全文获取类型
收费全文 | 4367篇 |
免费 | 750篇 |
国内免费 | 287篇 |
专业分类
化学 | 1632篇 |
晶体学 | 14篇 |
力学 | 311篇 |
综合类 | 61篇 |
数学 | 918篇 |
物理学 | 2468篇 |
出版年
2024年 | 7篇 |
2023年 | 41篇 |
2022年 | 98篇 |
2021年 | 94篇 |
2020年 | 100篇 |
2019年 | 98篇 |
2018年 | 138篇 |
2017年 | 173篇 |
2016年 | 167篇 |
2015年 | 115篇 |
2014年 | 242篇 |
2013年 | 679篇 |
2012年 | 247篇 |
2011年 | 278篇 |
2010年 | 222篇 |
2009年 | 253篇 |
2008年 | 264篇 |
2007年 | 274篇 |
2006年 | 222篇 |
2005年 | 186篇 |
2004年 | 206篇 |
2003年 | 157篇 |
2002年 | 157篇 |
2001年 | 145篇 |
2000年 | 130篇 |
1999年 | 95篇 |
1998年 | 113篇 |
1997年 | 80篇 |
1996年 | 73篇 |
1995年 | 59篇 |
1994年 | 35篇 |
1993年 | 40篇 |
1992年 | 34篇 |
1991年 | 29篇 |
1990年 | 21篇 |
1989年 | 19篇 |
1988年 | 15篇 |
1987年 | 15篇 |
1986年 | 14篇 |
1985年 | 8篇 |
1984年 | 10篇 |
1983年 | 5篇 |
1982年 | 7篇 |
1981年 | 9篇 |
1980年 | 7篇 |
1979年 | 4篇 |
1978年 | 3篇 |
1977年 | 4篇 |
1976年 | 3篇 |
1971年 | 2篇 |
排序方式: 共有5404条查询结果,搜索用时 15 毫秒
101.
Kinetic parameters of interphase exchange of oxygen in high-temperature proton conductors BaCe0.95Nd0.05O3- and SrCe0.95Y0.05O3- are determined using an isotope exchange method in the temperature range 630-820°C at oxygen pressures of 2.7-13.3 gPa and diffusion coefficients for oxygen are calculated. Effective energies of activation of oxygen exchange and diffusion coefficients for oxygen are calculated. Dependence of exchange characteristics and the diffusion coefficients on the oxygen pressure in the gas phase is investigated. The oxygen exchange on the surface of studied oxides is shown to proceed only with the participation of oxygen of the oxides, which causes high rates of interphase exchange of oxygen of studied cerates of barium and strontium. It is shown that the obtained data satisfactorily agree with those found in the relevant literature. 相似文献
102.
Halland N Alstrup Lie M Kjaersgaard A Marigo M Schiøtt B Jørgensen KA 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(23):7083-7090
The mechanism for the 2,5-diphenylpyrrolidine-catalyzed enantioselective alpha-chlorination of aldehydes with electrophilic halogenation reagents has been investigated by using experimental and computational methods. These studies have led us to propose a mechanism for the reaction that proceeds through an initial N-chlorination of the chiral catalyst-substrate complex, followed by a 1,3-sigmatropic shift of the chlorine atom to the enamine carbon atom. The suggested reaction course is different from previously proposed mechanisms for organocatalytic enamine reactions, in which the carbon-electrophile bond is formed directly. Furthermore, the rate-determining step in the overall reaction was determined and the presence of nonlinear effects was probed. 相似文献
103.
聚合物微晶尺寸和晶格畸变是对聚合物材料性能有着重要影响的结构参数。本文介绍了应用X射线衍射方法测定聚合物微晶尺寸和结构畸变的几种方法:近似函数、次晶模型法、方差法、矩法。 相似文献
104.
Ralph Jaquet 《Theoretical chemistry accounts》1987,71(6):425-448
We are trying to investigate systematically the application of the finite element method (FEM) for solving the Schrödinger equation. The present paper is devoted to the calculation of vibrational transition probabilities for the collinear reactive system A + BC (i.e. H+H2 and their isotopes). The calculations are fully two-dimensional and the results are compared with earlier FEM calculations and conventional basis set expansion methods using the the R-matrix or S-matrix propagation.We made extensive analysis of FEM on the vector-computer Cyber 205 and developed a vector code for the efficient use in two dimensions, so that in the near future applications even in three dimensions will be possible.For the hydrogen exchange reactions we investigated the following isotope combinations: (a) H + H2, b) H + DH, D + HD and H + MuH (symmetric reaction), (c) D + HH, H + DD and Mu + DD (asymmetric reaction). We calculated the transition probabilities for up to five open vibrational channels and found excellent agreement with known exact values. 相似文献
105.
