全文获取类型
收费全文 | 3922篇 |
免费 | 476篇 |
国内免费 | 337篇 |
专业分类
化学 | 2854篇 |
晶体学 | 48篇 |
力学 | 163篇 |
综合类 | 22篇 |
数学 | 499篇 |
物理学 | 1149篇 |
出版年
2024年 | 8篇 |
2023年 | 83篇 |
2022年 | 105篇 |
2021年 | 153篇 |
2020年 | 193篇 |
2019年 | 168篇 |
2018年 | 143篇 |
2017年 | 131篇 |
2016年 | 174篇 |
2015年 | 201篇 |
2014年 | 195篇 |
2013年 | 330篇 |
2012年 | 341篇 |
2011年 | 339篇 |
2010年 | 200篇 |
2009年 | 199篇 |
2008年 | 233篇 |
2007年 | 218篇 |
2006年 | 170篇 |
2005年 | 170篇 |
2004年 | 100篇 |
2003年 | 122篇 |
2002年 | 88篇 |
2001年 | 83篇 |
2000年 | 66篇 |
1999年 | 64篇 |
1998年 | 55篇 |
1997年 | 41篇 |
1996年 | 54篇 |
1995年 | 38篇 |
1994年 | 40篇 |
1993年 | 40篇 |
1992年 | 25篇 |
1991年 | 26篇 |
1990年 | 11篇 |
1989年 | 30篇 |
1988年 | 16篇 |
1987年 | 8篇 |
1986年 | 21篇 |
1985年 | 14篇 |
1984年 | 12篇 |
1983年 | 5篇 |
1982年 | 5篇 |
1979年 | 2篇 |
1977年 | 3篇 |
1975年 | 3篇 |
1973年 | 3篇 |
1940年 | 1篇 |
1938年 | 1篇 |
1936年 | 1篇 |
排序方式: 共有4735条查询结果,搜索用时 31 毫秒
101.
Zhenchuan Wen Xuejian Ma Xiaoyu Yang Pengqing Bi Mengsi Niu Kangning Zhang Lin Feng Xiaotao Hao 《中国化学快报》2019,30(5):995-999
In this work, the donor:acceptor ratio effected photophysical properties of non-fullerene organic solar cells are comparatively investigated. Effective transportation of the photo-generated charge carriers can be obtained with the PDBD-T:ITIC ratio variation. There is no significant energy loss variation exists in the process of changing the D:A ratio. 相似文献
102.
103.
del Mar Graciani M Rodríguez A Muñoz M Moyá ML 《Journal of colloid and interface science》2001,235(2):260-264
The reaction of dehydrobromination of 2-(p-nitrophenyl)ethyl bromide with hydroxide ions has been studied in aqueous micellar solutions of N-tetradecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate, SB3-14. The kinetic effects of added salts (NaF, NaCl, NaBr, and NaNO(3)) on the reaction rate in SB3-14 aqueous micellar solutions have also been studied. They were rationalized by considering the binding of the anions, which come from the salt, to the sulfobetaine micelles and their competition with the reactive hydroxide ions for the micellar surface. The equilibrium binding constant of the 2-(p-nitrophenyl)ethyl bromide to the sulfobetaine micelles was estimated by recording the changes in the spectra of the organic substrate when the SB3-14 concentration in the micellar medium changed. This value was in agreement with that obtained from fitting of kinetic data. The second-order rate constant in the micellar pseudophase revealed that the reaction is faster in SB3-14 micelles than in water. This acceleration seems independent of the presence of added salts and can be explained by considering that SB3-14 micelles favor reactions in which charge is delocalized in the transition state. Copyright 2001 Academic Press. 相似文献
104.
Chen A Kamata K Nakagawa M Iyoda T Haiqiao Wang H Li X 《The journal of physical chemistry. B》2005,109(39):18283-18288
We have recently demonstrated a one-step process to fabricate silver-polypyrrole (PPy) coaxial nanocables (Chen, A.; Wang, H.; Li, X. Chem. Commun. 2005, 14, 1863). The formation process of silver-PPy coaxial nanocables is discussed in this article. It was found from the results of TEM and SEM images that large numbers of silver atoms were formed when AgNO3 was added to a pyrrole solution. Then silver atoms transform to silver-PPy nanosheets with regular morphology, which will connect together to be more stable. Silver-PPy nanocables will be able to grow at the expense of the silver-PPy nanosheets. Poly(vinylpyrrolidone) (PVP) plays crucial roles in this process: as a capping agent to form silver nanowires, and as a dispersant of pyrrole monomers, which can influence the site at which pyrrole monomer exists. On the basis of experimental analysis, the possible mechanism was proposed. Because of the effect of PVP, silver ions and pyrrole monomers are apt to be adsorbed at the [111] and [100] facets of silver nanosheets, respectively. Obvious polymerization will take place on the boundary of the [111] and [100] facets. The PPy layer stays stable on the [100] facets. Meanwhile, newly formed silver atoms and silver nanosheets will further ripen and grow on the [111] facets. In a word, the morphology of final products and the formation process are determined by the reaction site between AgNO3 and the pyrrole monomer, which is influenced by PVP. 相似文献
105.
