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1、LIPID PHYSICAL AND CHEMICAL CHARACTERISTIC,Zhang Dequan,物理性质,气味和色泽 芝麻油香气：乙酰吡嗪 椰子油香气：壬基甲酮 菜子油气味：黑芥子苷分解 熔点和沸点 油脂熔点最高40-55 熔点温度低于37，消化率达到96%熔点高于37，不容易消化,烟点、闪点和着火点 smoking point：发烟的温度 flash point：被点燃但不能燃烧的温度 fire point：持续燃烧5s以上的温度 精练油脂烟点在240左右 折射率 分子量大分子量小的饱和脂肪酸 饱和脂肪酸不饱和脂肪酸 油脂鉴别,结晶特性 Polymorphism 转变-2排列
2、(DCL)-3排列(TCL)简单甘油酯容易形成稳定的结晶,DCL排列 混合甘油酯容易形成结晶,TCL排列,结晶：大豆油、玉米油、花生油、椰子油、橄榄油、可可脂油、猪油结晶：棉子油、棕榈油、菜子油、乳脂、牛脂、改性猪油“调温”获得某种结晶产品 可可脂生产 Sn-StOSt、Sn-POSt,熔融特性 融化 SFI（Solid Fat Index）SFI测定方法：差示扫描量热仪（DSC）NMR 脉冲NMR为AOCS的官方方法,油脂塑性 塑性是指在一定的外力下，表观固体脂肪具有的抗变形的能力，油脂塑性取决于：SFI、脂肪晶型、熔化温度范围Shortening oil油脂的液晶态（介晶相）层状：六方 立
3、方,乳化与乳化剂 分散相（01-50微米的小滴）分散在连续相中 乳浊液的制备：油脂、水、乳化剂、能量 乳浊液不稳定的因素：分层、絮凝、聚结乳化剂选择方法：HLB值,一些常见乳化剂的HLB值,化学性质,水解氧化,1.Hydrolysis and saponification,动物脂肪 不利 有利植物油鱼脂水解性质的应用构造脂质,2、氧化(酸败),自动氧化光敏氧化酶促氧化热氧化辐射氧化,Flavor Quality Loss Rancid flavorChanges of color and textureConsumer Acceptance Economic loss Nutritional
4、Quality LossEssential Fatty Acids Vitamins Health Risks Growth Retardation Heart Diseases,2.1 氧化机制,酶与非酶氧化两种机制自催化机制的与分子氧的反应是脂类氧化变质的主要反应光敏氧化触发了自动氧化,2.1.1 自动氧化的一般特性,遵循自由基机制，具有5个特点干扰自由基反应的化学物质能显著抑制自动氧化光和产生自由基的物质能促进自动氧化产生大量的氢过氧化物由光引发的氧化反应量子产额超过1当原始物质为纯物质时存在一个相当长的诱导期,Mechanisms of Lipid Oxidation,Reaction
5、s Activation Energy Protein Denaturation 100 kcal/molNonenzymatic Browning Reaction 50Enzyme Catalyzed Reaction 10-15Lipid Oxidation 10-15,Activation Energy for Chemical Reaction,History of Oxygen,Oxygen-Scheele and Priestly in 1772.Triplet oxygen-Millikan in 1928.Singlet oxygen-Herzberg in 1934.,Tr
6、iplet Oxygen Oxidation,C,H,C,H,C,H,2,C,H,C,H,C,H,2,(,C,H,2,),6,C,O,O,H,C,H,2,(,C,H,2,),3,C,H,3,100,75,50,Bond Energy of Carbon and Hydrogen,kcal/mol,Stearic acidOleic acid Linoleic acid Linolenic acid,C,H,3,(,C,H,2,),14,C,O,O,H,C,H,3,(,C,H,2,),6,C,H,C,H,(,C,H,2,),7,C,O,O,H,C,H,3,(,C,H,2,),4,C,H,C,H,
7、C,H,2,C,H,C,H,(,C,H,2,),7,C,O,O,H,C,H,3,C,H,2,C,H,C,H,C,H,2,C,H,C,H,C,H,2,C,H,C,H,(,C,H,2,),7,C,O,O,H,C,H,2,C,H,2,C,H,2,Initiation of Triplet Oxygen Oxidation,RH+引发剂,R,H,+,Initiation of autoxidation occurs when hydrogen atom at-methylene group in double bonds of unsaturated fatty acids is removed to
8、 form an alkyl radical(R).,Propagation,ROO,+,RH,ROOH,+,R,+,+,ROOH,+,OH,RO,RH,RO,ROH,R,R,+,3O2,ROO,Termination,2RO,ROOR,+,+,+,ROOR,RO,ROR,ROO,ROOR,R,+,R-R,R,ROO,+,R,R,ROO,O2,Linoleic Acid Oxidation by Triplet Oxygen,14,13 12 11 10 9,12 11 10 9,-H,+O,2,12 11 10 9,+H,C,H,2,C,H,C,H,C,H,2,C,H,C,H,C,H,2,R
