气相色谱--质谱法测定XO酱中BHA、BHT和TBHQ

采用气相色谱—质谱(全扫描方式)测定XO酱中丁基羟基茴香醚(BHA)、二丁基羟基甲苯(BHT)和叔丁基对苯二酚(TBHQ)。样品用甲醇振荡萃取，以DB—5MS为分析柱。3种组分的回收率在85％～99％之间，相对标准偏差小于8．4％；样品中BHA、BHT和TBHQ的检测限分别为0．05、0．05和0．10(mg／kg)。该法简单、快速、准确，可用于XO酱等基质复杂的富油食品中BHA、BHT和TBHQ的检测和确证。     

Antioxidant migration resistance of SiOx layer in SiOx/PLA coated film

As novel materials for food contact packaging, inorganic silicon oxide (SiO_x) films are high barrier property materials that have been developed rapidly and have attracted the attention of many manufacturers. For the safe use of SiO_x films for food packaging it is vital to study the interaction between SiO_x layers and food contaminants, as well as the function of a SiO_x barrier layer in antioxidant migration resistance. In this study, we deposited a SiO_x layer on polylactic acid (PLA)-based films to prepare SiO_x/PLA coated films by plasma-enhanced chemical vapour deposition. Additionally, we compared PLA-based films and SiO_x/PLA coated films in terms of the migration of different antioxidants (e.g. t-butylhydroquinone [TBHQ], butylated hydroxyanisole [BHA], and butylated hydroxytoluene [BHT]) via specific migration experiments and then investigated the effects of a SiO_x layer on antioxidant migration under different conditions. The results indicate that antioxidant migration from SiO_x/PLA coated films is similar to that for PLA-based films: with increase of temperature, decrease of food simulant polarity, and increase of single-sided contact time, the antioxidant migration rate and amount in SiO_x/PLA coated films increase. The SiO_x barrier layer significantly reduced the amount of migration of antioxidants with small and similar molecular weights and similar physical and chemical properties, while the degree of migration blocking was not significantly different among the studied antioxidants. However, the migration was affected by temperature and food simulant. Depending on the food simulants considered, the migration amount in SiO_x/PLA coated films was reduced compared with that in PLA-based films by 42–46%, 44–47%, and 44–46% for TBHQ, BHA, and BHT, respectively.     

Gas Chromatographic Determination of Butylated Hydroxyanisole, Butylated Hydroxytoluene and Tertiarybutyl Hydroquinone in Soybean Oil

Oils containing different levels of the most common phenolic antioxidants, butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), and tertiarybutyl hydroquinone (TBHQ) from 0–200 ppm were analyzed by a new gas chromatographic method. The antioxidants in oils were isolated by nitrogen gas purging, collected on Tenax GC coated with polymetaphenoxylene, and then separated and quantitated by gas chromatography. This method requires neither extraction of antioxidants from oil nor derivatization of antioxidants. The correlation coefficients (r) between gas chromatographic peak heights or peak area and their concentrations in oils were 0.99 for BHA, BHT, and TBHQ. This simple gas chromatographic method can determine as little as 10 ppm pf BHA, BHT, or TBHQ in oils in an hour.     

Rapid micropreparation procedure for the gas chromatographic-mass spectrometric determination of BHT, BHA and TBHQ in edible oils

A rapid, accurate and organic solvent saving procedure has been developed for the GC/MS determination of three phenolic antioxidants butylated hydroxytoluene (BHT), butylated hydroxyanisole (BHA) and butyl hydroquinone (TBHQ) in vegetable oils. The method involves two-step microextraction and a centrifugal procedure in a 2 mL autosampler vial, consuming only 50 mg sample and total 1 mL acetonitrile. Recoveries of the phenolic antioxidants when spiked to soya bean oil, peanut oil and cereal cooking oil at 50, 200 and 250 mg/kg, respectively were in the ranges 95.6-104.3% for BHT, 99.7-107.5% for BHA and 93.6-103.8% for TBHQ with the relative standard deviation (RSD) were less than 3% for their independent measurements. The developed method was repeatable and could be applied to determine trace amounts of phenolic antioxidants in vegetable oils.     

