全文获取类型
收费全文 | 1703篇 |
免费 | 165篇 |
国内免费 | 103篇 |
专业分类
化学 | 536篇 |
晶体学 | 12篇 |
力学 | 88篇 |
综合类 | 19篇 |
数学 | 640篇 |
物理学 | 676篇 |
出版年
2024年 | 4篇 |
2023年 | 12篇 |
2022年 | 20篇 |
2021年 | 28篇 |
2020年 | 36篇 |
2019年 | 50篇 |
2018年 | 33篇 |
2017年 | 47篇 |
2016年 | 59篇 |
2015年 | 44篇 |
2014年 | 73篇 |
2013年 | 181篇 |
2012年 | 84篇 |
2011年 | 75篇 |
2010年 | 67篇 |
2009年 | 80篇 |
2008年 | 119篇 |
2007年 | 90篇 |
2006年 | 85篇 |
2005年 | 87篇 |
2004年 | 68篇 |
2003年 | 64篇 |
2002年 | 66篇 |
2001年 | 53篇 |
2000年 | 66篇 |
1999年 | 60篇 |
1998年 | 44篇 |
1997年 | 23篇 |
1996年 | 36篇 |
1995年 | 27篇 |
1994年 | 17篇 |
1993年 | 17篇 |
1992年 | 15篇 |
1991年 | 7篇 |
1990年 | 12篇 |
1989年 | 9篇 |
1988年 | 14篇 |
1987年 | 11篇 |
1986年 | 10篇 |
1985年 | 11篇 |
1984年 | 10篇 |
1983年 | 7篇 |
1982年 | 9篇 |
1981年 | 14篇 |
1980年 | 6篇 |
1979年 | 3篇 |
1978年 | 7篇 |
1976年 | 2篇 |
1975年 | 3篇 |
1969年 | 2篇 |
排序方式: 共有1971条查询结果,搜索用时 15 毫秒
21.
Dr. Alexey S. Kiryutin Mikhail S. Panov Dr. Alexandra V. Yurkovskaya Prof. Dr. Konstantin L. Ivanov Prof. Dr. Geoffrey Bodenhausen 《Chemphyschem》2019,20(5):766-772
A study of long-lived spin order in chlorothiophene carboxylates at both high and low magnetic fields is presented. Careful sample preparation (removal of dissolved oxygen in solution, chelating of paramagnetic impurities, reduction of convection) allows one to obtain very long-lived singlet order of the two coupled protons in chlorothiophene derivatives, having lifetimes of about 130 s in D2O and 240 s in deuterated methanol, which are much longer than the T1-relaxation times (18 and 30 s, respectively, at a field =9.4 T). In protonated solvents the relaxation times become shorter, but the lifetime is still substantially longer than . In addition, long-lived coherences are shown to have lifetimes as long as 30 s. Thiophene derivatives can be used as molecular tags to study slow transport, slow dynamics and slow chemical processes, as has been shown in recent years. 相似文献
22.
Some of the piezoelectric coefficients of poly(vinylidene fluoride) are distinctly stress dependent. We report on their dependence on the frequency of an oscillatory stress excitation, on the amount of the remanent polarization in the sample materials, and on the magnitude of an offset stress. In order to explain the observed dynamic and nonlinear piezoelectric properties, a model is developed that attributes them to changes in the local polarization in an interphase between the crystalline and amorphous phases in this semicrystalline polymer. 相似文献
23.
L. Montrucchio 《Journal of Optimization Theory and Applications》1994,80(3):385-406
We study the relationship between the dynamical complexity of optimal paths and the discount factor in general infinite-horizon discrete-time concave problems. Given a dynamic systemx
t+1=h(x
t
), defined on the state space, we find two discount factors 0 < * ** < 1 having the following properties. For any fixed discount factor 0 < < *, the dynamic system is the solution to some concave problem. For any discount factor ** < < 1, the dynamic system is not the solution to any strongly concave problem. We prove that the upper bound ** is a decreasing function of the topological entropy of the dynamic system. Different upper bounds are also discussed.This research was partially supported by MURST, National Group on Nonlinear dynamics in Economics and Social Sciences. The author would like to thank two anonymous referees for helpful comments and suggestions. 相似文献
24.
