全文获取类型
收费全文 | 4832篇 |
免费 | 173篇 |
国内免费 | 152篇 |
专业分类
化学 | 4698篇 |
晶体学 | 2篇 |
力学 | 209篇 |
数学 | 63篇 |
物理学 | 185篇 |
出版年
2023年 | 5篇 |
2022年 | 19篇 |
2021年 | 52篇 |
2020年 | 41篇 |
2019年 | 69篇 |
2018年 | 44篇 |
2017年 | 51篇 |
2016年 | 108篇 |
2015年 | 107篇 |
2014年 | 102篇 |
2013年 | 133篇 |
2012年 | 162篇 |
2011年 | 212篇 |
2010年 | 201篇 |
2009年 | 265篇 |
2008年 | 208篇 |
2007年 | 198篇 |
2006年 | 301篇 |
2005年 | 424篇 |
2004年 | 271篇 |
2003年 | 212篇 |
2002年 | 121篇 |
2001年 | 82篇 |
2000年 | 116篇 |
1999年 | 112篇 |
1998年 | 75篇 |
1997年 | 121篇 |
1996年 | 106篇 |
1995年 | 104篇 |
1994年 | 83篇 |
1993年 | 73篇 |
1992年 | 91篇 |
1991年 | 81篇 |
1990年 | 89篇 |
1989年 | 68篇 |
1988年 | 92篇 |
1987年 | 68篇 |
1986年 | 58篇 |
1985年 | 51篇 |
1984年 | 69篇 |
1983年 | 50篇 |
1982年 | 78篇 |
1981年 | 60篇 |
1980年 | 37篇 |
1979年 | 59篇 |
1978年 | 28篇 |
排序方式: 共有5157条查询结果,搜索用时 9 毫秒
61.
Highly selective and efficient separations of a wide range of acidic species in capillary electrophoresis employing non-aqueous media 总被引:2,自引:0,他引:2
Summary The novel application of CE using non-aqueous media has been studied for the separation of a range of acidic compound types.
This enabled the first quantitative assay by CE employing non-aqueous media to be performed. Separation selectivity manipulation
for closely related species was achieved through variation of organic solvent types and composition, ionic strength changes,
alteration of pH* values and the addition of cyclodextrin additives soluble in organic solvents. This offers a greater range of possibilities
during method development than use of aqueous buffer. The generation of low operating currents permitted rapid, highly efficient
and selective separations to be achieved by applying high field strengths across short capillaries.
Optimised rinsing and capillary regenerating procedures were devised which allowed highly repeatable separations to be achieved
with migration time repeatability below 1% RSD. Use of internal standards also allowed 1% RSD values to be obtained for injection
precision. Routine operating effects were assessed and it was observed that stacking effects remain important in non-aqueous
CE. Also, optimal separations are obtained when the samples are diluted in the pure solvent used to prepare the electrolyte.
The application range of non-aqueous CE was appreciably extended to include acidic drugs, dyes, surfactants and preservatives. 相似文献
62.
A new method for the determination of triphenyltin hydroxide using capillary column gas chromatography with a tin-selective flame photometric detector has been developed. Triphenyltin hydroxide and its potential metabolites are converted to methyl derivatives and separated on glass capillary columns coated with OV-101. Derivatization of triphenyltin hydroxide, triphenyltin chloride, diphenyltin dichloride, phenyltin trichloride, and bis-triphenyltin oxide is nearly quantitative with a minimum of redistribution products. The selectivity of the flame photometric detector is cearly demonstrated by the comparison of chromatographic profiles obtained from using both the flame photometric and flame ionization detectors. The use of this chromatographic system in the analysis of triphenyltin hydroxide in a fortified water sample demonstrates the potential use of this system in organotin residue chemistry. 相似文献
63.
A. J. Berry D. E. Games I. C. Mylchreest J. R. Perkins S. Pleasance 《Journal of separation science》1988,11(1):61-64
A frit restrictor interface for capillary column supercritical fluid chromatography/mass spectrometry (SFC/MS) has been constructed and used for the analysis of high boiling point alkanes. Packed column SFC/MS is described using both a moving belt liquid chromatographic/mass spectrometric interface and a thermospray source in the filament-on mode. 相似文献
64.
A method of quickly determining ascorbic acid and sorbic acid by capillary zone electrophoresis with ultraviolet detection was developed. The choice of background electrolyte, wavelength, injection time and applied voltage were discussed. Ascorbic acid and sorbic acid were well separated in 80 mmol L−1 boric acid-5 mmol L−1borax (pH = 8.0) in 5 min at the detecting wavelength of 270 nm. Under the optimum condition, the method has linear ranges of 2.54-352.00 mg L−1 for ascorbic acid and 1.08-336.39 mg L−1 for sorbic acid with the detection limit of 1.70 mg L−1 for ascorbic acid and 0.54 mg L−1 for sorbic acid, respectively. Other organic acids in fruit juices have no effect on the detection. This method is very feasible and simple and can be used to detect ascorbic acid and sorbic acid in fruit juices. 相似文献
65.
