毛细管气相色谱法测定食用油中的酚类抗氧化剂BHA、BHT、TBHQ

建立了同时测定植物油中BHA、BHT、TBHQ等3种酚类抗氧化剂的测定方法。样品中的抗氧化剂经石油醚提取、乙腈萃取后采用HP-5毛细管柱分离。样品加标回收率为82.8?.6%,相对标准偏差为1.06%~3.11%,BHA、BHT、TBHQ的最低检出量分别为5、10、5ng。该方法具有快速、灵敏度高、重现性好、前处理简单等优点。     

Low‐density‐solvent‐based air‐assisted liquid–liquid microextraction followed by gas chromatography with flame ionization detection for the determination of synthetic phenolic antioxidants in milk samples

A simple and rapid sample pretreatment technique termed low‐density‐solvent‐based air‐assisted liquid–liquid microextraction has been developed for the extraction and preconcentration of three synthetic phenolic antioxidants including butylated hydroxyanisole, butylated hydroxytoluene, and tert‐butyl hydroquinone from milk samples prior to their analysis by gas chromatography with flame ionization detection. In this method, initially trichloroacetic acid as a proteins precipitation agent is added to the sample, and then it is sonicated and centrifuged. The obtained aqueous phase is removed and the analytes extracted by the proposed method using a low‐density organic solvent. Some important parameters such as type and volume of extraction solvent, ionic strength, pH, and centrifugation rate and time were studied. Under the optimum conditions, enrichment factors were obtained in the range of 501–614. LODs and quantification were between 0.76–1.16 and 2.66–3.96 ng mL^–1, respectively. This method is rapid and requires less than 15 min for sample preparation.     

固相萃取–气相色谱–串联质谱法测定塑料食品包装材料中3种抗氧化剂的残留量

建立了气相色谱–串联质谱法测定塑料食品包装材料中抗氧化剂二丁基羟基甲苯(BHT)、丁基羟基茴香醚(BHA)和特丁基对苯二酚(TBHQ)残留量的分析方法。样品采用环己烷–乙酸乙酯混合溶剂超声萃取,经固相萃取法富集和净化,采用气相色谱–串联质谱在多反应监测模式下进行测定。结果表明,3种抗氧化剂质量浓度在0.05~20 mg/L范围内线性关系良好,线性相关系数大于0.999;BHT,BHA,TBHQ的检出限分别为0.005,0.01,0.03mg/kg;平均添加回收率为88.7%~104.0%;测定结果的相对标准偏差小于5.5%(n=6)。该方法操作简便,灵敏度高,重复性好,可用于塑料食品包装材料中抗氧化剂BHT,BHA,TBHQ残留量的测定。     

气相色谱法测定高分子食品包装材料中抗氧化剂的残留量

建立了气相色谱测定高分子食品包装材料中抗氧化剂丁基羟基茴香醚(BHA)、二丁基羟基甲苯(BHT)和特丁基对苯二酚(TBHQ)残留量的分析方法。用环己烷超声萃取高分子食品包装材料样品,考察了萃取时间、温度对抗氧化剂萃取量的影响。萃取液经气相色谱柱HP-50+毛细管柱(30 m×0.53 mm×1 μm)分离,电子捕获检测器(ECD)检测,外标法定量。结果表明: 在抗氧化剂添加量为3.00～10.0 mg/kg范围内,BHT、BHA、TBHQ在高分子食品包装材料中的平均添加回收率分别为88%～93%、92%～101%和83%～97%,相对标准偏差(RSD, n=5)分别为2.01%～2.89%、2.11%～3.19%和2.99%～4.02%;检出限(信噪比为3)分别为0.5、0.5和0.8 mg/kg。对实际高分子食品包装材料样品的检测结果表明3种抗氧化剂在不同材质中均有检出: 塑料材料中抗氧化剂的含量较少,仅有BHT、BHA被检出,含量为6.3～7.8 mg/kg;橡胶材料中3种抗氧化剂均被检出,含量为9.3～28.4 mg/kg。该方法准确、灵敏、重现性好,适用于高分子食品包装材料中抗氧化剂残留量的检测。     

