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。     

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。     

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.     

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.     

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%。     

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。     

Capillary electrophoresis coupled with electrochemical detection using porous etched joint for determination of antioxidants

Capillary electrophoresis coupled with electrochemical detection (CE-EC) for determination of antioxidants, propyl gallate (PG) and tert-butylhydroquinone (TBHQ), in cosmetic samples was proposed in this work. A porous etched joint was used to isolate the electrochemical detection from the electrophoretic high voltage. Compared with the 25 microm i.d. capillary without a decoupler in a CE-EC system, a 75 microm i.d. capillary applied in the present system gave an improvement in both sample injection and sensitivity. Moreover, the carbon fiber working electrode could be directly in touch with the end of separation capillary due to the elimination of the effect of separation voltage on the EC detection, so the alignment of working electrode and capillary became easy and the dead volume was also decreased. Baseline separation of the two antioxidants was achieved by CE in a 50 cm long x 75 microm i.d. capillary at 20 kV using 5.0 mmol L(-1) phosphate buffer (pH 8.00). 0.7 V (versus Ag/AgCl) was applied to the carbon fiber electrode for electrochemical detection. Under the optimal condition, the precisions (RSD, n=4) of peak height and migration time of PG and TBHQ were 2.39-3.59% and 0.34-0.44%, respectively. The detection limits of PG and TBHQ were 2.51x10(-6) and 4.88 x 10(-6) mol L(-1) for standard solution and 0.0751 and 0.0328 mg g(-1) for the real cosmetic samples with consumption of 0.3g sample. Analysis of TBHQ and PG in cosmetics samples was also achieved with the present system and the spiked recoveries of two analytes in cosmetics samples were in the range of 93.6-98.8%.     

抗氧化剂没食子酸丙酯合成纳米银及其应用

在十六烷基三甲基溴化铵(CTAB)存在下, 硝酸银与没食子酸丙酯在碱性介质中发生还原反应, 制得纳米银; 考察了反应时间、 氢氧化钠浓度、 反应温度以及PG/Ag⁺浓度比等条件对合成纳米银粒子的影响. 利用扫描电子显微镜对纳米银颗粒形貌和尺寸进行了表征, 结果表明获得了分散性良好的球形粒子. 实验中还发现在还原银离子制备纳米银过程中会产生强烈的表面等离子共振峰, 用紫外-可见光谱监测制备过程得到的纳米银紫外吸收带范围为400~450 nm, 最大吸收波长为420 nm, 光谱强度与抗氧化剂的浓度成正比. 将纳米银的这一特性用于定量测定没食子酸丙酯(PG)、 二丁基羟基甲苯(BHT)、 叔丁基对羟基茴香醚(BHA)和叔丁基对苯二酚(TBHQ)等抗氧化剂, 所得检出限分别为0.0752, 0.1242, 0.0693和0.0701 mg/L, 线性范围分别为0.2~1.8, 0.2~3.4, 0.2~3.4和0.2~3.0 mg/L.     

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.     

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。     

A Sensitive Sensor Based on CuTSPc and Reduced Graphene Oxide for Simultaneous Determination of the BHA and TBHQ Antioxidants in Biodiesel Samples

A novel and sensitive electrochemical sensor was developed for the simultaneous determination of the butylated hydroxyanisole (BHA) and tert‐butylhydroquinone (TBHQ) antioxidants in biodiesel samples employing the differential pulse voltammetry (DPV). In this sense, a glassy carbon electrode (GCE) modified with copper (II) tetrasulfonated phthatocyanine immobilized on reduced graphene oxide (CuTSPc/rGO) allowed the detection of BHA and TBHQ at potentials lower than those observed at unmodified electrodes. The sensor was characterized by cyclic voltammetry (CV) and linear scan voltammetry (LSV). After optimization of the experimental parameters, the analytical curves for simultaneous determination of BHA and TBHQ by DPV technique demonstrated an excellent linear response from 0.1 to 500 µmol L^?1 with detection limit of 0.045 µmol L^?1 for TBHQ and 0.036 µmol L^?1 for BHA. Finally, the proposed method was successfully applied in the simultaneous determination of BHA and TBHQ in six biodiesel samples, and the results obtained were found to be similar to those obtained using the HPLC method with agreement at 95 % confidence level.     

