全文获取类型
收费全文 | 84586篇 |
免费 | 641篇 |
国内免费 | 453篇 |
专业分类
化学 | 28041篇 |
晶体学 | 1005篇 |
力学 | 6909篇 |
综合类 | 4篇 |
数学 | 32944篇 |
物理学 | 16777篇 |
出版年
2022年 | 71篇 |
2020年 | 93篇 |
2019年 | 142篇 |
2018年 | 10501篇 |
2017年 | 10334篇 |
2016年 | 6178篇 |
2015年 | 951篇 |
2014年 | 467篇 |
2013年 | 854篇 |
2012年 | 4051篇 |
2011年 | 10803篇 |
2010年 | 5834篇 |
2009年 | 6221篇 |
2008年 | 6799篇 |
2007年 | 8960篇 |
2006年 | 415篇 |
2005年 | 1456篇 |
2004年 | 1677篇 |
2003年 | 2149篇 |
2002年 | 1168篇 |
2001年 | 338篇 |
2000年 | 377篇 |
1999年 | 215篇 |
1998年 | 238篇 |
1997年 | 212篇 |
1996年 | 273篇 |
1995年 | 199篇 |
1994年 | 156篇 |
1993年 | 176篇 |
1992年 | 150篇 |
1991年 | 150篇 |
1990年 | 123篇 |
1989年 | 168篇 |
1988年 | 134篇 |
1987年 | 127篇 |
1986年 | 138篇 |
1985年 | 172篇 |
1984年 | 160篇 |
1983年 | 129篇 |
1982年 | 139篇 |
1981年 | 139篇 |
1980年 | 131篇 |
1979年 | 142篇 |
1978年 | 108篇 |
1977年 | 119篇 |
1976年 | 95篇 |
1975年 | 102篇 |
1974年 | 103篇 |
1973年 | 119篇 |
1972年 | 74篇 |
排序方式: 共有10000条查询结果,搜索用时 19 毫秒
841.
Mátyás Milen László Hazai Pál Kolonits György Kalaus Lajos Szabó Ágnes Gömöry Csaba Szántay 《Central European Journal of Chemistry》2005,3(1):118-136
Transformation of β-carboline derivatives into optically active entities were studied and the de and ee values of the resulted compounds were detected.
Dedicated to Professor Károly Lempert on his 80th birthday. 相似文献
842.
Wong KL Lin X Kwon KY Pawin G Rao BV Liu A Bartels L Stolbov S Rahman TS 《Langmuir : the ACS journal of surfaces and colloids》2004,20(25):10928-10934
Para-halosubstituted thiophenols (X-TPs, where X is Br, Cl, or F) form ordered islands and monolayers on Cu(111) at temperatures as low as 81 K. At incomplete coverages, all X-TPs adsorb with the dehydrogenated thiol group attached to the substrate and the substituted ring inclined toward the surface, as verified experimentally and theoretically. The structure of ordered islands has a pronounced dependence on the nature of the halogen substituent: while unsubstituted TP and pentafluoro-TP molecules do not self-assemble into extended ordered patterns at 81 K, X-TP molecules form a range of different structures which depend both on the size and electronegativity of the substituent, as well as on the coverage. 相似文献
843.
R. Parthasarathy Ravi V. Prasad P. R. Sarode K. J. Rao 《Journal of Chemical Sciences》1982,91(3):201-205
The exafs of Co2+ has been studied in rare earth cobaltites and in sulphate and borate glasses. It has been found that the environment of Co2+ ions is very similar in these cases. It appears feasible to study local structures in glasses using probe ion exafs.
Communication No. 151 from the Solid State and Structural Chemistry Unit. 相似文献
844.
Thermodynamics and crystallization kinetics of the hydrothermal synthesis of Na4Ti4Si3O10 (NaTS) were systemically studied by both experiments and model simulation. Experimental results showed that the curve of
crystallinity with time was a characteristic signmoid in the shape that indicated the crystallization of Na4Ti4Si3O10 was a typical spontaneous nucleation process on the laboratory scale. Crystallization of NaTS belongs to the liquid-liquid
transformation mechanism and the reaction is endothermic (ΔH = 15.3 kJ/mol). A mathematic model of crystallization kinetics was developed to simulate the synthesis of NaTS. Runge-Kutta
and simplex methods were adopted to solve the partial differential equations. Model results fitted well with the experimental
data and showed that the synthesis process belongs to spontaneous nucleation and crystal growth. Moreover, the very small
crystal growth constant (5.6·10−7) and gel dissolution constant (7.0·10−7) indicate they are the rate-limiting steps of the whole synthesis process. 相似文献
845.
Complex systems of paramagnetic centres existing in demineralised flame coal (71.4 wt% C), medium-rank coal (85.6 wt% C) and
anthracite (94.9 wt% C) were analysed by electron paramagnetic resonance spectroscopy (EPR). Different groups of paramagnetic
centres were searched in macerals (exinite, vitrinite, inertinite) of coals with carbon contents of 73.8 wt% C and 85.6 wt%
C. Experimental EPR spectra were fitted by different superposition of theoretical lines. Total concentration of paramagnetic
centres both in coal and macerals increases with carbon content in the sample. Total concentration of paramagnetic centres
in macerals increases from exinite to inertinite. Four groups of paramagnetic centres were found in medium-rank coal, and
only two groups exist in flame coal and anthracite. The EPR spectrum of medium-rank coal is a superposition of two broad and
two narrow lines. Both broad and narrow, and two narrow lines were measured in EPR spectra of flame coal and anthracite, respectively.
