CN107254181A - The application of the supersonically preparation method and functional food of casein polysaccharide nanogel - Google Patents
The application of the supersonically preparation method and functional food of casein polysaccharide nanogel Download PDFInfo
- Publication number
- CN107254181A CN107254181A CN201710411552.5A CN201710411552A CN107254181A CN 107254181 A CN107254181 A CN 107254181A CN 201710411552 A CN201710411552 A CN 201710411552A CN 107254181 A CN107254181 A CN 107254181A
- Authority
- CN
- China
- Prior art keywords
- sodium
- sodium alginate
- casein
- frequency
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000005018 casein Substances 0.000 title claims abstract description 146
- 235000021240 caseins Nutrition 0.000 title claims abstract description 146
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 229920001282 polysaccharide Polymers 0.000 title abstract description 14
- 239000005017 polysaccharide Substances 0.000 title abstract description 14
- 235000013376 functional food Nutrition 0.000 title abstract description 7
- -1 casein polysaccharide Chemical class 0.000 title abstract description 3
- 239000000661 sodium alginate Substances 0.000 claims abstract description 137
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 137
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 claims abstract description 135
- 239000011734 sodium Substances 0.000 claims abstract description 96
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 91
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 90
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 88
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 87
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000011282 treatment Methods 0.000 claims abstract description 9
- OENHQHLEOONYIE-UKMVMLAPSA-N all-trans beta-carotene Natural products CC=1CCCC(C)(C)C=1/C=C/C(/C)=C/C=C/C(/C)=C/C=C/C=C(C)C=CC=C(C)C=CC1=C(C)CCCC1(C)C OENHQHLEOONYIE-UKMVMLAPSA-N 0.000 claims description 86
- 235000013734 beta-carotene Nutrition 0.000 claims description 86
- TUPZEYHYWIEDIH-WAIFQNFQSA-N beta-carotene Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1=C(C)CCCC1(C)C)C=CC=C(/C)C=CC2=CCCCC2(C)C TUPZEYHYWIEDIH-WAIFQNFQSA-N 0.000 claims description 86
- 239000011648 beta-carotene Substances 0.000 claims description 86
- 229960002747 betacarotene Drugs 0.000 claims description 86
- OENHQHLEOONYIE-JLTXGRSLSA-N β-Carotene Chemical compound CC=1CCCC(C)(C)C=1\C=C\C(\C)=C\C=C\C(\C)=C\C=C\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C OENHQHLEOONYIE-JLTXGRSLSA-N 0.000 claims description 86
- 239000000243 solution Substances 0.000 claims description 59
- 238000002604 ultrasonography Methods 0.000 claims description 43
- 238000012545 processing Methods 0.000 claims description 32
- 239000011259 mixed solution Substances 0.000 claims description 25
- 238000013019 agitation Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 230000033228 biological regulation Effects 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 238000005354 coacervation Methods 0.000 claims description 11
- 239000012153 distilled water Substances 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 230000001360 synchronised effect Effects 0.000 claims description 9
- 238000004108 freeze drying Methods 0.000 claims description 8
- 239000003814 drug Substances 0.000 claims description 7
- 238000011068 loading method Methods 0.000 claims description 6
- 238000001694 spray drying Methods 0.000 claims description 6
- 238000000527 sonication Methods 0.000 claims description 5
- 235000013402 health food Nutrition 0.000 claims description 3
- 229940071162 caseinate Drugs 0.000 claims 4
- 235000018102 proteins Nutrition 0.000 abstract description 12
- 102000004169 proteins and genes Human genes 0.000 abstract description 12
- 108090000623 proteins and genes Proteins 0.000 abstract description 12
- 230000000975 bioactive effect Effects 0.000 abstract description 10
- 239000004615 ingredient Substances 0.000 abstract description 10
- 230000002776 aggregation Effects 0.000 abstract description 9
- 238000004220 aggregation Methods 0.000 abstract description 9
- 238000005516 engineering process Methods 0.000 abstract description 9
- 150000004804 polysaccharides Polymers 0.000 abstract description 8
- 230000008859 change Effects 0.000 abstract description 5
- 230000002209 hydrophobic effect Effects 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 230000003993 interaction Effects 0.000 abstract description 4
- 150000004676 glycans Polymers 0.000 abstract description 3
- 239000003094 microcapsule Substances 0.000 abstract 1
- 102000011632 Caseins Human genes 0.000 description 105
- 108010076119 Caseins Proteins 0.000 description 105
- 239000000499 gel Substances 0.000 description 46
- 238000000034 method Methods 0.000 description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 235000013305 food Nutrition 0.000 description 10
- 239000007788 liquid Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000000523 sample Substances 0.000 description 7
- 241000220259 Raphanus Species 0.000 description 5
- 235000006140 Raphanus sativus var sativus Nutrition 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 230000001804 emulsifying effect Effects 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000001338 self-assembly Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 238000002525 ultrasonication Methods 0.000 description 3
- 102000014171 Milk Proteins Human genes 0.000 description 2
- 108010011756 Milk Proteins Proteins 0.000 description 2
- 238000003287 bathing Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 210000000481 breast Anatomy 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 235000020247 cow milk Nutrition 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 230000010148 water-pollination Effects 0.000 description 2
- AEMOLEFTQBMNLQ-SYJWYVCOSA-N (2s,3s,4s,5s,6r)-3,4,5,6-tetrahydroxyoxane-2-carboxylic acid Chemical compound O[C@@H]1O[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@@H]1O AEMOLEFTQBMNLQ-SYJWYVCOSA-N 0.000 description 1
- 208000017667 Chronic Disease Diseases 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 102000004407 Lactalbumin Human genes 0.000 description 1
- 108090000942 Lactalbumin Proteins 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 108010073771 Soybean Proteins Proteins 0.000 description 1
- 229960001126 alginic acid Drugs 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 150000004781 alginic acids Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SWEYNHYBJHPVJL-UHFFFAOYSA-N butanoic acid;sodium Chemical compound [Na].CCCC(O)=O SWEYNHYBJHPVJL-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000014156 coffee whiteners Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 235000013601 eggs Nutrition 0.000 description 1
- 239000005712 elicitor Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 235000015243 ice cream Nutrition 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 230000000050 nutritive effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035790 physiological processes and functions Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 239000006041 probiotic Substances 0.000 description 1
- 235000018291 probiotics Nutrition 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 235000019710 soybean protein Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- 235000021247 β-casein Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L89/00—Compositions of proteins; Compositions of derivatives thereof
- C08L89/005—Casein
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
- A23L29/03—Organic compounds
- A23L29/045—Organic compounds containing nitrogen as heteroatom
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
- A23L29/30—Foods or foodstuffs containing additives; Preparation or treatment thereof containing carbohydrate syrups; containing sugars; containing sugar alcohols, e.g. xylitol; containing starch hydrolysates, e.g. dextrin
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
- A23L33/10—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
- A23L33/105—Plant extracts, their artificial duplicates or their derivatives
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L5/00—Preparation or treatment of foods or foodstuffs, in general; Food or foodstuffs obtained thereby; Materials therefor
- A23L5/30—Physical treatment, e.g. electrical or magnetic means, wave energy or irradiation
- A23L5/32—Physical treatment, e.g. electrical or magnetic means, wave energy or irradiation using phonon wave energy, e.g. sound or ultrasonic waves
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23P—SHAPING OR WORKING OF FOODSTUFFS, NOT FULLY COVERED BY A SINGLE OTHER SUBCLASS
- A23P10/00—Shaping or working of foodstuffs characterised by the products
- A23P10/30—Encapsulation of particles, e.g. foodstuff additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
- C08L5/04—Alginic acid; Derivatives thereof
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/04—Alginic acid; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2389/00—Characterised by the use of proteins; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/04—Alginic acid; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2489/00—Characterised by the use of proteins; Derivatives thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Food Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nutrition Science (AREA)
- Botany (AREA)
- Mycology (AREA)
- Molecular Biology (AREA)
- Jellies, Jams, And Syrups (AREA)
- Coloring Foods And Improving Nutritive Qualities (AREA)
Abstract
The invention discloses the application of the supersonically preparation method and functional food of casein polysaccharide nanogel, it is related to functional food microcapsules technology field.It is to be prepared from by the raw material of following parts by weight：Casein sodium：2~40 parts；Sodium alginate：2.5~25 parts.The present invention adds sodium alginate into casein sodium, change the higher structure of casein sodium, open its structure, exposure active group, protein and polysaccharide form small aggregation simultaneously, so as to promote each aggregation to provide basis by hydrophobic interaction formation gel for embedding bioactive ingredients.The present invention is during using casein sodium sodium alginate plural gel embedding bata-carotene, use frequency sweep ultrasonic ripple treatment technology or multi-mode ultrasonic technology, protein is promoted by the physical force of ultrasonic wave and polysaccharide is cross-linked into aggregation, so as to promote each aggregation by hydrophobic interaction formation gel, basis is provided for embedding bioactive ingredients.
