CN111349126B - Steviolbioside metal copper complex and preparation method thereof - Google Patents
Steviolbioside metal copper complex and preparation method thereof Download PDFInfo
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- CN111349126B CN111349126B CN202010210614.8A CN202010210614A CN111349126B CN 111349126 B CN111349126 B CN 111349126B CN 202010210614 A CN202010210614 A CN 202010210614A CN 111349126 B CN111349126 B CN 111349126B
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- Prior art keywords
- steviolbioside
- copper
- metal
- acid
- complex
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 70
- 239000002184 metal Substances 0.000 title claims abstract description 69
- OMHUCGDTACNQEX-OSHKXICASA-N Steviolbioside Natural products O([C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@]12C(=C)C[C@@]3(C1)CC[C@@H]1[C@@](C)(CCC[C@]1([C@@H]3CC2)C)C(O)=O)[C@@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O OMHUCGDTACNQEX-OSHKXICASA-N 0.000 title claims abstract description 65
- JLPRGBMUVNVSKP-AHUXISJXSA-M chembl2368336 Chemical compound [Na+].O([C@H]1[C@@H](O)[C@H](O)[C@H](CO)O[C@H]1O[C@]12C(=C)C[C@@]3(C1)CC[C@@H]1[C@@](C)(CCC[C@]1([C@@H]3CC2)C)C([O-])=O)[C@@H]1O[C@@H](CO)[C@@H](O)[C@H](O)[C@@H]1O JLPRGBMUVNVSKP-AHUXISJXSA-M 0.000 title claims abstract description 53
- 150000004699 copper complex Chemical class 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000010949 copper Substances 0.000 claims abstract description 33
- 229910052802 copper Inorganic materials 0.000 claims abstract description 32
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 31
- 230000000536 complexating effect Effects 0.000 claims abstract description 28
- -1 steviolbioside copper complex Chemical class 0.000 claims abstract description 25
- 239000000243 solution Substances 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 15
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 12
- 239000008139 complexing agent Substances 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 150000001879 copper Chemical class 0.000 claims abstract description 5
- 150000007524 organic acids Chemical class 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 229930188195 rebaudioside Natural products 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 25
- 239000013078 crystal Substances 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 13
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 9
- LTPSRQRIPCVMKQ-UHFFFAOYSA-N 2-amino-5-methylbenzenesulfonic acid Chemical compound CC1=CC=C(N)C(S(O)(=O)=O)=C1 LTPSRQRIPCVMKQ-UHFFFAOYSA-N 0.000 claims description 8
- 238000002386 leaching Methods 0.000 claims description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 5
- 239000003963 antioxidant agent Substances 0.000 claims description 5
- 239000012295 chemical reaction liquid Substances 0.000 claims description 5
- 235000015165 citric acid Nutrition 0.000 claims description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 claims description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 4
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 4
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 244000228451 Stevia rebaudiana Species 0.000 claims description 3
- 235000006092 Stevia rebaudiana Nutrition 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 229940116318 copper carbonate Drugs 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- LITQZINTSYBKIU-UHFFFAOYSA-F tetracopper;hexahydroxide;sulfate Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Cu+2].[Cu+2].[Cu+2].[Cu+2].[O-]S([O-])(=O)=O LITQZINTSYBKIU-UHFFFAOYSA-F 0.000 claims description 3
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- ONZWNZGVZFLMNZ-UHFFFAOYSA-N 1-aminonaphthalene-2-sulfonic acid Chemical compound C1=CC=C2C([NH3+])=C(S([O-])(=O)=O)C=CC2=C1 ONZWNZGVZFLMNZ-UHFFFAOYSA-N 0.000 claims description 2
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 2
- HEAHMJLHQCESBZ-UHFFFAOYSA-N 2,5-diaminobenzenesulfonic acid Chemical compound NC1=CC=C(N)C(S(O)(=O)=O)=C1 HEAHMJLHQCESBZ-UHFFFAOYSA-N 0.000 claims description 2
- KZKGEEGADAWJFS-UHFFFAOYSA-N 2-amino-5-methoxybenzenesulfonic acid Chemical compound COC1=CC=C(N)C(S(O)(=O)=O)=C1 KZKGEEGADAWJFS-UHFFFAOYSA-N 0.000 claims description 2
- ZMCHBSMFKQYNKA-UHFFFAOYSA-N 2-aminobenzenesulfonic acid Chemical compound NC1=CC=CC=C1S(O)(=O)=O ZMCHBSMFKQYNKA-UHFFFAOYSA-N 0.000 claims description 2
- NJBCRXCAPCODGX-UHFFFAOYSA-N 2-methyl-n-(2-methylpropyl)propan-1-amine Chemical compound CC(C)CNCC(C)C NJBCRXCAPCODGX-UHFFFAOYSA-N 0.000 claims description 2
- SNKZJIOFVMKAOJ-UHFFFAOYSA-N 3-Aminopropanesulfonate Chemical compound NCCCS(O)(=O)=O SNKZJIOFVMKAOJ-UHFFFAOYSA-N 0.000 claims description 2
- MTJGVAJYTOXFJH-UHFFFAOYSA-N 3-aminonaphthalene-1,5-disulfonic acid Chemical compound C1=CC=C(S(O)(=O)=O)C2=CC(N)=CC(S(O)(=O)=O)=C21 MTJGVAJYTOXFJH-UHFFFAOYSA-N 0.000 claims description 2
- RXCMFQDTWCCLBL-UHFFFAOYSA-N 4-amino-3-hydroxynaphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(N)=C(O)C=C(S(O)(=O)=O)C2=C1 RXCMFQDTWCCLBL-UHFFFAOYSA-N 0.000 claims description 2
- YUNBHHWDQDGWHC-UHFFFAOYSA-N 6-aminonaphthalene-1-sulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC2=CC(N)=CC=C21 YUNBHHWDQDGWHC-UHFFFAOYSA-N 0.000 claims description 2
- CYJJLCDCWVZEDZ-UHFFFAOYSA-N 8-aminonaphthalene-1-sulfonic acid Chemical compound C1=CC(S(O)(=O)=O)=C2C(N)=CC=CC2=C1 CYJJLCDCWVZEDZ-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 2
- 229940043237 diethanolamine Drugs 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 claims description 2
- 229940043276 diisopropanolamine Drugs 0.000 claims description 2
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000006911 enzymatic reaction Methods 0.000 claims description 2
- 229940031098 ethanolamine Drugs 0.000 claims description 2
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 2
- 229940102253 isopropanolamine Drugs 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 claims description 2
- 229960004418 trolamine Drugs 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-O N-dimethylethanolamine Chemical compound C[NH+](C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-O 0.000 claims 1
