外卖餐具中16种合成酚类抗氧化剂的迁移测定

摘 要：目的 测定外卖餐具中16种合成酚类抗氧化剂(Synthetic phenolic antioxidants, SPAs)的含量,分析外卖餐具中这类污染物的迁移行为。方法 本研究通过液相/气相色谱串联三重四极杆质谱联用技术,测定了6大类不同品牌外卖餐具中16种SPAs的含量,分别以纯净水、4%醋酸(v/v)、10%乙醇水溶液(v/v)、50%乙醇水溶液(v/v)和95%乙醇水溶液(v/v)为食品模拟物,开展不同品牌外卖餐具中主要SPAs的迁移实验。结果 外卖餐具中均可以检出一种以上SPAs,其中丁基化羟基甲苯及其代谢物的含量和检出率最高,2,4-二叔丁基苯酚和新兴化合物2,2''-亚甲基双-(4-甲基-6-叔丁基苯酚)次之,然而2,4-二叔丁基苯酚是外卖餐具最主要的迁移物。 结论 外卖餐具中合成酚类抗氧化剂广泛存在。 2,4-二叔丁基苯酚在外卖餐具中大量迁出,其健康危害需要引起足够关注。     

Quantitative determination of the phenolic antioxidants using voltammetric techniques

Synthetic antioxidants, such as butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT) and tert-butylhydroquinone (TBHQ), show sensitivity to voltammetric waves. The waves of these antioxidants, however, are seriously overlapped and it is difficult to determine them simultaneously. The influence of different parameters (working electrode, supporting electrolyte, pH, voltammetric technique) was evaluated in a quantitative simultaneous determination of three antioxidants in alcoholic mixtures and real sample foods. Glassy carbon (GC) and platinum (Pt) working electrodes were investigated as mediators of oxireduction reactions. Two supporting electrolytes were investigated: Britton-Robinson 0.1 mol l⁻¹ buffer (pH 2.0) and HCl 0.1 mol l⁻¹ (pH 2.0) both with 2 g l⁻¹ (p/v) of methanol. In this paper, voltammetric conditions for the analysis of up to three-component mixtures of antioxidant present at levels: 2.0-100.0 mg l⁻¹ for BHA, 4.0-100.0 mg l⁻¹ for TBHQ and 2.0-20.0 mg l⁻¹ for BHT at GC in HCl 0.1 mol l⁻¹ and 8.0-120.0, 10.0-130.0 and 4.0-30.0 mg l⁻¹ for BHA, TBHQ and BHT, respectively, at Pt in the same supporting electrolyte. The results show that for real food samples, the parameters investigated were satisfactory for quantitative determination using square wave voltammetry (SWV) without chemometric approaches and without suffering overlapping problems.     

Determination of phenolic antioxidants in tuna fillets canned in hydrosols with HPLC-DAD

Canned tuna was fortified with a mixture of brine and hydrosols of aromatic plants (i.e. oregano, laurel, sage and lemon balm). An HPLC-DAD method was developed and validated for the simultaneous determination of thirteen antioxidants in tuna fillets, including phenolic acids (gallic acid, vanillic acid, syringic acid and rosmarinic acid), flavonoids (catechin, epicatechin, vanillin, myricetin, rutin, quercetin, luteolin and apigenin) and one hydroxybenzaldehyde (syringaldehyde). The analytes showed satisfying recovery efficiency (82.1–92.1%), and the method presented excellent linearity (r² > 0.99). The precision limit was ≤5.6% RSD_r for intra-day and ≤7.2% RSD_R for inter-day experiments. The determined analytes ranged between 8.86 mg (quercetin) and 512 mg (rosmarinic acid) per 100g tuna flesh (n = 10), verifying that the hydrosols fortified the tuna fillets.     

