全文获取类型
收费全文 | 38053篇 |
免费 | 4070篇 |
国内免费 | 7601篇 |
专业分类
化学 | 42277篇 |
晶体学 | 208篇 |
力学 | 1224篇 |
综合类 | 319篇 |
数学 | 884篇 |
物理学 | 4812篇 |
出版年
2024年 | 79篇 |
2023年 | 546篇 |
2022年 | 921篇 |
2021年 | 1384篇 |
2020年 | 1925篇 |
2019年 | 1589篇 |
2018年 | 1601篇 |
2017年 | 1506篇 |
2016年 | 1811篇 |
2015年 | 1694篇 |
2014年 | 2309篇 |
2013年 | 3938篇 |
2012年 | 2291篇 |
2011年 | 2497篇 |
2010年 | 1931篇 |
2009年 | 2104篇 |
2008年 | 2261篇 |
2007年 | 2503篇 |
2006年 | 2230篇 |
2005年 | 2083篇 |
2004年 | 1993篇 |
2003年 | 1675篇 |
2002年 | 1222篇 |
2001年 | 898篇 |
2000年 | 913篇 |
1999年 | 772篇 |
1998年 | 681篇 |
1997年 | 628篇 |
1996年 | 563篇 |
1995年 | 529篇 |
1994年 | 407篇 |
1993年 | 358篇 |
1992年 | 345篇 |
1991年 | 240篇 |
1990年 | 198篇 |
1989年 | 158篇 |
1988年 | 136篇 |
1987年 | 95篇 |
1986年 | 83篇 |
1985年 | 86篇 |
1984年 | 77篇 |
1983年 | 36篇 |
1982年 | 50篇 |
1981年 | 51篇 |
1980年 | 43篇 |
1979年 | 38篇 |
1978年 | 37篇 |
1977年 | 35篇 |
1976年 | 45篇 |
1974年 | 41篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
91.
利用激光溅射 分子束的技术 ,结合反射飞行时间质谱计 ,研究了Cu+、Ag+、Au+与乙硫醇的气相化学反应。结果显示这三种金属离子与 (CH3 CH2 SH) n 反应形成一系列团簇离子M+(CH3 CH2 SH) n,且团簇离子尺寸不一样。Ag+、Au+与乙硫醇的反应还生成了 (CH3 CH2 SH) +n ,由此推测Cu+、Ag+、Au+与乙硫醇团簇的反应存在两种通道 ,一种通道是生成M+(CH3 CH2 SH) n,另一种是生成 (CH3 CH2 SH) +n 。Cu+、Au+与乙硫醇的反应还生成了M+(H2 S) (M =Cu、Au) ,但是实验中没有观察到Ag+(H2 S) ,理论计算表明Ag+(H2 S)很不稳定。另外 ,分析产物离子M+(CH3 CH2 SH) n 的强度发现 ,n =1~ 2之间存在明显的强度突变现象 相似文献
92.
Silica@copper (SiO2@Cu) core–shell nanoparticles were synthesized and well characterized by XRD, TEM, AFM, XPS, UV/Vis, TGA–MS, and ICP–AES techniques. The synthesized SiO2@Cu core–shell nanoparticles were employed as catalysts for the conjugate addition of amines to α,β‐unsaturated compounds in water to obtain β‐amino carbonyl compounds in excellent yields in shorter reaction times. Furthermore, the catalyst works well for hetero‐Michael addition reactions of heteroatom nucleophiles such as thiols to α,β‐unsaturated compounds. As the reaction is performed in water, it allows for easy recycling of the catalyst with consistent activity. 相似文献
93.
