不同极性没食子酸酯对水包油型乳状液物理和氧化稳定性的影响
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摘要
为了阐明抗氧化剂极性与其在乳状液中抗氧化活性的关系,本文以不同极性没食子酸酯为研究对象,首先以乳液颗粒粒径和ζ-电位为指标,考察抗氧化剂极性对水包油型乳状液物理稳定性的影响,然后以过氧化值和己醛含量为评价指标,比较它们在乳状液中的抗氧化效果,再结合HPLC法和16-ArN~(2+)探针法分别测定其在乳状液水相和界面膜中的分布情况。结果表明:添加抗氧化剂后乳状液粒径均变小,然而不受抗氧化剂极性和浓度的影响。不同抗氧化剂对乳状液ζ-电位产生不同程度的影响,可能与其疏水性大小相关。油滴ζ-电位随着抗氧化剂添加浓度的增大反而减小。不同极性没食子酸酯在乳液中抗氧化活性依次为没食子酸丙酯(R3)>没食子酸月桂酯(R12)>没食子酸辛酯(R8)>没食子酸(R0)>没食子酸十八酯(R18)。它们在界面膜中的分布依次为R3>R12>R8>R18>R0。研究表明不同极性没食子酸酯均能有效增强乳状液的物理和氧化稳定性,其抗氧化活性除与极性相关外,还受其分布模式的影响。抗氧化剂在界面膜中分布越多,在乳液中的抗氧化活性就越强。
In order to elucidate the relationship between the polarity of antioxidants and its antioxidant activities in emulsions, gallic acid esters with different chain lengths were added into the oil/water emulsions and their effects on the physical stability(using the particle size and ζ-potential of emulsions as the indexes) and oxidation stability of the emulsions(using peroxide value and hexanal content as evaluation indexes) were compared. In addition, the distribution of the antioxidants in the aqueous phase and in the interfacial film were determined by HPLC and 16-ArN_2~+ probe method respectively. The results showed that the particle size decreased after the addition of antioxidants, but it was not affected by the polarity and concentration of the antioxidants. Different antioxidants had different effects on the ζ-potential of the emulsion, might be related to their hydrophobicity, and the ζ-potential of oil droplets was found to decrease with increasing concentration of antioxidant. The antioxidant activities of different gallates in the emulsion were decreased as follows: propyl gallate(R3)> lauryl gallate(R12)> octyl gallate(R8)> gallic acid(R0)> stearyl gallate(R18). Similar trend of their distribution in the interfacial film was found as: R3> R12> R8> R18> R0. This indicated that the physical and oxidation stability of the emulsions could be effectively enhanced by the different polarity of the gallic acid ester.The activity of antioxidants was not only related to their polarity, but also affected by their distribution pattern. The more antioxidant distributed in the interfacial film, the stronger the antioxidant activity will be in the emulsion.
In order to elucidate the relationship between the polarity of antioxidants and its antioxidant activities in emulsions, gallic acid esters with different chain lengths were added into the oil/water emulsions and their effects on the physical stability(using the particle size and ζ-potential of emulsions as the indexes) and oxidation stability of the emulsions(using peroxide value and hexanal content as evaluation indexes) were compared. In addition, the distribution of the antioxidants in the aqueous phase and in the interfacial film were determined by HPLC and 16-ArN_2~+ probe method respectively. The results showed that the particle size decreased after the addition of antioxidants, but it was not affected by the polarity and concentration of the antioxidants. Different antioxidants had different effects on the ζ-potential of the emulsion, might be related to their hydrophobicity, and the ζ-potential of oil droplets was found to decrease with increasing concentration of antioxidant. The antioxidant activities of different gallates in the emulsion were decreased as follows: propyl gallate(R3)> lauryl gallate(R12)> octyl gallate(R8)> gallic acid(R0)> stearyl gallate(R18). Similar trend of their distribution in the interfacial film was found as: R3> R12> R8> R18> R0. This indicated that the physical and oxidation stability of the emulsions could be effectively enhanced by the different polarity of the gallic acid ester.The activity of antioxidants was not only related to their polarity, but also affected by their distribution pattern. The more antioxidant distributed in the interfacial film, the stronger the antioxidant activity will be in the emulsion.
引文
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[5]FRANKEL E N, HUANG S W, KANNER J, et al.Interfacial phenomena in the evaluation of antioxidants-bulk oils vs emulsions[J]. Journal of Agricul tural and Food Chemistry, 1994, 42(5):1054-1059.
[6]ALEMáN M, BOU R, GUARDIOLA F, et al. Antioxidative effect of lipophilized caffeic acid in fish oil enriched mayonnaise and milk[J]. Food Chemistry, 2015, 167:236-244.
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[8]侯党社.没食子酸酯的合成及没食子酸酯与柿子提取物对食用油脂抗氧化性能研究[D].西安:西北大学, 2003.
[9]RAMíREZ-SUáREZ J C, XIONG Y L. Rheological properties of mixed muscle/nonmuscle protein emulsions treated with transglutaminase at two ionic strengths[J]. International Journal of Food Science and Technology, 2003, 38(7):777-785.
