Determination of Copper,Cobalt, Lead,and Iron in Table Salt by FAAS After Separation Using Violuric Acid and Multiwalled Carbon Nanotubes

A separation–enrichment technique for the determination of trace amounts of copper(II), cobalt(II), lead(II), and iron(III) as violuric acid chelates on multiwalled carbon nanotubes at pH 6.0 was established. Analytes were determined by flame atomic absorption spectrometry. The effects of some analytical parameters like pH, amounts of violuric acid, flow rates, eluent type, and sample volume were investigated. The influences of the matrix ions were also investigated. The relative standard deviations for analyte elements were below 10%. The quantification limits of the analyte ions were found as 0.36 μg g⁻¹ for copper, 0.43 μg g⁻¹ for lead, 0.15 μg g⁻¹ for cobalt, and 0.38 μg g⁻¹ for iron. The accuracy of presented method was checked by the analysis of TMDA 54.4 fortified lake water, NIST SRM 1515 apple leave, and HR-1 Humber river sediment certified reference materials. The method was applied to analyte contents of table salt samples from different origin. The levels of iron in the analyzed table salt samples were found in the range of 1.6–6.4 μg g⁻¹, while lead was found in only one sample as 5.0 μg g⁻¹. In all other samples, cobalt, lead, and copper were found below the quantification limits of the analytes.     

Micelle-Mediated Extraction and Flame Atomic Absorption Spectrometric Method for Determination of Trace Cobalt Ions in Beverage Samples

A new method has been developed for preconcentration of cobalt at trace levels in beverage samples using calcon carboxylic acid as chelating agent and cetyl pyridinium chloride as an auxiliary ligand and entrapped into Triton X-114 prior to its determination by flame atomic absorption spectrometry (FAAS). The main parameters affecting cloud point extraction (CPE) efficiency such as pH, concentration of the complexing agent, cationic and nonionic surfactant concentration, salt effect, the equilibrium time, and temperature were investigated and optimized. After optimization of the CPE conditions, a preconcentration factor of 60, an enhancement factor of 106, and a detection limit of 0.20 μg L⁻¹ by (R ² = 0.9978) were obtained from a calibration curve constructed in the range of 0.7–100 μg L⁻¹. The proposed preconcentration procedure was successfully applied to the determination of cobalt ions in some real samples including natural drinking water, tap water, and beer and wine samples. The accuracy and validity of the proposed CPE/FAAS method was tested by means of five repeated analysis of reference standard materials (TM-253, a low level fortified water standard for trace elements). A good agreement between analytical results (28.8 and 28.5 μg L⁻¹ with calibration curve and standard addition curve method, respectively) and certified value (27.9 μg L⁻¹) for Co (p < 0.05) were obtained and verified by means of calibration curve and standard addition curve method using CPE procedure.     

双色量子点多层膜用于水环境中 微量汞离子的定量检测

目的建立水环境中微量汞离子的定量检测方法。方法 通过层层自组装法将表面带有负电荷的Cd Te量子点与聚电解质PDDA交替沉积在石英板上,成功制备出双色量子点多层膜。在该方法中Hg2+对Cd Te量子点有荧光猝灭作用,据此发展了一种直接检测Hg2+的新型双色Cd Te量子点多层膜传感器。结果 实验结果表明:当Hg2+浓度在1.0×10-9~1.0×10-5mol/L范围时,量子点多层膜的荧光强度与Hg2+浓度之间有良好的线性关系,检出限为2.5×10-10mol/L。结论 与传统Hg2+检测方法相比,双色Cd Te荧光量子点多层膜作为一种新型传感器,具有快速、简单、选择性高和灵敏度高等优点,有望应用于水环境中痕量Hg2+的定量检测与早期预警。     

Determination of organic acids evolution during apple cider fermentation using an improved HPLC analysis method

