全文获取类型
收费全文 | 2857篇 |
免费 | 11篇 |
国内免费 | 100篇 |
专业分类
化学 | 1795篇 |
晶体学 | 1篇 |
综合类 | 9篇 |
数学 | 1篇 |
物理学 | 1162篇 |
出版年
2024年 | 1篇 |
2023年 | 11篇 |
2022年 | 16篇 |
2021年 | 15篇 |
2020年 | 16篇 |
2019年 | 15篇 |
2018年 | 16篇 |
2017年 | 23篇 |
2016年 | 28篇 |
2015年 | 36篇 |
2014年 | 35篇 |
2013年 | 85篇 |
2012年 | 272篇 |
2011年 | 153篇 |
2010年 | 126篇 |
2009年 | 129篇 |
2008年 | 108篇 |
2007年 | 162篇 |
2006年 | 180篇 |
2005年 | 180篇 |
2004年 | 190篇 |
2003年 | 134篇 |
2002年 | 130篇 |
2001年 | 118篇 |
2000年 | 114篇 |
1999年 | 107篇 |
1998年 | 70篇 |
1997年 | 65篇 |
1996年 | 39篇 |
1995年 | 54篇 |
1994年 | 53篇 |
1993年 | 58篇 |
1992年 | 47篇 |
1991年 | 76篇 |
1990年 | 37篇 |
1989年 | 31篇 |
1988年 | 14篇 |
1987年 | 4篇 |
1986年 | 3篇 |
1984年 | 5篇 |
1983年 | 1篇 |
1982年 | 2篇 |
1981年 | 3篇 |
1980年 | 2篇 |
1978年 | 1篇 |
1976年 | 1篇 |
1973年 | 2篇 |
排序方式: 共有2968条查询结果,搜索用时 15 毫秒
151.
152.
153.
A very sensitive flow system for the direct determination of copper in natural waters based on spectrophotometric detection 总被引:1,自引:0,他引:1
A very sensitive flow injection method with spectrophotometric detection has been developed for the on-line determination of copper in natural waters. The method exhibits a limit of detection three times lower than the most sensitive direct spectrophotometric method previously described and then allows the direct and simple in situ determination of copper in most natural waters.The method was based on the measurement of the absorbance of the coloured complex formed by copper with the chromogenic reagent di-2-pyridyl ketone benzoylhydrazone (dPKBH) in an alkaline medium. This complex presents stoichiometry 1:2 (Cu:dPKBH), and exhibits maximum absorbance at 370 nm. The manifold used was very simple, and consisted of two channels. The first one contained the sample while the second one contained the colorimetric reagent (3.3×10−4 M dPKBH in 10% ethanol), in a 1.6×10−2 M phosphate buffer solution at pH 8. The performance of the system was optimised by using both univariate and modified simplex methodologies. When modified simplex was used, the best signal was obtained for a sample injection volume of 529 μl, a reaction coil length of 1.29 m, and a reagent flow rate of 4.8 ml min−1. Under optimum conditions, the response was linear up to 3 mg l−1 copper, the equation of the straight line being y=0.314x+5.2×10−4 (r2=0.998). The method allowed a sampling frequency of 40 samples per hour and exhibited a precision of 2.11% (as R.S.D., n=11). The limit of detection was 4.6 μg l−1 (calculated as 3sb/m, where sb is the standard deviation of the y-intercept and m represents the slope of the straight line), and was therefore more sensitive than all the direct continuous methods reported previously.The method was successfully applied to the analysis of real water samples, with an average relative error of 5.32%. 相似文献
154.
Cássia Maria L. da Silva 《Talanta》2007,73(4):613-620
In this work, a flow injection system with spectrophotometric detection was developed for the determination of lithium in pharmaceutical formulations used in the treatment of bipolar disorder. Reaction between Quinizarine (1,4-dihydroxyanthraquinone) and Li(I) ion in alkaline medium containing dimethylsulfoxide (DMSO) was explored for this purpose. The flow system was optimized regarding to its chemical (DMSO, Quinizarine and NaOH concentrations and sample pH) and physical parameters (sample loop volume, carrier flow rate and reactor length) in order to establish better conditions in terms of sensitivity and sampling frequency. The results obtained showed that the concentration of DMSO in the reagent solution presents remarkable influence on the magnitude of analytical signal. Chemical species that could be found in the formulations such as Na(I), K(I), Mg(II), Ca(II), Ti(IV), Cl−, CO32− e sodium dodecylsulfate were tested as possible interfering ions. Among them, only non-monovalent cations presented noticeable interference on lithium signal. However, they were not found in concentrations high enough to cause interference in the determination of lithium in the samples. Sample preparation was performed by sonicating a slurry prepared by dispersing 100 mg of powdered sample in 15 mL of 0.10 mol L−1 HCl solution. Results obtained by developed methodology were not statistically different from those obtained by flame emission spectrometry. In the optimized conditions the method presented a linear range of 5-40 mg L−1 and a relative standard deviation of 3.6% at 5 mg L−1 Li concentration. Detection and quantification limits were 0.54 and 1.8 mg L−1, respectively. Sampling frequency, calculated as the time interval passed between two consecutive injections, was 60 samples per hour. The methodology was successfully applied in the determination of lithium in three commercial samples. 相似文献
155.
