Determination of various hemoglobin species with thermal-lens spectrometry

Desoxyhemoglobin, oxyhemoglobin, carboxyhemoglobin, methemoglobin, cyanohemoglobin, and hemichrome are determined using thermal-lens spectrometry, with the detection limits at the level of 10^?8 M/l (2–5 mcg/l depending on hemoglobin species). Signal behavior and detectability thresholds are in good agreement with theoretical modeling based on the approach proposed earlier by the authors to describe thermal-lens signal generation in complex (inhomogeneous) systems. The thermooptical response for all studied hemoglobin species depends on the power of laser radiation within the range of 1–50 mW (532, 514.5, and 488 nm). Under the conditions of a thermal-lens experiment, the total temperature growth (0.0001 K) due to heating of the studied solution as the radiation of the inducing laser is absorbed by hemoglobin is estimated. Due to the interference with oxyhemoglobin the error in determining desoxyhemoglobin using thermal-lens spectrometry (for a maximum radiation power of 532 nm, 210 mW) does not exceed 3% in the case when the ratio of the species is 10: 1. In the opposite case (determination of oxyhemoglobin in the presence of desoxyhemoglobin), the error does not exceed 5%, the ratio of test and interfering species being the same.     

Determination of diacetyl with spectrophotometry and thermal-lens spectrometry

The conditions for the spectrophotometric and thermal-lens determination of diacetyl with creatine and 2-naphthol are proposed. The obtained value of the detection limit for spectrophotometry (at 527 nm), which amounts to 10 ng/mL, is fivefold lower than the existing values of the spectrophotometric determination of diacetyl. The conditions for the thermal-lens determination of diacetyl (λ = 514.5 nm, strength of the inducing radiation: 40 mW) based on the unmodified procedure of spectrophotometric determination were proposed. Along with a fivefold (down to 2 ng/mL) decrease in the detection limit, which is comparable with that for the determination of diacetyl by means of gas chromatography with mass spectrometric detection (detection limit of 0.7 ng/mL), thermal-lens determination is characterized by the enhancement of other performance parameters of the determination. It was shown that, contrary to the case when gas chromatography is used, ethanol does not interfere with both the spectrophotometric and the thermal-lens determination of acetyl.     

Microchannel-assisted thermal-lens spectrometry for microchip analysis

We present a new method for homocysteine quantitation in human plasma based on in-capillary reaction of homocysteine with 2,2′-dipyridyl disulfide. Homocysteine is in this so-called thiol-exchange reaction quantitatively transformed in mixed disulfide concomitantly with formation of an equimolar amount of 2-thiopyridone that is further separated by micellar electrokinetic chromatography and determined specifically at 343 nm. The concentration of homocysteine is thus estimated indirectly from the result of 2-thiopyridone determination. The linear detection range for concentration versus peak area for the assay was from 0.03–3 mM (correlation coefficient 0.994) with a detection limit of 6 μM and a limit of quantitation 20 μM. The inter-day reproducibility of the peak area and the migration time were 1.37% and 0.05%, respectively. The method is simple, relatively rapid and can be easily automated. Moreover the common capillary electrophoresis apparatus with a UV detector can be used to distinguish between normal and pathological hyperhomocysteinemia plasma samples.     

Investigation of ionene adsorption on quartz surfaces by thermal-lens spectrometry

Thermal-lens spectrometry was used for the investigation of the adsorption of ionene to quartz surfaces. The thermooptical analysis of the surface makes it possible to distinguish the modified surface from a clean quartz surface and to provide sensitive direct concentration measurements of the light absorbing co-adsorbed substance. The co-adsorption of chromate ions and 2,10-ionene from aqueous solutions to quartz surfaces was investigated and the desorption procedure proposed.     

Determination of copper in urine by carbon-furnace atomic-emission spectrometry

A method is described for the direct determination of copper in urine at normal (10-30 mug l .) levels by carbon-furnace atomic-emission spectrometry. Wavelength modulation is used to achieve automatic background correction for scatter-signals produced by the furnace and matrix. The accuracy of the method has been assessed by comparison with continuum-source atomic-fluorescence and carbon-furnace atomic-absorption methods. Relative standard deviations of about 4-5% can be achieved for either the platform or probe atomization techniques.     

