高效液相色谱法同时测定食品中10种合成着色剂

目的 建立一种高效液相色谱法同时测定食品中10种合成着色剂(柠檬黄、新红、觅菜红、靛蓝、胭脂红、日落黄、诱惑红、亮蓝、喹琳黄、赤藓红).方法 用GB/T 5009.35-2003(食品中人工合成着色剂的测定方法)中试样处理方法制备样品溶液,聚酰胺吸附法提取色素,以甲酵/乙睛(3+1)+乙酸铵(0.02 mol/L,pH =4.0)为流动相,梯度淋洗分离,多波长检测定量.结果 线性范围分别为柠檬黄、觅菜红、靛蓝、胭脂红、日落黄于0.94-30.00p.g/ml,新红于0.94～30.00μg/ml,诱惑红于1.00～32.10μg/ml,亮蓝于0.31～10.00μg/ml,喹琳黄于1.219.68μg/ml,赤藓红于0.76～24.40μg/ml,线性关系良好,相关系数0.999 0～1.000 0,回收率87.5% - 101.4%,RSD 1.3%～5.7%,检出限分别为0.03～ 0.9 mg/kg.结论 该方法简单、准确、灵敏,适用于食品中10种合成着色剂的定量分析.     

Solid‐phase extraction and spectrophotometric determination of Allura Red (E129) in foodstuff,soft drink,syrup and energy drink samples: a comparison study

Amberlite XAD‐7 and XAD‐8 resins were used as adsorbents for preconcentration and determination of Allura Red (AR) food dye in aqueous medium. The effects of pH, sample volume, sample and eluent flow rates on the extraction of AR were optimised. The determination of dye was performed at 506.0 nm using spectrophotometry. Interference effects of matrix ions and some dyes were also investigated under optimised conditions. The methods permitted low detection limits which were 1.2 and 0.6 μg L^?1 for XAD‐7 and XAD‐8, respectively. Adsorption behaviours were investigated by adsorption isotherms and zero charge pH experiments. Validations of the method were performed by determination of AR contents in some foodstuffs. AR contents of liquid samples were found between 58 and 440 μg mL^?1. AR concentrations of solid samples were between 416 and 432 μg g^?1. The XAD‐7 and XAD‐8 resins presented a fast and reliable potential to determine AR dye in real samples.     

Total Mercury, Inorganic Mercury and Methyl Mercury Determination in Red Wine

This study deals with the development of a method for total Hg, inorganic Hg and methylmercury (MeHg) determination in red wine by using flow injection-cold vapour generation–inductively coupled plasma mass spectrometry (FI-CVG-ICP-MS) and gas chromatography-ICP-MS (GC-ICP-MS). For Hg speciation analysis, a derivatization step was carried out using a 1% (m/v) sodium tetraphenylborate (NaBPh₄) solution, followed by extraction of Hg species and their quantification by GC-ICP-MS. The main parameters evaluated were the make-up gas flow rate, volume of the NaBPh₄ solution, time for derivatization reaction/analyte extraction and solvent used for Hg species extraction. Accuracy was evaluated by analyte recovery, whereas recoveries ranged from 99% to 104% for Hg(II) and MeHg. The limits of detection (LODs) for Hg(II) and MeHg were 0.77 and 0.80 μg L⁻¹, respectively. Wine from Argentina, Brazil, Chile and Uruguay were analysed. The wine samples were also acid digested for total Hg determination by FI-CVG-ICP-MS. The LOD of the method used for total Hg determination was 0.01 μg L⁻¹. The concentrations of Hg species in red wine measured by GC-ICP-MS were lower than the respective LODs. Only total Hg was detected in the analysed samples, where the highest concentration of Hg found was 0.55 ± 0.02 μg L⁻¹.     

Determination of Rosmarinic Acid by High-Performance Liquid Chromatography and Its Application to Certain Salvia Species and Rosemary