高效液相色谱法测定食品中抗氧化剂BHA,BHT,PG

 用反相高效液相色谱法同时测定了食品中抗氧化剂丁基羟基茴香醚（ＢＨＡ）、二丁基羟基甲苯（ＢＨＴ）和焦性没食子酸丙酯（ＰＧ）。样品用正己烷提取，氮气吹干，水－乙醇（１４，Ｖ／Ｖ）溶解残留物，经０．５μｍ滤膜过滤，直接进样。方法简便、快速、回收率高、重现性好。     

Glassy carbon electrodes modified with gold nanoparticles for the simultaneous determination of three food antioxidants

Electrochemical behavior of three antioxidants: butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT) and butylated hydroquinone (TBHQ), was investigated at a glassy carbon electrode modified with gold nanoparticles (AuNPs/GCE). This electrode was characterized by scanning electron microscopy (SEM). The experimental results indicated that the modified electrode was strongly electroactive during the redox reactions of BHA, BHT and TBHQ, and this was confirmed by the observed increased redox peak currents and shifted potentials; in addition, the oxidation products of BHA and TBHQ were found to be the same. The experimental conditions were optimized and the oxidation peaks of BHA and BHT were clearly separated. Based on this, an electrochemical method was researched and developed for the simultaneous determination of BHA, BHT and TBHQ in mixtures with the use of first derivative voltammetry; the linear concentration ranges were 0.10–1.50 μg mL⁻¹, 0.20–2.20 μg mL⁻¹ and 0.20–2.80 μg mL⁻¹, and detection limits were 0.039, 0.080 and 0.079 μg mL⁻¹, for BHA, BHT and TBHQ, respectively. The proposed method was successfully applied for the analysis of the three analytes in edible oil samples.     

Spectrophotometric determination of Cu(II) with sequential injection analysis

A sensitive method is presented for the determination of the synthetic antioxidant butylated hydroxyanisole (BHA) based on the dansylation process of the phenolic hydroxy group. The fluorescence developed can be measured directly without previous extraction or chromatographic separation of the labelled fluorescent compound. It is shown the effect of numerous experimental variables affecting the fluorescence intensity and the signal-to-noise ratio of the dansyl derivative. The compound was determined over the range 0.05-5 mug ml(-1), with a relative S.D. of 3.8% (300 ng ml(-1)) and a detection limit of 52 ng ml(-1). The selectivity conferred by the dansylation reaction has permitted to avoid the interference of normally accompanying antioxidants, such as butylated hydroxytoluene (BHT), due to steric impediment. The stability of the DNS-derivative is well suited for the analysis of different foodstuffs.     

Determination of synthetic phenolic antioxidants in essence perfume by high performance liquid chromatography with vortex-assisted,cloud-point extraction using AEO-9

This study aimed to establish a rapid analytical method to determine antioxidants in essence. A simple,efficient and practical, vortex-assisted, cloud-point extraction(VACPE) procedure is proposed for extracting and pre-concentrating four different of synthetic phenolic antioxidants(SPAs), propyl gallate(PG), tert-butylhydroquinone(TBHQ), butylated hydroxyanisole(BHA), butylated hydroxytoluene(BHT) in essence prior to high performance liquid chromatography(HPLC) analysis. The non-ionic surfactant, fatty alcohol polyoxyethylene ether-9(AEO-9), was used as extractant and vortex-mixing was utilized to reduce extraction time and improve extraction efficiency. The effective parameters of the extraction process, such as volume of extraction solvent, pH, vortex-mixing time, equilibration temperature and time, were optimized. Under the optimum conditions, the linear range of PG, TBHQ,BHA and BHT was 8.0–800 ng/mL. All correlation coefficients of the calibration curves were higher than0.996 and relative standard deviations(RSD, n = 5) were 2.36%–5.46%. The proposed method was successfully applied to the extraction and determination of antioxidants in essence samples with satisfactory relative recoveries of 89.4%–103.5%. The results confirmed the SPAs of essence could be effectively monitored by this method and also established good reference criteria for essence.     

