全文获取类型
收费全文 | 2817篇 |
免费 | 87篇 |
国内免费 | 10篇 |
专业分类
化学 | 1896篇 |
晶体学 | 48篇 |
力学 | 56篇 |
数学 | 450篇 |
物理学 | 464篇 |
出版年
2023年 | 12篇 |
2022年 | 50篇 |
2021年 | 71篇 |
2020年 | 63篇 |
2019年 | 60篇 |
2018年 | 47篇 |
2017年 | 55篇 |
2016年 | 86篇 |
2015年 | 84篇 |
2014年 | 94篇 |
2013年 | 188篇 |
2012年 | 154篇 |
2011年 | 177篇 |
2010年 | 144篇 |
2009年 | 117篇 |
2008年 | 173篇 |
2007年 | 151篇 |
2006年 | 129篇 |
2005年 | 128篇 |
2004年 | 110篇 |
2003年 | 91篇 |
2002年 | 83篇 |
2001年 | 30篇 |
2000年 | 37篇 |
1999年 | 33篇 |
1998年 | 27篇 |
1997年 | 28篇 |
1996年 | 26篇 |
1995年 | 27篇 |
1994年 | 23篇 |
1993年 | 18篇 |
1992年 | 25篇 |
1991年 | 40篇 |
1990年 | 27篇 |
1989年 | 21篇 |
1988年 | 22篇 |
1987年 | 14篇 |
1986年 | 15篇 |
1985年 | 25篇 |
1984年 | 25篇 |
1983年 | 13篇 |
1982年 | 18篇 |
1981年 | 13篇 |
1980年 | 20篇 |
1979年 | 11篇 |
1978年 | 14篇 |
1977年 | 18篇 |
1976年 | 16篇 |
1975年 | 7篇 |
1969年 | 6篇 |
排序方式: 共有2914条查询结果,搜索用时 15 毫秒
71.
Kopel Pavel Trávníček Zdeněk Kvítek Libor Biler Martin Pavlíček Marek Šindelář Zdeněk Marek Jaromír 《Transition Metal Chemistry》2001,26(3):282-286
NiII mixed-ligand complexes of compositions [Ni(pmdien)(ttcH)] (1), [Ni(baphen)2(ttcH)] · 4H2O (2), [Ni-(dpa)(ttcH)(H2O)] (3), [Ni(cyclam)(ttcH)] · 2H2O (4), [Ni(hexaa)](ttcH) (5) and [Ni(hexab)(ttcH)] · 2H2O (6), (baphen = 4,7-diphenyl-1,10-phenanthroline, dpa = 2,2-dipyridylamine, cyclam = 1,4,8,11-tetraazacyclotetradecane, hexaa = 1,3,6,9,11,14-hexaazatricyclo[12.2.1.16,9]-octadecane, hexab = 1,8-dimethyl-1,3,6,8,10,13-hexaazacyclotetradecane) have been prepared and characterized by means of i.r., u.v.–vis. spectroscopies and magnetochemical measurements. The redox properties of the complexes were studied by cyclic voltammetry. The crystal and molecular structure of [Ni(pmdien)(ttcH)] was determined. The nickel atom is penta-coordinated by three N atoms of pmdien, and by S and N atoms of trithiocyanurate(2–) anion. 相似文献
72.
73.
74.
Klara Markova Klaudia Chmelova Srgio M. Marques Philippe Carpentier David Bednar Jiri Damborsky Martin Marek 《Chemical science》2020,11(41):11162
Computational design of protein catalysts with enhanced stabilities for use in research and enzyme technologies is a challenging task. Using force-field calculations and phylogenetic analysis, we previously designed the haloalkane dehalogenase DhaA115 which contains 11 mutations that confer upon it outstanding thermostability (Tm = 73.5 °C; ΔTm > 23 °C). An understanding of the structural basis of this hyperstabilization is required in order to develop computer algorithms and predictive tools. Here, we report X-ray structures of DhaA115 at 1.55 Å and 1.6 Å resolutions and their molecular dynamics trajectories, which unravel the intricate network of interactions that reinforce the αβα-sandwich architecture. Unexpectedly, mutations toward bulky aromatic amino acids at the protein surface triggered long-distance (∼27 Å) backbone changes due to cooperative effects. These cooperative interactions produced an unprecedented double-lock system that: (i) induced backbone changes, (ii) closed the molecular gates to the active site, (iii) reduced the volumes of the main and slot access tunnels, and (iv) occluded the active site. Despite these spatial restrictions, experimental tracing of the access tunnels using krypton derivative crystals demonstrates that transport of ligands is still effective. Our findings highlight key thermostabilization effects and provide a structural basis for designing new thermostable protein catalysts.Illustration of cooperative thermostabilization effects of the double-lock system that: (i) induced backbone changes, (ii) closed the molecular gates, (iii) reduced the volumes of the main and slot access tunnels, and (iv) occluded the active site. 相似文献
75.
