全文获取类型
收费全文 | 3496篇 |
免费 | 229篇 |
国内免费 | 108篇 |
专业分类
化学 | 3722篇 |
晶体学 | 11篇 |
力学 | 2篇 |
综合类 | 9篇 |
数学 | 1篇 |
物理学 | 88篇 |
出版年
2024年 | 4篇 |
2023年 | 51篇 |
2022年 | 154篇 |
2021年 | 74篇 |
2020年 | 115篇 |
2019年 | 113篇 |
2018年 | 127篇 |
2017年 | 195篇 |
2016年 | 206篇 |
2015年 | 199篇 |
2014年 | 156篇 |
2013年 | 255篇 |
2012年 | 259篇 |
2011年 | 280篇 |
2010年 | 258篇 |
2009年 | 308篇 |
2008年 | 152篇 |
2007年 | 194篇 |
2006年 | 144篇 |
2005年 | 138篇 |
2004年 | 110篇 |
2003年 | 109篇 |
2002年 | 39篇 |
2001年 | 21篇 |
2000年 | 24篇 |
1999年 | 30篇 |
1998年 | 26篇 |
1997年 | 32篇 |
1996年 | 21篇 |
1995年 | 19篇 |
1994年 | 4篇 |
1993年 | 6篇 |
1992年 | 1篇 |
1991年 | 1篇 |
1990年 | 1篇 |
1989年 | 2篇 |
1988年 | 1篇 |
1987年 | 1篇 |
1986年 | 1篇 |
1983年 | 1篇 |
1982年 | 1篇 |
排序方式: 共有3833条查询结果,搜索用时 15 毫秒
991.
The ultrasonic nebulization extraction coupled with headspace hollow fiber microextraction (UNE-HS-HFME) was applied for the extraction of pesticides from root of Panax ginseng C.A. Mey. Experimental parameters, which affect the performances of ultrasonic nebulization extraction coupled with headspace hollow fiber microextraction, such as the kind of acceptor solvent in the pore of the fiber wall, the sample amount, extraction time, salt concentration in extraction solvent, pH of the acceptor solution, the elution time, and times were studied and optimized. The analytes were determined by high-performance liquid chromatography. The detection limits for simeton, monolinuron, chlortoluron, karmex, and prebane are 20.9, 18.4, 18.2, 12.4, and 22.2 μg/kg, respectively. Besides volatile and semi-volatile compounds, the non-volatile compounds also can be determined by the proposed method. The extraction and enrichment process can be performed simultaneously. 相似文献
992.
León-González Z Ferreiro-Vera C Priego-Capote F de Castro MD 《Journal of chromatography. A》2011,1218(20):3013-3021
The in vivo metabolism of the xenobiotic agent 2-ethylhexyl 4-(N,N-dimethylamino)benzoate (EDP), a UV filter commonly used in sunscreen cosmetic products, was studied by targeting metabolomics analysis in human urine. The metabolomic study involved the use of urine from male and female volunteers before and after application of an EDP-containing sunscreen cosmetic. The metabolism of EDP in urine was studied by using the triple quadrupole detector in a combination of Precursor Ion Scanning and Neutral Loss Scanning modes, with and without enzymatic hydrolysis. Detected metabolites were subsequently confirmed as glucuronide conjugates of 4-(N,N-dimethylamino)benzoic acid and 4-(N-methylamino)benzoic acid by liquid chromatography-time-of-flight/mass spectrometry (LC-TOF/MS) in the accurate mass mode. In this way, the existence of phase II metabolism in the detoxification of EDP by effects of the lipophilic character of this sunscreen agent was confirmed. Hence, to study the in vivo metabolism of EDP, a fully automated method using a solid-phase extraction (SPE) workstation connected on-line to a liquid chromatograph and a triple quadrupole mass analyzer (LC-MS/MS) was developed. The ensuing hyphenated method is very simple and requires minimal human intervention. Following thorough optimization of the SPE and LC-MS/MS conditions, the analytical procedure was validated and standard addition calibration used for the quantitative correction of matrix effects. The proposed method was applied to determine the phase I metabolites of EDP in urine samples and afforded limits of detection from 0.1 to 1.1 ng and accuracy of 91-107% with relative standard deviations in the range 1.5-8.7% (sample volume: 100 μL). Based on the results of in vivo percutaneous absorption of a single application of the sunscreen, about 0.5% of the amount of the applied EDP is excreted in urine. 相似文献
993.
