全文获取类型
收费全文 | 2232篇 |
免费 | 47篇 |
国内免费 | 1篇 |
专业分类
化学 | 1682篇 |
晶体学 | 1篇 |
力学 | 11篇 |
数学 | 253篇 |
物理学 | 333篇 |
出版年
2023年 | 12篇 |
2021年 | 5篇 |
2020年 | 13篇 |
2019年 | 17篇 |
2018年 | 13篇 |
2017年 | 10篇 |
2016年 | 33篇 |
2015年 | 50篇 |
2014年 | 43篇 |
2013年 | 125篇 |
2012年 | 153篇 |
2011年 | 167篇 |
2010年 | 73篇 |
2009年 | 55篇 |
2008年 | 168篇 |
2007年 | 165篇 |
2006年 | 187篇 |
2005年 | 161篇 |
2004年 | 124篇 |
2003年 | 94篇 |
2002年 | 75篇 |
2001年 | 66篇 |
2000年 | 82篇 |
1999年 | 28篇 |
1998年 | 11篇 |
1997年 | 22篇 |
1996年 | 33篇 |
1995年 | 26篇 |
1994年 | 24篇 |
1993年 | 17篇 |
1992年 | 28篇 |
1991年 | 17篇 |
1990年 | 12篇 |
1989年 | 11篇 |
1988年 | 11篇 |
1986年 | 8篇 |
1985年 | 17篇 |
1984年 | 7篇 |
1983年 | 8篇 |
1982年 | 14篇 |
1981年 | 6篇 |
1980年 | 12篇 |
1979年 | 10篇 |
1978年 | 4篇 |
1977年 | 8篇 |
1976年 | 4篇 |
1975年 | 4篇 |
1974年 | 4篇 |
1972年 | 6篇 |
1966年 | 3篇 |
排序方式: 共有2280条查询结果,搜索用时 78 毫秒
61.
A sequential injection system based on the ABTS (2,2′-azino-bis-(3-ethylbenzothiazoline-6-sulphonic-acid) methodology was developed. The proposed method, incorporating a mixing chamber in the side port of the selection valve, was evaluated to measure the total antioxidant activity of several beverages and foods.The ABTS+ is generated by oxidation of ABTS with potassium persulfate and is reduced in presence of hydrogen-donating antioxidants converting into a colourless product. The applicability of the developed method was tested by measurement of the antioxidant activity of pure compounds as well as by analysing complex food and beverage samples. The antioxidant activity was presented as l(+) ascorbic acid equivalence. The values obtained by this methodology were not significantly different from the results obtained by the original spectrophotometric ABTS assay. For most of the studied antioxidants, antioxidant activity varied with pH and dilution. The proposed SIA system is suitable for screening direct or diluted total antioxidant activity of pure compounds or food samples. 相似文献
62.
A fast and effective method to study the aquation of rhodium(III) chlorocomplex in hydrochloric solutions using capillary zone electrophoresis (CZE) is developed. At least five species, some of which seem to be oligomeric, are formed in solution during the aquation process at pH>1. The fast hydration of RhCl63− makes this species impossible to detect. The first species detected in the optimised conditions is RhCl5(H2O)2− although RhCl4(H2O)2− is the main species during the first stage of the aquation process. When equilibrium is reached either RhCl3(H2O)3 or a cationic complex, RhCl2(H2O)4+, is formed as the main species. Matrix Assisted Laser Desorption Ionisation Time of Flight Mass Spectrometry (MALDI-TOF MS) is used as a novel technique to elucidate the structure of the rhodium aqua/chloro complexes formed in solution. Results obtained by CZE are confirmed by spectrophotometry. 相似文献
63.
This perspective article describes the combination of experimental data and quantum chemical methods for the determination of structure and reaction mechanisms of uranyl(vi) complexes in aqueous solution. The first part assesses the accuracy of the chemical and thermodynamic properties of solvated uranyl(vi) complexes as obtained by various quantum chemical methods. The second part discusses structure determination, mechanisms for ligand exchange and the lability of coordinated water molecules for various uranyl(vi) complexes using a combination of NMR and quantum chemical data. 相似文献
64.
Two methods are developed, when solving the related time-independent Schrodinger equation (TISE), to cope with the singular terms of the vibrational kinetic energy operator of a triatomic molecule given in orthogonal internal coordinates. The first method provides a mathematically correct treatment of all singular terms. The vibrational eigenfunctions are approximated by linear combinations of functions of a three-dimensional nondirect-product basis, where basis functions are formed by coupling Bessel-DVR functions, where DVR stands for discrete variable representation, depending on distance-type coordinates and Legendre polynomials depending on angle bending. In the second method one of the singular terms related to a distance-type coordinate, deemed to be unimportant for spectroscopic applications, is given no special treatment. Here the basis set is obtained by taking the direct product of a one-dimensional DVR basis with a two-dimensional nondirect-product basis, the latter formed by coupling Bessel-DVR functions and Legendre polynomials. With the basis functions defined, matrix representations of the TISE are set up and solved numerically to obtain the vibrational energy levels of H3+. The numerical calculations show that the first method treating all singularities is computationally inefficient, while the second method treating properly only the singularities having physical importance is quite efficient. 相似文献
65.