An efficient method for analyzing ten organic acids in food, namely citric, pyruvic, malic, lactic, succinic, formic, acetic, adipic, propionic and butyric acids, using HPLC was developed. Boric acid was added into the mobile phase to separate lactic and succinic acids, and a post-column buffer solution [5 mmol/L p-toluensulfonic acid (p-TSA) + 20 mmol/L bis (2-hydroxyethyl) iminotris (hydroxymethyl) methane (bis–tris) + 100 μmol/L sodium ethylenediaminetetraacetic (EDTA-2Na)] was used to improve the sensitivity of detection. The average spiked recoveries for the ten organic acids ranged from 82.9 to 127.9% with relative standard deviations of 1.44–4.71%. The linear ranges of determination were from 15 to 1,000 mg/L with correlation coefficients of 0.9995–0.9999. The metabolism of organic acids in cider, and the effect of nutrients including diammonium phosphate (DAP), thiamine, biotin, niacinamide and pantothenic acid on their metabolism, were studied using this method of analysis. We found that before cider brewing, additions of 200 mg/L DAP and 0.3 mg/L thiamine to apple juice concentrate results in a high quality cider. F. Zhou and B. Ji contributed equally to this work.     

Optimization analysis by capillary electrophoresis of thiamine in meat: comparison with high perfomance liquid chromatography

 A new capillary electrophoresis (CE) method for the analysis of thiamine in meat is proposed. Samples were submitted to acidic and enzymatic hydrolysis and the extracts were purified using ethanol and an ion exchange column. The thiamine content was determined by CE using 100 mM sodium tetraborate, 50 mM sodium phosphate (pH 7.6), 50 mM sodium dodecyl sulphate and 10% isopropyl alcohol as a separation buffer solution. The analysis was carried out at 15 kV and 50  °C in a 70 cm effective length× 75 μm i.d. fused-silica capillary using on-column UV detection at 254 nm and 7 s injection time (27 nl injection volume). The results obtained by CE for thiamine contents in meat were compared to those obtained by HPLC using an ion-pair reverse phase column with post-column derivatization and fluorescence detection. Received: 24 August 1998 / Revised version: 21 January 1999     

Development of a Direct Competitive Biomimetic Enzyme-Linked Immunosorbent Assay Based on a Hydrophilic Molecularly Imprinted Membrane for the Determination of Trichlorfon Residues in Vegetables

In recent years, there has been an increasing demand on the determination of trace trichlorfon residues in fresh vegetables. In this study, a sensitive direct competitive biomimetic enzyme-linked immunosorbent assay (BELISA) method was developed for the determination of trichlorfon based on a hydrophilic imprinted membrane, which was directly synthesized on the well surface of MaxiSorp polystyrene 96-well plate through bulk polymerization technology. This novel imprinted membrane was characterized with high binding ability and specificity. Under the optimal conditions, the sensitivity (IC₅₀, half maximal inhibitory concentration) and the limit of detection (LOD, IC₁₅) of this method were 6800 ± 60 μg/L and 6.8 ± 0.20 μg/L, respectively. This BELISA method had been applied to the determination of trichlorfon with good recoveries ranging from 106.0 to 110.5%, and the results were correlated with that obtained by the gas chromatography method. Moreover, this method was applied to quantitative detection of trichlorfon residues in the leek samples.     

Development of an Analytical Method for the Combined Determination of Water-Soluble Vitamins and Minerals Through High-Performance Liquid Chromatography–Inductively Coupled Plasma Atomic Emission Spectrometry Hyphenation

The capabilities of inductively coupled plasma atomic emission spectrometry (ICP-AES) for the determination of water-soluble vitamins after high-performance liquid chromatography (HPLC) separation have been evaluated for the first time in the present work. Thanks to the multielemental capability of ICP-AES, it has been possible to develop a method for the joint determination of several water-soluble vitamins and minerals. The vitamin chromatograms were obtained by plotting the carbon corrected emission intensity against time. Meanwhile, minerals were determined through the measurement of the emission intensity at their characteristic wavelengths. The established method was applied to the determination of thiamine, riboflavin, pantothenic acid, nicotinamide, ascorbic acid, Cr, Mo, Se, Mn, Zn, Fe, Mg, Ca, and K in multivitamin complexes. Good linearities were obtained, with correlation coefficients above 0.999 for all the vitamins and metals. The detection limits using ICP-AES for vitamins were lower than 10 mg L⁻¹ except for biotin (18 mg L⁻¹) and ascorbic acid (35 mg L⁻¹). Moreover, the limits of detection for metals ranged from 0.3 mg L⁻¹ for K and 0.02 mg L⁻¹ for Mo. Even though the ICP is less sensitive than PDA and MS for vitamin determination, the HPLC-ICP-AES allows determination of vitamins and minerals in a period of time not much higher than that required for the simple determination of the minerals, and it is less sensitive to interferences in trace quantities.     