Thermodynamic and kinetic parameters have been established for the reaction between the carbon acid, 4-nitrophenylnitromethane,
(4-NPNM), and the base N’-n-propyl-N,N-di-n-propylbenzimidamide, (N’PDPBA), in mesitylene and in chlorobenzene. In some cases deuteron transfer from 4-(D2)NPNM to the base has also been studied. In addition, some results for the proton transfer reaction in tetrahydrofuran have
been collected. Spectrophotometric methods have been employed to monitor the ion-pair product, which is solvatochromic. In
general the solvent dependence of the parameters is as expected, but there is some indication of specific solvation. The kinetic
isotope effects of 11 and 8 in mesitylene and chlorobenzene, respectively, are larger than those predicted classically. However,
as is discussed the n-propyl group on the secondary nitrogen of the base may serve to reduce the extent of tunneling compared
to that in an unsubstituted analogue by a steric effect. 相似文献
106.
邢凤鸣 《中国科学B辑(英文版)》1991,(11)
It is considered that the early Jinning period granitoids from southern Anhui Province belong to the continental crust transformation (S) type and have their own characteristics which are different from those for general continental crust transformation type granitoids. They were formed at the early stage of the late Proterozoic era when that region was at an island-arc stage of the continental margin environment. By that time the continental crust was just formed and had a nature of juvenile crust. It is this juvenile crust that determined a series of characteristics of that type granitoids and made them a relatively independent rock type. They are the products formed by the continental crust in a certain stage of development. 相似文献
107.
A new mechanism and formalism for proton transfer in donor-acceptor complexes with long hydrogen bonds introduced recently [1], is applied to a proton transfer in liquid water. Structural diffusion of hydroxonium ions is regarded as totally adiabatic process, with synchronous hindered translation of two closest water molecules to and from the reaction complex as crucial steps. The water molecules induce a gated shift of the proton from the donor to the acceptor in the double-well potential with simultaneous breaking/formation of hydrogen bonds between these molecules and the proton donor and acceptor. The short-range and long-range proton transfer as structural diffusion of Zundel complexes is also considered. The theoretical formalism is illustrated with the use of Morse, exponential, and harmonic molecular potentials. This approach is extended to proton transfer in strongly hydrogen-bonded donor-acceptor complexes. In contrast to the above model [1], the short hydrogen bond between the donor and acceptor moieties, however, completely erodes the barrier along the proton transfer mode. This introduces some physical pattern differences from proton transfer reactions in truly double-well potentials with a finite proton transfer barrier at the transition configuration with respect to the environmental nuclear coordinates. The differences apply particularly to the origin of the kinetic isotope effect. We discuss explicitly details of the excess proton conductivity in aqueous solution, but the concepts and formalism apply broadly to acid-base reactions, proton conduction channels, and other strongly hydrogen-bonded O- and N-proton donor-acceptor systems. 相似文献
108.
微型柱在线分离-ICP-MS法测定高纯氧化铕中的14个稀土杂质 总被引:7,自引:0,他引:7
研究了微型柱在线分离-电感耦合等离子质谱法(ICP-MS)测定高纯Eu2O3中痕量Tm的方法,研制了Cyanex272负载树脂微型分离柱,优化了分离Eu2O3基体的实验条件,在线分离测定时间为25min。建立了在线柱分离测定Tm,内标补偿法直接测定其余稀土杂质的高纯Eu2O3中14个稀土杂质的ICP-MS分析方法。方法检出限为0.01μg/g-0.15μg/g,加标回收率为91.5%-110%,相对标准偏差为1.7%-4.9%。可满足快速测定99.999%Eu2O3中14个稀土杂质的要求。 相似文献
109.
Minoru Isobe Prof. Dr. Masakuni Kurono Dr. Katsunori Tsuboi Dr. Akira Takai Prof. Dr. 《化学:亚洲杂志》2007,2(3):377-385
We have accomplished the synthesis of 13C‐labeled tautomycin at the C18, C19, C21, and C22 positions starting from 100 % [13C]triethylphosphonoacetate for the purpose of elucidating the dynamics and conformation of the C17–C26 moiety. NMR spectroscopy of 13C‐labeled tautomycin revealed strong binding with protein phosphatase type 1 and new features in the 13C NMR spectrum, such as the very small three‐bond coupling constants (2J). 相似文献
110.
This paper reports our results for the direct experimental determination of the equilibrium constant for the hydrogen-isotope-exchange
reaction, 1/2D2(g)+HCl(hexOH)=1/2H2(g)+DCl(hexOD), where hexOH isn-hexanol and hexOD isn-hexanol with deuterium substitution in the alcohol function. The reaction was studied in electrochemical double cells without
liquid junction for which the net cell reaction is the above isotope-exchange reaction. The experimentally determined value
of ε° (296.0°K) for this cell is 4.03±0.95 mV (strong electrolyte standard states, mole-fraction composition scale); the value
of the equilibrium constant for the reaction is 1.17±0.05. The contributions of isotope-exchange and transfer effects to the
magnitude of the standard Gibbs energy change for the above reaction and for the analogous reaction 1/2D2(g)+HCl(aq)=DCl(daq)+1/2H2(g) are considered. Our results support the conclusion of Heinzinger and Weston that the formulation of the solvated proton
in water as H3O+, as opposed to H9O4
+, is sufficient for the interpretation of the thermodynamics of hydrogen-isotope-exchange reactions in water. We also find
that the formulation of the solvated proton inn-hexanol as ROH
2
+
is sufficient for the interpretation of our results on the thermodynamics of hydrogen-isotope-exchange inn-hexanol. 相似文献