全文获取类型
收费全文 | 4663篇 |
免费 | 1199篇 |
国内免费 | 681篇 |
专业分类
化学 | 3826篇 |
晶体学 | 70篇 |
力学 | 209篇 |
综合类 | 28篇 |
数学 | 193篇 |
物理学 | 2217篇 |
出版年
2024年 | 12篇 |
2023年 | 55篇 |
2022年 | 110篇 |
2021年 | 184篇 |
2020年 | 270篇 |
2019年 | 192篇 |
2018年 | 150篇 |
2017年 | 180篇 |
2016年 | 255篇 |
2015年 | 241篇 |
2014年 | 339篇 |
2013年 | 427篇 |
2012年 | 358篇 |
2011年 | 336篇 |
2010年 | 286篇 |
2009年 | 297篇 |
2008年 | 310篇 |
2007年 | 284篇 |
2006年 | 279篇 |
2005年 | 249篇 |
2004年 | 270篇 |
2003年 | 208篇 |
2002年 | 151篇 |
2001年 | 127篇 |
2000年 | 118篇 |
1999年 | 115篇 |
1998年 | 101篇 |
1997年 | 95篇 |
1996年 | 90篇 |
1995年 | 70篇 |
1994年 | 66篇 |
1993年 | 48篇 |
1992年 | 51篇 |
1991年 | 34篇 |
1990年 | 27篇 |
1989年 | 24篇 |
1988年 | 23篇 |
1987年 | 14篇 |
1986年 | 21篇 |
1985年 | 8篇 |
1984年 | 11篇 |
1983年 | 3篇 |
1982年 | 12篇 |
1981年 | 7篇 |
1980年 | 8篇 |
1979年 | 10篇 |
1977年 | 3篇 |
1976年 | 3篇 |
1974年 | 4篇 |
1973年 | 2篇 |
排序方式: 共有6543条查询结果,搜索用时 99 毫秒
91.
Kenji Okada 《Journal of Molecular Structure》1996,380(3):223-233
The crystal and molecular structures of 2,2-bis(4-hydroxyphenyl)propane (Bisphenol A, BPA) (1), benzyl 4-hydroxybenzoate (2), 1,7-bis(4-hydroxyphenylthio)-3,5-dioxaheptane (3) and 4-hydroxyphenyl 4-isopropoxyphenyl sulfone (4) have been determined by X-ray crystal structure analysis. Theoretical calculations of the steric hindrance and semiempirical quantum chemical calculations to determine the color characteristics have been carried out. It is clear that the energy barriers for the variation of the orientation of phenol group in 1 to 4 are due to steric hindrance caused by the other moiety and the peak profiles are due to repulsive interactions of the other moiety. Net atomic charges on the hydrogen of the OH group are larger than those on the other atoms in the molecules. This high electron charge of the para orientation will cause the different thermosensitivity and stabilization. 相似文献
92.
93.
In this paper,p-tricyanovinyl-N,N-dialkylanilines were synthesized as model compounds and through their spectroscopic behavior,the photo-induced electron transfer,charge separation were discussed and the aggregation in DMSO-H_2O system was investigated. 相似文献
94.
95.
A novel asymmetric, edge-sharing bioctahedral complex with formamidinato ligands (
2-DAniF)Mo(-DAniF)2(-O,Cl)MoCl2, 1, (DAniF=N,N-di-p-anisylformamidinate) has been isolated as a byproduct from the preparation of the dimolybdenum(II,III) compound Mo2(DAniF)3Cl2. An X-ray crystallographic study shows that the structure consists of edge-sharing bioctahedra, with the shared edge defined by the vector joining the: -O and -Cl ligands. Compound 1 is best formulated as a mixed-valent MoIIIMoV compound, the Mo(V) ion being that with the two terminal Cl– ligands. The cyclic voltammogram of 1 shows a reversible reduction at –0.472 V and a reversible oxidation at 1.028 V vs. the Ag/AgCl reference electrode, while the absorption spectrum of 1 reveals an intense low energy absorption at 523 nm (
max=12 500) which is attributed to an intervalence charge transfer transition. Crystallographic data for 1 are as follows: a=13.387(1) Å, b=15.500(2) Å, c=21.855(2) Å, =98.786(2)°, V=4481.8(8) Å3, P21/c, R1 (wR2)=0.082 (0.177). 相似文献
96.