9、,(,C,H,2,),3,C,H,3,INITIATION,(METAL),(,C,H,2,),4,C,H,3,C,H,C,H,C,H,C,H,C,H,2,R,C,H,(,C,H,2,),4,C,H,3,C,H,C,H,C,H,C,H,C,H,2,R,C,H,O,O,PROPAGATION,R=(CH2)6-COOH,12 11 10 9,HYDROPEROXIDE,DECOMPOSION,-OH,+H,12 11 10 9,TERMINATION,(PENTANE),C,H,C,H,C,H,C,H,C,H,C,H,2,R,(,C,H,2,),4,C,H,3,O,O,H,(,C,H,2,),4
10、,C,H,3,C,H,C,H,C,H,C,H,C,H,2,R,C,H,O,C,H,3,(,C,H,2,),3,C,H,2,C,H,3,(,C,H,2,),3,C,H,3,O,C,H,C,H,C,H,C,H,C,H,C,H,2,R,+,R=(CH2)6-COOH,Singlet and Triplet Oxygen,Molecular Orbital of Triplet Oxygen,RH+O2自由基35kcal/mol,Molecular Orbital of Singlet Oxygen,Singlet Oxygen Formation,3O2+Sensitizer,H2O2+OCI-,H
11、2O2+O2-,Ozone,Endoperoxides,OH-+O2-,Enzymes,O2-+Y+,1O2,O2-,O2-+O2-,H2O2+HO2-,RCOO+RCOO,C,H,3,C,H,2,C,H,C,H,C,H,2,C,H,C,H,C,H,2,C,H,C,O,O,H,(,C,H,2,),6,C,H,2,C,H,O,C,H,3,C,H,2,C,H,C,H,C,H,2,C,H,C,H,C,H,2,C,H,O,C,H,3,C,H,2,C,H,C,H,C,H,2,C,H,O,O,C,H,C,H,2,C,H,1O2,1O2,O,氢过氧化物形成：Reversion Flavor from Lin
12、olenic Acid by Singlet Oxygen Oxidation,O,2-(2-pentenyl)-furan,-H2O,C,H,3,C,H,2,C,H,C,H,C,H,2,C,H,O,O,C,H,C,H,2,C,H,C,H,3,C,H,2,C,H,C,H,C,H,2,C,C,H,2,O,C,H,2,C,H,O,C,H,3,C,H,2,C,H,C,H,C,H,2,C,C,H,C,H,C,H,O,H,O,H,C,H,3,C,H,2,C,H,C,H,C,H,2,O,C,H,3,C,H,2,C,H,C,H,C,H,2,C,H,O,O,C,H,C,H,2,C,H,O,H,-OH,氢过氧化
13、物裂解：Reversion Flavor Compounds from Soybean Oil,2-(2-pentenyl)-furan,C,H,3,C,H,2,C,H,C,H,C,H,2,O,C,H,3,C,H,2,C,H,C,H,C,H,O,2,2-(1-pentenyl)-furan,Reaction of 3O2 and 1O2 with Linoleic Acid,R,R,R,R,O,O,H,3O2,Conjugated,Conjugated,R,R,R,R,R,R,HOO,3O2,-H,R,R,R,R,O,O,H,O,O,H,R,R,1O2,R,R,H,O,O,R,R,H,O,O,
14、Conjugated,Nonconjugated,Reaction Rates of Lipid Oxidation,R+3O2K=109 M-1sec-1ROO+Oleic AcidK=1 M-1sec-1ROO+Linoleic AcidK=60 M-1sec-1ROO+Linolenic AcidK=120 M-1sec-1ROO+ROO K=105-107 M-1sec-1R+AntioxidantsK=107 M-1sec-1RH+1O2K=105 M-1sec-1,Relative Reaction Rates of 3O2 and 1O2 with Oleic,Linoleic,
15、and Linolenic Acids,Triplet oxygen 3 104 4 104 7 104,Singlet oxygen 12777,Oleic Linoleic LinolenicAcid Acid Acid,Formation of 1O2 by Sensitizers,Ground State,Excited State,hv,FluorescenceK=2108/sec,1Sen,1Sen*,K=1-20108/sec ISC,Phosphorescence,K=10-104/sec,Singlet Oxygen,1O2,K=1-3109/sec,3Sen*,3O2,光敏
16、氧化,Lipid,Free Radical,型,型,Photosensitizers in Foods,Chlorophyll Protoporphyrine Riboflavin Red No.3,Enzymatic Oxidation（lipoxygenase,Lox）,Hydropeorxide at the-6 position of unsaturated fatty acid,Poly unsaturated fatty acids(a cis,cis-1,4-pentadiene unit),Lipoxygenase,热氧化,热分解热聚合热缩合,辐射氧化,过氧化脂质几乎可以与食品
17、中的任何成分反应，降低品质氢过氧化物几乎与人体内所有分子或细胞反应，破坏和细胞结构脂质在常温或高温下氧化均产生有害物质,油脂氧化的安全性,影响自动氧化的因素,脂肪酸性质氧与氧分压温度表面积水分过渡金属元素光和射线抗氧化剂乳化,Control of Lipid Oxidation,Application of antioxidants Elimination of oxygen by nitrogen flushing or vacuum packaging Elimination of photosensitizers Denaturation of lipoxygenase Low temp