Determination of synthetic phenolic antioxidants in soft drinks by stir-bar sorptive extraction coupled to gas chromatography-mass spectrometry

The synthetic phenolic antioxidants butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT) and tert-butyl hydroquinone (TBHQ) were pre-concentrated by stir-bar sorptive extraction and thermally desorbed (SBSE-TD) before analysis by GC-MS. Several parameters affecting the derivatisation step and both SBSE extraction and thermal desorption were carefully optimised. When the analyses of BHA and TBHQ in their acetylated, silylated and underivatised forms were compared, the best results were obtained when the in-situ derivatisation procedure with acetic anhydride was employed. Quantification was carried out using carvacrol as the internal standard, providing quantification limits of between 0.11 and 0.15 ng ml^?1, depending on the compound. Recovery assays for samples spiked at two concentration levels, 1 and 5 ng ml^?1, provided recoveries in the 81–117% range. The proposed method was applied in the analysis canned soft drinks and the analytes were found in five of the 10 samples analysed.     

ENHANCEMENT OF THE SHELF-LIFE OF FLAVORED BUTTER OILS BY SYNTHETIC ANTIOXIDANTS

The shelf-life of flavored butter oils was enhanced by adding permitted antioxidants butylated hydroxyanisole (BHA) and butylated hydroxytoluene (BHT) at 0.02% level. Such samples competed well with conveitional ghee. Tertbuthydroquinone (TBHQ) (permitted antioxidant for vegetable fats) showed the greatest antioxidant potency and could be recommended even at a very low level (0.005%) for imparting a longer shelf-life to flavored butter oils.     

Direct Spectroscopic Observation of Singlet Oxygen Quenching and Kinetic Studies of Physical and Chemical Singlet Oxygen Quenching Rate Constants of Synthetic Antioxidants (BHA,BHT, and TBHQ) in Methanol

Abstract: Singlet oxygen quenching by synthetic antioxidants (BHA, BHT, and TBHQ) was directly observed by spectroscopic monitoring of luminescence at 1268 nm. The luminescence data showed unambiguous evidence of singlet oxygen quenching by synthetic phenolic antioxidants with the highest activity for TBHQ, followed by BHA and BHT. The protective activities of these synthetic antioxidants on α-terpinene oxidation with chemically-induced singlet oxygen under dark further confirmed their singlet oxygen quenching abilities. Total singlet oxygen quenching rate constants (k_r + k_q) of BHA, BHT, and TBHQ were determined in a system containing α-terpinene (as a singlet oxygen trap) and methylene blue (as a sensitizer) during light irradiation, and the values were 5.14 × 10⁷, 3.41 × 10⁶, and 1.99 × 10⁸ M⁻¹s⁻¹, respectively. After the k_r value of α-terpinene was first determined, the k_r values of the synthetic antioxidants were calculated by measuring their relative reaction rates with singlet oxygen to that of α-terpinene under the identical conditions. The k_r values of the BHA, BHT, and TBHQ were 3.90 × 10⁵, 1.23 × 10⁵, and 2.93 × 10⁶, M⁻¹s⁻¹. The percent partition of chemical quenching over total singlet oxygen quenching (k_r × 100)/(k_r + k_q) for BHA, BHT, and TBHQ were 0.76%, 3.61%, and 1.47%, respectively. The results showed that the synthetic antioxidants quench singlet oxygen almost exclusively through the mechanism of physical quenching. This represents the first report on the singlet oxygen quenching mechanism of these synthetic antioxidants. Practical Application: The synthetic antioxidants, especially TBHQ, have been found to have a strong singlet oxygen quenching ability. This article also clearly showed that singlet oxygen quenching by synthetic antioxidants was mainly by the physical quenching mechanism. The results suggested that these synthetic antioxidants, especially TBHQ, could be used practically for the protection of the food components such as edible oils and vitamins against singlet oxygen induced oxidations without significant losses of antioxidant activity during storage under light.     

