全文获取类型
收费全文 | 41560篇 |
免费 | 8983篇 |
国内免费 | 2450篇 |
专业分类
化学 | 44990篇 |
晶体学 | 430篇 |
力学 | 732篇 |
综合类 | 91篇 |
数学 | 2592篇 |
物理学 | 4158篇 |
出版年
2024年 | 15篇 |
2023年 | 85篇 |
2022年 | 183篇 |
2021年 | 376篇 |
2020年 | 1434篇 |
2019年 | 2747篇 |
2018年 | 1190篇 |
2017年 | 864篇 |
2016年 | 3597篇 |
2015年 | 3758篇 |
2014年 | 3742篇 |
2013年 | 4415篇 |
2012年 | 3400篇 |
2011年 | 2696篇 |
2010年 | 3246篇 |
2009年 | 3152篇 |
2008年 | 2755篇 |
2007年 | 2067篇 |
2006年 | 1745篇 |
2005年 | 1897篇 |
2004年 | 1646篇 |
2003年 | 1511篇 |
2002年 | 2236篇 |
2001年 | 1547篇 |
2000年 | 1417篇 |
1999年 | 502篇 |
1998年 | 142篇 |
1997年 | 115篇 |
1996年 | 62篇 |
1995年 | 61篇 |
1994年 | 43篇 |
1993年 | 40篇 |
1992年 | 39篇 |
1991年 | 44篇 |
1990年 | 29篇 |
1989年 | 19篇 |
1988年 | 28篇 |
1987年 | 19篇 |
1986年 | 21篇 |
1985年 | 20篇 |
1984年 | 7篇 |
1983年 | 11篇 |
1982年 | 15篇 |
1981年 | 8篇 |
1980年 | 7篇 |
1979年 | 7篇 |
1978年 | 8篇 |
1977年 | 7篇 |
1975年 | 4篇 |
1936年 | 2篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
961.
Kinetics of radical‐molecule reactions in aqueous solution: A benchmark study of the performance of density functional methods 下载免费PDF全文
The performance of 18 density functional approximations has been tested for a very challenging task, the calculations of rate constants for radical‐molecule reactions in aqueous solution. Despite of the many difficulties involved in such an enterprise, six of them provide high quality results, and are recommended to that purpose. They are LC‐ωPBE, M06‐2X, BMK, B2PLYP, M05‐2X, and MN12SX, in that order. This trend was obtained using experimental data as reference. The other relevant aspects used in this benchmark are: (i) the SMD model for mimicking the solvent; (ii) the conventional transition state, the zero‐curvature tunneling correction, and the limit imposed by diffusion for the calculation of the rate constants. Even though changing any of these aspects might alter the trend in performance, at least, when using them, the aforementioned functionals can be successfully used to obtain high quality kinetic data for the kind of reactions investigated in this work. © 2014 Wiley Periodicals, Inc. 相似文献
962.
963.
Simultaneous determination of nine lignans from Schisandra chinensis extract using ultra‐performance liquid chromatography with tandem mass spectrometry in rat plasma,urine, and gastrointestinal tract samples: Application to the pharmacokinetic study of Schisandra chinensis 下载免费PDF全文
You‐Jin Kim Hee Ju Lee Chul Young Kim Sun‐Young Han Young‐Won Chin Young Hee Choi 《Journal of separation science》2014,37(20):2851-2863
The fruit of Schisandra chinensis is a well‐known herbal medicine and dietary supplement due to a variety of biological activities including antihepatotoxic and antihyperlipidemic activities. However, the simultaneous validation methodology and pharmacokinetic investigation of nine lignans of S. chinensis extract in biological samples have not been proved yet. Thus, the present study was undertaken to develop the proper sample preparation method and simultaneous analytical method of schisandrol A, gomisin J, schisandrol B, tigloylgomisin H, angeloylgomisin H, schisandrin A, schisandrin B, gomisin N, and schisandrin C in the hexane‐soluble extract of S. chinensis to apply for the pharmacokinetic study in rats. All intra‐ and interprecisions of nine lignans were below 13.7% and accuracies were 85.1–115% and it is enough to evaluate the pharmacokinetic parameters after both intravenous and oral administration of hexane‐soluble extract of S. chinensis to rats. 相似文献
964.
