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   2438篇
  免费   79篇
  国内免费   274篇
化学   2186篇
晶体学   16篇
力学   8篇
数学   6篇
物理学   575篇
  2024年   2篇
  2023年   29篇
  2022年   43篇
  2021年   48篇
  2020年   61篇
  2019年   64篇
  2018年   39篇
  2017年   78篇
  2016年   83篇
  2015年   86篇
  2014年   117篇
  2013年   120篇
  2012年   174篇
  2011年   189篇
  2010年   158篇
  2009年   192篇
  2008年   165篇
  2007年   188篇
  2006年   153篇
  2005年   123篇
  2004年   113篇
  2003年   91篇
  2002年   65篇
  2001年   59篇
  2000年   48篇
  1999年   44篇
  1998年   45篇
  1997年   29篇
  1996年   33篇
  1995年   31篇
  1994年   24篇
  1993年   20篇
  1992年   19篇
  1991年   18篇
  1990年   14篇
  1989年   8篇
  1988年   5篇
  1987年   3篇
  1986年   3篇
  1982年   2篇
  1980年   2篇
  1979年   1篇
  1978年   2篇
排序方式: 共有2791条查询结果,搜索用时 93 毫秒
21.
本文将超声雾化技术与MIP-AAS联用,以“L”型吸收管代替“T”型吸收管作为AAS测量的吸收池,采用水冷凝和浓H_2SO_4吸收相结合去溶,研究TUSN-MIP-AAS方法测银时的某些影响因素,讨论了微波前向功率,载气流速、去溶系统、溶液酸度、共存离子及易也离元素等对吸收信号的影响,本法所得的测银的特征浓度为0.01μg/ml(328.1nm)和0.03μg/ml(338.3nm),相对标准偏差为7.5%.  相似文献   
22.
《Electroanalysis》2004,16(16):1359-1365
Electrochemical oxidation of catechols has been studied in the presence of cyanide ion as nucleophile in aqueous solution, by means of cyclic voltammetry and controlled‐potential coulometry. The results indicate that the participation of catechols in the Michael reaction with cyanide ion to form the corresponding o‐dihydroxybenzonitrile. Based on an EC mechanism, the homogeneous rate constants were estimated by comparing the experimental cyclic voltammetric responses with the digital simulated results.  相似文献   
23.
The coordination of silver cation to diphosphene Mes*P=PMes* ( 1 , Mes* = tBu3C6H2) was investigated in detail. The reaction of 1 with Ag[Al(ORF)4] (ORF = OC(CF3)3) in the ratios of 2 : 1, 3 : 2 and 1 : 2 led to the formation of the first cationic silver linked diphosphene complexes 2 — 4 . Complexes 2 and 3 contain two and three diphosphene molecules linked by the linear Ag(I) cation, respectively, and they feature unusual zig‐zag topologies. Complex 4 is a dinuclear silver complex, and each Ag(I) center features a tetrahedral geometry, coordinated by one phosphorus atom of diphosphene 1 and three chloro atoms of two CH2Cl2 molecules.  相似文献   
24.
《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   
25.
Trimethylsilyl acetylenes can be selectively deprotected in the presence of a catalytic amount of silver salts. AgNO3 and AgOTf proved to be the most effective catalyst in a mixture of methanol, water and dichloromethane. Other functional groups, and especially silyl ethers, are not affected in these conditions.  相似文献   
26.
Ethylene/ethane sorption characteristics were determined for dry Pebax™ (poly(amide 12-block-tetramethylenoxide) copolymer)/AgBF4 membranes by using an electronic microbalance. The membranes containing 0.7 and 22 wt.% AgBF4 showed a dual-mode sorption isotherm. The ethane isotherms for all the membranes were of the Henry-type, which is the normal sorption for gases in rubbery polymers. The abnormal presence of Langmuir sorption sites only for ethylene in the rubbery copolymer, never reported sofar, is attributed to the silver-based specific complexation sites. The silver salt which dissolved in limited amounts in the rubbery copolymer had a much smaller Langmuir sorption capacity than the salt that crystallized in the copolymer. The sorption kinetics indicate that the crystallized salt did adsorb slowly ethylene according to a zeroth-order kinetics, but not ethane. The gas uptake kinetics resulting from a step of the pressure surrounding the copolymer exhibited one stage for ethane but two stages for ethylene. For the latter, there was first a fast Fickian sorption stage, then a drift of the zeroth-order sorption of ethylene on salt crystals, which contributes for a large part to the total uptake. The zeroth-order sorption suggests that the sorbed ethylene amount in the second-stage is independent of the crystal-surface coverage. The value of the Fickian diffusion coefficient calculated by fitting the kinetics with a solution of the second Fick’s law was 5 × 10−12 m2/s for both ethylene (the first stage) and ethane, and is typical for small organic compounds in a rubbery material.  相似文献   
27.
触头用银合金粉末的氧化性能和氧化后的组织结构   总被引:1,自引:0,他引:1  
通过热重实验和扫描电子显微等方法,研究了4种触头用银合金粉末的氧化性能及氧化后的组织结构。发现Ag-Sn-RE合金粉末氧化以后,在粉末表层形成一层纯银层,其组织结构理想;它的氧化性能最好,适于制备触头材料。Ag-Sn-RE合金粉末的优良氧化性能与其氧化后理想的组织结构有关。稀土元素可以降低合金粉末的氧化温度,其它影响作用有待于进一步研究。  相似文献   
28.
A range of room temperature 1,3-dipolar cycloaddition reactions of imines of 2-amino-γ-lactone and thiolactone, catalysed by a combination of AgOAc or Ag2O with NEt3 or DBU, are described. The spiro lactones/thiolactones are formed regio- and stereoselectively as single cycloadducts in good yield via the syn dipoles and an endo-transition states.  相似文献   
29.
Solvothermal Synthesis and Crystal Structure Determination of AgBiI4 and Ag3BiI6 AgBiI4 and Ag3BiI6 were synthesized by solvothermal reaction from AgI and BiI3 in diluted HI‐solution (20 %) at a temperature of 160 °C. The greyish‐black crystals grow as octahedra (AgBiI4) or hexagonal/trigonal platelets (Ag3BiI6). AgBiI4 crystallizes in space group Fd3¯m with a = 1222.3(1) pm (300 K) and Z = 8 whereas Ag3BiI6 shows the space group R3¯m with a = 435.37(6) pm, c = 2081.0(4) pm (300 K) and Z = 1. Both crystal structures show stacking sequence abcabc… of hexagonal layers containing Iodine. Bismuth and silver are sharing octahedral sites with different mass ratio in both structures. The part of silver which could be localized varies with temperature. This behaviour indicates mobility of silver within the crystal structure. The ionic conductivity of AgBiI4 is explored. AgBiI4 and Ag3BiI6 show close structural relationship, with AgBiI4 as a variant with a higher degree of order.  相似文献   
30.
《Electroanalysis》2004,16(5):410-414
Mercury electrodes modified with supercoiled (sc) DNA have been used as highly sensitive tools for the detection of DNA strand breaks or as sensors for DNA cleaving substances. In this paper we show that silver solid amalgam electrode (AgSAE), in connection with alternating current voltammetry, provides similar information about DNA damage as the hanging mercury drop electrode. The AgSAE can be used for the detection of enzymatic or chemical DNA cleavage in solution or at the electrode surface. AgSAE modified with scDNA can be utilized as a sensor for DNA nicking substances.  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