This study describes a method development for the determination of rosmarinic acid (RA) by using a gradient high-performance liquid chromatography (HPLC) and its application to certain plant materials. The analysis was performed by utilizing a two solvents system [A: methanol/water/formic acid (10:88:2; v:v:v); B: methanol/water/formic acid (90:8:2; v:v:v)] on a reverse-phase column. The flow rate and injection volume were 1 ml min⁻¹ and 10 μl, respectively. Signals were detected at 280 nm. In addition, an internal standard (IS) technique was applied for the analysis of RA to increase precision, and propylparaben was employed for this purpose. The repeatability results as RSD% were 1.66, 1.17 and 1.26 for intra-day and 1.38 was for inter-day with the employment of (3.67 × 10⁻⁵ M) RA. A limit of linearity (LOL) was observed in a wide (1.13 × 10⁻⁵–5.65 × 10⁻⁴ M) concentration range. Linearity parameters were also examined in the range of 5.95 × 10⁻⁶–7.14 × 10⁻⁵ M RA, and very good correlation was observed. The limit of detection (LOD) and limit of quantification (LOQ) (for inter-day) were 1.60 × 10⁻⁶ M (signal/noise [S/N] = 3.3) and 4.80 × 10⁻⁶ M (S/N = 10), respectively. The method was applied to the extracts of certain Lamiaceae plants (Salvia candidissima Vahl. subsp. candidissima, S. sclarea L., S. verticillata L. subsp. verticillata and R. officinalis L.), and reasonable results were obtained.     

Co-production of Lactic Acid and <Emphasis Type="Italic">Lactobacillus rhamnosus</Emphasis> Cells from Whey Permeate with Nutrient Supplements

Lactic acid and cell production from whey permeate by Lactobacillus rhamnosus with different nutrient supplements were investigated in this study. Yeast extract was identified as the most effective nutrient affecting lactic acid production. Increase in inoculum size from 0.05% to 1% (v/v) resulted in a substantial increase in lactic acid productivity from 0.66 to 0.83 g L⁻¹ h⁻¹ (P < 0.001). The optimal temperature for lactic acid production was 37 °C, while the highest cell production was obtained at 42 °C. When whey permeate and yeast extract concentrations were 6.8% (w/v) and 3 g L⁻¹, respectively, lactic acid productivity reached 0.85 g L⁻¹ h⁻¹ after 48-h cultivation, which is 3.40 times of those without nutrient supplements.     

Determination of Melamine in Liquid Milk and Milk Powder by Titania-Based Ligand-Exchange Hydrophilic Interaction Liquid Chromatography

A simple and rapid high-performance liquid chromatography (HPLC) procedure for the analysis of melamine in liquid milk and milk powder has been developed. Decrease of acetonitrile percentage and phosphate buffer concentration in mobile phase, and lowering of buffer pH and column temperature would benefit the retention of melamine on titania. Taking advantage of the ligand-exchange and hydrophilic interaction mixed retention mode on bare titania column, neither complex pretreatment nor ion-pair reagent was required. The whole analysis for one sample including sample pretreatment and HPLC analysis could be accomplished within 30 min. The method presented good linearity (R ² = 0.9998) in a wide range of 0.02–10 μg mL⁻¹. The limit of detection (3σ) and limit of quantification (10σ) of the method were 6 and 20 μg L⁻¹, respectively, which were equivalent to 15 and 50 μg kg⁻¹ melamine in liquid milk, 60 and 200 μg kg⁻¹ melamine in milk powder, respectively. Such sensitivity could be compared with those obtained by HPLC with solid-phase extraction or HPLC coupled with tandem mass spectrometry and was adequate for the screening of melamine in tainted dairy products. The repeatability (RSDs) of the retention times and peak areas of 11 replicate detections of 1.0 μg mL⁻¹ melamine were 0.32% and 2.5%, respectively. The intermediate precision on three consecutive days (RSDs, n = 6) of the retention times and peak areas were 1.1% and 2.3%, respectively. The recovery of spiked melamine in dairy samples ranged from 95.2% to 105%. The simplicity, sensitivity and rapidity of the proposed method make it an effective alternative detecting technique for melamine.     

高效液相色谱法同时检测虾制品中合成色素

采用高效液相色谱与二极管阵列检测器联用,建立了虾制品中柠檬黄、日落黄、偶氮玉红、苋菜红、胭脂红、赤藓红、红色2G和诱惑红等8种合成色素的多组分同时检测方法。样品采用甲醇-尿素溶液提取,提取液经固相萃取聚酰胺柱净化后,在XDB-C 18色谱柱上,由甲醇-乙腈和乙酸钠溶液组成流动相梯度洗脱条件下8种合成色素在17 min内实现了成功分离。各色素在0.05 mg/L～50 mg/L范围内具有良好的线性关系,方法的检出限在0.02 mg/L～0.10 mg/L之间。在实际样品的检测中合成色素的加标回收率在85.2%～98.9%之间,相对标准偏差在1.49%～5.64%之间。方法简单、高效,可用于虾制品中合成色素的日常检测。     

Development of a HPLC method combined with ultraviolet/diode array detection for determination of monosodium glutamate in various food samples

