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   9006篇
  免费   1964篇
  国内免费   1444篇
化学   8249篇
晶体学   359篇
力学   251篇
综合类   84篇
数学   332篇
物理学   3139篇
  2024年   12篇
  2023年   108篇
  2022年   270篇
  2021年   380篇
  2020年   453篇
  2019年   357篇
  2018年   337篇
  2017年   382篇
  2016年   519篇
  2015年   597篇
  2014年   743篇
  2013年   951篇
  2012年   747篇
  2011年   805篇
  2010年   674篇
  2009年   674篇
  2008年   616篇
  2007年   588篇
  2006年   524篇
  2005年   454篇
  2004年   408篇
  2003年   351篇
  2002年   211篇
  2001年   191篇
  2000年   161篇
  1999年   136篇
  1998年   98篇
  1997年   121篇
  1996年   137篇
  1995年   87篇
  1994年   53篇
  1993年   50篇
  1992年   46篇
  1991年   45篇
  1990年   25篇
  1989年   18篇
  1988年   19篇
  1987年   15篇
  1986年   10篇
  1985年   7篇
  1984年   6篇
  1983年   6篇
  1982年   4篇
  1981年   4篇
  1980年   3篇
  1979年   4篇
  1978年   3篇
  1977年   2篇
  1973年   2篇
排序方式: 共有10000条查询结果,搜索用时 78 毫秒
101.
《中国化学快报》2019,30(9):1659-1662
The development of efficient methods for the detection of hazardous and toxic elements is extremely important for environmental security and public health. In this work, we developed a facile colorimetric assaying system for Ag+ detection in aqueous solution. Chitosan-stabilized platinum nanoparticles (Ch-PtNPs) were synthesized and severed as an artificial oxidase to catalyze the oxidation of the substrate 3,3′,5,5′-tetramethylbenzidine (TMB) and generate color signal. In the presence of Ag+, due to the strong metallophilic interactions between Ag+ and Pt2+ on the surface of Ch-PtNPs, Ag+ can weaken the affinity to the substrates and inactivate the catalytic activity of Ch-PtNPs, leading to decreased absorbance signal to varying degrees depending on Ag+ amount. Combing the specific binding between Ch-PtNPs and Ag+ with signal amplification procedure based on the Ch-PtNPs-catalyzed TMB oxidation, a sensitive, selective, simple, cost-effective, and rapid detection method for Ag+ can be realized. Ag+ ions in tap and lake waters have been successfully detected. We ensured that the proposed method can be a potential alternative for Ag+ determination in environmental samples.  相似文献   
102.
研究了新疆阿尔泰特地区阿克提什坎金矿床的稀土元素及矿区二长花岗岩平衡的热液中稀土元素的组成特征及配分模型,并应用Grang等位线方法讨论了热液蚀变作用过程中稀土元素的行为。研究表明,在热液蚀变作用过程中,稀土元素保持惰性,成矿热液与岩浆热液关系不大,成矿物质主要来源于围岩。  相似文献   
103.
Chronoamperograms for gold in solutions containing 0.1 M thiourea, 0.5 M H2SO4, and catalytically active sulfide ions at the concentration c 1 from 1 × 10?5 to 4 × 10?5 M are obtained at different potentials with the aid of an automated setup intended for renewing the electrode surface directly in the solution by cutting off a thin surface layer of the metal. It is shown that the results of measurements of the current practically coincide at a constant value of the product c 1 t, where t is the time period elapsed after the renewal of the electrode surface. Such a coincidence testifies to a diffusion nature of processes that hamper accumulation of sulfide ions at the gold surface. This fact permitted the use of a procedure developed previously for the calculation of polarization curves at constant values of surface coverage θ by catalytically active ions. At θ = const, the voltammetric curves for gold in sulfide-containing thiourea solutions are shown to correspond to the Tafel equation. With the surface coverage increasing, the effective values of the exchange current i 0, transfer coefficient α, and anodic reaction order with respect to thiourea P a increase from the values i }~ 10?5 A cm?2, α }~ 0.12, and P a = 0.2, which are characteristic of pure solutions, to 2 × 10?4 A cm?2, α }~ 0.5, and P a = 1.1 (at θ }~ 0.5). An interpretation to the established regularities is given.  相似文献   
104.
Two different methods for the quantification of human tissue inhibitor of metalloproteinases-2 (TIMP-2) were developed using surface plasmon resonance (SPR) and gold nanoparticles for signal enhancement. The first method, a competitive assay, used TIMP-2 immobilized to the sensor surface and the inactive form of matrix metalloproteinase-2 (proMMP-2) (EC 3.4.24.24) adsorbed to gold nanoparticles. The sensor signals resulting from the interaction of MMP-2-gold nanoparticles with immobilized TIMP-2 were inversely proportional to the amounts of TIMP-2 of the sample. The measuring range for TIMP-2 was about 15–180 pM. The second method, a one-step sandwich assay, used proMMP-2 immobilized to the sensor surface and an anti-TIMP-2 monoclonal antibody coupled to gold nanoparticles. The lower detection limit of this assay format was 0.5 pM of TIMP-2. The binding signals were highly reproducible up to 100 pM of the inhibitor. The improvements obtained in TIMP-2 quantification over already existing tests could contribute to a better understanding and diagnosis of diseases like cancer.  相似文献   
105.