Estimates of the theoretical maximum daily intake of phenolic antioxidants BHA, BHT and TBHQ in Brazil

The theoretical maximum daily intakes (TMDI) of the phenolic antioxidants butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT) and tertbutyl hydroquinone (TBHQ) in Brazil were estimated using food consumption data derived from a household economic survey and a packaged goods market survey. The estimates were based on maximum levels of use of the food additives specified in national food standards. The calculated intakes of the three additives for the mean consumer were below the ADIs. Estimates of TMDI for BHA, BHT and TBHQ ranged from 0.09 to 0.15, 0.05 to 0.10 and 0.07 to 0.12mg/kg of body weight, respectively. To check if the additives are actually used at their maximum authorized levels, analytical determinations of these compounds in selected food categories were carried out using HPLC with UV detection. BHT and TBHQ concentrations in foodstuffs considered to be representive sources of these antioxidants in the diet were below the respective maximum permitted levels. BHA was not detected in any of the analysed samples. Based on the maximal approach and on the analytical data, it is unlikely that the current ADI of BHA (0.5mg/kg body weight), BHT (0.3mg/kg body weight) and TBHQ (0.7mg/kg body weight) will be exceeded in practice by the average Brazilian consumer.     

Estimated daily intakes of butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT) and tert-butyl hydroquinone (TBHQ) antioxidants in Korea.

The study was conducted to establish the estimated daily intake (EDI) of antioxidants such as butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT) and tert-butyl hydroquinone (TBHQ) in Korea. The EDIs were obtained from two sources. One of the estimations was based on the analytical determination of BHA, BHT and TBHQ in 12 food categories (ten food categories for TBHQ) and on individual dietary intake data obtained from the National Health and Nutrition Survey in 1998 (n=11 525, age > 1 year). The other EDIs of BHA, BHT and TBHQ were based on the maximum permitted levels specified in national food standards in Korea and on individual dietary intake data obtained from the National Health and Nutrition Survey in 1998 (n=11 525, age > 1 year). To establish the EDIs based on the analytical determination and on individual dietary intake data, 133 food samples in 12 food categories were selected from the foods considered to be representative sources of BHA, BHT and TBHQ in the Korean diet. Selected samples were analysed by GC with FID. BHA was not detected in any of the samples analysed. BHT and TBHQ were detected in the samples, but the levels were significantly lower than their maximum limits. The EDIs1 of BHT, and TBHQ for average consumers were 0.0156(-3), and 0.0012(-3) mg kg(-1) body weight bw day(-1) and as a proportion of the ADI were 0.0052 and 0.0002%, respectively. For 95th percentile consumers, the EDIs of BHT and TBHQ were 0.0080 and 0.0006 mg kg(-1) bw day(-1), and as a proportion of the ADI were 2.67 and 0.09%, respectively. EDIs for BHA, BHT and TBHQ based on the maximum permitted levels and on individual dietary intake data were 0.04, 0.04 and 0.04 mg kg(-1) bw day(-1), respectively. The EDIs of BHA, BHT and TBHQ for average consumers ranged from 6.00 to 14.42% of the ADI of each antioxidant. According to these results, the EDIs of BHA, BHT and TBHQ in Korea were significantly lower than ADI of these antioxidants established by the JECFA.     