Determination of copper and cadmium by atomic absorption spectrometry with electrochemical and sorption preconcentration

A method is proposed for the determination of copper and cadmium by atomic absorption spectrometry in a propane-butane-air flame with electrochemical and sorption preconcentration. Electrochemical preconcentration was performed on metal (tantalum, titanium, molybdenum, and platinum), glassy-carbon, and spectrographic graphite electrodes. Sorption preconcentration was performed on filter paper with immobilized dithizone, 8-hydroxyquinoline, and rubeanic acid. It is demonstrated that copper and cadmium can be determined in water within the concentration range 1–10 ώg/L.     

火焰原子吸收法测定粗锡中的铜含量

本文讨论了用火焰原子吸收法测定粗锡中的铜含量的方法。试料用盐酸、硝酸、酒石酸溶解。在5%盐酸介质中,使用空气-乙炔火焰,波长选用324.7 nm,用原子吸收光谱法测量铜的吸光度。以工作曲线法计算铜含量。研究了仪器的最佳测量条件,元素测定的质量数以及酸度的影响等实验。方法测定结果准确、可靠,样品加标回收率在97.20%~102.00%。能满足日常检测应用。     

Determination of copper in sulfide minerals by Zeeman electrothermal atomic absorption spectrometry

A method for the determination of copper in some sulfide minerals (lorandite, realgar, orpiment, marcasite, stibnite, galenite and sphalerite) by Zeeman electrothermal atomic absorption spectrometry is presented. After the dissolution of samples, copper was extracted with sodium diethyldithiocarbamate into different organic solvents (carbon tetrachloride, chloroform and methylisobutyl ketone) at pH 11.0–12.0. The procedure was verified by standard addition. The standard deviation (SD) for 0.5 ng Cu is 0.01 ng, the relative standard deviation ranges from 3.5 to 5.5% and the detection limit of the method, calculated as 3 SD of the blank, was found to be 0.05 μg · g^–1.     

Determination of copper in powdered chocolate samples by slurry-sampling flame atomic-absorption spectrometry

Chocolate is a complex sample with a high content of organic compounds and its analysis generally involves digestion procedures that might include the risk of losses and/or contamination. The determination of copper in chocolate is important because copper compounds are extensively used as fungicides in the farming of cocoa. In this paper, a slurry-sampling flame atomic-absorption spectrometric method is proposed for determination of copper in powdered chocolate samples. Optimization was carried out using univariate methodology involving the variables nature and concentration of the acid solution for slurry preparation, sonication time, and sample mass. The recommended conditions include a sample mass of 0.2 g, 2.0 mol L^–1 hydrochloric acid solution, and a sonication time of 15 min. The calibration curve was prepared using aqueous copper standards in 2.0 mol L^–1 hydrochloric acid. This method allowed determination of copper in chocolate with a detection limit of 0.4 g g^–1 and precision, expressed as relative standard deviation (RSD), of 2.5% (n=10) for a copper content of approximately 30 g g^–1, using a chocolate mass of 0.2 g. The accuracy was confirmed by analyzing the certified reference materials NIST SRM 1568a rice flour and NIES CRM 10-b rice flour. The proposed method was used for determination of copper in three powdered chocolate samples, the copper content of which varied between 26.6 and 31.5 g g^–1. The results showed no significant differences with those obtained after complete digestion, using a t-test for comparison.     

