全文获取类型
收费全文 | 526篇 |
免费 | 13篇 |
专业分类
化学 | 485篇 |
晶体学 | 2篇 |
力学 | 2篇 |
数学 | 25篇 |
物理学 | 25篇 |
出版年
2023年 | 1篇 |
2022年 | 6篇 |
2021年 | 6篇 |
2020年 | 7篇 |
2019年 | 5篇 |
2018年 | 6篇 |
2017年 | 5篇 |
2016年 | 14篇 |
2015年 | 13篇 |
2014年 | 8篇 |
2013年 | 16篇 |
2012年 | 20篇 |
2011年 | 27篇 |
2010年 | 13篇 |
2009年 | 10篇 |
2008年 | 23篇 |
2007年 | 28篇 |
2006年 | 26篇 |
2005年 | 24篇 |
2004年 | 26篇 |
2003年 | 37篇 |
2002年 | 22篇 |
2001年 | 19篇 |
2000年 | 14篇 |
1999年 | 22篇 |
1998年 | 5篇 |
1997年 | 9篇 |
1996年 | 12篇 |
1995年 | 4篇 |
1994年 | 8篇 |
1993年 | 8篇 |
1992年 | 7篇 |
1991年 | 9篇 |
1990年 | 21篇 |
1989年 | 10篇 |
1988年 | 8篇 |
1987年 | 13篇 |
1986年 | 10篇 |
1985年 | 8篇 |
1984年 | 6篇 |
1980年 | 1篇 |
1939年 | 2篇 |
排序方式: 共有539条查询结果,搜索用时 328 毫秒
11.
The tautomeric properties of isoguanine (also named 2-oxoadenine or 2-hydroxyadenine) have been studied in the gas phase, in different pure solvents, and in the DNA environment using state of the art theoretical methods. Our results show that isoguanine constitutes an unique example of how tautomerism can be modulated by the environment. Compared to the tautomeric preference in the gas phase, both polar solvents and the DNA microenvironment dramatically change the intrinsic tautomeric properties of isoguanine. Tautomers which are important in physiological conditions are less than 1/10(5) of the total population of isoguanine in the gas phase. The impact of the present findings in the understanding of spontaneous mutations and in the design of new nucleobases with multiple recognition properties is discussed. 相似文献
12.
13.
14.
Andrés Izquierdo Pilar Linares M. D. Luque de Castro Miguel Valcarcel 《Fresenius' Journal of Analytical Chemistry》1990,336(6):490-493
Summary Two fluorimetric methods are proposed for the simultaneous determination of ammonia and urea based on the reaction of the former with o-phthalaldehyde/2-mercaptoethanol and on the use of a dual injection system in which the valves are coupled in series or in parallel. An enzymatic reactor converts urea into ammonia which is determined by the same reaction. These configurations provide very similar results with a linear determination range between 0.5 and 10.0 g ml–1 and a sampling frequency of 60 h–1. The proposed methods are very tolerant to foreign species commonly found in water, as shown by applying them to samples of different origins. 相似文献
15.
Begoña Hernández Modesto Orozco Francisco J. Luque 《Journal of computer-aided molecular design》1997,11(2):153-162
The tautomerism of 2-azaadenine and 2-hypoxanthine has been examined in the gas phase and in aqueous solution. The tautomerism in the gas phase has been studied by means of semiempirical and ab initio quantum-mechanical computations, as well as density-functional calculations. The influence of the aqueous solvent on the relative stability between tautomers has been estimated from self-consistent reaction field calculations performed with different high-level continuum models. The results provide a detailed picture of the tautomeric preference for these purine bases. The importance of tautomerism in the substrate recognition by xanthine oxidase is discussed. Finally, the rate of oxidation of 2-azaadenine and 2- hypoxanthine by xanthine oxidase is discussed in terms of the recognition model at the enzyme active site. 相似文献
16.