Ionic liquid-based dispersive liquid-liquid microextraction was developed for the extraction and preconcentration of aromatic amine from environmental water. A suitable mixture of extraction solvent (100 μL, 1-butyl-3-methylimidazolium hexafluorophoshate) and dispersive solvent (750 μL, methanol) were injected into the aqueous samples (10.00 mL), forming a cloudy solution. After centrifuging, enriched analytes in the sediment phase were determined by HPLC-UV. The effect of various factors, such as the extraction and dispersive solvent, sample pH, extraction time and salt effect were investigated. Under optimum conditions, enrichment factors for 2-anilinoethanol, o-chloroaniline and 4-bromo-N,N-dimethylaniline were above 50 and the limits of detection (LODs) were 0.023, 0.015 and 0.026 ng/mL, respectively. Their linear ranges were 0.8-400 ng/mL for 2-anilinoethanol, 0.5-200 ng/mL for o-chloroaniline and 0.4-200 ng/mL for 4-bromo-N,N-dimethylaniline, respectively. Relative standard deviations (RSDs) were below 5.0%. The relative recoveries from samples of environmental water were in the range of 82.0-94.0%. Compared with other methods, dispersive liquid-liquid microextraction is simple, rapid, sensitive and economical. 相似文献
994.
Hollow fiber-based liquid-liquid-liquid microextraction (HF-LLLME) followed by flow injection analysis and diode array detection (FIA-DAD) was applied as a simple and sensitive quantitative method for the determination of phenazopyridine in urine and plasma samples. Flow injection system included a conventional HPLC system (without a chromatographic column) and a diode array detector. The extraction of phenazopyridine was carried out using diphenyl ether as the organic phase for filling the pores of the hollow fiber wall, and 0.1 M H(2)SO(4) solution as acceptor phase in the lumen of the fiber. The factors affecting the HF-LLLME and flow injection analysis including type of organic solvent, pH of donor phase, extraction temperature, extraction time, stirring rate, and pH of mobile phase were investigated and the optimal extraction conditions were established. With the consumption of 5 mL of sample solution, the enrichment factor was about 230. The limit of detection was 0.5 μg/L with inter- and intra-day precision being (RSD%) 6.9 and 4.9, respectively. Excellent linearity was found between 5 and 200 μg/L. 相似文献
995.
Chiva-Blanch G Urpi-Sarda M Rotchés-Ribalta M Zamora-Ros R Llorach R Lamuela-Raventós RM Estruch R Andrés-Lacueva C 《Journal of chromatography. A》2011,1218(5):698-705
Beer is one of the most commonly consumed undistilled alcoholic beverages in many countries. In recent studies, the stilbenes resveratrol and piceid have been found in some hop varieties which are used in the production of beer. Therefore, they could be transferred to beer. The aim of the present work was to validate a method to study the potential content of trans- and cis-resveratrol and piceid in 110 commercial beers from around the world. The resveratrol and piceid contents of 110 beers were analyzed by liquid chromatography-tandem mass spectrometry (LC-MS/MS) after a solid-phase extraction (SPE) using optimized and validated procedures for the beer matrix. The beer matrix effect was also studied. Stilbenes were found in quantifiable amounts in 92 beers, while concentrations below the limit of quantification (LOQ) were found in 18 beers. Resveratrol was found in the range of 1.34-77.0μg/L in 79% of the beers analyzed, and piceid was found in the range of 1.80-27.3μg/L in only 33% of them. The mean of total resveratrol in all the beers was 14.7±20.5μg/L. The content of resveratrol has been compared with other resveratrol containing foods. A serving of beer contains similar amounts of stilbenes as berries, less than chocolate and grape products but more than pistachios, peanuts or tomatoes. Overall, beer is one of the products with the lowest levels of total resveratrol (μg/L), and despite its high consumption it should not be considered as a representative source of resveratrol. 相似文献
996.