Gold in iron ore samples is separated from iron (major matrix cation), antimony and vanadium using anion exchange resin in (0.2 M) HBr, potassium peroxodisulfate and acetone:water:nitric acid media. The exchangeable anion Cl− of the ion exchanger Dowex 1X 4 is replaced by Br− using (6 M) HBr solution. Certified reference material DGP-M1, spiked ferric magnetic oxide, gold radioactive tracer 198Au and gold standard solutions are used to study the adsorption efficiency and the yield recovery of tetrabromoaurate AuBr4− from the resin. Ten eluents have been tried to elute gold from the column, and it has been found that a 10 ml potassium peroxodisulfate and 240 ml acetone:water:nitric acid [125:5:5] solution fulfills the objective. The set up of the separation procedure allows quantitative adsorption of gold by the resin, while the major matrix cation (Fe) and others (Cd, Ag, Cu, V, Sb, Ti) have been passed through the column with the feeding solution (0.2 M) HBr. The resin selectivity coefficient (K) of separating Au from Fe has been found to be KFeAu≈6.4×1011. The eluted Au is treated with K2S2O8 and H2O2 for spectrophotometric determination as rhodamine-B complex at 555.6 nm. The linearity, detection limit, precision, and accuracy of the determination method have been found to be up to 2.0 μg g−1, 0.018 μg g−1, 0.009 μg g−1 and 3%, respectively. 相似文献
156.
157.
pH 4.1的条件下,铜与洛美沙星、曙红反应生成三元络合物,使曙红溶液褪色并产生新的吸收峰,最大褪色峰谷波长位于508 nm,三元络合物吸收峰波长位于546 nm.利用吸收峰、谷的高度差,进行洛美沙星的测定,洛美沙星的质量浓度在0.7~3.8 mg/L范围内符合比耳定律.方法的表观摩尔吸光系数为5.47×104 L·mol-1·cm-1,检出限为0.46 mg/L.该方法用于HCl洛美沙星片剂样品中洛美沙星的测定,准确、灵敏、选择性好.对样品平行6次测定,相对标准偏差为0.42%~3.1%,回收率为92.6%~106.9%. 相似文献
158.
159.
镉(Ⅱ)—4—甲醛基重氮氨基偶氮苯显色反应的研究 总被引:2,自引:0,他引:2
本文研究了Cd(Ⅱ)与4-甲醛基重氮氨基偶氮苯的显色反应。试验结果表明:在TritonX-100的存在下,pH9.50的Na_2B_4O_7-NaOH缓冲体系中,显色反应的灵敏度高,络合物的最大吸收峰在525nm处,表观摩尔吸光系数为1.33×10~5L·mol~(-1)·cm~(-1),Cd(Ⅱ)浓度在0~10μg/25ml范围内符合比耳定律。利用阴离子交换树脂(717)小柱分离干扰离子后,测定地质试样中微量镉,结果满意。 相似文献
160.
Kamal A. Idriss Magda S. Saleh Mohamed M. Seleim Fatma S. Hassan Sherif K. Idriss 《Monatshefte für Chemie / Chemical Monthly》1990,121(8-9):625-634
Summary A simple, rapid, selective, and sensitive method for the spectrophotometric determination of palladium is developed based on the reaction of Pd(II) with 1-amino-4-hydroxyanthraquinone (AMHA). The reaction is carried out atpH 3.8 in 50% (v/v) ethanol-water medium. The molar absorptivity of the complexed ligand is 1.1 · 104 l mol–1 cm–1 at 620 nm. Calibration plots are linear up to 17 µg Pd cm–3. The optimum concentration range (Ringbom plot) is between 3–14.5 µg cm–3. The spectral study of the reaction in solutions containing equimolar concentrations or an excess of one component, in thepH range 0.3–6.5, indicate the possible complex transitions that occur in solution. Complete graphical and logarithmic analysis of the absorbance-pH graphs was performed to demonstrate and characterize the complexation equilibria in solution. Under the optimum conditions, palladium can be determined as the noncharged complex Pd(AMHA)2 in the presence of a large number of foreign ions. Interferences caused by zirconium(IV) could be masked with fluoride ions.
Eine neue spektrophotometrische Methode für die Bestimmung von Palladium in Spuren
Zusammenfassung Eine einfache, schnelle und empfindliche Methode für die spektrophotometrische Bestimmung von Palladium wurde auf der Basis der Reaktion von Pd(II) mit 1-Amino-4-hydroxyanthrachinon (AMHA) entwickelt. Die Reaktion wird in 50% (v/v) Ethanol/Wasser beipH 3.8 ausgeführt. Die molare Absorption des komplexierten Liganden beträgt 1.1 · 104 l mol–1 cm–1 bei 620 nm. Kalibrierungskurven verlaufen bis zu 17 µg Pd cm–3 linear. Der optimale Konzentrationsbereich (Ringbom-Plot) liegt zwischen 3 und 14.5 µg cm–3. Spektroskopische Untersuchungen der Reaktion in Lösungen, entweder mit equimolaren Konzentrationen oder mit einem Überschuß an einer Komponente impH-Bereich 0.3–6.5, lassen Rückschlüsse auf mögliche Komplex-Übergänge in Lösung zu. Es wurde eine vollständige graphische, logarithmische Analyse der Absorptions-pH-Graphen durchgeführt, um die Komplexgleichgewichte in Lösung aufzuklären und zu charakterisieren. Unter den Optimalbedingungen kann Palladium als nichtgeladener Komplex Pd(AMHA)2 in Gegenwart einer großen Anzahl an Fremd-Ionen bestimmt werden. Schwierigkeiten mit Zirkonium(IV) konnte durch Maskierung mit Fluorid-Ionen umgangen werden.相似文献