Determination of antioxidants in cosmetics by micellar electrokinetic capillary chromatography with electrochemical detection

A new and efficient method for the determination of antioxidants [Propyl gallate (PG), tert-butylhydroquinone (TBHQ), butylated hydroxyanisole (BHA), and butylated hydroxytoluene (BHT)] in cosmetics has been established by using micellar electrokinetic capillary chromatography with electrochemical detection (MECC-ED). Under the optimum conditions of the method, all analytes were successfully separated within 13 min at the separation voltage of 18 kV in a 20 mmol/L borate running buffer (pH 7.4) containing 25 mmol/L sodium dodecyl sulfate. The excellent linearity was obtained in the concentration range from 5.0 x 10(-4) to 2.0 x 10(-6) mol/L and the detection limits (S/N = 3) of PG, TBHQ, BHA, and BHT range from 3 x 10(-7) to 3 x 10(-6) mol/L.     

Capillary electrophoresis-amperometric determination of antioxidant propyl gallate and butylated hydroxyanisole in foods.

Capillary electrophoretic separation coupled with end-column amperometric detection for the simultaneous quantification of butylated hydroxyanisole (BHA) and propyl gallate (PG) in food was developed. Important factors affecting separation and detection, such as the running buffer, separation voltage, and detection potential, were investigated in detail. An improved working electrode preparation method was used, where a carbon disk of 33 microm in diameter was sealed in a tip and positioned opposite the outlet of a capillary. The experiments indicated that the preparation method was simple, and the obtained electrode exhibited good flexibility and stability for the determination of phenolic antioxidants. The separation was carried out within 5 min using a 50 cm length capillary, with a solution containing 5 mM phosphate and 5 mM borax of pH 8.84 as a separation buffer, and a separation potential of 20 kV. Amperometric detection was achieved with an applied potential of 0.70 V versus Ag|AgCl| saturated KCl. There was excellent linearity between the peak current and the concentrations of the analytes in the range of 1.8 - 180.2 microg/mL for BHA and 10.6 - 212.2 microg/mL for PG, respectively. Relative standard deviations of 4.92% for BHA and 5.27% for PG were obtained, respectively. The developed method was successfully applied for the determination of antioxidants in several commercial foods.     

Separation and Determination of Phenolic Antioxidants by HPLC with Surfactant/n‐Propanol Mobile Phases

The influence of cationic and anionic surfactants and short‐chain alcohols in the mobile phase on the retention of five antioxidants has been studied. The solutes chosen were butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), and propyl, octyl, and dodecyl gallates (PG, OG, DG).The surfactants were hexadecyltrimethylammonium bromide (CTAB) and sodium dodecyl sulfate (SDS), and n‐propanol (PrOH) was the selected alcohol. A simple isocratic reversed‐phase method for the antioxidant determination is proposed. Separation of five primary antioxidants takes 18 min with the mobile phase SDS 0.10 M/H₃PO₄ 0.01 M/PrOH 30%. Variation of the percentage of alcohol in the mobile phase permits optimization of the retention times of the antioxidants. Detection limits in the pg range were obtained for the all solutes. The method was used to determine the antioxidants in olive oil at three different levels, giving mean recoveries close to 100% for all the solutes (BHA 102%, PG 99%, OG 99%, DG 99%) except BHT (84%).     

Reversed‐phase single drop microextraction followed by high‐performance liquid chromatography with fluorescence detection for the quantification of synthetic phenolic antioxidants in edible oil samples

The reversed‐phase mode of single drop microextraction has been used as a preparation method for the extraction of some phenolic antioxidants from edible oil samples. Butylated hydroxyl anisole, tert‐butylhydroquinone and butylated hydroxytoluene were employed as target compounds for this study. High‐performance liquid chromatography followed by fluorescence detection was applied for final determination of target compounds. The most interesting feature of this study is the application of a disposable insulin syringe with some modification for microextraction procedure that efficiently improved the volume and stability of the solvent microdrop. Different parameters such as the type and volume of solvent, sample stirring rate, extraction temperature, and time were investigated and optimized. Analytical performances of the method were evaluated under optimized conditions. Under the optimal conditions, relative standard deviations were between 4.4 and 10.2%. Linear dynamic ranges were 20–10 000 to 2–1000 μg/g (depending on the analytes). Detection limits were 5–670 ng/g. Finally, the proposed method was successfully used for quantification of the antioxidants in some edible oil samples prepared from market. Relative recoveries were achieved from 88 to 111%. The proposed method had a simplicity of operation, low cost, and successful application for real samples.     

