CN111196757A - Antioxidant covalently bound linoleic acid and preparation method and application thereof - Google Patents
Antioxidant covalently bound linoleic acid and preparation method and application thereof Download PDFInfo
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- CN111196757A CN111196757A CN202010056016.XA CN202010056016A CN111196757A CN 111196757 A CN111196757 A CN 111196757A CN 202010056016 A CN202010056016 A CN 202010056016A CN 111196757 A CN111196757 A CN 111196757A
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- linoleic acid
- antioxidant
- activator
- mixing
- hydroxytyrosol
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- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 title claims abstract description 144
- 235000020778 linoleic acid Nutrition 0.000 title claims abstract description 117
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 title claims abstract description 117
- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 78
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 33
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 claims abstract description 20
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 19
- 239000012190 activator Substances 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 9
- JUUBCHWRXWPFFH-UHFFFAOYSA-N Hydroxytyrosol Chemical compound OCCC1=CC=C(O)C(O)=C1 JUUBCHWRXWPFFH-UHFFFAOYSA-N 0.000 claims description 76
- 235000006708 antioxidants Nutrition 0.000 claims description 68
- 235000003248 hydroxytyrosol Nutrition 0.000 claims description 38
- 229940095066 hydroxytyrosol Drugs 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 18
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical group CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 239000012304 carboxyl activating agent Substances 0.000 claims description 10
- 235000013305 food Nutrition 0.000 claims description 9
- 239000012074 organic phase Substances 0.000 claims description 8
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 6
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical group Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 244000178231 Rosmarinus officinalis Species 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical class [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- 235000005487 catechin Nutrition 0.000 claims description 3
- ADRVNXBAWSRFAJ-UHFFFAOYSA-N catechin Natural products OC1Cc2cc(O)cc(O)c2OC1c3ccc(O)c(O)c3 ADRVNXBAWSRFAJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000004440 column chromatography Methods 0.000 claims description 3
- 235000012734 epicatechin Nutrition 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- PFTAWBLQPZVEMU-DZGCQCFKSA-N (+)-catechin Chemical compound C1([C@H]2OC3=CC(O)=CC(O)=C3C[C@@H]2O)=CC=C(O)C(O)=C1 PFTAWBLQPZVEMU-DZGCQCFKSA-N 0.000 claims description 2
- PFTAWBLQPZVEMU-ZFWWWQNUSA-N (+)-epicatechin Natural products C1([C@@H]2OC3=CC(O)=CC(O)=C3C[C@@H]2O)=CC=C(O)C(O)=C1 PFTAWBLQPZVEMU-ZFWWWQNUSA-N 0.000 claims description 2
- PFTAWBLQPZVEMU-UKRRQHHQSA-N (-)-epicatechin Chemical compound C1([C@H]2OC3=CC(O)=CC(O)=C3C[C@H]2O)=CC=C(O)C(O)=C1 PFTAWBLQPZVEMU-UKRRQHHQSA-N 0.000 claims description 2
- 229950001002 cianidanol Drugs 0.000 claims description 2
- LPTRNLNOHUVQMS-UHFFFAOYSA-N epicatechin Natural products Cc1cc(O)cc2OC(C(O)Cc12)c1ccc(O)c(O)c1 LPTRNLNOHUVQMS-UHFFFAOYSA-N 0.000 claims description 2
- 238000012805 post-processing Methods 0.000 claims description 2
- GJYVZUKSNFSLCL-UHFFFAOYSA-N dichloromethanol Chemical compound OC(Cl)Cl GJYVZUKSNFSLCL-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 7
- 235000016709 nutrition Nutrition 0.000 abstract description 6
- 102000004882 Lipase Human genes 0.000 abstract description 5
- 108090001060 Lipase Proteins 0.000 abstract description 5
- 239000004367 Lipase Substances 0.000 abstract description 5
- 235000019421 lipase Nutrition 0.000 abstract description 5
- 238000005538 encapsulation Methods 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 description 38
- 238000007254 oxidation reaction Methods 0.000 description 38
- 229940049918 linoleate Drugs 0.000 description 26
- 238000005259 measurement Methods 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 16
- 150000002978 peroxides Chemical class 0.000 description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 239000000126 substance Substances 0.000 description 15
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 13
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- 150000001993 dienes Chemical class 0.000 description 11
- 230000015556 catabolic process Effects 0.000 description 10
- 238000006731 degradation reaction Methods 0.000 description 10
- RVBUGGBMJDPOST-UHFFFAOYSA-N 2-thiobarbituric acid Chemical compound O=C1CC(=O)NC(=S)N1 RVBUGGBMJDPOST-UHFFFAOYSA-N 0.000 description 9