[10]余辉,陈洁.可见分光光度法测定乳状液过氧化值的研究[J].食品科学, 2007, 28(11):401-404.
[11]PANYA A, LAGUERRE M, LECOMTE J, et al.Effects of chitosan and rosmarinate esters on the physical and oxidative stability of liposomes[J]. Journal of Agricultural and Food Chemistry, 2010, 58(9):5679-5684.
[12]SáNCHEZPAZ V, PASTORIZAGALLEGO M J,LOSADABARREIRO S, et al. Quantitative determination of alpha-tocopherol distribution in a tributyrin/Brij 30/water model food emulsion[J]. Journal of Colloid and Interface Science, 2008, 320(1):1-8.
[13]DOYLE M P, BRYKER W J. Alkyl nitrite-metal halide deamination reactions. 6. Direct synthesis of arenediazonium tetrafluoroborate salts from aromatic amines, tert-butyl nitrite, and boron trifluoride etherate in anhydrous media[J]. Journal of Organic Chemistry, 2002, 44(9):1572-1574.
[14]ATARéS L, MARSHALL L J, AKHTAR M, et al.Structure and oxidative stability of oil in water emulsions as affected by rutin and homogenization procedure[J]. Food chemistry, 2012, 134(3):1418-1424.
[15]LUO Z, MURRAY B S, YUSOFF A, et al. Particle-stabilizing effects of flavonoids at the oil-water interface[J]. Journal of Agricultural and Food Chemistry, 2011, 59(6):2636-2645.
[16]SHAO Y, TANG C H. Characteristics and oxidative stability of soy protein-stabilized oil-in-water emulsions:Influence of ionic strength and heat pretreatment[J]. Food Hydrocolloids, 2014, 37:149-158.
[17]邵云.大豆蛋白稳定乳液的物化性质及油脂氧化稳定性研究[D].广州:华南理工大学, 2014.
[18]李佑贵,缪丽华,胡晓露. O/W型乳状体系中油脂的氧化稳定性的研究[J].山东食品发酵, 2012,(3):50-53.
[19]陈琳,伍贤.酸酯类对食用油脂的抗氧化活性研究[J].食品科学, 1998,(3):36-40.
[20]FERGUSON J. The use of chemical potentials as indices of toxicity[J]. Royal Society of London Proceedings, 1939, 127(848):387-404.
[21]BALGAVyP, DEVíNSKY F. Cut-off effects in biological activities of surfactants[J]. Advances in Colloid and Interface Science, 1996, 66:23-63.
[22]PANYA A, KITTIPONGPITTAYA K, LAGUERRE M, et al. Interactions between alpha-tocopherol and rosmarinic acid and its alkyl esters in emulsions:synergistic, additive, or antagonistic effect?[J]. Journal of Agricultural and Food Chemistry, 2012, 60(41):10320-10330.
[23]GONZáLEZ M J, MEDINA I, MALDONADO O S,et al. Antioxidant activity of alkyl gallates and glycosyl alkyl gallates in fish oil in water emulsions:Relevance of their surface active properties and of the type of emulsifier[J]. Food Chemistry, 2015,183:190-196.
[24]PANYA A, LAGUERRE M, BAYRASY C, et al.An Investigation of the versatile antioxidant mechanisms of action of rosmarinate alkyl esters in oil-inwater emulsions[J]. Journal of Agricultural and Food Chemistry, 2012, 60(10):2692-2700.
[25]LAGUERRE M, GIRALDO L J L, LECOMTE J, et al. Relationship between hydrophobicity and antioxidant ability of “Phenolipids” in emulsion:a parabolic effect of the chain length of rosmarinate esters[J].Journal of Agricultural and Food Chemistry, 2010,58(5):2869-2876.
[26]LOSADA B S, BRAVO-DIAZ C, PAIVA-MARTINS F, et al. Maxima in antioxidant distributions and efficiencies with increasing hydrophobicity of gallic acid and its alkyl esters. The pseudophase model interpretation of the ‘cutoff effect’[J]. Journal of Agricultural and Food Chemistry, 2013, 61(26):6533-6543.
[2]徐琼,姚晓琳,王娜娜,等.共轭亚油酸水包油型乳液的物理化学稳定性[J].农业工程学报, 2013,29(11):270-277.
[3]时浩.食品油脂O/W乳状液稳定性的研究[D].南昌:南昌大学, 2010.
[4]PORTER W L, BLACK E D, DROLET A M. Use of polyamide oxidative fluorescence test on lipid emulsions-contrast in relativeeffectiveness of antioxidants in bulk versus dispersed systems[J]. Journal of Agricultural and Food Chemistry, 1989, 37(3):615-624.
[5]FRANKEL E N, HUANG S W, KANNER J, et al.Interfacial phenomena in the evaluation of antioxidants-bulk oils vs emulsions[J]. Journal of Agricul tural and Food Chemistry, 1994, 42(5):1054-1059.
