CN106890200A - Extract method and the medicine containing squalene of plant source spiny dogfish ene compositions and its preparation method and application - Google Patents
Extract method and the medicine containing squalene of plant source spiny dogfish ene compositions and its preparation method and application Download PDFInfo
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- CN106890200A CN106890200A CN201510958566.XA CN201510958566A CN106890200A CN 106890200 A CN106890200 A CN 106890200A CN 201510958566 A CN201510958566 A CN 201510958566A CN 106890200 A CN106890200 A CN 106890200A
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- squalene
- molecular distillation
- plant source
- spiny dogfish
- weight
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- BHEOSNUKNHRBNM-UHFFFAOYSA-N Tetramethylsqualene Natural products CC(=C)C(C)CCC(=C)C(C)CCC(C)=CCCC=C(C)CCC(C)C(=C)CCC(C)C(C)=C BHEOSNUKNHRBNM-UHFFFAOYSA-N 0.000 title claims abstract description 131
- PRAKJMSDJKAYCZ-UHFFFAOYSA-N dodecahydrosqualene Natural products CC(C)CCCC(C)CCCC(C)CCCCC(C)CCCC(C)CCCC(C)C PRAKJMSDJKAYCZ-UHFFFAOYSA-N 0.000 title claims abstract description 131
- 229940031439 squalene Drugs 0.000 title claims abstract description 131
- TUHBEKDERLKLEC-UHFFFAOYSA-N squalene Natural products CC(=CCCC(=CCCC(=CCCC=C(/C)CCC=C(/C)CC=C(C)C)C)C)C TUHBEKDERLKLEC-UHFFFAOYSA-N 0.000 title claims abstract description 131
- YYGNTYWPHWGJRM-UHFFFAOYSA-N (6E,10E,14E,18E)-2,6,10,15,19,23-hexamethyltetracosa-2,6,10,14,18,22-hexaene Chemical compound CC(C)=CCCC(C)=CCCC(C)=CCCC=C(C)CCC=C(C)CCC=C(C)C YYGNTYWPHWGJRM-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 238000000034 method Methods 0.000 title claims abstract description 72
- 239000000203 mixture Substances 0.000 title claims abstract description 67
- 239000003814 drug Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000284 extract Substances 0.000 title claims description 7
- 241000251778 Squalus acanthias Species 0.000 title 1
- 238000000199 molecular distillation Methods 0.000 claims abstract description 68
- 241000251774 Squalus Species 0.000 claims abstract description 47
- 239000002994 raw material Substances 0.000 claims abstract description 44
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000004202 carbamide Substances 0.000 claims abstract description 24
- 229930182558 Sterol Natural products 0.000 claims abstract description 22
- 150000003432 sterols Chemical class 0.000 claims abstract description 22
- 235000003702 sterols Nutrition 0.000 claims abstract description 22
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims description 24
- 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 claims description 22
- XJFYWGIWEYQMPK-UHFFFAOYSA-N ethanol;urea Chemical compound CCO.NC(N)=O XJFYWGIWEYQMPK-UHFFFAOYSA-N 0.000 claims description 15
- 238000002425 crystallisation Methods 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 229930003427 Vitamin E Natural products 0.000 claims description 11
- 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 claims description 11
- 235000019165 vitamin E Nutrition 0.000 claims description 11
- 229940046009 vitamin E Drugs 0.000 claims description 11
- 239000011709 vitamin E Substances 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 10
- 239000012074 organic phase Substances 0.000 claims description 9
- 230000008025 crystallization Effects 0.000 claims description 8
- 239000000546 pharmaceutical excipient Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 230000001877 deodorizing effect Effects 0.000 claims description 6
- 238000005886 esterification reaction Methods 0.000 claims description 5
- 239000010773 plant oil Substances 0.000 claims description 5
- 238000007445 Chromatographic isolation Methods 0.000 claims description 4
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- 235000006708 antioxidants Nutrition 0.000 claims description 4
- 230000032050 esterification Effects 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 4
- 238000005809 transesterification reaction Methods 0.000 claims description 4
- 239000008280 blood Substances 0.000 claims description 3
- 210000004369 blood Anatomy 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 230000036039 immunity Effects 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 230000008014 freezing Effects 0.000 claims description 2
- 238000007710 freezing Methods 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
- 238000000605 extraction Methods 0.000 abstract description 10
- 235000013376 functional food Nutrition 0.000 abstract description 2
- 241000196324 Embryophyta Species 0.000 description 38
- 239000000047 product Substances 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 14
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000006185 dispersion Substances 0.000 description 12
- 239000012071 phase Substances 0.000 description 12
- 239000003999 initiator Substances 0.000 description 11
- 239000004519 grease Substances 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 244000185386 Thladiantha grosvenorii Species 0.000 description 4
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- 238000012360 testing method Methods 0.000 description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OILXMJHPFNGGTO-UHFFFAOYSA-N (22E)-(24xi)-24-methylcholesta-5,22-dien-3beta-ol Natural products C1C=C2CC(O)CCC2(C)C2C1C1CCC(C(C)C=CC(C)C(C)C)C1(C)CC2 OILXMJHPFNGGTO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 241001465754 Metazoa Species 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 238000004332 deodorization Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- OQMZNAMGEHIHNN-UHFFFAOYSA-N 7-Dehydrostigmasterol Natural products C1C(O)CCC2(C)C(CCC3(C(C(C)C=CC(CC)C(C)C)CCC33)C)C3=CC=C21 OQMZNAMGEHIHNN-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000251730 Chondrichthyes Species 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 2
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 2
- HZYXFRGVBOPPNZ-UHFFFAOYSA-N UNPD88870 Natural products C1C=C2CC(O)CCC2(C)C2C1C1CCC(C(C)=CCC(CC)C(C)C)C1(C)CC2 HZYXFRGVBOPPNZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