- 238000002835 absorbance Methods 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000005286 illumination Methods 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000006870 function Effects 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 239000000524 Thiobarbituric Acid Reactive Substance Substances 0.000 description 3
- GLEVLJDDWXEYCO-UHFFFAOYSA-N Trolox Chemical compound O1C(C)(C(O)=O)CCC2=C1C(C)=C(C)C(O)=C2C GLEVLJDDWXEYCO-UHFFFAOYSA-N 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 3
- 239000004519 grease Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 230000000670 limiting effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- YKPXUVTWLVHJBM-UHFFFAOYSA-N 1,1,1,3-tetraethoxypropane Chemical compound CCOCCC(OCC)(OCC)OCC YKPXUVTWLVHJBM-UHFFFAOYSA-N 0.000 description 2
- AIJULSRZWUXGPQ-UHFFFAOYSA-N Methylglyoxal Chemical compound CC(=O)C=O AIJULSRZWUXGPQ-UHFFFAOYSA-N 0.000 description 2
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical group OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- WORJEOGGNQDSOE-UHFFFAOYSA-N chloroform;methanol Chemical compound OC.ClC(Cl)Cl WORJEOGGNQDSOE-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002376 fluorescence recovery after photobleaching Methods 0.000 description 2
- 230000007760 free radical scavenging Effects 0.000 description 2
- 235000013376 functional food Nutrition 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000035790 physiological processes and functions Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000004250 tert-Butylhydroquinone Substances 0.000 description 2
- 235000019281 tert-butylhydroquinone Nutrition 0.000 description 2
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KVJHGPAAOUGYJX-UHFFFAOYSA-N 1,1,3,3-tetraethoxypropane Chemical compound CCOC(OCC)CC(OCC)OCC KVJHGPAAOUGYJX-UHFFFAOYSA-N 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- 238000010159 Duncan test Methods 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000008351 acetate buffer Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- 238000000540 analysis of variance Methods 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000036772 blood pressure Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 150000001765 catechin Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- MGJZITXUQXWAKY-UHFFFAOYSA-N diphenyl-(2,4,6-trinitrophenyl)iminoazanium Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1N=[N+](C=1C=CC=CC=1)C1=CC=CC=C1 MGJZITXUQXWAKY-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000004626 essential fatty acids Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- JBXYCUKPDAAYAS-UHFFFAOYSA-N methanol;trifluoroborane Chemical compound OC.FB(F)F JBXYCUKPDAAYAS-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 235000020665 omega-6 fatty acid Nutrition 0.000 description 1
- 238000001543 one-way ANOVA Methods 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 230000036542 oxidative stress Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000013641 positive control Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229940092258 rosemary extract Drugs 0.000 description 1
- 235000020748 rosemary extract Nutrition 0.000 description 1
- 239000001233 rosmarinus officinalis l. extract Substances 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000007619 statistical method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
- A23L29/03—Organic compounds
- A23L29/035—Organic compounds containing oxygen as heteroatom
- A23L29/04—Fatty acids or derivatives
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
- A23L33/10—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
- A23L33/115—Fatty acids or derivatives thereof; Fats or oils
- A23L33/12—Fatty acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/587—Monocarboxylic acid esters having at least two carbon-to-carbon double bonds
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
- A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
Abstract
The invention discloses linoleic acid covalently bonded with an antioxidant, a preparation method and application thereof. Wherein the method for preparing linoleic acid with covalent combined antioxidant comprises the following steps: mixing and reacting linoleic acid, a carboxyl activator, an antioxidant, an alcoholic hydroxyl activator and a solvent to obtain the linoleic acid covalently combined with the antioxidant. The method combines linoleic acid and antioxidant through ester bond, breaks through the limit of the relative position of antioxidant and linoleic acid and the limit of encapsulation efficiency in the prior linoleic acid antioxidant protection method, and greatly improves the protection effect of the antioxidant on linoleic acid. Meanwhile, ester bonds formed between the linoleic acid and the antioxidant can be hydrolyzed by lipase in a human body, so that the linoleic acid is released, and the nutritional function of the linoleic acid cannot be influenced.
