全文获取类型
收费全文 | 2082篇 |
免费 | 208篇 |
国内免费 | 110篇 |
专业分类
化学 | 1921篇 |
晶体学 | 46篇 |
力学 | 68篇 |
综合类 | 6篇 |
数学 | 19篇 |
物理学 | 340篇 |
出版年
2024年 | 1篇 |
2023年 | 12篇 |
2022年 | 20篇 |
2021年 | 28篇 |
2020年 | 61篇 |
2019年 | 59篇 |
2018年 | 65篇 |
2017年 | 50篇 |
2016年 | 99篇 |
2015年 | 78篇 |
2014年 | 91篇 |
2013年 | 153篇 |
2012年 | 82篇 |
2011年 | 110篇 |
2010年 | 97篇 |
2009年 | 94篇 |
2008年 | 80篇 |
2007年 | 92篇 |
2006年 | 81篇 |
2005年 | 87篇 |
2004年 | 99篇 |
2003年 | 74篇 |
2002年 | 55篇 |
2001年 | 43篇 |
2000年 | 65篇 |
1999年 | 46篇 |
1998年 | 38篇 |
1997年 | 44篇 |
1996年 | 39篇 |
1995年 | 49篇 |
1994年 | 29篇 |
1993年 | 30篇 |
1992年 | 31篇 |
1991年 | 24篇 |
1990年 | 30篇 |
1989年 | 24篇 |
1988年 | 23篇 |
1987年 | 34篇 |
1986年 | 28篇 |
1985年 | 26篇 |
1984年 | 21篇 |
1983年 | 14篇 |
1982年 | 26篇 |
1981年 | 19篇 |
1980年 | 19篇 |
1979年 | 20篇 |
1978年 | 6篇 |
1977年 | 3篇 |
1973年 | 1篇 |
排序方式: 共有2400条查询结果,搜索用时 359 毫秒
31.
In this work the potential of hydrophilic interaction chromatography (HILIC) is explored for the analysis of tetracycline antibiotics. The choice of the polar stationary phase is first discussed and it is demonstrated that aminopropyl stationary phases lead to higher efficiencies and peak symmetry than bare silica ones. The influence of the composition of the mobile phase is studied next : the concentration of the weaker solvent (acetonitrile), the nature and concentration of the more polar solvent (water or methanol), pH, the nature and ionic strength of the buffer. It is shown that high efficiencies are reached only with a citrate buffer that impairs the interactions with the residual silanol groups whatever the mobile phase pH is. We demonstrate that the citrate buffer strongly interacts with the cationic moiety of the aminopropyl stationary phase and thus reduces the accessibility of silanols. The separation of oxytetracycline, tetracycline and chlortetracycline is achieved in a few minutes at pH 3.5 or 5, with no peak tailing as usually observed in reversed phase liquid chromatography with an opposite elution order when compared with reversed phase liquid chromatography. 相似文献
32.
33.
Summary A theoretical treatment is presented which considers differences between the composition of the mobile phase and solvents
that are incorporated into the bonded phase via preferential sorption. Equations are derived and used to analyze retention
data for various homologs chromatographed under reversed-phase conditions using alkyl bonded phases and combinations of water-methanol,
water-acetonitrile and watertetrahydrofuran as mobile phases. In the case of water-methanol the surface phase and bulk mobile
phase compositions are similar. However, significant differences in composition between the two phases are observed when binary
combinations of water-acetonitrile and water-tetrahydrofuran are used as the cluents. 相似文献
34.
Summary A new expression which permits the prediction of the net retention volumes in gas chromatography with column packings of coated
porous polymers is reported. The porous polymers Chromosorb 101 and Chromosorb 102 were used as supports and squalane, Ethofat
and Carbowax 20M as stationary phases at three different column temperatures of 80°C, 100°C and 150°C. Several organic compounds
of various polarity were used as test compounds and the net retention volumes, VNtheor, have been calculated according to this new expression. The VNtheor values were compared with the experimental net retention volumes, VNexp, and it was found that the difference between these two values is dependent on the type of compound and column packing. Nevertheless,
the elution order could be predicted in most cases. 相似文献
35.
36.
Summary The advantages and disadvantages of high performance precipitation liquid chromatography have been demonstrated for polystyrene
homopolymers. Depending on the mobile phase composition at the dissolution point of the polymeric sample and surface properties
of the stationary phase, elution is governed either by a solution process or by adsorption. A contribution by adsorption was
noticed on silica as well as on reversed phases based on silica with a normal phase gradient of increasing polarity (heptane
to dichloromethane). Elution was solely governed by solubility of the polymers on both types of stationary phase for polystyrenes
with a molecular weight above 35 000 and reversed phase gradient of decreasing polarity (methanol to dichloromethane). Under
these conditions an identical dependence of elution solvent composition on sample size was found as for turbidity titrations.
