CN103005007B - Fat-soluble AOB and preparation method thereof - Google Patents
Fat-soluble AOB and preparation method thereof Download PDFInfo
- Publication number
- CN103005007B CN103005007B CN201210571602.3A CN201210571602A CN103005007B CN 103005007 B CN103005007 B CN 103005007B CN 201210571602 A CN201210571602 A CN 201210571602A CN 103005007 B CN103005007 B CN 103005007B
- Authority
- CN
- China
- Prior art keywords
- aob
- fat
- soluble
- acid
- oil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 75
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 58
- 239000003921 oil Substances 0.000 claims abstract description 42
- NGSWKAQJJWESNS-UHFFFAOYSA-N 4-coumaric acid Chemical compound OC(=O)C=CC1=CC=C(O)C=C1 NGSWKAQJJWESNS-UHFFFAOYSA-N 0.000 claims abstract description 36
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 36
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 28
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 235000013305 food Nutrition 0.000 claims abstract description 20
- NGSWKAQJJWESNS-ZZXKWVIFSA-M 4-Hydroxycinnamate Natural products OC1=CC=C(\C=C\C([O-])=O)C=C1 NGSWKAQJJWESNS-ZZXKWVIFSA-M 0.000 claims abstract description 18
- DFYRUELUNQRZTB-UHFFFAOYSA-N Acetovanillone Natural products COC1=CC(C(C)=O)=CC=C1O DFYRUELUNQRZTB-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000008157 edible vegetable oil Substances 0.000 claims abstract description 11
- 150000004668 long chain fatty acids Chemical class 0.000 claims abstract description 8
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 6
- 150000002148 esters Chemical class 0.000 claims abstract description 4
- 150000002632 lipids Chemical class 0.000 claims abstract description 4
- CMXPERZAMAQXSF-UHFFFAOYSA-M sodium;1,4-bis(2-ethylhexoxy)-1,4-dioxobutane-2-sulfonate;1,8-dihydroxyanthracene-9,10-dione Chemical compound [Na+].O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=CC=C2O.CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC CMXPERZAMAQXSF-UHFFFAOYSA-M 0.000 claims abstract description 4
- 230000003035 anti-peroxidant effect Effects 0.000 claims abstract description 3
- 239000000837 restrainer Substances 0.000 claims abstract description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 22
- 239000000047 product Substances 0.000 claims description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 18
- 239000012043 crude product Substances 0.000 claims description 15
- 150000001263 acyl chlorides Chemical class 0.000 claims description 14
- 238000010521 absorption reaction Methods 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 13
- 230000000694 effects Effects 0.000 claims description 12
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- 239000002798 polar solvent Substances 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 7
- 235000021314 Palmitic acid Nutrition 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 6
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 6
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 claims description 5
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 claims description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 5
- 235000013985 cinnamic acid Nutrition 0.000 claims description 5
- 229930016911 cinnamic acid Natural products 0.000 claims description 5
- 239000000284 extract Substances 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000012141 concentrate Substances 0.000 claims description 4
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 claims description 4
- 238000009472 formulation Methods 0.000 claims description 4
- 238000004433 infrared transmission spectrum Methods 0.000 claims description 4
- 239000001632 sodium acetate Substances 0.000 claims description 4
- 235000017281 sodium acetate Nutrition 0.000 claims description 4
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 4
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 claims description 3
- 229940070765 laurate Drugs 0.000 claims description 3
- 239000012669 liquid formulation Substances 0.000 claims description 3
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 claims description 2
- 239000004157 Nitrosyl chloride Substances 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- 238000005917 acylation reaction Methods 0.000 claims description 2
- 239000000428 dust Substances 0.000 claims description 2
- VPCDQGACGWYTMC-UHFFFAOYSA-N nitrosyl chloride Chemical group ClN=O VPCDQGACGWYTMC-UHFFFAOYSA-N 0.000 claims description 2
- 235000019392 nitrosyl chloride Nutrition 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 239000012074 organic phase Substances 0.000 claims description 2
- BZCGWAXQDLXLQM-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O.ClP(Cl)(Cl)=O BZCGWAXQDLXLQM-UHFFFAOYSA-N 0.000 claims description 2
- 238000007670 refining Methods 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 238000013517 stratification Methods 0.000 claims description 2
- 239000000523 sample Substances 0.000 description 61
- 235000006708 antioxidants Nutrition 0.000 description 54
- 235000019198 oils Nutrition 0.000 description 40
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 30
- 239000003381 stabilizer Substances 0.000 description 24
- 235000019197 fats Nutrition 0.000 description 23
- 239000002540 palm oil Substances 0.000 description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 235000019482 Palm oil Nutrition 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 19
- 239000000243 solution Substances 0.000 description 19
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 18
- 238000000034 method Methods 0.000 description 15
- 235000013824 polyphenols Nutrition 0.000 description 15
- 239000004250 tert-Butylhydroquinone Substances 0.000 description 15
- 235000019281 tert-butylhydroquinone Nutrition 0.000 description 15
- 230000003647 oxidation Effects 0.000 description 14
- 238000007254 oxidation reaction Methods 0.000 description 14
- 235000013606 potato chips Nutrition 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 239000004519 grease Substances 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 150000008442 polyphenolic compounds Chemical class 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 235000013616 tea Nutrition 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000006872 improvement Effects 0.000 description 8
- -1 phenolic acid compound Chemical class 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- ZTHYODDOHIVTJV-UHFFFAOYSA-N Propyl gallate Chemical compound CCCOC(=O)C1=CC(O)=C(O)C(O)=C1 ZTHYODDOHIVTJV-UHFFFAOYSA-N 0.000 description 6
- 241001122767 Theaceae Species 0.000 description 6
- 230000003026 anti-oxygenic effect Effects 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 6
- ARBOVOVUTSQWSS-UHFFFAOYSA-N hexadecanoyl chloride Chemical compound CCCCCCCCCCCCCCCC(Cl)=O ARBOVOVUTSQWSS-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- QAIPRVGONGVQAS-DUXPYHPUSA-N trans-caffeic acid Chemical compound OC(=O)\C=C\C1=CC=C(O)C(O)=C1 QAIPRVGONGVQAS-DUXPYHPUSA-N 0.000 description 6
- YXGOYRIWPLGGKN-UHFFFAOYSA-N 2,3-ditert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=C(O)C=CC(O)=C1C(C)(C)C YXGOYRIWPLGGKN-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 235000013373 food additive Nutrition 0.000 description 5
- 239000002778 food additive Substances 0.000 description 5
- 230000002401 inhibitory effect Effects 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000012488 sample solution Substances 0.000 description 5
- 238000000527 sonication Methods 0.000 description 5
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 4
- 229940074360 caffeic acid Drugs 0.000 description 4
- 229940074393 chlorogenic acid Drugs 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229930003944 flavone Natural products 0.000 description 4
- 235000011949 flavones Nutrition 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 235000013372 meat Nutrition 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- ACEAELOMUCBPJP-UHFFFAOYSA-N (E)-3,4,5-trihydroxycinnamic acid Natural products OC(=O)C=CC1=CC(O)=C(O)C(O)=C1 ACEAELOMUCBPJP-UHFFFAOYSA-N 0.000 description 3
- CWVRJTMFETXNAD-FWCWNIRPSA-N 3-O-Caffeoylquinic acid Natural products O[C@H]1[C@@H](O)C[C@@](O)(C(O)=O)C[C@H]1OC(=O)\C=C\C1=CC=C(O)C(O)=C1 CWVRJTMFETXNAD-FWCWNIRPSA-N 0.000 description 3
- WIGIZIANZCJQQY-UHFFFAOYSA-N 4-ethyl-3-methyl-N-[2-[4-[[[(4-methylcyclohexyl)amino]-oxomethyl]sulfamoyl]phenyl]ethyl]-5-oxo-2H-pyrrole-1-carboxamide Chemical compound O=C1C(CC)=C(C)CN1C(=O)NCCC1=CC=C(S(=O)(=O)NC(=O)NC2CCC(C)CC2)C=C1 WIGIZIANZCJQQY-UHFFFAOYSA-N 0.000 description 3
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 3
- 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 3
- PZIRUHCJZBGLDY-UHFFFAOYSA-N Caffeoylquinic acid Natural products CC(CCC(=O)C(C)C1C(=O)CC2C3CC(O)C4CC(O)CCC4(C)C3CCC12C)C(=O)O PZIRUHCJZBGLDY-UHFFFAOYSA-N 0.000 description 3
