全文获取类型
收费全文 | 20545篇 |
免费 | 1269篇 |
国内免费 | 1105篇 |
专业分类
化学 | 18846篇 |
晶体学 | 33篇 |
力学 | 625篇 |
综合类 | 69篇 |
数学 | 332篇 |
物理学 | 3014篇 |
出版年
2024年 | 42篇 |
2023年 | 267篇 |
2022年 | 492篇 |
2021年 | 458篇 |
2020年 | 642篇 |
2019年 | 621篇 |
2018年 | 588篇 |
2017年 | 752篇 |
2016年 | 929篇 |
2015年 | 868篇 |
2014年 | 841篇 |
2013年 | 1283篇 |
2012年 | 1360篇 |
2011年 | 1266篇 |
2010年 | 1031篇 |
2009年 | 1254篇 |
2008年 | 1107篇 |
2007年 | 1313篇 |
2006年 | 1070篇 |
2005年 | 989篇 |
2004年 | 902篇 |
2003年 | 766篇 |
2002年 | 598篇 |
2001年 | 394篇 |
2000年 | 366篇 |
1999年 | 350篇 |
1998年 | 311篇 |
1997年 | 262篇 |
1996年 | 275篇 |
1995年 | 255篇 |
1994年 | 218篇 |
1993年 | 178篇 |
1992年 | 162篇 |
1991年 | 192篇 |
1990年 | 108篇 |
1989年 | 86篇 |
1988年 | 63篇 |
1987年 | 46篇 |
1986年 | 38篇 |
1985年 | 35篇 |
1984年 | 28篇 |
1983年 | 19篇 |
1982年 | 24篇 |
1981年 | 18篇 |
1980年 | 9篇 |
1979年 | 11篇 |
1978年 | 8篇 |
1976年 | 7篇 |
1973年 | 4篇 |
1959年 | 2篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
991.
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
992.
Improvement of a sample preparation method assisted by sodium deoxycholate for mass‐spectrometry‐based shotgun membrane proteomics† 下载免费PDF全文
In current shotgun‐proteomics‐based biological discovery, the identification of membrane proteins is a challenge. This is especially true for integral membrane proteins due to their highly hydrophobic nature and low abundance. Thus, much effort has been directed at sample preparation strategies such as use of detergents, chaotropes, and organic solvents. We previously described a sample preparation method for shotgun membrane proteomics, the sodium deoxycholate assisted method, which cleverly circumvents many of the challenges associated with traditional sample preparation methods. However, the method is associated with significant sample loss due to the slightly weaker extraction/solubilization ability of sodium deoxycholate when it is used at relatively low concentrations such as 1%. Hence, we present an enhanced sodium deoxycholate sample preparation strategy that first uses a high concentration of sodium deoxycholate (5%) to lyse membranes and extract/solubilize hydrophobic membrane proteins, and then dilutes the detergent to 1% for a more efficient digestion. We then applied the improved method to shotgun analysis of proteins from rat liver membrane enriched fraction. Compared with other representative sample preparation strategies including our previous sodium deoxycholate assisted method, the enhanced sodium deoxycholate method exhibited superior sensitivity, coverage, and reliability for the identification of membrane proteins particularly those with high hydrophobicity and/or multiple transmembrane domains. 相似文献
993.
Mohammad Saraji Taghi Khayamian Zahra Hashemian 《Journal of separation science》2014,37(23):3518-3525
In this work, a polypyrrole/multiwalled carbon nanotubes composite decorated with Fe3O4 nanoparticles was chemically synthesized and applied as a novel adsorbent for the extraction of methocarbamol from human plasma. Electrospray ionization ion mobility spectrometry was used for the determination of the analyte. The properties of the magnetic‐modified adsorbent were characterized by scanning electron microscopy, transmission electron microscopy, Fourier transform IR spectroscopy, and X‐ray diffraction. The effects of experimental parameters on the extraction efficiency of the sorbent were investigated. Under the optimized conditions, the linear dynamic range was found to be 2–150 ng/mL with the detection limit of 0.9 ng/mL. The relative standard deviation was 5.3% for three replicate measurements of methocarbamol in plasma sample. The extraction efficiency of the sorbent for the determination of different drugs with various polarities was also compared to that of Fe3O4‐polypyrrole and Fe3O4‐multiwalled carbon nanotubes sorbents. Finally, the method was used for the determination of methocarbamol in blood samples. 相似文献
994.
Microextraction by packed sorbent liquid chromatography with time‐of‐flight mass spectrometry of triazines employing a molecularly imprinted polymer† 下载免费PDF全文
Felipe Nascimento Andrade Álvaro José Santos‐Neto Fernando Mauro Lanças 《Journal of separation science》2014,37(21):3150-3156
Molecularly imprinted polymers for the determination of triazines were synthesized by precipitation using atrazine as template, methacrylic acid as functional monomer, ethylene glycol dimethacrylate as crosslinker, and 2,2′‐azobisisobutrynitrile as initiator. The polymers were characterized by infrared spectroscopy and scanning electron microscopy and packed in a device for microextraction by packed sorbent aiming for the preconcentration/cleanup of herbicides, such as atrazine, simazine, simetryn, ametryn, and terbutryn in corn samples. Liquid chromatography coupled with time‐of‐flight mass spectrometry was used for the separation and determination of the herbicides. The selectivity coefficient of molecularly imprinted polymers was compared with that of nonimprinted polymer for the binary mixtures of atrazine/propanil and atrazine/picloram, and the values obtained were 15.6 and 2.96, respectively. The analytical curve ranged from 10 to 80 μg/kg (r = 0.989) and the limits of detection and quantification in the corn matrices were 3.3 and 10 μg/kg, respectively. Intra‐ and interday precisions were < 14.8% and accuracy was better than 90.9% for all herbicides. Polymer synthesis was successfully applied to the cleanup and preconcentration of triazines from fortified corn samples with 91.1–109.1% of recovery. 相似文献
995.
