全文获取类型
收费全文 | 2020篇 |
免费 | 156篇 |
国内免费 | 113篇 |
专业分类
化学 | 893篇 |
晶体学 | 2篇 |
力学 | 92篇 |
综合类 | 16篇 |
数学 | 821篇 |
物理学 | 465篇 |
出版年
2023年 | 23篇 |
2022年 | 34篇 |
2021年 | 56篇 |
2020年 | 67篇 |
2019年 | 59篇 |
2018年 | 40篇 |
2017年 | 75篇 |
2016年 | 79篇 |
2015年 | 61篇 |
2014年 | 76篇 |
2013年 | 235篇 |
2012年 | 109篇 |
2011年 | 126篇 |
2010年 | 96篇 |
2009年 | 105篇 |
2008年 | 78篇 |
2007年 | 125篇 |
2006年 | 94篇 |
2005年 | 73篇 |
2004年 | 86篇 |
2003年 | 71篇 |
2002年 | 58篇 |
2001年 | 50篇 |
2000年 | 52篇 |
1999年 | 61篇 |
1998年 | 42篇 |
1997年 | 33篇 |
1996年 | 32篇 |
1995年 | 39篇 |
1994年 | 22篇 |
1993年 | 19篇 |
1992年 | 12篇 |
1991年 | 19篇 |
1990年 | 3篇 |
1989年 | 10篇 |
1988年 | 9篇 |
1987年 | 8篇 |
1986年 | 5篇 |
1985年 | 12篇 |
1984年 | 3篇 |
1983年 | 6篇 |
1982年 | 3篇 |
1981年 | 3篇 |
1980年 | 4篇 |
1979年 | 9篇 |
1976年 | 1篇 |
1973年 | 1篇 |
1971年 | 1篇 |
1970年 | 1篇 |
1969年 | 1篇 |
排序方式: 共有2289条查询结果,搜索用时 15 毫秒
991.
A flow-injection biosensor system with an on-line microdialysis sampling is proposed for the simultaneous assay of l-lactate and pyruvate in serum and rat brain. The dialysate collected in the sample loop by perfusing Ringer’s solution through the microdialysis probe is automatically injected into the flow-injection line with a dual enzyme electrode arranged in parallel for the flow direction. The dual enzyme electrode is constructed by hybridizing a poly(1,2-diaminobenzene) film to two sensing parts, which respond selectively to l-lactate and pyruvate, respectively, without any cross-reactivity. Both the sensing parts respond linearly to the concentrations of both analytes between 0.01 and 5 mM, without any interference from oxidizable species and low-molecular weight proteins present in the dialysate. The proposed flow-injection analysis (FIA) method can be successfully applied to the simultaneous in vitro and in vivo assays of both analytes in serum and rat brain, respectively. The system can be automatically processed at an analytical speed of 19 dialysates h−1 over a period of 5 h. 相似文献
992.
Gmez Alvarez E. 《Talanta》2007,72(5):1757-1766
The implementation of an experimental set-up for sampling, and characterisation of parameters related to absorptive sampling solid phase microextraction (SPME) in the EUPHORE photoreactor is described. Toluene was taken as probe compound. Optimisation of the sampling and calibration curves are presented. Equilibrium was achieved in just 30 s due to the good agitation in the chambers and the LOD was 0.24 ppbV. The precision was ±0.02 expressed as relative standard deviation (n = 9). The inter-fibre reproducibility was ±0.03 expressed as relative standard deviation. The effect of the temperature and the sun radiation on absorption in the fibre is also studied using a relative method to calculate the ratio K/K0 (ratio of absorption constants at two different times during the experiment at which temperature and radiation conditions experimented important variations) calculated through known parameters, avoiding in this way the need for external calibrations in the calculation of K. The results showed a difficult to predict dependence of absorption over the combination of temperature and sun radiation and the need to develop sampling systems with absorptive SPME in which sun radiation has no influence. The stability in different conditions of compounds absorbed in the fibre was also subject to study. At room temperature half of the compound absorbed is expected to desorb in 1.21 h. Conversely, when fibres were kept at low temperatures (−86 °C) after 21 days, desorption was negligible. 相似文献
993.