- CWVRJTMFETXNAD-KLZCAUPSSA-N Neochlorogenin-saeure Natural products O[C@H]1C[C@@](O)(C[C@@H](OC(=O)C=Cc2ccc(O)c(O)c2)[C@@H]1O)C(=O)O CWVRJTMFETXNAD-KLZCAUPSSA-N 0.000 description 3
- 229930187677 Orientoside Natural products 0.000 description 3
- JMFSHKGXVSAJFY-UHFFFAOYSA-N Saponaretin Natural products OCC(O)C1OC(Oc2c(O)cc(O)c3C(=O)C=C(Oc23)c4ccc(O)cc4)C(O)C1O JMFSHKGXVSAJFY-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 244000061456 Solanum tuberosum Species 0.000 description 3
- 235000002595 Solanum tuberosum Nutrition 0.000 description 3
- GAMYVSCDDLXAQW-AOIWZFSPSA-N Thermopsosid Natural products O(C)c1c(O)ccc(C=2Oc3c(c(O)cc(O[C@H]4[C@H](O)[C@@H](O)[C@H](O)[C@H](CO)O4)c3)C(=O)C=2)c1 GAMYVSCDDLXAQW-AOIWZFSPSA-N 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 230000003064 anti-oxidating effect Effects 0.000 description 3
- 235000014121 butter Nutrition 0.000 description 3
- 235000019282 butylated hydroxyanisole Nutrition 0.000 description 3
- 235000004883 caffeic acid Nutrition 0.000 description 3
- 239000003183 carcinogenic agent Substances 0.000 description 3
- CWVRJTMFETXNAD-JUHZACGLSA-N chlorogenic acid Chemical compound O[C@@H]1[C@H](O)C[C@@](O)(C(O)=O)C[C@H]1OC(=O)\C=C\C1=CC=C(O)C(O)=C1 CWVRJTMFETXNAD-JUHZACGLSA-N 0.000 description 3
- 235000001368 chlorogenic acid Nutrition 0.000 description 3
- FFQSDFBBSXGVKF-KHSQJDLVSA-N chlorogenic acid Natural products O[C@@H]1C[C@](O)(C[C@@H](CC(=O)C=Cc2ccc(O)c(O)c2)[C@@H]1O)C(=O)O FFQSDFBBSXGVKF-KHSQJDLVSA-N 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- BMRSEYFENKXDIS-KLZCAUPSSA-N cis-3-O-p-coumaroylquinic acid Natural products O[C@H]1C[C@@](O)(C[C@@H](OC(=O)C=Cc2ccc(O)cc2)[C@@H]1O)C(=O)O BMRSEYFENKXDIS-KLZCAUPSSA-N 0.000 description 3
- QAIPRVGONGVQAS-UHFFFAOYSA-N cis-caffeic acid Natural products OC(=O)C=CC1=CC=C(O)C(O)=C1 QAIPRVGONGVQAS-UHFFFAOYSA-N 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 235000019261 food antioxidant Nutrition 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- IPCSVZSSVZVIGE-UHFFFAOYSA-M hexadecanoate Chemical compound CCCCCCCCCCCCCCCC([O-])=O IPCSVZSSVZVIGE-UHFFFAOYSA-M 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- MYXNWGACZJSMBT-VJXVFPJBSA-N isovitexin Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1C1=C(O)C=C(OC(=CC2=O)C=3C=CC(O)=CC=3)C2=C1O MYXNWGACZJSMBT-VJXVFPJBSA-N 0.000 description 3
- OYJCWTROZCNWAA-UHFFFAOYSA-N isovitexin Natural products OCC1OC(C(O)C(O)C1O)c2c(O)cc3CC(=CC(=O)c3c2O)c4ccc(O)cc4 OYJCWTROZCNWAA-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 235000016709 nutrition Nutrition 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 235000010388 propyl gallate Nutrition 0.000 description 3
- 239000013558 reference substance Substances 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 238000004904 shortening Methods 0.000 description 3
- 239000011782 vitamin Substances 0.000 description 3
- VHBFFQKBGNRLFZ-UHFFFAOYSA-N vitamin p Natural products O1C2=CC=CC=C2C(=O)C=C1C1=CC=CC=C1 VHBFFQKBGNRLFZ-UHFFFAOYSA-N 0.000 description 3
- WOGITNXCNOTRLK-VOTSOKGWSA-N (e)-3-phenylprop-2-enoyl chloride Chemical compound ClC(=O)\C=C\C1=CC=CC=C1 WOGITNXCNOTRLK-VOTSOKGWSA-N 0.000 description 2
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 241001330024 Bambusoideae Species 0.000 description 2
- 239000004255 Butylated hydroxyanisole Substances 0.000 description 2
- 241000206601 Carnobacterium mobile Species 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 235000019542 Cured Meats Nutrition 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 241000745988 Phyllostachys Species 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 235000015173 baked goods and baking mixes Nutrition 0.000 description 2
- 230000033228 biological regulation Effects 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
- 229940043253 butylated hydroxyanisole Drugs 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 239000002285 corn oil Substances 0.000 description 2
- 235000005687 corn oil Nutrition 0.000 description 2
- NQGIJDNPUZEBRU-UHFFFAOYSA-N dodecanoyl chloride Chemical compound CCCCCCCCCCCC(Cl)=O NQGIJDNPUZEBRU-UHFFFAOYSA-N 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000010812 external standard method Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 150000002212 flavone derivatives Chemical class 0.000 description 2
- 239000010200 folin Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 230000003859 lipid peroxidation Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 235000013622 meat product Nutrition 0.000 description 2
- 239000004530 micro-emulsion Substances 0.000 description 2
- 230000035764 nutrition Effects 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000004366 reverse phase liquid chromatography Methods 0.000 description 2
- 238000004007 reversed phase HPLC Methods 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- VUQPJRPDRDVQMN-UHFFFAOYSA-N 1-chlorooctadecane Chemical compound CCCCCCCCCCCCCCCCCCCl VUQPJRPDRDVQMN-UHFFFAOYSA-N 0.000 description 1
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- DCXYFEDJOCDNAF-UHFFFAOYSA-N Asparagine Natural products OC(=O)C(N)CC(N)=O DCXYFEDJOCDNAF-UHFFFAOYSA-N 0.000 description 1
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 1
- 241000792859 Enema Species 0.000 description 1
- DCXYFEDJOCDNAF-REOHCLBHSA-N L-asparagine Chemical compound OC(=O)[C@@H](N)CC(N)=O DCXYFEDJOCDNAF-REOHCLBHSA-N 0.000 description 1
- 240000005856 Lyophyllum decastes Species 0.000 description 1
- 235000013194 Lyophyllum decastes Nutrition 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 101710138657 Neurotoxin Proteins 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- 235000019495 Pecan oil Nutrition 0.000 description 1
- 235000004347 Perilla Nutrition 0.000 description 1
- 244000124853 Perilla frutescens Species 0.000 description 1
- 241000209504 Poaceae Species 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 235000019486 Sunflower oil Nutrition 0.000 description 1
- 229930003268 Vitamin C Natural products 0.000 description 1
- 229930003427 Vitamin E Natural products 0.000 description 1
- 238000011481 absorbance measurement Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229960001230 asparagine Drugs 0.000 description 1
- 235000009582 asparagine Nutrition 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000010495 camellia oil Substances 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000007920 enema Substances 0.000 description 1
- 229940095399 enema Drugs 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 235000021323 fish oil Nutrition 0.000 description 1
- 150000002213 flavones Chemical group 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 235000021393 food security Nutrition 0.000 description 1
- 235000012020 french fries Nutrition 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 229940074046 glyceryl laurate Drugs 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 239000013056 hazardous product Substances 0.000 description 1
- 238000000703 high-speed centrifugation Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 235000008446 instant noodles Nutrition 0.000 description 1
- 238000012417 linear regression Methods 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 235000013310 margarine Nutrition 0.000 description 1
- 239000003264 margarine Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000002581 neurotoxin Substances 0.000 description 1
- 231100000618 neurotoxin Toxicity 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 235000014571 nuts Nutrition 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- 239000010470 pecan oil Substances 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 235000021110 pickles Nutrition 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 235000021067 refined food Nutrition 0.000 description 1
- 235000020748 rosemary extract Nutrition 0.000 description 1
- 235000013580 sausages Nutrition 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000009777 vacuum freeze-drying Methods 0.000 description 1
- 235000019154 vitamin C Nutrition 0.000 description 1
- 239000011718 vitamin C Substances 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
Landscapes
- Fats And Perfumes (AREA)
Abstract
The invention discloses a kind of fat-soluble AOB AOB-o, total phenol content >=20%, p-Coumaric Acid content >=0.5%, solubility >=3% in ethyl acetate, yellowish-brown or yellowish-brown powder, slightly ester taste; Directly can be dissolved in edible oil and fat, middle LCFA and non-polar solven, show good anti peroxidation of lipid performance and heat endurance; And effectively can suppress the formation of rich amyloid Assessments of Acrylamide Generated in Heated Foodstuffs, can use as oil antioxidant and acrylic amide restrainer in the food industry simultaneously.The present invention also also discloses the preparation method of above-mentioned fat-soluble AOB AOB-o.
