不同热处理条件对亚麻酸中持久性自由基产生的影响
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摘要
本研究采用电子顺磁共振波谱仪和紫外分光光度计,分别测定不同热处理方式和时间下,亚麻酸中持久性自由基信号和化学结构特征,以期探究亚麻酸结构变化及其自由基形成位点间的关系.结果表明,亚麻酸在电炉加热和微波复热后均能产生自由基,且复热后样品中的自由基信号强度明显增强,并随微波复热时间的增加而增强.这归因于电炉加热对亚麻酸起到启动作用,并提高其分子极性,而后在氧气的引入和微波辐射的作用下,导致其共轭双键断裂,进而产生以氧为中心的自由基(g因子值> 2.0040).微波复热时间增加时,衰减速率常数K随之增加,相应的,半衰期t_(1/2)随之减少.这是由于随着微波复热时间的增加,产生的较短寿命、高自旋的自由基增多.亚麻酸样品的羟基自由基随微波加热时间的增加而增强,这是因为微波加热有利于促进过氧化物的生成及其O—O键的断裂,进而贡献羟基自由基的形成.
This study aims to investigate the relationship between the linolenic acid(LNA) structure alternation and generation of persistent free radicals(PFRs). In the experiments, LNA samples were heated by electric stove and microwave for different time. The structure of the treated samples and PFRs generation were characterized by(UV-Vis) spectroscopy and electron paramagnetic resonance(EPR) techniques. The results showed that both electric stove heating and microwave reheating of LNA generated PFRs. The intensity of the PFRs signal increased with the microwave reheating time. Breaking of chemical bonds in LNA with consequent rise in polarity initiated PFRs generation due to electric stove heating. In the presence of oxygen, destruction of the conjugated double bonds enabled growth of oxygen-centered free radicals(g factor value > 2.0040). Increasing microwave reheating time elevated the decay rate constant K and reduced the half-life(t_(1/2)). Significant rise in the number of short-lived high-spinning radicals with increasing microwave reheating time attributed to this phenomenon. The increasing concentration of hydroxyl radicals indicated that microwave heating led to the peroxide generation and subsequent breakage of O—O bonds during LNA degradation.
This study aims to investigate the relationship between the linolenic acid(LNA) structure alternation and generation of persistent free radicals(PFRs). In the experiments, LNA samples were heated by electric stove and microwave for different time. The structure of the treated samples and PFRs generation were characterized by(UV-Vis) spectroscopy and electron paramagnetic resonance(EPR) techniques. The results showed that both electric stove heating and microwave reheating of LNA generated PFRs. The intensity of the PFRs signal increased with the microwave reheating time. Breaking of chemical bonds in LNA with consequent rise in polarity initiated PFRs generation due to electric stove heating. In the presence of oxygen, destruction of the conjugated double bonds enabled growth of oxygen-centered free radicals(g factor value > 2.0040). Increasing microwave reheating time elevated the decay rate constant K and reduced the half-life(t_(1/2)). Significant rise in the number of short-lived high-spinning radicals with increasing microwave reheating time attributed to this phenomenon. The increasing concentration of hydroxyl radicals indicated that microwave heating led to the peroxide generation and subsequent breakage of O—O bonds during LNA degradation.
引文
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[2] VEJERANO E W,RAO G,KHACHATRYAN L,et al.Environmentally persistent free radicals:Insights on a new class of pollutants [J].Environmental Science & Technology,2018,52(5):2468-2481.
[3] SCHULTZ E S,LITONJUA A A,MELEN E.Effects of long-term exposure to traffic-related air pollution on lung function in children [J].Current Allergy & Asthma Reports,2017,17(6):41-54.
[4] LEE A,LEON H H H,MATHILDA C Y H,et al.Prenatal fine particulate exposure and early childhood asthma:Effect of maternal stress and fetal gender [J].Journal of Allergy & Clinical Immunology,2017,141(5):1880-1886.
[5] AI P H L,HUA H,CHUONG P H.Free radicals,antioxidants in disease and health [J].International Journal of Biomedical Science Ijbs,2008,4(2):89-96.
[6] GUI M M,LEE K T,BHATIA S.Feasibility of edible oil vs.non-edible oil vs.waste edible oil as biodiesel feedstock [J].Energy,2008,33(11):1646-1653.
[7] AOYAMA T,NOSAKA N,KASAI M.Research on the nutritional characteristics of medium-chain fatty acids [J].J Med Invest,2007,54(3-4):385-388.
[8] DJOUSSEL,ARNETT D K,CARR J J,et al.Dietary linolenic acid is inversely associated with calcified atherosclerotic plaque in the coronary arteries:The national heart,lung,and blood institute family heart study [J].Circulation,2005,111(22):2921-2926.
