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   2138篇
  免费   105篇
  国内免费   13篇
化学   1586篇
晶体学   10篇
力学   65篇
数学   321篇
物理学   274篇
  2024年   6篇
  2023年   15篇
  2022年   36篇
  2021年   41篇
  2020年   31篇
  2019年   41篇
  2018年   32篇
  2017年   41篇
  2016年   88篇
  2015年   54篇
  2014年   110篇
  2013年   130篇
  2012年   162篇
  2011年   185篇
  2010年   109篇
  2009年   111篇
  2008年   144篇
  2007年   133篇
  2006年   121篇
  2005年   113篇
  2004年   114篇
  2003年   81篇
  2002年   73篇
  2001年   39篇
  2000年   35篇
  1999年   22篇
  1998年   22篇
  1997年   19篇
  1996年   17篇
  1995年   14篇
  1994年   13篇
  1993年   9篇
  1992年   6篇
  1991年   8篇
  1989年   3篇
  1988年   4篇
  1987年   6篇
  1986年   4篇
  1985年   17篇
  1984年   6篇
  1983年   3篇
  1982年   4篇
  1981年   4篇
  1980年   3篇
  1979年   6篇
  1977年   4篇
  1976年   3篇
  1975年   3篇
  1971年   2篇
  1958年   2篇
排序方式: 共有2256条查询结果,搜索用时 15 毫秒
81.
82.
Demand for long‐lasting antifouling surfaces has steered the development of accessible, novel, biocompatible and environmentally friendly materials. Inspired by lubricin (LUB), a component of mammalian synovial fluid with excellent antifouling properties, three block polymers offering stability, efficacy, and ease of use were designed. The bottlebrush‐structured polymers adsorbed strongly on silica surfaces in less than 10 minutes by a simple drop casting or online exposure method and were extremely stable in high‐salinity solutions and across a wide pH range. Antifouling properties against proteins and bacteria were evaluated with different techniques and ultralow fouling properties demonstrated. With serum albumin and lysozyme adsorption <0.2 ng cm?2, the polymers were 50 and 25 times more effective than LUB and known ultralow fouling coatings. The antifouling properties were also tested under MPa compression pressures by direct force measurements using surface forces apparatus. The findings suggest that these polymers are among the most robust and efficient antifouling agents currently known.  相似文献   
83.
For high values of the quantum number of the total angular momentum J (up to J = 20), quantum mechanical eigenstates (eigenvalues and eigenfunctions) are calculated by the method of Gatti et al. (J. Mol. Spectrosc. 181 (1997) 403) for the bending deformations of HCN and CNH. In particular, we have examined the l-type resonances in highly excited rovibrational states within the framework of a one-dimensional model, i.e. along the reaction pathway for the isomerization reaction HCN/CNH. The potential energy surface used is that of Bowman et al. (J. Chem. Phys. 99 (1993) 308).  相似文献   
84.
85.
Dynamics of an enzymatic substitution reaction in haloalkane dehalogenase   总被引:1,自引:0,他引:1  
Reactive flux molecular dynamics simulations have been carried out using a combined QM/MM potential to study the dynamics of the nucleophilic substitution reaction of dichloroethane by a carboxylate group in haloalkane dehalogenase and in water. We found that protein dynamics accelerates the reaction rate by a factor of 2 over the uncatalyzed reaction. Compared to the thermodynamic effect in barrier reduction, protein dynamic contribution is relatively small. However, analyses of the friction kernel reveal that the origins of the reaction dynamics in water and in the enzyme are different. In aqueous solution, there is significant electrostatic solvation effect, which is reflected by the slow reorganization relaxation of the solvent. On the other hand, there is no strong electrostatic coupling in the enzyme and the major effect on reaction coordinate motion is intramolecular energy relaxation.  相似文献   
86.
Despite the presence of a single amino substituent, an amino-anthryl-carbene was found to behave as a strong sigma-donor weak pi-acceptor ligand toward rhodium(I) fragments.  相似文献   
87.
Bossuyt X 《Electrophoresis》2004,25(10-11):1485-1487
Capillary zone electrophoresis (CZE) of serum proteins has become a well-accepted method for the separation of serum proteins and for the detection of monoclonal proteins in clinical laboratories. As CZE uses ultraviolet detection for direct protein quantification, exogenous ultraviolet-absorbing substances are a novel challenge, not present in conventional gel-based methods in which protein is quantified by dye binding. This minireview gives a survey of interfering substances, including iodinated contrast agents and antibiotics.  相似文献   
88.
89.
Stereoselective syntheses of P-chiral ammonium phosphonite-borane complexes in the gluco- and manno-like series have been developed from P(V) phostone derivatives. The coupling reactions of these phostone donors with alcohols have been investigated with particular emphasis on the influence of protecting groups and conditions on stereoselectivity. The phosphonite-borane complexes may be applied directly in the coupling reactions and the products oxidized in situ to give phostone-mimetics of disaccharides. On the basis of these studies, successful protocols were established for the synthesis of β-gluco and α- and β-manno-configured phostones of primary alcohols. Deprotection of the dimeric compounds leads to novel families of α- or β-(1→6)-linked glycomimetics.  相似文献   
90.
One of the principal objectives of sustainable and green processing development remains the dissemination and teaching of green chemistry in colleges, high schools, and academic laboratories. This paper describes simple glassware that illustrates the phenomenon of extraction in a conventional microwave oven as energy source and a process for green analytical chemistry. Simple glassware comprising a Dean-Stark apparatus (for extraction of aromatic plant material and recovery of essential oils and distilled water) and a Vigreux column (as an air-cooled condenser inside the microwave oven) was designed as an in-situ extraction vessel inside a microwave oven. The efficiency of this experiment was validated for extraction of essential oils from 30 g fresh orange peel, a by-product in the production of orange juice. Every laboratory throughout the world can use this equipment. The microwave power is 100 W and the irradiation time 15 min. The method is performed at atmospheric pressure without added solvent or water and furnishes essential oils similar to those obtained by conventional hydro or steam distillation. By use of GC-MS, 22 compounds in orange peel were separated and identified; the main compounds were limonene (72.1%), β-pinene (8.4%), and γ-terpinene (6.9%). This procedure is appropriate for the teaching laboratory, does not require any special microwave equipment, and enables the students to learn the skills of extraction, and chromatographic and spectroscopic analysis. They are also exposed to a dramatic visual example of rapid, sustainable, and green extraction of an essential oil, and are introduced to successful sustainable and green analytical chemistry.  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