利用场诱导光电压谱(简称FISPS)和瞬态光伏(简称TPV)技术研究了TiO2的光生电荷的产生和传输机制.发现光生电荷在体块TiO2上的迁移机制不同于在纳米TiO2上的迁移机制,也不同于在结界面空间电荷区的迁移机制. 400 ℃处理的TiO2颗粒表面具有大量的表面态,光生电荷被表面态捕获-释放机制控制着光伏行为的过程是慢过程. 800 ℃处理的TiO2已经形成了完整的能带结构,光伏响应除了表现带-带跃迁外,还有一个在带边的自由激子带,光生电荷被表面自建场驱动进行传递的过程是快过程. 600 ℃处理的TiO2混晶由锐钛矿型和金红石型两种构型组成,在两相之间存在着较低势垒的结界面.它的光伏响应受控于两种机制 :光生电荷在两相间结界面空间电荷区的传输和在表面自建场驱动下的传输.当激发光强较小时,界面空间电荷区的光生电子由于积累的浓度较小而不能隧穿过结界面,这种场助隧穿只有在外场作用下才能发生. 相似文献
97.
F López Arbeloa J Ba?uelos Prieto V Martínez Martínez T Arbeloa López I López Arbeloa 《Chemphyschem》2004,5(11):1762-1771
Absorption and fluorescence (steady-state and time-correlated) techniques are used to study the photophysical characteristics of the pyrromethene 650 (PM650) dye. The presence of the cyano group at the 8 position considerably shifts the absorption and fluorescence bands to lower energies with respect to other related pyrromethene dyes; this is attributed to the strong electron-acceptor character of the cyano group, as is theoretically confirmed by quantum mechanical methods. The fluorescence properties of PM650 are intensively solvent-dependent. The fluorescence band is shifted to lower energies in polar/protic solutions, and the evolution of the corresponding wavelength with the solvent is analysed by a multicomponent linear regression. The fluorescence quantum yield and the lifetime strongly decrease in polar/protic solvents, which can be ascribed to an extra nonradiative deactivation, via an intramolecular charge-transfer state (ICT state), favoured in polar media. 相似文献
98.
Native non‐covalently bonded protein‐protein and protein‐substrate complexes are of great interest and have been extensively studied by electrospray ionization mass spectrometry (ESI‐MS). Multiply charged protein homomultimeric complexes are shown to form by ESI‐MS. This study addresses factors that can artificially induce the formation of multiply charged protein homomultimeric complexes. Cytochrome c (Cyt c) and ubiquitin, which are monomers in solution, were found to generate (Cyt c)mn+ by electrospray ionization (ESI). The homomultimeric complexes were not limited to dimeric complexes but include also multiply charged trimers, tetramers, and pentamers. The observation of these homomultimeric complexes has never been revealed from a Cyt c solution at the concentration as low as 10 μM. Increasing the concentration of Cyt c enhanced the formation of (Cyt c)mn+ as expected; however, the protein concentration does not affect the relative intensities of monomeric and dimeric complexes. Additionally the enrichment of NH4OH also promotes the formation of (Cyt c)mn+. Notably, source collision‐induced dissociations (source‐CID) of (Cyt c)mn+ alter the charge state distribution (CSD) and may lead to an incorrect interpretation of Cyt c conformations. Hence, extra care should be taken when using CSD to interpret the conformation of a protein derived from ESI‐MS. 相似文献
99.
The synthesis and cationic photopolymerization of different cationically polymerizable monomers containing electroactive groups are reviewed with 98 references. The preparation of various compounds containing electron‐donor or electron‐acceptor moieties and photopolymerizable functional groups is described. After a short discussion of basic principles of cationic polymerization, photoinduced cationic polymerizations of various cationically polymerizable monomers containing both electron‐donor or electron‐acceptor chromophores and the functional groups such as epoxy, vinyl, thiiranyl, oxetanyl and others are reviewed. Copyright © 2005 John Wiley & Sons, Ltd. 相似文献
100.
M.E. Kletskii A.A. Millov A.V. Metelitsa M.I. Knyazhansky 《Journal of photochemistry and photobiology. A, Chemistry》1997,110(3):857-270
The mechanism of light-induced transformation in the salicylideneaniline molecule was studied by semiempirical PM3 calculations. The structures and energies of the minima and saddle points (transition states) on the S0, S1 and T1 potential energy hypersurfaces (PESs) were obtained, together with the gradient lines on the PESs. The structure-energy scheme was compared with the experimental findings. According to the results obtained, the following principle processes are observed: fast S1 excited state intramolecular proton transfer (ESIPT), followed by typical ESIPT fluorescence; the formation of two S1 twisted intramolecular charge transfer (TICT) structures which quench the ESIPT fluorescence; the diabatic formation of two ground state metastable coloured “post-TICT” structures responsible for photochromism. 相似文献