Construction of a portable sample preparation device with a magnetic poly(methacrylic acid‐co‐ethylene dimethacrylate) monolith as the extraction medium and its application in the enrichment of UV filters in water samples 下载免费PDF全文
Jing Li Li Xu Qiong‐Wei Yu Zhi‐Guo Shi Ting Zhang Yan Liu 《Journal of separation science》2014,37(19):2732-2737
A portable sample preparation device with a magnetic polymer monolith as the extraction medium was constructed. The monolith was synthesized by polymerizing methacrylic acid and ethylene dimethacrylate around a cylindrical magnet. In this way, the monolith with a magnetic core could be readily attached to the extraction device by magnetism. The constructed device was evaluated for the enrichment of UV filters in water samples, followed by high‐performance liquid chromatographic analysis. The extraction efficiency for the targets was satisfactory with no matrix interference. Good linearities were obtained for the UV filters with the correlation coefficients >0.9986. The limits of detection and quantification for the UV filters were 0.3–0.8 and 1.0–2.4 ng/mL, respectively. The recoveries of the UV filters from the spiked water samples at the concentration of 100 ng/mL were 95.3–101.7%, with relative standard deviations <10%. Accordingly, the proposed portable device was demonstrated to be suitable for on‐site simultaneous sampling, purification, and preconcentration within a single step. 相似文献
965.
Development of an automated dual‐mode supercritical fluid chromatography and reversed‐phase liquid chromatography mass‐directed purification system for small‐molecule drug discovery 下载免费PDF全文
Kanaka Hettiarachchi May Kong Andersen Yun John R. Jacobsen Qifeng Xue 《Journal of separation science》2014,37(7):775-781
We report the development of a dual‐mode mass‐directed supercritical fluid chromatography and reversed‐phase liquid chromatography purification system. The addition of a third pump allows for flexible mobile phase control between the two techniques, and enables operation of either chromatography mode within minutes by activation of a set of switching valves on a single system. Software control, fluidic pathways, interface to the mass spectrometer, and fraction collection have been modified for compatibility between both separation methods. The conditioning solvent and tuning parameters for the mass spectrometer were adjusted to achieve an ideal signal trace in either mode with good linearity (r2 > 0.970) over a range of concentrations and minimal noise for accurate peak detection and isolation. The registration success rate is 90% and overall sample recovery for either technique is 80?90%. Combining two orthogonal separation and purification modes in one single system has improved the purification throughput of complex mixtures and has been a valuable, cost‐saving tool in our laboratory. 相似文献
966.
5‐O‐Caffeoylshikimic acid from Solanum somalense leaves: Advantage of centrifugal partition chromatography over conventional column chromatography 下载免费PDF全文
Saïda Chideh Serge Pilard Jacques Attoumbré Robert Saguez Alshaimaa Hassan‐Abdallah Dominique Cailleu Anne Wadouachi Sylvie Baltora‐Rosset 《Journal of separation science》2014,37(17):2331-2339
Solanum somalense leaves, used in Djibouti for their medicinal properties, were extracted by MeOH. Because of the high polyphenol and flavonoid contents of the extract, respectively, determined at 80.80 ± 2.13 mg gallic acid equivalent/g dry weight and 24.4 ± 1.01 mg quercetin equivalent/g dry weight, the isolation and purification of the main polyphenols were carried out by silica gel column chromatography and centrifugal partition chromatography. Column chromatography led to 11 enriched fractions requiring further purification, while centrifugal partition chromatography allowed the easy recovery of the main compound of the extract. In a solvent system composed of CHCl3/MeOH/H2O (9.5:10:5), 21.8 mg of this compound at 97% purity was obtained leading to a yield of 2.63%. Its structure was established as 5‐O‐caffeoylshikimic acid by mass spectrometry and NMR spectroscopy. This work shows that S. somalense leaves contain very high level of 5‐O‐caffeoylshikimic acid (0.74% dry weight), making it a potential source of production of this secondary metabolite that is not commonly found in nature but could be partly responsible of the medicinal properties of S. somalense leaves. 相似文献
967.
Fitting formula for the injection volume of a gas chromatograph for radio‐xenon sampling in the lower troposphere 下载免费PDF全文
Liu Shu‐jiang Chen Zhan‐ying Wang Shi‐lian Chang Yin‐zhong Li Qi Fan Yuan‐qing Zhao Yun‐gang Jia Huai‐mao Zhang Xin‐jun Wang Jun 《Journal of separation science》2014,37(12):1456-1459
GC is usually used for xenon concentration and radon removal in the International Monitoring System of the Comprehensive Nuclear‐Test‐Ban Treaty. In a gas chromatograph, the injection volume is defined to calculate the column capacity. In this paper, the injection volume was investigated and a fitting formula for the injection volume was derived and discussed subsequently. As a consequence, the xenon injection volume exponentially decreased with the column temperature increased, but exponentially increased as the flow rate increased. 相似文献
968.