Muñiz K 《Chemical Society reviews》2004,33(3):166-174
Imido complexes of osmium tetroxide are versatile compounds for olefin functionalisation. This tutorial review offers a brief historical overview on these compounds and discusses the electronic properties and reactivities of isolated imido osmium compounds in what had been the original stoichiometric aminohydroxylation reaction. The recently emerging catalytic Sharpless aminohydroxylation is discussed with special emphasis on mechanistic details. The final section deals with diamination of olefins, which relies on the chemistry of bisimido and trisimido osmium complexes. 相似文献
106.
Maria Luisa Moyá Antonio Barrios Maria del Mar Graciani Rafael Jiménez Ernestina Muñoz Francisco Sánchez John Burgess 《Transition Metal Chemistry》1991,16(2):165-168
Summary The kinetics of replacement of 4,4-bipyridine, (4,4-bipy), and 4-cyanopyridine, (4-CNpy), by cyanide in [Fe(CN)5-(4,4-bipy)]3-. at 298 K have been studied in binary aqueous mixtures containing different amounts of t-butanol, methanol, glycerol, ethyleneglycol and sucrose. The plots of logarithms of the limiting rate constantsversus the mole fraction of water are linear over the entire composition range studied, showing the importance of solvation phenomena. A different straight line of log (kL/s–1)versus XH2O is obtained for each mixture, indicating the influence of other solvent parameters on the reaction rate. A multiparameter regression of G
exp
with A (acidity vector), B (basicity vector) and GE is used for both reactions; plots of G
calc
versus G
exp
are linear with slopes of near unity. 相似文献
107.
Muñoz MA Ferrero R Carmona C Balón M 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2004,60(1-2):193-200
The NH-pi interactions of indole with benzene, naphthalene, phenanthrene, toluene, m-xylene, and mesitilene, in carbon tetrachloride solutions, have been studied by Fourier transform infrared spectroscopy. The experiments, carried out on the NH stretching band of indole, prove the formation of 1:1 complexes in which the NH bond of indole is engaged. The NH frequency shifts are independent of the number of rings in the base, but they progressively increase as the electron density is enhanced by methylation. The association constants increase with the increase of both, the number of rings and the methyl groups on the base. At higher base concentrations, further shifts on the free NH and associated bands indicate the formation of 1:2 complexes, which suggest hybride NH-pi and van der Waals interactions between one indole ring and two benzene acceptor molecules. 相似文献
108.
109.
The unimolecular reaction of CF_2HCl on W filament has been studied. This reaction shows zero order at rather high pressure. The temperature threshold is about 440 ℃. The apparent activation energy of this reaction is 119.7 kJ mol~(-1) which is about a half of the activation energy for homogeneous unimolecular reaction of CF_2HCl, 233.5 kJ mol~(-1). 相似文献
110.
Muñoz-Hernández MA Montiel-Palma V Huitrón-Rattinger E Cortés-Llamas S Tiempos-Flores N Grevy JM Silvestru C Power P 《Dalton transactions (Cambridge, England : 2003)》2005,(1):193-199
Dichloro and chloromethyl Ga(III) complexes of general formulae [XClGa-eta2-{R2P(E)NP(E'R'2-E,E'}](X = Cl, R, R'= Ph, E, E'= O (1), S (2), Se (3); R = Ph, R'= OEt, E = O, E'= S (4); R = Me, R'= Ph, E, E'= S (5) and X = Me, E, E'= O (6), S (7), Se (8)) were synthesised by either metathesis reactions between GaCl3 and the potassium salt of the ligand (X = Cl) or by methane eliminations from in situ prepared GaMe2Cl and the protonated ligands LH (X = Me). Redistribution reaction of (3) in either CDCl3 or THF afforded the solvent-free tetracoordinate gallium spirocycle cation [Ga-{eta2-{Ph2P(Se)NP(Se)Ph2-Se,Se'})2]+ (9+). The molecular structures of complexes 2, 4, 5, 7 and 9(+) show non-planar gallacycle rings. 相似文献