Kobrak MN 《Journal of computational chemistry》2003,24(12):1437-1446
A common technique for the numerical calculation of free energies involves estimation of the probability density along a given coordinate from a set of configurations generated via simulation. The process requires discretization of one or more reaction coordinates to generate a histogram from which the continuous probability density is inferred. We show that the finite size of the intervals used to construct the histogram leads to quantifiable systematic error. The width of these intervals also determines the statistical error in the free energy, and the choice of the appropriate interval is therefore driven by the need to balance the two sources of error. We present a method for the construction of the optimal histogram for a given system, and show that the use of this technique requires little additional computational expense. We demonstrate the efficacy of the technique for a model system, and discuss how the principles governing the choice of discretization interval could be used to improve extended sampling techniques. 相似文献
994.
An ultrasonic slurry sampling electrothermal atomic absorption spectrometric method with a molybdenum tube atomizer has been developed for the determination of copper in herbal medicine samples. Glycerol solution (10%) was used as the slurry medium. The optimum pyrolysis temperature was 760 °C. The detection limit was 72 fg (3×S/N ratio). Matrix element interference was investigated and it was found that glycerol as a chemical modifier eliminated the interference. The amounts of copper in herbal medicines determined by the method proposed are in good accordance with those measured in dissolved acid-digested samples. The method enables rapid calibration, and simple and rapid analysis of copper in herbal medicine samples at low cost. 相似文献
995.
非完全消化-悬浮液进样-火焰原子光谱法测定蘑菇中的钾、镁、锌 总被引:1,自引:0,他引:1
将非完全消化法与悬浮液进样技术相组合处理蘑菇样品 ,即先用浓HNO3低温消解样品至溶液呈透明 ,再用琼脂溶液悬浮极少量不溶物 ,制成样品溶液。分别以Sr2 +溶液和NaCl溶液作为测定镁、钾的释放剂和消电离剂。以原子吸收光谱法测定镁、锌 ,以原子发射光谱法测定钾。对样品处理方法、干扰、线性范围及检出限进行了考察。建立了快速测定蘑菇中钾、镁、锌的火焰原子光谱法。相对标准偏差小于 2 8% ,加标回收率为 97 9%~ 1 0 1 6%。 相似文献
996.
A flow-injection ultrafiltration sampling chemiluminescence system for on-line determination of drug–protein interaction 总被引:1,自引:0,他引:1
A flow-injection ultrafiltration sampling chemiluminescence system for on-line determination of cimetidine–bovine serum albumin (BSA) interaction is proposed in this paper. Cimetidine can be oxidized by N-bromosuccinimide (NBS) and sensitized by fluorescein to produce high chemiluminescence emission in basic media. The concentration of cimetidine is linear with the CL intensity in the range 3×10–7–1×10–4 mol L–1 with a detection limit of 1×10–7 mol L–1 (3). The drug and protein were mixed in different molar ratios in 0.067 mol L–1 phosphate buffer, pH 7.4, and incubated at 37 °C in a water bath. The ultrafiltration probe was utilized to sample the mixed solution at a flow rate of 5 µL min–1. The data obtained by the proposed ultrafiltration flow-injection chemiluminescence method was analyzed with Scrathard analysis and a Klotz plot. The estimated association constant (K) and the number of the binding site (n) on one molecule of BSA by Scrathard analysis and Klotz plot were 3.15×104 L mol–1 and 0.95, 3.25×104 L mol–1 and 0.92, respectively. The proposed system proved that flow-injection chemiluminescence analysis coupled with on-line ultrafiltration sampling is a simple and reliable technique for the study of drug–protein interaction. 相似文献
997.
Summary To determine toxic organic compounds (methanol, ethanol, n-propanol, acetone, methyl ethyl ketone, methyl isobutyl ketone)
in air a method was developed for their headspace gas chromatographic analysis with preconcentration in n-butanol (alcohols)
and in n-pentanol (ketones). The distribution coefficients of analytes in the air-absorbent system have been measured: 1051
(MeOH), 5630 (EtOH), 6773 (n-PrOH), 307 (Me2CO), 580 (MeCOEt), 1035 (MeCOBu-i). The minimum detectable level (mg m−3) was determined as low as 0.9 (MeOH), 4.0 (EtOH), 0.9 (n-PrOH), 0.2 (Me2CO), 0.1 (MeCOEt), 0.4 (MeCOBu-i). The method was effectively used for gas effluent air control in the workplace and in the
atmosphere.