Determination of copper in sulfide minerals by Zeeman electrothermal atomic absorption spectrometry

A method for the determination of copper in some sulfide minerals (lorandite, realgar, orpiment, marcasite, stibnite, galenite and sphalerite) by Zeeman electrothermal atomic absorption spectrometry is presented. After the dissolution of samples, copper was extracted with sodium diethyldithiocarbamate into different organic solvents (carbon tetrachloride, chloroform and methylisobutyl ketone) at pH 11.0–12.0. The procedure was verified by standard addition. The standard deviation (SD) for 0.5 ng Cu is 0.01 ng, the relative standard deviation ranges from 3.5 to 5.5% and the detection limit of the method, calculated as 3 SD of the blank, was found to be 0.05 μg · g^–1. Received: 26 May 1997 / Revised: 10 September 1997 / Accepted: 16 September 1997     

蒸气发生火焰原子吸收法测定面粉中的铜

用自制的蒸气发生装置,在强还原剂存在下,对铜蒸气的生成进行了详细研究,并通过该装置测定非蒸气发生元素镁和在络合剂掩蔽下测铜两种不同的方法进行了验证。对酸的种类及浓度、NaBH4溶液流速及浓度、反应管道长度的影响等实验参数和干扰情况进行了研究。用该方法测定了面粉中铜的质量分数,检出限为6μg L。     

浊点萃取-原子吸收光谱法测定塑料中的痕量铜

建立了以1-(2-吡啶偶氮)-2-萘酚(PAN)为络合剂、Triton X-100为表面活性剂的浊点萃取-原子吸收光谱法测定痕量铜的分析方法。探讨了溶液的pH、络合剂和表面活性剂用量、平衡温度和平衡时间等因素对浊点萃取的影响。最佳条件下,线性方程为Y=0.1049X+0.0016,相关系数为0.9988,检出限为0.7μg/L,相对偏差为2.3%,富集倍数为15倍。用该方法对几种塑料制品中的痕量铜进行测定,回收率为97.5%～101.9%。     

Optimization of cloud point extraction of copper with neocuproine from aqueous solutions using Taguchi fractional factorial design

Taguchi method was applied to optimize cloud point extraction (CPE) conditions for preconcentration and determination of trace amounts of copper by UV-Vis spectrophotometry. Briefly, the copper ions formed complexes with neocuproine in aqueous solution; then, Triton X-114 (0.15%, w/v) was added and phase separation occurred upon heating to 60°C. The copper complexes were preconcentrated into the small volume of the surfactant-rich phase; after centrifugation, the surfactant-rich phase was diluted with methanol and absorbance was measured at 455 nm. The main factors affecting the CPE were evaluated and optimized with Taguchi orthogonal array design (OA ₂₅). Under the optimum conditions, the calibration curve was linear in the range 2–500 μg/L (r ² > 0.997). The limit of detection and preconcentration factor were 1.8 μg/L and 37.2, respectively. The applicability of the proposed method was successfully confirmed by preconcentration and determination of trace amounts of copper in water samples and satisfactory results were obtained.     

电气材料铜及铜合金中痕量杂质砷元素的氢化物发生-原子荧光光谱法测定

本文建立了氢化物发生-原子荧光光谱法测定电气材料铜及铜合金中痕量杂质元素砷的方法。通过使用L-半胱氨酸与铜基体形成络合物,抗坏血酸充分预还原砷,消除了基体干扰,并实现了铜及铜合金中痕量杂质砷的准确测定。在经过优化的实验条件下,砷的检出限为0.12 ng·m L-1,线性相关系数优于0.999,相对标准偏差小于4%。用加标回收法测定实际样品,回收率在92%到103%之间。该法操作简便,灵敏度高,无需基体预分离。     

八极杆碰撞/反应池-ICP-MS测定纯铜中的磷

利用ORS-ICP-MS测定纯铜中的磷. 对ICP-MS测定条件进行了最佳化的选择, 利用动态反应池技术(ORS)和在线内标加入技术, 可降低基体干扰, 提高灵敏度. 分析方法的检出限为0.33 ng/mL, 加标回收率为94%～97%.     

Determination of copper in geological material by neutron activation and gamma-gamma coincidence spectrometry

The copper content of some geological samples has been determined by thermal neutron activation and subsequent coincidence gamma-spectrometry, taking advantage of the 180 degrees annihilation quanta of (64)Cu. By this means the interference of (24)Na, which is often the major gamma-activity induced in geological materials, is greatly reduced. The method is precise to about +/- 5 %, and the error is of the same order. The method should be especially attractive for application to samples with a copper content of 100-1000 ppm.     