Description
Technical field
The present invention relates to natural goods food additives field, specifically refer to fat-soluble AOB (AOB-o) and its production and use.The inhibitory action relating more specifically to the lipid-antioxidant activity effect in the food manufacturing industry of oil prodution industry and high temperature thereof, high oil processing and the amyloid Assessments of Acrylamide Generated in Heated Foodstuffs of richness is formed.
Background technology
Oxidation of Fat and Oils is the key factor affecting oil quality.The product of Oxidation of Fat and Oils can produce harmful effect, as reduced nutritional quality, shortening shelf life, producing new hazardous material to the local flavor of edible oil and fat and goods thereof, color and luster and quality.Food antioxidant refers to and can stop or delay the food additives that Oxidation of Fat and Oils goes bad, improves food stability and extend shelf life.In grease, directly add antioxidant is delay its oxidation deterioration effective method the most.Oil antioxidant conventional in current food industry mainly contains: butylated hydroxy anisole (BHA), dibutyl hydroxy toluene (BHT), n-propyl gallate (PG), ditert-butylhydro quinone (TBHQ), vitamin E, vitamine C palmitate (AP), Rosmarinus officinalis extract, oil-soluble tea polyphenol (OTP) etc.Wherein BHA, BHT, PG, TBHQ are chemical synthesis antioxidant, best with TBHQ antioxidant effect; Vitamine C palmitate (AP), oil-soluble tea polyphenol (OTP) are the novel synthetized oxidation preventive agents occurred in recent years, treat as natural goods, they are the complex compound of vitamin C and palmitic acid, Tea Polyphenols and aliphatic acid respectively, can be used as fat-soluble antioxidant and nutrition fortifier makes an addition in grease or food.Although the food antioxidant of chemical synthesis is cheap, there is certain safety risks, oneself is extensively restricted in the use of BHT and BHA, and TBHQ is the antioxidant be most widely used at present, but is also forbidden by developed countries such as Canada and European Union; Natural is comparatively safe, but due to price costly, limit their application industrially to a certain extent.
AOB (Antioxidant ofbamboo leaves, AOB) be the antioxidant from natural food of a kind of safe and efficient economy that the present inventor formulates, list at the beginning of 2004 " People's Republic of China's food additives use sanitary standard " (GB2760), oneself application of approval comprises substantially water-free fat and oil at present, shortening nut and seed class, frying surface goods, ready-to-eat cereal, bakery product, pickle cured meat product class, stewed meat products class, (smoked, burn, roasting) meat, fried meat, Western-style ham, meat enema class, fermentation meat product class, aquatic products and goods thereof, Juice (meat) beverage, 16 classes (GB2760-2011) such as tea beverage class and dilated food.AOB adopts special process, the phenol preparation obtained from the tender leaf of grass family (Graminae), Bambusoideae (Bambusoideae), Phyllostachys (Phyllostachys Sieb.Et Zucc) kind, its antioxidant content is flavones and phenolic acid compound mainly.Wherein, flavone compound is mainly with the flavone c-glycoside that orientoside, Lutonaretin, Vitexina and Saponaretin are representative, and the derivative of phenolic acid compound mainly cinnamic acid, comprises p-Coumaric Acid, chlorogenic acid, caffeic acid and forulic acid etc.AOB has good antioxidation activity, can effective anti-lipid peroxidation, to the generation of lipid peroxidation product MDA (MDA), there is obvious inhibitory action, can effectively resist acidolysis, pyrolysis and enzymolysis, oneself is applied in Western Sausage, Chinese style bowel lavage, pickled and cured meat, dilated food and flavouring, and obtains good result.A lot of research and application test shows, AOB is except having good antioxygenic property, also show and effectively suppress the effect that in thermally processed foods, carcinogen (acrylamide) is formed, the height as fried food (as potato chips, instant noodles, fried chicken, deep-fried twisted dough sticks, fried dough twist etc.) hazards of acrylamide just exposes and excessive risk field.But existing AOB preparation (unified be denoted as AOB-w) is a kind of composition of medium polarity bigger than normal, and by force water-soluble, oil-soluble is weak, greatly limit its application in oils industry and high oil food field.
Acrylamide (AA) is a kind of white crystal sample material, relative molecular mass 71.08, room-temperature stable, soluble in water, in ethanol, ether, acetone and other organic solvent, easily there is polymerization and copolymerization, hydrolysis occurs in sour environment and generates acrylic acid.The researcher of Stockholm Univ Sweden in 2002 finds, in the drinking-water that in fried, high temperature bakery product, the content of acrylamide specify than the World Health Organization acrylamide limit the quantity (0.5 μ g/L) exceed more than 500 times.October in the same year, the research in Reading university of Britain and Nestle research center shows jointly, the acrylamide in food be mainly derived from asparagine in the rich amyloid raw-food material such as potato and cereal and reduced sugar at high temperature (> 120 DEG C) produced by Maillard reaction.Acrylamide is a kind of neurotoxin and carcinogenic substance, and acrylamide is classified as 2A group " carcinogenic substance that the mankind are possible " by international cancer research institution (International Agency Research on Cancer, IARC).Therefore, reduce food endogenous chemical pollutant acrylamide content oneself become the target that food industry technological progress chases.Control frying temperature, the time and with low ph value solution rinsing raw material, in grease or formula for a product, add phenol antioxidant (as AOB-w, Tea Polyphenols, Bulbus Allii Cepae extract, apple polyphenol extract etc.) effectively can reduce acrylamide content in fried food, play the effect preventing acrylamide toxicity.Common plant polyphenol mostly is hydrophilic food antioxidant, and addition manner is mainly and makes an addition in blending process or soaking solution.
Along with the whole society's improving constantly food security and nutrient health attention rate, the frying oil of various high-grade special grease, nutrition oil, household oil and food industry, shortening, margarine oil's wet goods product need natural, safety, high-quality, efficiently oil-soluble inhibitor badly.The fat-soluble conventional method of current increase antioxidant has solvent method, emulsion process and molecular modification method.The product system that first two method obtains is unstable, and low temperature or high speed centrifugation can make dissolved matter separate out once again.In order to increase the solubility of AOB-w in grease, inventor once attempted AOB-w microemulsified, but the stability of AOB microemulsion is very large by environment (as temperature etc.) impact in actual use.Because high temperature frying is processing mode common in food industry, under hot conditions, microemulsion is easy to breakdown of emulsion oil product outward appearance and quality is declined all greatly.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of fat-soluble AOB (AOB-o) and its production and use.
In order to solve the problems of the technologies described above, the invention provides a kind of fat-soluble AOB AOB-o, total phenol content >=20%, p-Coumaric Acid content >=0.5%, solubility >=3% in ethyl acetate, yellowish-brown or yellowish-brown powder, slightly ester taste; Can directly be dissolved in edible oil and fat, middle LCFA and non-polar solven, there is the non-oxidizability and heat endurance that are better than commercially available similar oil antioxidant product (oil-soluble tea polyphenol, ditert-butylhydro quinone), and effectively can suppress the formation of rich amyloid Assessments of Acrylamide Generated in Heated Foodstuffs, can use as oil antioxidant and acrylic amide restrainer in the food industry simultaneously.
Improvement as fat-soluble AOB AOB-o of the present invention: with water-soluble AOB AOB-w be raw material, with the fat acyl chloride (acylate of aliphatic acid; as aliphatic acid donor during reaction) Powdered, the graininess of ester exchange or Formulation, dissolve in edible oil and fat and/or in, become liquid formulation in LCFA.
Further improvement as fat-soluble AOB AOB-o of the present invention: the infrared transmission spectra after pressing potassium bromide troche is all presented at 1700cm
-1near have strong carbonyl absorption peak, and 3400cm
-1neighbouring hydroxyl group absorption peak comparatively AOB-w significantly weakens.
Invention also provides the preparation method of a kind of fat-soluble AOB AOB-o, comprise the following steps:
1) in low polar solvent I, under the effect of base catalyst, water-soluble AOB AOB-w and fat acyl chloride are in 30 DEG C ~ 50 DEG C acylation reaction 5h ~ 10h; Water-soluble AOB AOB-w: fat acyl chloride: the mol ratio of base catalyst is 1:0.5 ~ 2.5:0.8 ~ 3;
2) by step 1) pH value of gained product is adjusted to neutrality, shaken well, stratification; Get the organic phase on upper strata, washing final vacuum concentrates, and obtains fat-soluble AOB AOB-o crude product.