Description
Technical field
The present invention relates to protein-polysaccharide nanogel technical field, one kind is refered in particular to casein sodium and sodium alginate
Nano gel system is prepared for raw material, using frequency sweep ultrasonic processing or multi-mode frequency ultrasound wave technology and to beta carotene
Carry out the method that embedding prepares functional food.
Background technology
Functional food because containing the bioactive ingredients such as vitamin, unrighted acid, polyphenol compound or probiotics,
Function with regulation human physiological functions, can delay the generation with preventing chronic disease.However, many active components are to food
Product process and storage in the factor such as temperature, oxygen, light, pH and metal ion it is sensitive, it is prone to aoxidize, isomerization, aggregation
Or degraded etc. structural change, cause bioactivity reduce or lose.Moreover, hydrophobicity and amphipathic active component dissolve in water
Degree is very low.These greatly limit application of the active component in food and medicine industry.Natural biology is big
Molecule (such as protein, polysaccharide) not only has high nutritive value, and with a variety of functional characteristics, has been widely used as bag
Bury the raw material in technology.Therefore, the gel rubber system of exploitation natural macromolecular (protein and polysaccharide) is carried out to bioactive ingredients
Embedding and protection, are the keys for developing functional food and medicine.
Casein accounts for the 80% of cow's milk protein total amount, is the main component of cow's milk protein.Casein contains needed by human
8 kinds of amino acid, be a kind of full price phosphor protein matter, mainly by αs1- casein, αs2- casein, beta-casein and K- junket eggs
White composition, mean molecule quantity is between 75000-350000, and isoelectric point is about 4.6.Casein sodium, also known as casein sodium,
Casein-sodium, butyric acid sodium or casein, are the compounds of casein and sodium.It is that casein and sodium hydroxide are heated to reflux system
It is standby, by the casein of water-insoluble into soluble protein salt, that is, form casein sodium.Casein sodium has thickening
Many characteristics such as property, emulsibility, foaming characteristic, heat endurance and interfacial characteristics, are a kind of safe and harmless thickener and emulsification
Agent, therefore widely it is used as the emulsion stabilizer of food (such as ice cream, coffee whitener, whipped toppings).
There is hydrophilic radical and hydrophobic grouping in caseinic acid sodium molecule, thus with certain emulsibility.Can be by certain
Environmental condition influenceed, such as pH change can significantly affect its emulsifiability, breast of the casein sodium in isoelectric point
Change power minimum, its emulsifying ability can increase during less than isoelectric point, and its emulsifying ability is larger in the basic conditions, and increase with pH and add
Greatly.It is worth it is specifically intended that because casein sodium is very heat-resisting, can be big when being heat-treated under the conditions of specific pH to it
It is big to improve emulsifying ability.Generally, the emulsifying agent being made using casein sodium, its stability is than the institute such as lactalbumin, soybean protein
The emulsifying agent of preparation is more preferable.
Sodium alginate (Sodium Alginate), alias sodium alginate, be alginic acid (by α-L- guluronic acids (G) and
Beta-D-mannuronic acid (M) is polymerized) sodium salt, be largely present in brown alga, the security with height, be nontoxic food
Product, American Pharmacopeia has just been incorporated into early in 1938.Sodium alginate is dissolved in after water, there is good gel characteristic and film forming ability,
There is extensive research in the industry such as medicine and food and apply.The aqueous solution of sodium alginate has higher viscosity, has been used as
Thickener, stabilizer, emulsifying agent of food etc..Sodium alginate contains substantial amounts of-COO-, can show in aqueous it is poly- cloudy from
Sub-line is that, with certain adhesion, can be used as treating the pharmaceutical carrier of mucous membrane tissue.In acid condition ,-COO- changes
Into-COOH, degree of ionization reduction, the hydrophily reduction of sodium alginate, strand shrinks, and during pH value increase ,-COOH group is constantly
Dissociation, the hydrophily increase of sodium alginate, molecule chain-unfolding.Therefore, sodium alginate has obvious pH sensitiveness.Sodium alginate
Quick under conditions of extremely gentle gel can be formed, when there is Ca2+、Sr2+In the presence of cation, the Na on G units+With two
Ion-exchange reactions occurs for valency cation, and G units are accumulated to form cross-linked network structure, so as to form hydrogel.Sodium alginate shape
Into the mild condition of gel, this can be avoided the inactivation of sensitive drug, protein, cell and enzyme isoreactivity material.
Research finds that the interphase interaction formation plural gel of protein and polysaccharide can overcome one-component pH sensitive, steady
Bioactive ingredients are played embedding and protective effect well by the low deficiency of qualitative poor, embedding efficiency.Therefore domestic and foreign scholars
The substantial amounts of preparation method about protein-polysaccharide plural gel and its research embedded to bioactive ingredients are carried out.Breast
Change method is the common method for preparing plural gel, and the deficiency of this method, which is shown, needs addition organic in the preparation process of plural gel
Solvent, surfactant, glutaraldehyde cross-linking agent etc., the residual of these reagents make plural gel have certain toxicity；Remove solvent method
The introducing of toxic cross-linking agents is directed to chemical crosslink technique；Three of the above method is not the Perfected process for preparing plural gel.From
Sub- cross-linking method and self-assembly method prepare plural gel, mild condition, it is not necessary to poisonous crosslinking agent, and chemical combination key is not generated, only according to
By non-covalent bond connection, thus it is widely used.Particularly self-assembly method, for nutrient delivery system design, security
Deng relatively more preferably.But protein and polysaccharide are two kinds of macromoleculars of different nature after all, are entered only by simple self-assembly method
Row cohesion, flocculating result is poor, and condensation product is low to the embedding efficiency of bioactive ingredients.