A. A. Zazhogin A. P. Zazhogin A. I. Komyak A. I. Serafimovich 《Journal of Applied Spectroscopy》2003,70(6):827-831
Based on the analysis of electronic absorption and luminescence spectra, the processes of complexing in an aqueous solution of uranyl nitrate hexahydrate (UO2(NO3)2·6H2O) on gradual addition of small amounts of acetone have been investigated. In a pure aqueous solution, uranyl exists as the UO2·5H2O complex. It is shown that addition of acetone to the solution leads to displacement of some water molecules from the first coordination sphere of uranyl and formation of uranyl nitrate dihydrate complexes, UO2(NO3)2·2H2O. It has been established that the stability of these complexes is determined by the decrease in both the water activity and the degree of hydration of uranyl and nitrate. This is the result of the local increase in the concentration of the molecules of acetone (due to its hydrophobicity) in those regions of the solution in which there are uranyl and nitrate ions. The experimental facts supporting the proposed mechanism are given. 相似文献
94.
A Raney-Ag catalyst was prepared by leaching out aluminium from a Raney Ag-Al alloy with NaOH solution. The kinetics of leaching
has been investigated in a stirred-batch-reactor at various temperatures by using alloy particles of different sizes. The
kinetic model best fitting the experimental results has been determined.
This revised version was published online in June 2006 with corrections to the Cover Date. 相似文献
95.
从现有的PCDFs分子的正辛醇 /水分配系数 (logKow)实验数据出发 ,建立定量结构 性质关系方程(QSPR) .采用G98W程序包中的PM3方法对 13 5个多氯代二苯并呋喃 (PCDFs)分子和二苯并呋喃进行了优化计算 ,作业命令为 #pPM3optfreqscf(conver =9) ,以计算所得的分子轨道能量、碳原子电荷作为PCDFs分子结构描述符 ,运用多元线性回归技术建立了PCDFs的logKow与分子结构描述符的四元方程 ,最优相关系数为 0 .95 0 7,标准偏差为 0 .173 7,经检验该模型的稳健性好 ,并对未有实验数据的 85个PCDFs的logKow进行预测 相似文献
96.
《Magnetic resonance in chemistry : MRC》2003,41(1):37-41
The oxidation of symmetrical disulfides [D ,L ‐cystine ( 1 ) and 3,3′‐dithiobis(propionic acid) ( 2 )] with hydrogen peroxide in D2O–NaOH solution (pH 10–11) was studied by NMR spectroscopy. Assignments of the proton and carbon NMR signals of starting materials ( 1 and 2 ) and products of oxidation are based on conventional 1D NMR methods (DEPT, selective spin decoupling). Formation of C—S bond cleavage products or, in case of 2 , partially oxidized intermediates was not detected. The accelerating effect of Cu2+ cations, but not Fe3+ cations, on the oxidation rate of 1 in basic medium was demonstrated. Copyright © 2002 John Wiley & Sons, Ltd. 相似文献
97.
Luc Martinon Stéphane Azoulay E. Peter Kündig 《Journal of organometallic chemistry》2004,689(23):3831-3836
A Pd-catalyzed three-component assembling of highly functionalized 4-benzyl-(and allyl-)pyrrolidines was achieved based on a combination of allyl amines, gem-diactivated alkenes, and unsaturated halides (or triflate). 相似文献
98.
K. K. Turgunov B. Tashkhodzhaev L. V. Molchanov Kh. M. Shakhidoyatov 《Journal of Structural Chemistry》2004,45(5):912-916
The structure of bis-(2,3-pentamethylene-3,4-dihydro-4-oxoquinazolinium) tetrachlorocuprate (II) sesquihydrate, (C13H15N2O)2[CuCl4]·1.5H2O, was determined by single crystal X-ray diffraction. In contrast to the previously studied analogs, the compound contains crystallization water molecules.Original Russian Text Copyright © 2004 by K. K. Turgunov, B. Tashkhodzhaev, L. V. Molchanov, and Kh. M. Shakhidoyatov__________Translated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 5, pp. 955–959, September–October, 2004. 相似文献
99.
The Mannich-type reaction of imines with (1-methoxy-2-methylpropenyloxy)trimethylsilane and aza-Diels-Alder reaction of imines with Danishefsky's diene can be carried out in scCO2 in the presence of lithium heptadecafluorooctanesulfonate which offer a way to synthesize β-amino carbonyl compounds and nitrogen-containing six-membered ring compounds under environmentally benign conditions. 相似文献
100.
Recent developments in the aerobic oxidation of alcohols 总被引:1,自引:0,他引:1