全文获取类型
收费全文 | 528篇 |
免费 | 17篇 |
国内免费 | 2篇 |
专业分类
化学 | 398篇 |
晶体学 | 13篇 |
力学 | 18篇 |
数学 | 62篇 |
物理学 | 56篇 |
出版年
2023年 | 2篇 |
2022年 | 5篇 |
2021年 | 5篇 |
2020年 | 8篇 |
2019年 | 8篇 |
2018年 | 10篇 |
2017年 | 14篇 |
2016年 | 10篇 |
2015年 | 15篇 |
2014年 | 11篇 |
2013年 | 19篇 |
2012年 | 26篇 |
2011年 | 34篇 |
2010年 | 31篇 |
2009年 | 19篇 |
2008年 | 29篇 |
2007年 | 21篇 |
2006年 | 28篇 |
2005年 | 9篇 |
2004年 | 20篇 |
2003年 | 40篇 |
2002年 | 30篇 |
2001年 | 24篇 |
2000年 | 23篇 |
1999年 | 15篇 |
1998年 | 7篇 |
1997年 | 9篇 |
1996年 | 5篇 |
1995年 | 1篇 |
1994年 | 1篇 |
1993年 | 3篇 |
1992年 | 3篇 |
1991年 | 4篇 |
1990年 | 2篇 |
1989年 | 1篇 |
1988年 | 7篇 |
1987年 | 8篇 |
1986年 | 6篇 |
1985年 | 6篇 |
1984年 | 4篇 |
1983年 | 3篇 |
1982年 | 2篇 |
1981年 | 3篇 |
1980年 | 1篇 |
1977年 | 5篇 |
1976年 | 2篇 |
1975年 | 1篇 |
1974年 | 5篇 |
1973年 | 1篇 |
1971年 | 1篇 |
排序方式: 共有547条查询结果,搜索用时 46 毫秒
131.
Stella S. Brudin Robert A. Shellie Paul R. Haddad Peter J. Schoenmakers 《Journal of chromatography. A》2010,1217(43):6742-6746
In the work presented here a novel approach to comprehensive two-dimensional liquid chromatography is evaluated. Ion chromatography is chosen for the first-dimension separation and reversed-phase liquid chromatography is chosen for the second-dimension separation mode. The coupling of these modes is made possible by neutralising the first-dimension effluent, containing KOH, prior to transfer to the second-dimension reversed-phase column. A test mixture of 24 low-molar-mass organic acids is used for optimisation of the system. Three food and beverage samples were analysed in order to evaluate the developed methodology, the resulting two-dimensional separation is near-orthogonal, the set-up is simple and all instrumental components are available commercially. The method proved to be robust and suitable for the analysis of wine, orange juice and yogurt. 相似文献
132.
Arianne Soliven Gary R. Dennis Georges Guiochon Emily F. Hilder Paul R. Haddad R. Andrew Shalliker 《Journal of chromatography. A》2010,1217(39):6085-6091
This study investigates the synthesis and chromatographic behaviour of an analytical size cyanopropyl “cyano” bonded silica monolith. Surface modification was undertaken by treating a neat silica monolith with chloro(3-cyanopropyl)dimethyl silane in dry heptane over a two day period. The resulting monolith showed stability over the duration of the testing program that involved flushing the column with more than 2000 column volumes of mobile phase. Efficiency measurements before and after sylation verified that the integrity of the silica monolith itself was not affected by the modification process, the highest number of theoretical plates (N/m) using anisole was 81,650. A brief selectivity test was then undertaken to assess methylene selectivity and phenyl selectivity. Elemental analysis was used to determine the homogeneity of the carbon load throughout the monolithic bed, and was compared to two commercial C18 and one ‘self’ modified C18 silica monoliths. The development of the in situ modification is also discussed. 相似文献
133.
134.
Kenneth Berg David Gove Kamel Haddad 《Proceedings of the American Mathematical Society》1998,126(3):899-905
Enveloping semigroups of topological actions of semigroups on compact spaces are studied. For zero dimensional spaces, and under modest conditions on , the enveloping semigroup is shown to be the Stone-\v{C}ech compactification if and only if some Cartesian product has the two-shift as a factor. Examples are discussed showing that, unlike in the measure theory case, positive entropy does not imply the existence of such a factor even if the Cartesian product has large entropy.
135.
Indirect photometric detection in capillary electrophoresis (CE) has been predominantly performed in the UV region, in part due to a lack of suitable high-intensity and low-noise light sources in the visible spectral region. A new photometric detector based on light-emitting diodes (LEDs) as light sources and compatible with a commercially available CE instrument has been designed and constructed and its performance evaluated. The utility of this detector was successfully demonstrated by the indirect photometric detection of anions using a dye as probe and absorbance measured in the visible region. The detector exhibited very low baseline noise (around 0.03 mAU), stable output, and improved upper limit of detection linearity (502 mAU) compared with previously used LED detectors. The detector was tested for indirect detection of anions separated with an electrolyte containing 4 mM Orange G as the indirect detection probe, 10 mM histidine as an isoelectric buffer, and 0.05% hydroxypropylmethylcellulose to suppress the electroosmotic flow. Extremely low detection limits were obtained ranging from 0.16-0.36 microM (excluding chloride 0.56 microM), with separation efficiencies in the range of 154,000-274,000 theoretical plates. 相似文献
136.