A continuous method, easy to automate, for the determination of anthocyanins in wine based on the coupling of continuous liquid–solid extraction, evaporation, HPLC individual separation and photometric detection is proposed. The target analytes are removed from the wine in a continuous fashion using a C18 minicolumn and eluted with an aqueous solution (pH 2) with 16% acetonitrile. The eluted fraction is concentrated by solvent evaporation assisted by heat and dragging off the vapour using a flow of N2. For in-line preconcentration, a continuous evaporation module was designed and located in the manifold between the solid-phase minicolumn and the injection valve of the chromatograph. In this way, injection of the sample into the dynamic system leads the plug through it for liquid–solid extraction of the anthocyanins, partial evaporation of the eluent (with a preconcentration factor as required) and transport to the high-pressure injection valve of the chromatograph, where individual separation and subsequent photometric detection take place. The method thus developed for the determination of malvidin-3-glucoside, cyanidin-3-glucoside and peonidin-3-glucoside anthocyanins in Spanish red wines is more sensitive than the batch manual method based on the same steps, has better linearity of the calibrations curves with lower detection limits and much wider determination range for the most abundant anthocyanins in wine. In addition, the method can be fully automated with low acquisition and maintenance costs. 相似文献
17.
A flow-through/first derivative synchronous spectrofluorimetric sensor for the determination of PAH has been described. This sensor has been used for the simultaneous determination of PAH mixtures (pyrene, benzo(e)pyrene and benzo(ghi)perylene). Linear calibration ranges between 10 and 500 ng/ml with acceptable precision (repeatability, expressed as relative standard deviation, smaller than 4.6%, and sampling frequency of 12 h(-1)) have been obtained. The method has been applied to the determination of the target analytes in spiked water samples with excellent results (recoveries between 94 and 108%). 相似文献
18.
Study of spectral analytical data using fingerprints and scaled similarity measurements 总被引:1,自引:0,他引:1
Urbano Cuadrado M Luque de Castro MD Gómez-Nieto MA 《Analytical and bioanalytical chemistry》2005,381(4):953-963
A new chemoinformatic model has been developed for enlarging the differences between spectra and applied to differentiation of wines according to the criteria grape origin and variety and ageing process. The model is based on generation of fingerprints from normalised spectra, using empirical parameters and a set of 120 samples. After generation of the fingerprints, similarity matrixes were built on the basis of the Tanimoto similarity index between the fingerprints of the samples. Calculation of the Tanimoto index was modified to adapt the index to the characteristics of the analytical measurements. Thus, scaling factors taking into account pattern fingerprints generated from a group of samples with common characteristics were used. In addition, a modified expression for calculating the Tanimoto index was employed. Principal-components analysis (PCA) and soft independent modelling of class analogy (SIMCA) were applied to the similarity matrixes. The results obtained are discussed as a function of the normalisation method employed, the empirical factor used in generation of the fingerprints, and selection of samples for building the pattern fingerprint, etc. Finally, results from differentiation of wines are compared with those obtained by applying PCA to the unprocessed spectra as stated by the proposed model. 相似文献
19.
The effects of ultrasonic irradiation on transport and reactions in several flow-injection manifolds are described. The influences of ultrasound on the physical dispersion of the injected plug is considered. Its effects on systems involving homogeneous (catalytic and non-catalytic) and heterogeneous (liquid/liquid extraction, precipitation) reactions are critically evaluated. In general, greater sensitivity is obtained, especially for heterogeneous systems, slow reactions and low analyte concentrations. Finally, practical considerations and potential uses of the combination of ultrasonic irradiation with flow-injection analysis are discussed. 相似文献
20.
J. A. Infantes M. D. Luque de Castro M. Valcárcel 《Fresenius' Journal of Analytical Chemistry》1991,339(1):58-61
Summary Two methods based on the use of the normal and stopped-flow injection modes were developed for the determination of oxalate based on its inhibitory effect on the catalytic action of Fe(III) on the 2,4-diaminophenol/hydrogen peroxide system. The linear determination ranges achieved were between 0.2 and 12.0 g ml–1 and between 0.2 and 40.0 g ml–1, the precision was ±5.4%, and ±3.5%, and the sampling rate was 30 and 20 samples h–1 for the normal and stopped-flow method, respectively. Both methods have been applied to the determination of oxalate in urine with excellent results. 相似文献