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- 125000001931 aliphatic group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000003064 anti-oxidating effect Effects 0.000 description 2
- LGJMUZUPVCAVPU-UHFFFAOYSA-N beta-Sitostanol Natural products C1CC2CC(O)CCC2(C)C2C1C1CCC(C(C)CCC(CC)C(C)C)C1(C)CC2 LGJMUZUPVCAVPU-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000010495 camellia oil Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
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- 125000005456 glyceride group Chemical group 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 235000020778 linoleic acid Nutrition 0.000 description 2
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- HCXVJBMSMIARIN-PHZDYDNGSA-N stigmasterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)/C=C/[C@@H](CC)C(C)C)[C@@]1(C)CC2 HCXVJBMSMIARIN-PHZDYDNGSA-N 0.000 description 2
- 235000016831 stigmasterol Nutrition 0.000 description 2
- 229940032091 stigmasterol Drugs 0.000 description 2
- BFDNMXAIBMJLBB-UHFFFAOYSA-N stigmasterol Natural products CCC(C=CC(C)C1CCCC2C3CC=C4CC(O)CCC4(C)C3CCC12C)C(C)C BFDNMXAIBMJLBB-UHFFFAOYSA-N 0.000 description 2
- -1 triterpene compound Chemical class 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- LXEKPEMOWBOYRF-QDBORUFSSA-N AAPH Chemical compound Cl.Cl.NC(=N)C(C)(C)\N=N\C(C)(C)C(N)=N LXEKPEMOWBOYRF-QDBORUFSSA-N 0.000 description 1
- OILXMJHPFNGGTO-NRHJOKMGSA-N Brassicasterol Natural products O[C@@H]1CC=2[C@@](C)([C@@H]3[C@H]([C@H]4[C@](C)([C@H]([C@@H](/C=C/[C@H](C(C)C)C)C)CC4)CC3)CC=2)CC1 OILXMJHPFNGGTO-NRHJOKMGSA-N 0.000 description 1
- SGNBVLSWZMBQTH-FGAXOLDCSA-N Campesterol Natural products O[C@@H]1CC=2[C@@](C)([C@@H]3[C@H]([C@H]4[C@@](C)([C@H]([C@H](CC[C@H](C(C)C)C)C)CC4)CC3)CC=2)CC1 SGNBVLSWZMBQTH-FGAXOLDCSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 244000147058 Derris elliptica Species 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 108010022535 Farnesyl-Diphosphate Farnesyltransferase Proteins 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- BTEISVKTSQLKST-UHFFFAOYSA-N Haliclonasterol Natural products CC(C=CC(C)C(C)(C)C)C1CCC2C3=CC=C4CC(O)CCC4(C)C3CCC12C BTEISVKTSQLKST-UHFFFAOYSA-N 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical class [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 1
- 241001122767 Theaceae Species 0.000 description 1
- OILXMJHPFNGGTO-ZRUUVFCLSA-N UNPD197407 Natural products C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)C=C[C@H](C)C(C)C)[C@@]1(C)CC2 OILXMJHPFNGGTO-ZRUUVFCLSA-N 0.000 description 1
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- 150000001298 alcohols Chemical class 0.000 description 1
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- OILXMJHPFNGGTO-ZAUYPBDWSA-N brassicasterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)/C=C/[C@H](C)C(C)C)[C@@]1(C)CC2 OILXMJHPFNGGTO-ZAUYPBDWSA-N 0.000 description 1
- 235000004420 brassicasterol Nutrition 0.000 description 1
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- SGNBVLSWZMBQTH-PODYLUTMSA-N campesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CC[C@@H](C)C(C)C)[C@@]1(C)CC2 SGNBVLSWZMBQTH-PODYLUTMSA-N 0.000 description 1
- 235000000431 campesterol Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000036996 cardiovascular health Effects 0.000 description 1
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- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
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- 229930195729 fatty acid Natural products 0.000 description 1
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- 239000007789 gas Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000007954 hypoxia Effects 0.000 description 1
- 239000000568 immunological adjuvant Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000007721 medicinal effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000007764 o/w emulsion Substances 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 235000020777 polyunsaturated fatty acids Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000010686 shark liver oil Substances 0.000 description 1
- 229940069764 shark liver oil Drugs 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- GFNHODBBCUPTMB-UHFFFAOYSA-N silver;methanol;nitrate Chemical compound [Ag+].OC.[O-][N+]([O-])=O GFNHODBBCUPTMB-UHFFFAOYSA-N 0.000 description 1
- NLQLSVXGSXCXFE-UHFFFAOYSA-N sitosterol Natural products CC=C(/CCC(C)C1CC2C3=CCC4C(C)C(O)CCC4(C)C3CCC2(C)C1)C(C)C NLQLSVXGSXCXFE-UHFFFAOYSA-N 0.000 description 1
- 230000036559 skin health Effects 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical class S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K36/00—Medicinal preparations of undetermined constitution containing material from algae, lichens, fungi or plants, or derivatives thereof, e.g. traditional herbal medicines
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/01—Hydrocarbons
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
- A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
Abstract
The present invention relates to functional food field, method and the medicine containing squalene of a kind of extraction plant source spiny dogfish ene compositions and its preparation method and application are disclosed, the method for extracting plant source spiny dogfish ene compositions includes：The raw material that will be enriched in squalene carries out urea clathrate and molecular distillation successively, wherein, the condition of the molecular distillation is controlled so that the squalene containing 35-80 weight %, the sterol of squalene and 10-40 weight % containing 5-30 weight % in the raw material rich in squalene in the plant source spiny dogfish ene compositions for obtaining.The new plant source spiny dogfish ene compositions that obtain being extracted using the method for the present invention, the squalene (purity is usually above 90%) of high-purity that is provided with prior art quite even preferably antioxidant effect is provided on the premise of it need not further purify.
