全文获取类型
收费全文 | 242篇 |
免费 | 5篇 |
国内免费 | 3篇 |
专业分类
化学 | 151篇 |
晶体学 | 1篇 |
力学 | 1篇 |
数学 | 32篇 |
物理学 | 65篇 |
出版年
2023年 | 1篇 |
2022年 | 2篇 |
2021年 | 5篇 |
2020年 | 5篇 |
2019年 | 6篇 |
2018年 | 7篇 |
2017年 | 3篇 |
2016年 | 2篇 |
2015年 | 5篇 |
2014年 | 5篇 |
2013年 | 23篇 |
2012年 | 12篇 |
2011年 | 16篇 |
2010年 | 9篇 |
2009年 | 8篇 |
2008年 | 12篇 |
2007年 | 9篇 |
2006年 | 15篇 |
2005年 | 18篇 |
2004年 | 8篇 |
2003年 | 10篇 |
2002年 | 8篇 |
2001年 | 3篇 |
2000年 | 6篇 |
1999年 | 5篇 |
1998年 | 5篇 |
1997年 | 2篇 |
1996年 | 4篇 |
1995年 | 8篇 |
1993年 | 4篇 |
1992年 | 4篇 |
1991年 | 5篇 |
1989年 | 1篇 |
1988年 | 2篇 |
1987年 | 4篇 |
1986年 | 1篇 |
1985年 | 1篇 |
1984年 | 1篇 |
1982年 | 1篇 |
1981年 | 2篇 |
1977年 | 1篇 |
1969年 | 1篇 |
排序方式: 共有250条查询结果,搜索用时 593 毫秒
1.
We study two estimators of the long-range parameter of a covariance stationary linear process. We show that one of the estimators
achieve the optimal semiparametric rate of convergence, whereas the other has a rate of convergence as close as desired to
the optimal rate. Moreover, we show that the estimators are asymptotically normal with a variance, which does not depend on
any unknown parameter, smaller than others suggested in the literature. Finally, a small Monte Carlo study is included to
illustrate the finite sample relative performance of our estimators compared to other suggested semiparametric estimators.
More specifically, the Monte-Carlo experiment shows the superiority of the proposed estimators in terms of the Mean Squared
Error.
The first author research was funded by the Economic and Social Research Council (ESRC) reference number: R000238212. The
second author research was funded by the Ministry of Education, Culture, Sports and Technology of Japan, reference number:
09CE2002 and B(2)10202202. 相似文献
2.
Hidalgo ME Bascuñan L Quilhot W Fernández E Rubio C 《Photochemistry and photobiology》2005,81(6):1447-1449
Lichens synthesize and accumulate photoprotective compounds against possible damage induced by UV radiation in the photobiont. A biological model has been recently formulated that allows the use of lichens to evaluate changes at different UV radiation levels. The thermodynamics, photophysical and photochemical properties of lobaric acid were studied in acetonitrile, ethanol and Brij 35(3%) micelles at different pH values. Also the sun protector factor (SPF) was determined by in vitro methods. Lobaric acid was extracted from Stereoculon alpinum Laur. and characterized by means of standard procedures. Solutions were irradiated in oxygen and under nitrogen conditions with a UV medium pressure lamp. Lobaric acid absorbs at 287, 303 nm, and no fluorescence emission was observed. The maximum value of the molar extinction coefficient (5479.6 M(-1) cm(-1)) was obtained in Brij 35 at pH 12. Solubility is pH dependant and is highest in Brij 35 at pH 12 (4.45 x 10(-4) M). Photoconsumption quantum yields ranged between 10(-4) and 10(-5) in aerobic and anaerobic experimental conditions. Lobaric acid SPF was very low (0.5) compared with homosalate (4.0), (reference solar filter). Two pKa values, 5.05 (carboxylic acid group deprotonation) and 9.75 (phenolic OH deprotonation), were determined. 相似文献
3.