A simple method is described for the quantitative determination of organochlorine pesticides and polychlorinated biphenyls (PCB's) in water at the sub-ppb level. A micro gas-phase extractor advantageously replaces other preconcentration and purification techniques. The extract is analyzed by capillary gas chromatography without further enrichment. The recovery at the ppb level was nearly 100% for organochlorine pesticides and more than 80% for PCB's. The complete procedure including sample preparation, steam distillation-extraction, and capillary gas chromatographic analysis is carried out in less than four hours. 相似文献
66.
GC headspace analyses of various aromatizing herbs have been compared with those relating to the essential oils, obtained by steam distillation, of the same plants. In this way it was possible to establish the most significant differences between the composition of a herb flavor and that of its essential oil. In particular, we observed some very volatile compounds in the headspace samples which were absent from the essential oil; these components may make an important contribution to the herb flavor. The identification of these substances is still in progress. 相似文献
67.
Capillary GC coupled to an atomic emission detector (AED) provides a powerful new hyphenated technique for the separation and characterization of complex mixtures and compounds. The AED provides simultaneous and truly specific multi-element detection. The specificity of detection reduces the need for the complex sample pretreatment procedures which are necessary to reduce the interference from co-eluted substances which is experienced with detectors such as the FID and the ECD. A range of environmentally significant problems has been studied, including PCB analysis, the characterization of the reaction products of a novel waste treatment process, and the profiling of sulfur-containing species formed by the pyrolysis of various types of coal. 相似文献
68.
This paper presents systematic investigation of the microchannel surface properties in microCE chips. Three popular materials for microCE chips, polydimethylsiloxane (PDMS), quartz, and glass, are used. The zeta potentials of these microchannels are calculated by measuring the EOF velocity to evaluate the surface properties after surface modification. The hydrophobic PDMS is usually plasma-treated for microCE applications. In this study, a new method using a high-throughput atmospheric plasma generator is adopted to treat the PDMS surface under atmospheric conditions. In this approach, the cost and time for surface treatment can be significantly reduced compared with the conventional vacuum plasma generator method. Experimental results indicate that new functional groups could be formed on the PDMS surface after treatment, resulting in a change in the surface property. The time-dependent surface property of the plasma-treated PDMS is then measured in terms of the zeta potential. Results show that the surface property will reach a stable condition after 1 h of plasma treatment. For glass CE chips, two new methods for changing the microchannel surface properties are developed. Instead of using complicated and time-consuming chemical silanization procedures for CE channel surface modification, two simple and reliable methods utilizing organic-based spin-on-glass and water-soluble acrylic resin are reported. The proposed method provides a fast batch process for controlling the surface properties of glass-based CE channels. The proposed methods are evaluated using PhiX-174 DNA maker separation. The experimental data show that the surface property is modified and separation efficiency greatly improved. In addition, the long-term stability of both coatings is verified in this study. The methods proposed in this study show potential as an excellent solution for glass-based microCE chip surface modification. 相似文献
69.
《Journal of separation science》2003,26(5):425-428
This paper describes a method for analysing some acids of milk whey by Capillary Zone Electrophoresis. After eliminating the whey proteins by ultrafiltration, the whey underwent electrophoretic separation in the presence of anodic electroosmotic flow. The following analytes were detected: citric, orotic, uric, and hippuric acids. A procedure is described for sample preparation and the operating conditions for electrophoretic capillary separation established. Finally, orotic acid is quantitatively determined. 相似文献
70.
Ivan panik Jan Krupcik Ivan Skacani Jaap De Zeeuw Mario Galli Pat Sandra 《Journal of separation science》1997,20(12):688-692
The separation of isomers and enantiomers of branched C10-C12 phenylalkanes by gas chromatography on fused silica capillary columns coated with some modified β- and γ-cyclodextrins was studied. It was shown that the separation of positional isomers of C10-C12 phynylalkanes on modified cyclodextrin capillary columns is not better than that on a column coated with modified polyethylene glycol. Differences were found in the enantioselectivity of modified β- and γ-cyclodextrins for the separation of C10-C12 secondary phenylalkane enantiomers. While alkylderivatives of β-CDs resolve enantiomers of 3-phenylalkanes, alkyl derivatives of γ-CD resolve enantiomers of 2-phenylalkanes. Since shape selectivity factors of modified cyclodextrins have indicated no inclusion of the considered solutes in cyclodextrin cavities, enantioselective interactions most probably occur on the outer sphere of cyclodextrins. 相似文献