[9] JOVANOVSKI E,LI D,THANH HO H V,et al.The effect of alpha-linolenic acid on glycemic control in individuals with type 2 diabetes:A systematic review and meta-analysis of randomized controlled clinical trials [J].Medicine,2017,96(21):6531-6542.
[10] BURDGE G C,CALDER P C.Conversion of alpha-linolenic acid to longer-chain polyunsaturated fatty acids in human adults [J].Reproduction Nutrition Development,2005,45(5):581-597.
[11] RAFFI J,YORDANOV N D,CHABANE S,et al.Identification of irradiation treatment of aromatic herbs,spices and fruits by electron paramagnetic resonance and thermoluminescence [J].Spectrochimica Acta Part A Molecular & Biomolecular Spectroscopy,2000,56(2):409-416.
[12] ?ABANOWSKA,M,WESELUCHA-BIRCZYNSKA A,KURDZIEL M,et al.The mechanism of thermal activated radical formation in potato starch studied by electron paramagnetic resonance and Raman spectroscopies [J].Carbohydrate Polymers,2013,91(1):339-347.
[13] FAN D M,HU B,LIN L F,et al.Rice protein radicals:growth and stability under microwave treatment [J].Rsc Advances,2016,6(100):97825-97831.
[14] EMMA C,MARIATERIATERESA R E,ELENA V,et al.Microwave heating of different vegetable oils:Relation between chemical and thermal parameters [J].LWT-Food Science and Technology,2010,43(7):1104-1112.
[15] TASCA J,LAVAT A,NESPRIAS K,et al.Cyclic organic peroxides thermal decomposition in the presence of CuFe2O4,magnetic nanoparticles [J].Journal of Molecular Catalysis A Chemical,2012,363-364(11):166-170.
[16] HALES B J,CASE E E.Immobilized radicals.IV.Biological semiquinone anions and neutral semiquinones [J].BBA-Bioenergetics,1981,637(2):291-302.
[17] DI V C,NEYMAN K M,RISSE T,et al.Density-functional model cluster studies of EPR g tensors of Fs+ centers on the surface of MgO [J].Journal of Chemical Physics,2006,124(4):1-7.
[18] INWATI G K,RAO Y,SINGH S.In situ free radical growth mechanism of platinum nanoparticles by microwave irradiation and electrocatalytic properties [J].Nanoscale Research Letters,2016,11(1):458-466.
[19] TYAGI V K,VASISHTHA A K.Changes in the characteristics and composition of oils during deep-fat frying [J].Journal of the American Oil Chemists′ Society,1996,73(4):499-506.
[20] 王冬梅,郭书贤,刘凤霞,等.共轭双键对脂肪酸紫外吸收的影响[J].安徽农业科学,2007,35(20):5999-6000.WANG D M,GUO S X,LIU F X,et al.Influence of conjugated double bond on ultraviolet absorption of fatty acid [J].Anhui Agricultural Sciences,2007,35(20):5999-6000 (in Chinese).
[21] WAKAKO T,AKIKO M,KAORI U.Formation of trans fatty acids in edible oils during the frying and heating process [J].Food Chemistry,2010,123(4):976-982.
[22] THOSTENSON E T,CHOU T W.Microwave processing:fundamentals and applications [J].Composites Part A Applied Science & Manufacturing,1999,30(9):1055-1071.
[23] MASKOS Z,LAVRENT K A,DELLINGER B.Precursors of Radicals in tobacco smoke and the role of particulate matter in forming and stabilizing radicals [J].Energy Fuels,2005,19(6):2466-2473.
[24] KUMAR S.Free radicals and antioxidants:human and food system [J].Advances in Applied Science Research,2011,2(1):129-135.
[25] FENN J A P,KNIGHT J A.The value of graduate education in clinical laboratory science [J].Laboratory Medicine,1995,26(8):537-541.
[26] LI Y,ZHAO J,SHANG E,et al.Effects of chloride ions on dissolution,ROS generation,and toxicity of silver nanoparticles under UV irradiation [J].Environmental Science & Technology,2018,52(8):4842-4849.
[27] BARRETO G P,ALVAREZ E E,EYLER G N,et al.Thermal decomposition of diethylketone cyclic triperoxide in polar solvents [J].Australian Journal of Chemistry,2014,67(6):881-886.
[28] NESPRIAS R,EYLER G.Mono,di and trifunctional cyclic organic peroxides:the effect of substituents and ring size on their thermolysis in 1,4-dioxan [J].Australian Journal of Chemistry,2013,66(9):1080-1087.
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