全文获取类型
收费全文 | 2606篇 |
免费 | 180篇 |
国内免费 | 142篇 |
专业分类
化学 | 2411篇 |
晶体学 | 2篇 |
力学 | 63篇 |
综合类 | 63篇 |
数学 | 120篇 |
物理学 | 269篇 |
出版年
2024年 | 7篇 |
2023年 | 53篇 |
2022年 | 179篇 |
2021年 | 148篇 |
2020年 | 113篇 |
2019年 | 110篇 |
2018年 | 90篇 |
2017年 | 123篇 |
2016年 | 95篇 |
2015年 | 102篇 |
2014年 | 92篇 |
2013年 | 176篇 |
2012年 | 221篇 |
2011年 | 121篇 |
2010年 | 109篇 |
2009年 | 132篇 |
2008年 | 141篇 |
2007年 | 126篇 |
2006年 | 111篇 |
2005年 | 107篇 |
2004年 | 78篇 |
2003年 | 63篇 |
2002年 | 57篇 |
2001年 | 38篇 |
2000年 | 42篇 |
1999年 | 41篇 |
1998年 | 30篇 |
1997年 | 41篇 |
1996年 | 31篇 |
1995年 | 27篇 |
1994年 | 21篇 |
1993年 | 8篇 |
1992年 | 15篇 |
1991年 | 14篇 |
1990年 | 9篇 |
1989年 | 9篇 |
1988年 | 8篇 |
1987年 | 6篇 |
1986年 | 10篇 |
1985年 | 4篇 |
1984年 | 6篇 |
1982年 | 3篇 |
1981年 | 3篇 |
1980年 | 4篇 |
1979年 | 3篇 |
1976年 | 1篇 |
排序方式: 共有2928条查询结果,搜索用时 0 毫秒
21.
建立了超高效液相色谱-三重四极杆质谱联用技术测定血浆和尿液中马桑中毒标志物马桑亭和马桑宁的方法。血浆和尿液样品经固相支持液液萃取法提取净化后,溶于15%(v/v)甲醇水溶液中,以Cortecs C18色谱柱(100 mm×2.1 mm,1.6 μm)作为分析柱进行分离,电喷雾负离子多反应监测(MRM)模式下检测,以氟苯尼考作为内标物,基质工作曲线内标法定量。血浆和尿液中马桑亭和马桑宁的平均加标回收率为86.2%~110%,相对标准偏差为5.1%~14.6%(n=6),血浆中马桑亭和马桑宁的检出限(S/N=3)分别为0.01 μg/L和0.1 μg/L,尿液中马桑亭和马桑宁的检出限分别为0.03 μg/L和0.3 μg/L。本法简单、灵敏、准确,可用于血浆和尿液中马桑亭和马桑宁的中毒检测。 相似文献
22.
Interfacial layers have been widely applied to study the formation and stability of emulsion-based systems. However, the application of isolated interfaces to address digestibility of emulsions is often limited because of the complexity of experimental methods and results. This review summarizes the latest developments in analytical methods and literature data on effects of digestion on interfacial layers. Particular emphasis is given to understand the changes on interfacial magnitudes during oral, gastric, and duodenal digestion, either applied separately or sequentially. Limitations of interfacial aspects and key factors that influence emulsion microstructure in bulk and lipid digestion are identified. Understanding the behavior of interfacial layers upon gastrointestinal digestion promotes an accurate tracking of the physiological fate of emulsions. 相似文献
23.
A simple high-performance liquid chromatographic method, using photodiode array detection was developed for the determination
of propylene glycol in human plasma and in the fluid retreived after continuous veno-venous hemofiltration. The method entailed
alkaline derivatization with benzoyl chloride and ethylene glycol as internal standard. The separation of the compounds, after
extraction with pentane, was carried out on a Pursuit C8 column with UV-detection at 230 nm. Validation samples were analyzed
with an accuracy between 95 and 105%, and intra- and inter-day coefficients of variation of less than 8%. The calibration
curve was linear over a concentration range of 5–100 mg L−1 with a detection limit of 1 mg L−1. Blood plasma samples of several patients were analysed by using the prescribed method with propylene glycol concentrations
varying from 5 to 98 mg L−1. Compared to previously described LC methods, this method is ten times more sensitive and thus suitable for use in pharmacokinetic
studies of propylene glycol. 相似文献
24.
25.
J. Miguel Vadillo M. Esther Gonzalez Isabel Carretero J. Javier Laserna 《Mikrochimica acta》1995,118(3-4):273-282
Micellar liquid chromatography (MLC) and capillary zone electrophoresis (CZE) have been evaluated for the analysis of twelve banned drugs in sport including diuretics and -blockers. In MLC, a sodium dodecylsulphate aqueous solution has been used as mobile phase using an octadecylsilica column. In CZE, a pH 8 buffer solution and a silica capillary have been employed. Parameters of retention and efficiency have been compared. Limits of detection with UV detection at 254 nm and relative standard deviations for atenolol, furosemide, nadolol, spironolactone and triamterene were established and compared in both techniques. Examples of direct urine injection into the separation systems are presented. Drugs overlapping in MLC are well resolved in CZE, while the opposite is true for a limited number of drugs. Some interferences from urine may arise in CZE. The selectivity of analysis would be greatly enhanced by using both techniques, which require only filtration as pre-treatment. 相似文献
26.