The feasibility of using capillary columns equipped with silica frits and packed with a polymer-based anion exchanger (Dionex AS9-HC) for CEC separations of inorganic anions has been investigated. Experiments using a conventional 25 cm packed bed, and mobile phase flow that is a combination of hydrodynamic and electroosmotic flow were used to demonstrate that by varying the applied voltage (electrophoresis component) or the concentration of the competing ion in the mobile phase (ion-exchange component), considerable changes in the separation selectivity could be obtained. Using an artificial neural network, this separation system was modelled and the results obtained used to determine the optimum conditions (9 mM perchlorate and −10 kV) for the separation of eight inorganic anions. When a short (8 cm) packed bed was used, with detection immediately following the packed section, the separation of eight test analytes in under 2.2 min was possible using pressure-driven flow and a simple step voltage gradient. A more rapid separation of these analytes was obtained by only applying high voltage (−30 kV), where many of the same analytes were separated in less than 20 s and with a different separation selectivity to that obtained in conventional ion-exchange or capillary electrophoresis separations. 相似文献
137.
Sensitive indirect photometric detection of inorganic and small organic anions by capillary electrophoresis using Orange G as a probe ion 总被引:2,自引:0,他引:2
This study addresses the two major problems in the use of dyes as highly absorbing probes for indirect photometric detection in capillary electrophoresis (CE). First, effective electroosmotic flow (EOF) modification or suppression to allow separation and detection of a wide mobility range of analytes is not straightforward when electrolytes containing increased dye concentrations are used. The suppression of EOF to less than + 5x10(-9) m(2)V(-1)s(-1) was achieved with a combination of a poly(ethylenimine) (PEI)-coated capillary and the addition of the neutral polymer hydroxypropylmethylcellulose (HPMC) to the background electrolyte. Second, the deterioration of baselines due to adsorption of the dye probe to the capillary wall is generally a problem. In this work, baseline quality at higher probe concentrations was significantly improved by a rather unusual but highly effective combination of a simultaneous application of a slight overpressure (25 mbar) at the injection end during the separation, and the use of a relatively narrow capillary of 50 microm inner diameter. Both measures would appear to be counterproductive. Optimisation of the probe concentration with regard to signal-to-noise ratio resulted in an electrolyte of 4 mM Orange G, 0.05% HPMC buffered at pH 7.7 by the addition of 10.0 mM histidine isoelectric buffer. Very high separation efficiencies of 128 000-297 000 plates were made possible by the relatively high probe concentration. Combined with excellent detection sensitivity, even with the introduction of hydrodynamic flow and a reduced optical path length, these measures resulted in limits of detection ranging from 0.216 to 0.912 microM with a deuterium lamp light source (248 nm) and from 0.147 to 0.834 microM with a 476 nm blue light-emitting diode (LED) light source. Reproducibility over 30 consecutive runs without changing the electrolyte was excellent, with relative standard deviation (RSD) values of 0.14-0.80% for migration time, 1.27-3.36% for peak area and 0.88-5.12% for peak heights. The optimised electrolyte was used for the analysis of inorganic anions in air filter samples, providing good agreement with results obtained by ion chromatography. 相似文献
138.
Ibrahim Haddad C. S. Marvel 《Journal of polymer science. Part A, Polymer chemistry》1974,12(6):1301-1311
Poly(phenylene sulfides) containing various amounts of pendant cyano groups were synthesized from m-benzenedithiol and the corresponding amounts of p-dibromobenzene and 3,5-dichlorobenzonitrile. The polymers prepared by the use of 10, 15, 20, and 25% of the nitrile-containing dichloro compound were slightly off-white with melting ranges below 100°C and had inherent viscosities of about 0.15 dl/g in hexamethylphosphoric triamide at 30°C. The polymers prepared from m-benzenedithiol and the stoichiometric amounts of 2,4-dichlorobenzonitrile or 3,5-dichlorobenzonitrile looked similar to those described above, yet they possessed much higher melting ranges. The poly(phenylene sulfide) prepared by the use of 2,4-dichlorobenzonitrile had an inherent viscosity of 0.06 dl/g while the polymer prepared from the 3,5-dichloro isomer had an inherent viscosity of 0.38 dl/g. All the polymers listed above were crosslinked by heating alone or in the presence of anthracene-9,10-bisnitrile oxide to give black resinous polymers that were insoluble in hexamethylphosphoric triamide in which the original polymers dissolved quite readily. 相似文献
139.
The stereoselectivity in [2+2] photocycloaddition was studied on System I. Compounds
,
, and
cyclize in high yield and the selectivity is higher than 94%. 相似文献
140.
Control of selectivity in the enantiomeric separation of three aromatic amino acids (phenylalanine, tyrosine and tryptophan) is demonstrated by electrokinetic capillary chromatography utilising temperature variations coupled with the use of sulphated-beta-cyclodextrin (s-beta-CD) as a pseudostationary phase. The concentration of s-beta-CD and temperature were used as experimental variables to control the observed selectivity. A double-coated capillary was used and proved very robust with reproducibility of migration times being <2.0% R.S.D. between runs and <2.6% on using a new capillary. The system was modelled successfully using an artificial neural network (ANN) comprising one input layer, two hidden layers and one output layer. The model accurately described the observed separations with a correlation coefficient of 0.999 being observed between predicted and observed migration times. Selectivity optimisation was achieved using the normalised resolution product and minimum resolution criteria, with both providing optima at different experimental conditions. The selectivity changes observed also allowed the estimation of electrolyte temperatures within the capillary at high operating currents (>100 microA). Using a 50 microm i.d. capillary and an electrolyte comprising 20 mM phosphate and 15 mM s-beta-CD, a temperature of 52 degrees C was calculated within the capillary at an applied voltage of +30 kV. 相似文献