Description
Technical field
The present invention relates to functional food field, in particular it relates to a kind of method for extracting plant source spiny dogfish ene compositions, a kind of preparation method of medicine containing squalene and the medicine containing squalene prepared by the method and its application.
Background technology
Squalene is a kind of highly undersaturated hydrocarbon compound, is a kind of colourless oil liquid with special odor, and its systematic naming method is 2,6,10,15,19,23- hexamethyl -2, the alkene of 6,10,14,18,22- tetracosa carbon six, and molecular formula is C30H50.Squalene belongs to a kind of highly undersaturated straight chain triterpene compound, and structural formula is：
Squalene has anti-oxidant, promotion skin health, promotes cardiovascular health, improves many effects such as human body hypoxia-bearing capability, is widely used in medicine, cosmetic field, and the application in field of health care products in the last few years also progressively extends.
Presently commercially available squalene product is and extracts what is obtained from eepwater shark liver oil; as the animal protection cry to deepwater shark is surging; European Union member countries are increasingly deficient which results in the squalene resource with hydrogenated hydro carbons grease as raw material in fishing in Atlantic Ocean northeastward limitation deepwater shark in 2006.
Scientific research personnel also attempts to expand by chemistry or the method for biosynthesis the market supply of squalene, but the technological process of chemical reaction is long, and use poisonous chemical agent more, also there is a certain distance in production technology distance industrialization large-scale production, and the squalene double bond structure of chemical synthesis has difference with the alltrans structure of natural squalene.
In addition, CN102257149B discloses a kind of method for preparing purifying yeast, the squalene of high-purity is prepared using the yeast of excess production squalene, for preparing oil-in-water emulsion as immunologic adjuvant.CN103266137B is related to a kind of production method of squalene, and squalene synthetase gene is cloned and coexpression, the method so as to construct the recombinant bacterial strain that can synthesize squalene in Escherichia coli.But, biosynthesis is all also undesirable at the aspect such as yield of strain and purpose thing, and also in the presence of some limitation, distance industrialization large-scale production also has certain distance.
Because squalene is also widely present in plant, have research work carries out extraction research as raw material with olive oil or deodorization distillate to the squalene of plant source, because squalene content is relatively low in raw material, in view of production cost, squalene carries out purification and does not have industrialized production and commercialized condition, therefore the mechanisms such as research institute and colleges and universities are confined to the work of plant source squalene more.
Because material system component is complicated, and squalene product of the purification production of involved plant source squalene with higher degree (more than 90%) is as target, prior art is required to be only possible to reach using multi-step process the purpose for isolating and purifying, and the process step of use is more, experiment flow is long, solvent and energy ezpenditure are big, low production efficiency.
The plant oil deodorizing distillate for producing during vegetable oil deodorized at present, squalene is especially extracted in olive oil deodorization distillate turns into an effective method, according to China's national situation, most of olive oil is all to rely on import, lacks the stable resources of olive oil deodorization distillate.Therefore the technique that design separation squalene is developed from the existing oil resource of China is a kind of economically viable processing mode.
CN102146014A discloses the method for extracting squalene as raw material with tea seed, and the technological process of its extracting method is：Continue to concentrate after extraction, concentration, esterification, complexant-borax reaction, macroreticular resin chromatographic separation and purification, concentration, extraction and washing, supercritical carbon dioxide extracting is carried out again after obtaining squalene crude oil, obtain the squalene product that content is more than 80%.However, the method process route is complicated, the consumption of solvent energy consumption is big, and chromatographic isolation has that dead absorption, filler need regeneration, increased production cost.
CN1284752C discloses a kind of extracting method of plant squalene, and the benevolence or seed of Momordica grosvenori are crushed, and liposoluble substance is gone out with organic solvent Soakage extraction, removes organic solvent, and Momordica grosvenori squalene crude product is obtained；Momordica grosvenori squalene crude product is crossed into silica gel column chromatography, is eluted with organic solvent, collect eluent colourless part, organic solvent is removed with distillation under vacuum, Momordica grosvenori squalene fine work is obtained.However, the method has a raw material squalene content relatively low, extraction cost shortcoming high.
It is auxiliary agent that CN103483305A is disclosed and used urea and solvent, it is set to mix with grease deodorized distillate dissolving, carry out vacuum outgas and seal, again condense using super-pressure the rapid crystallizations such as the saturated fatty acid in distillate, aliphatic hydrocarbon and sterol, press filtration obtains filter residue and filtrate after separating, and the mixture of VE, squalene and the polyunsaturated fatty acid of higher degree can be obtained after desolvation.This technique also uses super-pressure, and needs vacuum outgas, increased the difficulty of energy consumption and subsequent treatment.
Application No. 201410375211.3 is prior art discloses a kind of technique of complex extractions squalene, the benevolence of tea oil tree is crushed, plus petroleum ether carries out ultrasonic extraction, filtering, filtrate decompression is concentrated, and then mixes gained camellia oil liposoluble substance concentrate with strong alkali alcosol, is extracted with petroleum ether after being heated to reflux, being subsequently adding silver nitrate methanol aqueous solution carries out complex reaction, then proceedes to be stripped the squalene petroleum ether organic phase after being dissociated with petroleum ether；By squalene petroleum ether organic phase with vacuum distillation is carried out after NaCl aqueous cleanings, cleaned with distilled water again, be vacuum dried, that is, obtain end-product squalene fine work.However, silver nitrate is introduced in the technological process of the prior art carries out complex reaction, process costs have been increased considerably, and generated the possibility of chemical contamination, be unfavorable for industrial popularization.