- 238000000605 extraction Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 150000002739 metals Chemical class 0.000 abstract description 5
- 238000001914 filtration Methods 0.000 abstract description 2
- 235000019441 ethanol Nutrition 0.000 description 25
- 239000000047 product Substances 0.000 description 21
- 229910021645 metal ion Inorganic materials 0.000 description 19
- 150000004696 coordination complex Chemical class 0.000 description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 8
- 239000011573 trace mineral Substances 0.000 description 8
- 235000013619 trace mineral Nutrition 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- 229910052725 zinc Inorganic materials 0.000 description 8
- 230000009286 beneficial effect Effects 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 7
- 239000003446 ligand Substances 0.000 description 7
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 6
- 239000013522 chelant Substances 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 238000002835 absorbance Methods 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229940079877 pyrogallol Drugs 0.000 description 5
- 239000012488 sample solution Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 235000011171 Thladiantha grosvenorii Nutrition 0.000 description 4
- 244000185386 Thladiantha grosvenorii Species 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000010668 complexation reaction Methods 0.000 description 4
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- 230000031700 light absorption Effects 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 238000007605 air drying Methods 0.000 description 3
- 238000006701 autoxidation reaction Methods 0.000 description 3
- 239000013256 coordination polymer Substances 0.000 description 3
- 229920001795 coordination polymer Polymers 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- HHEAADYXPMHMCT-UHFFFAOYSA-N dpph Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1[N]N(C=1C=CC=CC=1)C1=CC=CC=C1 HHEAADYXPMHMCT-UHFFFAOYSA-N 0.000 description 3
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- 150000003254 radicals Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- UEDUENGHJMELGK-HYDKPPNVSA-N Stevioside Chemical compound O([C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@]12C(=C)C[C@@]3(C1)CC[C@@H]1[C@@](C)(CCC[C@]1([C@@H]3CC2)C)C(=O)O[C@H]1[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O1)O)[C@@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O UEDUENGHJMELGK-HYDKPPNVSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000002015 acyclic group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000003064 anti-oxidating effect Effects 0.000 description 2
- 230000004071 biological effect Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 235000003599 food sweetener Nutrition 0.000 description 2
- 230000012010 growth Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
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- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 238000010979 pH adjustment Methods 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- 230000035790 physiological processes and functions Effects 0.000 description 2
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- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 229960004889 salicylic acid Drugs 0.000 description 2
- 230000002000 scavenging effect Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229940013618 stevioside Drugs 0.000 description 2
- OHHNJQXIOPOJSC-UHFFFAOYSA-N stevioside Natural products CC1(CCCC2(C)C3(C)CCC4(CC3(CCC12C)CC4=C)OC5OC(CO)C(O)C(O)C5OC6OC(CO)C(O)C(O)C6O)C(=O)OC7OC(CO)C(O)C(O)C7O OHHNJQXIOPOJSC-UHFFFAOYSA-N 0.000 description 2
- 235000019202 steviosides Nutrition 0.000 description 2
- 239000003765 sweetening agent Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 description 1
- 206010010957 Copper deficiency Diseases 0.000 description 1
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- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 1
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- 150000002576 ketones Chemical class 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
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- HELXLJCILKEWJH-NCGAPWICSA-N rebaudioside A Chemical compound O([C@H]1[C@H](O)[C@@H](CO)O[C@H]([C@@H]1O[C@H]1[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O1)O)O[C@]12C(=C)C[C@@]3(C1)CC[C@@H]1[C@@](C)(CCC[C@]1([C@@H]3CC2)C)C(=O)O[C@H]1[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O1)O)[C@@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O HELXLJCILKEWJH-NCGAPWICSA-N 0.000 description 1
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- 235000005074 zinc chloride Nutrition 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
- C07H15/20—Carbocyclic rings
- C07H15/24—Condensed ring systems having three or more rings
- C07H15/256—Polyterpene radicals
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P39/00—General protective or antinoxious agents
- A61P39/06—Free radical scavengers or antioxidants
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
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Abstract
The invention provides a steviolbioside metal copper complex and a preparation method thereof, wherein the structure of the steviolbioside metal copper complex is shown as a formula (I), and the complexing rate of metal copper is more than 77%. The preparation method of the steviolbioside metal copper complex comprises the steps of dissolving steviolbioside in lower alcohol, dissolving copper salt in organic acid aqueous solution, mixing the two solutions, adjusting the pH value to be alkalescent, adding an auxiliary complexing agent, heating and stirring, cooling and crystallizing the reaction solution, filtering, washing and drying to obtain the steviolbioside copper complex. In the complexes formed by a plurality of steviolbiosides and metals, the complex formed by the steviolbiosides and the metal copper has obvious antioxidant effect, and the complex formed by other metals and the steviolbiosides has no obvious antioxidant effect, so that the advantages of the steviolbioside metal copper complex provided by the invention are highlighted.