Two types of paramagnetic centres with broad lines and one group with narrow lines exist in exinite and vitrinite from medium-rank
coal. Two narrow components were observed in EPR spectra of its inertinite. Two different broad electron paramagnetic resonance
signals were detected for macerals from low-coalificated coal. Paramagnetic centres systems of medium-rank coal samples reveal
the most complex character. Broad EPR lines were not observed for the higher coalificated samples, i.e., anthracite and inertinite
from medium-rank coal. Narrow lines do not occur in EPR spectra of low-coalificated macerals. Strong dipolar interactions
and fast spin-lattice relaxation processes are characteristic for paramagnetic centres with broad lines. Strong exchange interactions
and short spin-lattice relaxation time were measured for paramagnetic centres with the narrowest EPR signals. 相似文献
846.
The kinetics of the oxidation of five catecholamines viz., dopamine (A), L-dopa (B), methyldopa (C), epinephrine (D) and norepinephrine
(E) by sodium N-chloro-p-toluenesulfonamide or chloramine-T (CAT) in presence of HClO4 was studied at 30±0.1 °C. The five reactions followed identical kinetics with a first-order dependence on [CAT]
o
, fractional-order in [substrate]
o
, and inverse fractional-order in [H+]. Under comparable experimental conditions, the rate of oxidation of catecholamines increases in the order D>E>A>B>C. The
variation of ionic strength of the medium and the addition of p-toluenesulfonamide or halide ions had no significant effect
on the reaction rate. The rate increased with decreasing dielectric constant of the medium. The solvent isotope effect was
studied using D2O. A Michaelis-Menten type mechanism has been suggested to explain the results. Equilibrium and decomposition constants for
CAT-catecholamine complexes have been evaluated. CH3C6H4SO2NHCl of the oxidant has been postulated as the reactive oxidizing species and oxidation products were identified. An isokinetic
relationship is observed with β=361 K, indicating that enthalpy factors control the reaction rate. The mechanism proposed
and the derived rate law are consistent with the observed kinetics. 相似文献
847.
Rao CN Kundu AK Seikh MM Sudheendra L 《Dalton transactions (Cambridge, England : 2003)》2004,(19):3003-3011
Electronic phase separation is increasingly getting recognized as a phenomenon of importance in understanding the magnetic and electron transport properties of transition metal oxides. The phenomenon dominates the rare-earth manganates of the formula Ln(1-x)A(x)MnO(3)(Ln = rare earth and A = alkaline earth) which exhibit ferromagnetism and metallicity as well as charge-ordering, depending on the composition, size of A-site cations and external factors such as magnetic and electric fields. We discuss typical phase separation scenarios in the manganates, with particular reference to Pr(1-x)Ca(x)MnO(3)(x= 0.3-0.4), (La(1-x)Ln(x))(0.7)Ca(0.3)MnO(3)(Ln = Pr, Nd, Gd and Y) and Nd(0.5)Sr(0.5)MnO(3). Besides discussing the magnetic and electron transport properties, we discuss electric field effects. Rare-earth cobaltates of the type Pr(0.7)Ca(0.3)CoO(3) and Gd(0.5)Ba(0.5)CoO(3) also exhibit interesting magnetic and electron transport properties which can be understood in terms of phase separation. 相似文献
848.
P. S. Verma T. Venkateshwar Rao A. Jayaraman P. S. N. Murthy G. C. Joshi 《Fresenius' Journal of Analytical Chemistry》1994,348(11):742-744
The Fe(III)-EDTA complex reacts with sulfide ion in a fast electron transfer reaction, oxidising the latter to elemental sulfur and getting itself reduced to Fe(II). The reaction has been developed for the quantitative estimation of sulfide ion by titration against the Fe(III)-EDTA complex, measuring the redox potential of the system. Repeated use of a given quantity of the complex solution by the process of regeneration has been demonstrated. The possibility of its practical application in liquid phase oxidation processes of recovering sulfur from H2S is emphasized. 相似文献
849.
S. Prabhakara Rao M. Santappa 《Journal of polymer science. Part A, Polymer chemistry》1968,6(1):95-107
Graft polymers from poly(vinyl chloride) (PVC) and chlorinated rubber (CIR) with side chains of poly(methyl methacrylate) (PMMA), poly(methyl acrylate) (PMA), or poly(ethyl methacrylate) (PEMA) were synthesized. For this purpose, a vinyl monomer was polymerized in the presence of small quantities of PVC or CIR with benzoyl peroxide as catalyst. The graft polymers were separated from both homopolymers by precipitation with methanol from methyl ethyl ketone solutions of the reaction products and the grafting efficiency was calculated. The graft polymers were characterized by infrared spectra, elemental analysis, NMR, and osmometric or light-scattering determinations. From the results it is concluded that the PVC or CIR molecules contain side chains of PMMA, PMA, or PEMA. The graft polymers showed higher molecular weights, and the values of second virial coefficient for these polymers were much different from those of the starting polymers. 相似文献
850.
The reaction of titanium isopropoxide with a Schiff base ligand containing an isobutenyl linker leads to double stranded dinuclear titanium(IV)-Schiff base complexes through self-assembly with concomitant formation of intramolecular mu-oxo bridges upon hydrolysis. 相似文献