In order to solve this problem, the present invention introduces advanced frequency sweep type ultrasonic processing and multi-mode ultrasonication skill
Art, it is desirable to which two kinds of biological macromolecule solns of ultrasonic wave energy elicitor protein matter and polysaccharide produce what is matched with its own intrinsic frequency
Resonant frequency, produces crosslinking, obtains a kind of high embedding efficiency, pH stabilizations, the protein-polysaccharide plural gel of uniform particle diameter,
Bioactive ingredients are embedded and protected using the protein-polysaccharide plural gel of gained.
The content of the invention
To solve the above problems, the present invention is by carrying out complex coacervation, addition β-Hu Luo to casein sodium-sodium alginate
Bu Su, prepares casein sodium-sodium alginate multiple using technological means such as frequency sweep type ultrasonic processing and multi-mode ultrasonications
Gel is closed, and studies its embedding effect to beta carotene.
Casein sodium of the present invention-sodium alginate plural gel, is prepared from by the raw material of following parts by weight：
Casein sodium：2~40 parts；
Sodium alginate：2.5~25 parts.
It is preferred that the raw material of following parts by weight is prepared from：
Casein sodium：10 parts；
Sodium alginate：4 parts.
The preparation method of casein sodium-sodium alginate plural gel, is carried out as steps described below：
(1) casein sodium is dissolved into distilled water, magnetic agitation to albumen is completely dissolved；Obtain casein sodium dense
Spend for (2-40) mg/mL solution；
(2) sodium alginate is dissolved into the aqueous solution, magnetic agitation is to being completely dissolved；Concentration is obtained for (2.5-25) mg/
ML sodium alginate solns；
(3) it is 1 by volume by step (2) sodium alginate soln:1 ratio is added dropwise to step (1) casein sodium
In solution so that the mass ratio of casein sodium and sodium alginate is：(2~40)：(2.5~25), then regulation mixing is molten
The pH=4-7 of liquid.
(4) mixed solution for obtaining step (3) carries out the processing of double frequency frequency sweep ultrasonic ripple, and ultrasound condition is：Between upper and lower plates
Away from for 10cm, frequency sweep cycle 300s, intermittently than 1:1 (ultrasonic 5s, interval 5s), every piece of vibration plate power is 600W up and down.
(5) after ultrasound terminates, 1h is stood at room temperature, casein sodium-sodium alginate plural gel solution is produced, and spraying is dry
Casein sodium-sodium alginate complex coacervation thing is obtained after dry or freeze-drying.
The pH=5 of preferred regulation mixed solution wherein in step (3).
The mass ratio of casein sodium and sodium alginate wherein described in step (3) is preferably 10：4.
Double frequency combination of frequency wherein described in step (4) is：40kHz/68kHz、28kHz/40kHz、68kHz/
28kHz、33kHz/40kHz；Optimized frequency is combined as 40kHz/68kHz.
Casein sodium-sodium alginate plural gel loads the preparation method of beta carotene, carries out as steps described below：
(1) casein sodium is dissolved into distilled water, magnetic agitation to albumen is completely dissolved；Obtain casein sodium dense
Spend for (2-40) mg/mL solution；
(2) sodium alginate is dissolved into the aqueous solution, magnetic agitation is to being completely dissolved；Concentration is obtained for (2.5-25) mg/
ML sodium alginate solns；
(3) it is 1 by volume by step (2) sodium alginate soln:1 ratio is added dropwise to step (1) casein sodium
In solution so that the mass ratio of casein sodium and sodium alginate is：(2~40)：(2.5~25), then regulation mixing is molten
The pH=4-7 of liquid.
(4) concentration is added dropwise to the casein of step (3) preparation for the ethanol solution of (1-5) mg/mL beta carotene
In sour sodium and sodium alginate plural gel solution so that the mass ratio of casein sodium and beta carotene is 1：0.5；
(5) mixed solution at room temperature obtaining step (4) carries out the processing of double frequency frequency sweep ultrasonic ripple, and ultrasound condition is：On
Lower plate spacing is 10cm, frequency sweep cycle 300s, intermittently than 1:1 (ultrasonic 5s, interval 5s), every piece of vibration plate power is 600W up and down；
(6) after ultrasound terminates, casein sodium-sodium alginate plural gel solution of load beta carotene, spraying are produced
Dry or obtain loading after being freeze-dried casein sodium-sodium alginate complex coacervation thing of beta carotene.
The pH=5 of preferred regulation mixed solution wherein in step (3).
The mass ratio for causing casein sodium and sodium alginate wherein described in step (3) is preferably 10：4.
Double frequency combination of frequency wherein described in step (5) is：40kHz/68kHz、28kHz/40kHz、68kHz/
28kHz、33kHz/40kHz；Optimized frequency is combined as 40kHz/68kHz.
The preparation method of casein sodium-sodium alginate plural gel, or carry out as steps described below：
(1) casein sodium is dissolved into distilled water, magnetic agitation to albumen is completely dissolved；Obtain casein sodium dense
Spend for (2-40) mg/mL solution；
(2) sodium alginate is dissolved into the aqueous solution, magnetic agitation is to being completely dissolved；Concentration is obtained for (2.5-25) mg/
ML sodium alginate solns；
(3) it is 1 by volume by step (2) sodium alginate soln:1 ratio is added dropwise to step (1) casein sodium
In solution so that the mass ratio of casein sodium and sodium alginate is：(2~40)：(2.5~25), then regulation mixing is molten
The pH=4-7 of liquid.
(4) multifrequency mode ultrasound processing is carried out to the mixed solution of step (3), wherein described multiple frequency ultrasonic tupe
For：Three frequency synchronizing ultrasounds are handled or double-frequency synchronous is ultrasonically treated or single-frequency is ultrasonically treated, and ultrasonic power density 100~
150W/L；Ultrasonic pulse working time 10s；Interpulse period 5s, sonication treatment time is 40min.
(5) after ultrasound terminates, 1h is stood at room temperature, casein sodium-sodium alginate plural gel solution is produced, and spraying is dry
Casein sodium-sodium alginate complex coacervation thing is obtained after dry or freeze-drying.
The pH=5 of preferred regulation mixed solution wherein in step (3).
Wherein the mass ratio of casein sodium and sodium alginate is preferably 10 in step (3)：4.
Three frequency synchronizing ultrasounds processing or that double-frequency synchronous is ultrasonically treated or single-frequency is ultrasonically treated is super wherein in step (4)
Frequency of sound wave is combined as：28kHz, 35kHz, 35/40kHz or 28/35/40kHz, preferably 28/35/40kHz.