A novel and simple method for the determination of active endocrine disrupter compounds (octylphenol OP, and nonylphenol NP) in paper using microwave-assisted extraction (MAE) and headspace solid-phase microextraction, coupled with gas chromatography-mass spectrometry has been developed. Parameters affecting the efficiency in the MAE process such as exposure time and extraction solvent were studied in order to determine operating conditions. The optimised method was linear over the range studied (1.25-125 microg kg(-1) for OP and 9.50-950 microg kg(-1) for NP) and showed good level of precision, with a RSD lower than 10% and detection limits at 0.10 and 4.56 microg kg(-1) for OP and NP, respectively. The results obtained from six different types of paper revealed the presence of the target compounds in all samples analysed, at levels ranging between 3 and 211 microg kg(-1). 相似文献
66.
Summary A numerically stable and well-parallelizable curve variational algorithm is described for determining tangent curves of vector fields between two given stationary points. In particular, the method is suitable for finding reaction paths and saddle points on potential energy hypersurfaces (PHS). The stability of the procedure is illustrated by an artificial mathematical function, showing phases of following the reaction on the PHS.Dedicated to Professor Zoltán G. Szabó, the great teacher and scientist in reaction kinetics and in many other fields of physical chemistry, on his 84th birthday. 相似文献
67.
For the first time, the existence of a strong intramolecular 1,4-interaction between the phosphorus atom and the oxygen atom in alpha-keto-stabilized ylides has been demonstrated by means of theoretical calculations. This interaction has a notable influence on the conformational preferences and rotational barriers of alpha-stabilized phosphorus ylides and bis-ylides. 相似文献
68.
Lázló Markó 《Journal of organometallic chemistry》1981,213(1):271-275
Two new mixed iron cobalt carbonyl sulphide clusters HFe2(CO)9S and Fe2Co(CO)8(NO)S have been prepared and characterized. The hydride complex undergoes acidic dissociation in polar solvents and the resulting anion was isolated as (Et4N)[Fe2Co(CO)9S]. An efficient high pressure synthesis has been found for H2Fe3(CO)9S. 相似文献
69.
Bouchoux G Defaye D McMahon T Likholyot A Mó O Yáñez M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(13):2900-2909
The various protonated forms of phenol (1), catechol (2), resorcinol (3), and hydroquinone (4) were explored by ab initio quantum chemical calculations at the MP2/6-31G(d) and B3LYP/6-31G(d) levels. Proton affinities (PA) of 1-4 were calculated by the combined G2(MP2,SVP) method, and their gas-phase basicities were estimated after calculation of the change in entropy on protonation. These theoretical data were compared with the corresponding experimental values determined in a high-pressure mass spectrometer. This comparison confirmed that phenols are essentially carbon bases and that protonation generally occurs in a position para to the hydroxyl group. Resorcinol is the most effective base (PA = 856 kJ mol-1) due to the participation of both oxygen atoms in the stabilization of the protonated form. Since protonation is accompanied by a freezing of the two internal rotations, a significant decrease in entropy is observed. The basicity of catechol (PA = 823 kJ mol-1) is due to the existence of an intramolecular hydrogen bond, which is strengthened upon protonation. The lower basicity of hydroquinone (PA = 808 kJ mol-1) is a consequence of the fact that protonation necessarily occurs in a position ortho to the hydroxyl group. When the previously published data are reconsidered and a corrected protonation entropy is used, a proton affinity value of 820 kJ mol-1 is obtained for phenol. 相似文献
70.
Summary The peroxidation of molybdenum(VI) was investigated in neutral and alkaline media. The stability constants of the peroxo complexes were determined by spectrophotometric measurement as (9.12±0.67)×10–7, (2.68±0.17) ×105, (1.26±0.06)×106 and (1.58±0.02) for the 11, 21 (yellow), 31 and 41 (red) species. The diperoxomolybdate disproportionates into the tetraperoxo derivative when treated with alkali. Formation of the tetraperoxo complex was found to be pH dependent according to a curve, with maximum at pH 10. Acidification of tetraperoxomolybdate solution results in the regeneration of hydrogen peroxide and the diperoxo complex is reformed. 相似文献