Determination of copper in glasses by flame atomic absorption and plasma emission spectrometry

Summary Ground samples (150m, 0.5 g) are decomposed in a mixture of HF and HNO₃ acids followed by evaporation to dryness, dissolution of the residue in dilute HNO₃ acid, and dilution to 50 ml. Spectral interferences of 14 tested elements are negligible for AAS but in some cases (Nb, Ti, Zr) minor spectral corrections must be made for plasma techniques depending on the level of interferent and analyte. Nonspectral (matrix) interferences at the 1000g/ml interferent level are all less than 3.5% relative for AAS and less than 5% relative for ICP (except for Ca, Li, and Na where the effects are depressions of 7 to 10% relative). Matrix effects for DCP at the same interferent level are generally more pronounced and amount to enhancements of 5 to 15% relative for 11 of the 14 elements tested. Plasma matrix effects, especially alkali effects, can be compensated by the use of an alkali-aluminum buffer medium (1000g Na/ml plus 500g Al/ml as used in this study), a procedure which is most useful for the DCP approach. Copper can be determined down to 10 ppm in the original sample. A comparison of results shows AAS and ICP to be in good agreement with the DCP being slightly less accurate, although the differences in results may be of little practical significance. In terms of freedom from spectral and non-spectral interference, AAS was judged to have a slight advantage for copper.

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Bestimmung von Kupfer in Gläsern durch Flammen-Atomabsorption und Plasma-Emissions-Spektrometrie

Zusammenfassung Gemahlene Proben (150m, 0,5 g) werden in einem Gemisch aus HF und HNO₃ aufgeschlossen, zur Trockne verdampft, in verd. HNO₃ gelöst und auf 50 ml verdünnt. Spektrale Interferenzen 14 geprüfter Elemente sind bei der AAS ohne Belang, aber in manchen Fällen (Nb, Ti, Zr) sind je nach der Größenordnung der Störfaktoren geringe spektrale Korrekturen erforderlich. Nichtspektrale (der Matrix zuzuschreibende) Störfaktoren in der Größenordnung von 1000g/ml bewirken weniger als 3,5% rel. Abweichung bei der AAS und weniger als 5% rel. bei ICP (inductively coupled plasma) (ausgenommen Ca, Li und Na, die eine Minderung der Werte um 7–10% bewirken). Matrixeffekte bei DCP (direct coupled plasma) bei gleicher Größenordnung des Störfaktors sind im allgemeinen stärker ausgeprägt und bewirken bei 11 von 14 geprüften Elementen Steigerungen um 5–15% rel. Plasma-Matrix-Effekte, besonders Alkali-Effekte lassen sich mit Hilfe eines Puffermediums (1000g Na/ml+500g Al/ml) kompensieren, was sich vor allem bei DCP bewährt hat. Cu kann bis zu 10 ppm in der ursprünglichen Probe bestimmt werden. Die Ergebnisse von AAS und ICP stimmen gut überein mit denen von DCP, die etwas weniger genau sind; diese Differenzen dürften aber praktisch nur wenig bedeuten. Abgesehen von spektralen Störungen erwies sich AAS für Cu etwas vorteilhafter.

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Presented at the 9th International Symposium on Microchemical Techniques, Amsterdam, August 28–September 2, 1983.     

新铜试剂分光光度法测定片剂中的对乙酰氨基酚含量及其反应机理的研究

使用分光光度法测定扑热息痛中主要化学成分对乙酰氨基酚的含量。结果表明:在0.04~8.00 mg·L-1范围内对乙酰氨基酚含量与吸光度(A)呈良好的线性关系,其线性方程:A=0.1210c+0.0261,相关系数r=0.9968。表观摩尔吸光系数为1.8×104 L·mol-1·cm-1,平均回收率为100.2%,相对标准偏差RSD为1.51%。该实验所用仪器简单,且操作方便、快速。用该方法测定扑热息痛片剂对乙酰氨基酚的含量,取得了较好的效果。