Casein sodium-sodium alginate plural gel loads the preparation method of beta carotene, or enters as steps described below
OK：
(1) casein sodium is dissolved into distilled water, magnetic agitation to albumen is completely dissolved；Obtain casein sodium dense
Spend for (2-40) mg/mL solution；
(2) sodium alginate is dissolved into the aqueous solution, magnetic agitation is to being completely dissolved；Concentration is obtained for (2.5-25) mg/
ML sodium alginate solns；
(3) it is 1 by volume by step (2) sodium alginate soln:1 ratio is added dropwise to step (1) casein sodium
In solution so that the mass ratio of casein sodium and sodium alginate is：(2~40)：(2.5~25), then regulation mixing is molten
The pH=4-7 of liquid.
(4) concentration is added dropwise to the caseinic acid of step (3) preparation for (1-5) mg/mL beta carotene ethanol solution
In sodium and sodium alginate plural gel solution so that the mass ratio of casein sodium and beta carotene is 1：0.5；
(5) multifrequency mode ultrasound processing is carried out to the mixed solution of step (4), wherein described multiple frequency ultrasonic tupe
For：Three frequency synchronizing ultrasounds are handled or double-frequency synchronous is ultrasonically treated or single-frequency is ultrasonically treated, and ultrasonic power density 100~
150W/L；Ultrasonic pulse working time 10s；Interpulse period 5s, sonication treatment time is 40min.
(6) after ultrasound terminates, 1h is stood at room temperature, and the casein sodium-sodium alginate for producing load beta carotene is combined
Obtain loading casein sodium-sodium alginate complex coacervation of beta carotene after gel solution, spray drying or freeze-drying
Thing.
The pH=5 of preferred regulation mixed solution wherein in step (3).
Wherein the mass ratio of casein sodium and sodium alginate is preferably 10 in step (3)：4.
Three frequency synchronizing ultrasounds processing or that double-frequency synchronous is ultrasonically treated or single-frequency is ultrasonically treated is super wherein in step (5)
Frequency of sound wave is combined as：28kHz, 35kHz, 35/40kHz or 28/35/40kHz, preferably 28/35/40kHz.
Load casein sodium-sodium alginate plural gel of beta carotene, with stability is good, good biocompatibility,
Slow-release time length, the advantages of rate is high is contained, can be applied to make health food, food or medicine.
The beneficial effects of the present invention are：
(1) present invention adds sodium alginate into casein sodium, changes the higher structure of casein sodium, makes its structure
Open, exposure active group, while protein and polysaccharide form small aggregation, so that it is hydrophobic mutual to promote each aggregation to pass through
Effect forms gel and provides basis for embedding bioactive ingredients.
(2) present invention is used during using casein sodium-sodium alginate plural gel embedding beta carotene
Frequency sweep ultrasonic ripple treatment technology or multi-mode ultrasonic technology, promote protein by the physical force of ultrasonic wave and polysaccharide are handed over
Aggregation is unified into, so as to promote each aggregation by hydrophobic interaction formation gel, base is provided for embedding bioactive ingredients
Plinth.
(3) preparation method of casein sodium-sodium alginate plural gel of beta carotene, technique are embedded in the present invention
It is simple to operate, organic reagent, suitable industrialized production, and casein sodium and sodium alginate raw material valency are not directed in preparation process
Lattice are cheap, and preparation technology is simple.
(4) casein sodium-sodium alginate plural gel of embedding beta carotene of the invention has stability good, raw
Thing compatibility is good, slow-release time length, contain the advantages of rate is high, can be applied to multiple necks such as food, health products, medicine and cosmetics
Domain.
Brief description of the drawings
Fig. 1 is the multi-mode ultrasonic wave biological processing equipment structure chart of the present invention, wherein 1,2,3 be ultrasonic vibrating plate, 4 be Sheng
Liquid device, 5 be water-bath, and 6 be temp probe, and 7 be circulating pump, and 8 be Computerized controller, and 9,10,11 be ultrasonic controller.
Fig. 2 is the equipment drawing of frequency sweep double-frequency ultrasound pretreatment unit, 1- ultrasounds pond, 2- thermometers, 3- thermostatted water bathing pools, 4-
Vibration plate under vibration plate on ultrasonic wave, 5- ultrasonic waves, 6- sample treatments region, 7- computer controllers, 8- supersonic generators.
Embodiment
Used term, unless otherwise indicated, can typically be understood by those of ordinary skill in the art in the present invention.
The present invention is described in further detail with reference to specific embodiment, and with reference to data.Illustrate hereby：These embodiments are
In order to demonstrate the invention, rather than in any way the scope of the present invention is limited.
Fig. 1 is multi-mode ultrasonic wave biological processing equipment of the invention, and the equipment is furnished with a Computerized controller 8,
Ultrasound works parameter (ultrasonic power density, frequency, pulse working time, intermittent time and processing total time) can be set to control respectively
Three ultrasonic controllers 9,10,11 are made, the ultrasonic vibrating plate 1,2,3 of three different frequencies is connected respectively, single-frequency/two can be achieved
Individual frequency/tri- frequency ultrasonic wave processing；Solution input to be processed will be needed to contain single-frequency/double frequency/multiple frequency ultrasonic is carried out in liquid device 4
Processing, starts circulating pump 7 and solution is circulated.Automatically controlling for solution temperature is realized by water-bath 5 and temp probe 6.
The equipment drawing for the frequency sweep double-frequency ultrasound pretreatment unit that Fig. 2 uses for the present invention, is Jiangsu University's independent development.It is super
Acoustic generator 8 can send the ultrasonic wave for determining frequency and frequency sweep both of which, and separate unit supersonic generator power is 600W.In ultrasonic pond
Placement ultrasonic wave vibration plate upper plate 4 symmetrical above and below and ultrasonic wave lower plate 5, are controlled on ultrasonic wave vibration plate by supersonic generator 8 in 1
Plate 4 and ultrasonic wave lower plate 5；After the setting each parameter of ultrasonic wave of computer controller 7, supersonic generator 8 is controlled, sends and meets the requirements
Ultrasonic wave；3 be the thermostatted water bathing pool of equipment in the present invention, passes through the monitoring temperature, and being adjusted according to need of work in real time of thermometer 2
Save medium temperature；Need to liquid raw material to be processed be placed in sample sack to be placed in treatment fluid region 6 and carry out ultrasonication.
Casein sodium and sodium alginate in the present invention are commercially available prod, food grade products.
Beta carotene in the present invention is commercially available prod, and food grade products, purity is more than 90%.
Embodiment 1-6 (is not added with ultrasound)
Casein sodium-sodium alginate plural gel loads the preparation method of beta carotene, carries out as steps described below：
(1) casein sodium is dissolved into distilled water, magnetic agitation to albumen is completely dissolved；Obtain casein sodium dense
Spend for (2-40) mg/mL solution；
(2) sodium alginate is dissolved into the aqueous solution, magnetic agitation is to being completely dissolved；Concentration is obtained for (2.5-25) mg/
ML sodium alginate solns；
(3) it is 1 by volume by step (2) sodium alginate soln:1 ratio is added dropwise to step (1) casein sodium
In solution so that the mass ratio of casein sodium and sodium alginate is shown in Table 1, the pH=5 of mixed solution is then adjusted.