Determination of cysteine,homocysteine, cystine,and homocystine in biological fluids by HPLC using fluorosurfactant‐capped gold nanoparticles as postcolumn colorimetric reagents 下载免费PDF全文
We have demonstrated for the first time the suitability of fluorosurfactant‐capped spherical gold nanoparticles as HPLC postcolumn colorimetric reagents for the direct assay of cysteine, homocysteine, cystine, and homocystine. The success of this work was based on the use of an on‐line tris(2‐carboxyethyl)phosphine reduction column for cystine and homocystine. Several parameters affecting the separation efficiency and the postcolumn colorimetric detection were thoroughly investigated. Under the optimized conditions, cysteine, homocysteine, cystine, and homocystine in human urine and plasma samples were determined. Detection limits for cysteine, homocysteine, cystine, and homocystine ranged from 0.16–0.49 μM. The accuracy in terms of recoveries ranged between 94.0–102.1%. This proposed method was rapid, inexpensive, and simple. 相似文献
969.
Multiresidue method for the fast determination of pesticides in nutraceutical products (Camellia sinensis) by GC coupled to triple quadrupole MS 下载免费PDF全文
Gerardo Martínez‐Domínguez Patricia Plaza‐Bolaños Roberto Romero‐González Antonia Garrido Frenich 《Journal of separation science》2014,37(6):665-674
A method based on QuEChERS (quick, easy, cheap, effective, rugged, and safe) has been developed and validated for the determination and quantification of more than 140 pesticides in nutraceutical products obtained from green tea (Camellia sinensis). Extraction was performed with acidified acetonitrile (acetic acid 1%, v/v) and a clean‐up step using primary secondary amine (50 mg), graphitized black carbon (100 mg) and magnesium sulfate (200 mg) was needed. Pesticide determination was achieved utilizing GC coupled to triple quadrupole MS/MS using the selective‐reaction monitoring mode. The total run time was 23 min. Pesticides were quantified using matrix‐matched calibration. Recoveries ranged from 70 to 120% and relative SD was lower than 25% at 10, 50, and 100 μg/kg. LOQs were lower than 10 μg/kg. 148 pesticides were validated. The validated method was applied to commercial nutraceutical products, detecting 4,4‐dichlorobenzophenone (28 μg/kg), o,p′‐dicofol (38 μg/kg) and p,p‐dicofol (44 μg/kg) in a few samples. 相似文献
970.
Ultra‐trace level determination of diquat and paraquat residues in surface and drinking water using ion‐pair liquid chromatography with tandem mass spectrometry: A comparison of direct injection and solid‐phase extraction methods 下载免费PDF全文
Jin‐Aa Oh Jun‐Bae Lee Soo‐Hyung Lee Ho‐Sang Shin 《Journal of separation science》2014,37(20):2900-2910
Direct injection and solid‐phase extraction methods for the determination of diquat and paraquat in surface and drinking water were developed using liquid chromatography with tandem mass spectrometry. The signal intensities of analytes based on six ion‐pairing reagents were compared with each other, and 12.5 mM nonafluoropentanoic acid was selected as the best suited amongst them. A clean‐up method was developed using Oasis hydrophilic–lipophilic balance; this was compared to the direct injection method, with respect to limits of detection, interference, precision, and accuracy. Limits of quantification of diquat and paraquat were 0.03 and 0.01 μg/L using the direct injection method, and 0.002 and 0.001 μg/L using the hydrophilic–lipophilic balance method. When the hydrophilic–lipophilic balance method was used to analyze target compounds in 114 surface water and 30 drinking water samples, paraquat and diquat were detected within a concentration range of 0.001–0.12 and 0.002–0.038 μg/L in surface water, respectively. When the direct injection method was used to analyze target compounds in the same samples, the detected concentrations of paraquat and diquat were within 25% in samples being >0.015 μg/L using the hydrophilic–lipophilic balance method. The liquid chromatography with tandem mass spectrometry method using direct injection can thus be used for routine monitoring of paraquat and diquat in surface and drinking water. 相似文献