全文获取类型
收费全文 | 4598篇 |
免费 | 984篇 |
国内免费 | 461篇 |
专业分类
化学 | 5337篇 |
晶体学 | 37篇 |
力学 | 28篇 |
综合类 | 11篇 |
数学 | 30篇 |
物理学 | 600篇 |
出版年
2024年 | 17篇 |
2023年 | 95篇 |
2022年 | 160篇 |
2021年 | 193篇 |
2020年 | 331篇 |
2019年 | 229篇 |
2018年 | 236篇 |
2017年 | 179篇 |
2016年 | 325篇 |
2015年 | 332篇 |
2014年 | 375篇 |
2013年 | 509篇 |
2012年 | 318篇 |
2011年 | 301篇 |
2010年 | 243篇 |
2009年 | 242篇 |
2008年 | 283篇 |
2007年 | 226篇 |
2006年 | 183篇 |
2005年 | 192篇 |
2004年 | 170篇 |
2003年 | 136篇 |
2002年 | 92篇 |
2001年 | 81篇 |
2000年 | 81篇 |
1999年 | 85篇 |
1998年 | 60篇 |
1997年 | 72篇 |
1996年 | 62篇 |
1995年 | 51篇 |
1994年 | 27篇 |
1993年 | 28篇 |
1992年 | 32篇 |
1991年 | 17篇 |
1990年 | 15篇 |
1989年 | 10篇 |
1988年 | 7篇 |
1987年 | 8篇 |
1986年 | 6篇 |
1985年 | 6篇 |
1984年 | 6篇 |
1983年 | 8篇 |
1982年 | 5篇 |
1981年 | 2篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1978年 | 2篇 |
1977年 | 1篇 |
1974年 | 1篇 |
1973年 | 1篇 |
排序方式: 共有6043条查询结果,搜索用时 9 毫秒
41.
The key factors influencing the Diels—Alder reaction rate at ambient and elevated pressures were elucidated using data on the reactivity of various diene—dienophile systems in usual and Lewis acid-catalyzed Diels—Alder reactions, the reaction enthalpy, complex formation, dissolution, and solvation, and the donor-acceptor properties of the reactants. It was found that taking account of both the orbital interaction energy and the balance of bond rupture and formation energies allows correct prediction of the reaction rate in the absence or in the presence of Lewis acids. 相似文献
42.
The mathematical evaluation of the activation
energy, E, of non-isothermal degradation
reactions is usually made using the Ozawa/Flynn–Wall isoconversion principle
and involves the numerical resolution of a set of integrals without closed
form solution, which are solved by polynomial approximation or by numeric
integration. In the present work, the isoconversion principle, originally
described and maintained until now as an algebraic problem, was written as
a set of ordinary differential equations (ODEs). The individual ODEs obtained
are integrated by numeric methods and are used to estimate the activation
energy of simulated examples. A least square error (LSE) objective function
using the introduced ODEs was written to deal with multiple heating rate CaCO3
thermal decomposition TG experiments. 相似文献
43.
Wieczorek-Ciurowa K. Gamrat K. Shirokov Ju. G. 《Journal of Thermal Analysis and Calorimetry》2003,72(1):323-328
A catalytic action of the mechanochemical products of copper hydroxocarbonate with calcium carbonate was investigated in n-butyl
alcohol oxidation tests. The solid products of high-energy milling were identified using thermogravimetry supplemented by
X-ray diffraction method. It was shown that the mechanical activation induces more effective tested catalyst because it promotes
the alcohol conversion at lower temperatures than that unmilled one.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
44.
T. Vlase Gabriela Vlase A. Chiriac N. Doca 《Journal of Thermal Analysis and Calorimetry》2005,80(1):87-90
Summary In order to obtain catalysts, the thermal decomposition of the precursors is a compulsory step. However, kinetic analysis of the decomposition data obtained under non-isothermal conditions lead very seldom to the intimate reaction mechanism. There is also a lack of information because in non-isothermal kinetics, the compensation effect, is rather a rule and unfortunately a source of debate. In order to discriminate between these processes, and the influence of conversion, respectively temperature on the reaction rate, the NPK (non-parametric kinetic - Sempere and Nomen) method was used. This method is based on the singular value decomposition algorithm (SVD) applied on the matrix of reaction rate at corresponding conversion and temperature. This method allows a less speculative determination of the conversion functions and of the kinetic parameters. 相似文献
45.
I. A. Stepanov 《Monatshefte für Chemie / Chemical Monthly》1997,128(8-9):837-839
Summary It has been shown that joined segments of straight lines are observed upon plotting the logarithm of the rate constant against the reciprocal temperature, exhibiting sharp breaks at so-called critical temperatures indicating sudden changes in activation energy [3, 5–8]. If the integration of the differential form of theArrhenius equation from 0 toT K is taken into account, the compensation effect can easily be explained.