18、erature and dark storage,Characteristics of Free Radicals in Oxidation,H:Hydrogen atom The simplest free radicalO2-:SuperoxideanionAn oxygen-centered radical.Limited reactivityHO:HydroxylA highly reactive oxygen-centered radical.Indeed attacks all molecules in human bodyRO2:PeroxylOxygencentered rad
19、icals formed during the RO:Alkoxy breakdown of organic peroxides,Function of Antioxidant on Lipid Oxidation,Inhibits or slows the formation of free alkyl radicals in the initiation step Interrupts the propagation of free radical chain Delays the start or slows the chemical reaction rate of lipid oxi
20、dation.,Types of Antioxidants,Hydrogen donating compounds Singlet oxygen quenchers Metal chelators Enzymes Oxygen scavengers and Reducing agents,Hydrogen Donating Antioxidants,Standard One-Electron Reduction Potential,Compounds E(mV),HO,H+/H2O 2310RO,H+/ROH1600ROO,H+/ROOH1000PUFA,H+/PUFA600Catechol,
21、H+/Catechol530-Tocopheroxyl,H+/-Tocopherol500Ascorbate-,H+/Ascorbate282,Characteristics of Hydrogen Donating Antioxidants,The major hydrogen donating antioxidants are monohydroxy or polyhydroxy phenolic compounds with various ring substitutions.The antioxidant free radical does not initiate another
22、free radical due to the stabilization of delocalization of radical.,Reaction of Antioxidants with Radicals,R+AHRH+A,RO+AHROH+A,ROO+AHROOH+A,Reaction of Antioxidants with Radicals,Effectiveness of Antioxidants,The difference of one-electron reduction potential between lipid radical and antioxidant ra
23、dical.The stability of antioxidant radicals-The resonance delocalization-Further oxidation of antioxidant radicals,Resonance of Antioxidant Radicals,O,H,C,(,C,H,3,),3,O,C,H,3,C,(,C,H,3,),3,O,C,H,3,O,.,O,C,H,3,C,(,C,H,3,),3,O,.,C,(,C,H,3,),3,O,C,H,3,O,.,O,C,H,3,C,(,C,H,3,),3,O,.,R,RO,ROO,RH,ROH,ROOH,
24、Stability of Antioxidant Radical,O,C,C,H,3,C,H,3,C,H,3,O,C,H,3,Targets of Antioxidant,Antioxidants can react with peroxyl radicals rather than alkoxyl radicals.The most prevalent radical is peroxyl(ROO)radical.Peroxyl radical has the lowest standard one electron reduction potential among alkyl,alkox
25、yl and peroxyl radicals,Synthetic Antioxidants,Butylatedhydroxyanisole(BHA),Butylatedhydroxytoluene(BHT),Propyl gallate,Tertiary butylhydroquionone(TBHQ),Natural Antioxidants,Benefits Health implication Stability in food systemLimits Characteristic flavor Safety test required,Tocotrienols,O,H,O,R,1,