Description
Technical Field
The invention relates to the field of food, in particular to linoleic acid covalently bonded with an antioxidant, a preparation method and application thereof.
Background
Linoleic acid is omega-6 polyunsaturated fatty acid, is essential fatty acid for human body, and has physiological functions of lowering blood pressure, resisting inflammation, reducing oxidative stress, etc. However, since the structure contains non-conjugated double bonds, oxidation is likely to occur, thereby causing loss of physiological functions. In addition, the oxidation of linoleic acid also produces a range of toxic substances, such as aldehydes, ketones, quinones, and the like.
Aiming at the problem that linoleic acid is easy to oxidize, the solution proposed in the prior art mainly comprises: (1) adding antioxidant directly, such as synthetic antioxidant, Butyl Hydroxy Anisole (BHA), 2, 6-di-tert-butyl-4-methylphenol (BHT), and tert-butylhydroquinone (TBHQ); also natural antioxidants such as rosemary extract and the like. (2) The linoleic acid is embedded with protein, polysaccharide, etc. (such as casein, cyclodextrin, etc.). However, the protective effect of the direct addition of the antioxidant on linoleic acid is limited by the relative positions of both the antioxidant and linoleic acid in the system; the protective effect of linoleic acid with material encapsulation is influenced by the low encapsulation efficiency. Therefore, the existing method for performing antioxidant protection on linoleic acid still needs to be improved.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. To this end, it is an object of the present invention to propose a method for preparing linoleic acid to which an antioxidant is covalently bound, linoleic acid to which an antioxidant is covalently bound prepared by such a method, and the use of linoleic acid to which such an antioxidant is covalently bound for the preparation of a food product.
In one aspect of the invention, a method of preparing an antioxidant covalently bound linoleic acid is provided. According to an embodiment of the invention, the method comprises: mixing and reacting linoleic acid, a carboxyl activator, an antioxidant, an alcoholic hydroxyl activator and a solvent to obtain the linoleic acid covalently combined with the antioxidant.
According to the method for preparing the linoleic acid with the covalent bond of the antioxidant, disclosed by the embodiment of the invention, after the carboxyl in the linoleic acid and the alcoholic hydroxyl in the antioxidant are activated, the activated carboxyl and the alcoholic hydroxyl are utilized to react to generate an ester bond, so that the linoleic acid and the antioxidant are covalently bonded through the ester bond, the limitation of the relative position of the antioxidant and the linoleic acid and the limitation of the encapsulation efficiency in the existing linoleic acid antioxidant protection method are broken, and the protection effect of the antioxidant on the linoleic acid is greatly improved. Meanwhile, ester bonds formed between the linoleic acid and the antioxidant can be hydrolyzed by lipase in a human body, so that the linoleic acid is released, and the nutritional function of the linoleic acid cannot be influenced.
In addition, the method for preparing linoleic acid with covalently bound antioxidant according to the above embodiment of the present invention may also have the following additional technical features:
in some embodiments of the invention, the antioxidant is selected from at least one of hydroxytyrosol, catechins, epicatechins, rosmarins.
In some embodiments of the invention, the carboxyl activating agent is 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDC).
In some embodiments of the invention, the alcoholic hydroxyl activator is 4-Dimethylaminopyridine (DMAP).
In some embodiments of the invention, the solvent is selected from at least one of tetrahydrofuran, dichloromethane.
In some embodiments of the present invention, the mixing of the linoleic acid, the carboxyl activating agent, the antioxidant, and the alcoholic hydroxyl activating agent is performed in a mass ratio of (0.5-1.0): 0.1-0.2.
In some embodiments of the invention, the mixing comprises: mixing the linoleic acid, the carboxyl activating agent and the solvent to obtain a first mixed solution; mixing the antioxidant, the alcoholic hydroxyl activator and the solvent to obtain a second mixed solution; and dropwise adding the second mixed solution into the first mixed solution.
In some embodiments of the present invention, the method for preparing an antioxidant-covalently bound linoleic acid, after completion of the reaction, further comprises: carrying out post-treatment on the reaction product to obtain linoleic acid covalently bonded with the antioxidant; the post-processing comprises: and washing the reaction product with saturated sodium bicarbonate, extracting to obtain an organic phase, and performing column chromatography separation on the organic phase to obtain the linoleic acid covalently bound with the antioxidant.