Further improvement as the preparation method of fat-soluble AOB AOB-o of the present invention: fat-soluble AOB AOB-o crude product is refined:
Fat-soluble AOB AOB-o crude product volumetric concentration is after the ethanol-water solution dissolving of 85% ~ 92%, extracts, then concentrate with low polar solvent I, dry, obtains fat-soluble AOB AOB-o.
Remarks illustrate: above-mentioned volumetric concentration is that the consumption of the ethanol-water solution of 85% ~ 92% only need ensure that fat-soluble AOB AOB-o crude product is dissolved almost completely.
Further improvement as the preparation method of fat-soluble AOB AOB-o of the present invention: step 1) in base catalyst be sodium acetate, sodium acid carbonate or triethylamine.
Further improvement as the preparation method of fat-soluble AOB AOB-o of the present invention: fat acyl chloride is the fat acyl chloride formed after the aliphatic acid of C8 ~ C18 chain length and acylating reagent acidylate.
Further improvement as the preparation method of fat-soluble AOB AOB-o of the present invention:
The aliphatic acid of C8 ~ C18 chain length is sad, capric acid, palmitic acid, laurate, cinnamic acid or stearic acid;
Acylating reagent is nitrosyl chloride, chlorosulfuric acid, phosphoryl chloride phosphorus oxychloride or thionyl chloride.
In the present invention, fat acyl chloride can select lauroyl chloride, cinnamoyl chloride, palmitoyl chloride, stearyl chloride; The palmitoyl chloride of preferred C16.
Further improvement as the preparation method of fat-soluble AOB AOB-o of the present invention:
Step 1) in: low polar solvent I is ethyl acetate, n-hexane, benzene or acetone, and the amount ratio of water-soluble AOB AOB-w and low polar solvent I is 1g:25 ~ 125mL;
Step 2) in: being the watery hydrochloric acid of 0.8 ~ 1.2mol/L, dilute sulfuric acid or dust technology regulating step 1 with concentration) pH value of gained product adjusts 7.0 ± 0.5.
Further improvement as the preparation method of fat-soluble AOB AOB-o of the present invention:
AOB-o crude product carries out in the step of refining, and low polar solvent I is benzinum, ether or n-hexane.
Technological parameter of the present invention is preferably as follows:
Water-soluble AOB AOB-w (hereinafter referred to as AOB-w): fat acyl chloride: the mol ratio of base catalyst is 1:0.8 ~ 1.5:0.8 ~ 1.5.
Step 1 in preparation method of the present invention) in:
When reaction temperature is lower than 30 DEG C, AOB-w cannot be esterified, and modified-reaction occurs hardly.When temperature is higher than 50 DEG C, the AOB-o sample color and luster obtained is partially black, antioxygenic property be deteriorated, be dissolved in edible oil and/or in, after LCFA on east of oil impact larger.Test proves, preferred range of reaction temperature is 35 DEG C ~ 45 DEG C.
Step 1 in preparation method of the present invention) set by raw material ratio and temperature conditions under react, the time is too short, and degree of esterification is inadequate, and dissolubility is poor; Overlong time, degree of esterification is too high, although oil-soluble is better, esterified because crossing polyhydroxy, easily causes antioxygenic property to decline.Test proves, the preferred reaction time is 6h ~ 8h.
Sample yield of the present invention is generally 0.65 ~ 0.90g/g (AOB-o/AOB-w).
Fat-soluble AOB AOB-o (hereinafter referred to as AOB-o) provided by the invention can directly be dissolved in edible oil and fat and/or in, LCFA, indissoluble or water insoluble; There is the effect of Anti-oxidant.Preparation method of the present invention is oxygen acidylate method, AOB-o of the present invention is had be better than the anti-oxidant and acrylamide rejection of commercially available similar oil antioxidant product (OTP, TBHQ, frying oil antioxidant).
The infrared transmission spectra of AOB-o of the present invention after pressing potassium bromide troche is presented at 1700cm
-1near have strong carbonyl absorption peak, and 3400cm
-1neighbouring hydroxyl group absorption peak comparatively AOB-w significantly weakens (see Fig. 1).
AOB-o ultra-violet absorption spectrum of the present invention respectively has the last one absworption peak (see Fig. 2) between 240 ~ 280nm and 300 ~ 350nm.
AOB-o of the present invention directly can be dissolved in edible oil and fat (as palm oil, peanut oil, corn oil, rapeseed oil, lard, butter, butter, fish oil, camellia oil, pecan oil, linseed oil, olive oil, sunflower oil, purple perilla wet goods), general addition is the 0.01-0.05% of oil quality mark, also in AOB-o can being added to certain proportion (mass fraction 1 ~ 20%), in long-chain fat acid solution (as pungent certain herbaceous plants with big flowers acid glyceride, glyceryl laurate ester, tristerin etc.), the oil antioxidant as liquid state uses.
The present invention compared with prior art, its advantage is: compared with water-soluble AOB (AOB-w), AOB-o of the present invention can directly be dissolved in edible oil and fat, middle LCFA and non-polar solven, shows good anti peroxidation of lipid performance and heat endurance.Grease oxidation rancid instrument (Rancimat) is adopted to compare the impact that at 130 DEG C, AOB-o and other antioxidants are tested lard and palmitic antioxidative stabilizer, result shows that AOB-o can make that the antioxygenic property of lard increases by 3.74 times, palmitic antioxygenic property increases by 1.58 times, and under its high temperature, the performance of Anti-oxidant and heat endurance thereof are better than commercially available similar oil antioxidant product (OTP, TBHQ, frying oil antioxidant).AOB-o of the present invention is used for fried potato goods, can service life of significant prolongation frying oil, and significantly reduce the content of acrylamide in goods, show anti-oxidant and suppress the double effects of the third poison.AOB-o is applied to oil prodution industry, the high oily food processing industry of high temperature or rich grease-contained field of health care products, the antioxygenic property of lipid can be extended, and show the heat endurance being better than commercial like product (OTP, TBHQ, frying oil antioxidant), therefore have broad application prospects in the food industry.
In sum, main purpose of the present invention is on the basis of water-soluble AOB (AOB-w), further acquisition oil-soluble goods, can directly make an addition in edible oil and fat, the double action playing Anti-oxidant in mode more easily and suppress acrylamide to be formed.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in further detail.
Fig. 1: AOB-o and AOB-w infrared transmission spectra comparison diagram;
Fig. 2: AOB-o and AOB-w ultra-violet absorption spectrum comparison diagram;
Fig. 3: AOB-o and AOB-w RPLC (RP-HPLC) finger-print comparison diagram;
In Fig. 3: 1--chlorogenic acid; 2--caffeic acid; 3--Lutonaretin; 4--orientoside; 5--p-Coumaric Acid; 6--Saponaretin; 7--Vitexina; 8--forulic acid.
(note: different instrument, different splitter, even different time sample introduction, the retention time of each component can be different, but the eluting order of each component is substantially identical in RP-HPLC spectrogram.)
Detailed description of the invention
The preparation (for routine techniques) of embodiment 1 palmitoyl chloride
Take palmitic acid 12.821g (0.05mol), put in 250mL cucurbit, add 7.254mL thionyl chloride (0.10mol), slowly shake, absorb tail gas (HCl and SO by 1mol/L NaOH solution
2) or reaction unit is placed in fume hood, 37 DEG C of reaction 5h produce to bubble-free, and when cooling afterwards without solid, decompression distillation steams residual thionyl chloride.Whether remain through UV scanning qualification thionyl chloride and whether have fat acyl chloride peak.
Palmitoyl chloride finished product stores in 4 DEG C of condition lower seals, requires that strict water proof is preserved (palmitoyl chloride is met water and namely decomposed).
UV scanning authentication method (absorbing wavelength 250nm place is fat acyl chloride, and 280nm place is then the complete thionyl chloride of unreacted).
Sample concentration: 0.01mL/mL chloroform.
Embodiment 2 oxygen acidylate legal system is for AOB-o
AOB-w is purchased from Hangzhou Youmeite Technology Co., Ltd., general flavone content >=20%, phenolic content >=20%, Lutonaretin >=2.0%.Take AOB-w17.114g (to calculate by the mean molecule quantity of wherein 8 characteristic phenolic compounds and be about 0.2mol; lower same) as raw material; add proper amount of acetone (about 500mL; raw material is made to be immersed in acetone as far as possible; Sonication assisted treatment can be adopted); add lauroyl chloride (lauric acylate; as laurate donor during reaction) 115.6mL (0.5mol); divide and add sodium acid carbonate 40.205g (0.5mol) for 3 times, 35 DEG C of reaction 8h.After reaction terminates, add 1mol/L watery hydrochloric acid and regulate pH7.0, vibration, leave standstill, layering.After washing is positioned at the organic layer twice (consumption of each pure water is 250mL) on upper strata, Vacuum Concentration, reclaims acetone to dry, collects AOB-o crude product 25.96g.