Potential of Sawdust as a Green and Economical Sorbent for Simultaneous Preconcentration of Trace Amounts of Cadmium,Cobalt, and Lead from Water,Biological, Food,and Herbal Samples

Application of treated sawdust with NaOH as a green and economical sorbent for simultaneous preconcentration of trace amounts of Cd(II), Co(II), and Pb(II) ions from liver, lettuce, fish, and water as test samples with complicated matrices was investigated. Various parameters, such as effect of pH and contact time, breakthrough volume, type, and concentration of eluent and interference of ions were studied. The sorption was quantitative in the pH of 5.0 to 7.0 and desorption occurred instantaneously with 5.0 mL of mixed solutions of ethanol and 2.0 mol/L HNO₃–HCl and the amount of ions was measured by using flame atomic absorption spectrometry. Linearity was maintained at 3 to 500 μg/L for cobalt, 5.0 to 800 μg/L for lead, and 2.0 to 300 μg/L for cadmium in the original solution. The relative standard deviation was less than 1.80% (n = 6, with concentration of 0.3 mg/L for cadmium and 0.5 mg/L for lead and cobalt). Detection limits and maximum capacity of the sorbent for Co (II), Cd (II), and Pb (II) in the original solution were 0.86, 0.50, and 1.7 μg/L and 28.5, 30.6, and 47.3 mg/g, respectively. The results for spiked real samples, effect of interfering ions, and adsorption capacity indicated that the applicability of this method for lead preconcentration is better than cadmium and cobalt preconcentration from complicated matrices. Practical Application : Sawdust can be applied as a green and economical sorbent for simultaneous preconcentration and solid‐phase extraction of metal ions from food and environmental samples with complicated matrices.     

Enzymatic Catalytic Spectrophotometric Determination of Thiamine in Food

A highly sensitive and simple spectrophotometric method for the determination of thiamine based on inhibitory effect of thiamine on the hemoglobin-catalyzed reaction of H₂O₂ with acid chrome blue K was developed. The concentration of thiamine is linear with the percentage inhibition of system under the optimal experimental conditions. The calibration curve is linear in the range 3 × 10⁻⁷ to 3.00 × 10⁻⁵ M with the detection limit of 1.2 × 10⁻⁸ M. This method can be used for the determination of thiamine in food with satisfactory results.     

Determination of capsaicinoids in foods using ultra high performance liquid chromatography

A sensitive, precise, and specific ultra high performance liquid chromatographic (u-HPLC) method was developed for the analysis of capsaicin in foods. The method validation parameters yielded good results, including linearity, precision, accuracy, and recovery. The u-HPLC separation was performed on a reversed column C₁₈ (particle size 2 μm, i.d. 2 mm, length 50 mm, followed by fluorescence detection-excitation 280 nm, emission 325 nm). The recovery of capsaicin in gochujang was more than 91%, and the detection limit and lower determination limit of u-HPLC analysis were 0.054 and 0.163 μg/mL for capsaicin and 0.053 and 0.160 μg/mL for dihydrocapsaicin, respectively. The calibration graph for capsaicin and dihydrocapsaicin was linear from 0.2 to 10.0 μg/mL for u-HPLC analysis. The inter-day and intra-day precisions (relative standard deviations) were <5.21% for capsaicin and <9.79% for dihydrocapsaicin while the average recoveries obtained were quantitative 91.1–94.8% for capsaicin, 91.4–97.0% for dihydrocapsacin, indicating good accuracy of the u-HPLC method.     

纸质食品包装材料中荧光增白剂迁移规律的研究

采用浸泡方式提取纸质食品包装中的荧光增白剂,并以VBL为标准物质建立了对纸质食品包装中荧光增白剂定量检测的方法。该方法激发波长345nm,发射波长430nm;定量标准曲线为y=121.58x-0.6535,在0～0.8μg/ml范围内线性相关性R2=0.9997;回收率在78%～90%之间,三种加标浓度测定值的相对标准偏差RSD均小于3%,可满足检测要求。通过对荧光增白剂迁移规律的探讨,发现浸泡时间到2h时,迁移量会出现大的跳跃;温度升高会使荧光增白剂的迁移量增大;VBL在酸性条件下的荧光强度明显下降,而碱性条件下荧光强度会增强。     