26、R,2,R,3,C,H,3,C,H,3,C,H,3,C,H,3,Trivial NameChemical NameR1R2R3-Tocotrienol5,7,8-TrimethyltocotrienolCH3CH3CH3-Tocotrienol5,8-DimethyltocotrienolCH3HCH3-Tocotrienol7,8-DimethyltocotrienolHCH3CH3-Tocotrienol8-MethyltocotrienolHHCH3,Antioxidant Mechanism of Tocopherol,Transfer of phenolic hydrogen Sca
27、venging of singlet oxygen Regeneration of tocopherol in the presence of ascorbate,Tocopherol,A chain breaking antioxidant competes with polyunsaturated lipid for the lipid peroxyl radicals.,-Tocopherol-Tocopheryl semiquinone,Lipid radicals,Lipid radicals,-Tocopheryl quinone,Resonance of-Tocopherol R
28、adicals,O,O,C,H,3,H,3,C,C,H,3,C,16,H,33,C,H,3,R,RO,or ROO,-Tocopherol,O,H,O,C,H,3,H,3,C,C,H,3,C,H,3,C,H,3,C,H,3,C,H,3,O,C,H,3,C,H,3,H,3,C,C,H,3,C,16,H,33,O,O,C,H,3,H,3,C,O,C,16,H,33,C,H,3,C,H,3,O,C,H,3,H,3,C,O,C,16,H,33,C,H,3,C,H,3,RH,ROH,ROOH,R,RO,or ROO,Effects of Diet Tocopherol on the Content of
29、 Tocopherol in Egg Yolk,Effects of Tocopherol on the Stability of Egg York,0,5,10,15,20,25,30,35,40,45,0,2,4,6,8,Time(Days),Total Headspace Volatiles(1000),25g Tocopherol/g yolk,45 g Tocopherol/g yolk,50 g Tocopherol/g yolk,75 g Tocopherol/g yolk,Control,Ascorbic Acid,Hydrogen donation to lipid radi
30、cals Quenching of singlet oxygen Removal of molecular oxygen Regenerate tocopherol radicals Prooxidant Reduce ferric iron to ferrous iron,Ascorbic Acid,O,O,O,H,O,H,C,H,C,H,2,O,H,O,H,O,O,O,O,H,C,H,C,H,2,O,H,O,H,L-Ascorbic acid,Dehydroascorbic acid,-H,-H,R,RO,ROO,R,RO,ROO,Ascorbic Acid and Related Com
31、pounds,L-Ascorbic Acid,O,O,H,O,H,C,H,O,C,H,2,O,H,H,O,H,Erythorbic Acid,Ascorbic Palmitate,O,O,H,O,H,O,H,C,H,C,H,2,O,H,O,H,O,O,O,H,O,H,O,H,C,H,C,H,2,O,C,(,C,H,2,),14,C,H,3,O,H,Synergistic Effectof Tocopherol&Ascorbic Acid,Singlet Oxygen Quencher,Singlet Oxygen Quenching Mechanism,ISC,3O2,A,1Sen,1Sen*
32、,3Sen*,1O2,AO2,Kq,Kox-Q,QO2,Kd,Q,Q,1Sen,1Sen,3O2,3O2,hv,Carotenoids,C,H,O,b-,Carotene,Apo-8-carotenal,O,Canthaxanthin,O,b-,Peroxide Value(meq/kg oil),Storage Time(hr),Effects of-Apo-8-Carotenal,-Carotene or Canthaxanthin on the Soybean Oil Oxidative Quality,Quenching Mechanism of b-Carotene on Singl
33、et Oxygen Oxidation,1/Soybean Oil(1/M),1/Peroxide(1/M),Singlet Oxygen Quenching Rates of Carotenoids,Carotenoids Number of Conjugated Quenching RateDouble Bonds Constants(M-1sec-1)-Apo-8-carotenal 10 2.86 109-Carotene 11 4.60 109Canthaxanthin 13 1.12 1010,Singlet Oxygen Quenching Rate of Carotenoids