An effective, simple and rapid analytical method using HPLC was developed for the analysis of monosodium glutamate (MSG) in various food samples obtained from local market in Turkey. The determination of MSG was performed by its derivatisation with o-phthaldialdehyde (OPA). A high-performance liquid chromatography-ultraviolet/diode array detection method was performed by using C₁₈ (150 mm × 4.6 mm, 2.7 μm) column with the mobile phase consisting of 10 mm phosphate buffer solution (pH = 5.90) and methanol (75:25, v/v). The applied method was optimised and the validated. The method was linear from 1 to 50 μg mL⁻¹ of MSG. The correlation coefficient value of the developed method was obtained as R² = 0.9999. The limit of detection and limit of quantification limits were 0.015 and 0.050 μg mL⁻¹, respectively. MSG contents of the food samples range from 0.09 g kg⁻¹ to 120.80 g kg⁻¹. The validated method was successfully applied for the analysis of MSG in several food samples.     

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.     

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 copper in fish feed by graphite furnace atomic absorption spectrometry using slurry sampling

The present work develops and optimizes a method to determine copper in samples of feces and fish feed by graphite furnace atomic absorption spectrometry (GFAAS) through the direct introduction of slurries of the samples into the spectrometer’s graphite tube coated internally with metallic rhodium and tungsten carbide that acts as chemical modifiers. The limits of detection (LOD) and quantification (LOQ) calculated for 20 readings of the blank of the standard slurries (0.50% m/v of feces or feed devoid of copper) were 0.24 and 0.79 μg L⁻¹ for the standard feces slurries and 0.26 and 0.87 μg L⁻¹ for the standard feed slurries. The proposed method was applied in studies of absorption of copper in different fish feeds and their results proved compatible with that obtained from samples mineralized by acid digestion using microwave oven.     

A Sensitive, Selective New Analytical Reagent, 2, 6-Diacetylpyridine bis-4-phenyl-3-thiosemicarbazone for Extractive Spectrophotometric Determination of Mo(VI) in Food Samples

Synthesized a new reagent 2, 6-Diacetylpyridine bis-4-phenyl-3-thiosemicarbazone (2, 6-DAPBPTSC) characterized and is proposed as a sensitive and selective analytical reagent for the extractive spectrophotometric determination of molybdenum(VI) at pH 3.5 to form a yellowish orange colored 1:1 chelate complex. The absorbance was measured at a maximum wavelength, 500 nm. This method obeys Beer’s law in the concentration range 0.90–9.00 μg mL⁻¹ and the correlation coefficient of Mo(VI)–2,6-DAPBPTSC complex is 0.954, which indicates an adequate linearity between the two variables with good molar absorptivity and Sandell’s sensitivity, 1.212 × 10⁴ L mol⁻¹cm⁻¹, 0.0079 μg cm⁻², respectively. The precision and accuracy of the method is checked with calculation of relative standard deviation (n = 5), 0.894% and the detection limit value is 0.0056 μg mL⁻¹. The instability constant of the method has been calculated by Asmus’ method as 6.476 × 10^–5, at room temperature. The interfering effect of various cations and anions has also been studied. The method was successfully applied for the determination of Mo(VI) in food and water samples. The validity of the present method was evaluated in terms of Student ‘t’ test and Variance ‘f’ test, which indicates the significance of the present method an inter comparison of the experimental values, using atomic absorption spectrometer.     

Ultrasonically Assisted Extraction of Rutin from <Emphasis Type="Italic">Artemisia selengensis</Emphasis> Turcz: Comparison with Conventional Extraction Techniques

Ultrasonically assisted extraction (UAE) followed by high performance liquid chromatography (HPLC) analysis method for the fast extraction and determination of rutin in Artemisia selengensis Turcz has been developed. Artemisia selengensis Turcz has been used as food and herbal medicine for thousands of years in China. Rutin is one of the main active ingredients of this plant. The extraction of rutin from Artemisia selengensis Turcz was investigated by UAE. Special emphasis has been given to optimize the extraction conditions which were those with 90:10 (v/v) methanol–ethanol as solvent, 30:1 liquid–solid ratio, and 40 min extraction time. In order to show the superiority of UAE, other extractions were investigated, including microwave-assisted extraction, reflux extraction, and marinated extraction. The results showed that UAE was most suitable for the extraction of rutin in Artemisia selengensis Turcz because of its high extraction efficiency. Reversed phase-HPLC with ultraviolet detection was employed for the analysis of rutin in Artemisia selengensis Turcz. Under the optimum conditions, the calibration curve for the analyte was linear in the range of 0.34–20.7 μg mL⁻¹. The mean recovery of rutin was 100.77%, and its relative standard deviation was 0.37% (n = 5). Three kinds of Artemisia selengensis Turcz from different habitats were investigated. The total content of rutin was 9.90, 6.23, 5.56 mg g⁻¹, respectively.     

