全文获取类型
收费全文 | 255021篇 |
免费 | 3421篇 |
国内免费 | 748篇 |
专业分类
化学 | 122780篇 |
晶体学 | 3757篇 |
力学 | 8395篇 |
综合类 | 11篇 |
数学 | 22036篇 |
物理学 | 66489篇 |
无线电 | 35722篇 |
出版年
2021年 | 1905篇 |
2020年 | 2348篇 |
2019年 | 2503篇 |
2018年 | 2761篇 |
2017年 | 2824篇 |
2016年 | 4458篇 |
2015年 | 2879篇 |
2014年 | 4533篇 |
2013年 | 10840篇 |
2012年 | 8014篇 |
2011年 | 9683篇 |
2010年 | 6993篇 |
2009年 | 7242篇 |
2008年 | 9297篇 |
2007年 | 9519篇 |
2006年 | 9121篇 |
2005年 | 8401篇 |
2004年 | 7691篇 |
2003年 | 7149篇 |
2002年 | 6789篇 |
2001年 | 7831篇 |
2000年 | 6208篇 |
1999年 | 4993篇 |
1998年 | 4136篇 |
1997年 | 4110篇 |
1996年 | 3976篇 |
1995年 | 3748篇 |
1994年 | 3603篇 |
1993年 | 3429篇 |
1992年 | 4091篇 |
1991年 | 3963篇 |
1990年 | 3838篇 |
1989年 | 3711篇 |
1988年 | 3609篇 |
1987年 | 3277篇 |
1986年 | 3095篇 |
1985年 | 3855篇 |
1984年 | 3879篇 |
1983年 | 3078篇 |
1982年 | 3167篇 |
1981年 | 3187篇 |
1980年 | 2949篇 |
1979年 | 3216篇 |
1978年 | 3234篇 |
1977年 | 3263篇 |
1976年 | 3089篇 |
1975年 | 2800篇 |
1974年 | 2716篇 |
1973年 | 2658篇 |
1972年 | 1868篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
31.
32.
33.
ABSTRACTQM(UB3LYP)/MM(AMBER) calculations were performed for the locations of the transition structure (TS) of the oxygen–oxygen (O–O) bond formation in the S4 state of the oxygen-evolving complex (OEC) of photosystem II (PSII). The natural orbital (NO) analysis of the broken-symmetry (BS) solutions was also performed to elucidate the nature of the chemical bonds at TS on the basis of several chemical indices defined by the occupation numbers of NO. The computational results revealed a concerted bond switching (CBS) mechanism for the oxygen–oxygen bond formation coupled with the one-electron transfer (OET) for water oxidation in OEC of PSII. The orbital interaction between the σ-HOMO of the Mn(IV)4–O(5) bond and the π*-LUMO of the Mn(V)1=O(6) bond plays an important role for the concerted O–O bond formation for water oxidation in the CaMn4O6 cluster of OEC of PSII. One electron transfer (OET) from the π-HOMO of the Mn(V)1=O(6) bond to the σ*-LUMO of the Mn(IV)4–O(5) bond occurs for the formation of electron transfer diradical, where the generated anion radical [Mn(IV)4–O(5)]-? part is relaxed to the ?Mn(III)4?…?O(5)- structure and the cation radical [O(6)=Mn(V)1]+ ? part is relaxed to the +O(6)–Mn(IV)1? structure because of the charge-spin separation for the electron-and hole-doped Mn–oxo bonds. Therefore, the local spins are responsible for the one-electron reductions of Mn(IV)4->Mn(III)4 and Mn(V)1->Mn(IV)1. On the other hand, the O(5)- and O(6)+ sites generated undergo the O–O bond formation in the CaMn4O6 cluster. The Ca(II) ion in the cubane- skeleton of the CaMn4O6 cluster assists the above orbital interactions by the lowering of the orbital energy levels of π*-LUMO of Mn(V)1=O(6) and σ*-LUMO of Mn(IV)4–O(5), indicating an important role of its Lewis acidity. Present CBS mechanism for the O–O bond formation coupled with one electron reductions of the high-valent Mn ions is different from the conventional radical coupling (RC) and acid-base (AB) mechanisms for water oxidation in artificial and native photosynthesis systems. The proton-coupled electron transfer (PC-OET) mechanism for the O–O bond formation is also touched in relation to the CBS-OET mechanism. 相似文献
34.