Description
Technical Field
The invention relates to a preparation method of a metal complex, in particular to a steviolbioside metal copper complex and a preparation method thereof.
Background
Metal complexes are a class of complexes formed by coordination bonds between ligands and metal ions. In recent years, scholars at home and abroad have a certain research on the activity of the traditional Chinese medicine metal complex, and mainly show the aspects of antioxidant activity, antitumor activity, bacteriostatic action and the like of the traditional Chinese medicine metal complex. In general, the traditional Chinese medicine metal complex has certain advantages in these aspects. The traditional Chinese medicine metal complex has more obvious effect than the original effective components.
The metal complex is composed of a ligand and a metal ion, and atoms such as nitrogen, oxygen, sulfur, phosphorus, halogen and the like in coordination sites have strong electron donating capability and are commonly used as coordination sites of organic ligands in coordination polymers, such as carboxyl, carbonyl, amino, hydroxyl, ketone and the like. The metal ions comprise iron, zinc, copper, manganese, calcium, aluminum, cobalt, nickel, rare earth and the like, wherein the iron, the zinc, the copper, the chromium and the cobalt are trace elements which are needed by the human body, such as manganese, silicon, nickel and vanadium which are possibly necessary for the human body, and the trace elements have very important physiological functions in the human body. The biochemical function of Cu in the body is mainly catalysis, and many copper-containing metalloenzymes are used as oxidases and participate in the oxidation-reduction process in the body. It can be used for maintaining stability of cell membrane, participating in metabolism and immunologic function process of enzymes, promoting growth and tissue regeneration of organism, and causing a series of metabolic disorders and pathological changes after copper deficiency. Ligands and metal ions are coordinated in different proportions to assemble into various geometric polymers, such as cyclic chelates and acyclic complexes, or closed triangular, square, cage polymers.
Steviolbioside (steviolbioside) is prepared by directly extracting and purifying dried leaves of stevia rebaudiana or by chemical or enzymatic catalysis, and has the effects of reducing blood sugar, resisting tuberculosis and the like while being used as a sweetener. At present, researches and reports on rebaudioside stay in the aspect of preparation and purification of rebaudioside and compounding of rebaudioside serving as a sweetening agent or a functional ingredient, few researches on structural modification or modification are carried out, and few researches and reports on rebaudioside metal complexes are carried out.
Stevioside has a carbonyl group which can be deprotonated to carry a negative charge, has two coordination site oxygen atoms, can be coordinated with metal ions in multiple coordination modes, and can be combined with multiple metal ions to form a multi-core building unit so as to synthesize various novel coordination polymer structures.
Where M is a metal and n is an integer from 1 to 3, for example n is 1,2 or 3.
Therefore, the rebaudioside and the beneficial metal copper element are formed by coordination and complexation, and a rebaudioside metal copper complex is developed, so that the product and the method in the aspect are not reported, and have important significance and economic value for researching a rebaudioside high value-added product.
Disclosure of Invention
The invention aims to solve the technical problem that steviolbioside and beneficial metal copper element are coordinated and assembled together to develop a steviolbioside metal copper complex. The method has simple process, strong operability and high complexing rate.
The invention solves the technical problems through the following technical scheme:
the first object of the invention is to provide a rebaudioside-copper complex, which is a complex formed by rebaudioside and copper metal, and has a structural formula shown as the following formula (I):
wherein x is any one of 1,2 and 3.
Preferably, in the steviolbioside metal copper complex, the complexing rate of copper (the proportion of metal ions in a complexed state to total metal copper ions) is more than or equal to 77 percent, and the complexing rate of copper is more than or equal to 84 percent.
The second purpose of the invention is to provide a preparation method of the steviolbioside metal copper complex, which comprises the following steps:
dissolving steviolbioside in lower alcohol, dissolving copper salt in organic acid water solution, mixing the two solutions, adjusting pH to alkalescence, adding auxiliary complexing agent, heating and stirring, cooling and crystallizing the reaction liquid, filtering, washing crystals, and drying to obtain steviolbioside copper complex.