In another aspect of the invention, the invention features an antioxidant covalently bound linoleic acid. According to an embodiment of the present invention, the antioxidant-covalently bonded linoleic acid is prepared by the method of preparing antioxidant-covalently bonded linoleic acid of the above embodiment. In the linoleic acid to which the antioxidant is covalently bonded, the antioxidant is covalently bonded to the linoleic acid. Therefore, the protective effect of the antioxidant on the linoleic acid is greatly improved. Meanwhile, ester bonds formed between the linoleic acid and the antioxidant can be hydrolyzed by lipase in a human body, so that the linoleic acid is released, and the nutritional function of the linoleic acid cannot be influenced.
In a further aspect of the invention, the invention proposes the use of the antioxidant-covalently bound linoleic acid of the above examples in the preparation of a food product. According to an embodiment of the present invention, the food may be a functional food, a health product, a medicine, or the like.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a schematic flow diagram of a method for preparing linoleic acid with covalently bound antioxidant according to one embodiment of the present invention;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of hydroxytyrosol linoleate (II)1H-NMR) chart;
FIG. 3 is an electrospray mass spectrum (ESI-MS) of hydroxytyrosol linoleate;
FIG. 4 is a schematic flow chart of a method for evaluating antioxidant oxidation resistance and oxidation stability of linoleic acid with covalently bound antioxidants according to one embodiment of the present invention;
FIG. 5 is a graph showing the results of measuring the peroxide values of a linoleic acid sample, a linoleic acid +200ppm BHT sample, and a hydroxytyrosol linoleate sample, wherein A is the measurement result at 37 ℃ and B is the measurement result under the illumination condition;
FIG. 6 is a graph showing the results of measuring the conjugated diene values of a linoleic acid sample, a linoleic acid +200ppm BHT sample, and a hydroxytyrosol linoleate sample, wherein A is the result of measurement at 37 ℃ and B is the result of measurement under light irradiation;
FIG. 7 is a graph showing the results of measuring thiobarbituric acid-reactive substances of a linoleic acid sample, a linoleic acid +200ppm BHT sample, and a hydroxytyrosol linoleate sample, wherein A is the measurement result at 37 ℃ and B is the measurement result under light irradiation;
FIG. 8 is a graph showing the results of measuring the degradation rates of a linoleic acid sample and a hydroxytyrosol linoleate sample, wherein A is the result of measurement at 37 ℃ and B is the result of measurement under light irradiation.
Detailed Description
The following describes embodiments of the present invention in detail. The following examples are illustrative only and are not to be construed as limiting the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
In one aspect of the invention, a method of preparing an antioxidant covalently bound linoleic acid is provided. According to an embodiment of the invention, the method comprises: mixing and reacting linoleic acid, a carboxyl activator, an antioxidant, an alcoholic hydroxyl activator and a solvent to obtain the linoleic acid with the antioxidant covalently combined.
According to an embodiment of the present invention, the antioxidant may be at least one selected from the group consisting of hydroxytyrosol, catechin, epicatechin, and rosmarin. The antioxidant has a site capable of being covalently bonded with linoleic acid, and substances formed by covalent bonding with linoleic acid still have oxidation resistance.
According to an embodiment of the present invention, the carboxyl activating agent may be 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDC). The carboxyl activating agent can effectively activate carboxyl in linoleic acid so as to react with alcoholic hydroxyl in antioxidant to generate ester bond, and is easy to remove after the reaction is completed.
According to an embodiment of the present invention, the alcoholic hydroxyl activator may be selected from at least one of 4-Dimethylaminopyridine (DMAP),. cndot. The alcoholic hydroxyl group activator can effectively activate alcoholic hydroxyl groups in the antioxidant so as to react with carboxyl groups in linoleic acid to generate ester bonds, and can be easily removed after the reaction is completed.
According to an embodiment of the present invention, the solvent may be at least one selected from tetrahydrofuran and dichloromethane.
According to an embodiment of the present invention, the linoleic acid, the carboxyl activating agent, the antioxidant, and the alcoholic hydroxyl activating agent may be mixed in a mass ratio of (0.5-1.0): (0.1-0.2). Specifically, the mass parts of the linoleic acid, the carboxyl activating agent and the antioxidant may be 0.5, 0.6, 0.8, 0.9, 1.0, etc., and the mass parts of the alcoholic hydroxyl activating agent may be 0.1, 0.15, 0.2, etc., respectively and independently.