Effect of natural and synthetic antioxidants incorporation on the gas permeation properties of poly(lactic acid) films

Gas permeation properties (permeability, diffusivity and solubility coefficients) were determined for carbon dioxide and oxygen in poly(lactic acid) (PLA) films enriched with 0, 2, 4 and 10 wt.% of different antioxidants, at three temperatures, 284, 293 and 303 K, using a time-lag apparatus. Three antioxidants, a natural, α-tocopherol (AT), and two synthetic, butylated hydroxytoluene (BHT) and tert-butylhydroquinone (TBHQ), were tested. DSC results show that the polymer glass transition temperature slightly decreases with the increase of the antioxidant content. The crystallinity degree of PLA films decreases with the addition of BHT and TBHQ, whereas the incorporation of AT increases the crystallinity of PLA films. The permeability towards water vapour, at 299 K and 45% of relative humidity, and surface energy show a decreased in the wettability of the prepared materials with the increase of the antioxidants content. The incapacity to measure gas permeation in PLA films with 10 wt.% of AT and BHT incorporated was due to phase separation, proved by SEM images. The CO₂ and O₂ permeation results show that PLA barrier properties can be improved by the incorporation of antioxidants but are strongly dependent on the amount and structure of the antioxidant added.     

SYNERGISTIC ACTIVITY OF CAPELIN PROTEIN HYDROLYSATES WITH SYNTHETIC ANTIOXIDANTS IN A MODEL SYSTEM

Capelin protein hydrolysates (CPHs) were examined in a β-carotene-linoleate model system together with synthetic antioxidants, namely butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), and tert-butyl hydroquinone (TBHQ). Addition of CPHs was at 0.25 and 1 mg per 5 mL in the above emulsion. BHA and BHT were added at levels of 2.5 and 5 μg and TBHQ at 5 and 10 μg. Absorbance of model emulsion system at 470 nm was recorded every 30 min for 2 h. CHPs and synthetic antioxidants inhibited oxidation of linoleic acid effectively. In the experiment with BHA, the influence of CPHs was significant (p<0.01) for the samples incubated for 60, 90, and 120 min; and in experiments with BHT and TBHQ during the entire incubation period. The influence of added BHA and BHT on inhibition of bleaching of β-carotene in the emulsion system was significant (p <0.01) during the incubation period and after 60, 90 and 120 min when TBHQ was used. A synergistic effect was observed only for CPHs and TBHQ when incubation time was 60, 90, and 120 min.     

Qualitative and Quantitative Effects of Antioxidants on the Flavor Stability of Oil

Qualitative and quantitative effects of the common antioxidants, BHA, BHT, PG and TBHQ on the rate of dissolved free oxygen disappearance in soybean oil during storage were studied. The order of effectiveness was BHA, BHT, PG and TBHQ with TBHQ as the most effective. Statistical analyses of the results showed that the effects of BHA and BHT were not significantly different from each other at the 5% level, but BHA or BHT was different from PG or TBHQ, and PG was different from TBHQ. The antioxidant effectiveness of levels of 0, 50, 100, 150 and 200 ppm BHA, BHT, PG or TBHQ was significantly different from one another at the 5% level. The higher the amounts of antioxidants added, the slower the rate of dissolved oxygen disappearance in the oil.     

Effect of BHA, BHT, TBHQ and PG on Growth and Toxigenesis of Selected Aspergilli

The antifungal effect of butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), tertiary butylhydroquinone (TBHQ) and propyl gallate (PC) alone or in combination on three toxigenic strains of aspergilli (NRRL 2999, NRRL 4123, NRRL 5835) and three nontoxigenic strains of aspergilli (NRRL 5521, NRRL 5917, NRRL 5918) was examined in a solid medium and in salami. BHT and PG (0.001,0.005,0.01,0.02g per plate) did not inhibit growth, sporulation, and toxigenesis of all six cultures. Aflatoxin production by toxigenic aspergilli (B₁, B₂, G₁ and G₂) in the presence of BHA, TBHQ, and a combination of BHA and TBHQ was reduced significantly (P < 0.05). In salami BHA, TBHQ alone or in combination at 100 ppm significantly (P < 0.05) decreased the aflatoxin production by aspergilli when compared to control samples. A combination of BHA and TBHQ showed synergistic inhibition in both studies (solid medium and salami studies).     