After dissolving above-mentioned AOB-o crude product with 91% ethanol-water solution (v/v) 200mL, with benzinum (30-60 DEG C) extracting twice (each solvent load is 200mL), Vacuum Concentration (at 40 DEG C) is to viscous liquid, vacuum drying lower than 8% of mass ratio, obtains fat-soluble AOB (AOB-o) 14.01g refined to moisture.
Embodiment 3 oxygen acidylate legal system is for AOB-o
The same AOB-w17.114g that takes is as reaction substrate; add appropriate benzene (about 800mL; raw material is made to be immersed in benzene as far as possible; Sonication assisted treatment can be adopted); add the cinnamoyl chloride (acylate of cinnamic acid; as cinnamic acid donor during reaction) 14.3mL (0.1mol), divides and adds sodium acetate 16.406g (0.2mol) for 3 times, 40 DEG C of reaction 8h.After reaction terminates, add 1mol/L watery hydrochloric acid and regulate pH7.0, vibrate in right amount, leave standstill, layering.After washing is positioned at the organic layer twice (consumption of each pure water is 250mL) on upper strata, Vacuum Concentration, reclaims benzene to dry, collects to obtain AOB-o crude product 29.24g.
After dissolving AOB-o crude product with 88% ethanol-water solution (v/v) 200mL, with benzinum (30-60 DEG C) extracting twice (each solvent load is 200mL), Vacuum Concentration (at 40 DEG C) is to viscous liquid, vacuum microwave drying lower than 8% of mass ratio, obtains fat-soluble AOB (AOB-o) 13.30g refined to moisture.
Embodiment 4 oxygen acidylate legal system is for AOB-o
The same AOB-w17.114g that takes is as reaction substrate; add appropriate ethyl acetate (about 500mL; raw material is made to be immersed in ethyl acetate as far as possible; Sonication assisted treatment can be adopted); add the palmitoyl chloride (acylate of palmitic acid; as palmitic acid donor during reaction) 60.8mL (0.2mol), divides and adds sodium acid carbonate 16.802g (0.2mol) for 3 times, 35 DEG C of reaction 6h.After reaction terminates, add 1mol/L watery hydrochloric acid and regulate pH7.0, vibrate in right amount, leave standstill, layering.After organic layer washing twice, Vacuum Concentration, reclaims ethyl acetate to dry, collects AOB-o crude product 22.35g.
After dissolving above-mentioned AOB-o crude product with 90% ethanol-water solution (v/v) 200mL, with benzinum (30-60 DEG C) extracting twice (each solvent load is 200mL), Vacuum Concentration (at 40 DEG C) is to viscous liquid, vacuum freeze drying lower than 8% of mass ratio, obtains the fat-soluble AOB AOB-o11.64g refined to moisture.
The method that the AOB-o sample of embodiment 4 gained and raw material (AOB-w) thereof specify according to GB/T6040 after pressing potassium bromide troche is carried out infrared spectrum analysis, and measurement result is shown in Fig. 1.AOB-w is at 3400cm
-1, 2930cm
-1, 1610cm
-1, 1075cm
-1deng near have characteristic absorption, show the stretching vibration of C-H bond on phenolic hydroxyl group, phenyl ring, phenyl ring skeleton and carbonyl respectively; And AOB-o is at 3400cm
-1the phenolic hydroxyl group absworption peak of left and right weakens, greatly at 1700cm
-1the carbonyl absorption peak that neighbouring appearance is strong.
The AOB-o sample of embodiment 4 gained and raw material (AOB-w) thereof are dissolved in and analyze the solution that pure methyl alcohol is made into about 0.15mg/mL concentration, in 200nm ~ 400nm wave-length coverage, carry out UV scanning, ultraviolet spectrogram is shown in Fig. 2.AOB-o and AOB-w all has the last one absworption peak between 240 ~ 280nm, once strong absworption peak between 300 ~ 350nm, but AOB-o peak strength is more obvious than AOB-w weakens.
Remarks illustrate: after testing, gained infrared spectrum is identical with embodiment 4 gained sample with the spectrogram of ultraviolet spectra for the AOB-o sample of embodiment 2, embodiment 3 gained.
The mensuration of the total phenol content of embodiment 5AOB-o, p-Coumaric Acid content, acetic acid ethyl dissolution degree and HPLC finger-print
(1) mensuration of total phenol content
Forint (Folin) reagent extremely unstable in the basic conditions, can make phenolic compound reduce and react in blue.Within the scope of P-hydroxybenzoic acid concentration 0.0005 ~ 0.016mg/mL, its concentration and absorbance meet Beer law, and available P-hydroxybenzoic acid is that reference substance carries out Quantitative colorimetric and measures to obtain the total phenol content of sample.
P-hydroxybenzoic acid standard liquid: take the P-hydroxybenzoic acid standard items 25.0mg being dried to constant weight, the dissolve with ethanol solution with 90% is also settled to 100mL, is made into 0.250mg/mL P-hydroxybenzoic acid standard liquid.
Accurate absorption P-hydroxybenzoic acid standard liquid 0,0.05,0.10,0.20,0.40,0.80,1.20mL, be equivalent to P-hydroxybenzoic acid 0,0.0125,0.025,0.050,0.10,0.20,0.30mg moves in 25mL tool plug test tube, is diluted with water to 10.0mL respectively; Respectively add 1.0mL Folin reagent and 2.0mL20%Na
2cO
3the aqueous solution (mass fraction), test tube heats 30min in the water bath with thermostatic control of 50 DEG C ± 1 DEG C, is then diluted to 25mL by water cooling.Room temperature places 30min, measures the absorbance of 745nm with 1cm cuvette.Take trap as ordinate, concentration is for abscissa drawing standard curve or ask for equation of linear regression.
Take the AOB-o sample of embodiment 2, embodiment 3 and embodiment 4 preparation, be made into volume ratio 90% ethanolic solution the solution that concentration is about 2mg/mL, filter with qualitative filter paper, obtain sample.Accurate absorption sample solution 1mL, by the operating procedure in above-mentioned standard curve making, in 745nm wavelength, place carries out absorbance measurement.
According to standard working curve, obtain the P-hydroxybenzoic acid content being equivalent to sample absorbance.P-hydroxybenzoic acid content is with w
1represent, its numerical value represents with %, calculates the total phenol content of sample by formula (1):
In formula:
W
1---the total phenol content in sample, %;
M
1---the phenolic content in the test solution that establishing criteria opisometer calculates, unit is milligram (mg);
V
2---liquid cumulative volume to be measured, unit is milliliter (mL);
M
2---for sample sampling amount, unit is milligram (mg);
V
1---liquid to be measured divides gets volume, and unit is milliliter (mL).
Measurement result shows that the total phenol content of AOB-o sample prepared by embodiment 2, embodiment 3 and embodiment 4 is respectively 22.57%, 23.19% and 28.46%.
(2) p-Coumaric Acid assay
Sample dissolves through methyl alcohol, with acetonitrile-1% acetic acid aqueous solution for mobile phase, in order to liquid-phase chromatographic column (the Luna C18ODS post that C18 is filler, column length 250mm, internal diameter 4.6mm, in-built C18 filler, particle diameter 5 μm or quite person) and UV-detector or PDAD, RPLC separated island form is carried out to the p-Coumaric Acid in sample, more qualitative with standard items retention time, peak area quantified by external standard method.
The configuration of standard reserving solution: accurately take p-Coumaric Acid standard items 10mg (being accurate to 0.0001g), dissolve and be settled to 10mL with methyl alcohol, mixing, puts in refrigerator and preserves.This solution 1mL is containing p-Coumaric Acid 1.0mg.
A certain amount of p-Coumaric Acid standard liquid of accurate absorption, dilute 8,10,16,32,64,128 and 256 times respectively, sample introduction 10 μ L respectively, under following regulation chromatographic condition, carry out chromatography, according to different sample size and the corresponding spectrum peak area of p-Coumaric Acid standard liquid, take chromatographic peak area as ordinate, p-Coumaric Acid concentration is abscissa, drawing standard curve.
Chromatographic column: Luna C18ODS post, column length 250mm, internal diameter 4.6mm, in-built C18 filler, particle diameter 5 μm or quite person.
Reference color spectral condition is as follows:
Determined wavelength: 330nm.Column temperature: 40 DEG C.Mobile phase: A. acetonitrile; B.1% acetic acid aqueous solution (v/v).Condition of gradient elution: during 0 ~ 15min, A15%, B85%; During 15 ~ 25min, A15% ~ 40%, B85% ~ 0%; During 25 ~ 34min, A40%, B60%; During 34 ~ 40min, A40% ~ 15%, B60% ~ 85%.Flow: 1.0mL/min.Sample size: 10 μ L.