Analysis of synthetic antioxidants and preservatives in edible vegetable oil by HPLC/TOF-MS

The application of high performance liquid chromatography time-of-flight mass spectrometry (HPLC/TOF-MS) for the qualitation and quantitation of 11 synthetic antioxidants and preservatives in edible vegetable oil samples is reported here. The qualitation by HPLC/TOF-MS is accomplished with the accurate mass of the deprotonated molecules [M−H]⁻, along with the accurate mass of their main fragment ion. In order to obtain sufficient sensitivity for quantitation purposes (using deprotonated molecule), segment programme of fragmentor voltage is designed in negative ion mode. The mass accuracy typically obtained is routinely better than 5 ppm. The 11 compounds behave linearly in the 0.05–5.0 mg/kg concentration range, with correlation coefficient >0.997. The recoveries at the tested concentrations of 0.1–2.0 mg/kg are 65.8–106.9%, with coefficients of variation <8.1%. The method illustrated is suitable for routine qualitative and quantitative analyses of synthetic antioxidants and preservatives in edible vegetable oils.     

Cloud-point extraction and reversed-phase high-performance liquid chromatography for the determination of synthetic phenolic antioxidants in edible oils

A cloud-point extraction (CPE) method using Triton X-114 (TX-114) nonionic surfactant was developed for the extraction and preconcentration of propyl gallate (PG), tertiary butyl hydroquinone (TBHQ), butylated hydroxyanisole (BHA), and butylated hydroxytoluene (BHT) from edible oils. The optimum conditions of CPE were 2.5% (v/v) TX-114, 0.5% (w/v) NaCl and 40 min equilibration time at 50 °C. The surfactant-rich phase was then analyzed by reversed-phase high-performance liquid chromatography with ultraviolet detection at 280 nm, using a gradient mobile phase consisting of methanol and 1.5% (v/v) acetic acid. Under the studied conditions, 4 synthetic phenolic antioxidants (SPAs) were successfully separated within 24 min. The limits of detection (LOD) were 1.9 ng mL(-1) for PG, 11 ng mL(-1) for TBHQ, 2.3 ng mL(-1) for BHA, and 5.9 ng mL(-1) for BHT. Recoveries of the SPAs spiked into edible oil were in the range 81% to 88%. The CPE method was shown to be potentially useful for the preconcentration of the target analytes, with a preconcentration factor of 14. Moreover, the method is simple, has high sensitivity, consumes much less solvent than traditional methods, and is environment-friendly. Practical Application: The method established in this article uses less organic solvent to extract SPAs from edible oils; it is simple, highly sensitive and results in no pollution to the environment.     

国外天然酚类抗氧化剂的研究进展

简述了国外天然酚类抗氧化剂最新研究概况,主要介绍一些当前研究得比较多的、具有较强抗氧化活性的天然提取物,以及天然提取物的各种抗氧化活性试验。     

Presence of synthetic antioxidants in organic and conventional milk

Samples of conventional (n = 11) and organic (n = 81) milk, both raw and heat-treated, were analysed for the presence of synthetic antioxidants (butylated hydroxytoluene, butylated hydroxyanisole, dodecyl gallate, propyl gallate and octyl gallate) to verify whether those labelled as “organic” corresponded to EU Regulations on the use of additives in such products. The analysis detected only the antioxidant BHT and its aldehyde BHT–CHO in all 11 conventional milk and in 18 of 81 organic milk samples. The investigation highlights the importance of strict control of organic dairy production, since synthetic antioxidants added to feedstuff to prevent rancidity can be transferred to milk.     