Phytochemical characterization of bioactive compounds composition of Rosmarinus eriocalyx by RP–HPLC–ESI–QTOF–MS

Rosmarinus eriocalyx (rosemary or Elyazir) is an endemic species growing in arid steppe and rocky mountain in the South-West Algeria. This plant is well known in Algeria and Morocco due to its medicinal properties. However, little is known about its phytochemical composition. For this purpose, natural antioxidant compounds from R. eriocalyx were recovered by solid-liquid extraction and characterized by reversed-phase high-performance liquid chromatography coupled to quadrupole-time-of-flight mass spectrometry using negative and positive ionization modes. This analytical methodology enabled the characterization of 101 compounds, which were distributed in five major categories namely hydroxycinnamic acid derivatives, hydroxybenzoic acid derivatives, flavonoids, phenolic diterpenes and phenolic triterpenes. Moreover, the studied extract generally showed free radical-scavenging and reductive abilities in the range of butylated hydroxyanisole, butylated hydroxytoluene, α-tocopherol^, and ascorbic acid. Therefore, the result suggests that the aqueous-methanolic extract of R. eriocalyx could serve as a potential source of antioxidants.     

固相萃取-高效液相法测定炒货食品及坚果制品中的多种抗氧化剂

运用固相萃取和高效液相色谱技术,建立炒货食品及坚果制品中丁基羟基茴香醚(BHA)、二丁基羟基甲苯(BHT)、叔丁基对苯二酚(TBHQ)、没食子酸丙酯(PG)等人工合成的抗氧化剂和茶多酚、甘草抗氧化物、迷迭香提取物等天然抗氧化剂的测定方法。样品经甲醇、异丙醇、乙腈等混合溶剂提取,冷冻离心后经C18柱固相萃取净化,用高效液相色谱检测。各抗氧化剂残留量在6~100 mg/L范围内呈良好线性关系,加标回收率为80%~106%。     

Monoparameter sensors for the determination of the antioxidants butylated hydroxyanisole and n-propyl gallate in foods and cosmetics by flow injection spectrophotometry.

A flow-through optosensor with solid phase UV spectroscopic detection is proposed for the direct determination of single antioxidants, namely butylated hydroxyanisole (BHA) and n-propyl gallate (n-PG), without previous derivatization. The methods are based on the transient retention behaviour of these compounds in a flow-through cell packed with C-18 silica using ethanol-water mixtures as a carrier, and on the intrinsic absorbance monitored at 290 and 283 nm, respectively. After recording the analytical signal, the antioxidants were easily and quickly desorbed from the solid support by the same carrier. For BHA, calibration graphs were linear over the range 1.0-300.0 mg L-1 using area as the analytical parameter. The relative standard deviation (RSD) was between 0.5 and 1.6%. For n-PG, calibration graphs were linear over the range 1.0-300.0 mg L-1 in area and the RSD was between 1.4 and 1.5%. The methods were applied to the determination of these antioxidants in several food and cosmetics samples, and were validated using the standard additions method and an HPLC reference method.     

Solid-phase ultraviolet absorbance spectrophotometric multisensor for the simultaneous determination of butylated hydroxytoluene and co-existing antioxidants

Continuous flow injection and UV spectrophotometric detection have been proposed for simultaneous determination of the two binary mixtures, butylated hydroxytoluene (BHT)/n-propyl gallate (n-PG) and butylated hydroxytoluene (BHT)/butylated hydroxyanisole (BHA), in food and cosmetics samples. The method is based on the different residence times of each antioxidant when the flow cell is packed to a height of 25 mm with silica C₁₈ using methanol-water 50:50% (v/v) as a carrier with a flow rate of 1.25 and 1.10 ml min⁻¹, respectively. The determination of each antioxidant is based on the measurement of its absorbance at its maximum wavelengths using a DAD detector at 30 and 180 s for the mixture n-PG-BHT and 90 and 220 s for BHA-BHT. Calibration graphs were linear over the range 10.0-300.0 μg ml⁻¹ for each antioxidant in both mixtures. The relative standard deviations were 2.5% for BHT and 2.0% for the co-existing antioxidant. Resolution of the n-PG-BHT mixture in ratios between 1:8 and 8:1 and the BHA-BHT mixture in ratios between 1:10 and 10:1 is possible. The method was applied to the determination of both antioxidants in fat foods and cosmetics samples with recoveries ranging between 101 and 105%.     