Sample detection: accurately take AOB sample 100mg (being accurate to 0.0001g), is settled to 100mL with dissolve with methanol solution, filters, obtain sample solution through miillpore filter (0.45 μm).Accurate absorption sample solution 10 μ L, under regulation chromatographic condition, carries out chromatography, qualitative with retention time, peak area quantified by external standard method.
P-Coumaric Acid content is with w
2represent, its numerical value represents with %, calculates by formula (2):
In formula:
W
2---the content of p-Coumaric Acid in sample, %;
C
1---the p-Coumaric Acid concentration in the test solution that establishing criteria opisometer calculates, unit is milligram every milliliter (mg/mL);
V
3---for sample constant volume, unit is milliliter (mL);
M
3---for sample sampling amount, unit is milligram (mg).
Measurement result shows that the p-Coumaric Acid content that embodiment 2, embodiment 3 and embodiment 4 prepare AOB-o is respectively 0.60%, 0.62% and 0.71%.
(3) mensuration of acetic acid ethyl dissolution degree
Get the tool plug triangular flask of 200mL, be dried to constant weight (m
4) after, accurately take 100g ethyl acetate (being accurate to 0.01g), then the AOB-o sample (being accurate to 0.01g) of 5 ~ 10g embodiment 2, embodiment 3 and embodiment 4 preparation is added, stir at 25 DEG C of following edgeds of condition, in 5min, make it fully dissolve, leave standstill 10min, pour out supernatant, bottle and residue are dried to constant weight (m
6), according to the Mass Calculation acetic acid ethyl dissolution degree alleviated.
Acetic acid ethyl dissolution degree is with w
3represent, its numerical value represents with gram each hectogram ethyl acetate (g/100g), calculates by formula (3)::
w
3=m
4+m
5-m
6……………………………………(3)
In formula:
W
3the acetic acid ethyl dissolution degree of-sample, unit is gram each hectogram (g/100g);
M
4the weight of-dry Vee formation bottle, unit is gram (g);
M
5-for sample sampling amount, unit is gram (g);
M
6the quality of-dry Vee formation bottle and residue, unit is gram (g).
Measurement result shows that the acetic acid ethyl dissolution degree that embodiment 2, embodiment 3 and embodiment 4 prepare AOB-o is respectively 3.69g/100g, 3.75g/100g and 4.62g/100g.
(4) mensuration of HPLC finger-print
AOB-o sample and raw material A OB-w thereof use methyl alcohol (chromatographically pure) to dissolve respectively, with acetonitrile (chromatographically pure)-1% acetic acid (top grade the is pure) aqueous solution for mobile phase, be the liquid-phase chromatographic column of filler and UV-detector or diode array detector in order to C18, contrast with the standard diagram and sample collection of illustrative plates that contain eight reference substances such as Lutonaretin, orientoside, Saponaretin, Vitexina, p-Coumaric Acid, chlorogenic acid, caffeic acid, forulic acid, determine active ingredient and the uneven class size of AOB-o sample.
Standard reserving solution: take a small amount of Lutonaretin, orientoside, Saponaretin, Vitexina, p-Coumaric Acid, chlorogenic acid, caffeic acid, forulic acid standard items (purity >=98.0%) respectively, dissolve with methyl alcohol (chromatographically pure) and be settled to 10mL, mixing, put in refrigerator and preserve, this solution is the mixed mark solution of eight reference substances.
Chromatographic column: Luna C18ODS post, column length 250mm, internal diameter 4.6mm, in-built C18 filler, particle diameter 5 μm or quite person.
Reference color spectral condition is as follows:
Determined wavelength: 330nm.Column temperature: 40 DEG C.Mobile phase: A. acetonitrile; B.1% acetic acid aqueous solution (v/v).Condition of gradient elution: during 0 ~ 15min, A15%, B85%; During 15 ~ 25min, A15% ~ 40%, B85% ~ 0%; During 25 ~ 34min, A40%, B60%; During 34 ~ 40min, A40% ~ 15%, B60% ~ 85%.Flow: 1.0mL/min.Sample size: 10 μ L.
Take AOB-o sample 10.75mg prepared by embodiment 4, dissolve with methyl alcohol (chromatographically pure) and be settled to 5mL, filter through miillpore filter (0.45 μm), obtain sample solution.Accurate absorption sample solution 10 μ L, under above-mentioned chromatographic condition, carries out chromatography, qualitative with retention time.
Measurement result is shown in Fig. 3.
Remarks illustrate: after testing, the result of gained HPLC finger-print is as the AOB-o of embodiment 4 gained for the AOB-o sample of embodiment 2, embodiment 3 gained.
Embodiment 6AOB-o is on the impact of lard antioxidative stabilizer
Leaf fat is purchased from market, Hangzhou, boils to obtain experiment lard.Take 20g lard, the concentration of pressing mass fraction 0,0.01%, 0.02%, 0.03%, 0.04%, 0.05% respectively adds the AOB-o sample of embodiment 2, embodiment 3 and embodiment 4 preparation, and Sonication assisted treatment 10min dissolves mixing to accelerate it.Take about 3g add AOB-o after lard sample; grease oxidation rancid instrument (Rancimat) is adopted to compare the impact that at 130 DEG C, AOB-o and other antioxidants are tested lard and palmitic antioxidative stabilizer; air velocity is 20L/h; the method specified according to GB/T21121-2007 is tested, and compares the impact of AOB-o sample on lard antioxidative stabilizer by protective factors (PF).Result of the test is as shown in table 1.
Show that AOB-o significantly can strengthen the antioxidative stabilizer of lard, and there is not proportional relationship between the impact of lard antioxidative stabilizer and additive capacity in it, strengthen lard antioxidation when mass fraction is the addition of 0.02% the most obvious, the AOB-o sample adding mass fraction 0.02% embodiment 2, embodiment 3 and embodiment 4 can strengthen respectively lard antioxidative stabilizer 2.93 times, 3.32 times and 3.74 times.
Table 1AOB-o is on the impact of lard antioxidative stabilizer
Embodiment 7AOB-o is on the impact of palm oil antioxidative stabilizer
Take 20g not containing the palm oil of additional antioxidant, the dosage pressing mass fraction 0,0.01%, 0.02%, 0.03%, 0.04%, 0.05% respectively adds the AOB-o sample of embodiment 2, embodiment 3 and embodiment 4 preparation, and Sonication assisted treatment 10min dissolves mixing to accelerate it.Take about 3g add AOB-o after palm oil sample; grease oxidation rancid instrument (Rancimat) is adopted to compare the impact that at 130 DEG C, AOB-o and other antioxidants are tested lard and palmitic antioxidative stabilizer; air velocity is 20L/h; the method specified according to GB/T21121-2007 is tested, and compares AOB-o sample to the impact on palm oil antioxidative stabilizer by protective factors (PF).
Result of the test is as shown in table 2, show that AOB-o can significantly strengthen palm oil antioxidative stabilizer, proportional relationship is there is not in it between the impact of palm oil antioxidative stabilizer and additive capacity, strengthen palm oil antioxidation with mass fraction 0.03% addition the most obvious, add mass fraction 0.03% embodiment 2, embodiment 3 and embodiment 4AOB-o sample can strengthen respectively palm oil antioxidative stabilizer 1.20 times, 1.31 times and 1.58 times.
Table 2AOB-o is on the impact of palm oil antioxidative stabilizer
The heat endurance of the different antioxidant of embodiment 8 and to the oxidation-stabilized sex comparison of palm oil
Not contain the palm oil of additional antioxidant for subjects, add AOB-o sample, oil-soluble tea polyphenol (OTP prepared by mass fraction 0.02% embodiment 2, embodiment 3 and embodiment 4 respectively, be purchased from Pu Li bio tech ltd beauteously, polyphenol content >=25%, lower with) and frying oil antioxidant (be purchased from Dongguan City Guangyi Food Additive Industry Co, product form be with ditert-butylhydro quinone, vitamine C palmitate for active ingredient make an addition to corn oil after the liquid formulation that formed; Lower same), in 175 DEG C of heating 20min.Get the palm oil sample adding above-mentioned antioxidant before and after about 3g heating, grease oxidation rancid instrument (Rancimat) is adopted to compare the impact that at 130 DEG C, AOB-o and other antioxidants are tested palmitic antioxidative stabilizer, air velocity is 20L/h, the method specified according to GB/T21121-2007 is tested, and compares the heat endurance of AOB-o sample and other antioxidants and the impact of anti-palm oil oxidation stability thereof by induction time.