Preferably, the steviolbioside is prepared by directly extracting and purifying stevia rebaudiana or by a chemical or enzymatic method from stevioside, and the content of the steviolbioside is 80-99 wt%.
The lower alcohol is one of ethanol, methanol and isopropanol, the volume consumption of the lower alcohol is 3-8 times (mL/mg) of the mass of the steviolbioside, and the mass percentage concentration of the lower alcohol is 80-95%. The lower alcohol is used as a reaction solvent of the ligand steviolbioside and the coordination atom metal, has large polarity, and can more effectively fill the coordination metal atom into a complex network structure of the ligand along with the solvent as an object, thereby being beneficial to the formation of coordination bonds.
Preferably, the copper salt is at least one of basic copper chloride, basic copper sulfate, basic copper carbonate, copper chloride and copper sulfate.
Preferably, the acidic aqueous solution is any one of citric acid, malic acid and tartaric acid, and the pH of the acidic aqueous solution is 5.5-6.5.
Preferably, the two solutions are mixed, the molar ratio of the steviolbioside to the metal ions is 1:0.5-3, the temperature is 50-80 ℃ in a constant-temperature water bath, and the two solutions are continuously stirred for 2-10 hours. The molar ratio is also one of the important factors for the coordination reaction, and one carboxylic acid can form 1 to 3 coordination bonds with a metal atom, that is, one carbonyl group can form a complex with 1 to 3 metal atoms on average. The proper temperature can be kept under the condition of lower alcohol boiling point and in a stirring state, so that the movement speed of ions can be accelerated, the probability of coordination is improved, and the reaction speed and the yield are improved.
Preferably, the pH adjustment to be weakly alkaline means that the pH adjustment is performed by using alkaline water to be 7.5-8.5, and the alkaline water is at least one of sodium bicarbonate, potassium bicarbonate and ammonia water. The pH value is adjusted to be beneficial to the carboxyl of the steviolbioside to release protons, and vacancies are reserved to give metal ions to form coordination.
The auxiliary complexing agent is at least one of alcohol amine, organic amine and sulfonic amino substances, and the addition amount of the auxiliary complexing agent is 2-4% of the mass of the metal salt. The addition of the auxiliary complexing agent can improve the complexing rate of the steviolbioside and the metal, and the high-quality steviolbioside metal complex can be obtained more effectively.
Further, the structural formula of the alcohol amine is NHm[(CH2)nOH]3-mWherein m is an integer of 0 to 2 and n is an integer of 1 to 4; further onSpecifically, the alcohol amine is at least one selected from ethanolamine, diethanolamine, triethanolamine, isopropanolamine, diisopropanolamine, triisopropanolamine and N, N-dimethylethanolamine; the organic amine is selected from aliphatic amine and/or alicyclic amine, the aliphatic amine is selected from at least one of monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine, dipropylamine, tripropylamine, n-butylamine, di-n-butylamine, isobutylamine, 1, 4-butanediamine, tert-butylamine, diisobutylamine and hexamethylenediamine, and the alicyclic amine is selected from at least one of triethylenediamine, diethylenetriamine, hexamethylenetetramine, cyclohexylamine and piperazine; the sulfonic acid amino substance is at least one selected from 4-amino-3-hydroxy-1-naphthalenesulfonic acid, 4-aminotoluene-3-sulfonic acid, 2-aminobenzenesulfonic acid, 3-aminopropanesulfonic acid, 1-aminonaphthalene-2-sulfonic acid, p-anisidine-3-sulfonic acid, 2, 5-diaminobenzenesulfonic acid, 6-amino-1-naphthalenesulfonic acid, 2-naphthylamine-4, 8-disulfonic acid and 8-aminonaphthalenesulfonic acid.
The inventor unexpectedly finds that the complexing rate can be effectively improved by adding a certain amount of auxiliary complexing agent, and particularly, the complexing efficiency of steviolbioside and copper ions can be remarkably improved by adding sulfonic acid amino substances.
Preferably, the cooling is to cool the mixture to a temperature of between 4 ℃ below zero and 10 ℃, the mixture is kept stand for 12 to 24 hours, the crystal washing solvent is lower alcohol, the lower alcohol is one of methanol, ethanol and isopropanol, the mass percentage concentration of the lower alcohol is more than or equal to 90 percent, and the crystal washing mode is leaching.
The long-time low temperature is beneficial to the precipitation and growth of crystals, the leaching of the high-concentration lower alcohol can effectively clean the uncombined metal ions, and meanwhile, the crystallization process is also a repeated crystallization process, so that the product content can be greatly improved.
Preferably, the drying is one of forced air drying or vacuum drying. The temperature of forced air drying is 50-60 ℃ in the early stage and 60-80 ℃ in the later stage. And the early stage is air-dried until no lower alcohol smell exists, and the later stage is dried at the constant weight. Vacuum drying at vacuum degree of-0.8-0.1 MPa and temperature of 40-50 deg.C until no alcohol is present, and drying at vacuum degree of-0.8-0.1 MPa and temperature of 60-80 deg.C to constant weight. The lower temperature is selected for drying in the early stage so as to avoid the problem that the high temperature causes partial crystals to be dissolved again, so that the crystal form is influenced, and the phase is further influenced. And under the condition of lower temperature, the crystals can be prevented from dissolving, and the crystals can not be dissolved after the lower alcohol is volatilized and heated, so that the uniformity of the crystal form is effectively guaranteed.