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。     

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%).     

Optimization of a high-performance liquid chromatography system by artificial neural networks for separation and determination of antioxidants

A high-performance liquid chromatography (HPLC) system was used to determine the antioxidants tert-butyl-hydroquinone (TBHQ), tert-butylhydroxyanisole (BHA), and 3,5-di-tert-butylhydroxytoluene (BHT) simultaneously in oils. The paper presents a new methodology for the optimized separation of antioxidants in oils based on the coupling of experimental design and artificial neural networks. The orthogonal design and the artificial neural networks with extended delta-bar-delta (EDBD) learning algorithm were employed to design the experiments and optimize the variables. The response function (Rf) used was a weighted linear combination of two variables related to separation efficiency and retention time, according to which the optimized conditions were obtained. The above-mentioned antioxidants in rapeseed oils were separated and determined simultaneously under optimized conditions by HPLC with UV detection at 280 nm. Linearity was obtained over the range of 10-200 microg/mL with recoveries of 98.3% (TBHQ), 98.1% (BHT), and 96.2% (BHA).     

Simultaneous Determination of Phenolic Additives in Cosmetics by Micellar Electrokinetic Capillary Chromatography with Electrochemical Detection

A micellar electrokinetic capillary chromatography method with electrochemical detection (MECC‐ED) has been developed for the simultaneous determination of eight phenolic additives, including propyl gallate (PG), tert‐butylhydroquinone (TBHQ), butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), methylparaben (MP), ethylparaben (EP), propylparaben (PP) and butylparaben (BP) in cosmetic products. Method development involved optimization of the working electrode, the pH value of running buffer, the concentration of sodium dodecyl sulfate (SDS), the separation voltage, and the sample injection time. Under the optimum conditions, all analytes can be well separated within 26 min at the separation voltage of 18 kV in a 9 mmol·L^?1 sodium dodecyl sulfate (SDS) ?60 mmol·L^?1 borate running buffer (pH 8.0). A 300 μm diameter carbon disk electrode generated good response at +0.90 V (vs. SCE) for all analytes. Linearity of the present method was over three orders of magnitude of analyte concentration with detection limits (S/N=3) ranging from 1.1×10^?7 to 1.2×10^?6 g·mL^?1 for all analytes. This proposed method has been successfully applied to the simultaneous determination of the above additives in commercial cosmetics, and the assay results were satisfactory.     

Flow Injection Analysis of Histidine with Enhanced Electrogenerated Chemiluminescence of Luminol

Histidine is one of the necessary basic amino acids in biological bases, which often controls the catalytic activity of enzymes and acts in holding the higher structure of proteins. Furthermore, it is also an important ingredient in pharmaceutical preparations used for treatment of hetpatosis and nephropathy. Therefore, the determination of histidine in biological fluids and pharmaceutical preparations is of great importance. Various methods have been proposed for the detection of histidine …     

胶束电动毛细管色谱安培检测中药马齿苋中多巴胺和去甲肾上腺素

建立了胶束电动毛细管色谱结合电化学安培检测同时分析中药马齿苋中多巴胺和去甲肾上腺素的方法。考察了缓冲液的浓度、pH值、十二烷基硫酸钠(SDS)浓度以及工作电极电势对分离检测的影响。在优化的条件下,多巴胺和去甲肾上腺素在1.0×10-6～5 0×10-4mol/L范围内有良好线性,浓度检测限(S/N=3)分别为8 7×10-7mol/L和4 2×10-7mol/L,质量检测限分别为1 45fmol和0 41fmol。该方法组分定性可靠,不需要衍生处理,选择性好。将该法应用于中药马齿苋样品的分析,获得了较好的结果。     