(4) by concentration for 2mg/mL beta carotene ethanol solution be added dropwise step (3) preparation casein sodium and
In sodium alginate plural gel solution so that the mass ratio of casein sodium and beta carotene is 1：0.5；
(5) 1h is stood at room temperature, produces casein sodium-sodium alginate plural gel solution of load beta carotene, spray
Mist is dried or obtains loading casein sodium-sodium alginate complex coacervation thing of beta carotene after being freeze-dried.
(6) measure of beta carotene envelop rate and load factor
Casein sodium-sodium alginate plural gel solution of load beta carotene is taken, using Rotary Evaporators at 40 DEG C
At a temperature of be concentrated into 40mL, take concentrate 1mL plus 5mL n-hexane, after mixing at 4 DEG C with 5000rpm centrifuge 10 minutes.Survey
It is the light absorption value at 450nm to determine n-hexane in wavelength, and calculates the free beta carotene (β-Hu for not embedding and loosely adsorbing
Radish element) quality.The envelop rate and load factor of beta carotene are calculated according to following formula：
The envelop rate (%) of the beta carotene=β of (beta carotene gross mass-free beta carotene quality) × 100/-Hu
Radish element gross mass；
The load factor (%) of the beta carotene=sample of (beta carotene gross mass-free beta carotene quality) × 100/
Gross mass.
Embodiment 1-6 preparation process is identical, and simply casein sodium/sodium alginate mass ratio is different, is specifically shown in Table 1 different
Influence of the casein sodium/sodium alginate of mass ratio to beta carotene envelop rate and load factor.
By comparative example 1-6 different qualities in table 1 than casein sodium/sodium alginate to beta carotene encapsulate
The influence of rate and load factor can be seen that (is not added with sodium alginate, i.e. embodiment 6) compared with the control, and addition sodium alginate can be with
Significantly improve the envelop rate that casein sodium embeds beta carotene；Casein sodium/sodium alginate mass ratio is 2:When 2.5
The envelop rate of beta carotene can be made to improve 46.1%, casein sodium/sodium alginate mass ratio is 10:Then make β-carrot when 4
The envelop rate of element improves 88.5%.
Different casein sodium/influences of the sodium alginate mass ratio to beta carotene envelop rate and load factor of table 1
Embodiment 7-10 (processing of frequency sweep dual-frequency ultrasonic wave)
Casein sodium：2 parts；
Sodium alginate：2.5 part.
Casein sodium-sodium alginate plural gel loads the preparation method of beta carotene, carries out as steps described below：
(1) casein sodium is dissolved into distilled water, magnetic agitation to albumen is completely dissolved；Obtain casein sodium dense
Spend for 2mg/mL solution；
(2) sodium alginate is dissolved into the aqueous solution, magnetic agitation is to being completely dissolved；Concentration is obtained for 2.5mg/mL marine algas
Acid sodium solution；
(3) it is 1 by volume by step (2) sodium alginate soln:1 ratio is added dropwise to step (1) casein sodium
In solution so that the mass ratio of casein sodium and sodium alginate is 2：2.5, then adjust the pH=5 of mixed solution.
(4) concentration is added dropwise to the casein of step (3) preparation for the ethanol solution of (1-5) mg/mL beta carotene
In sour sodium and sodium alginate plural gel solution so that the mass ratio of casein sodium and beta carotene is 1：0.5；
(5) mixed solution at room temperature obtaining step (4) carries out the processing of double frequency frequency sweep ultrasonic ripple, and ultrasound condition is：On
Lower plate spacing is 10cm, frequency sweep cycle 300s, intermittently than 1:1 (ultrasonic 5s, interval 5s), every piece of vibration plate power is 600W up and down；
Double frequency combination of frequency is shown in Table 1.
(6) after ultrasound terminates, casein sodium-sodium alginate plural gel solution of load beta carotene is produced.
(7) measure of beta carotene envelop rate and load factor
Casein sodium-sodium alginate plural gel solution of load beta carotene is taken, using Rotary Evaporators at 40 DEG C
At a temperature of be concentrated into 40mL, take concentrate 1mL plus 5mL n-hexane, after mixing at 4 DEG C with 5000rpm centrifuge 10 minutes.Survey
It is the light absorption value at 450nm to determine n-hexane in wavelength, and calculates the free beta carotene (β-Hu for not embedding and loosely adsorbing
Radish element) quality.The envelop rate and load factor of beta carotene are calculated according to following formula：
The envelop rate (%) of the beta carotene=β of (beta carotene gross mass-free beta carotene quality) × 100/-Hu
Radish element gross mass；
The load factor (%) of the beta carotene=sample of (beta carotene gross mass-free beta carotene quality) × 100/
Gross mass.
Embodiment 7-10 preparation process is identical, and simply ultrasound parameter is slightly changed, and the different ultrasound modes of table 2 are to β-Hu Luo
The influence of Bu Su envelop rates and load factor.
Influence of the different ultrasound modes of table 2 to beta carotene envelop rate and load factor
| Embodiment | Supersonic frequency or pattern | Envelop rate % | Load factor % |
| Comparative example (i.e. embodiment 1) | It is not ultrasonic | 43.1 | 5.4 |
| Embodiment 7 | 40kHz/68kHz | 63.8 | 6.0 |
| Embodiment 8 | 40kHz/28kHz | 56.4 | 5.5 |
| Embodiment 9 | 68kHz/28kHz | 52.3 | 5.2 |
| Embodiment 10 | 33kHz/40kHz | 56.7 | 5.6 |
The frequency sweep ultrasonic ripple combined by comparative example 7-10 different frequencies in table 2 is to beta carotene envelop rate and bears
The influence of load rate, it can be found that the processing of frequency sweep ultrasonic ripple can significantly improve casein sodium-sodium alginate plural gel embedding
The envelop rate of beta carotene, compared with the control (not ultrasonic), the processing of double frequency frequency sweep ultrasonic ripple can make the encapsulating of beta carotene
Rate improves 21.3%~48.0%, and the processing of 40/68kHz double frequency frequency sweep ultrasonic ripple then improves the envelop rate of beta carotene
48.0%.
Embodiment 11-14 (processing of multi-mode frequency ultrasonic wave)
Casein sodium：2 parts；
Sodium alginate：2.5 part.
Casein sodium-sodium alginate plural gel loads the preparation method of beta carotene, carries out as steps described below：
(1) casein sodium is dissolved into distilled water, magnetic agitation to albumen is completely dissolved；Obtain casein sodium dense
Spend for 2mg/mL solution；
(2) sodium alginate is dissolved into the aqueous solution, magnetic agitation is to being completely dissolved；Concentration is obtained for 2.5mg/mL marine algas
Acid sodium solution；
(3) it is 1 by volume by step (2) sodium alginate soln:1 ratio is added dropwise to step (1) casein sodium
In solution so that the mass ratio of casein sodium and sodium alginate is 2：2.5, then adjust the pH=5 of mixed solution.
