全文获取类型
收费全文 | 2403篇 |
免费 | 130篇 |
国内免费 | 10篇 |
专业分类
化学 | 1652篇 |
晶体学 | 4篇 |
力学 | 62篇 |
数学 | 446篇 |
物理学 | 379篇 |
出版年
2023年 | 24篇 |
2022年 | 58篇 |
2021年 | 78篇 |
2020年 | 59篇 |
2019年 | 59篇 |
2018年 | 52篇 |
2017年 | 43篇 |
2016年 | 118篇 |
2015年 | 94篇 |
2014年 | 94篇 |
2013年 | 151篇 |
2012年 | 198篇 |
2011年 | 230篇 |
2010年 | 96篇 |
2009年 | 104篇 |
2008年 | 168篇 |
2007年 | 157篇 |
2006年 | 158篇 |
2005年 | 131篇 |
2004年 | 98篇 |
2003年 | 87篇 |
2002年 | 70篇 |
2001年 | 27篇 |
2000年 | 18篇 |
1999年 | 23篇 |
1998年 | 13篇 |
1997年 | 13篇 |
1996年 | 14篇 |
1995年 | 5篇 |
1994年 | 13篇 |
1993年 | 18篇 |
1992年 | 15篇 |
1991年 | 9篇 |
1990年 | 6篇 |
1989年 | 9篇 |
1988年 | 6篇 |
1987年 | 3篇 |
1985年 | 1篇 |
1984年 | 3篇 |
1983年 | 2篇 |
1982年 | 2篇 |
1981年 | 3篇 |
1980年 | 2篇 |
1979年 | 2篇 |
1978年 | 1篇 |
1977年 | 2篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1973年 | 1篇 |
1967年 | 1篇 |
排序方式: 共有2543条查询结果,搜索用时 15 毫秒
31.
Matiide Angulo Mercedes Ruiz Montoya Rafael Marin Galvin José Miguel Rodriguez Mellado 《Electroanalysis》1997,9(4):345-349
The electroreductions of the NAD+ model compounds nicotinamide (I), N1-methyl nicotinamide (II), N′-methyl nicotinamide (III) and isonicotinamide (IV) on carbon electrodes have been studied in aqueous media in the pH range 0–12 by linear-sweep cyclic voltammetry (Scheme 1, I-IV). Logarithmic analyses of the reduction peaks were performed by computing the convolution of the current with time as a function of the potential. On the basis of the experimental results it was concluded that the irreversibility of the electron transfers increased when a glassy carbon electrode was used, and this irreversibility being more marked when a plastic formed carbon electrode was employed. The reduction processes occurred with more difficulty on carbon electrodes than on mercury electrodes. Both the reduction and the reoxidation (when occurred) processes changed with respect to those observed on mercury electrodes, being irreversible electron transfers the rate-determining steps in most cases. Thus, for compounds I, II and III at pH < 2 the reductions occurred by the uptake of two electrons and two H+ ions, and the rate determining step was found to be the first one-electron transfer, for I and III, and the irreversible second electron transfer, preceded by the uptake of an H+ ion, for II. At pH>3 the processes consisted of electrodimerization reactions, preceded by the protonation of the heterocyclic nitrogen in cases I and III. The second electron transfer of the electroreduction of IV always appeared irreversible, in contrast with that found for mercury electrodes. 相似文献
32.