The content of the invention
The purpose of the present invention is the defect for overcoming prior art, a kind of new plant source spiny dogfish ene compositions are provided on the premise of the effect of the product containing squalene is not reduced, and a kind of technological process of offer is simple, the method of the acquisition new plant source spiny dogfish ene compositions of low cost and suitable industrialized production, the new plant source spiny dogfish ene compositions that obtain being extracted using the method for the present invention, the squalene (purity is usually above 90%) of high-purity that is provided with prior art quite even preferably medicinal effects are provided on the premise of it need not further purify.
The present inventor is based on completion technical scheme considered below：There is very big difference with the squalene raw material of animal sources in the squalene raw material of plant source, the content of some components is relatively fewer in animal sources, and then rich content in the raw material of plant source, by taking stigmasterol as an example, its molecular weight is 412.69, with the molecular weight (410.72) of squalene closely, it is difficult to be separated with squalene.If inventor considers that squalene content can be obtained by simple technological operation moderate and can retain the composition of other various active materials in plant source squalene raw material, then can greatly save production cost and realize the green production of the product containing squalene.Based on this, inventor has carried out a series of creative researches, and it is it was found that moderate by squalene content that simple technological operation is obtained and to retain squalene of the composition of other various active materials in plant source squalene raw material with high-purity (more than 90%) in effect suitable or even better.
In a first aspect, the present invention provides a kind of method for extracting plant source spiny dogfish ene compositions, the method includes：The raw material that will be enriched in squalene carries out urea clathrate and molecular distillation successively, wherein, the condition of the molecular distillation is controlled so that the squalene containing 35-80 weight %, the sterol of squalene and 10-40 weight % containing 5-30 weight % in the raw material rich in squalene in the plant source spiny dogfish ene compositions for obtaining.
Second aspect, the present invention provides a kind of preparation method of the medicine containing squalene, and the method includes：
(1) plant source spiny dogfish ene compositions are extracted：Plant source spiny dogfish ene compositions are extracted using the method for the foregoing extraction plant source spiny dogfish ene compositions of the present invention；
(2) medicine is prepared：The pharmacy activity component of the plant source spiny dogfish ene compositions obtained containing step (1) is mixed with pharmaceutic adjuvant.
The third aspect, the present invention provides the medicine containing squalene prepared by preceding method of the invention.
Fourth aspect, the present invention provides application of the foregoing medicine containing squalene in for strengthen immunity, anti-oxidant and reduction blood fat density product.
Also contain sterol isoreactivity material in the plant source spiny dogfish ene compositions obtained by the method for extraction plant source spiny dogfish ene compositions involved in the present invention in addition to the squalene containing 35-80 weight %, extracting the plant source spiny dogfish ene compositions for obtaining by the method for the present invention can keep even preferably pharmaceutical active suitable with prior art.And, the method process is simple for extracting plant source spiny dogfish ene compositions of the invention, low production cost is suitable as industrial method and is promoted.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute the part of specification, is used to explain the present invention together with following specific embodiment, but be not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the result schematic diagram of the test case that the present invention is provided.
Specific embodiment
Specific embodiment of the invention is described in detail below.It should be appreciated that specific embodiment described herein is merely to illustrate and explain the present invention, it is not intended to limit the invention.
In a first aspect, the invention provides a kind of method for extracting plant source spiny dogfish ene compositions, the method includes：The raw material that will be enriched in squalene carries out urea clathrate and molecular distillation successively, wherein, the condition of the molecular distillation is controlled so that the squalene containing 35-80 weight %, the sterol of squalene and 10-40 weight % containing 5-30 weight % in the raw material rich in squalene in the plant source spiny dogfish ene compositions for obtaining.
Preferably, the condition of the molecular distillation is controlled to cause the squalene containing 40-70 weight % in the plant source spiny dogfish ene compositions for obtaining.
Under preferable case, the sterol of squalene and 10-40 weight % containing 10-30 weight % in the raw material rich in squalene.
Further contain the sterol of 0.5-10 weight % in the plant source spiny dogfish ene compositions；It is further preferred that further containing the sterol of 0.5-5 weight % in the plant source spiny dogfish ene compositions.
Sterol of the present invention is at least one in phytosterol, including stigmasterol, campesterol and brassicasterol.
Other a small amount of hydro carbons, alcohols and Ester etc. can also be contained in the raw material rich in squalene of the present invention.
In the present invention, the raw material rich in squalene can be the various conventional raw materials for meeting above-mentioned composition.In a preferred embodiment, the raw material rich in squalene can be obtained by the technique for comprising the following steps：
(1) plant oil deodorizing distillate is carried out into esterification and transesterification successively, and the product that will be obtained carries out the first Crystallization Separation, obtains the first solid phase and first liquid phase；
(2) gained first liquid is mutually carried out into the first molecular distillation, obtains the cut rich in vitamin E and squalene；And
(3) the resulting cut rich in vitamin E and squalene is carried out into the first chromatographic isolation and evaporation successively, obtains the vitamin E and the raw material rich in squalene of high-purity.
In the present invention, it is preferred to the plant oil deodorizing distillate is the accessory substance that vegetable oil is produced during refining and deodorizing.