THERMAL STABILITY OF SOME COMMERCIAL NATURAL AND SYNTHETIC ANTIOXIDANTS AND THEIR MIXTURES

The thermal stability of some commercially available antioxidants alone or in binary or ternary mixtures was investigated in order to find the optimal combination of antioxidants for food processing. The synthetic antioxidants used were butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), propyl gallate (PG) and tertiary-butyhydroquinone (TBHQ). Other antioxidants such as ascorbyl palmitate (AP), mixed tocopherols (TOCO) and monoacylglycerol citrate (MGC) were also employed. The effectiveness of these antioxidants and their combinations was assessed using the Rancimat test by measuring the induction period for the oxidation of sunflower oil after heating at 180C for 1 h and comparing it to the oxidation kinetics of the oil without added antioxidants. All antioxidants and their binary or ternary mixtures showed different degrees of thermal instability. TBHQ individually, among all the examined antioxidants, showed the highest thermal stability. On the other hand, AP as an antioxidant in sunflower oil exhibited low stability during heating. The thermal stability of AP could be enhanced by the addtion of BHA or BHT in binary mixtures at a ratio of 1:3 (w/w). In addition, the ternary mixture of AP, TOCO and MGC (65:25:10) in sunflower oil also showed a higher stability to thermal inactivation. However, the ternary mixture containing 0.13% AP, 0.05% TBHQ and 0.02% MGC provided the optimal protection during thermal treatment. Although a combination of 0.13% BHT, 0.05% AP and 0.02% MG was very effective synergistically at room temperature, it showed a higher susceptibility to thermal inactivation. It was     

Kinetics of Growth and Inhibition of Listeria monocytogenes in the Presence of Antioxidant Food Additives

Listeria monocytogenes strain Scott A in Tryptose Broth was treated with 100-300 ppm butylated hydroxyanisole (BHA), 300-700 ppm butylated hydroxytoluene (BHT) and 10-30 ppm tertiary butylhydroquinone (TBHQ). Resulting growth curves were fitted using the logistic model, and growth parameters [lag period (LP), generation time (GT), and maximum growth (MG)] were calculated. BHA and BHT inhibited Listeria monocytogenes by increasing LP and GT and decreasing MG. Extent of inhibition was concentration-dependent for cultures with BHA, but not with BHT. TBHQ at 10-30 ppm increased LP but did not affect other parameters. LP increased exponentially with increased BHA or TBHQ in Listeria culture. Concentrations of additive required to increase LP by one order of magnitude were 240 ppm for BHA and 26 ppm for TBHQ.     

STABILIZATION OF MARINE OILS WITH FLAVONOIDS

Antioxidant activity of a number of flavonoids in refined-bleached and deodorized (RBD) seal blubber oil (SBO) and menhaden oil (MHO) was compared with that of commercially used antioxidants, namely butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT) and tert-butylhydroquinone (TBHQ) as well as α-tocopherol. The study was carried under Schaal oven conditions at 65C and progression of oxidation was followed by monitoring weight gain, peroxide value (PV) and 2-thiobarbituric acid reactive substances (TBARS) value. Among the flavonoids tested in this study, the flavonols, namely myricetin, quercetin and morin exhibited a stronger antioxidant activity than BHA and BHT and effectively stabilized both SBO and MHO. Myricetin was the most effective flavonoid tested in this study and its effect in reducing lipid oxidation was similar to that of TBHQ.     

Antioxidant activity of natural plant sources in dairy dessert (Sandesh) under thermal treatment

