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。     

植物油中3种抗氧化剂的同时快速分析

建立了向量–子空间夹角判据结合紫外分光光度法测定植物油中3种抗氧化剂的方法,可用于植物油中特丁基对苯二酚(TBHQ)、丁基羟基茴香醚(BHA)、二丁基羟基甲苯(BHT)3种抗氧化剂的同时快速分析。采用紫外光谱–高效液相色谱(UV-HPLC)联用方法对植物油样品进行分离,构建不含待测组分的本底光谱数据库,基于向量-子空间夹角判据算法的步骤分析植物油中3种抗氧化剂的含量。实际样品加标回收率在95.2%~103.3%之间,RSD小于3%(n=6)。对市售15种植物油样品进行分析,其中12种植物油样品检出TBHQ,含量为21.34~30.12μg/m L,15种植物油样品均未检出BHA和BHT。方法适用于植物油中TBHQ,BHA和BHT 3种抗氧化剂的同时快速分析。     

中空纤维膜液相微萃取技术／气相色谱-质谱法对食品中防腐剂与抗氧化剂的测定

将中空纤维膜液相微萃取技术与气相色谱-离子阱质谱联用,测定食品中的4种防腐剂(对羟基苯甲酸甲酯(MP)、对羟基苯甲酸乙酯(EP)、对羟基苯甲酸丙酯(PP)及对羟基苯甲酸丁酯(BP))和3种抗氧化剂(叔丁基-4-羟基苯甲醚(BHA)、叔丁基苯二酸(TBHQ)、2,6-二叔丁基对甲酚(BHT)).优化的萃取条件:以15%(质量分数)Na2SO4的盐溶液为稀释溶剂,5 μL甲苯为萃取溶剂,搅拌速率为1 200 r/min,萃取时间为15 min.该方法的线性范围为0.4 ～80 mg/kg,检出限为0.002 ～8.0 μg/kg,加标回收率为94% ～115%,相对标准偏差为4.38% ～9.34%.     

气相色谱-质谱法同时测定食用植物油中三种抗氧化剂

本文研究了用乙醇提取食用植物油中的丁基羟基茴香醚(BHA)、二丁基羟基甲苯(BHT)和叔丁基对苯二酚(TBHQ),并用气相色谱-质谱法对三种抗氧化剂进行分离与测定。方法的线性范围为0.100~20.0 mg/L,检出限为:BHA,3.33μg/L;BHT,3.02μg/L;TBHQ,37.9μg/L。平均回收率为80.6%~123%,相对标准偏差为2.01%~8.77%。该方法具有简便、快速、准确、无毒等特点,应用于大豆油、花生油、芝麻油、菜籽油、茶油、食用调和油中的抗氧化剂的测定,结果令人满意。     

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%。     

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。     

高效液相色谱法测定芝麻油中的叔丁基羟基茴香醚、2,6-二叔丁基对甲酚、特丁基对苯二酚

建立高效液相色谱法测定芝麻油中叔丁基羟基茴香醚(BHA)、2,6-二叔丁基对甲酚(BHT)、特丁基对苯二酚(TBHQ)的含量。用25 mL甲醇分5次涡旋超声提取芝麻油中的BHA,BHT,TBHQ,以La Chrom C18(250mm×4.6 mm,5μm)为色谱柱,以甲醇–0.5%甲酸水溶液为流动相进行梯度洗脱,流量为1.0 mL/min,进样体积为5μL,柱温为35℃,检测波长为280 nm。BHA,BHT,TBHQ的质量浓度在20～300 mg/L范围内与其色谱峰面积呈良好的线性关系,相关系数大于0.999,方法检出限为0.5～1.0 mg/kg。样品加标回收率为95.1%～99.8%,测定结果的相对标准偏差为2.1%～4.7%(n=6)。该方法操作简单,试剂用量少,准确度高,精密度好,适用于芝麻油中BHA,BHT,TBHQ含量的日常检测。     

