全文获取类型
收费全文 | 31397篇 |
免费 | 3151篇 |
国内免费 | 3789篇 |
专业分类
化学 | 26091篇 |
晶体学 | 458篇 |
力学 | 1584篇 |
综合类 | 207篇 |
数学 | 3225篇 |
物理学 | 6772篇 |
出版年
2023年 | 351篇 |
2022年 | 562篇 |
2021年 | 909篇 |
2020年 | 1101篇 |
2019年 | 1047篇 |
2018年 | 931篇 |
2017年 | 1141篇 |
2016年 | 1249篇 |
2015年 | 1135篇 |
2014年 | 1427篇 |
2013年 | 2228篇 |
2012年 | 1808篇 |
2011年 | 1998篇 |
2010年 | 1653篇 |
2009年 | 2087篇 |
2008年 | 1882篇 |
2007年 | 1896篇 |
2006年 | 1713篇 |
2005年 | 1572篇 |
2004年 | 1617篇 |
2003年 | 1249篇 |
2002年 | 1549篇 |
2001年 | 908篇 |
2000年 | 737篇 |
1999年 | 614篇 |
1998年 | 514篇 |
1997年 | 469篇 |
1996年 | 484篇 |
1995年 | 489篇 |
1994年 | 460篇 |
1993年 | 325篇 |
1992年 | 333篇 |
1991年 | 203篇 |
1990年 | 156篇 |
1989年 | 151篇 |
1988年 | 163篇 |
1987年 | 126篇 |
1986年 | 96篇 |
1985年 | 94篇 |
1984年 | 82篇 |
1983年 | 30篇 |
1982年 | 80篇 |
1981年 | 113篇 |
1980年 | 118篇 |
1979年 | 121篇 |
1978年 | 95篇 |
1977年 | 72篇 |
1976年 | 67篇 |
1973年 | 32篇 |
1972年 | 25篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
961.
Martí S Andrés J Moliner V Silla E Tuñón I Bertrán J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(4):984-991
In this paper a deeper insight into the chorismate-to prephenate-rearrangement, catalyzed by Bacillus subtilis chorismate mutase, is provided by means of a combination of statistical quantum mechanics/molecular mechanics simulation methods and hybrid potential energy surface exploration techniques. The main aim of this work is to present an estimation of the preorganization and reorganization terms of the enzyme catalytic rate enhancement. To analyze the first of these, we have studied different conformational equilibria of chorismate in aqueous solution and in the enzyme active site. Our conclusion is that chorismate mutase preferentially binds the reactive conformer of the substrate--that presenting a structure similar to the transition state of the reaction to be catalyzed--with shorter distances between the carbon atoms to be bonded and more diaxial character. With respect to the reorganization effect, an energy decomposition analysis of the potential energies of the reactive reactant and of the reaction transition state in aqueous solution and in the enzyme shows that the enzyme structure is better adapted to the transition structure. This means not only a more negative electrostatic interaction energy with the transition state but also a low enzyme deformation contribution to the energy barrier. Our calculations reveal that the structure of the enzyme is responsible for stabilizing the transition state structure of the reaction, with concomitant selection of the reactive form of the reactants. This is, the same enzymatic pattern that stabilizes the transition structure also promotes those reactant structures closer to the transition structure (i.e., the reactive reactants). In fact, both reorganization and preorganization effects have to be considered as the two faces of the same coin, having a common origin in the effect of the enzyme structure on the energy surface of the substrate. 相似文献
962.
The study deals with the analysis of diffusion and mass transfer modelling during pervaporation in a true ternary system involving a polar liquid mixture (ETBE/EtOH) and a polar block copolymer (polyurethaneimide or PUI). A survey of methods of pervaporative transfer modelling in ternary systems is first developed. From differential permeation experiments carried out with both pure liquids, it appears that both permeants obey a Fickian law. Moreover, the diffusional behaviour is consistent with Long's model, which has thus been assumed for the related ternary system. An extension of the Brun's model is then derived, which takes into account the diffusion coupling as well the significant deviation from sorption ideality. From a practical point of view, the calculated values of fluxes show generally good agreement with the experimental results, although a small deviation occurs for mixtures of low ethanol content. Diffusion coefficients of both pure solvents corresponding to transient or steady state are compared. A very good agreement is found for the aprotic permeant (ETBE). whereas the diffusion coefficient of ethanol in transient state is only the quarter of the value corresponding to steady state. The results are discussed in comparison with related investigations in the literature, involving specific liquid-polymer interactions. 相似文献
963.
N. Turemis E. Kafkas S. Kafkas M. Kurkcuoglu K. H. C. Baser 《Chemistry of Natural Compounds》2003,39(2):174-176
The aromatic composition of five blackberry cultivars (Bursa 2, Navaho, Nessy, Chester Thornless, and Jumbo) was studied. The Im-SPME (Immersion Solid Phase Micro Extraction) extraction technique was applied and the samples were analyzed by GC/MS. Furfural and its derivatives were found to be the major aromatic compounds and 5-hydroxymethylfurfural was the most abundant compound in all the blackberry varieties. 相似文献
964.