The invention further provides the use of the rebaudioside metal complex as an antioxidant.
The steviolbioside copper complex provided by the invention has excellent effects of eliminating DPPH and superoxide anion free radical (O)2-) and the hydroxyl radical (. OH). Test data prove that in a plurality of complexes formed by steviolbioside and metal, the complex formed by the steviolbioside and the metal copper has obvious antioxidant effect, and the complex formed by other metal and the steviolbioside has no obvious antioxidant effect, so that the advantages of the steviolbioside metal copper complex provided by the invention are highlighted.
The principle of the method of the invention is as follows:
the steviolbioside has carbonyl groups which can be easily deprotonated to carry a negative charge, has two coordination site oxygen atoms, can be coordinated with metal ions in multiple coordination modes, and can be combined with multiple metal ions to form a multi-core building unit so as to synthesize various novel coordination polymer structures. The metal trace elements of iron, zinc, copper, manganese, calcium, aluminum, cobalt, nickel, rare earth and the like, wherein the iron, the zinc, the copper, the chromium and the cobalt are trace elements required by a human body, and the manganese, the silicon, the nickel and the vanadium are trace elements possibly required by the human body, and the trace elements have very important physiological functions in the human body. The rebaudioside with carbonyl groups is used as a ligand and metal ions to be coordinated and assembled into various geometrical polymers in different proportions, such as cyclic chelate and acyclic complex, or closed triangular, square and cage-shaped polymers, so that the rebaudioside metal complex is obtained. Finally, the method of alcohol phase crystallization is used for removing the unbound metal ions and other impurities, thereby further improving the product content.
The method has the following beneficial effects:
the invention provides a method for preparing a steviolbioside metal copper complex, which can form the steviolbioside and trace elements of beneficial metals of human bodies into the metal copper complex, thereby expanding the modification range of the steviolbioside.
The complexing rate of the metal complex of the product obtained by the method is more than 77%, and the complexing rate of the metal complex can reach more than 84% in the preferred embodiment.
Thirdly, the inventor unexpectedly finds that the complex formed by the steviolbioside and the metal copper has obvious and advantageous antioxidation in a plurality of complexes formed by the steviolbioside and the metal, and the complex formed by other metals and the steviolbioside has no obvious antioxidation, thus highlighting the advantages of the steviolbioside metal copper complex provided by the invention.
Fourthly, preferably, the inventor further finds that the complexing rate can be effectively improved by adding a certain amount of auxiliary complexing agent, particularly, the complexing efficiency of the steviolbioside and copper ions can be remarkably improved by adding sulfonic acid amino substances.
The method is a production method suitable for industrial large-scale popularization, has strong operability of technological process, no pollution, low cost and content, and is suitable for industrial production.
Drawings
Figure 1 is an infrared spectrum of steviolbioside.
Figure 2 steviolbioside copper complex infrared spectra.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The momordica grosvenori pectin, momordica grosvenori polysaccharide, momordica grosvenori oligosaccharide, momordica grosvenori mannitol and 11-oxidation-momordica grosvenori glycoside V used in the embodiment of the invention are all from Hainan China-Cheng biological resources GmbH.
The test method adopted by the present invention is explained as follows:
1. determination of trace element complexation rate: reference is made to GB/T13080.2-2005 (gel filtration chromatography for determination of iron (copper, manganese, zinc) methionine chelation rate), which is based on the principle that organic chelate and metal ions are separated by gel, eluted under specified conditions, the metal ions form hydroxide precipitates, the hydroxide precipitates are fixed at the top end of a gel column and cannot be eluted, and the rest organic combination can be eluted from the gel column by carrying a ligand, so that the separation of the organic chelate from the metal ions is realized; after the organic chelate elution separation is completed, EDTA solution is added to elute the metal ions from the chromatographic column. And (3) measuring the contents of the organic chelate state and the metal ions by using an atomic absorption spectrometry, and respectively calculating the proportion of the organic chelate state to the total amount of the metal elements, namely the complexation rate.
2. And (3) characterization:IR Infrared Spectroscopy.
3. Determination of biological Activity (antioxidant)：
(1) Scavenging test of free radical DPPH: 1, 1-diphenylpicrylphenylhydrazine method.
Adding 4.0mL of the LDPPH solution and a sample solution (100 mu g/mL) into a 10mL colorimetric tube in sequence, adding absolute ethyl alcohol to the scale, immediately mixing, measuring a light absorption value (A) at a wavelength of 517nm by using a 1cm cuvette, marking the light absorption value as Ai, then measuring the light absorption value after storing in a greenhouse in a dark place for 30min, marking as Aj, and marking the light absorption value as Ac in a contrast test by using an ethanol solution only added with DPPH. The radical clearance (K) was calculated as follows:
K(％)＝[1-(Ai-Aj)/Ac]*100％
the test was repeated three times, and the average value was taken as the final result.
(2) Superoxide anion radical (O)2-) clearance test: pyrogallol autoxidation method.