Anna Rakowska Robert Filipek Krzysztof Sikorski Marek Danielewski Renata Bachorczyk 《Mikrochimica acta》2004,145(1-4):183-186
The interdiffusion process in thin and thick (500nm–60µm) Au–Ni layers deposited on different substrates is studied using the EDS technique. In-depth X-ray analysis based on the Pouchou and Pichoir method is applied for obtaining the concentration profiles in nanometre scale multi-layers. A theoretical analysis using the Darken method is employed for modelling interdiffusion in the Au–Ni system. Computer simulations, where intrinsic diffusivities of the Au and Ni are functions of composition, are presented and compared with experimental results. 相似文献
76.
Ewa Lada Xiubin Lei Marek K. Kalinowski 《Monatshefte für Chemie / Chemical Monthly》1992,123(5):425-433
Summary The formation constants,K
S, of the 18-crown-6 complex with thallium(I) ion were studied by polarographic measurements in binary mixtures of acetonitrile, acetone, tetrahydrofuran, and dimethylsulfoxide with water, as a function of the solvent mole fraction. In all the cases, the variation of the stability constant can be described by the empirical relation logK
S=a[(–1)/(2+1)]+b where stands for relative permittivity of a given mixture anda andb mark the regression coefficients. The values ofa calculated for four series of binary mixtures showed correlation with the Gutmann donor numbers of the neat organic solvents which form the mixture.On leave from the Department of Chemistry, Jingzhou Teacher's College, Jingzhou, Hubei, China 相似文献
77.
The combination of capillary isotachophoresis (ITP) and capillary zone electrophoresis (CZE) in the column coupling configuration was optimized in a mode where the electrolyte for the CZE step is different from the leading and terminating ITP electrolytes. Two colored markers, picric acid and 1-nitroso-2-naphthol, were used for exact timing of the transfer of isotachophoretically stacked analyte zones into the CZE column and for the control of the residual amount of the leading and terminating ITP electrolytes entering the CZE capillary together with the analytes, thus controlling the duration of transient ITP migration in the CZE capillary and ensuring good separation of the analytes and reproducibility of the migration times (relative standard deviations 1%). ITP-CZE was applied to the simultaneous assay of several cinnamic acid derivatives and flavonoids in methanolic extracts of Sambucus flowers and Crataegus leaves and flowers. The preconcentrating and cleansing effect of the ITP step allowed injection of relatively large sample volumes (30 microL). The limits of detection were approximately 20-50 ng x mL(-1) and 100 ng x mL(-1) for the acids and flavonoids, respectively ( thick similar 200-times lower compared to conventional CE) with spectrophotometric detection at 254 nm. The ITP-CZE exhibited satisfactory linearity and precision when using CZE buffer of pseudo "pH" 9.0; 1-nitroso-2-naphthol was employed as the internal standard. The separation took approximately 35 min. The ITP-CZE results for rutin, hyperoside, and vitexin-2-O"-rhamnoside were in good accordance with those obtained previously by high-performance liquid chromatography. 相似文献
78.
Marek Chmielewski 《Tetrahedron》1980,36(16):2345-2352
Synthesis of stereoisomeric 3-deoxy-hexoses 24–27 and 3,6-dideoxy-hexoses 28–31 is reported. Butyl (E)-2,6-dihydroxy-hex-4-enoate (2) was used as the starting material for the synthesis of 3-deoxy-hexoses. For the synthesis of 3,6-dideoxy-hexoses, butyl (E)-2-acetoxy-hex-4-enoate (7) was employed. The synthesis involved the following successive steps: cis or trans hydroxylation of the double bond in 2 or 7, lactonisation of the resulting aldonic acid esters followed by acetylation and chromatographical separation of γ-lactones, reduction of lactones 16–23 to lactols with disiamylborane, and acetylation of lactols to free sugars. All compounds were obtained as pure diastereomers in racemic form. 相似文献
79.
We construct a solution to stochastic Navier-Stokes equations in dimension n4 with the feedback in both the external forces and a general infinite-dimensional noise. The solution is unique and adapted to the Brownian filtration in the 2-dimensional case with periodic boundary conditions or, when there is no feedback in the noise, for the Dirichlet boundary condition. The paper uses the methods of nonstandard analysis.The research of this author was supported by an SERC Grant. 相似文献
80.
Marek Demiański Zdzislaw Golda Waldemar Puszkarz 《General Relativity and Gravitation》1991,23(8):917-939
We study the dynamics of the generalizedD-dimensional (D = 1+3+d) Friedman-Robertson-Walker (FRW) cosmological models in the framework of an extended gravity theory obtained by adding the Gauss-Bonnet term to the standard Einstein-Hilbert action. In our discussion we extensively use methods of dynamical systems. We consider models filled in with a perfect fluid obeying the equation of statep=(–1) and vacuum but non-flat models. We present a detailed analysis of the ten dimensional model and in particular we study the vacuum case. Several phase portraits show how the evolution of this model depends on the parameter. 相似文献