全文获取类型
收费全文 | 417篇 |
免费 | 14篇 |
国内免费 | 5篇 |
专业分类
化学 | 265篇 |
晶体学 | 12篇 |
力学 | 8篇 |
数学 | 64篇 |
物理学 | 87篇 |
出版年
2023年 | 3篇 |
2022年 | 6篇 |
2021年 | 13篇 |
2020年 | 6篇 |
2019年 | 18篇 |
2018年 | 14篇 |
2017年 | 7篇 |
2016年 | 15篇 |
2015年 | 15篇 |
2014年 | 21篇 |
2013年 | 18篇 |
2012年 | 18篇 |
2011年 | 38篇 |
2010年 | 23篇 |
2009年 | 19篇 |
2008年 | 36篇 |
2007年 | 23篇 |
2006年 | 10篇 |
2005年 | 14篇 |
2004年 | 12篇 |
2003年 | 10篇 |
2002年 | 14篇 |
2001年 | 12篇 |
2000年 | 8篇 |
1999年 | 12篇 |
1998年 | 4篇 |
1997年 | 7篇 |
1996年 | 4篇 |
1995年 | 4篇 |
1994年 | 3篇 |
1993年 | 2篇 |
1992年 | 5篇 |
1991年 | 1篇 |
1990年 | 4篇 |
1989年 | 4篇 |
1987年 | 1篇 |
1986年 | 3篇 |
1984年 | 1篇 |
1983年 | 2篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1980年 | 1篇 |
1978年 | 1篇 |
1977年 | 1篇 |
1973年 | 1篇 |
排序方式: 共有436条查询结果,搜索用时 31 毫秒
111.
Interaction of catechol and gallic acid with titanium dioxide in aqueous suspensions. 1. Equilibrium studies 总被引:1,自引:0,他引:1
Araujo PZ Morando PJ Blesa MA 《Langmuir : the ACS journal of surfaces and colloids》2005,21(8):3470-3474
The adsorption isotherms of catechol (1,2-dihydroxybenzene) and gallic acid (3,4,5-trihydroxybenzoic acid) onto titanium dioxide (Degussa P-25) were measured at various pH values and room temperature using attenuated total reflection Fourier transform infrared (FTIR-ATR) data, processed by singular value decomposition. The affinity is largely pH independent, although the deprotonatation of the carboxylic group in gallic acid might produce a slight increase in the affinity. Catechol was shown to form two complexes, with Langmuir stability constants log K of 4.66 (strong mode) and 3.65 (weak mode). Both complexes have the same spectral signature, and mononuclear and binuclear chelate structures are proposed for them. Gallic acid chemisorbs by complexation through two -OH groups and forms one complex only, log K = 4.70. The third -OH and the pendant carboxylate do not influence much the stability of the surface complex. Comparison with literature data demonstrates that the affinity of 4-chlorocatechol is also similar, whereas 2,3-dihidroxynaphthalene and 4-nitrocatechol form more stable complexes, probably because of the solvation contribution to the overall Gibbs adsorption energy. All quoted constants refer to the surface complexation equilibria written as follows: ([triple bond]Ti-OH)2 + H2L = ([triple bond]Ti)2-L + 2H2O, i.e., as electroneutral processes. The FTIR-ATR spectra of the surface complexes are also discussed. 相似文献
112.
Dos Santos WN da Silva EG Fernandes MS Araujo RG Costa AC Vale MG Ferreira SL 《Analytical and bioanalytical chemistry》2005,382(4):1099-1102
Chocolate is a complex sample with a high content of organic compounds and its analysis generally involves digestion procedures that might include the risk of losses and/or contamination. The determination of copper in chocolate is important because copper compounds are extensively used as fungicides in the farming of cocoa. In this paper, a slurry-sampling flame atomic-absorption spectrometric method is proposed for determination of copper in powdered chocolate samples. Optimization was carried out using univariate methodology involving the variables nature and concentration of the acid solution for slurry preparation, sonication time, and sample mass. The recommended conditions include a sample mass of 0.2 g, 2.0 mol L–1 hydrochloric acid solution, and a sonication time of 15 min. The calibration curve was prepared using aqueous copper standards in 2.0 mol L–1 hydrochloric acid. This method allowed determination of copper in chocolate with a detection limit of 0.4 g g–1 and precision, expressed as relative standard deviation (RSD), of 2.5% (n=10) for a copper content of approximately 30 g g–1, using a chocolate mass of 0.2 g. The accuracy was confirmed by analyzing the certified reference materials NIST SRM 1568a rice flour and NIES CRM 10-b rice flour. The proposed method was used for determination of copper in three powdered chocolate samples, the copper content of which varied between 26.6 and 31.5 g g–1. The results showed no significant differences with those obtained after complete digestion, using a t-test for comparison. 相似文献
113.