A Highly Sensitive Adsorptive Stripping Voltammetric Method for Simultaneous Determination of Lead and Vanadium in Foodstuffs

This work describes a procedure for the simultaneous determination of vanadium and lead in some food and water samples using adsorptive stripping voltammetric method. The method is based on the adsorptive accumulation of cupferron complexes of these elements onto hanging mercury drop electrode, followed by reduction of adsorbed species by voltammetric scan using differential pulse modulation. Optimal analytical conditions were found to be cupferron concentration of 8.00 × 10⁻⁵ M, pH of 4.8 (phosphate buffer), an accumulation potential at −100 mV, and a scan rate of 80 mV s⁻¹. With an accumulation time of 50 s, the peak currents proportional to the concentration of lead and vanadium over the 0.05–80.00 and 0.10–105.00 ng mL⁻¹ ranges with detection limit of 0.02 and 0.01 ng mL⁻¹, respectively. The procedure was applied to simultaneous determination of vanadium and lead in some food and water samples with satisfactory results.     

Simultaneous Determination of 69 Pesticide Residues in Coffee by Gas Chromatography?CMass Spectrometry

A method using gel permeation chromatography (GPC) combined with solid-phase extraction (SPE) cleanup followed by gas chromatography–mass spectrometry (GC-MS) has been established for quantitative determination of 69 pesticide residues in coffee. Based on an appraisal of the characteristics of GC-MS, validation experiments were conducted for 69 pesticides. In the method, 2.0 g samples were mixed with 5 ml water and 1 g sodium chloride and extracted with 5 ml of ethyl acetate by blender homogenization, centrifugation, and filtration. Evaporation was conducted and the sample was injected into a 250 mm × 10 mm S-X3 GPC column, with ethyl acetate–n-hexane (1:2 v/v) as the mobile phase at a flow rate of 3 ml/min. The 4–15 min fraction was collected for the SPE cleanup, which was Envi-Carb SPE cartridge coupled with NH₂-LC SPE cartridge with acetone–ethyl acetate (2:5 v/v) as the eluted solvent. The eluents were collected and then evaporated to dryness, which was redissolved in 0.5 ml ethyl acetate for GC-MS analysis. For the 69 pesticides determined by GC-MS, the portions collected from GPC were concentrated to 0.5 ml and exchanged with 5 ml n-hexane. In the linear range of each pesticide, the correlation coefficient was R ² ≥ 0.99. At the low, medium, and high fortification levels of 0.05–1.0 mg/kg, recoveries fell within 60–120%. The relative standard deviation was between 1.3% and 22.3% for all 69 pesticides. The limits of detection for the method were 10 μg/kg to 150 μg/kg, depending on each pesticide.     

Multielement analysis of Chinese tea (Camellia sinensis) by total-reflection X-ray fluorescence

 Total-reflection X–ray fluorescence (TXRF) was used for the simultaneous determination of 15 elements in tea samples which were produced either by acid digestion or acidified infusion of tea leaves (Camellia sinensis). The accuracy and precision of the method were checked by its application to a certified reference material (GBW 08505 : tea). A variety of 39 tea samples of different kinds and/or qualities produced in different regions of China were analysed. The range and mean of the concentrations of elements in the tea leaves (0.1–30.000 μg g^–1) and their solubility in infusions (0.5–85%) were determined and the influence of the origin, type and quality of the tea samples was studied. In some tea leaves produced in a Se-rich region, the content of Se was found to be very high (up to 7.5 μg g^–1), in contrast to a concentration of only about 0.1 μg g^–1 Se in most of the tea leaves examined. Received: 27 January 1998     

Magnetic solid-phase extraction coupled with HPLC for the determination of Allura Red in food and beverage samples

A magnetic solid-phase extraction (MSPE) protocol prior to HPLC was developed for the extraction and determination of Allura Red in food samples. Magnetic nanoparticles were coated with tetraethylorthosilicate and 3-aminopropyltriethoxysilane and modified by graphene. Scanning electron microscopy, transmission electron microscopy and Fourier-transform infrared spectrometry were used to characterise the graphene-functionalised sorbents; and the main parameters affecting the extraction such as sample volume, temperature, pH and time were investigated and established. Under optimised conditions, the pre-concentration factor of Allura Red was 200, and the calibration curve was linear at a concentration range of 5–1500 μg kg^?1. The LOD was 2 μg kg^?1, the limit of quantification was 7 μg kg^?1, and the relative standard deviation was 3.3%. The prepared MSPE procedure was simple and fast, and it was successfully applied for the determination of Allura Red in beverages, candy and jelly.     

