全文获取类型
收费全文 | 8847篇 |
免费 | 1022篇 |
国内免费 | 597篇 |
专业分类
化学 | 6259篇 |
晶体学 | 31篇 |
力学 | 230篇 |
综合类 | 103篇 |
数学 | 303篇 |
物理学 | 3540篇 |
出版年
2024年 | 30篇 |
2023年 | 133篇 |
2022年 | 386篇 |
2021年 | 394篇 |
2020年 | 340篇 |
2019年 | 307篇 |
2018年 | 233篇 |
2017年 | 401篇 |
2016年 | 428篇 |
2015年 | 444篇 |
2014年 | 593篇 |
2013年 | 581篇 |
2012年 | 624篇 |
2011年 | 515篇 |
2010年 | 466篇 |
2009年 | 550篇 |
2008年 | 496篇 |
2007年 | 505篇 |
2006年 | 438篇 |
2005年 | 446篇 |
2004年 | 391篇 |
2003年 | 243篇 |
2002年 | 185篇 |
2001年 | 125篇 |
2000年 | 126篇 |
1999年 | 129篇 |
1998年 | 106篇 |
1997年 | 101篇 |
1996年 | 90篇 |
1995年 | 98篇 |
1994年 | 56篇 |
1993年 | 64篇 |
1992年 | 59篇 |
1991年 | 35篇 |
1990年 | 53篇 |
1989年 | 45篇 |
1988年 | 51篇 |
1987年 | 40篇 |
1986年 | 28篇 |
1985年 | 28篇 |
1984年 | 18篇 |
1983年 | 16篇 |
1982年 | 30篇 |
1981年 | 14篇 |
1980年 | 5篇 |
1979年 | 11篇 |
1978年 | 3篇 |
1971年 | 2篇 |
1969年 | 1篇 |
1959年 | 1篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
91.
Evaluation of free hydroxyl radical scavenging activities of some Chinese herbs by capillary zone electrophoresis with amperometric detection 总被引:2,自引:0,他引:2
Due to the severe damage caused by free hydroxyl radicals (OH·) to cells and tissues, there is much interest in finding and studying effective and non-toxic OH· scavengers, including traditional Chinese herbs. In this paper, the simple and highly-sensitive technique of capillary zone electrophoresis with amperometric detection (CZE-AD) was used to study the OH· scavenging activities of aqueous extracts from some traditional Chinese herbs. Salicylic acid (SAL) was used as an OH· trap, and the content of OH· could be determined by assaying their products, 2,3-dihydroxybenzoic acid (2,3-DHBA) and 2,5-dihydroxybenzoic acid (2,5-DHBA). The optimum conditions for CZE-AD for the determination of 2,3-DHBA and 2,5-DHBA were explored. The linearity ranges of 2,3-DHBA and 2,5-DHBA were 1.0 ×10–7~1.0 ×10–4 mol L–1, and their detection limits were as low as 2×10–8 mol L–1, which were much better than the CE-UV method often used. The traditional Chinese herbs studied included Radix angelicae sinensis, Rhizoma coptidis, Ligustrum lucidum, Ligusticum wallichii, Radices glycyrrhizae and Semen plantaginis. The experiments showed that the aqueous extracts from all of the above traditional Chinese herds had free OH· scavenging activities, although to different degrees. 相似文献
92.
Summary A fully integrated chromatographic system was developed for the determination of leukotrienes in biological samples using
photodiode-array detection (PDAD), which eliminates time consuming manual sample handling steps. A special solid phase extraction,
(SPE) methodology for leucotriene metabolite stability was developed which increased the recoveries and eliminates the contamination
risk of biological samples. The inherent instability (autooxidation) of many of the leukotriene mediators, and the adsorption
effects onto exposed surfaces in vials and in the chromatographic system were found to be very important parameters to control
in order to circumvent high loss of sample analytes. By binding the cell supernatants to the functionalities of the SPE support
stabilised these mediators. Cell culture samples were eluted through a disposable C18 SPE column. The SPE columns were allowed to thaw and deposited in an automated sample handling unit (ASPEC XL). Desorption
of the analytes was followed by a second on-line SPE step, to eliminate remaining interfering matrix compounds. Typical recoveries
when stored at −70°C were in-between 55–97% except for (LTE4) which was found to be around 40% after 72 days of storage. Seven reversed-phase packings were studied. Selectivity factors,
as well as the separation efficiencies, were found to differ for the various C18 bonded silica stationary phases. This integrated on-line column liquid chromatographic system was applied to the determination
of leukotriene B4, leukotriene C4, leukotriene D4, leukotriene and E4 in human cell extracts using prostaglandin B2 as the internal standard. More than 1500 biological samples were analysed. Some validation data are presented for unattended
operations. 相似文献
93.
Traceability of the measurement of analytical parameters capable of evaluating the performance of methods is an important
concept for the assessment of quality for the routine control, especially for residue monitoring of non-authorized medicinal
substances in food from animal origin. The European Decision no. 657/2002/EC recommends to calculate two statistical limits,
CCα and CCβ, which allow to evaluate the critical concentrations above which the method reliably distinguish and quantify
a substance taking into account the variability of the method and the statistical risk to take a wrong decision. The calculation,
which can be derived from the ISO standard no. 11843 is applied on a routine basis. An example displays a very simple way
for evaluating the performance of an LC-MSMS method which has been validated a few years ago and is qualified onto a Micromass
Quattro LCZ tandem mass spectrometer to monitor and confirm the nitrofuran metabolite residues in food from animal origin.
Community Reference Laboratory for Antimicrobial Veterinary Drug Residue Control in Food from Animal Origin 相似文献
94.