In the present invention, it is preferred to the squalene of the aliphatic acid, the glyceride of 10-30 weight %, the vitamin E of 0.5-20 weight %, the phytosterol of 0.5-20 weight %, the phytosterin ester of 0.5-20 weight % and 0.5-30 weight % containing 10-80 weight % in the plant oil deodorizing distillate.
In the present invention, in order to obtain the raw material rich in squalene, can be obtained using the method described in the patent application of Publication No. CN105016956A.The present invention will not be repeated here.
Preferably, the step of urea clathrate includes：
1) urea-ethanol solution is prepared, in the urea-ethanol solution, relative to every g urea, the content of the ethanol is 2-10mL, then to the raw material rich in squalene of addition in the urea-ethanol solution, and relative to every g urea, the consumption of the raw material rich in squalene is 0.2-1g, and it is heated to reflux 0.5-10h and is included；
2) by step 1) product that obtains is cooled to room temperature, and crystallisation by cooling and filtering are carried out successively at being subsequently placed in subzero 20 DEG C to 15 DEG C above freezing；
3) collection step 2) filtering after organic phase and concentrated.
Preferably, in step 1) in, relative to every g urea, the content of the ethanol is 2-5mL.Preferably, relative to every g urea, the consumption of the raw material rich in squalene is 0.4-0.7g.
Preferably, in step 2) in, the time of the crystallisation by cooling is 1-48h.
Preferably, in step 3) in, the filter residue of gained after filtering is washed with organic solvent.The organic solvent for example can be at least one in n-hexane, methyl alcohol and petroleum ether.
The method of the present invention also includes step 3) in the organic phase that obtains washed with such as 5 weight % sodium chloride solutions and water successively, then regather organic phase and concentrated.
Preferably, the method for the present invention is further included：Before the molecular distillation is carried out, urea clathrate step is repeated 1-4 times.That is, the method for the present invention includes first carrying out 2-5 molecular distillation, the product of gained after last time molecular distillation is then carried out into molecular distillation.
To the method for the concentration, there is no particular limitation, for example, can be the methods such as rotary evaporation.
Preferably, the step of molecular distillation is carried out using three-level molecular distillation.
Wherein, the condition of the first order molecular distillation in the three-level molecular distillation includes：Pressure is 5-25Pa, and temperature is 120-140 DEG C, and knifing rotating speed is 200-300rpm；The condition of second level molecular distillation includes：Pressure is 5-25Pa, and temperature is 110-125 DEG C, and knifing rotating speed is 200-300rpm；The condition of third level molecular distillation includes：Pressure is 5-25Pa, and temperature is 100-115 DEG C, and knifing rotating speed is 200-300rpm.The inventors found that, control the temperature of the third level molecular distillation lower 5-10 DEG C than the temperature of the second level molecular distillation, and when controlling the temperature of the temperature of the third level molecular distillation and the second level molecular distillation in above range of the invention, enable to the antioxidant effect of plant source spiny dogfish ene compositions for obtaining more excellent.
Second aspect, the invention provides a kind of preparation method of the medicine containing squalene, the method includes：
(1) plant source spiny dogfish ene compositions are extracted：Plant source spiny dogfish ene compositions are extracted using the foregoing method of the present invention；
(2) medicine is prepared：The pharmacy activity component of the plant source spiny dogfish ene compositions obtained containing step (1) is mixed with pharmaceutic adjuvant.
In the second aspect of the present invention, about the method for extracting plant source spiny dogfish ene compositions as described in aforementioned first aspect of the invention, in order to avoid repeating, the present invention will not be repeated here.
Preferably, in step (1), the sterol of 0.5-10 weight % is further contained in the plant source spiny dogfish ene compositions；It is further preferred that further containing the sterol of 0.5-5 weight % in the plant source spiny dogfish ene compositions.
The plant source spiny dogfish ene compositions that step (1) of the present invention obtains just directly can be mixed to prepare medicine on the premise of it need not further purify with pharmaceutic adjuvant.This greatlys save production cost, the reservation of other active components being also beneficial in the raw material rich in squalene of the invention.
Pharmaceutic adjuvant of the present invention can be conventional use of various pharmaceutic adjuvants in the art, such as glycerine, gelatin etc..Preferably, in the preparation method of the medicine containing squalene of the present invention, those skilled in the art can determine the usage ratio of the pharmacy activity component and pharmaceutic adjuvant according to the conventional amount used of this area, such as described pharmacy activity component can be 1 with the consumption weight ratio of pharmaceutic adjuvant：0.1-1000.
The third aspect, the invention provides the medicine containing squalene prepared by preceding method.
Fourth aspect, the invention provides application of the foregoing medicine containing squalene in for strengthen immunity, anti-oxidant and reduction blood fat density product.
Below will the present invention will be described in detail by embodiment.
In case of no particular description, various raw materials used below are all from commercially available.
Water used below is the homemade deionized water in laboratory.
The percentage composition of the pure material gross weight that the rate of recovery (%) in the present invention is accounted in raw material according to the weight of finally obtained pure material is calculated.
Following squalene is analyzed by HPLC, and analysis condition is that, using XunionC18 posts (5um, 4.6mm × 150mm), mobile phase volume ratio is acetonitrile：Methyl alcohol=60：40, flow velocity is 2mL/min, detection UV absorption at 210nm, and it is 25 DEG C to control column temperature.
Sterol is measured using GC, and analysis condition is that split ratio is 39：1, nitrogen flow is 40mL/min, and injection port and detector (fid detector) temperature are 300 DEG C.Using temperature programming, initial temperature is 210 DEG C, and 275 DEG C are risen to 10 DEG C/min, retains 25min.
Preparation example 1 is used to illustrate the source of the raw material rich in squalene of the invention.