Due to differences in the velocity of the eluent front and the polymeric sample with porous stationary phases the polymers
can be eluted as colloidal solutions Non-porous stationary phases are superior in this respect because the velocities of eluent
and solutes are identical. 相似文献
37.
V. G. Berezkin V. R. Alishoyev E. N. Victorova V. S. Gavrichev V. M. Fateeva 《Chromatographia》1982,16(1):126-131
Summary The use of crystallohydrates, crystallohydrate solutions and melts as stationary phases in gas chromatography has been proposed. Crystallohydrates have been shown to display high selectivity in the separation of polar organic compounds when use is made of water vapours as the mobile phase. Some aspects of gas-liquid chromatography in water vapours and with the stationary phase comprising crystallohydrates have been studied, and the preliminary results obtained point to the desirability of further progress in this field.Presented at the 14th International Symposium on Chromatography London, September, 1982 相似文献
38.
Six isotypic R6ZTe2 phases have been synthesized in Ta at elevated temperatures and characterized by single crystal X-ray refinements for R=Y, Z=Rh, Pd, Ag, Y and for R=Lu, Z=Cu, Ag. All crystallize in the Sc6PdTe2-type structure, Pnma, Z=4, a∼21.5 Å, b∼4.1 Å, c∼11.4 Å. The results can be viewed as the replacement of Te3 atoms in the parent isotypic Sc2Te (or in the hypothetical Y2Te or Lu2Te analogues) by the above the Z, the Y example giving the new binary phase Y7Te2. The shorter (and stronger) metal-metal bonds concentrate in the region of metal (Z, Y) substitution, as revealed by larger integrated crystal orbital Hamilton population (ICOHP) values derived from linear muffin-tin-orbital (LMTO) calculations. Partial densities-of-states data for Y7Te2 reflect a similar behavior. Individual R-R bond distances are seen to deviate appreciably from the more fundamental overlap population measures for each. 相似文献
39.
This paper describes some thermal analysis experiments conducted on high explosive samples. These employ differential scanning calorimetry to monitor thermal effects at elevated temperatures (around 200 °C) and heat conduction calorimetry to record thermal effects at much lower temperatures (below 100 °C).The work shows that, due to the generally high thermal stability of many high explosive compositions, heat generation rates are very low, if detectable at all, at normal storage temperatures, even when using a very sensitive instrument. The sensitivity and reproducibility of this technique has been investigated in detail by Wilker et al. [S. Wilker, U. Ticmanis, G. Pantel, Detailed investigation of sensitivity and reproducibility of heat flow calorimetry, in: Proceedings of the 11th Symposium on Chemical Problems Connected with the Stability of Explosives, Sweden, 1998] and shown to be capable of recording heat generation rates of less than a microwatt. This allows continuous measurement of decomposition processes in nitrate ester based propellants at temperatures as low as 40 °C. However, the measurement of very low levels of heat generation is difficult, time consuming and therefore expensive. If the assumption is made that the life limiting process is invariably the slow decomposition of the energetic component, this will frequently lead to very long service lifetime predictions.A number of possible complications are identified. Firstly, due to its low detection threshold, a heat conduction calorimeter may detect other reactions which will not lead to failure, but which may still dominate the heat flow signal. Secondly, the true failure process may generate little energy and be overlooked. In view of these considerations, at present it seems unwise to rely on heat conduction microcalorimetry as the only tool for the assessment of the life of high explosive energetic systems.Based on examples of life terminating processes in high explosives during storage and use, it is clear that decomposition of the energetic material is not invariably the cause of system failure. It is also by no means the only reaction that may take place in, and be observed by, a heat conduction calorimeter. 相似文献
40.
A chemically bonded cellulose tris(3,5-dimethylphenylcarbamate) chiral stationary phase (CSP) was prepared by a radical polymerization reaction. The prepared CSP was packed into fused-silica capillaries with inner diameter of 75 microm to perform enantiomer separations in CEC. The electrochromatographic behavior of the CSP was investigated. On the prepared CSP, high EOF could be generated under acidic mobile phases, which represented an advantage for the separation of acidic enantiomers. Several neutral, acidic, and basic enantiomers were resolved on the prepared CSP under aqueous mobile phases. The column efficiencies were between 20,000 and 100,000 plates/m, which were much higher than those of HPLC. In addition, it was observed that the separation of some enantiomers benefited from the adoption of THF as mobile phase modifier. 相似文献