According to an embodiment of the present invention, the mixing includes: mixing linoleic acid, a carboxyl activating agent and a solvent to obtain a first mixed solution; mixing an antioxidant, the alcoholic hydroxyl activator and the solvent to obtain a second mixed solution; and dropwise adding the second mixed solution into the first mixed solution.
According to an embodiment of the present invention, the method for preparing linoleic acid with covalently bound antioxidant further comprises, after the reaction is completed: carrying out post-treatment on the reaction product to obtain linoleic acid covalently bonded with the antioxidant; the post-treatment comprises the following steps: washing the reaction product with saturated sodium bicarbonate, extracting to obtain an organic phase, and performing column chromatography separation on the organic phase to obtain the linoleic acid covalently bonded with the antioxidant.
In another aspect of the invention, the invention features an antioxidant covalently bound linoleic acid. According to an embodiment of the present invention, the antioxidant-covalently bonded linoleic acid is prepared by the method of preparing antioxidant-covalently bonded linoleic acid of the above embodiment. In the linoleic acid to which the antioxidant is covalently bonded, the antioxidant is covalently bonded to the linoleic acid. Therefore, the protective effect of the antioxidant on the linoleic acid is greatly improved. Meanwhile, ester bonds formed between the linoleic acid and the antioxidant can be hydrolyzed by lipase in a human body, so that the linoleic acid is released, and the nutritional function of the linoleic acid cannot be influenced.
In addition, it should be noted that all the features and advantages described above for "preparing linoleic acid covalently bound to an antioxidant" are also applicable to the "linoleic acid covalently bound to an antioxidant", and are not described in detail herein.
In a further aspect of the invention, the invention proposes the use of the antioxidant-covalently bound linoleic acid of the above examples in the preparation of a food product. According to an embodiment of the present invention, the food may be a functional food, a health product, a medicine, or the like. The linoleic acid covalently bonded by the antioxidant is used for preparing food, so that the oxidation stability of the linoleic acid is better, and the covalently bonded antioxidant can be hydrolyzed by lipase in a human body, so that the linoleic acid is released, the nutritional function of the linoleic acid cannot be influenced, and the nutrition of the food cannot be influenced.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not to be limiting in any way.
Example 1
This example uses the antioxidant hydroxytyrosol as an example, and linoleic acid (hydroxytyrosol linoleate) to which the antioxidant is covalently bound is synthesized. Linoleic acid has a structure shown in formula a, hydroxytyrosol has a structure shown in formula b, and the covalent bonding product has a structure shown in formula c.
The oxidation resistance active site of the hydroxytyrosol is an o-diphenol structure, and after the oxidation resistance active site is combined with the linoleic acid in an esterification mode, the o-diphenol structure is reserved so as to achieve the oxidation resistance of removing free radicals, chelating metal ions and the like.
Referring to fig. 1, the specific synthesis method is as follows:
connecting a magnetic stirrer and a three-neck flask (with a rubber plug) as a reaction device, placing the reaction device in an ice bath environment, introducing nitrogen to obtain the temperature of 0 ℃ and the temperature of N2The experimental conditions of (1). 0.8g of linoleic acid, 0.6g of EDC was added to 20.0mL of dry Tetrahydrofuran (THF) and stirred magnetically for 0.5 h. The mixture was then added dropwise (0.5g hydroxytyrosol dissolved in 0.1g DMAP in 10.0mL dry THF). Removing ice bath device, gradually raising temperature to room temperature, continuing reaction for 24h, and pouring the mixture into saturated NaHCO after the reaction is finished3The solution is washed, then extracted 3 times with 30.0mL of dichloromethane, the organic phase is separated and Na is added2SO4Dried and concentrated by rotary evaporation at 25rpm/min at a temperature below 50 ℃ to obtain the crude reaction. The crude reaction was purified by silica gel column chromatography (mobile phase dichloromethane: methanol mixture). Warp beam1H-NMR identifies the chemical structure of the purified substance, ESI-MS proves the molecular weight of the purified substance, and the synthetic substance is judged to be the target compound,1H-NMR is shown in FIG. 2, and ESI-MS is shown in FIG. 3.