A computational study of viscous flow between two eccentrically rotating cylinders is presented in which the effect of viscous dissipation is taken into account. The space discretization is based on piecewise linear finite elements with velocity stabilization, while the method of characteristics is used for time integration. Numerical results illustrate the efficiency of the adopted approach. 相似文献
114.
Carolina Araujo 《Transactions of the American Mathematical Society》2002,354(11):4303-4312
Recently Johnson and Kollár determined the complete list of anticanonically embedded quasi-smooth log del Pezzo surfaces in weighted projective -spaces. They also proved that many of those surfaces admit a Kähler-Einstein metric, and that some of them do not have tigers.
The aim of this paper is to settle the question of the existence of Kähler-Einstein metrics and tigers for those surfaces for which the question was left open. In order to do so, we will use techniques developed earlier by Nadel, Demailly and Kollár.
115.
Let M be a complete metric space. If admits an isometric shift, then M is separable.
(Received 2 February 2001; in revised form 9 April 2001) 相似文献
116.
Huy N. Hoang Chongyang Wu Timothy A. Hill Aline Dantas de Araujo Paul V. Bernhardt Ligong Liu David P. Fairlie 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(52):19049-19053
The introduction of an amide bond linking side chains of the first and fifth amino acids forms a cyclic pentapeptide that optimally stabilizes the smallest known α‐helix in water. The origin of the stabilization is unclear. The observed dependence of α‐helicity on the solvent and cyclization linker led us to discover a novel long‐range n to π* interaction between a main‐chain amide oxygen and a uniquely positioned carbonyl group in the linker of cyclic pentapeptides. CD and NMR spectra, NMR and X‐ray structures, modelling, and MD simulations reveal that this first example of a synthetically incorporated long‐range n to π* CO???Cγ=Ο interaction uniquely enforces an almost perfect and remarkably stable peptide α‐helix in water but not in DMSO. This unusual interaction with a covalent amide bond outside the helical backbone suggests new approaches to synthetically stabilize peptide structures in water. 相似文献
117.
118.
119.
Gravitational waves are perturbations in the space-time that propagate at the speed of light. The study of such phenomenon is interesting because many cosmological processes and astrophysical objects, such as binary systems, are potential sources of gravitational radiation and can have their emissions detected in the near future by the next generation of interferometric detectors. Concerning the astrophysical objects, an interesting case is when there are several sources emitting in such a way that there is a superposition of signals, resulting in a smooth spectrum which spans a wide range of frequencies, the so-called stochastic background. In this paper, we are concerned with the stochastic backgrounds generated by compact binaries (i.e., binary systems formed by neutron stars and black holes) in the coalescing phase. In particular, we obtain such backgrounds by employing a new method developed in our previous studies. 相似文献
120.
Licarion Pinto César Horacio Díaz Nieto María Alicia Zón Héctor Fernández Mario Cesar Ugulino de Araujo 《Analytica chimica acta》2016
Biogenic amines (BAs) are used for identifying spoilage in food. The most common are tryptamine (TRY), 2-phenylethylamine (PHE), putrescine (PUT), cadaverine (CAD) and histamine (HIS). Due to lack of chromophores, chemical derivatization with dansyl was employed to analyze these BAs using high performance liquid chromatography with a diode array detector (HPLC-DAD). However, the derivatization reaction occurs with any primary or secondary amine, leading to co-elution of analytes and interferents with identical spectral profiles, and thus causing rank deficiency. When the spectral profile is the same and peak misalignment is present on the chromatographic runs, it is not possible to handle the data only with Multivariate Curve Resolution and Alternative Least Square (MCR-ALS), by augmenting the time, or the spectral mode. A way to circumvent this drawback is to receive information from another detector that leads to a selective profile for the analyte. To overcome both problems, (tri-linearity break in time, and spectral mode), this paper proposes a new analytical methodology for fast quantitation of these BAs in fish with HPLC-DAD by using the icoshift algorithm for temporal misalignment correction before MCR-ALS spectral mode augmented treatment. Limits of detection, relative errors of prediction (REP) and average recoveries, ranging from 0.14 to 0.50 µg mL−1, 3.5–8.8% and 88.08%–99.68%, respectively. These are outstanding results obtained, reaching quantification limits for the five BAs much lower than those established by the Food and Agriculture Organization of the United Nations and World Health Organization (FAO/WHO), and the European Food Safety Authority (EFSA), all without any pre-concentration steps. The concentrations of BAs in fish samples ranged from 7.82 to 29.41 µg g−1, 8.68–25.95 µg g−1, 4.76–28.54 µg g−1, 5.18–39.95 µg g−1 and 1.45–52.62 µg g−1 for TRY, PHE, PUT, CAD, and HIS, respectively. In addition, the proposed method spends less than 4 min in an isocratic run, consuming less solvent in accordance with the principles of green analytical chemistry. 相似文献