Embodiment 1-6 is used for the method for illustrating extraction plant source spiny dogfish ene compositions of the invention.
Test case 1 is used to illustrate the application of the composition containing squalene of the invention.
Preparation example 1
(composition and relevant parameter are as shown in table 1 to take 1000g rapeseed oil deodorized distillates, remaining is impurity), add the 35g concentrated sulfuric acids and 300g methyl alcohol carries out esterification at 70 DEG C, esterification reaction product wash and dehydration by evaporation is to below the weight % of moisture 0.4, be subsequently adding 40g sodium methoxides and 300g methyl alcohol carries out transesterification at a temperature of 70 DEG C, and transesterification product then is carried out into the first Crystallization Separation.15 DEG C are cooled to the rate of temperature fall of 8 DEG C/h in the first Crystallization Separation step, this temperature growing the grain is maintained 10 hours, first time separation of solid and liquid is then carried out；The liquid that first time separation of solid and liquid is obtained carries out the second cooling, and rate of temperature fall is 4 DEG C/h, is cooled to 5 DEG C, maintains this temperature growing the grain 10 hours, carries out second separation of solid and liquid.Separation of solid and liquid gained solid (i.e. thick phytosterol solid) obtains the phytosterol 118.14g that purity is 94.8 weight %, the rate of recovery 71.79% after ethanol cleaning, recrystallization, drying twice.
Second separation of solid and liquid gained filtrate carries out the first molecular distillation, and the wherein pressure of first order molecular distillation is 15Pa, and temperature is 120 DEG C, and knifing rotating speed is 280rpm；The pressure of second level molecular distillation is 20Pa, and vapo(u)rizing temperature is 160 DEG C, and knifing rotating speed is 280rpm；The pressure of third level molecular distillation is 15Pa, and vapo(u)rizing temperature is 200 DEG C, and knifing rotating speed is 280rpm；
First order molecular distillation and second level molecular distillation light phase cut are collected, fatty acid ester about 750g is obtained；
Collect third level molecular distillation gained light phase cut and carry out the first chromatographic isolation, filler uses anion exchange resin, and mobile phase uses absolute ethyl alcohol, is rinsed with mobile phase after loading, collects unadsorbed material, that is, obtain the raw material rich in squalene.
The composition and content of the resulting raw material rich in squalene are respectively the weight % of squalene 15, the weight % of sterol 28.
Desorbed toward pouring carbon dioxide in chromatographic column again, rinsed with mobile phase, collect to desorb and be mutually the liquid phase rich in vitamin E, the liquid phase that vitamin E will be obtained being enriched with is concentrated, refined again, obtain the vitamin E product 43.19g that purity is 90.3 weight %, the rate of recovery 90.70%.
Table 1
| Component | Content (weight %) |
| Aliphatic acid and glyceride | 77.01 |
| Content of phytosterol | 15.60 |
| Content of vitamin E | 4.30 |
| Squalene content | 2.01 |
Embodiment 1
Extract plant source spiny dogfish ene compositions：
Urea clathrate：1) (liquid ratio is 4 to preparation urea-ethanol solution：1 (mL/g)), then to added in the urea-ethanol solution 20g preparation examples 1 obtain described in the raw material rich in squalene, the consumption of wherein urea-ethanol solution causes that urea is 1 with the weight ratio of the raw material rich in squalene：0.7, and it is heated to reflux 1h；
2) by step 1) product that obtains is cooled to room temperature, and crystallisation by cooling clathration is carried out under conditions of being subsequently placed in 0 DEG C, and standing time is 48h, is then filtered；
3) crystallization filtered is washed using n-hexane, collects the organic phase obtained after washing and merge and concentrated with foregoing filtrate；
4) by step 3) the concentrate repeat step 2 that obtains) and step 3) once, obtain grease.
Molecular distillation：The grease that will be obtained after urea clathrate carries out molecular distillation, is purified by three-level molecular distillation and obtains spiny dogfish ene compositions, wherein,
The pressure of first order molecular distillation is 10Pa, and temperature is 125 DEG C, and knifing rotating speed is 250rpm；
The pressure of second level molecular distillation is 10Pa, and temperature is 115 DEG C, and knifing rotating speed is 250rpm；
The pressure of third level molecular distillation is 10Pa, and temperature is 108 DEG C, and knifing rotating speed is 250rpm.
As a result, the content of squalene is 62.31% in third level molecular distillation gained light phase, and the content of sterol is 2.31 weight %.
Embodiment 2
Extract plant source spiny dogfish ene compositions：
Urea clathrate：1) (liquid ratio is 3 to preparation urea-ethanol solution：1 (mL/g)), then to added in the urea-ethanol solution 20g preparation examples 1 obtain described in the raw material rich in squalene, the consumption of wherein urea-ethanol solution causes that urea is 1 with the weight ratio of the raw material rich in squalene：0.5, and it is heated to reflux 3h；
2) by step 1) product that obtains is cooled to room temperature, and crystallisation by cooling clathration is carried out under conditions of being subsequently placed in -5 DEG C, and standing time is 35h, is then filtered；
3) crystallization filtered is washed using n-hexane, collects the organic phase obtained after washing and merge and concentrated with foregoing filtrate, obtain grease.
Molecular distillation：The grease that will be obtained after urea clathrate carries out molecular distillation, is purified by three-level molecular distillation and obtains spiny dogfish ene compositions, wherein,
The pressure of first order molecular distillation is 10Pa, and temperature is 125 DEG C, and knifing rotating speed is 260rpm；
The pressure of second level molecular distillation is 12Pa, and temperature is 118 DEG C, and knifing rotating speed is 260rpm；
The pressure of third level molecular distillation is 10Pa, and temperature is 108 DEG C, and knifing rotating speed is 250rpm.