毛细管电泳在拮抗药物对氨基苯甲酸、对羟基苯甲酸和磺胺分析测定中的应用 总被引:2,自引:0,他引:2
本文报道了一种用毛细管区带电泳法(CZE)分离与测定对氨基苯甲酸、对羟基苯甲酸及磺胺类药物的新方法.电泳条件为:用 20mmol/L硼砂-20mmol/L H_3PO_4-20 mmol/Lβ-环糊精-4%乙醇(pH 7.0)作电泳液,L-抗坏血酸为内标,280nm为检测波长,样品由电进样方式(10kV/10s)引入毛细管(51.2 cm×50μm i.d.,有效分离长度为 38.5 cm).在24.5°C下,6 min内三者可达基线分离(电泳电压 25kV),且在一定范围内可进行定量分析,保留时间(Tr)及A_(样品)/A_(内标)的RSD值分别小于1.0%和5.0%.本法的建立为研究这三者共存于高等动物及微生物体内时的生理作用提供了一种可共选择的新方法. 相似文献
95.
Nadica Ivošević DeNardis Vera Žutić Vesna Svetličić Ranieri Urbani 《Electroanalysis》2007,19(4):473-478
In situ amperometric characterization of an aggregating system in terms of molecular adsorption and single microparticle interactions at the electrode interface is demonstrated using a model system: alginate/Ca(II) in an aqueous electrolyte solution. Recording of chronoamperometric curves of oxygen reduction at the dropping mercury electrode is designed for detection of dip‐shaped signals of individual gel microparticles. By addition of Ca(II) decrease of alginate adsorption is accompanied by appearance of signals indicating vesicle type association of alginate molecules and microparticles of gel phase. AFM imaging provided evidence of initial stage in calcium alginate gel formation. 相似文献
96.
Summary The highly complex matrix of diesel particulate extracts was analyzed for nitrated polycyclic aromatic hydrocarbons (nitro-PAH)
using fused-silica capillary-column gas chromatography along with a thermionic nitrogen-phosphorus detector (TID) and high-performance
liquid chromatography followed by on-line catalytic reduction of the nitro-PAH to amino-PAH and subsequent fluorescence detection.
Positive isomer identification and quantitation of nitro-PAH are from retention times of authentic standards and their mass
spectra. The ease of nitro-PAH formation by nitration of PAH raises the question regarding the origin of these species, whether
they are produced as “native” products during the engine combustion process and/or in the exhaust, or instead, formed as the
result of chemical conversion to produce artifacts during the sampling procedure. This problem is assessed examing 1-nitropyrene-concentration
in particulates of three light-duty diesel engines for different sampling times. 1-Nitropyrene concentrations show only a
moderate increase with sampling time under average sampling conditions.
Presented at the 15th International Symposium on Chromatography, Nürnberg, October 1984 相似文献
97.
Barnes JH Schilling GD Stone SF Sperline RP Denton MB Young ET Barinaga CJ Koppenaal DW Hieftje GM 《Analytical and bioanalytical chemistry》2004,380(2):227-234
The use of a separation step, such as liquid chromatography, prior to inductively coupled plasma mass spectrometry (ICP–MS) has become a common tool for highly selective and sensitive analyses. This type of coupling has several benefits including the ability to perform speciation analysis or to remove isobaric interferences. Several limitations of conventional instruments result from the necessity to scan or pulse the mass spectrometer to obtain a complete mass spectrum. When the instrument is operated in such a non-continuous manner, duty cycle is reduced, resulting in poorer absolute limits of detection. Additionally, with scanning instruments, spectral skew can be introduced into the measurement, limiting quantitation accuracy. To address these shortcomings, a high-performance liquid chromatograph has been coupled to an ICP–MS capable of continuous sample introduction and simultaneous multimass detection. These features have been realized with a novel detector array, the focal plane camera. Instrument performance has been tested for both speciation analysis and for the elimination of isobaric interferences. Absolute limits of detection in the sub picogram to tens of picograms regime are obtainable, while the added mass dimension introduced by simultaneous detection dramatically increases chromatographic peak capacity. 相似文献
98.
Bernard Herbreteau Michel Lafosse Luc Morin-Allory Michel Dreux 《Journal of separation science》1990,13(4):239-243
An evaluation of the most commonly used HPLC system (reversed phase octadecyl sillica gel) was undertaken in order to determine the level of certain carbohydrates in molasses produced in the refining of sugar beet. Chromatographic parameters and purification operations prior to analysis are discussed in order to develop an analytical method permitting automation of sugar determination. A Zorbax ODS column (250 × 9.4 mm), water elution, and light scattering detection allow easy determination of glucose + fructose, sucrose, and raffinose in molasses using an internal standard (maltose). 相似文献
99.
Summary A packed flow cell was used for fluorometric detection in micro high-performance liquid chromatography. The flow cell consisted of fused-silica tubing packed with the same material as the separation column. A focusing effect of the stationary phase on the signal intensity was observed, leading to an improvement of the mass detection limit, as achieved by on-column detection. 相似文献
100.
Summary Four most frequently used presentation forms of the ECD response are described. Equations describing the dependence of the
sensitivity, linearity and minimum detectable concentration of the ECD working under constant frequency mode of operation
on the pulse period are derived from Wenthworth’s kinetic model for all four forms mentioned above. The forms presented are
compared on the basis of equations derived. Results of the calculations are given and some predictions are experimentally
tested for sulphur hexafluoride. Good agreement was found between the predicted and observed relationships.
Presented at the 15th International Symposium on Chromatography, Nürnberg, October 1984 相似文献