(4) concentration is added dropwise to the casein of step (3) preparation for the ethanol solution of (1-5) mg/mL beta carotene
In sour sodium and sodium alginate plural gel solution so that the mass ratio of casein sodium and beta carotene is 1：0.5；
(5) multifrequency mode ultrasound processing is carried out to the mixed solution of step (4), wherein described multiple frequency ultrasonic tupe
For：Three frequency synchronizing ultrasounds are handled or double-frequency synchronous is ultrasonically treated or single-frequency is ultrasonically treated, ultrasonic power density 150W/L；It is super
Ping working time 10s；Interpulse period 5s, sonication treatment time is 40min；The processing of three frequency synchronizing ultrasounds or double frequency
Synchronizing ultrasound processing or the ultrasonically treated ultrasonic frequency combination of single-frequency are shown in Table 3.
(6) after ultrasound terminates, 1h is stood at room temperature, and the casein sodium-sodium alginate for producing load beta carotene is combined
Obtain loading casein sodium-sodium alginate complex coacervation of beta carotene after gel solution, spray drying or freeze-drying
Thing.
(7) measure of beta carotene envelop rate and load factor
Casein sodium-sodium alginate plural gel solution of load beta carotene is taken, using Rotary Evaporators at 40 DEG C
At a temperature of be concentrated into 40mL, take concentrate 1mL plus 5mL n-hexane, after mixing at 4 DEG C with 5000rpm centrifuge 10 minutes.Survey
It is the light absorption value at 450nm to determine n-hexane in wavelength, and calculates the free beta carotene (β-Hu for not embedding and loosely adsorbing
Radish element) quality.The envelop rate and load factor of beta carotene are calculated according to following formula：
The envelop rate (%) of the beta carotene=β of (beta carotene gross mass-free beta carotene quality) × 100/-Hu
Radish element gross mass；
The load factor (%) of the beta carotene=sample of (beta carotene gross mass-free beta carotene quality) × 100/
Gross mass.
Embodiment 11-14 preparation process is identical, and simply ultrasound parameter is slightly changed, and the different ultrasound modes of table 3 are to β-Hu
The influence of radish element envelop rate and load factor.
Influence of the different ultrasound modes of table 3 to beta carotene envelop rate and load factor
The ultrasonic wave combined by comparative example 11-14 different modes multi-frequency in table 3 to beta carotene envelop rate and
The influence of load factor, is combined it can be found that the processing of multi-mode frequency ultrasonic wave can significantly improve casein sodium-sodium alginate
The envelop rate of gel embedding beta carotene, compared with the control (not ultrasonic), the processing of double frequency frequency sweep ultrasonic ripple can make β-carrot
The envelop rate of element improves 16.5%~44.1%, and the processing of 28kHz/35kHz/40kHz three frequently combined ultrasonic ripples then makes β-Hu
The envelop rate of radish element improves 44.1%.
Claims (10)
1. casein sodium-sodium alginate plural gel, it is characterised in that be prepared from by the raw material of following parts by weight：
Casein sodium：2~40 parts；
Sodium alginate：2.5~25 parts.
2. casein sodium according to claim 1-sodium alginate plural gel, it is characterised in that by following parts by weight
Raw material is prepared from：
Casein sodium：10 parts；
Sodium alginate：4 parts.
3. the preparation method of casein sodium according to claim 1 or 2-sodium alginate plural gel, it is characterised in that
Carry out as steps described below：
（1）Casein sodium is dissolved into distilled water, magnetic agitation to albumen is completely dissolved；Obtaining caseinic acid na concn is
（2-40）Mg/mL solution；
（2）Sodium alginate is dissolved into the aqueous solution, magnetic agitation is to being completely dissolved；Obtaining concentration is（2.5-25）Mg/mL seas
Solution of sodium alginate；
（3）By step（2）Sodium alginate soln is 1 by volume:1 ratio is added dropwise to step（1）Na caseinate solution
In so that the mass ratio of casein sodium and sodium alginate is：（2~40）：（2.5~25）, then adjust mixed solution
pH=4-7；
（4）By step（3）Obtained mixed solution carries out the processing of double frequency frequency sweep ultrasonic ripple, and ultrasound condition is：Upper and lower plates spacing is
10cm, frequency sweep cycle 300s, intermittently than 1:1（Ultrasonic 5s, interval 5s）, every piece of vibration plate power is 600W up and down；
（5）After ultrasound terminates, 1h is stood at room temperature, casein sodium-sodium alginate plural gel solution is produced, spray drying or
Casein sodium-sodium alginate complex coacervation thing is obtained after person's freeze-drying.
4. the preparation method of casein sodium according to claim 3-sodium alginate plural gel, it is characterised in that wherein
Step（3）In preferred regulation mixed solution pH=5；
Wherein step（3）Described in casein sodium and the mass ratio of sodium alginate be preferably 10：4；
Wherein step（4）Described in double frequency combination of frequency be： 40 kHz/ 68kHz、28kHz/40kHz、68 kHz/28
kHz、33 kHz/40 kHz；Optimized frequency is combined as 40 kHz/68 kHz.
5. casein sodium-sodium alginate plural gel loads the preparation method of beta carotene, it is characterised in that according to following steps
It is rapid to carry out：
（1）Casein sodium is dissolved into distilled water, magnetic agitation to albumen is completely dissolved；Obtaining caseinic acid na concn is
（2-40）Mg/mL solution；
（2）Sodium alginate is dissolved into the aqueous solution, magnetic agitation is to being completely dissolved；Obtaining concentration is（2.5-25）Mg/mL seas
Solution of sodium alginate；
（3）By step（2）Sodium alginate soln is 1 by volume:1 ratio is added dropwise to step（1）Na caseinate solution
In so that the mass ratio of casein sodium and sodium alginate is：（2~40）：（2.5~25）, then adjust mixed solution
pH=4-7；
（4）It is by concentration（1-5）Step is added dropwise in the ethanol solution of mg/mL beta carotene（3）The casein sodium of preparation
In sodium alginate plural gel solution so that the mass ratio of casein sodium and beta carotene is 1：0.5；
（5）At room temperature by step（4）Obtained mixed solution carries out the processing of double frequency frequency sweep ultrasonic ripple, and ultrasound condition is：Upper and lower plates
Spacing is 10cm, frequency sweep cycle 300s, intermittently than 1:1（Ultrasonic 5s, interval 5s）, every piece of vibration plate power is 600W up and down；
（6）After ultrasound terminates, casein sodium-sodium alginate plural gel solution of load beta carotene, spray drying are produced
Or obtain loading casein sodium-sodium alginate complex coacervation thing of beta carotene after freeze-drying.
6. casein sodium according to claim 5-sodium alginate plural gel loads the preparation method of beta carotene,
It is characterized in that wherein step（3）In preferred regulation mixed solution pH=5；
Wherein step（3）Described in the mass ratio for causing casein sodium and sodium alginate be preferably 10：4；
Wherein step（5）Described in double frequency combination of frequency be：40 kHz/ 68kHz、28kHz/40kHz、68 kHz/28
kHz、33 kHz/40 kHz；Optimized frequency is combined as 40 kHz/68 kHz.