Adopting a pyrogallol autooxidation method, taking 4mL of 0.1mol/L Tris-HCl buffer solution with pH8.2 and 2mL of distilled water, uniformly mixing, preserving heat in a water bath at 25 ℃ for 20min, then adding 2mL of sample solution (100 mu g/mL), taking out, immediately adding 0.5mL of 5mmol/L pyrogallol preheated at 25 ℃ (prepared by 10mmol/L HCL, using 10mmol/L HCL for a blank tube to replace HCL solution of the pyrogallol), shaking uniformly, pouring into a cuvette, measuring absorbance at 325nm every 30s, continuously measuring for 4min, and calculating the increase of the absorbance per minute in a linear range. The volume of distilled water was reduced while a volume of sample solution was added.
The inhibition ratio (%) (. DELTA.A 0-. DELTA.A)/. DELTA.A 0X 100 formula: delta A0 is the autoxidation rate of pyrogallol; delta A is the autoxidation rate of pyrogallol after the addition of the sample solution.
(3) Hydroxyl radical (. OH) scavenging test: fenton method.
Taking 2 colorimetric tubes (sample tubes and blank tubes) of 25mL, respectively adding 5mL of 1mmol/L ferrous sulfate solution and 5mL of 3mmol/L H2O2 solution, adding 1mL of sample solution (100 mu g/mL) into the sample tubes, adding 1mL of distilled water into the blank tubes, uniformly mixing, fixing the volume to the scale by using 3mmol/L salicylic acid solution, reacting in constant temperature water at 37 ℃ (0.1 +/-DEG C) for 15min, and then measuring the absorbance of each tube by using a spectrophotometer at the wavelength of 510 nm. Zero adjustment was carried out with 3mmol/L salicylic acid solution.
The removal rate SA (%) of OH radicals can be calculated according to the following formula: in the formula: a0 — absorbance without sample addition; a1-absorbance of the added sample
Clearance rate
The present invention will be further described with reference to the following examples.
Example 1
1. Dissolving: fully dissolving 100g of steviolbioside with the content of 85.2 wt% in 400ml of 95% ethanol, dissolving 15g of basic copper sulfate in 120ml of apple aqueous solution with the pH value of 6.0, and fully stirring and dissolving.
2. Reaction: the two solutions of step 1 were mixed and adjusted to pH 8.0 with ammonia, after which 0.3g triethanolamine was added with stirring and reacted at constant temperature 60 ℃ for 8 h.
3. And (3) crystallization: and (3) standing and cooling the reaction liquid obtained in the step (2) to 10 ℃, allowing the crystal to continue to grow, keeping for 24 hours, performing solid-liquid separation on the crystal in a suction filtration mode, and leaching the extract with 90% ethanol at the temperature of-4 ℃ until the leacheate is colorless.
4. And (3) drying: and putting the obtained crystal in an air drying oven at 55 ℃ for early-stage drying until no obvious alcohol smell exists, and then raising the temperature to 80 ℃ for continuous drying until the weight is constant. To obtain 89.6g of steviolbioside metal copper complex. The complexing rate of the product metal copper is 80.2%.
Example 2
1. Dissolving: 100g of rebaudioside 85. twt% was dissolved in 600ml of 90% methanol, and 15g of basic copper chloride was dissolved in 150ml of citric acid solution having a pH of 6.0, and the resultant solution was sufficiently stirred and dissolved.
2. Reaction: the two solutions of step 1 were mixed and adjusted to pH 8.0 with ammonia, after which 0.4g of tripropylamine was added and reacted at constant temperature of 80 ℃ for 10 hours with stirring.
3. And (3) crystallization: and (3) standing the reaction liquid obtained in the step (2), cooling to-4 ℃, allowing the crystal to continue to grow, keeping for 12 hours, performing solid-liquid separation on the crystal in a suction filtration mode, and leaching with 90% methanol at the temperature of-4 ℃ until leaching liquor is colorless.
4. And (3) drying: the obtained crystal is placed in a vacuum drying oven with the vacuum degree of-0.8 Mpa and the temperature of 45 ℃ for early drying until no obvious alcohol smell exists, and then the temperature is raised to 60 ℃ for continuous drying until the constant weight is achieved. 90.7g of steviolbioside metal copper complex was obtained. The complexing rate of the metal copper of the product is 78.4%.
Example 3
1. Dissolving: 100g of steviolbioside with a content of 85.2 wt% was sufficiently dissolved in 800ml of 90% isopropyl alcohol, and 15g of basic copper chloride was dissolved in 150ml of a citric acid solution with a pH of 6.0, and sufficiently stirred and dissolved.
2. Reaction: the two solutions of step 1 were mixed and adjusted to pH 8.0 with aqueous ammonia, after which 0.3g of 4-aminotoluene-3-sulfonic acid was added with stirring and reacted at a constant temperature of 75 ℃ for 10 hours.
3. And (3) crystallization: and (3) standing the reaction liquid obtained in the step (2), cooling to 0 ℃, allowing the crystal to continue to grow, keeping for 16 hours, performing solid-liquid separation on the crystal in a suction filtration mode, and leaching with 90% isopropanol at 0 ℃ until leaching liquor is colorless.