[6]ALEMáN M, BOU R, GUARDIOLA F, et al. Antioxidative effect of lipophilized caffeic acid in fish oil enriched mayonnaise and milk[J]. Food Chemistry, 2015, 167:236-244.
[7]LAGUERRE M, GIRALDO L J, LECOMTE J, et al. Chain length affects antioxidant properties of chlorogenate esters in emulsion:the cutoff theory behind the polar paradox[J]. Journal of Agricultural and Food Chemistry, 2009, 57(23):11335-11342.
[8]侯党社.没食子酸酯的合成及没食子酸酯与柿子提取物对食用油脂抗氧化性能研究[D].西安:西北大学, 2003.
[9]RAMíREZ-SUáREZ J C, XIONG Y L. Rheological properties of mixed muscle/nonmuscle protein emulsions treated with transglutaminase at two ionic strengths[J]. International Journal of Food Science and Technology, 2003, 38(7):777-785.
[10]余辉,陈洁.可见分光光度法测定乳状液过氧化值的研究[J].食品科学, 2007, 28(11):401-404.
[11]PANYA A, LAGUERRE M, LECOMTE J, et al.Effects of chitosan and rosmarinate esters on the physical and oxidative stability of liposomes[J]. Journal of Agricultural and Food Chemistry, 2010, 58(9):5679-5684.
[12]SáNCHEZPAZ V, PASTORIZAGALLEGO M J,LOSADABARREIRO S, et al. Quantitative determination of alpha-tocopherol distribution in a tributyrin/Brij 30/water model food emulsion[J]. Journal of Colloid and Interface Science, 2008, 320(1):1-8.
[13]DOYLE M P, BRYKER W J. Alkyl nitrite-metal halide deamination reactions. 6. Direct synthesis of arenediazonium tetrafluoroborate salts from aromatic amines, tert-butyl nitrite, and boron trifluoride etherate in anhydrous media[J]. Journal of Organic Chemistry, 2002, 44(9):1572-1574.
[14]ATARéS L, MARSHALL L J, AKHTAR M, et al.Structure and oxidative stability of oil in water emulsions as affected by rutin and homogenization procedure[J]. Food chemistry, 2012, 134(3):1418-1424.
[15]LUO Z, MURRAY B S, YUSOFF A, et al. Particle-stabilizing effects of flavonoids at the oil-water interface[J]. Journal of Agricultural and Food Chemistry, 2011, 59(6):2636-2645.
[16]SHAO Y, TANG C H. Characteristics and oxidative stability of soy protein-stabilized oil-in-water emulsions:Influence of ionic strength and heat pretreatment[J]. Food Hydrocolloids, 2014, 37:149-158.
[17]邵云.大豆蛋白稳定乳液的物化性质及油脂氧化稳定性研究[D].广州:华南理工大学, 2014.
[18]李佑贵,缪丽华,胡晓露. O/W型乳状体系中油脂的氧化稳定性的研究[J].山东食品发酵, 2012,(3):50-53.
[19]陈琳,伍贤.酸酯类对食用油脂的抗氧化活性研究[J].食品科学, 1998,(3):36-40.
[20]FERGUSON J. The use of chemical potentials as indices of toxicity[J]. Royal Society of London Proceedings, 1939, 127(848):387-404.
[21]BALGAVyP, DEVíNSKY F. Cut-off effects in biological activities of surfactants[J]. Advances in Colloid and Interface Science, 1996, 66:23-63.
[22]PANYA A, KITTIPONGPITTAYA K, LAGUERRE M, et al. Interactions between alpha-tocopherol and rosmarinic acid and its alkyl esters in emulsions:synergistic, additive, or antagonistic effect?[J]. Journal of Agricultural and Food Chemistry, 2012, 60(41):10320-10330.
[23]GONZáLEZ M J, MEDINA I, MALDONADO O S,et al. Antioxidant activity of alkyl gallates and glycosyl alkyl gallates in fish oil in water emulsions:Relevance of their surface active properties and of the type of emulsifier[J]. Food Chemistry, 2015,183:190-196.
[24]PANYA A, LAGUERRE M, BAYRASY C, et al.An Investigation of the versatile antioxidant mechanisms of action of rosmarinate alkyl esters in oil-inwater emulsions[J]. Journal of Agricultural and Food Chemistry, 2012, 60(10):2692-2700.
[25]LAGUERRE M, GIRALDO L J L, LECOMTE J, et al. Relationship between hydrophobicity and antioxidant ability of “Phenolipids” in emulsion:a parabolic effect of the chain length of rosmarinate esters[J].Journal of Agricultural and Food Chemistry, 2010,58(5):2869-2876.
[26]LOSADA B S, BRAVO-DIAZ C, PAIVA-MARTINS F, et al. Maxima in antioxidant distributions and efficiencies with increasing hydrophobicity of gallic acid and its alkyl esters. The pseudophase model interpretation of the ‘cutoff effect’[J]. Journal of Agricultural and Food Chemistry, 2013, 61(26):6533-6543.