全文获取类型
收费全文 | 5339篇 |
免费 | 146篇 |
国内免费 | 41篇 |
专业分类
化学 | 3218篇 |
晶体学 | 26篇 |
力学 | 295篇 |
数学 | 878篇 |
物理学 | 1109篇 |
出版年
2023年 | 33篇 |
2022年 | 85篇 |
2021年 | 101篇 |
2020年 | 89篇 |
2019年 | 86篇 |
2018年 | 78篇 |
2017年 | 70篇 |
2016年 | 174篇 |
2015年 | 138篇 |
2014年 | 148篇 |
2013年 | 300篇 |
2012年 | 283篇 |
2011年 | 301篇 |
2010年 | 216篇 |
2009年 | 180篇 |
2008年 | 286篇 |
2007年 | 285篇 |
2006年 | 261篇 |
2005年 | 235篇 |
2004年 | 247篇 |
2003年 | 208篇 |
2002年 | 195篇 |
2001年 | 98篇 |
2000年 | 85篇 |
1999年 | 81篇 |
1998年 | 59篇 |
1997年 | 66篇 |
1996年 | 79篇 |
1995年 | 65篇 |
1994年 | 73篇 |
1993年 | 59篇 |
1992年 | 57篇 |
1991年 | 47篇 |
1990年 | 38篇 |
1989年 | 35篇 |
1988年 | 44篇 |
1987年 | 38篇 |
1986年 | 31篇 |
1985年 | 63篇 |
1984年 | 53篇 |
1983年 | 42篇 |
1982年 | 45篇 |
1981年 | 39篇 |
1980年 | 38篇 |
1979年 | 39篇 |
1978年 | 26篇 |
1977年 | 23篇 |
1976年 | 30篇 |
1975年 | 26篇 |
1974年 | 27篇 |
排序方式: 共有5526条查询结果,搜索用时 15 毫秒
41.
42.
Fry BG Wüster W Ryan Ramjan SF Jackson T Martelli P Kini RM 《Rapid communications in mass spectrometry : RCM》2003,17(18):2047-2062
The evolution of the venomous function of snakes and the diversification of the toxins has been of tremendous research interest and considerable debate. It has become recently evident that the evolution of the toxins in the advanced snakes (Colubroidea) predated the evolution of the advanced, front-fanged delivery mechanisms. Historically, the venoms of snakes lacking front-fanged venom-delivery systems (conventionally grouped into the paraphyletic family Colubridae) have been largely neglected. In this study we used liquid chromatography with mass spectrometry (LC/MS) to analyze a large number of venoms from a wide array of species representing the major advanced snake clades Atractaspididae, Colubrinae, Elapidae, Homalopsinae, Natricinae, Psammophiinae, Pseudoxyrhophiinae, Xenodontinae, and Viperidae. We also present the first sequences of toxins from Azemiops feae as well as additional toxin sequences from the Colubrinae. The large body of data on molecular masses and retention times thus assembled demonstrates a hitherto unsuspected diversity of toxins in all lineages, having implications ranging from clinical management of envenomings to venom evolution to the use of isolated toxins as leads for drug design and development. Although definitive assignment of a toxin to a protein family can only be done through demonstrated structural studies such as N-terminal sequencing, the molecular mass data complemented by LC retention information, presented here, do permit formulation of reasonable hypotheses concerning snake venom evolution and potential clinical effects to a degree not possible till now, and some hypotheses of this kind are proposed here. The data will also be useful in biodiscovery. 相似文献
43.
VISIBLE CHEMILUMINESCENCE ASSOCIATED WITH THE REACTION BETWEEN METHEMOGLOBIN OR OXYHEMOGLOBIN WITH HYDROGEN PEROXIDE 总被引:1,自引:0,他引:1
Eduardo A. Lissi Jorge Escobar Carlos Pascual Maria del Castillo Tais H. Schmitt Paolo Di Mascio 《Photochemistry and photobiology》1994,60(5):405-411
Abstract Visible chemiluminescence is emitted in the irreversible deactivation of hemoglobin or methemoglobin with excess H2 O2 . The emission takes place in two phases. The most intense one lasts a few seconds and is followed by a second phase of lower intensity that remains for longer periods. This second phase presents chaotic or sustained oscillations. Free radicals are implicated in the luminescent process since the emission can be reduced by free radical scavengers such as 6-hydroxy-2,5,7,8,-tetramethylchroman-2-carboxylic acid (Trolox) or ascorbic acid. These additives lead to a delay in reaching the maximum intensity, which can be related to their consumption, implying substantial recycling of the hemoprotein. Chemiluminescence is also observed in the oxidation of hemin by H2 O2 , suggesting a role for the heme group in the processes leading to the excited state production. The lower intensity observed in the presence of hemin can be related to the contribution of the globin chains. 相似文献
44.
José Fernández Bertrán Boris La Serna Klaus Doerffel Klaus Dathe Gunther Kabish 《Journal of Molecular Structure》1982
The Fermi doublet V2?V3 + V4 of CH3CN in basic, inert and acidic solvents has been studied by IR and Raman spectroscopy. The values of W, the Fermi coupling coefficient, obtained from IR spectra varies with the nature of the solvent while W evaluated from Raman data remains constant at 12.5 ± 0.5 cm?1. The similar effects of Bronsted and Lewis acids on the band frequencies and intensities is evidence that the CN group complexes with acids via the N atom “n” electron pair and not the π bond. 相似文献
45.