Coupled-column liquid chromatography with fluorescence detection was applied to the determination of o-phenylphenol and bitertanol residues in orange and banana fruits. After extraction with a mixture of acetone, dichloromethane-petroleum ether, and ethyl acetate, an extract aliquot of 100 microL was injected directly without any additional clean-up into the chromatographic system using two reversed phase C18 coupled columns. The LC-LC approach allowed automated sample clean up of the vegetal extracts, leading to a simple and rapid analytical procedure, with limits of quantification between 0.01 and 0.05 mg kg(-1). Recovery experiments performed on orange and banana samples fortified at different concentrations (0.01 - 4 mg kg(-1)) gave average recoveries between 70 and 113% with relative standard deviations lower than 15%. The procedure developed was finally applied to orange and banana samples from different geographical locations and the results were confirmed by GC-MS. 相似文献
4.
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
5.
A polarographic DC(tast) method with the static mercury drop electrode, SMDE, was developed for determination of the flotation collector ethyl xanthate (EtX) in the concentration range from 1x10(-5) to 8x10(-5) M. The potentiality of the method was demonstrated by evaluating the capacity of powdered galena ore (PbS) to adsorb EtX in a titration-like procedure. Sulfide could be determined simultaneously with EtX because in NaOH electrolyte their anodic waves are well separated (E(1/2) congruent with-0.72 and -0.42 V versus Ag/AgCl, respectively). In addition, a new FIA method was developed by adapting a simple device to the tip of the glass capillary of a mercury electrode and doing amperometric detection at a fixed potential of -0.1 V, always in the DC(tast) mode. No oxygen removal was required. Reproducible results were obtained at a frequency of 72 injections per h, with automatic renewal of the SMDE every second. The calibration curve for freshly prepared EtX standards rendered a straight line from 5x10(-6) to 8x10(-5) M with correlation coefficient of 0.997, suitable for real applications in flotation processes and its effluents. 相似文献
6.
The catalytic (C/Pd) hydrogenation of 3-arylamino-2-nitro-2-enones ( 1 ) in the presence of carboxylic ortho esters ( 2 ) affords 4-acyl-1-arylimidazoles ( 3 ) in yields (20–70%) which depend on the degree of substitution of the imidazole ring. The spectral properties of compounds 3 , and particularly the 13C-nmr spectra, reflect both the electronic and steric effects of the substituents on the π-electron delocalization and planarity of the bicyclic system. 相似文献
7.
J. Hidalgo E. Roldan D. Gonzlez-Arjona M. Snchez 《Journal of photochemistry and photobiology. A, Chemistry》1987,41(1)
Quantum yields and lifetimes of several derivatives of the Peganum Harmala and Rauwolfia alkaloids have been measured. The natural lifetimes of these alkaloids have been calculated from a modified form of the Strickler—Berg equation and the results are compared with the observed lifetimes. 相似文献
8.
Hidalgo C Rios C Hidalgo M Salvadó V Sancho JV Hernández F 《Journal of chromatography. A》2004,1035(1):153-157
An existing method for the determination of glyphosate and its main metabolite aminomethylphosphonic acid (AMPA) in water has been improved. It is based on precolumn derivatization with the fluorescent reagent 9-fluorenylmethylcloroformate (FMOC) followed by large-volume injection in a coupled-column LC system using fluorescence detection (LC-LC-FD). The derivatization step was slightly modified by changing parameters such as volume and/or concentration of sample and reagents to decrease the limits of quantification (LOQ) of glyphosate and AMPA to 0.1 microg/l. Additionally, the use of Amberlite IRA-900 for preconcentration of glyphosate, prior to the derivatization step, was investigated; the LOQ of glyphosate was lowered to 0.02 microg/l. Drinking, surface and ground water spiked with glyphosate and AMPA at 0.1-10 microg/l concentrations were analysed by the improved LC-LC-FD method. Recoveries were 87-106% with relative standard deviations lower than 8%. Drinking and ground water spiked with glyphosate at 0.02 and 0.1 microg/l were analysed after preconcentration on the anion-exchange resin with satisfactory recoveries (94-105%) and precision (better than 8%). 相似文献
9.
10.