全文获取类型
收费全文 | 1034篇 |
免费 | 23篇 |
国内免费 | 1篇 |
专业分类
化学 | 794篇 |
晶体学 | 18篇 |
力学 | 18篇 |
数学 | 93篇 |
物理学 | 135篇 |
出版年
2023年 | 6篇 |
2021年 | 6篇 |
2020年 | 10篇 |
2019年 | 10篇 |
2018年 | 10篇 |
2016年 | 14篇 |
2015年 | 13篇 |
2014年 | 21篇 |
2013年 | 42篇 |
2012年 | 50篇 |
2011年 | 66篇 |
2010年 | 33篇 |
2009年 | 38篇 |
2008年 | 65篇 |
2007年 | 75篇 |
2006年 | 76篇 |
2005年 | 58篇 |
2004年 | 64篇 |
2003年 | 40篇 |
2002年 | 60篇 |
2001年 | 11篇 |
2000年 | 6篇 |
1999年 | 10篇 |
1998年 | 11篇 |
1997年 | 16篇 |
1996年 | 21篇 |
1995年 | 19篇 |
1994年 | 13篇 |
1991年 | 4篇 |
1990年 | 5篇 |
1989年 | 6篇 |
1988年 | 3篇 |
1987年 | 9篇 |
1985年 | 8篇 |
1984年 | 14篇 |
1983年 | 3篇 |
1982年 | 20篇 |
1981年 | 12篇 |
1980年 | 8篇 |
1979年 | 11篇 |
1978年 | 10篇 |
1977年 | 7篇 |
1976年 | 8篇 |
1975年 | 7篇 |
1974年 | 13篇 |
1973年 | 5篇 |
1972年 | 3篇 |
1971年 | 6篇 |
1969年 | 4篇 |
1968年 | 4篇 |
排序方式: 共有1058条查询结果,搜索用时 15 毫秒
11.
The oxidation of uric acid has been studied by thin-layer spectroelectrochemistry using an optically transparent gold minigrid electrode and enzymatically using peroxidase. Under both enzymatic and electrochemical conditions a u.v.-absorbing intermediate (λmax=302–304 nm between pH 7–9.3) is observed. This intermediate is proposed to be an imine-alcohol species formed by rapid hydration of the primary reaction product which is a diimine. Under the conditions employed in both the enzymatic electrochemical studies the imine-alcohol intermediate is hydrated in a first order reaction with an observed rate constant of 3.5×10?3s?1 between pH 7–9.3. This study establishes the similarity between the electrochemical and enzymatic oxidation of uric acid and indicates that electrochemical investigations of the redox behavior of purines can provide unique insights into their biological redox properties. 相似文献
12.
Anthony Winston Glenn R. McLaughlin 《Journal of polymer science. Part A, Polymer chemistry》1976,14(9):2155-2165
The iron chelating ability of hydroxamic acid polymers was studied as a function of the atomic chain spacing separating neighboring hydroxamic acid units. Two polymers were prepared, one having the hydroxamic acid group separated by 11 atoms and the other by three atoms. The iron binding of these polymers was compared with the model compound desferrioxamine B (DFO) and with a previously prepared polymer having a nine-atom spacing. Mole ratio plots indicated the following order of stability: DFO ≈ 11 atom > 9 atom > 3 atom. These results are in accordance with the picture derived from molecular models which shows that with a spacing of 11 atoms, three neighboring hydroxamic acids can fit the octahedral arrangement of the iron (III) complex without appreciable strain. Some strain is introduced when the spacing becomes only nine atoms, and with three atoms, complex formation between three neighboring groups becomes virtually impossible. 相似文献
13.
Michael T. Cleary James L. Owens Glenn Dryhurst 《Journal of Electroanalytical Chemistry》1981,123(2):265-290
The electrochemical oxidation of 9-methylxanthine proceeds via four voltammetric oxidation peaks at the pyrolytic graphite electrode. The first voltammetric oxidation peak (peak Ia) is a 1e reaction giving a radical which dimerizes to 8,8′-bi-9-methyl-9H-purine-2,6-(1H, 3H)-dione. Peak IIa is a further 2e electrooxidation of the peak Ia dimer to another yellow dimer 8,8′-bi-9-methyl-9H-purine-2,6-(1H)-dione-3,5-(3H)-diiminylidene. This dimer is not very stable and it hydrolyzes to 1-methyl allantoin. Peak IIIa is an adsorption pre-peak to peak IVa which corresponds, overall, to a direct 4e?4H+ electrooxidation of 9-methylxanthine to an unstable diimine of 9-methyluric acid. Hydrolysis of this diimine leads to a variety of ultimate products. 相似文献
14.