In the reaction process, a small amount of reaction substances, linoleic acid and hydroxytyrosol are taken by a capillary suction tube and respectively spotted at one end of a thin-layer silica gel chromatographic plate, and the synthesis condition of the linoleic acid esterification product is judged by taking dichloromethane and methanol as mobile phases with the ratio of 20:1 (v/v).
Example 2
Referring to fig. 4, oxidation resistance measurement and oxidation stability evaluation were performed on hydroxytyrosol linoleate prepared in example 1, thereby verifying whether oxidation resistance of hydroxytyrosol was maintained. 1, 1-diphenyl-2-trinitrophenylhydrazine (DPPH) free radical scavenging activity and iron reducing power (FRAP) were used as measurement indexes of oxidation resistance.
1. DPPH free radical scavenging Activity assay
mu.L of 5mM sample (dissolved in methanol) was added to 3mL of 0.5mM DPPH-methanol solution, the reaction was carried out for 30min under conditions of protection from light and room temperature, the absorbance was measured at 517nm, methanol was used instead of the sample measurement blank, and each set of samples was triplicated. DPPH radical clearance was calculated according to the following formula:
clearance (%) - (1-A)s/Ao)×100
AsAs absorbance value of the sample, AoFor blank absorbance values, standard curves were plotted against known concentrations of Trolox and the results expressed as mtrolox equivalents per mM sample (mM TE/mM sample).
2. Determination of iron reduction force
0.5mL of a 0.15mM sample was added to 4.5mL of a freshly prepared FRAP reagent [10mM2,4, 6-tripyridyltriazine (TPTZ) solution, 20mM FeCl3The solution was mixed with 300mM acetate buffer pH3.6 at a ratio of 10:1:1, v/v/v]The mixture was incubated in a 37 ℃ water bath for 30min, cooled to room temperature and absorbance was measured at 595nm, in triplicate for each sample. The blank was assayed with methanol instead of the sample and a standard curve was plotted against known concentrations of Trolox, and the results are expressed as relative to mMTrolox equivalents per mM sample (mM TE/mM sample).
3. Evaluation of Oxidation stability of linoleic acid
Linoleic acid and hydroxytyrosol linoleate are respectively stored at 37 ℃ under the illumination condition, the peroxide value, the conjugated diene value, the thiobarbituric acid reaction substance and the degradation rate are used as indexes for monitoring the oxidation stability, and meanwhile BHT added with the maximum addition amount (200ppm) is used as a positive control group to compare the protection effect of the BHT with the protection effect of the hydroxytyrosol linoleate.
3.1 accelerated Oxidation conditions
The same mass of each set of samples (linoleic acid, linoleic acid with 200ppm BHT added, hydroxytyrosol linoleate) was stored under different accelerated oxidation conditions. High-temperature oxidation conditions: at 37 ℃ in the dark; and (3) illumination oxidation conditions: the illumination intensity is 5500Lux, and the temperature is room temperature. Samples were taken at 0, 1,3, 5, 7, and 9 days of oxidation for peroxide number, conj ugated diene number, thiobarbituric acid reactive species, and degradation rate determinations, respectively.
3.2 determination of peroxide number
To 5mL of a 0.6mg/mL sample (dissolved in chloroform-methanol solution, 7:3, v/v) were added 25. mu.L of ammonium thiocyanate solution (300g/L) and 25. mu.L of FeCl2The solution (3.5g/L) was vortexed for 15 seconds, reacted at room temperature for 5min, absorbance was measured at 500nm, a chloroform-methanol solution was used instead of the sample to measure a blank, and a peroxide value was calculated according to the following formula:
in the formula, AsAs absorbance value of the sample, AoFor blank absorbance values, 55.84 is the mass of the iron atom, 2 is the conversion factor for Fe to peroxide, m is the mass of linoleic acid (g), and b is the slope of the Fe (III) standard curve.
3.3 determination of conjugated diene number
Taking 5mL of 0.4mg/mL sample (dissolved in n-hexane), measuring absorbance at 234nm, taking n-hexane as blank, and expressing conjugated diene value as A per mg/mL linoleic acid sample234Value [ A ]234/(mg/mL)]。
3.4 determination of thiobarbituric acid reacting substance
mu.L of 20mg/mL sample (dissolved in trichloroacetic acid), 150. mu.L of 20mM TBA solution was added, the mixture was boiled for 15min, and after cooling to room temperature, the absorbance was measured at 532 nm. A standard curve was plotted with trichloroacetic acid instead of the sample and 1,1,3, 3-Tetraethoxypropane (TEP), one mole of TEP being converted to one mole of propanedione (MDA), the thiobarbituric acid reactant species being expressed as equivalents per μmol of MDA per gram of linoleic acid (μmol MDA equivalents/g linoleic acid).