7. the preparation method of casein sodium according to claim 1 or 2-sodium alginate plural gel, it is characterised in that
Or carry out as steps described below：
（1）Casein sodium is dissolved into distilled water, magnetic agitation to albumen is completely dissolved；Obtaining caseinic acid na concn is
（2-40）Mg/mL solution；
（2）Sodium alginate is dissolved into the aqueous solution, magnetic agitation is to being completely dissolved；Obtaining concentration is（2.5-25）Mg/mL seas
Solution of sodium alginate；
（3）By step（2）Sodium alginate soln is 1 by volume:1 ratio is added dropwise to step（1）Na caseinate solution
In so that the mass ratio of casein sodium and sodium alginate is：（2~40）：（2.5~25）, then adjust mixed solution
pH=4-7；
（4）To step（3）Mixed solution carry out multifrequency mode ultrasound processing, wherein described multiple frequency ultrasonic tupe is：
Three frequency synchronizing ultrasounds are handled or double-frequency synchronous is ultrasonically treated or single-frequency is ultrasonically treated, the W/L of ultrasonic power density 100 ~ 150；
The s of ultrasonic pulse working time 10；The s of interpulse period 5, sonication treatment time is 40min；
（5）After ultrasound terminates, 1h is stood at room temperature, casein sodium-sodium alginate plural gel solution is produced, spray drying or
Casein sodium-sodium alginate complex coacervation thing is obtained after person's freeze-drying.
8. the preparation method of casein sodium according to claim 7-sodium alginate plural gel, it is characterised in that wherein
Step（3）In preferred regulation mixed solution pH=5；
Wherein step（3）The mass ratio of middle casein sodium and sodium alginate is preferably 10：4；
Wherein step（4）In the processing of three frequency synchronizing ultrasounds or double-frequency synchronous is ultrasonically treated or single-frequency is ultrasonically treated ultrasonic wave
Combination of frequency is：28kHz, 35kHz, 35/40 kHz or 28/35/40 kHz, preferably 28/35/40 kHz.
9. casein sodium-sodium alginate plural gel loads the preparation method of beta carotene, it is characterised in that or under
State step progress：
（1）Casein sodium is dissolved into distilled water, magnetic agitation to albumen is completely dissolved；Obtaining caseinic acid na concn is
（2-40）Mg/mL solution；
（2）Sodium alginate is dissolved into the aqueous solution, magnetic agitation is to being completely dissolved；Obtaining concentration is（2.5-25）Mg/mL seas
Solution of sodium alginate；
（3）By step（2）Sodium alginate soln is 1 by volume:1 ratio is added dropwise to step（1）Na caseinate solution
In so that the mass ratio of casein sodium and sodium alginate is：（2~40）：（2.5~25）, then adjust mixed solution
pH=4-7；
（4）It is by concentration（1-5）Step is added dropwise in mg/mL beta carotene ethanol solution（3）The casein sodium of preparation and
In sodium alginate plural gel solution so that the mass ratio of casein sodium and beta carotene is 1：0.5；
（5）To step（4）Mixed solution carry out multifrequency mode ultrasound processing, wherein described multiple frequency ultrasonic tupe is：
Three frequency synchronizing ultrasounds are handled or double-frequency synchronous is ultrasonically treated or single-frequency is ultrasonically treated, the W/L of ultrasonic power density 100 ~ 150；
The s of ultrasonic pulse working time 10；The s of interpulse period 5, sonication treatment time is 40min；
（6）After ultrasound terminates, 1h is stood at room temperature, produces casein sodium-sodium alginate plural gel of load beta carotene
Obtain loading casein sodium-sodium alginate complex coacervation thing of beta carotene after solution, spray drying or freeze-drying；
Wherein step（3）In preferred regulation mixed solution pH=5；
Wherein step（3）The mass ratio of middle casein sodium and sodium alginate is preferably 10：4；
Wherein step（5）In the processing of three frequency synchronizing ultrasounds or double-frequency synchronous is ultrasonically treated or single-frequency is ultrasonically treated ultrasonic wave
Combination of frequency is：28kHz, 35kHz, 35/40 kHz or 28/35/40 kHz, preferably 28/35/40 kHz.
10. load beta carotene casein sodium-sodium alginate plural gel purposes, can be applied to make health food,
Food or medicine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710411552.5A CN107254181A (en) | 2017-06-05 | 2017-06-05 | The application of the supersonically preparation method and functional food of casein polysaccharide nanogel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710411552.5A CN107254181A (en) | 2017-06-05 | 2017-06-05 | The application of the supersonically preparation method and functional food of casein polysaccharide nanogel |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107254181A true CN107254181A (en) | 2017-10-17 |
Family
ID=60022983
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710411552.5A Withdrawn CN107254181A (en) | 2017-06-05 | 2017-06-05 | The application of the supersonically preparation method and functional food of casein polysaccharide nanogel |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107254181A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107970227A (en) * | 2017-11-02 | 2018-05-01 | 天津大学 | A kind of preparation method of casein/sodium alginate composite microcapsule |
| CN108208834A (en) * | 2018-01-05 | 2018-06-29 | 华南理工大学 | A kind of soybean protein base nano particle for loading curcumin and its preparation method and purposes |
| CN108578357A (en) * | 2018-05-15 | 2018-09-28 | 北京林业大学 | A kind of protein-polysaccharide self-assembled nanometer gel and the preparation method and application thereof with nucleocapsid structure |
| CN110613135A (en) * | 2019-09-27 | 2019-12-27 | 安徽大学 | Nano carrier loaded with lycopene, preparation method and application |
| CN113230234A (en) * | 2021-04-27 | 2021-08-10 | 江苏大学 | Ultrasonic preparation method of bioactive ingredient-loaded protein peptide-polysaccharide nanoparticles |
| CN114009775A (en) * | 2021-10-21 | 2022-02-08 | 江苏大学 | Stepped ultrasonic preparation of protein-polysaccharide emulsion and application of functional food |
| CN114098068A (en) * | 2021-11-30 | 2022-03-01 | 四川南溪徽记食品有限公司 | Dispersoid and application thereof in protein gel food |
| CN114437371A (en) * | 2022-01-14 | 2022-05-06 | 陕西科技大学 | Preparation method of casein-based nano hybrid hydrogel based on double cross-linking mechanism |
| CN115073768A (en) * | 2022-05-07 | 2022-09-20 | 浙江工业大学 | Preparation method of functional component-loaded double-network hydrogel |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101711969A (en) * | 2009-10-30 | 2010-05-26 | 江苏大学 | Device and method for biological processing with pulsed multi-frequency ultrasonic waves in sweep-frequency mode and use thereof |
| CN103351629A (en) * | 2013-07-25 | 2013-10-16 | 中国烟草总公司郑州烟草研究院 | Tobacco protein/pulullan edible composite film and preparation method thereof |