Result of the test is as shown in table 3.As can be seen from the table, after adding different antioxidant, lipid-antioxidant activity stability all has enhancing, best with frying oil antioxidant effect; But all oil sample antioxidative stabilizers all reduce after heating, its empty fall is maximum, reaches 71.6%.After heating 20min, the anti-palm oil oxidation stability of OTP declines 58.9%, the anti-palm oil oxidation stability of frying oil antioxidant declines 26.7%, the palm oil oxidation stability of adding mass fraction 0.02% embodiment 2, embodiment 3 and embodiment 4AOB-o sample declines 23.9%, 21.3% and 19.5% respectively, illustrate that, compared with commercially available similar oil antioxidant product, AOB-o shows good heat endurance and anti-palm oil oxidisability.
Table 3AOB-o and other antioxidant heat endurances and sexly comparing palm oil is oxidation-stabilized
The different antioxidant of embodiment 9 is on the impact of potato chips antioxidative stabilizer
Take 3kg not containing the palm oil of additional antioxidant, add AOB-o sample, oil-soluble tea polyphenol (OTP), frying oil antioxidant prepared by mass fraction 0.02% embodiment 2, embodiment 3 and embodiment 4 respectively, until completely dissolved, in 175 DEG C of potato chips 35s, often organizing potato chips consumption is 200g.After potato chips cooling, add the grease in a certain amount of benzinum (30-60 DEG C) submergence 12h extraction potato chips.Accurately take 3g oil sample; grease oxidation rancid instrument (Rancimat) is adopted to compare the impact that at 130 DEG C, AOB-o and other antioxidants are tested palmitic antioxidative stabilizer; air velocity is 20L/h; test according to GB/T21121-2007 prescriptive procedure, determine the impact of different antioxidant on palm oil antioxidative stabilizer by protective factors.
Result of the test is as shown in table 4.Add the antioxidative stabilizer that different antioxidants all can increase potato chips, wherein frying oil antioxidant can strengthen potato chips antioxidative stabilizer 1.47 times, OTP can increase potato chips antioxidative stabilizer 1.41 times, it is best that AOB-o sample prepared by the present invention strengthens potato chips oil resistant lipid peroxidation performance, can reach 2.01 times.
The different antioxidant of table 4 is on the impact of potato chips antioxidative stabilizer
| Group | Protective factors |
| 0.02% frying oil antioxidant | 1.47±0.01 |
| 0.02%OTP | 1.41±0.02 |
| The AOB-o of 0.02% embodiment 2 | 1.78±0.04 |
| The AOB-o of 0.02% embodiment 3 | 1.91±0.02 |
| The AOB-o of 0.02% embodiment 4 | 2.01±0.03 |
The different antioxidant of embodiment 10 is to the inhibition of potato chips acrylamide
Take 2kg not containing the palm oil of additional antioxidant, add AOB-o sample and ditert-butylhydro quinone (the TBHQ powder formulation of the preparation of mass fraction 0.02% embodiment 2, embodiment 3 and embodiment 4 respectively, be purchased from Dongguan City Guangyi Food Additive Industry Co, lower same), until completely dissolved, in 180 DEG C of fries 7min, often organizing French fries consumption is 200g.Get appropriate chip potato sample and pulverize rear detection acrylamide content with mortar.Result of the test is as shown in table 5.Result shows, TBHQ is only 5.1% to the inhibiting rate that acrylamide generates, and the AOB-o sample of embodiment 2, embodiment 3 and embodiment 4 preparation is respectively 16.5%, 18.8% and 20.6% to the inhibiting rate that acrylamide generates, and effect is all better than TBHQ.
The different antioxidant of table 5 is to the comparison of potato chips acrylamide inhibition
| Group | Acrylamide content (μ g/kg) | Inhibiting rate (%) |
| Blank | 2340±22.37 | 0 |
| 0.02%TBHQ | 2221±27.57 | 5.09±0.31 |
| The AOB-o of 0.02% embodiment 2 | 1954±14.57 | 16.5±1.09 |
| The AOB-o of 0.02% embodiment 3 | 1901±17.27 | 18.8±1.25 |
| The AOB-o of 0.02% embodiment 4 | 1858±15.73 | 20.6±1.03 |
The different antioxidant of embodiment 11 is on the impact of cake peroxide value
Take 100g not containing the palm oil of additional antioxidant, add AOB-o sample, oil-soluble tea polyphenol (OTP), ditert-butylhydro quinone (TBHQ powder formulation) prepared by mass fraction 0.02% embodiment 2, embodiment 3 and embodiment 4 respectively, stand-by after dissolving completely.Take 300g white sugar and 500g egg, 120r/min adds the different antioxidant of the above-mentioned interpolation of 20g butter after beating at a slow speed 8min mixing forms egg paste, contrasts with blank oil sample.400g flour and 5g baking powder are added egg to stick with paste, stir evenly at a slow speed formation batter.Injected by batter in mould, 180 DEG C bake 20min.After cake cooling, add the grease in a certain amount of benzinum (30-60 DEG C) submergence 12h extraction cake.Accurately take 2g and extract oil sample, the method specified according to GB/T5009.37-2003 is tested, and measures peroxide (POV) value of each cake sample oil sample.Result is as shown in table 6, add above-mentioned antioxidant and can reduce the POV value baking cake, in blank sample, POV value is 0.319g/100g, bake cake POV value after adding mass fraction 0.02%TBHQ and reduce to 0.227g/100g, bake cake POV value after adding mass fraction 0.02%OTP and reduce to 0.253g/100g, add mass fraction 0.02% embodiment 2, embodiment 3 and embodiment 4AOB-o sample and can be down to 0.191g/100g by baking cake POV value, 0.188g/100g and 0.181g/100g, effect is better than TBHQ and OTP.
The different antioxidant of table 6 is on the impact of cake peroxide value
| Group | POV value (g/100g) |
| Blank | 0.319±0.015 |
| 0.02%TBHQ | 0.227±0.009 |
| 0.02%OTP | 0.253±0.013 |
| The AOB-o of 0.02% embodiment 2 | 0.191±0.008 |
| The AOB-o of 0.02% embodiment 3 | 0.188±0.009 |
| The AOB-o of 0.02% embodiment 4 | 0.181±0.011 |
Comparative example 1 ~ comparative example 2
Change the AOB-w in embodiment 2: fat acyl chloride: the mol ratio of catalyst, and reaction time and reaction temperature, all the other are equal to embodiment 2; Thus corresponding acquisition comparative example 1 ~ comparative example 2.Specifically as shown in table 7.
The preparation parameter of table 7 comparative example 1 ~ comparative example 2
The AOB-o of above-mentioned comparative example 1 ~ comparative example 2 gained is carried out every detection according to the method described in embodiment 6 ~ embodiment 11, and acquired results is as shown in table 8 below.
The Performance comparision of the AOB-o that table 8 comparative example 1 ~ comparative example 2 is prepared and obtained
Finally, it is also to be noted that what enumerate above is only several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be had.All distortion that those of ordinary skill in the art can directly derive from content disclosed by the invention or associate, all should think protection scope of the present invention.
Claims (7)
1. fat-soluble AOB AOB-o, is characterized in that: total phenol content>=20%, p-Coumaric Acid content>=0.5%, solubility>=3% in ethyl acetate, yellowish-brown or yellowish-brown powder, slightly ester taste; Directly can be dissolved in edible oil and fat, middle LCFA and non-polar solven, show good anti peroxidation of lipid performance and heat endurance; And effectively can suppress the formation of rich amyloid Assessments of Acrylamide Generated in Heated Foodstuffs, can use as oil antioxidant and acrylic amide restrainer in the food industry simultaneously; And the described infrared transmission spectra of fat-soluble AOB AOB-o after pressing potassium bromide troche is all presented at 1700cm
-1near have strong carbonyl absorption peak, 3400cm
-1neighbouring hydroxyl group absorption peak comparatively AOB-w significantly weakens;
The preparation method of described fat-soluble AOB AOB-o, comprises the following steps:
1), in low polar solvent I, under the effect of base catalyst, water-soluble AOB AOB-w and fat acyl chloride are in 30 DEG C ~ 50 DEG C acylation reaction 5h ~ 10h; Water-soluble AOB AOB-w: fat acyl chloride: the mol ratio of base catalyst is 1:0.5 ~ 2.5:0.8 ~ 3;
2), by step 1) pH value of gained product is adjusted to neutrality, shaken well, stratification; Get the organic phase on upper strata, washing final vacuum concentrates, and obtains fat-soluble AOB AOB-o crude product;
3), fat-soluble AOB AOB-o crude product is refined:
Fat-soluble AOB AOB-o crude product volumetric concentration is after the ethanol-water solution dissolving of 85% ~ 92%, extracts, then concentrate with low polar solvent II, dry, obtains fat-soluble AOB AOB-o;
And described step 1) in base catalyst be sodium acetate, sodium acid carbonate or triethylamine.