3.4 determination of degradation Rate
The degradation rate of linoleic acid was determined by Gas Chromatography (GC). To 500. mu.L of 4mg/mL linoleic acid or hydroxytyrosol linoleate (dissolved in n-hexane) was added 400. mu.L of BF3-methanol solution, boiling the mixture in boiling water for 2h, cooling, adding 600 μ L K2CO3(6%, w/v) solution, and collecting the upper layerThe organic phase was used for GC analysis. The GC conditions were as follows: shimadzu technologies Nexis GC-2030 gas phase analysis software (Shimadzu, Tokyo, Japan); a chromatographic column: HP-5 column (30 m.times.0.25 mm,0.25 μm); column temperature: the initial temperature is 160 ℃ and is maintained for 2min, and the temperature is increased to 220 ℃ at the speed of 5 ℃/min and is maintained for 10 min; carrier gas: nitrogen at a rate of 1.5 mL/min; injector and detector temperatures of 230 ℃ and 250 ℃, respectively; the split ratio was 30: 1. The degradation rate was calculated from a standard curve and the result was expressed as a percentage (%) of the amount of linoleic acid degraded relative to the initial amount of linoleic acid.
3.5, statistical analysis
For the same assay index, each set of samples was prepared identically and three determinations were made, expressed as mean ± standard deviation. Data were analyzed with IBM SPSS Statistics software (v.21.0, IBM Corp., Armonk, NY, USA). Statistical significance of the data was assessed using one-way analysis of variance (ANOVA) Duncan test, with p <0.05 considered statistically significant differences.
3.6 measurement results
(1) Results of measurement of Oxidation resistance
TABLE 1 results of measurement of antioxidation Properties of linoleic acid, hydroxytyrosol linoleate, and BHT
Note: data results are presented as mean ± standard deviation (n ═ 3), and ND indicates no detectable oxidation resistance. TE represents Trolox equivalent. The different letters in the same column represent significant differences (p <0.05)
The results in Table 1 show that hydroxytyrosol linoleate retained the antioxidant properties of hydroxytyrosol.
(2) Measurement of peroxide number
The peroxide value is used for reflecting the generation condition of peroxide in the early stage of grease oxidation, as shown in fig. 5, the peroxide value of linoleic acid is rapidly increased under the condition of accelerated oxidation, BHT has a good protection effect on linoleic acid within 5 days, and the peroxide value is obviously increased after 5 days. The peroxide value of the hydroxytyrosol linoleate is always at a low level in the oxidation process of 9 days, and the peroxide value is only below 2.0 percent of that of linoleic acid in the oxidation process of 37 ℃ (figure 5A) or 9 days of illumination oxidation (figure 5B), which shows that the hydroxytyrosol linoleate has a good inhibition effect on the generation of peroxide in the oxidation process of the linoleic acid.
(3) Measurement results of conjugated diene value
The conjugated diene value is a common index for monitoring the generation of the conjugated structure substances in the early stage of grease oxidation. As shown in fig. 6, the conjugated diene value of linoleic acid increased relatively rapidly during oxidation, and after the addition of BHT, the conjugated diene value did not change significantly within 5 days, but increased significantly after 5 days. After oxidation at 37 deg.C (FIG. 6A) or under light conditions (FIG. 6B) for 9 days, the conjugated diene values of hydroxytyrosol linoleate were 24.4% and 16.1% of linoleic acid, respectively, indicating that hydroxytyrosol linoleate effectively inhibits the generation of conjugated structural substances thereof.