On‐line solid‐phase extraction for liquid chromatography–mass spectrometry analysis of pesticides 下载免费PDF全文
Public concern about pesticides in food and water has increased dramatically in the last two decades. In order to guarantee consumers’ health and safety, analytical methods that could provide fast and reliable answers without compromising accuracy and precision are required. Sample treatment is probably the most tedious and time‐consuming step in many analytical procedures and, despite the significant advances in chromatographic separations and mass spectrometry techniques, sample treatment is still one of the most important parts of the analytical process for achieving good analytical results. Therefore, over the last years, considerable efforts have been made to simplify the stage and to develop fast, accurate, and robust methods that allow the determination of a wide range of pesticides without compromising the integrity of the extraction process. This review article intends to give a short overview of recently developed on‐line solid‐phase extraction, preconcentration, and clean‐up procedures for the determination of pesticides in complex matrices by liquid chromatography–mass spectrometry techniques. 相似文献
996.
Gang Cao Qiyang Shou Qinglin Li Jianping Jiang Xiaocheng Chen 《Journal of separation science》2014,37(21):3090-3093
The processing procedure can alter the nature and chemical transformation of traditional Chinese medicine to accommodate different clinical dispensing and preparation requirements. In this study, static headspace‐multicapillary column with gas chromatography coupled to ion mobility spectrometry was developed for the rapid and sensitive discrimination of crude and processed traditional Chinese medicine. Using Radix Paeoniae Alba as a traditional Chinese medicine model, the combined power of this approach was illustrated by classifying the crude and processed Radix Paeoniae Alba samples into two main categories. The contents of the main components in Radix Paeoniae Alba varied significantly. The established method could promote the use of ion mobility spectrometry in intrinsic quality control and differentiation of herbal medicines from other processed products or preparations. 相似文献
997.
Noel Kong Rong Yi Sarah Zhao Jasmeet Sandhu Geoffrey Lam Devan Loganathan Barbara Morrissey 《Journal of separation science》2014,37(21):3015-3023
A sensitive hydrophilic interaction liquid chromatography coupled with tandem mass spectrometry method was developed and validated for the simultaneous detection and quantification of etilefrine and oxilofrine in equine blood plasma and urine. The method is highly sensitive and specific with good precision and accuracy. In plasma the limit of detection and limit of quantification are 0.03 and 0.1 ng/mL, respectively, for both analytes. In urine the limit of detection and limit of quantification are 0.3 and 1 ng/mL, respectively, for both analytes. The suitability of the method for doping control analysis in equine species is demonstrated by analyzing postadministration samples collected after a single intravenous administration of 50 mg etilefrine to a standardbred mare. Etilefrine was detected up to 120 h in urine and up to 48 h in plasma. Etilefrine is highly conjugated in equine urine whereas it exists in the free form in equine plasma. Therefore, enzyme hydrolysis prior to sample preparation is recommended for the detection and quantification of etilefrine and oxilofrine in equine urine. 相似文献
998.
随着科学技术的飞速发展,质谱检测及其联用技术方法正以前所未有的速度、广度和深度全面渗透到环境分析化学中,其在环境监测中的使用已经或正在日常化.近年来,一些高分辨质谱及其与色谱等的联用技术在目标污染物和非目标污染物的同时甄别鉴定和分析中发挥了重要作用,其对于阐明污染物在环境的归趋具有重要意义.本文对质谱技术及其与气相色谱和液相色谱的联用技术在污染物尤其是新型污染物分析中的进展进行了总结,并对高分辨质谱技术的环境应用研究给于关注,对环境质谱技术的发展方向进行了展望. 相似文献
999.
1000.
FAN RuoJing ZHANG Fang WANG HaoYang ZHANG Li ZHANG Jing ZHANG Ying YU ChongTian GUO YinLong 《中国科学:化学(英文版)》2014,57(5):669-677
The widespread use of pesticides induces heavy adverse effects on human health,especially for the pregnant women and the newborns.In this study,a screening method has been developed for the determination of multi-pesticides in maternal and umbilical cord sera.All pesticides in sera were collected using solid phase extraction(SPE),and analyzed by gas chromatography-quadrupole time of flight mass spectrometry(GC-QTOF MS).To set up the quality criteria,a database of 50 pesticides was created and the accurate masses of 3 up to 5 representative ions with their intensity ratios were included for each pesticide.In addition,a novel"identification points"(IPs)system relying on the accurate MS1 and MS2 spectra was used to interpret the data for each suspected pesticide.The methodology was then applied to a pair of maternal and umbilical cord sera.A total of six pesticide residues were screened out successfully.In conclusion,GC-QTOF MS combined with an accurate mass database seemed to be one of the most efficient tools for systematic pesticide analysis. 相似文献