As a result, the content of squalene is 52.89% in third level molecular distillation gained light phase, and the content of sterol is 1.34 weight %.
Embodiment 3
Extract plant source spiny dogfish ene compositions：
Urea clathrate：1) (liquid ratio is 4 to preparation urea-ethanol solution：1 (mL/g)), then to added in the urea-ethanol solution 20g preparation examples 1 obtain described in the raw material rich in squalene, the consumption of wherein urea-ethanol solution causes that urea is 1 with the weight ratio of the raw material rich in squalene：0.6, and it is heated to reflux 2h；
2) by step 1) product that obtains is cooled to room temperature, and crystallisation by cooling clathration is carried out under conditions of being subsequently placed in -5 DEG C, and standing time is 24h, is then filtered；
3) crystallization filtered is washed using n-hexane, collects the organic phase obtained after washing and merge and concentrated with foregoing filtrate, obtain grease.
Molecular distillation：The grease that will be obtained after urea clathrate carries out molecular distillation, is purified by three-level molecular distillation and obtains spiny dogfish ene compositions, wherein,
The pressure of first order molecular distillation is 12Pa, and temperature is 125 DEG C, and knifing rotating speed is 260rpm；
The pressure of second level molecular distillation is 12Pa, and temperature is 115 DEG C, and knifing rotating speed is 260rpm；
The pressure of third level molecular distillation is 12Pa, and temperature is 110 DEG C, and knifing rotating speed is 260rpm.
As a result, the content of squalene is 51.16% in third level molecular distillation gained light phase, and the content of sterol is 1.35 weight %.
Embodiment 4
The present embodiment is carried out using method similar to Example 2, except that, the temperature of second level molecular distillation is 120 DEG C in the present embodiment.
Remaining is in the same manner as in Example 2.
As a result the content of squalene is 51.56 weight % in third level molecular distillation gained light phase, and the content of sterol is 1.35 weight %.
Embodiment 5
The present embodiment is carried out using method similar to Example 2, except that, the temperature of second level molecular distillation is 110 DEG C in the present embodiment.
Remaining is in the same manner as in Example 2.
As a result the content of squalene is 50.89 weight % in third level molecular distillation gained light phase, and the content of sterol is 1.34 weight %.
Embodiment 6
The present embodiment is carried out using method similar to Example 2, except that, the temperature of second level molecular distillation is 108 DEG C in the present embodiment, and the temperature of third level molecular distillation is 98 DEG C.
Remaining is in the same manner as in Example 2.
As a result the content of squalene is 50.12 weight % in third level molecular distillation gained light phase, and the content of sterol is 1.31 weight %.
Test case 1
The antioxidation of the composition containing squalene prepared using following methods test embodiments of the invention.
Prepare micella dispersion liquid：Quantitative linoleic acid is dissolved in a small amount of chloroform, chloroform is dried up with argon gas again, make linoleic acid that thin film is formed in bottle wall, 10min is vacuumized to remove the chloroform of possible remaining, it is subsequently adding the 50mmol phosphate buffers containing surfactant (pH value is 7.0), add the EDTA of 0.1mmol to be complexed trace metal impurities that may be present in buffer solution, the mixture solution vibrates 5min in CQ250 type ultrasonic oscillators and forms transparent micella dispersion liquid.
Oxygen absorption is determined with SP-2 type oxygen absorptions instrument, and the current potential of oxygen electrode is recorded with YEW3066 types electron potentiometer, and sensitivity is 5 microvolts, and the device can measure 10-8The oxygen of mol/L, during measure, the above-mentioned micella dispersion liquid for preparing of the invention is placed in the reactor with electromagnetic agitation, it is closed, lucifuge, 37 DEG C of constant temperature, oxygen content is determined with oxygen electrode, then AAPH initiators (18mmol/L) is added to trigger linoleic peroxidating, or the composition (10 μm of ol/L) containing squalene that addition initiator (18mmol/L) and above-described embodiment are prepared simultaneously with injector, continuous record oxygen content changes with time, result is as shown in fig. 1, wherein, in Fig. 1
A is represented not to addition initiator in the micella dispersion liquid and/or the situation of the composition containing squalene；
B is represented to the situation that initiator is added in the micella dispersion liquid；
C represents the situation to the composition containing squalene that initiator and embodiment 1 are added in the micella dispersion liquid；
D represents the situation to the composition containing squalene that initiator and embodiment 2 are added in the micella dispersion liquid；
E represents the situation to the composition containing squalene that initiator and embodiment 3 are added in the micella dispersion liquid；
F represents the situation to the composition containing squalene that initiator and embodiment 4 are added in the micella dispersion liquid；
G represents the situation to the composition containing squalene that initiator and embodiment 5 are added in the micella dispersion liquid；
H represents the situation to the composition containing squalene that initiator and embodiment 6 are added in the micella dispersion liquid；
I represents the situation to the squalene for adding initiator and the embodiment 1 in CN105016956A to prepare in the micella dispersion liquid.
It can be seen that the antioxidation of the composition containing squalene of present invention offer is substantially better than the antioxidant effect of the squalene of the high-purity of prior art offer.
The preferred embodiment of the present invention described in detail above; but, the present invention is not limited to the detail in above-mentioned implementation method, in range of the technology design of the invention; various simple variants can be carried out to technical scheme, these simple variants belong to protection scope of the present invention.
It is further to note that, each particular technique feature described in above-mentioned specific embodiment, in the case of reconcilable, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention is no longer separately illustrated to various possible combinations.