4. And (3) drying: the obtained crystal is placed in a vacuum drying oven with the vacuum degree of-0.1 Mpa and the temperature of 40 ℃ for early drying until no obvious alcohol smell exists, and then the temperature is raised to 80 ℃ for continuous drying until the constant weight is achieved. To obtain 89.5g of steviolbioside metal copper complex. The complexing rate of the product metal copper is 86.1%.
Example 4
The rebaudioside metal complex was prepared in the same manner as in example 3, except that 15g of basic copper chloride was replaced with 15.5g of basic copper carbonate in step 1. 88.9g of rebaudioside copper complex was finally obtained. The complexing rate of the metal copper of the product is 85.1 percent.
Example 5
The preparation method of steviolbioside metal complex is the same as that in example 3, except that the amount of 4-aminotoluene-3-sulfonic acid used in step 2 was changed to 0.5 g. 91.3g of rebaudioside copper complex was obtained. The complexing rate of the product metal copper is 87.2%.
Example 6
The preparation method of steviolbioside metal complex is the same as that in example 3, except that the amount of 4-aminotoluene-3-sulfonic acid used in step 2 was changed to 0.65 g. 91.5g of rebaudioside copper complex was obtained. The complexing rate of the metal copper of the product is 86.8 percent.
Example 7
The preparation method of steviolbioside metal complex is the same as that in example 3, except that the amount of 4-aminotoluene-3-sulfonic acid used in step 2 was changed to 0.6 g. Finally, 90.8g of rebaudioside copper complex was obtained. The complexing rate of the metal copper of the product is 84.6 percent.
Example 8
The preparation method of steviolbioside metal complex is the same as that in example 3, except that the amount of 4-aminotoluene-3-sulfonic acid used in step 2 was changed to 0.2 g. Finally, 90.4g of rebaudioside copper complex was obtained. The complexing rate of the metal copper of the product is 81.6 percent.
Example 9
The preparation method of steviolbioside metal complex is the same as that in example 3, except that the amount of 4-aminotoluene-3-sulfonic acid used in step 2 was changed to 0.7 g. Finally, 90.7g of rebaudioside copper complex was obtained. The complexing rate of the metal copper of the product is 79.3 percent.
Example 10
The rebaudioside metal complex was prepared in the same manner as in example 3, except that 15g of basic copper chloride was replaced with 9.5g of anhydrous copper chloride in step 1. Finally 87.3g of rebaudioside copper complex was obtained. The complexing rate of the metal copper of the product is 77.8 percent.
Example 11
The rebaudioside metal complex was prepared in the same manner as in example 3, except that 15g of basic copper chloride was replaced with 11.2g of anhydrous copper sulfate in step 1. 88.1g of rebaudioside copper complex was finally obtained. The complexing rate of the metal copper of the product is 78.2 percent.
Example 12
The rebaudioside metal complex was prepared as in example 3 except that the citric acid solution at pH6.0 was replaced with a dilute hydrochloric acid solution at pH6.0 in step 1. Finally 86.3g of rebaudioside copper complex was obtained. The product has a copper complexing rate of 79.2%.
Comparative example 1
The rebaudioside metal complex was prepared in the same manner as in example 3, except that 15g of basic copper chloride was replaced with 8g of basic zinc chloride in step 1. Finally, 90.4g of steviolbioside metal zinc complex is obtained. The complexing rate of the metal zinc of the product is 81.6 percent.
Comparative example 2
The rebaudioside metal complex was prepared as in example 3 except that 15g of basic copper chloride was replaced with 10.7g of basic magnesium chloride in step 1. Finally, 84.8g of steviolbioside metal magnesium complex is obtained. The complexation rate of the magnesium metal of the product is 76.8 percent.
Comparative example 3
The rebaudioside metal complex was prepared as in example 3 except that 15g of basic copper chloride was replaced with 11.5g of ferric chloride in step 1. 82.7g of rebaudioside iron complex was obtained. The complexing rate of the metal iron of the product is 73.5 percent.
Application example
Structural characterization: the sample of example 3 was physically mixed at a ratio of 1:1:1, then scanned by infrared scanning, and compared to the rebaudioside a standard. As shown in fig. 1 and 2. Fig. 1 is an infrared spectrum of steviolbioside, and fig. 2 is an infrared spectrum of steviolbioside copper complex obtained in example 1. As can be seen by comparison, 1747.98cm-1Nearby is the C ═ O shock absorption peak of steviolbioside, while in its copper metal complex, 1747.98cm-1Nearby 1709.73cm-1The reduction to almost no absorption peak indicates that only one carbonyl group of the steviolbioside participates in metal coordination.
Example 11
Determination of biological activity (antioxidant): the antioxidant capacity of the rebaudioside metal complex obtained in the examples and comparative examples was tested and compared with rebaudioside standards and Vc. The concentration of each sample was 100. mu.g/mL, and the results are shown in Table 1 below:
TABLE 1
As can be seen from the data in table 1, the rebaudioside metal copper complex provided by the present invention has significantly improved antioxidant properties compared to rebaudioside, and although the antioxidant properties of complexes of other metals, such as zinc, magnesium, iron, and the like, and rebaudioside are improved to some extent, the improvement is not significant as that of the rebaudioside metal copper complex. The possible reason is that copper can participate in coordination more effectively under the action of the auxiliary complexing agent, and the metal complexing rate of the obtained complex is higher, so that the oxidation resistance is stronger.