Alessandro?De?Robertis Concetta?De?Stefano Demetrio?Milea Silvio?SammartanoEmail author 《Journal of solution chemistry》2005,34(10):1211-1226
Complex formation constants were determined potentiometrically (by a ISE-H+, glass electrode) in the systems, M2+ – Lz – H+ [M2+ = (C2H5)2Sn2+, Lz = malonate, glycinate and ethylenediamine] at t = 25 ∘C and 0.1 mol-L−1≤ I/ ≤ 1 mol-L−1 in NaClaq (0.1 mol-L−1 ≤ I ≤ 0.75 mol-L−1 for the ethylenediamine system). Thermodynamic values of formation constants, at infinite dilution, are [± 95% confidence
interval, Tβpqr refer to the equilibrium, pM2+ + qLz + rH+ = MpLqHr(2+z+r)]: for malonate, log10 Tβ110 = (5.47 ± 0.10); for glycinate, log10 Tβ110 = (9.54 ± 0.08), log10 Tβ111 = (12.97 ± 0.10); and for ethylenediamine, log10 Tβ110 = (10.47 ± 0.10), log10 Tβ120 = (16.17 ± 0.12) and log10 Tβ111 = (15.46 ± 0.10). The dependence on ionic strength of the formation constants was modeled by a simple Debye–Hückel type equation
and by the SIT approach. By analyzing the stability of the species in the three different systems we found a simple additivity
rule that can be expressed by the relationship: log10 K = 6.46 nN + 3.96 nO − 0.60 (nN2+ nO2), with a mean deviation, ε(log10 K) = 0.15 (K = equilibrium constant for the interaction of the organometal cation with the unprotonated or protonated ligand, nN = number of amino groups and nO = number of carboxylic groups of the ligand(s) involved in the formation reaction of complex species). 相似文献
25.
V. G. Berezkin A. A. Korolev I. V. Malyukova R. G. Mardanov 《Russian Chemical Bulletin》1997,46(12):2064-2073
The effects of the carrier gas nature and pressure on the relative retention values of organic compounds were studied using
a series of capillary columns differing in the film thickness of the polar stationary phase (PEG-20M). Relative retention
depends linearly on the carrier gas pressure. This dependence becomes more pronounced in the following order of carrier gases:
helium < nitrogen < carbon dioxide. The limiting relative retention at a carrier gas pressure approaching zero rather than
relative retention values measured experimentally (relative retention time, Kovats retention index,etc.) is an invariant characteristic of a compound subjected to chromatography. For the carrier gases studied, the limiting retention
values almost does not depend on the nature of the carrier gas used. The limiting indicating the complex absorption-adsorption
nature of these parameters. Dissolution of a carrier gas in the stationary liquid phase has an effect on the relative retention.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2177–2186, December, 1997. 相似文献
26.
Simple two-parameter Hückel and Pitzer equations were used for the calculation of the activity coefficients of aqueous hydrochloric acid at temperatures 0–60°C up to a molality of 2.0 mol-kg–1. The data obtained by Harned and Ehlers(2,3) on galvanic cells without a liquid junction were used in the parameter estimations of these equations. These data consist of sets of measurements at the temperature intervals of 5°C. It was observed that all estimated parameters follow very simple equations with respect to temperature. They are either constant or depend linearly on the temperature. The values for the activity coefficient parameters calculated by these simple equations are recommended here. The recommended parameter values were tested by predicting the data of Gupta, Hills, and Ives,(5) consisting of cell measurements from 5 to 45°C and molalities up to 1.0 mol-kg–1, and the data of Bates and Bower,(4) which extend to 95°C but measurements were only made on molalities less than about 0.1 mol-kg–1. The activity coefficients obtained by the new equations were also compared to those calculated by the Pitzer equations with the parameter values determined by Saluja, Pitzer, and Phutela(6) from calorimetric data. The agreement observed was excellent up to a molality of 1.5 mol-kg–1 at temperatures from 0 to 60°C. 相似文献
27.