(4) Determination result of thiobarbituric acid reaction substance
The thiobarbituric acid reaction substance is used for reflecting the decomposition condition of the peroxide in the late oxidation stage of the grease. As shown in FIG. 7, the thiobarbituric acid-reactive substance of linoleic acid was continuously increased at 37 ℃ or under light conditions, and at 9 days, the thiobarbituric acid-reactive substance of linoleic acid at 37 ℃ (FIG. 7A) or under light conditions (FIG. 7B) was increased to 28-fold and 39-fold, respectively, of the original. BHT showed a better protective effect on linoleic acid in the first 5 days, but the inhibitory effect was significantly reduced after 5 days. The thiobarbituric acid reactant substance of hydroxytyrosol linoleate is remarkably lower than that of other groups within 9 days, which shows that the thiobarbituric acid reactant substance of hydroxytyrosol linoleate continuously inhibits the oxidation of linoleic acid
(5) Measurement results of degradation rate
The degradation rate of linoleic acid was determined to directly reflect the degradation of linoleic acid, as shown in fig. 8. Upon oxidation at 37 ℃ for 9 days, linoleic acid was degraded by 51.0% (FIG. 8A), while hydroxytyrosol linoleate was degraded by only 8.2%. Upon oxidation under light for 9 days (FIG. 8B), linoleic acid was degraded by 61.0% while hydroxytyrosol linoleate was degraded by only 14.2%. The above results show that hydroxytyrosol linoleate significantly inhibited oxidative degradation of linoleic acid.
3.7, conclusion
After hydroxytyrosol is combined with linoleic acid through ester bond, most of the oxidation resistance of hydroxytyrosol is kept. Under different accelerated oxidation conditions, the measurement results of the peroxide value, the conjugated diene value, the thiobarbituric acid reaction substance and the degradation rate show that hydroxytyrosol linoleate effectively inhibits the oxidation of linoleic acid, and the protection effect of hydroxytyrosol linoleate is obviously better than that of hydroxytyrosol linoleate added with 200ppm of BHT.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A method of preparing an antioxidant covalently bound linoleic acid comprising:
mixing and reacting linoleic acid, a carboxyl activator, an antioxidant, an alcoholic hydroxyl activator and a solvent to obtain the linoleic acid covalently combined with the antioxidant.
2. The method of claim 1, wherein the antioxidant is selected from at least one of hydroxytyrosol, catechin, epicatechin, and rosmarin.
3. The method of claim 1, wherein the carboxyl activating agent is 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride.
4. The method of claim 1, wherein the alcoholic hydroxyl activator is 4-dimethylaminopyridine.
5. The method according to claim 1, wherein the solvent is at least one selected from the group consisting of tetrahydrofuran and dichloromethanol.
6. The method according to claim 1, wherein the mixing of the linoleic acid, the carboxyl group activator, the antioxidant, and the alcoholic hydroxyl group activator is carried out in a mass ratio of (0.5-1.0): 0.5-1.0: (0.1-0.2).
7. The method of claim 1, wherein the mixing comprises:
mixing the linoleic acid, the carboxyl activating agent and the solvent to obtain a first mixed solution;
mixing the antioxidant, the alcoholic hydroxyl activator and the solvent to obtain a second mixed solution;
and dropwise adding the second mixed solution into the first mixed solution.
8. The method of claim 1, wherein after the reaction is completed, further comprising: carrying out post-treatment on the reaction product to obtain linoleic acid covalently bonded with the antioxidant; the post-processing comprises: and washing the reaction product with saturated sodium bicarbonate, extracting to obtain an organic phase, and performing column chromatography separation on the organic phase to obtain the linoleic acid covalently bound with the antioxidant.
9. An antioxidant-covalently bonded linoleic acid, wherein the antioxidant-covalently bonded linoleic acid is prepared by the method of any one of claims 1 to 8.
10. Use of linoleic acid covalently bound to an antioxidant according to claim 9 in the preparation of a food product.
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| WO2004005237A1 (en) * | 2002-07-03 | 2004-01-15 | Consejo Superior De Investigaciones Científicas | Method of preparing hydroxytyrosol esters, esters thus obtained and use of same |
| CN105166885A (en) * | 2015-08-07 | 2015-12-23 | 江南大学 | Conjugated linoleic acid embedded microcapsule preparation method |
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| WO2004005237A1 (en) * | 2002-07-03 | 2004-01-15 | Consejo Superior De Investigaciones Científicas | Method of preparing hydroxytyrosol esters, esters thus obtained and use of same |
| US20050154058A1 (en) * | 2002-07-03 | 2005-07-14 | Gonzalez Felipe A. | Method of preparing hydroxytyrosol esters, esters thus obtained and use of same |
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