In this work, we report on poly(2-hydroxyethyl methacrylate) (PHEMA) hydrogels obtained by a low heat curing reaction. These materials are suitable for in situ preparation and therefore endowed with a potential for several biomedical applications. The novel procedure adopted involves as the first step the synthesis of a soluble oligomeric PHEMA precursor containing polymerizable functions as side substituents. As the second step, the precursor is dissolved in equal amounts of 2-hydroxyethyl methacrylate (HEMA) and water, to form a viscous but still injectable syrup. A low temperature water soluble initiator is then added. The curing reaction starts promptly and is completed within few minutes. During the entire process the internal temperature never rises above 40 degrees C. Preliminary mechanical characterizations performed on the hydrogels in their water-swollen state and diffusion tests in absorption/desorption experiments clearly indicated that on all respects the novel hydrogels are comparable with conventional PHEMA hydrogels obtained according to literature from HEMA in the presence of divinyl crosslinkers. However, the much shorter curing time combined with the far lower curing temperature endow the new hydrogels with a higher potential in view of specific surgical requirements, and particularly for in situ preparation. 相似文献
46.
We redraw, using state-of-the-art methods for free-energy calculations, the phase diagrams of two reference models for the liquid state: the Gaussian and inverse-power-law repulsive potentials. Notwithstanding the different behaviors of the two potentials for vanishing interparticle distances, their thermodynamic properties are similar in a range of densities and temperatures, being ruled by the competition between the body-centered-cubic (bcc) and face-centered-cubic (fcc) crystalline structures and the fluid phase. We confirm the existence of a reentrant bcc phase in the phase diagram of the Gaussian-core model, just above the triple point. We also trace the bcc-fcc coexistence line of the inverse-power-law model as a function of the power exponent n and relate the common features in the phase diagrams of such systems to the softness degree of the interaction. 相似文献
47.
Vincenzo Bertini Angela De Munno Paolo Pelosi Piero Pino 《Journal of heterocyclic chemistry》1968,5(5):621-624
Cycloaddition of fulminic acid to 1-butyn-3-ol gave a mixture of 5-α-hydroxyethylisoxazole (I) and 4-α-hydroxyethylisoxazole (II) in the ratio 9:1. By the dehydration of 1, 5-vinylisoxazole (III) was obtained. Compound III has also been prepared by cyclization of 4-penten-2-ynal as well as its diethylacetal with hydroxylamine hydrochloride; in both instances no isomers have been obtained. Compound III spontaneously polymerizes even at room temperature yielding a polymer still containing isoxazole rings. 相似文献
48.
The cyclic voltammetric technique is used to study hydrogen-bond formation in some polar organic solvents (S) of electroanalytical interest (1,2-dimethoxy, tetrahydrofuran, dimethylformamide, dimethyl sulphoxide and pyridine). The cathodic shift of the proton reduction caused by stepwise addition of the solvent investigated to a solution of anhydrous perchloric acid in acetonitrile is utilized. The theoretical treatment applied produced evidence that HS+ and HS+2 are the only acidic species involved, so that the relevant formation constants can be evaluated. The data obtained mostly compare well with those available in the literature. The features that condition the tendency to hydrogen-bonding and the effect of hydrogen bonding on solvent basicity are discussed. 相似文献
49.
Visintin RF Lapasin R Vignati E D'Antona P Lockhart TP 《Langmuir : the ACS journal of surfaces and colloids》2005,21(14):6240-6249
A waxy crude oil which gels below a threshold temperature has been investigated under static and dynamic conditions, using a combination of rheological methods, optical microscopy, and DSC. Particular attention is given in this work to the influence of the mechanical history on gel strength and to describing the time-dependent rheological behavior. The gels display a strong dependence of the yield stress and moduli on the shear history, cooling rate, and stress loading rate. Of particular interest is the partial recovery of the gel structure after application of small stress or strain (much smaller than the critical values needed for flow onset) during cooling, which can be used to reduce the ultimate strength of the crude oil gel formed below the pour point. A second focus of this study is to further develop the physical interpretation of the mechanism by which wax crystallization produces gelation. Gelation of the waxy crude oil studied is suggested to be the result of the association between wax crystals, which produces an extended network structure, and it is shown that the system displays features common to attractive colloidal gels, for one of which, fumed silica (Aerosil 200) in paraffin oil, rheological data are reported. The colloidal gel model provides a simple and economical basis for explaining the response of the gelled oil to various mechanical perturbations and constitutes a fruitful basis from which to develop technologies for controlling the gelation phenomenon, as suggested by the rheological results reported. 相似文献
50.
[structure: see text] The conventional interpretation of proton NMR chemical shifts is supported by large basis set ab initio quantum mechanical calculations. The benzene protons are predicted to lie within the deshielding zone defined in terms of the out-of-plane magnetic shielding domain. However, ring currents by themselves are not sufficient to account quantitatively for the observed benzene proton downfield chemical shift. sigma-Electron contributions must also be taken into account. The conventional explanation for the ethyne proton chemical shift is valid. 相似文献