In this study, the investigation of the volatile compounds of dried rhizomes of Coptis chinensis Franch, C. deltoidea C. Y. Cheng et Hsiao, and C. teeta Wall was carried out to complete the chemical composition of these valuable natural products. Volatile profiles were established and compared after headspace solid-phase microextraction (HS-SPME) using a polydimethylsiloxane/divinylbenzene (PDMS/DVB, 65 μm) fibre coupled to comprehensive 2D gas chromatography time-of-flight mass spectrometry (GC×GC-TOFMS). Analyses were performed and compared on two column-phase combinations (non-polar/polar and polar/non-polar). The majority of the identified compounds eluted as well-separated (pure) components as a result of high-resolution capability of the GC×GC method, which significantly reduces co-elution. Therefore, this increases the likelihood that pure mass spectra can be obtained. More than 290 volatile and semi-volatile organic compounds were tentatively characterized by means of GC×GC in tandem with TOFMS detection. Improved result interpretations were obtained in terms of compound classification based on the organized structure of the peaks of structurally related compounds in the GC×GC contour plot. These compounds are distributed over the chemical groups of hydrocarbons, acids, alkenes, alkynes, aldehydes, ketones, alcohols, esters, furans, and terpenoids. Among all the chemical groups, terpenoids present the higher number of identified compounds (44), alkenes (41), and aldehydes and ketones (28). This study completed the volatile phytochemical analysis of the headspace composition of various Coptis species rhizomes, and should serve as a means to identify the difference between the rhizomes and may also be useful to confirm individual species based on their volatile chemical profile. 相似文献
997.
A novel solid-phase microextraction (SPME) fiber coated with multiwalled carbon nanotubes/polypyrrole (MWCNTs/Ppy) was prepared with an electrochemical method and used for the extraction of pyrethroids in natural water samples. The results showed that the MWCNTs/Ppy coated fiber had high organic stability, and remarkable acid and alkali resistance. In addition, the MWCNTs/Ppy coated fiber was more effective and superior to commercial PDMS and PDMS/DVD fibers in extracting pyrethroids in natural water samples. Under optimized conditions, the calibration curves were found to be linear from 0.001 to 10 μg mL−1 for five of the six pyrethroids studied, the exception being fenvalerate (which was from 0.005 to 10 μg mL−1), and detection limits were within the range 0.12-0.43 ng mL−1. The recoveries of the pyrethroids spiked in water samples at 10 ng mL−1 ranged from 83 to 112%. 相似文献
998.
Methyl tert-butyl ether (MTBE) is commonly used as chemical additive to increase oxygen content and octane rating of reformulated gasoline. Despite its impact on enhancing cleaner combustion of gasoline, MTBE poses a threat to surface and ground water when gasoline is released into the environment. Methods for onsite analysis of MTBE in water samples are also needed. A less common technique for MTBE detection from water is ion mobility spectrometry (IMS). We describe a method for fast sampling and screening of MTBE from water by solid phase microextraction (SPME) and IMS. MTBE is adsorbed from the head space of a sample to the coating of SPME fiber. The interface containing a heated sample chamber, which couples SPME and IMS, was constructed and the SPME fiber was introduced into the sample chamber for thermal desorption and IMS detection of MTBE vapors. The demonstrated SPME-IMS method proved to be a straightforward method for the detection of trace quantities of MTBE from waters including surface and ground water. We determined the relative standard deviation of 8.3% and detection limit of 5 mg L−1 for MTBE. Because of short sampling, desorption, and detection times, the described configuration of combined SPME and IMS is a feasible method for the detection of hazardous substances from environmental matrices. 相似文献
999.
1000.