Quantification of synthetic phenolic antioxidants in dry foods by reversed-phase HPLC with photodiode array detection

Propyl gallate (PG), octyl gallate (OG), 2-and 3-tert-butyl-4-hydroxyanisole (BHA), 3,5-di-tert-butyl-4-hydroxytoluene (BHT) and tert-butylhydroquinone (TBHQ) are permitted in a limited number of food products according to local legislations, with individual maximum limits in each case. This study describes an in-house validated reversed-phase HPLC method for the quantitative determination of PG and BHA in gravies and dehydrated soups, BHA in bouillons, dehydrated meat and dry pet food, and OG in dehydrated meat. Two extraction methods were developed to optimise the recovery of the phenolic antioxidants. Methanol was more suitable for the extraction of BHA and OG from dehydrated meat, PG from gravies and BHA from hard and soft bouillons while hexane/2-propanol was more suitable for the extraction of BHA from gravies and dehydrated soups, and PG in dehydrated soups. On the other hand, PG could not be quantified accurately in soft bouillons using either of these extraction methods, due to a lack of selectivity. The relative standard deviation of repeatability was between 0.9 and 5.5% and recoveries from spiked samples in the ranges 85–106% for PG, 95–104% for BHA and 83–85% for OG. The procedure allows also the detection of 2 mg/kg of TBHQ and BHT, which are not permitted in the EU for use in dehydrated soups, bouillons, gravies and dehydrated meat.     

高效液相色谱法同时测定食品中7种合成色素

建立了食品中柠檬黄、新红、苋菜红、胭脂红、日落黄、诱惑红和赤藓红7种合成色素的高效液相色谱分析法。样品经含有1%氨水的70%乙醇提取,聚酰胺粉末吸附、净化和富集后进行HPLC分析。采用Eclipse plus C18（250 mm×4.6 mn,5μm）色谱柱为分析柱,0.02 mmol/L乙酸铵水溶液-甲醇为流动相梯度洗脱,二极管阵检测器检测,外标法定量。结果表明：7种色素在0.5~20.0mg/L范围内有良好的线性关系,方法的检出限（S/N=3）分别为0.05、0.05、0.03、0.03、0.05、0.06和0.07 mg/kg,加标回收率为82.83%~105.39%,相对标准偏差不大于8.40%。     

高效液相色谱法同时测定食用油中9种抗氧化剂

采用乙腈提取食用油脂中的抗氧化剂PG、THBP、TBHQ、NDGA、BHA、OG、IONOX-100、DG、BHT,浓缩后用乙腈-水淋洗的反相高效色谱法测定其中的抗氧化剂的含量,方法最低检测限:PG、THBP、NDGA、OG、DG为0.5μg/g,TBHQ、BHA、IONOX-100、BHT为1μg/g,相对标准偏差为1.01%～6.89%,回收率为88.85%～102.57%。该方法简便、快速,稳定可靠。     

Simultaneous voltammetric determination of phenolic antioxidants in food using a boron-doped diamond electrode

A method for the simultaneous determination of butylated hydroxyanisole (BHA) and butylated hydroxytoluene (BHT) in food was developed using square-wave voltammetry (SWV). The determination of these phenolic antioxidants was carried out using a cathodically pre-treated boron-doped diamond electrode (BDD) and an aqueous-ethanolic (30% ethanol, v/v) 10 mmol L⁻¹ KNO₃ solution (pH_cond. 1.5) as supporting electrolyte. In the SWV measurements using the BDD electrode, the oxidation peak potentials of BHA and BHT present in binary mixtures were separated by about 0.3 V. The attained detection limits for the simultaneous determination of BHA and BHT (0.14 and 0.25 μmol L⁻¹, respectively) are lower than the ones by voltammetric techniques reported in the literature. The proposed method was successfully applied in the simultaneous determination of BHA and BHT in food products, with results similar to those obtained using a high-performance liquid chromatography method, at a 95% confidence level.     