Volker Strauss Huize Wang Simon Delacroix Marc Ledendecker Pablo Wessig 《Chemical science》2020,11(31):8256
Luminescent compounds obtained from the thermal reaction of citric acid and urea have been studied and utilized in different applications in the past few years. The identified reaction products range from carbon nitrides over graphitic carbon to distinct molecular fluorophores. On the other hand, the solid, non-fluorescent reaction product produced at higher temperatures has been found to be a valuable precursor for the CO2-laser-assisted carbonization reaction in carbon laser-patterning. This work addresses the question of structural identification of both, the fluorescent and non-fluorescent reaction products obtained in the thermal reaction of citric acid and urea. The reaction products produced during autoclave–microwave reactions in the melt were thoroughly investigated as a function of the reaction temperature and the reaction products were subsequently separated by a series of solvent extractions and column chromatography. The evolution of a green molecular fluorophore, namely HPPT, was confirmed and a full characterization study on its structure and photophysical properties was conducted. The additional blue fluorescence is attributed to oligomeric ureas, which was confirmed by complementary optical and structural characterization. These two components form strong hydrogen-bond networks which eventually react to form solid, semi-crystalline particles with a size of ∼7 nm and an elemental composition of 46% C, 22% N, and 29% O. The structural features and properties of all three main components were investigated in a comprehensive characterization study.Products of the thermal reaction of citric acid and urea have been identified as a complex mixture of fluorophores and particles. 相似文献
33.
Irene Fonseca David Kinderlehrer Pablo Pedregal 《Calculus of Variations and Partial Differential Equations》1994,2(3):283-313
In this paper we deal with energy functionals depending on elastic strain and chemical composition and we obtain lower semicontinuity results, existence theorems and relaxation in the spacesH
1,p(; n)×L
q
(; d) with respect to weak convergence. Our proofs use parametrized measures associated with weakly converging sequences.The research was partially supported by the National Science Foundation under Grants No. DMS-9000133 and DMS-9201215 and also by the Army Research Office and the National Science Foundation through the Center for Nonlinear Analysis.The research was partially supported by the National Science Foundation uncer Grants No. DMs 911572, the AFOSR 91 0301, the ARO DAAL03 92 G 003 and also by the ARO and the NSF through the Center for Nonlinear Analysis.The research was supported by DGICYT (Spain) through Programa de Perfeccionamiento y Movilidad del Personal Investigador and through grant PB90-0245, by the Army Research Office and the National Science Foundation through the Center for Nonlinear Analysis and also by the project EurHomogenization SC1-CT91-0732 of the European Comunity. 相似文献
34.
Oscillatory properties of a weak convergent sequence of functions bounded inL
p
, 1 ≤p ≤ ∞, may be summarized by the parametrized measure it generates. When such a measure is generated by the gradients of a sequence
of functions bounded inH
1,p
, it must have special properties. The purpose of this paper is to characterize such parametrized measures as the ones that
obey Jensen’s inequality for all quasiconvex functions with the appropriate growth at infinity. We have found subtle differences
between the casesp < ∞ andp = ∞. A consequence is that any measure determined by biting convergence is in fact generated by a sequence convergent in
a stronger sense. We also give a few applications.
Research groupTransitions and Defects in Ordered Materials, funded by the NSF, the AFOSR, and the ARO. The work of the second author is also supported by DGICYT (Spain) through “Programa
de Perfeccionamiento y Movilidad del Personal Investigador” and through Grant PB90-0245. 相似文献
35.
C. Angulo W. H. Schulte D. Zahnow G. Raimann C. Rolfs 《Zeitschrift für Physik A Hadrons and Nuclei》1993,345(3):333-334
The absolute cross section of the fusion reaction
10B(p, 1)7
has been measured at the c.m. energy range E=48 to 159 keV via the 429 keV secondary -ray transition. The studies involved high proton currents and thick solid
10Btargets. The resulting cross sections have the same energy dependence as those of the
10B(p,0)7Bereaction but they are lower by a factor 600.Supported in part by the Deutsche Forschungsgemeinschaft (Ro429/18-2 and Ro429/21-3), the Landesamt Nordrhein Westfalen (IVA5-10600387), and the Comision Intel-ministerial de Ciencia y Technologia (AEN90-0932). 相似文献
36.