Determination of Butylated Hydroxyanisole by Briggs‐Rauscher Oscillating Reaction Catalyzed by a Macrocyclic Nickel (II) Complex

A novel analytical approach for quantitative measurement of butylated hydroxyanisole (BHA) is dis‐ cussed in this paper. Such a method depends on the inhibitory effect of BHA on a Briggs‐Rauscher (B‐R) oscillating reaction. Unlike the classical B‐R system which involves Mn²⁺ as the catalyst, such a B‐R sys‐ tem is catalyzed by a macrocyclic nickel (II) complex [NiL](ClO₄)₂, where L in the complex is an unsatu‐ rated ligand 5,7,7,12,14,14‐hexemethyl‐1,4,8,11‐tetraazacyclotetradeca‐4,11‐diene. By perturbation of BHA on the system, the oscillation was inhibited in the presence trace amounts of BHA and the inhibition time was found to be proportional to the concentration of BHA over the range 1.00×10^?7–1.20×10^?4 mol/L. Two calibration curves were obtained: the first linear regression is over the range of 1.00×10^?7–2.00×10^?6 mol/L, and the second linear regression is over the range between 2.00×10^?6 and 1.20×10^?4 mol/L, with a lowest limit of detection of 4.00×10^?8 mol/L. UV spectra measurements were employed to clarify the possible perturbation mechanism caused by BHA on the B‐R oscillating reaction.     

Determination of hesperidin and synephrine in Pericarpium Citri Reticulatae by capillary electrophoresis with electrochemical detection

A method based on capillary electrophoresis with electrochemical detection (CE-ED) has been developed for the determination of hesperidin (HP) and synephrine (SP) in the Chinese traditional herbal drug, Pericarpium Citri Reticulatae, the dried rind of the ripe fruits of Citrus reticulata Blanco (mandarin orange). The effects of some important factors such as the acidity and concentration of running buffer, separation voltage, and detection potential were investigated to determine the optimum conditions. The working electrode was a 300 microm diameter carbon disc electrode positioned opposite the outlet of the capillary. Both analytes could be well separated within 5 min in a 40 cm long capillary at a separation voltage of 12 kV in 50 mmol L(-1) borate buffer (pH 9.0). Excellent linearity was observed for the dependence of peak current on analyte concentration in the range from 2.5 x 10(-6) to 1.0 x 10(-3) mol L(-1) for SP and from 5.0 x 10(-6) to 1.0 x 10(-3) mol L(-1) for HP. The detection limits (S/N=3) for SP and HP were 4.96 x 10(-7) mol L(-1) and 6.54 x 10(-7) mol L(-1), respectively. This method has been successfully applied for the analysis of real samples, with satisfactory results.     

Simultaneous determination of five synthetic antioxidants in edible vegetable oil by GC–MS

A simple, quick and nontoxic analytical method for the simultaneous determination of five synthetic antioxidants [t-butyl-4-hydroxyanisole (BHA), 2,6-di-t-butyl-hydroxytoluene (BHT), t-butyl hydroquinone (TBHQ), ethoxyquin (EQ) and 2,6-di-tert-butyl-4-hydroxymethyl-phenol (Ionox 100)] in edible vegetable oil has been developed. The analytes were extracted by ethanol, then separated and detected by GC–MS. Extraction conditions such as volume of ethanol required, mixing time and number of extractions were investigated and optimized by an orthogonal array experimental design. The five compounds behaved linearly in the 0.100∼20.0 mg/L concentration range, and the limits of detection (LOD) for BHA, BHT, TBHQ, EQ and Ionox-100 were 1.00, 0.92, 11.5, 0.83 and 1.39 μg/L, respectively. The recoveries at the tested concentrations of 1.00, 20.0 and 100 mg/kg were 75.6∼123%, with coefficients of variation <10.0%. The proposed procedure was successfully applied to the simultaneous analysis of the five antioxidants in soybean oil, tea oil, edible blended oil, rap oil, peanut oil, peanut blended oil and sesame oil samples purchased from local supermarkets.