Simultaneous determination of antioxidants, preservatives and sweeteners permitted as additives in food by mixed micellar electrokinetic chromatography.

A micellar electrokinetic chromatography method was developed to simultaneously analyse commonly used food additives. The additive mixture, comprising propyl gallate, octyl gallate, dodecyl gallate, butylated hydroxyanisole, butylated hydroxytoluene, tertiary butylhydroquinone, p-hydroxybenzoic acid methyl ester, p-hydroxybenzoic acid ethyl ester, benzoic acid, sorbic acid, saccharin, aspartame and acesulfame-K, was not resolved using single surfactant micellar systems consisting of sodium dodecyl sulfate (SDS), sodium cholate (SC) or sodium deoxycholate (SDC). The separation of these additives using mixed micellar systems, involving SDS/SC, SDS/SDC and SC/SDC, was investigated. Organic solvents were added to the mixed micellar phases to optimise the separation. The mixture was successfully separated using a 20 mM borate buffer with 35 mM SC, 15 mM SDS and 10% methanol added at pH 9.3. Additives in cola beverages and low-joule jam were investigated and quantified using this method.     

Determination of Phenolic Anti-Oxidants in Edible Oil by High-Performance Liquid Chromatography with Amperometric Detector

Abstract

A high-performance liquid chromatography (HPLC) with amperometric detection was investigated for the analysis of 2-and 3-tert-butyl-4-hydroxyanisole (BHA), 3,5-di-tert?butyl-4-hydroxytoluene (BHT), and tert?butyl-hydroquinone (TBHQ) in edible oil. The reversed-phase system developed was combined with an amperometric detector, the working electrode of which was made of glassy carbon, in order to compare the sensitivity and selectivity of ultraviolet and fluorometric detection. For the amperometric detection of HPLC, cyclic voltammetry was used to monitor the electrochemical properties of the phenolic antioxidants. A simple isolation procedure, based on the continuous liquid-liquid partition technique, was examined for the extraction and clean up of the antioxidants from edible oil. The recovery rates of BHA, BHT, and TBHQ added salad oil were between 90.2-107.7% in the range of 1-50 ppm of the antioxidants. By the present method, BHA, BHT, and TBHQ were well separated, identified and quantitated with a high sensitivity.     

液相色谱-串联质谱法测定食品中甜味剂和抗氧化剂

建立了液相色谱-四级杆飞行时间串联质谱联用技术同时测定4种甜味剂(安赛蜜、糖精钠、甜蜜素、阿斯巴甜)及2种抗氧化剂(叔丁基对苯二酚、丁基羟基茴香醚)的方法.试验采用Extend-C18色谱柱分离与ESI(-)检测,以乙腈-1 mmol/L乙酸铵为流动相梯度洗脱,在6 min内实现6种目标物的快速分离,检测限为0.250 0~5.00 0 ng/m L,日间精密度小于10.71%(n=3),液态样品平均回收率为83.24%~118.3%.方法准确、灵敏,可快速检测食品中的甜味剂和抗氧化剂.     

气相-质谱选择离子法测定化妆品中抗氧化剂丁基羟基茴香醚、二丁基羟基甲苯

 采用气相 质谱 (选择离子方式 )测定化妆品中抗氧化剂丁基羟基茴香醚 (BHA)和二丁基羟基甲苯(BHT) ,样品用甲醇振荡萃取 ,以SupelcoWAXTM 10 (30m× 0 2 5mmi.d .× 0 2 5 μm)为分析柱。该方法对样品中BHA和BHT的检测限分别为 2 5 μg/g和 0 5 μg/g。方法简便、快速、灵敏 ,可用于多种化妆品的检验。