Abstract— In order to introduce fullerene cages into an aqueous environment, pendant [60]fullerene-poly(propionylethyle-neimine-co-ethyleneimine) was prepared photochemical-ly. The pendant polymer is highly water soluble, with equivalent aqueous solubilities of the polymer-bound [60]fullerene much higher than the solubility of [60]ful-lerene in toluene. The photochemical reaction between [60]fullerene and secondary amine moieties in the ami-nopolymers likely follows a photoinduced electron transfer-proton transfer mechanism. The pendant polymer structures, which are represented by dehydrogenated di-and tetra-aminofullerene linkages, were characterized by use of proton and 13C NMR, Fourier transform-infrared spectroscopy, gel-permeation chromatography and optical spectroscopic methods. 相似文献
15.
Alexandra Alimova A. Katz Rakhi Podder Glenn Minko Hul Wei R. R. Alfano Paul Gottlieb 《Photochemistry and photobiology》2004,80(1):41-46
Native fluorescence spectroscopy was used for in situ investigations of two lipid‐containing bacteriophages from the cystovirus family as well as their Pseudomonad host cells. Both the viruses φ6 and φ12 and their bacterial host proteins contain the amino acid tryptophan (trp), which is the predominant fluorophore in UV. Within proteins, trp's structural environment differs, and the differences are reflected in their spectroscopic signatures. It was observed that the peak of the trp emission from both viruses was at 330 nm, a significantly shorter wavelength than trp in either the Pseudomonad host cells or the amino acid's chemical form. This allowed us to monitor the viral attachment process and subsequent lytic release of progeny virus particles by measurement of the trp emission spectra during the infection process. This work demonstrates that fluorescence may offer a novel tool to detect viruses and monitor viral infection of cells and may be part of a biodefense application. 相似文献
16.
17.
Photoelectron energy and angular distributions are measured for the 2+1 multiphoton ionization process H2 X1Σg+ (ν = 0,J) + 2hv → E,F1Σg+(νE,JE = J) + hν → H2+X2Σg+ (ν+) + e?, for νE = 0, 1, or 2 and for JE = 0 or 1 of the inner well of the double-minimum E,F state. Although a strong preference is found for ν+ = νE, the detailed H2+ vibrational distribution does not exhibit Franck-Condon behavior, and the photoelectron angular distributions vary markedly with both the JE value of the intermediate state and the ν+ value of the ion. 相似文献
18.
Addition of an aldehyde and zinc chloride to a cyclobutanone enolate, prepared by the reaction of an α-chlorocyclobutanone with dimethylcopperlithium, gave an aldol adduct in good yield. 相似文献
19.
Burley GA Fowler PW Soncini A Sandall JP Taylor R 《Chemical communications (Cambridge, England)》2003,(24):3042-3043
Ipsocentric current-density maps for a fluorofullerene derivative, C60F15H3, modelling the addition pattern of the experimentally characterised C60F15[CBr(CO2Et)2]3 which contains an [18]trans-annulene system, reveal a diamagnetic ring current dominated by the contribution of the four HOMO electrons, as in a classical (4n + 2) aromatic annulene. 相似文献
20.
The syntheses of boronates derived from the reaction of dioxaborolanes and dioxaborinanes with either organolithium or organomagnesium reagents are investigated along with their subsequent use in the palladium cross coupling reaction. The intrinsic stability of these cyclic esters contributes to their facile reaction with both lithium and magnesium nucleophiles at mild and safe conditions. We have found that many of the reactions proceed at room temperature which is a significant improvement over the traditional routes which require cryogenic temperatures. The scope of these reactions and their practical application to large scale process synthesis is described. 相似文献