Single Crystal Investigations on Fluoroperovskites MPdF3 (M = Rb, K) and PdF2 Single crystal investigations on PdF2 (violet) confirm the tetragonale rutile structure [1, 2] with a = 495.44(3) pm, c = 338.48(3) pm, Z = 2, space group P42/mnm-D (No. 136) (xF = 0.3058(8)). RbPdF3 and KPdF3 have been obtained. RbPdF3 and KPdF3 both ruby-red single crystals crystallize cubic (perovskite-structure), space group Pm3m-O (No. 221) with a = 429.41(8) pm (RbPdF3) respectively a = 424.30(4) pm (KPdF3).  相似文献   
106.
Electronic structure of optimized Ge5, Ge17, Ge5–O and Ge5 embedded in SiO2 nanoparticles have been studied by density functional theory to find out the effect of cluster size and Ge–O bond(s) on the optical energy gap between LUMO and HOMO. It was found that the optical energy gap depends on both cluster size and the number of Ge–O bonds nonlinearly. The optical energy gap was found to be in visible light range when the Ge5 nanoparticle has been embedded in SiO2 matrix.  相似文献   
107.
The reaction of the di-gold cation [Au2(dppx)]2+ with the heptanuclear cluster dianion [Os7(CO)20]2– affords the mixed metal cluster [Os7(CO)20{Au2(dppx)}] (x=m (1), e (2), b (3)). On standing, in solution, this complex undergoes decarbonylation to give the cluster [Os7(CO)19{Au2(dppx)}] (x=m (4), e (5), b (6)). The complexes have been characterised spectroscopically, and an X-ray structure determination of the dppm derivative shows that it contains a metal core based on an Os7 edge-bridged bicapped tetrahedron with the two 3-Au atoms capping adjacent triangular Os3 faces of the central tetrahedron. In an analogous reaction, the carbido anion [Os7(H)C(CO)19] affords the neutral cluster [Os7C(CO)19{Au2(dppm)}] (7) when treated with [Au2(dppm)]2+ in the presence of base.  相似文献   
108.
The fluoride ion adsorption from a gas phase on various faces of a single crystal of silver is studied by a density functional method within a cluster model for metal. The adsorption bond energy is found to increase in the series Ag(100) < Ag(111) < Ag(311) < Ag(110). A substantial structural and energetic heterogeneity of various adsorption sites is revealed. The results are utilized to simulate the electrochemical interface between individual faces of a single crystal of silver and aqueous solutions containing the fluoride ion. It is assumed that the adsorption potential may be represented as the sum of two contributions, one of which describes the metal–ion interaction and the other, the ion solvation energy. The plotted adsorption terms take into account partial degradation of the fluoride ion when adsorbed from an aqueous solution. Estimates of discreteness of the electrical double layer are presented. A conclusion on the maximum manifestation of specific adsorption of the fluoride ion for the Ag(100) face is made.Translated from Elektrokhimiya, Vol. 41, No. 2, 2005, pp. 232–238.Original Russian Text Copyright © 2005 by Nazmutdinov, Zinkicheva.This revised version was published online in April 2005 with corrections to the article note and article title and cover date.  相似文献   
109.
油溶性金属Ni纳米微粒的制备与表征   总被引:8,自引:0,他引:8       下载免费PDF全文
纳米材料的制备、性能与应用已成为近年来的研究热点之一犤1犦。由于在催化、光学和电学材料中的广泛应用,超细单分散的金属微粒的制备与性质已引起人们的广泛兴趣。通常制备金属纳米微粒的方法有两种:一是把固体金属材料分裂为纳米尺寸的颗粒,如机械粉碎、电弧放电及金属原子蒸气沉积犤2犦,用这种方法制备的金属微粒粒径一般都比较大,且粒子尺寸分布宽,另一种是把金属原子制成纳米尺度的颗粒,如乳液聚合法犤3犦、热解犤4犦、γ-射线辐照犤5犦、脉冲电沉积犤6犦和化学还原犤7犦等,这种方法制备的微粒粒径通常分布窄且粒子小…  相似文献   
110.
通过吸附在铂纳米颗粒表面的氢交替还原氯金酸和氯铂酸,得到了复合型纳米颗粒Pt@Au/Pt,用UV-Vis光谱、TEM和XRD对其进行了表征.  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