An introduction to population approaches for optimization and hierarchical objective functions: A discussion on the role of tabu search 总被引:3,自引:0,他引:3
Pablo Moscato 《Annals of Operations Research》1993,41(2):85-121
Population approaches suitable for global combinatorial optimization are discussed in this paper. They are composed of a number of distinguishable individuals called "agents", each one using a particular optimization strategy. Periods of independent search follow phases on which the population is restarted from new configurations. Due to its intrinsic parallelism and the asynchronicity of the method, it is particularly suitable for parallel computers. Results on two test problems are presented in this paper. The individual search optimization strategies for each agent have been chosen having the basic characteristics of tabu search. This has been done in order to avoid mixing the hypothesized properties of these population approaches with those of more elaborate tabu search strategies, but remarking on its main characteristics. A set of four test problem "landscapes" is discussed and their use to improve and benchmark the results by using tabu search as the individual optimization strategy within a population heuristic is suggested and explored. The application of tabu search to new problem areas, like molecular biology, is also investigated. 相似文献
37.
den Brok MW Nuijen B Miranda E Floriano P Munt S Manzanares I Beijnen JH 《Journal of chromatography. A》2003,1020(2):251-258
ES-285 x HCl [(2S,3R)-2-amino-3-octadecanol hydrochloride] is a novel investigational anticancer agent, which has shown in vitro and in vivo cytotoxic activity against various tumor cell lines with selectivity for certain solid tumors. The pharmaceutical development of ES-285 x HCl warranted the availability of an assay for the quantification and purity determination of ES-285 x HCl active pharmaceutical ingredient (API) and its pharmaceutical dosage form. A liquid chromatographic method (LC) comprising of derivatisation of ES-285 x HCl with phenylisothiocyanate and UV-detection was developed. The method was found to be linear, precise and accurate. The assay also proved selectivity as determined by analysing ES-285 x HCl in combination with 15 analogues and in combination with hydroxypropyl-beta-cyclodextrin, the excipient used in the lyophilised pharmaceutical dosage form. Stress testing showed that the degradation products were separated from the parent compound, confirming its stability indicating capacity. The method was found robust as determined with design of experiments (DoE), which made it possible to predict system suitability responses in worst case experimental conditions and to define criteria for system suitability testing. 相似文献
38.
Different transformations of chiral epoxy esters 1 afford two different amino gamma-butyrolactones 2 and 6, and amino gamma-butenolides 8, by different nucleophilic opening-closing processes. [reaction: see text] 相似文献
39.
Mary E. R. McHale Ann-Sofi M. Kauppila Joyce R. Powell Pablo Otero Jr. Melani Jayasekera William E. Acree Jr. 《Journal of solution chemistry》1996,25(3):295-302
Experimental solubilities are reported for benzil dissolved in six binary mixtures containing dibutyl ether with hexane, heptane, octane, cyclohexane, methylcyclohexane, and 2,2,4-trimethylpentane at 25°C. Results of these measurements are compared to the predictions of equations developed previously for solubility in systems of nonspecific interactions. The most successful equation in terms of goodness of fit involved a volume fraction average of the excess Gibbs energies relative to the Flory-Huggins model, and predicted the experimental solubilities in the six systems studied to within an overall average absolute deviation of 3.4% and with a maximum deviation of 6.0%. 相似文献
40.
A computational study of hydration, solution structure, and dynamics in dilute carbohydrate solutions 总被引:1,自引:0,他引:1
We report results from a molecular simulation study of the structure and dynamics of water near single carbohydrate molecules (glucose, trehalose, and sucrose) at 0 and 30 degrees C. The presence of a carbohydrate molecule has a number of significant effects on the microscopic water structure and dynamics. All three carbohydrates disrupt the tetrahedral arrangement of proximal water molecules and restrict their translational and rotational mobility. These destructuring effects and slow dynamics are the result of steric constraints imposed by the carbohydrate molecule and of the ability of a carbohydrate to form stable H bonds with water, respectively. The carbohydrates induce a pronounced decoupling between translational and rotational motions of proximal water molecules. 相似文献