Summary The dependence of the chloride distribution coefficient on the co-ion of solutions of different alkali fluorides, MF, up to 11M is tested on the strongly basic anion-exchange resin AG1-X10. Under the same experimental conditions the distribution coefficient decreases in the following order for M+: Na+>K+>Rb+>Cs+. This can be explained by the different co-ion-chloride interactions. The consequence of this interaction for a chromatographic separation of chloride is shown with 5M KF and CsF solutions, used as eluants. Depending on the fluoride concentration, the distribution coefficient passes through a minimum value to increase again at higher electrolyte concentration. The non-exchange electrolyte in the resin phase is responsible for this effect. In addition, the bromide and the iodide distribution coefficients up to 10M KF solutions are determined. One results is that the selectivity coefficient between halide ions increases at higher electrolyte concentrations. 相似文献
28.
G. Barone S. Capasso P. Del Vecchio C. De Sena D. Fessas C. Giancola G. Graziano P. Tramonti 《Journal of Thermal Analysis and Calorimetry》1995,45(6):1255-1264
In a previous paper, we report a preliminary DSC study on bovine (BSA) and human (HSA) serum albumins. However, at accurate HPLC analysis the commercial proteins show three peaks: Fraction V-I, probably globulins (as declared by the producers), Fraction V-II (about 15–18% of the product) and Fraction V-III that represents pure BSA or HSA. A hypothesis is that the Fraction II is a covalent dimer, or trimer or a mixture of both, generated during the scalf-life of the commercial product. Denaturation enthalpies of the purified Fraction V-III and Fraction V-II of BSA, have been determined calorimetrically, at changing thepH, and the results of both compared with those obtained on the untreated protein. Few calorimetric experiments have been also carried on a BSA monomer derivative with sulphidril group protected. Computer program have been developed for the deconvolution of exo- and endothermic effects and for the analysis of thermal denaturation profiles. 相似文献
29.
A.?González-PérezEmail author J.?Czapkiewicz J.?M.?Ruso J.?R.?Rodríguez 《Colloid and polymer science》2004,282(10):1169-1173
The specific conductivity of dodecyldimethylbenzylammonium bromide (C12BBr) in aqueous solutions, in the temperature range of 15 to 40 °C, has been measured as a function of molality. The two breaks which were found on the conductivity against molality plots were attributed to the critical micelle concentration, cmc, and second critical micelle concentration, 2nd cmc, respectively. The ratio of the slopes, S, of the three linear fragments on the plots, S2/S1 and S3/S1, was attributed to the degree of ionization of the micelles at cmc and 2nd cmc respectively. It was shown that the values of the 2nd cmc estimated above 27 °C are only apparent due to thermal disintegration of the micelles. In the temperature range of 15 to 27 °C, the values of the 2nd cmc increase gradually and the plot of the 2nd cmc against temperature is concave. The ratio of 2nd cmc/cmc for C12BBr at 25 °C amounts to 15 and appears to be high compared to the literature values for other surfactants. For comparative purposes the cmc and 2nd cmc values were also estimated conductometrically for decyldimethylbenzylammonium bromide (C10BBr) at 25 °C. The 2nd cmc value for this surfactant is higher compared to the value for the C12 homologue by a factor of 2.6.The standard Gibbs free energies of micellization at cmc and at the 2nd cmc were estimated from the experimental data for both surfactants at 25 °C. 相似文献
30.
The relation between thermochromism and thermal motion of aromatic rings on model bithiophene and 3-butylbithiophene molecules was studied by molecular dynamics (MD) simulations based on semiempirical AM1 hamiltonian. Theoretical optical spectra at various temperatures are generated from the conformations obtained from MD calculations. Alkyl chains have a tendency to tilt bithiophene fragments from co-planarity (connected with blue shift) whereas the unsubstituted systems prefer the higher degree of planarity (connected with red shift) upon the temperature increase. The slope of the linear temperature dependence of the reciprocal maximal wavelengths consists of the above electronic and of the vibrational contribution that (according to Wien’s displacement law) causes always the increase of the above mentioned slope by reciprocal Wien’s constant. This model explains the temperature dependence of experimental UV–vis spectra for dibutylheptathiophene and 3′,3,4′,4-tetrahexylhexathiophene. 相似文献