Der Kompensationseffekt als Ergebnis der Integration derArrhenius-Gleichung
Zusammenfassung Wenn man den Logarithmus der Geschwindigkeitskonstante gegen die reziproke Temperatur aufträgt, erhält man aufeinanderfolgende Teilstücke von Geraden mit scharfen Knicks bei sogenannten kritischen Temperaturen, welche jeweils eine Änderung der Aktivierungsenergie anzeigen [3, 5–8]. Integration derArrhenius-Gleichung zwischen 0 undT K führt zu einer zwanglosen Erklärung des Kompensationseffekts.相似文献
46.
凝胶型聚合物电解质的电导率与温度的关系孙晓光,林云青,齐力,景遐斌,王佛松(中国科学院长春应用化学研究所长春130022)关键词凝胶电解质,离子电导率,活化能无定形聚合物电解质电导与温度的依赖关系一般可用Vogel-Tamman-Fulcherc(V... 相似文献
47.
一代树状碳硅烷液晶的光化学研究--端基含12个4-丁氧基氮苯介晶基元 总被引:2,自引:0,他引:2
研究了新的含12个丁氧基偶氮苯介晶基元的五代树状碳硅烷液晶D1及偶氮苯介 晶基元化合物M5在氯仿、四氢呋喃、N,N-二甲基甲酰胺、乙醇和苯等溶剂中的量 子产率、反-顺光异构化、光回复异构、反/顺异构组分比、热回复异构及活化能 。D1和M5的光致变色速率常数为10~(-1)s~(-1),而含同一偶氮基元的光致变色液 晶聚硅氧烷的光致变色速率常数为10~(-8)s~(-1),因此,液晶树状物D1的光响应 速度比后者快10~7倍。 相似文献
48.
Chan Sik Cho Tae Kyung Kim Bok Tae Kim Tae-Jeong Kim Sang Chul Shim 《Journal of organometallic chemistry》2002,650(1-2):65-68
Nitroarenes react with trialkylamines in the presence of a catalytic amount of a ruthenium catalyst together with tin(II) chloride dihydrate at 180 °C in an aqueous medium (toluene–H2O) to afford the corresponding quinolines in moderate to good yields. The catalytic pathway seems to be proceeded via a sequence involving initial reduction of nitroarenes to anilines, alkyl group transfer from alkylamines to anilines to form an imine, dimerization of imine, and heterocyclization. 相似文献
49.
Kehayias JJ 《Analytical and bioanalytical chemistry》2004,379(2):188-191
Body composition has become the main outcome of many nutritional intervention studies including osteoporosis, malnutrition, obesity, AIDS, and aging. Traditional indirect body composition methods developed with healthy young adults do not apply to the elderly or diseased. Fast neutron activation (for N and P) and neutron inelastic scattering (for C and O) are used to assess in vivo elements characteristic of specific body compartments. Non-bone phosphorus for muscle is measured by the 31P(n,)28Al reaction, and nitrogen for protein via the 14N(n,2n)13N fast neutron reaction. Inelastic neutron scattering is used to measure total body carbon and oxygen. Body fat is derived from carbon after correcting for contributions from protein, bone, and glycogen. Carbon-to-oxygen ratio (C/O) is used to measure the distribution of fat and lean tissue in the body and to monitor small changes of lean mass. A sealed, D–T neutron generator is used for the production of fast neutrons. Carbon and oxygen mass and their ratio are measured in vivo at a radiation exposure of less than 0.06 mSv. Gamma-ray spectra are collected using large BGO detectors and analyzed for the 4.43 MeV state of carbon and 6.13 MeV state of oxygen, simultaneously with the irradiation. P and N analysis by delayed fast neutron activation is performed by transferring the patient to a shielded room equipped with an array of NaI(Tl) detectors. A combination of measurements makes possible the assessment of the quality of fat-free mass. The neutron generator system is used to evaluate the efficacy of new treatments, to study mechanisms of lean tissue depletion with aging, and to investigate methods for preserving function and quality of life in the elderly. It is also used as a reference method for the validation of portable instruments of nutritional assessment. 相似文献
50.
Michiko Iwamura Yuka Gotoh Tomoyuki Hashimoto Reiko Sakurai 《Tetrahedron letters》2005,46(37):6275-6277
Michael addition reactions of acetoacetates and malonates with acrylates in a 5 M KOH aqueous solution without using any other catalysts are described. When they are either tert-butyl or benzyl esters, the reaction proceeded very rapidly to afford moderate to high yields of the corresponding bis-Michael adducts that are unexpectedly stable under these conditions. 相似文献