Assay of Total Mercury in Commercial Food Supplements of Marine Origin by Means of DLLME/ICP-AES

In this work, we have developed a sensitive and cost-effective preconcentration and quantification methodology for total mercury (Hg) at trace levels in food supplements of marine origin. Dispersive liquid–liquid microextraction was successfully employed for the preconcentration of mercury at trace levels prior to inductively coupled plasma atomic emission spectrometry. The mercury was extracted as mercury-1, 5-diphenyl-3-formazathiol complex, at pH 1.0 mediated by multidroplet formation of microextraction solvent assisted by disperser solvent. The lower limit of detection obtained under the optimal conditions was 0.24 μg L⁻¹. The calibration graphs were linear up to 500 μg L⁻¹. The precision of the method in terms of relative standard deviation was 4.8% for the concentration of 100 μg L⁻¹. In order to validate the proposed method, a certified reference material RTC-QCI-049 was analyzed with the proposed procedure. Moreover, potential interference by 20 species was also evaluated.     

A Rapid Spectrophotometric Method for Trace Determination of Zinc

A simple, sensitive, and highly selective method is proposed for the determination of zinc(II) using a bis-azo dye, 2,6-bis(1-hydroxy-2-naphthylazo)pyridine as spectrophotometric reagent. At pH 7.8, in 50% (v/v) ethanol–water medium, the complex is found to obey Beer’s law up to 1.3 mg/L with an optimum concentration range between 0.19 and 1.0 mg/L. Sandell’s sensitivity of the color reaction was calculated to be 0.0011 μg cm⁻² with molar absorptivity of 6.0 × 10⁴ L mol⁻¹ cm⁻¹ at 560 nm. The optimum conditions for the determination of Zn(II) with the reagent were ascertained. The complexation at different pH was studied in water–ethanol medium. The composition of the complex is 1:2. The action of some interfering ions was verified, and the developed method applied successfully for the estimation of zinc levels in food and milk samples, and the results were then compared with those obtained by using AAS.     

Determination of low levels of aziridine in official EU food simulants by capillary gas chromatography

 An analytical method for the determination of the specific migration of aziridine (ethyleneimine) into food simulants at trace levels is described. The method comprises a two-phase (aqueous-organic solvent) derivatization procedure with 4-fluorobenzoyl chloride, using propyleneimine as an internal standard. The derivatization reaction is accomplished very quickly and the organic layer containing the derivatized imine is analysed by capillary gas chromatography using selective nitrogen detection (nitrogen-phosphorus detector). The detection limits of the method were lower than 5 μg/kg in the food simulant. Received: 5 June 1996     

Quantification of Nitrite/Nitrate in Food Stuff Samples Using 2-Aminobenzoic Acid as a New Amine in Diazocoupling Reaction

2-Aminobenzoic acid has been used as an amine in diazocoupling reaction to form an azo dye in the quantification of nitrite/nitrate at trace level. The formed azo dye has an absorption maximum at 550 nm in aqueous phase, and the resulted dye can be extracted into organic solvent to lower the detection limit. The method obeys Beer's law in the concentration range 0–10 μg of nitrite in 25 ml of aqueous solution with a molar absorptivity of 3.6 × 10³ L mol⁻¹ cm⁻¹ and 0–2 μg of nitrite in 5 ml of organic phase. The detection limit of the dye has been found to be 0.056 μg ml⁻¹. Nitrate is determined by reducing it to nitrite after passing through a copperized cadmium reductor column. The effect of interfering ions on the determination of nitrite/nitrate has been described. The developed method has been applied to determine the nitrite/nitrate trace level in vegetable, fruit juice, and milk powder samples.     

Generation of a green fluorescent protein gene chromosomal insertion containing Escherichia coli strain for gene induction-based quantification of bioavailable lysine