饮料中四种食用色素、维生素C以及咖啡因的LC测定

目的：探讨含咖啡因类饮料中四种食用色素、维生素C以及咖啡因的高效液相色谱检测方法。方法：样液经脱气、去蛋白等处理,调节pH值,定容过滤,在C18柱（250mm×4.6mm×5μm）上,以甲醇与乙酸铵溶液为流动相,梯度洗脱,柱温38℃,紫外254nm检测,外标法定量。结果：在不同品种饮料中加入各浓度色素、维生素C及咖啡因,平均回收率均达到满意的结果。结论：检测过程控制各试验条件：梯度洗脱,各组分分离效果很好,回收率满意。     

Effect of synthetic antioxidants on storage stability of Khoa – a semi-solid concentrated milk product

Effect of synthetic antioxidants on storage stability of freshly prepared khoa was evaluated. Free fatty acids (FFA), peroxide value (POV) and iodine values (IV) were used to assess the development of rancidity during 30 days of storage of khoa at 25 and 45 °C. Butylated hydroxy anisole (BHA) and butylated hydroxy toluene (BHT) were added to freshly prepared khoa to extend the storage life. After 30 days of storage at 45 °C, freshly prepared khoa containing 200 ppm of BHA and BHT showed lower values of FFA (0.066%, 0.058%) and POVs (23.0, 21.0 meq/kg) than the control samples (FFA 0.320%, POV 127 meq/kg). Iodine values of khoa sample containing 200 ppm of BHA and BHT were 67 and 69 after 30 days storage at 45 °C. However, iodine value of a khoa sample without antioxidant (control) after 30 days of storage at 45 °C was 30. Similarly, khoa samples treated with 100 ppm of BHA, along with 100 ppm of BHT, showed FFA value (19.0%), POV (0.049 meq/kg) and iodine value (72) after storage for 30 days at 45 °C. These results illustrate that synthetic antioxidants inhibited the development of rancidity during storage of khoa. Therefore, storage life of khoa can easily be extended for 30 days by the addition of BHA and BHT.     

油炸薯条中酚类抗氧化剂的高效液相色谱法测定

采用反相高效液相色谱法测定油炸薯条中PG、TBHQ、BHA、4HR、BHT、2246.其中PG、TBHQ用50%甲醇(体积分数1%的冰醋酸)作流动相,BHA、4HR、BHT、2246用80%的甲醇作流动相,检测波长为280nm,用纯甲醇提取样品中的PG、TBHQ;用甲醇∶二氯甲烷=9∶ 1(V/V)提取BHA、4HR、BHT、2246.相关系数在0.9983～0.9996之间,检出限为1.0～2.0μg/g ,标准偏差在0.21%～5.30%之间,平均回收率均在85%以上.     

Development of an HPLC method for measurements of the stability of Irganox-type polymer antioxidants in fatty food simulants

 A reversed-phase high-performance liquid chromatography (RP-HPLC) method has been developed to measure the stability of four Irganox-type polymer antioxidants (Irganox 245, Irganox 1035, Irganox 1098 and Irganox 3114) in an olive oil food simulant and isooctane, which has been proposed as an alternative fatty food simulant. The tests of stability in olive oil were carried out under three different conditions, i.e. 40°C for 10 days, 100°C for 1 h and 175°C for 1 h. The exposure conditions for isooctane were 60°C for 3 h. Results showed that for all additives tested no instability phenomena in olive oil or isooctane simulants were observed under the exposure conditions applied. The analytical methodology developed could eventually be used for stability testing and migration studies of other similarly structured antioxidants in fatty food simulants. Received: 11 September 1997     

Development of an HPLC method for measurements of the stability of Irganox-type polymer antioxidants in fatty food simulants

 A reversed-phase high-performance liquid chromatography (RP-HPLC) method has been developed to measure the stability of four Irganox-type polymer antioxidants (Irganox 245, Irganox 1035, Irganox 1098 and Irganox 3114) in an olive oil food simulant and isooctane, which has been proposed as an alternative fatty food simulant. The tests of stability in olive oil were carried out under three different conditions, i.e. 40°C for 10 days, 100°C for 1 h and 175°C for 1 h. The exposure conditions for isooctane were 60°C for 3 h. Results showed that for all additives tested no instability phenomena in olive oil or isooctane simulants were observed under the exposure conditions applied. The analytical methodology developed could eventually be used for stability testing and migration studies of other similarly structured antioxidants in fatty food simulants. Received: 11 September 1997     