The applicant states that the present invention is illustrated by the above examples to describe the detailed preparation method of the present invention, but the present invention is not limited to the above detailed preparation method, i.e. it does not mean that the present invention must rely on the above detailed preparation method to be carried out. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (13)
1. A steviolbioside metal copper complex is a complex formed by steviolbioside and metal copper, and has a structural formula shown as formula (I)
Wherein x is any one of 1,2 and 3.
2. The rebaudioside copper complex of claim 1, wherein the complexing rate of copper in the rebaudioside copper complex is at least 77%.
3. The steviolbioside metal copper complex of claim 2, wherein the copper complexing rate is 84% or more.
4. The method of preparing a steviolbioside metal copper complex according to any one of claims 1 to 3, comprising the steps of:
dissolving steviolbioside in lower alcohol, dissolving copper salt in organic acid aqueous solution, mixing the two solutions, adjusting pH to alkalescence, adding an auxiliary complexing agent, heating and stirring, cooling and crystallizing reaction liquid, performing suction filtration, washing crystals, and drying to obtain steviolbioside copper complex; the lower alcohol is one of methanol, ethanol and isopropanol.
5. The method of claim 4, wherein the rebaudioside is obtained by direct extraction and purification from stevia rebaudiana Bertoni or by chemical or enzymatic method, and the content of rebaudioside is 80-99 wt%.
6. The method of claim 4, wherein the copper salt is at least one of basic copper chloride, basic copper sulfate, basic copper carbonate, copper chloride, and copper sulfate; the organic acid is any one of citric acid, malic acid and tartaric acid, and the pH of the organic acidic aqueous solution is 5.5-6.5.
7. The method according to claim 4, wherein the adjustment of pH to weak alkalinity is adjustment of pH to 7.5 to 8.5 with an alkali water, and the alkali water is at least one of sodium bicarbonate, potassium bicarbonate and ammonia water.
8. The method according to claim 4, wherein the auxiliary complexing agent is at least one of an organic amine and a sulfonic acid amino substance, and the amount of the auxiliary complexing agent added is 2 to 4% by mass of the metal salt.
9. The method according to claim 8, wherein the organic amine is an alcohol amine.
10. The method of claim 8, wherein the alcohol amine has the formula NHm[(CH2)nOH]3-mWherein m is an integer of 0 to 2 and n is an integer of 1 to 4.
11. The method according to claim 9, wherein the alcohol amine is at least one selected from the group consisting of ethanolamine, diethanolamine, triethanolamine, isopropanolamine, diisopropanolamine, triisopropanolamine, N-dimethylethanolamine; the organic amine is selected from aliphatic amine and/or alicyclic amine, the aliphatic amine is selected from at least one of monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine, dipropylamine, tripropylamine, n-butylamine, di-n-butylamine, isobutylamine, 1, 4-butanediamine, tert-butylamine, diisobutylamine and hexamethylenediamine, and the alicyclic amine is selected from at least one of triethylenediamine, diethylenetriamine, hexamethylenetetramine, cyclohexylamine and piperazine; the sulfonic acid amino substance is at least one selected from 4-amino-3-hydroxy-1-naphthalenesulfonic acid, 4-aminotoluene-3-sulfonic acid, 2-aminobenzenesulfonic acid, 3-aminopropanesulfonic acid, 1-aminonaphthalene-2-sulfonic acid, p-anisidine-3-sulfonic acid, 2, 5-diaminobenzenesulfonic acid, 6-amino-1-naphthalenesulfonic acid, 2-naphthylamine-4, 8-disulfonic acid and 8-aminonaphthalenesulfonic acid.
12. The preparation method according to claim 4, wherein the cooling is cooling to-4 to 10 ℃, and standing for 12 to 24 hours, the crystal washing solvent is lower alcohol, the lower alcohol is one of methanol, ethanol and isopropanol, the mass percent concentration of the lower alcohol is more than or equal to 90%, and the crystal washing mode is leaching.
13. Use of a steviolbioside metal copper complex according to any of claims 1 to 3 or prepared by the preparation method according to any of claims 4 to 12 as an antioxidant.
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| US4449997A (en) * | 1981-04-02 | 1984-05-22 | Junichi Iwamura | Plant growth regulator |
| CN106243176A (en) * | 2016-08-01 | 2016-12-21 | 南宁市泽威尔饲料有限责任公司 | The copper complex formazan preparation method of sucrose |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4449997A (en) * | 1981-04-02 | 1984-05-22 | Junichi Iwamura | Plant growth regulator |
| CN106243176A (en) * | 2016-08-01 | 2016-12-21 | 南宁市泽威尔饲料有限责任公司 | The copper complex formazan preparation method of sucrose |
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| Diterpenoid Sweeteners. Synthesis and Sensory Evaluation of Stevioside Analogues with Improved Organoleptic Properties;Grant E. DuBois，等;《Journal of Medicinal Chemistry》;19851231;第28卷(第1期);93-98 * |
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