Additionally, can also be combined between a variety of implementation methods of the invention, as long as it is without prejudice to thought of the invention, it should equally be considered as content disclosed in this invention.
Claims (10)
1. a kind of method for extracting plant source spiny dogfish ene compositions, the method includes：Will be enriched in squalene
Raw material carry out urea clathrate and molecular distillation successively, wherein, control the condition of the molecular distillation to cause
Squalene containing 35-80 weight % in the plant source spiny dogfish ene compositions for obtaining, it is described rich in squalene
Raw material in the squalene containing 5-30 weight % and 10-40 weight % sterol.
2. method according to claim 1, wherein, control the condition of the molecular distillation to cause
Squalene containing 40-70 weight % in the plant source spiny dogfish ene compositions for obtaining.
3. method according to claim 1, wherein, the raw material rich in squalene is by bag
The technique for including following steps is obtained：
(1) plant oil deodorizing distillate is carried out into esterification and transesterification successively, and will be obtained
Product carry out the first Crystallization Separation, obtain the first solid phase and first liquid phase；
(2) gained first liquid is mutually carried out into the first molecular distillation, is obtained rich in vitamin E and spiny dogfish
The cut of alkene；And
(3) the resulting cut rich in vitamin E and squalene is carried out into the first chromatographic isolation successively
And evaporation, respectively obtain the vitamin E and the raw material rich in squalene of high-purity.
4. method according to claim 1, wherein, include the step of the urea clathrate：
1) urea-ethanol solution is prepared, in the urea-ethanol solution, relative to every g urea, institute
The content of ethanol is stated for 2-10mL, it is then described rich in squalene to adding in the urea-ethanol solution
Raw material, and relative to every g urea, the consumption of the raw material rich in squalene is 0.2-1g, and is heated
Backflow 0.5-10h is included；
2) by step 1) product that obtains is cooled to room temperature, is subsequently placed in subzero 20 DEG C to 15 DEG C above freezing
Under carry out crystallisation by cooling and filtering successively；
3) collection step 2) filtering after organic phase and concentrated.
5. method according to claim 1, wherein, the method is further included：Described in carrying out
Before molecular distillation, urea clathrate step is repeated 1-4 times.
6. the method according to any one in claim 1-5, wherein, the molecular distillation
Step is carried out using three-level molecular distillation；Preferably
The condition of the first order molecular distillation in the three-level molecular distillation includes：Pressure is 5-25Pa, temperature
It is 120-140 DEG C to spend, and knifing rotating speed is 200-300rpm；The condition of second level molecular distillation includes：Pressure
Power is 5-25Pa, and temperature is 110-125 DEG C, and knifing rotating speed is 200-300rpm；Third level molecular distillation
Condition include：Pressure is 5-25Pa, and temperature is 100-115 DEG C, and knifing rotating speed is 200-300rpm.
7. a kind of preparation method of the medicine containing squalene, the method includes：
(1) plant source spiny dogfish ene compositions are extracted：Using described in any one in claim 1-6
Method extracts plant source spiny dogfish ene compositions；
(2) medicine is prepared：The medicine of the plant source spiny dogfish ene compositions that will be obtained containing step (1)
Active component is learned to be mixed with pharmaceutic adjuvant.
8. method according to claim 7, wherein, in step (1), the plant source angle
Further contain the sterol of 0.5-10 weight % in MF59 composition；Preferably
Further contain the sterol of 0.5-5 weight % in the plant source spiny dogfish ene compositions.
9. the medicine containing squalene that the method as described in claim 7 or 8 is prepared.
10. the medicine containing squalene described in claim 9 is for strengthen immunity, anti-oxidant and drop
Application in the product of low blood fat density.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110283034A (en) * | 2019-07-12 | 2019-09-27 | 陕西海斯夫生物工程有限公司 | A method of obtaining high-purity squalene from plant oil deodorizing distillate |
| WO2019214410A1 (en) * | 2018-05-07 | 2019-11-14 | 宜春大海龟生命科学有限公司 | Plant squalene composition and preparation method therefor and application thereof, and product applying same |
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| CN103483305A (en) * | 2013-09-25 | 2014-01-01 | 潘见 | Method for gathering/recovering VE (Vitamins E), squalene and polyunsaturated fatty acids from deodorized distillate of plant oil |
| CN103571633A (en) * | 2013-11-15 | 2014-02-12 | 潘见 | Esterification-ultrahigh pressure crystallization separation method for distillate of vegetable oil |
| CN105016956A (en) * | 2014-04-23 | 2015-11-04 | 中粮营养健康研究院有限公司 | Squalene extracting method |
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| CN103483305A (en) * | 2013-09-25 | 2014-01-01 | 潘见 | Method for gathering/recovering VE (Vitamins E), squalene and polyunsaturated fatty acids from deodorized distillate of plant oil |
| CN103571633A (en) * | 2013-11-15 | 2014-02-12 | 潘见 | Esterification-ultrahigh pressure crystallization separation method for distillate of vegetable oil |
| CN105016956A (en) * | 2014-04-23 | 2015-11-04 | 中粮营养健康研究院有限公司 | Squalene extracting method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2019214410A1 (en) * | 2018-05-07 | 2019-11-14 | 宜春大海龟生命科学有限公司 | Plant squalene composition and preparation method therefor and application thereof, and product applying same |
| CN110283034A (en) * | 2019-07-12 | 2019-09-27 | 陕西海斯夫生物工程有限公司 | A method of obtaining high-purity squalene from plant oil deodorizing distillate |
| CN110283034B (en) * | 2019-07-12 | 2022-04-12 | 陕西海斯夫生物工程有限公司 | Method for obtaining high-purity squalene from vegetable oil deodorized distillate |
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