聚丙烯餐盒复用过程中邻苯二甲酸酯类塑化剂和合成酚类抗氧化剂的检测及迁移规律研究

目的 建立气相色谱-质谱法(gas chromatography-mass spectrometry,GC-MS)同时测定聚丙烯(polypropylene,PP)餐盒中邻苯二甲酸酯类塑化剂和合成酚类抗氧化剂含量的分析方法,并研究其在复用过程中向酸性食品模拟物(4%乙酸)、非酸性食品模拟物(10%乙醇、水)以及油脂类食品模拟物(异辛烷、橄榄油)的迁移量。方法 PP餐盒经正己烷超声提取,食品模拟物根据其不同的性质选择不同萃取液,液液萃取辅以超声提取,经SH-Rxi-5MS (30 m×0.25 mm, 0.25 μm)石英毛细管柱分离,单离子监测(single ion monitoring, SIM)模式扫描,外标法定量。结果 20种化合物的线性关系在0.01~1.00 mg/L范围内表现良好,其相关系数均大于0.99,检出限和定量限分别是0.01~0.02 mg/L和0.03~0.06 mg/L。5种食品模拟物在0.05、0.10和0.50 mg/L 3个水平下加标回收率为80.4%~108.4%,相对标准偏差为1.3%~10.6% (n=6)。结论 该方法实验过程简便,灵敏度、精密度、回收率高,适用于PP餐盒中邻苯二甲酸酯类塑化剂和合成酚类抗氧化剂含量和迁移量的测定。实验结果可知,PP餐盒在热接触和微波加热的复用过程中均有一定程度的迁移,需要引起重视。     

HPLC method for screening of flavonoids and phenolic acids in berries

An HPLC method is described for the simultaneous detection of selected flavonoids (kaempferol, quercetin, myricetin) and phenolic acids (p-coumaric, caffeic, ferulic, p-hydroxybenzoic, gallic and ellagic acids) in berries. Three extraction and hydrolysis methods and three HPLC column and solvent systems were tested for strawberry and blackcurrant. The optimal extraction and hydrolysis of these phenolics was obtained by incubating freeze-dried berry samples for 16 h at 35°C in 50% methanol and 1·2 M HCl. The best separation of the hydrolysed phenolics was achieved in ODS-Hypersil column using a ternary solvent system (dihydrogen ammonium phosphate, orthophosphoric acid and acetonitrile) with increasing hydrophobicity and changing pH. The method was used for the determination of the phenolic profiles of strawberry and blackcurrant. The relative content of flavonoids was low in strawberry but over 50% in blackcurrant. Ellagic acid was the main phenolic in strawberry while its relative content was very low in blackcurrant. Although the precision of the method was not equally good for all the phenolics, a reasonable amount of information was obtained within a single analysis. This simple, semiquantitative method is suitable for routine screening of the major phenolics in berries. © 1998 SCI.     

Determination of phenolic antioxidants by micellar electrokinetic capillary chromatography with electrochemical detection

A new and efficient method for the determination of synthetic phenolic antioxidants (SPAs) has been developed by using micellar electrokinetic capillary chromatography (MECC) with electrochemical detection. Under the optimum conditions, 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 × 10⁻⁴ to 2.0 × 10⁻⁶ mol/L and the detection limits (S/N = 3) of propyl gallate (PG), tert-butylhydroquinone (TBHQ), butylated hydroxyanisole (BHA), and butylated hydroxytoluene (BHT) range from 2.9 × 10⁻⁷ to 2.7 × 10⁻⁶ mol/L. This method has been proved to be effective and successfully applied for the determination of SPA in food products, providing a promising and convenient entry to monitor the superscale use of phenolic antioxidants.