of DASA and DASA-Na restrict self-assembly in water media, and no homogeneous suspensions were obtained. Therefore, the molecular self-assembly behavior of the long-chain alkyl derivatives of nucleoside analogues on water surface or in water media is determined by the number of alkyl chains and the charged state.  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