34、,Carotenoids Number of Conjugated Rate Constants Double Bonds(109 M-1sec-1)Astaxanthin 13 9.88Isozeaxanthin 11 7.31Zeaxanthin 11 7.03Lycopene 11 6.89Lutein 10 5.86,Singlet Oxygen Quenching Rates of Tocopherols,Singlet oxygen quenching ability:-Tocopherol,-Tocopherol:2.70 107(M-1sec-1),Singlet Oxygen
35、 Quenchers,Singlet Oxygen Quencher Quenching Rate(M-1sec-1)-Carotene 4.60 109Ascorbic acid 1.08 108-Tocopherol 2.70 107,Metal Chelators,Prooxidant Mechanisms of Metals,Hydroperoxide decomposition to form peroxyl radical and alkoxyl radical Fe3+ROOHFe2+ROO+H+Fe2+ROOHFe3+RO+OH-Formations of alkyl free
36、 radical by direct reaction Fe3+RH Fe2+R+H+Activation of oxygen for singlet oxygen formation Fe2+3O2Fe3+O-2 1O2 Formation of hydroxyl radical Fe2+H2O2Fe3+OH-+OH,k1,k2,k2 k1=105,Reaction between Metal and Hydroperoxide,Rapid Exponential increase in oxidation during propagation stepb-Scission of alkox
37、yl radical to low molecular weight compoundsCopper is 50 faster than ferrous ion in decomposing hydrogen peroxide Ferrous is 100 faster than ferric iron in decomposing hydrogen peroxideFerrous is 1015 times more soluble than ferric iron,Metal Chelators,Phosphoric acidCitric acidAscorbic acidEthylene
38、 Diamine Tetra Acetate.(EDTA)Proteins such as Transferrin,OvotransferrinAmino acids and Peptides,Mechanism of Metal Chelators,Formation of complex ions or coordination compounds with metals Prevention of metal redox cycling Occupation of all metal coordination sites Formation of insoluble metal comp
39、lexes Steric hindrance of interactions between metals and lipid intermediates,Phospholipids,Phosphatidyl ethanolamine,C,H,2,O,C,O,R,1,C,H,O,C,O,R,2,C,H,2,O,P,O,O,O,C,H,2,C,H,2,N,H,2,-,Phosphatic acid,-,C,H,2,O,C,O,R,1,C,H,O,C,O,R,2,C,H,2,O,P,O,O,O,-,M,O,C,O,C,H,2,O,C,O,C,H,2,N,C,H,2,C,H,2,O,O,N,C,O,
40、C,H,2,C,O,C,H,2,Ethylene Diamine Tetra Acetate(EDTA),Interaction of Chealator and Metal,Enzymatic Antioxidants,2 Glucose+2O2+2H2O 2 Gluconic acid+2H2O2,Glucose Oxidase/Catalase,2 Glucose+O2 2 Gluconic acid,2H2O2 2H2O+O2,Glucose Oxidase Catalase,Catalase,Glucose Oxidase,Oxygen Scavenging,Superoxide D
41、ismutase,2O,2,O,2,-,+,2H,+,+,Superoxide anion participates in oxidative reactions Maintaining transition metals in their reduced,active state Promoting the release of metals bound to proteins Producing singlet oxygen,Superoxide Dismutase,+,Catalase,2H,2,O,2,O,2,2H,2,O,3,Glutathione Peroxidase,H2O2+2
42、GSH 2H2O+GSSGLOOH+2GSH LOH+H2O+GSSG,GSH:Reduced glutathioneGSSH:Oxidized glutathione,Oxygen Scavengers,Oxygen Scavengers and Reducing Agents,Ascorbic acid Ascorbic palmitate Erythorbic acid Sodium erythorbate Sulfites,Oxygen Scavenger Mechanisms,C,H,3,S,H,C,H,3,S,S,C,H,3,O,2,+,O,O,O,O,H,C,H,C,H,2,O,