Gy. Marosi R. Lágner Gy. Bertalan P. Anna A. Tohl 《Journal of Thermal Analysis and Calorimetry》1996,47(4):1155-1161
Nucleating and transcrystallization behaviour of additives in engineering PP composites and the effect of modified interfacial structure is the subject of this series of papers. The first part concentrates on polypropylene/liquid crystalline polyester blends. Increased crystallisation temperature and degree of crystallinity of polypropylene is characteristic to the blends containing different amount of LCP additive. Transcrystallization process governs the formation of crystalline structure in these systems in course of isothermal crystallisation at 132C. The nucleating effect of LCP gives rise to more uniform crystalline structure in the polypropylene phase.The financial support of the OTKA 014194 is acknowledged with gratitude. 相似文献
965.
CuO/Ce-Zr-La-O催化剂的表征及CO氧化活性 总被引:5,自引:3,他引:5
采用柠檬酸溶胶-凝胶法制备的Ce-Zr-La-O固溶体为载体,制备CuO/Ce-Zr-La-O催化剂,用XRD,Raman,TPR等实验技术对Ce-Zr-La-O固溶体及CuO/Ce-Zr-La-O的物相、Redox性能进行了表征。实验结果表明,Ce0.7Cr0.3-yLayO固溶体的还原性能与La含量有关,适量的La能促进固溶体的氧化还原。CuO的负载量为6%时,CuO/Ce0.7Zr0.15La0.15O的活性最高,高分散且与载体相互作用的CuO是CO氧化活性相。 相似文献
966.
Lothar Hennig Mario Alva-Astudillo Gerhard Mann Thomas Kappe 《Monatshefte für Chemie / Chemical Monthly》1992,123(6-7):571-579
Summary Treatment of substituted benzylidene anilines1 a – df with cyclic CH-acidic compounds2a–m in ethanol at room temperature yields in additon/elimination reactions the corresponding arylidene derivatives4 and the 2:1 adducts5. The addition products3, which are formed as intermediates, could not be isolated in any case. The donor/acceptor effect of the substituents on the benzylidene moiety influences to a significant extent the reactivity towards the azomethine carbon.
Neue Aspekte der Reaktion von Azomethinen mit cyclischen CH-aciden Verbindungen
Zusammenfassung Bei der Umsetzung der substituierten Benzylidenaniline1 a – f mit den cyclischen CH-aciden Verbindungen2 a – m in Ethanol bei Raumtemperatur erhält man in Additions/Eliminierungsreaktionen die Arylidenderivate4 und die 2:1-Addukte5. Die als Intermediat gebildeten Additionsprodukte3 konnten in keinem Fall isoliert werden. Die Donor-bzw. Acceptorwirkung der Substituenten am Benzylidenrest beeinflußt maßgebend die Reaktivität am Azomethinkohlenstoff.相似文献
967.
968.
1 INTRODUCTION The tris(ethylenediamine) cobalt (Ⅲ) complex in which there are L and D configurations is one of the very interest cations due to the chirality among research complexes and the characterization of reaction on the ion-pair charge-transfer transitions. It has been mentioned in a lot of examples on the chirality and the structure, such as [L-Co(en)3]- [?Co(edta)]2Cl?0H2O[1], [(+)DCo(en)3]Cl3稨2O[2], [(+)-Co(en)3?-)-Cr(en)3]Cl?.1H2O[3], [()-Co(en)3] (SCN)3[4], [(+)D… 相似文献
969.
Pasynskii A. A. Semenova N. I. Torubaev Yu. V. Belousov P. V. Lyssenko K. A. Dobrokhotova Zh. V. 《Russian Chemical Bulletin》2001,50(11):2215-2220
Transmetallation of the Fe3(3-X)2(CO)9 clusters (X = S, Se, or Te) under the action of (-C8H12)PtCl2 afforded new heterometallic clusters (-C8H12)Pt(3-X)2Fe2(CO)6 (2—4, respectively), which were characterized by X-ray diffraction analysis. The (-C8H12)Pt fragment in these clusters is bound to two 3-bridging chalcogen atoms X. The iron atoms are linked to each other. The coordination environment about the Pt atom is planar-square; the Pt...Fe distance is larger than 3.2 . In the synthesis of cluster 4, a new Pt complex was also obtained for which the structure (CO)2Pt(-Te)2Pt(CO)2 (5) was proposed. According to the results of differential scanning calorimetry, thermal decomposition of complex 5 gave rise only to PtTe, whereas complexes 1—4 gave products with the empirical formula Fe2PtX2C2O2. The influence of the steric effects on the geometry of the clusters is discussed. 相似文献
970.
We present an integrated computational tool, rooted in density functional theory, the polarizable continuum model, and classical molecular dynamics employing spherical boundary conditions, to study the spectroscopic observables of molecules in solution. As a test case, a modified OPLS-AA force field has been developed and used to compute the UV and NMR spectra of acetone in aqueous solution. The results show that provided the classical force fields are carefully reparameterized and validated, the proposed approach is robust and effective, and can also be used by nonspecialists to provide a general and powerful complement to experimental techniques. 相似文献