Presented at the 21st ISC held in Stuttgart, Germany, 15th–20th September, 1996 相似文献
998.
Alessandra Furtado da Silva Bernhard Welz Adilson J. Curtius 《Spectrochimica Acta Part B: Atomic Spectroscopy》2002,57(12):2031-2045
Iridium, palladium, rhodium and ruthenium, thermally deposited on the platform, were investigated as permanent modifiers for the determination of mercury in ash, sludge, marine and river sediment reference materials, ground to a particle size of 50 μm, using solid sampling graphite furnace atomic absorption spectrometry. A total mass of 250 μg of each modifier was applied using 25 injections of 20 μl of modifier solution (500 mg l−1), and executing a temperature program for modifier conditioning after each injection. The performance of palladium was found to be most consistent, taking the characteristic mass as the major criterion, resulting in an excellent correlation between the measured integrated absorbance values and the certified mercury contents. Mercury was found to be lost in part from aqueous solutions during the drying stage in the presence of all the investigated permanent modifiers, as well as in the presence of the palladium and magnesium nitrates modifier added in solution. A loss-free determination of mercury in aqueous solutions could be reached only after the addition of potassium permanganate, which finally made possible the use of aqueous standards for the direct analysis of solid samples. A characteristic mass of 55–60 pg Hg was obtained for the solid samples, using Pd as a permanent modifier, and also in aqueous solutions after the addition of permanganate. The results obtained for mercury in ash, sludge and sediment reference materials, using direct solid sapling and calibration against aqueous standards, as well as the detection limit of 0.2 mg kg−1 were satisfactory for a routine procedure. 相似文献
999.
Summary Headspace-gas chromatography was used to determine the contents of toxic 1,4-dioxane, ethylene oxide and ethylene glycol in
ethoxylated alcohols and alkylamines, and in commercial cosmetics and washing products. A Permaphase PEG capillary column
was used for the determination of 1,4-dioxane and ethylene oxide and a DB-17 column for ethylene glycol determination. Dimethylformamide
was used as the solvent in the determination of 1,4-dioxane and ethylene oxide, and undecanol in the case of ethylene glycol.
The detection limits for ethylene oxide, 1,4-dioxane and ethylene glycol are 1,2 and 10 μg·g−1, respectively. 相似文献
1000.
Ndio Oleszczuk Jacira T. Castro Mrcia M. da Silva Maria das Graas A. Korn Bernhard Welz Maria Goreti R. Vale 《Talanta》2007,73(5):862-869
A method has been developed for the determination of cobalt, copper and manganese in green coffee using direct solid sampling electrothermal atomic absorption spectrometry (SS-ET AAS). The motivation for the study was that only a few elements might be suitable to determine the origin of green coffee so that the multi-element techniques usually applied for this purpose might not be necessary. The three elements have been chosen as test elements as they were found to be significant in previous investigations. A number of botanical certified reference materials (CRM) and pre-analyzed samples of green coffee have been used for method validation, and inductively coupled plasma optical emission spectrometry (ICP OES) after microwave-assisted acid digestion of the samples as reference method. Calibration against aqueous standards could be used for the determination of Mn and Co by SS-ET AAS, but calibration against solid CRM was necessary for the determination of Cu. No significant difference was found between the results obtained with the proposed method and certified or independently determined values. The limits of detection for Mn, Cu and Co were 0.012, 0.006 and 0.004 μg g−1 using SS-ET AAS and 0.015, 0.13 and 0.10 μg g−1 using ICP OES. Seven samples of Brazilian green coffee have been analyzed, and there was no significant difference between the values obtained with SS-ET AAS and ICP OES for Mn and Cu. ICP OES could not be used as a reference method for Co, as essentially all values were below the limit of quantification of this technique. 相似文献