Amphiphilic block copolymer self‐assemblies of poly(NVP)‐b‐poly(MDO‐co‐vinyl esters): Tunable dimensions and functionalities 下载免费PDF全文
Guillaume G. Hedir A. Pitto‐Barry Andrew P. Dove Rachel K. O'Reilly 《Journal of polymer science. Part A, Polymer chemistry》2015,53(23):2699-2710
Functional, degradable polymers were synthesized via the copolymerization of vinyl acetate (VAc) and 2‐methylene‐1,3‐dioxepane (MDO) using a macro‐xanthate CTA, poly(N‐vinylpyrrolidone), resulting in the formation of amphiphilic block copolymers of poly(NVP)‐b‐poly(MDO‐co‐VAc). The behavior of the block copolymers in water was investigated and resulted in the formation of self‐assembled nanoparticles containing a hydrophobic core and a hydrophilic corona. The size of the resultant nanoparticles was able to be tuned with variation of the hydrophilic and hydrophobic segments of the core and corona by changing the incorporation of the macro‐CTA as well as the monomer composition in the copolymers, as observed by Dynamic Light Scattering, Static Light Scattering, and Transmission Electron Microscopy analyses. The concept was further applied to a VAc derivative monomer, vinyl bromobutanoate, to incorporate further functionalities such as fluorescent dithiomaleimide groups throughout the polymer backbone using azidation and “click” chemistry as postpolymerization tools to create fluorescently labeled nanoparticles. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2699–2710 相似文献
35.
36.
37.
38.
39.
Siu-Chung Wong Tse C.K. Orabi M. Ninomiya T. 《IEEE transactions on circuits and systems. I, Regular papers》2006,53(2):454-462
This paper describes the modeling of power-factor-correction converters under average-current-mode control, which are widely used in switch-mode power supply applications. The objective is to identify stability boundaries in terms of major circuit parameters for facilitating design of such converters. The approach employs a double averaging procedure, which first applies the usual averaging over the switching period and subsequently applies generalized averaging over the mains period. The resulting model, after two averaging steps and application of a harmonic balance procedure, is nonlinear and capable of describing the low-frequency nonlinear dynamics of the system. The parameter ranges within which stable operation is guaranteed can be accurately and easily found using this model. Experimental measurements are provided for verification of the analytical results. 相似文献
40.
Y. Yin C.K. Erdonmez A. Cabot S. Hughes A.P. Alivisatos 《Advanced functional materials》2006,16(11):1389-1399
Formation of cobalt sulfide hollow nanocrystals through a mechanism similar to the Kirkendall Effect has been investigated in detail. It is found that performing the reaction at > 120 °C leads to fast formation of a single void inside each shell, whereas at room temperature multiple voids are formed within each shell, which can be attributed to strongly temperature‐dependent diffusivities for vacancies. The void formation process is dominated by outward diffusion of cobalt cations; still, the occurrence of significant inward transport of sulfur anions can be inferred as the final voids are smaller in diameter than the original cobalt nanocrystals. Comparison of volume distributions for initial and final nanostructures indicates excess apparent volume in shells, implying significant porosity and/or a defective structure. Indirect evidence for fracture of shells during growth at lower temperatures was observed in shell‐size statistics and transmission electron microscopy images of as‐grown shells. An idealized model of the diffusional process imposes two minimal requirements on material parameters for shell growth to be obtainable within a specific synthetic system. 相似文献