43、H,O,H,H O,2,+,O,2,+,H O,+,H,O,S,O,H,O,H,O,S,O,H,O,O,O,2,2,Superoxide Dismutase,2O,2,O,2,-,+,2H,+,+,H,2,O,2,Superoxide Dismutase,+,Catalase,O,2,2H,2,O,3,2H,2,O,2,Producing triplet oxygen from superoxide anion,3,Multifunctional Antioxidants,Tocopherol Ascorbic acid,Antioxidant Interactions,Combination
44、 of metal chelator and free radical scavenging antioxidants Combination of different antioxidants like-tocopherol and ascorbic acid,Antioxidant Sources,Flavonoids,O,H,O,H,O,H,O,O,O,H,H,O,Quercetin Flavonols,O,O,H,O,O,H,H,O,G,l,u,c,os,i,de,O,H,Cyanidin-3-glucoside Anthocyanins,Flavonoids,Secondary pr
45、oducts of plant metabolism Metal chelating ability Superoxide anion scavengersAnthocyanines,catechins,flavones,flavonols,isoflavone,and proanthocyanidins,Vegetables,Cacao beans,Potato,Tomato,Spinach,Legumes,Garlic,and SeaweedPolyphenolic compounds,Fruits,Wines:AnthocyaninPolyphenolic compounds,Tea,H
46、,O,O,H,O,O,H,O,H,O,H,Epicatechin,H,O,O,H,O,O,H,O,H,O,H,O,H,Epigallocatechin,Sesame Seed,Sesamol,O,O,O,H,Sesamolinol,O,O,O,O,O,O,C,H,3,O,H,Herb and Spice,Sage,Ginger,Green pepper,Lavender and Rosemary,Carnosoic Acid,C,O,H,3,C,C,H,3,H,O,O,H,C,H,3,C,H,3,O,Carnosol,O,H,O,H,H,O,O,H,O,O,H,O,O,C,Rosemarini
47、c Acid,Reaction Rates of Carnosol and Carnosic Acid,O,H,H,O,H,H,O,O,C,O,H,O,H,H,O,O,C,+,LOO,LOOH,+,Carnosic acid,3 107 M-1s-1,O,H,H,O,C,H,O,O,O,H,O,C,H,O,O,+,+,Carnosol,2 106 M-1s-1,LOO,LOOH,Soybean,Chlorogenic acid,caffeic acid,ferulic acid-Metal chelation and singlet oxygen quenching Isoflavones-p
48、hytoestrogen effects-Metal chelation and hydrogen donation,O,O,O,H,O,H,C,O,O,H,O,H,H,O,H,O,Chlorogenic acid,GenisteinOHOHDaidzeinHOH,IsoflavonesR1R2,1,2,Soybean,R,Ginseng,Ferulic acid,Caffeic acid,Ginseng,H,O,O,C,H,3,C,O,O,H,Vanillic acid,O,H,O,O,H,O,H,O,O,H,Kaempferol,H,O,O,C,H,3,C,H,C,H,C,O,O,H,H,
49、O,O,H,C,H,C,H,C,O,O,H,Ginseng,Singlet oxygen quenchers:Caffeic acid Kaempferol Vanillic acid Salicylic acid Ferulic acidLinoleic acid in aqueous system under dark:Kaempferol Maltol Vanillic acid Saponin Salicylic acid Ferulic acid Metal chelation activity:Kaempferol Maltol Vanillic acid Ferulic acid
50、 Caffeic acid,Amino Acid,Peptide and Protein,Glycine,methionine,and lysine in emulsion system-antioxidant activity at low concentration and high pH.Carnosine inhibits the activities of hemoglobin,lipoxygenase,iron,peroxyl,and hydroxyl radical.Ferritin and tranferritin proteins bind iron,Maillard Rea