《Analytica chimica acta》2004,512(2):287-295
The potential of non-aqueous capillary electrophoresis (NACE) was investigated for the simultaneous separation of paroxetine, tamoxifen, and their main metabolites. Baseline separation of the studied solutes was obtained on a μm capillary using a non-aqueous buffer composed of 18 mM ammonium acetate and 1.1% acetic acid in 80:20 (v/v) methanol-acetonitrile, with a temperature and voltage of 22 °C and 15 kV, respectively. Clomipramine was used as internal standard. Aspects such as stability of the solutions, linearity, accuracy, precision and ruggedness were examined in order to validate the proposed method. Detection limits obtained for all the studied compounds ranged between 3.0 and 7.1 μg l−1. The developed method is sensitive and robust and was used to determine paroxetine, tamoxifen, and their metabolites at clinically relevant levels in human urine. Before NACE determination, the samples were purified and enriched by means of an extraction-pre-concentration step with a pre-conditioned C18 cartridge. Determination of these analytes in the urine of four females urines was demonstrated. 相似文献
27.
Identification of selenium species in urine by ion-pairing HPLC–ICP–MS using laboratory-synthesized standards 总被引:1,自引:0,他引:1
Wrobel K Wrobel K Kannamkumarath SS Caruso JA 《Analytical and bioanalytical chemistry》2003,377(4):670-674
This study focused on the detection/identification of possible selenium metabolites in human urine. Organoselenium compounds not commercially unavailable were synthesized and characterized by electrospray mass spectrometry. Separation of selenomethionine, methylselenomethionine, trimethylselonium, selenoethionine, and selenoadenosylmethionine was achieved by ion-pairing HPLC with a mobile phase of 2 mmol L–1 hexanesulfonic acid, 0.4% acetic acid, 0.2% triethanolamine (pH 2.5), and 5% methanol. The column effluent was introduced on-line to inductively coupled plasma–mass spectrometry for selenium-specific detection (77Se and 78Se). For selenium speciation in urine, solid-phase extraction was carried out using C18 cartridges modified with hexanesulfonic acid. Selective retention of cationic species was observed from acidified urine (perchloric acid, pH 2.0). After elution with methanol, evaporation, and dissolution in the mobile phase, the sample was introduced to the HPLC–ICP–MS system and the chromatographic peaks were assigned by adding standards. The species identified in urine were selenomethionine, trimethylselonium ion, and selenoadenosylmethionine. The last species was detected for the first time and our results suggest that selenomethionine might enter the metabolic pathway of its sulfur analog in the activated methylation cycle.Kazimierz Wrobel and Katarzyna Wrobel are on the leave from the Institute of Scientific Research, University of Guanajuato, L. de Retana No. 5, 36000 Guanajuato, Gto., Mexico 相似文献
28.
A cDNA for human TNF-α (615bp) was isolated by means of polymerase chain reaction (PCR) using first strand cDNA from PMA-induced HL-60 cells as template. The result from sequencing the 615 bp cDNA fragment indicated that it corresponded to the entire sequence of mature human TNF coding region. Direct expression of mature human TNF was achieved using a plasmid pHT-1 constructed by ligation of the cDNA and a synthetic DNA. The IPTG-induced bacterial product (hTNF) showed cytotoxicity to mouse L-929 cells. The TNF activity was further identified by neutralization of a specific monoclonal antibody against human TNF-α. Approximately 80,000 units of activity were detected per ml of culture at A600=2. 相似文献
29.
Due to the widespread uses of Ni and Ni alloys, patients undergoing medical treatments can experience inadvertent exposure to the metal, present as a contaminant in fluids for intravenous administration or released from surgical implants and other medical devices. Because of the risk of acute allergic reactions in Ni-sensitive subjects, sources of metal exposure within medical care and its concentrations in biological fluids of potentially exposed patients should be periodically monitored, using reliable analytical procedures, which include strict measures of contamination control. The results of a recent survey on the concentrations of Ni and other potentially toxic metals in human albumin solutions are reported. 相似文献
30.
Arsenic Speciation in Urine and Blood Reference Materials 总被引:1,自引:0,他引:1
Todor I. Todorov John W. Ejnik Florabel G. Mullick Jose A. Centeno 《Mikrochimica acta》2005,151(3-4):263-268
Acute and chronic exposure to arsenic is a growing problem in the industrialized world. Arsenic is a potent carcinogen and
toxin in humans. In the body, arsenic is metabolized to produce several species, including inorganic forms, such as trivalent
(AsIII) and pentavalent (AsV), and the methylated metabolites such as monomethylarsonic acid, (MMAV), and dimethylarsinic acid (DMAV), in addition to arsenobetaine (AsB) which is ingested and excreted from the body in the same form. Each of these species
has been reported to possess a specific but different degree of toxicity. Thus, not only is the measurement of total As required,
but also quantification of the individual metabolites is necessary to evaluate the toxicity and risk assessment of this element.
There are a large number of reference materials that are used to validate methodology for the analysis of As in blood and
urine, but they are limited to total As concentrations. In this study, the speciation of five arsenic metabolites is reported
in blood and urine from commercial available control materials certified for total arsenic levels. The separation was performed
with an anion exchange column using inductively coupled plasma mass spectrometry as a detector. Baseline separation was achieved
for AsIII, AsV, MMAV, DMAV, and AsB, allowing us to quantify all five species. Excellent agreement between the total arsenic levels and the sum of the
speciated As levels was obtained. 相似文献