2. fat-soluble AOB AOB-o according to claim 1, it is characterized in that: with water-soluble AOB AOB-w be raw material, with Powdered, the graininess of fat acyl chloride ester exchange or Formulation, dissolve in edible oil and fat and/or in, become liquid formulation in LCFA.
3. fat-soluble AOB AOB-o according to claim 1 and 2, is characterized in that: described step 1) in base catalyst be sodium acetate or sodium acid carbonate.
4. fat-soluble AOB AOB-o according to claim 3, is characterized in that: described fat acyl chloride is the fat acyl chloride formed after the aliphatic acid of C8 ~ C18 chain length and acylating reagent acidylate.
5. fat-soluble AOB AOB-o according to claim 4, is characterized in that:
The aliphatic acid of described C8 ~ C18 chain length is sad, capric acid, palmitic acid, laurate, cinnamic acid or stearic acid;
Described acylating reagent is nitrosyl chloride, chlorosulfuric acid, phosphoryl chloride phosphorus oxychloride or thionyl chloride.
6. fat-soluble AOB AOB-o according to claim 5, is characterized in that:
Described step 1) in: low polar solvent I is ethyl acetate, n-hexane, benzene or acetone, and the amount ratio of described water-soluble AOB AOB-w and low polar solvent I is 1g:25 ~ 125mL;
Described step 2) in: being the watery hydrochloric acid of 0.8 ~ 1.2mol/L, dilute sulfuric acid or dust technology regulating step 1 with concentration) pH value of gained product adjusts 7.0 ± 0.5.
7. fat-soluble AOB AOB-o according to claim 6, is characterized in that:
Described AOB-o crude product carries out in the step of refining, and low polar solvent II is benzinum, ether or n-hexane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210571602.3A CN103005007B (en) | 2012-12-25 | 2012-12-25 | Fat-soluble AOB and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210571602.3A CN103005007B (en) | 2012-12-25 | 2012-12-25 | Fat-soluble AOB and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103005007A CN103005007A (en) | 2013-04-03 |
| CN103005007B true CN103005007B (en) | 2015-07-29 |
Family
ID=47954536
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210571602.3A Expired - Fee Related CN103005007B (en) | 2012-12-25 | 2012-12-25 | Fat-soluble AOB and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103005007B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103271253B (en) * | 2013-06-19 | 2014-07-02 | 贵阳学院 | Inhibitor for inhibiting generation of acrylamide in potato frying process and use method of inhibitor |
| CN105076915B (en) * | 2014-05-21 | 2020-04-10 | 杭州凝竹生物科技有限公司 | Fat-soluble bamboo leaf antioxidant prepared by enzyme method and application thereof |
| CN105724601B (en) * | 2014-12-12 | 2020-03-06 | 丰益(上海)生物技术研发中心有限公司 | Oil and fat composition and use thereof |
| CN105285732A (en) * | 2015-11-30 | 2016-02-03 | 天津科技大学 | Processing method for controlling content of heterocyclic amines in fried meat product |
| CN110538224A (en) * | 2019-09-30 | 2019-12-06 | 中国科学院山西煤炭化学研究所 | Method for preparing fat-soluble natural antioxidant from peony seed skin or sea buckthorn seed meal |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1528197A (en) * | 2003-10-08 | 2004-09-15 | ƽ | Bamboo leaf antioxide and use thereof |
| CN101255151A (en) * | 2007-12-26 | 2008-09-03 | 上海交大昂立股份有限公司 | High-performance fat-soluble antioxidant fat-soluble tea-polyphenol and preparation method thereof |
| CN101270108B (en) * | 2008-01-09 | 2011-05-18 | 上海交大昂立股份有限公司 | Method for preparing liposoluble tea polyphenol |
-
2012
- 2012-12-25 CN CN201210571602.3A patent/CN103005007B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1528197A (en) * | 2003-10-08 | 2004-09-15 | ƽ | Bamboo leaf antioxide and use thereof |
| CN101255151A (en) * | 2007-12-26 | 2008-09-03 | 上海交大昂立股份有限公司 | High-performance fat-soluble antioxidant fat-soluble tea-polyphenol and preparation method thereof |
| CN101270108B (en) * | 2008-01-09 | 2011-05-18 | 上海交大昂立股份有限公司 | Method for preparing liposoluble tea polyphenol |
Non-Patent Citations (4)
| Title |
|---|
| 竹叶抗氧化物;张英等;《第八届中国国际食品添加剂和配料展览会暨第十一届全国食品添加剂生产应用技术展示会学术论文集》;20041231;第89-93页 * |
| 竹叶抗氧化物在食品工业中的应用;张英等;《中国食品添加剂》;20061231;第59-62页 * |
| 竹叶黄酮最新研究进展之一--竹叶黄酮制剂中酚酸类化合物的存在及其作用;张英等;《中国食品添加剂》;20090830(第4期);第46-53页，正文第3段 * |
| 竹叶黄酮最新研究进展之二--竹叶酚性化学素抑制食品中丙烯酰胺形成及化解人体丙毒危害的作用和机制研究;张英等;《中国食品添加剂》;20091031(第5期);第56-62，第145页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103005007A (en) | 2013-04-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Hu et al. | Effects of roasting temperature and time on aldehyde formation derived from lipid oxidation in scallop (Patinopecten yessoensis) and the deterrent effect by antioxidants of bamboo leaves | |
| Roby et al. | Evaluation of antioxidant activity, total phenols and phenolic compounds in thyme (Thymus vulgaris L.), sage (Salvia officinalis L.), and marjoram (Origanum majorana L.) extracts | |
| Liu et al. | Effects of temperature and heating time on the formation of aldehydes during the frying process of clam assessed by an HPLC-MS/MS method | |
| Ananingsih et al. | Green tea catechins during food processing and storage: A review on stability and detection | |
| Brenes et al. | Influence of thermal treatments simulating cooking processes on the polyphenol content in virgin olive oil | |
| CN103005007B (en) | Fat-soluble AOB and preparation method thereof | |
| Fernando et al. | Application of an ultrasound-assisted extraction method to recover betalains and polyphenols from red beetroot waste | |
| Asha et al. | Antioxidant activities of orange peel extract in ghee (butter oil) stored at different storage temperatures | |
| WO2005032275A1 (en) | Antioxidant of bamboo leaves and its use | |
| Kozłowska et al. | Effects of spice extracts on lipid fraction oxidative stability of cookies investigated by DSC | |
| Elbandy et al. | Phytochemicals in pomegranate seeds and their effect as hypolipidemic agent in hypercholesterolemic rats. | |
| Povilaityee et al. | Antioxidative activity of purple peril (Perilla frutescens L.), moldavian dragonhead (Dracocephalum moldavica L.), and roman chamomile (Anthemis nobilis L.) extracts in rapeseed oil | |
| Ourradi et al. | Proximate composition of polyphenolic, phytochemical, antioxidant activity content and lipid profiles of date palm seeds oils (Phoenix dactylifera L.) | |
| de Carvalho et al. | The use of lemon juice and its role on polyunsaturated fatty acids and cholesterol oxides formation in thermally prepared sardines | |
| Agregán et al. | Recent advances in the extraction of polyphenols from eggplant and their application in foods | |
| CN106665891A (en) | Preparation and use method of snow chrysanthemum polyphenol | |
| KR20110011365A (en) | Method of preparing polyphenol with high antioxidant capacity, and antioxiant, antioxidant composition and antioxidant product comprising polyphenol obtained thereby | |
| Dhibi et al. | Comparative study of the phenolic profile and antioxidant activities of Moringa (Moringa oleifera Lam.) and Jujube (Ziziphus Lotus Linn.) leaf extracts and their protective effects in frying stability of corn oil | |
| Gao et al. | A novel strategy for inhibiting AGEs in fried fish cakes: Grape seed extract surimi slurry coating | |
| Niklová et al. | Effect of evening primrose extracts on oxidative stability of sunflower and rapeseed oils | |
| de Souza Correa et al. | Supercritical CO2 with co-solvent extraction of blackberry (Rubus spp. Xavante cultivar) seeds | |
| Okada et al. | A study on fatty acids in seeds of Euterpe oleracea Mart seeds | |
| EP3920721A1 (en) | Antioxidant composition comprising quercetagetin and gallic acid | |
| El-Shatanovi et al. | Antiatherogenic properties of vegetable juice rich in antioxidants in cholesterol-fed rats | |
| Patel et al. | Antioxidant potential of herbs and spices during deep frying of ghee |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150729 |