Square-Wave Adsorptive Stripping Voltammetry for Trace Determination of Dimoxystrobin and Azoxystrobin in Potatoes and Grapes

Square-wave voltammetry was used for trace determination of azoxystrobin and dimoxystrobin in potatoes, grapes, and grape juice. Experimental conditions have been optimized to achieve simultaneous determination of these analytes using the hanging mercury drop electrode. Supporting electrolyte was HCl 0.1 mol L⁻¹, and other optimized conditions were deposition potential (−300 mV), deposition time (30 s), amplitude (150 mV), frequency (150 Hz), and step height (2 mV). Azoxystrobin and dimoxystrobin redissolution peaks presented their maxima, respectively, at −928 mV and around −650 mV. Linear and homoscedastic analytical responses (r ² > 0.99) have been observed. Limits of quantification as low as 119 μg L⁻¹ (in grape juice) and 45 μg kg⁻¹ (in potatoes and grapes) were found. A previous solid-phase extraction was necessary to eliminate interferences from potato and grape samples. For grape juice, no sample treatment was required. Satisfactory recoveries (from 72.3% to 96.7% for dimoxystrobin and from 81.7% to 102.3% for azoxystrobin) were found. Interferences from other strobilurins (piraclostrobin and picoxystrobin) were evaluated.     

Combined Use of Liquid–Liquid Microextraction and Carbon Nanotube Reinforced Hollow Fiber Microporous Membrane Solid-Phase Microextraction for the Determination of Triazine Herbicides in Water and Milk Samples by High-Performance Liquid Chromatography

A simple, efficient and environmentally friendly method for the extraction and determination of five triazine herbicides in water and milk samples was developed by simultaneous liquid–liquid microextraction and carbon nanotube reinforced hollow fiber microporous membrane solid-phase microextraction coupled with high-performance liquid chromatography–diode array detection. The parameters that affect the extraction efficiencies, including the type and concentration of multi-walled carbon nanotube, type of membrane solvent and desorption solvent, the type and volume of the extraction solvent in sample solution, extraction time and temperature, the pH of sample solution, stirring rate, and ionic strength were investigated and optimized. Under the optimum conditions, the method shows a good linearity within a range of 0.5–200 ng mL⁻¹ for water samples and 1–200 ng mL⁻¹ for milk samples, with the correlation coefficients (r) varying from 0.9991 to 0.9998 and from 0.9989 to 0.9994, respectively. The limits of detection were in the range between 0.08 and 0.15 ng mL⁻¹ for water samples and 0.3 and 0.5 ng mL⁻¹ for milk samples, while the relative standard deviations varied from 4.6% to 6.9% and from 5.3% to 7.7%, respectively. The recoveries of the target analytes at spiking levels of 5.0 and 50.0 ng mL⁻¹ were in the range from 86.6% to 106.8% for water samples and from 81.3% to 97.4% for milk samples. The results demonstrated that the developed method was an efficient pretreatment and enrichment procedure for the determination of triazine pesticides in real water and milk samples.     

Antioxidant capacity and antioxidative compounds in barley (<Emphasis Type="Italic">Hordeum</Emphasis><Emphasis Type="Italic">vulgare</Emphasis> L.) grain optimized using response surface methodology in hot air roasting

Response surface methodology was used to predict optimum conditions for hot air roasting of barley grains (temperature, time, and amount). Antioxidant capacity in the grains was highest under optimum conditions of 250 °C, 63.5 min and 42 g (one and a half layers). A correlation of R ² = 0.74 (p < 0.05) was found between 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical scavenging activity and total phenolic contents. Ethanol and aqueous extracts were prepared from grains roasted under optimum conditions and assessed for antioxidant capacity. Antioxidative compounds in the extracts were then identified using GC–MS. The IC₅₀ value of ethanol extract was significantly lower (11.45 μg mL^–1) than that of aqueous extract (33.54 μg mL^–1) and α-tocopherol (12.6 μg mL^–1) but higher than BHT (9.59 μg mL^–1). The same trend was observed in linoleic acid assay. In reducing power, the ethanol extract and α-tocopherol were not significantly different. Phenolic acids p-hydroxybenzaldehyde, vallinic and gallic acids were identified as the major compounds in the extracts. The results obtained from this study show that it is possible to optimize antioxidant capacity in barley grains during roasting.