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。     

UPLC研究塑料食品包装材料中的抗氧化剂及其迁移

对塑料食品包装材料中的抗氧化剂叔丁基对羟基茴香醚(BHA)、2,6-二叔丁基对甲酚(BHT)、β-(4-羟基-3,5-二叔丁基苯基)丙酸正十八酯(Irganox1076)3种抗氧化剂进行了研究,建立了一种快速、高效的检测方法。方法包括:以甲醇为萃取溶剂,快速溶剂萃取(ASE)塑料食品包装中的抗氧化剂;以异辛烷为脂肪食品模拟物,对迁移进入异辛烷中的抗氧化剂进行旋转蒸发浓缩;使用超高效液相色谱(UPLC)进行检测。本方法有较好的相关线性(R20.99)、平均回收率(分别为75.8%~108.7%)、精密度(RSD分别为2.8%~12.7%)及低于欧盟法规规定的特定迁移限量(SML)的检出限。本方法用于市售食品的包装检测,各抗氧化剂在包装材料中被检测出,迁移量均低于特定迁移限量。     

反相高效液相色谱法测定化妆品中的抗氧化剂丁基羟基茴香醚和二丁基羟基甲苯

为了保证化妆品质量,要添加一定量的抗氧化剂。但抗氧化剂过量,会损害人体健康。合格食品的抗氧化剂的添加量必须符合国家卫生标准。卫生部对化妆品中丁基羟基茴香醚(BHA)和二丁基羟基甲苯(BHT)的最大限量要求均为0.15％,但化妆品中BHA和BHT尚无行业及国家卫生检验标准。食品中抗氧化剂的测定一直沿用薄层法、比色法和气相     

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.     

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.     

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.     

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。     

Collaborative study of a qualitative TLC-method for detection of antioxidants (BHA, BHT, gallates and NDGA) in food

Summary A method for the qualitative detection of antioxidants butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), the gallates and nordihydroguajaretic acid (NDGA) in bakery products and fat has been tested in a collaborative study. The method is similar to a IUPAC-method, an EEC-proposed method, and an official French method. After extraction, the compounds are detected by TLC. Being a qualitative method the probability of obtaining correct results is a measure of the goodness of the method, and the study examines the influence on the probability of the following 3 factors: type of antioxidant, type of food, and concentration of antioxidant. From the study is was concluded that the method worked quite well for BHA, with a detection limit about 15 mg/kg, whereas it worked badly for BHT, the detection limit being higher than 30 mg/kg. For the gallates and NDGA the detection limit was 30 mg/kg. Maize oil disturbed the readings on the TLC-plate, and cakes give more correct results than oil/fat.

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Gemeinschaftsuntersuchung einer qualitativen DC-Methode zum Nachweis von Antioxidantien (BHA, BHT, Gallate, NDGA) in Lebensmitteln

Zusammenfassung Ein Nachweisverfahren für Antioxidantien (butyliertes Hydroxyanisol BHA, butyliertes Hydroxytoluol BHT, Gallate, Nordihydroguajaretsäure NDGA) in Backwaren und Fett wurde im Rahmen einer Gemeinschaftsuntersuchung getestet. Die Methode ist ähnlich einer IUPAC-Methode, einem EEC-Vorschlag sowie einer amtlichen französischen Methode. Die DC-Trennung erfolgt nach Extraktion. Der Einfluß folgender 3 Faktoren auf die Güte der Ergebnisse wurde geprüft. Art des Antioxidans, Art des Lebensmittels, Konzentration des Antioxidans. Es ergab sich, daß die Methode für BHA gut brauchbar ist (Nachweisgrenze 15 mg/kg), während sie für BHT Nachweisgrenzen von über 30 mg/kg aufweist. Für Gallate und NDGA liegt die Nachweisgrenze bei 30 mg/kg. Maisöl stört die Ablesungen auf der DC-Platte. Bei Backwaren werden bessere Ergebnisse erhalten als bei Ölen und Fetten.

     

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.     

复杂基质食品中7种添加剂的气相色谱/质谱检测方法

建立了一种适用于复杂基质的食品中对羟基苯甲酸酯类（甲酯、乙酯、丙酯、丁酯）、丁基羟基茴香醚、2,6-二叔丁基对甲酚和特丁基对苯二酚等7种常见添加剂的简便快速的气相色谱-质谱（GC／MS）联用检测方法。样品通过乙腈提取,盐析后分层,上清液用乙酸乙酯稀释,以无水硫酸钠脱水,最后通过Gc／MS的选择离子监视模式检测。对于5.0g样品的7种添加剂的检出限范围为0.01-0.5mg／kg,3个水平添加的回收率范围为94.4％-105.1％;同一添加水平的回收率的相对标准偏差范围3.9％-9.9％。方法同时结合了筛选和确证两个过程,灵敏度理想,可靠性强,符合分析要求。