The importance of lysine determination in feed materials is crucial for the feed industry because this amino acid can be limiting in many of the cereal materials used for animal feeds. The bacterial gene induction-based assay developed in this study aimed to measure lysine bioavailability in feeds as an alternative analytical method for animal assays. The advantages of a gene induction-based approach include rapid and quantitative estimation of many samples and results that relate a bacterial response to a biological response observed in animals. A whole-cell biosensor strain was constructed using a fluorescent E. coli strain that has an inducible fluorescent phenotype sensitive to extracellular lysine contents. A genetic fusion that links the promoter of cad operon with a green fluorescent protein encoding gene (gfp) was constructed, and a fluorescent assay was developed. A standard lysine curve (R² = 0.95) was generated and used for lysine bioavailability quantification of four feed ingredients (whole egg protein, blood-, soybean-, and meat and bone meal). Quantities as low as 50 μg/ml protein of digested samples were sufficient for analyses using the biosensor, except for meat and bone meal. Because of the low levels of free lysine in non-digested samples, fluorescence of these protein sources containing lower than 500 μg/ml protein was not detected (except for soybean meal). The results using enzymatically digested protein sources showed that the test strain emitted a fluorescent response that was proportional to the level of lysine present in the feed samples.     

现代光度分析法测定食品中痕量铅的研究与应用

对现代光度分析法,主要是普通光度法、胶束增溶分光光度法、固相光度法、催化光度法、流动注射光度法、荧光光度法等测定食品中痕量铅的研究进展作一综述。     

The structure functional catalytic activity of rice bran lipase in the presence of selenium and lithium

Rice bran lipase (RBL), an esterase (EC 3.1.1.3) is a versatile enzyme that catalyzes the hydrolysis of ester linkages, primarily in neutral lipids, such as triglycerides. The catalytic activity of RBL in the presence of selenium and lithium has been investigated. Lipase isolated from rice bran was treated with different concentrations of selenium and lithium ions and further subjected to activity determination, along with the kinetics of inhibition of RBL in conjunction with structure–function relationship of the enzyme. Both ions showed competitive inhibition of RBL activity in a concentration-dependent manner (1 μM to 1 mM). At 1 mM concentration of SeO₂ and Li₂SO_4, the enzyme loses its activity by 78 and 71%, respectively. From the analysis of the kinetic data, the inhibition constant K _i is found to be 4 μM for Li₂SO_4, and 1 μM for SeO₂, respectively. Spectrofluorimeter analysis and far UV-CD data showed minor changes in the emission intensity and conformation of the RBL in the presence of these ions at the above concentration. The results suggest that both selenium and lithium specifically inhibit RBL by probably binding near to the catalytic site or distorting the geometry of the active site of the RBL triad.     

氢化物原子荧光光谱法测定蔬菜罐头中的痕量锡

本文研究了氢化物原子荧光光谱法测定蔬菜罐头食品中的痕量锡最佳检测条件以及样品基体介质、KBH4浓度、酸介质浓度对锡检测结果的影响,并对测定锡时共存离子的干扰和消除进行了探讨,建立了盐酸作为介质,铁氰化钾和草酸作为掩蔽剂的检测方法,本方法的线性范围为1.23～300μg/L,在0～160μg/L范围内,相关系数r=0.9997,检出限为1.23μg/L,相对标准偏差为1.22%～1.85%,回收率为89.6%～105.4%。     

氧化胭脂虫红酸用于蘑菇中的铁离子检测

为进一步开发胭脂虫红酸的荧光检测应用，以胭脂虫红酸为原料，高碘酸钾为氧化剂，通过乙醇/水热法一步合成水溶性可发射蓝色荧光的氧化胭脂虫红酸（oxidized carminic acid，OCA）。通过傅里叶变换红外光谱法和X射线光电子能谱分析表明OCA结构中含有共轭芳香环结构和丰富的含氧官能团，透射电子显微镜和动态散射光测试表明其平均粒径约为7.5 nm。光学测试表明，OCA的荧光发射位于380～620 nm区间，最大激发波长为336 nm，最大发射波长为445 nm；其荧光在pH 1～9的溶液和含有不同阴离子的盐溶液中稳定性良好；紫外-可见光测试显示其在波长225 nm处有最大吸收峰。OCA对铁离子（Fe3＋）有良好的选择性，加入Fe3＋会导致其荧光强度明显降低，荧光发射峰积分面积减小率与Fe3＋质量浓度在11.2～56.0 mg/L范围内具有良好的线性关系，检出限为2.5 mg/L。应用结果表明，基于OCA作为荧光传感器的荧光检测方法用于实际样品中Fe3＋的检测，样品回收率在95.3%～110.4%之间，相对标准偏差在2.3%～4.6%之间，表明该方法可用于香菇、白菇和杏鲍菇等蘑菇中Fe3＋的含量检测，方法可靠。