| CN105286011A (en) * | 2015-09-18 | 2016-02-03 | 华南理工大学 | Soluble soybean polysaccharide-soybean protein-curcumin compound as well as preparation and application |
| CN106119329A (en) * | 2016-07-08 | 2016-11-16 | 江苏大学 | A kind of synchronize the method that multiple frequency ultrasonic assisted immobilization enzyme enzymolysis prepares Semen Maydis polypeptide |
-
2017
- 2017-06-05 CN CN201710411552.5A patent/CN107254181A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101711969A (en) * | 2009-10-30 | 2010-05-26 | 江苏大学 | Device and method for biological processing with pulsed multi-frequency ultrasonic waves in sweep-frequency mode and use thereof |
| CN103351629A (en) * | 2013-07-25 | 2013-10-16 | 中国烟草总公司郑州烟草研究院 | Tobacco protein/pulullan edible composite film and preparation method thereof |
| CN105286011A (en) * | 2015-09-18 | 2016-02-03 | 华南理工大学 | Soluble soybean polysaccharide-soybean protein-curcumin compound as well as preparation and application |
| CN106119329A (en) * | 2016-07-08 | 2016-11-16 | 江苏大学 | A kind of synchronize the method that multiple frequency ultrasonic assisted immobilization enzyme enzymolysis prepares Semen Maydis polypeptide |
Non-Patent Citations (1)
| Title |
|---|
| 武英华等: ""超声辅助制备玉米醇溶蛋白与多糖接枝反应研究"", 《2016年粮食食品与营养健康产业发展科技论坛暨行业发展峰会论文集》 * |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107970227A (en) * | 2017-11-02 | 2018-05-01 | 天津大学 | A kind of preparation method of casein/sodium alginate composite microcapsule |
| CN108208834A (en) * | 2018-01-05 | 2018-06-29 | 华南理工大学 | A kind of soybean protein base nano particle for loading curcumin and its preparation method and purposes |
| CN108208834B (en) * | 2018-01-05 | 2021-03-30 | 华南理工大学 | Curcumin-loaded soybean protein-based nanoparticles and preparation method and application thereof |
| CN108578357A (en) * | 2018-05-15 | 2018-09-28 | 北京林业大学 | A kind of protein-polysaccharide self-assembled nanometer gel and the preparation method and application thereof with nucleocapsid structure |
| CN110613135A (en) * | 2019-09-27 | 2019-12-27 | 安徽大学 | Nano carrier loaded with lycopene, preparation method and application |
| GB2610727B (en) * | 2021-04-27 | 2023-12-13 | Univ Jiangsu | Ultrasonic preparation method of protein-derived peptide-polysaccharide nanoparticles loaded with bioactive components. |
| CN113230234A (en) * | 2021-04-27 | 2021-08-10 | 江苏大学 | Ultrasonic preparation method of bioactive ingredient-loaded protein peptide-polysaccharide nanoparticles |
| WO2022227700A1 (en) * | 2021-04-27 | 2022-11-03 | 江苏大学 | Ultrasonic preparation method for protein peptide-polysaccharide nanoparticle loaded with bioactive component |
| GB2610727A (en) * | 2021-04-27 | 2023-03-15 | Univ Jiangsu | Ultrasonic preparation method for protein peptide-polysaccharide nanoparticle loaded with bioactive component |
| CN114009775A (en) * | 2021-10-21 | 2022-02-08 | 江苏大学 | Stepped ultrasonic preparation of protein-polysaccharide emulsion and application of functional food |
| CN114009775B (en) * | 2021-10-21 | 2024-02-13 | 江苏大学 | Stepped ultrasonic preparation of protein-polysaccharide emulsion and functional food application |
| CN114098068A (en) * | 2021-11-30 | 2022-03-01 | 四川南溪徽记食品有限公司 | Dispersoid and application thereof in protein gel food |
| CN114437371A (en) * | 2022-01-14 | 2022-05-06 | 陕西科技大学 | Preparation method of casein-based nano hybrid hydrogel based on double cross-linking mechanism |
| CN114437371B (en) * | 2022-01-14 | 2023-09-05 | 陕西科技大学 | Preparation method of casein-based nano hybrid hydrogel based on double crosslinking mechanism |
| CN115073768B (en) * | 2022-05-07 | 2023-08-01 | 浙江工业大学 | Preparation method of functional component loaded double-network hydrogel |
| CN115073768A (en) * | 2022-05-07 | 2022-09-20 | 浙江工业大学 | Preparation method of functional component-loaded double-network hydrogel |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107254181A (en) | The application of the supersonically preparation method and functional food of casein polysaccharide nanogel | |
| CN107298863A (en) | The supersonically preparation method of peanut protein polysaccharide composite particle and functional food application | |
| CN106954861A (en) | Ultrasonic wave prepares the method that zeins embeds resveratrol nano particle | |
| CN106942703A (en) | Zeins chitosan complex coacervation thing and multi-mode supersonically preparation method | |
| Aranaz et al. | Functional characterization of chitin and chitosan | |
| CN102911380B (en) | Hyaluronan and biodegradable high polymer modified material and preparation method | |
| CN103980500B (en) | A kind of protein grafting natural polysaccharide as well as preparation method and application thereof | |
| CN110089753A (en) | A kind of preparation method for the nanoparticle improving curcumin bioavailability | |
| RU2012142708A (en) | METHOD FOR PROCESSING FIBERS AND / OR TEXTILE MATERIALS | |
| CN107298773A (en) | The frequency sweep ultrasonic ripple preparation method of rapeseed protein chitosan nano particle | |
| CN107114799A (en) | The ultrasonic preparation method of rapeseed protein microcapsules and the application as functional food | |
| CN113080468B (en) | Slow-digestion casein nano micelle powder and preparation method thereof | |
| CN104431285A (en) | Method for preparing ovalbumin with high foamability by microwave ultrasonic waves | |
| CN101481404A (en) | Zymohydrolysis lactoprotein ferrous complex compound microcapsule iron supplement agent and preparation thereof | |
| Weiss et al. | Physicochemical effects of high-intensity ultrasonication on food proteins and carbohydrates | |
| CN105030561A (en) | Silk fibroin microsphere with arbutin and vitamin C entrapped in and preparation method and application of silk fibroin microsphere | |
| CN107652373A (en) | A kind of preparation method of low-molecular weight chitoglycan | |
| CN111919991A (en) | Albumen protein-plant polyphenol covalent complex and preparation method thereof | |
| CN114176227A (en) | Layer-by-layer self-assembly probiotic microcapsule wrapped by sodium alginate and preparation method thereof | |
| CN104719434B (en) | A kind of enzyme crosslinking soybean protein egg coating fresh-keeping agent and preparation method thereof | |
| CN107189117A (en) | The application of the supersonically preparation method and functional food of soybean protein polysaccharide compound | |
| CN104490933B (en) | Crocodile blood nano microcapsule and preparation method thereof | |
| CN104432040A (en) | Rana japonica oil polypeptide micro-capsule powder and preparation method thereof | |
| CN108467487A (en) | The dextrin modified casein polypeptide conjugate of starch base, preparation method and application | |
| Guo et al. | Modifications of whey protein |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20171017 |
|
| WW01 | Invention patent application withdrawn after publication |