Natural sources of antioxidant viz. beet (Beta vulgaris), mint (Mentha spicata L.) and ginger (Zingiber officinale L.) have been used to fortify sandesh (a heat desiccated product of coagulated milk protein mass called chhana which is in turn a heat and acid coagulated product of milk, analogous to cottage cheese). Three sets of experiments viz. antioxidant activity, peroxide value and ultra-violet absorbance were done to evaluate the effectiveness of natural antioxidants in reducing lipid oxidation in sandesh as compared to synthetic antioxidants like tertiary butyl hydroquinone (TBHQ), butylated hydroxyanisole (BHA) and butylated hydroxytoluene (BHT) under thermal treatment. Among the natural sources, ginger has the highest antioxidant activity and it was similar to TBHQ and BHA-BHT combined. Results of the antioxidant activity differed from those of the oven test at 63 °C particularly for ginger and BHA-BHT combined. Control sandesh (without any antioxidants) showed the highest peroxide value and ultra-violet absorption. All the natural sources and their combinations significantly improved the oxidative stability of sandesh and their effectiveness was comparable with synthetic antioxidant TBHQ, a combination of BHA and BHT. Among the natural sources, although ginger had the highest antioxidant activity but mint showed better effectiveness in the inhibition of lipid oxidation. Regarding antioxidant activity and lipid oxidation, combination of mint or ginger with beet showed better result as compared to beet alone. Besides, sensory evaluation of freshly prepared natural source fortified sandesh samples was done as compared to control sandesh in order to commercialize the herbal sandesh in market. Sandesh containing beet, ginger, combination of beet with ginger or mint, or combination of mint with ginger were more acceptable to panelist than control sandesh.     

Two novel synthetic antioxidants for deep frying oils

Lauryl tert-butylated hydroquinone (LTBHQ) and its oxidized compound, lauryl tert-butylated quinone (LTBQ) were synthesized from tert-butylated hydroquinone (TBHQ) and lauryl alcohol. Their antioxidant activities were investigated. At temperatures higher than 140 °C, the antioxidant activity of LTBHQ and LTBQ was higher than TBHQ. In emulsions, these two compounds had stronger antioxidant activity than TBHQ, butylated hydroxytoluene (BHT) and butylated hydroxyanisole (BHA).     

Control of Lipid Oxidation in Cooked Ground Pork with Antioxidants and Dinitrosyl Ferrohemochrome

A number of antioxidants were added to ground meat prior to cooking to achieve oxidative stability. The 2-thiobarbituric acid (TBA) numbers of cooked-meat samples after storage for up to 35 days were determined. Of the antioxidants tested, butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), propyl gallate (PG), t-butylhydro-quinone (TBHQ), trihydroxybutyrophenone (THBP), nordihydro-guaiaretic acid (NDGA), catechol, and ethoxyquin were effective at a level of 200 ppm giving TBA values of less than one. BHA, TBHQ, and ethoxyquin were equally effective at a level of 30 ppm. Ascorbyl acetal and ascorbyl palmitate retarded lipid oxidation effectively (TBA values of slightly over one after five weeks of storage). The cooked cured-meat pigment showed some antioxidant effect which increased with increasing concentration, and at 18–24 ppm was better than that of 200 ppm of α-tocopherol.     

紫外光下4种抗氧化剂在猪油中的抗氧化效果

旨在研究光照对油脂抗氧化剂抗氧化效果的影响。分别研究在254、365 nm波长光照射下,猪油中添加丁基羟基茴香醚(BHA)、2,6-二叔丁基-4-甲基苯酚(BHT)、特丁基对苯二酚(TBHQ)、没食子酸丙酯(PG)对其过氧化值、酸价、丙二醛值、共轭二烯类值、共轭三烯类值的影响。结果表明,与空白相比,在254 nm光照下,4种抗氧化剂抑制猪油过氧化值、酸价、丙二醛值、共轭二烯类值、共轭三烯类值的效果差异不显著(p>0.05);在365 nm光照下,BHA、BHT、PG抑制猪油过氧化值、酸价、共轭二烯类值、共轭三烯类值效果差异性不显著(p>0.05),抑制丙二醛效果差异极显著(p<0.01)。TBHQ抑制猪油酸价、共轭三烯类值效果差异不显著(p>0.05),抑制过氧化值、共轭二烯类值差异显著(p<0.05),抑制丙二醛效果差异性极显著(p<0.01)。由此说明,在254、365 nm光照射下,BHA、BHT、PG基本没有抗氧化效果,TBHQ的效果也不够理想。