CN113081869A - Haematococcus pluvialis astaxanthin microcapsule and preparation method thereof - Google Patents
Haematococcus pluvialis astaxanthin microcapsule and preparation method thereof Download PDFInfo
- Publication number
- CN113081869A CN113081869A CN202110411084.8A CN202110411084A CN113081869A CN 113081869 A CN113081869 A CN 113081869A CN 202110411084 A CN202110411084 A CN 202110411084A CN 113081869 A CN113081869 A CN 113081869A
- Authority
- CN
- China
- Prior art keywords
- haematococcus pluvialis
- astaxanthin
- algae slurry
- preparation
- homogenized
- 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.)
- Granted
Links
- 241000168517 Haematococcus lacustris Species 0.000 title claims abstract description 97
- JEBFVOLFMLUKLF-IFPLVEIFSA-N Astaxanthin Natural products CC(=C/C=C/C(=C/C=C/C1=C(C)C(=O)C(O)CC1(C)C)/C)C=CC=C(/C)C=CC=C(/C)C=CC2=C(C)C(=O)C(O)CC2(C)C JEBFVOLFMLUKLF-IFPLVEIFSA-N 0.000 title claims abstract description 89
- 235000013793 astaxanthin Nutrition 0.000 title claims abstract description 89
- 239000001168 astaxanthin Substances 0.000 title claims abstract description 89
- 229940022405 astaxanthin Drugs 0.000 title claims abstract description 89
- MQZIGYBFDRPAKN-ZWAPEEGVSA-N astaxanthin Chemical compound C([C@H](O)C(=O)C=1C)C(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)C(=O)[C@@H](O)CC1(C)C MQZIGYBFDRPAKN-ZWAPEEGVSA-N 0.000 title claims abstract description 88
- 239000003094 microcapsule Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 241000195493 Cryptophyta Species 0.000 claims abstract description 81
- 239000002002 slurry Substances 0.000 claims abstract description 61
- 238000001694 spray drying Methods 0.000 claims abstract description 19
- 206010033546 Pallor Diseases 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 10
- 230000001105 regulatory effect Effects 0.000 claims abstract description 3
- 108010059892 Cellulase Proteins 0.000 claims description 16
- 108010059820 Polygalacturonase Proteins 0.000 claims description 16
- 229940106157 cellulase Drugs 0.000 claims description 16
- 108010093305 exopolygalacturonase Proteins 0.000 claims description 16
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 108090000790 Enzymes Proteins 0.000 claims description 2
- 102000004190 Enzymes Human genes 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 229940088598 enzyme Drugs 0.000 claims description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 2
- 239000001508 potassium citrate Substances 0.000 claims description 2
- 229960002635 potassium citrate Drugs 0.000 claims description 2
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 claims description 2
- 235000011082 potassium citrates Nutrition 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 239000003002 pH adjusting agent Substances 0.000 claims 1
- 238000000265 homogenisation Methods 0.000 abstract description 10
- 238000011084 recovery Methods 0.000 abstract description 9
- 230000007935 neutral effect Effects 0.000 abstract 1
- 108090000623 proteins and genes Proteins 0.000 description 9
- 102000004169 proteins and genes Human genes 0.000 description 9
- 238000001816 cooling Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 150000004676 glycans Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000005017 polysaccharide Substances 0.000 description 4
- 229920001282 polysaccharide Polymers 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 235000016709 nutrition Nutrition 0.000 description 2
- KBPHJBAIARWVSC-XQIHNALSSA-N trans-lutein Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1=C(C)CC(O)CC1(C)C)C=CC=C(/C)C=CC2C(=CC(O)CC2(C)C)C KBPHJBAIARWVSC-XQIHNALSSA-N 0.000 description 2
- JKQXZKUSFCKOGQ-JLGXGRJMSA-N (3R,3'R)-beta,beta-carotene-3,3'-diol Chemical compound C([C@H](O)CC=1C)C(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)C[C@@H](O)CC1(C)C JKQXZKUSFCKOGQ-JLGXGRJMSA-N 0.000 description 1
- 201000001320 Atherosclerosis Diseases 0.000 description 1
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- 229930003427 Vitamin E Natural products 0.000 description 1
- JKQXZKUSFCKOGQ-LQFQNGICSA-N Z-zeaxanthin Natural products C([C@H](O)CC=1C)C(C)(C)C=1C=CC(C)=CC=CC(C)=CC=CC=C(C)C=CC=C(C)C=CC1=C(C)C[C@@H](O)CC1(C)C JKQXZKUSFCKOGQ-LQFQNGICSA-N 0.000 description 1
- QOPRSMDTRDMBNK-RNUUUQFGSA-N Zeaxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1=C(C)CCC(O)C1(C)C)C=CC=C(/C)C=CC2=C(C)CC(O)CC2(C)C QOPRSMDTRDMBNK-RNUUUQFGSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 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 description 1
- JKQXZKUSFCKOGQ-LOFNIBRQSA-N all-trans-Zeaxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1=C(C)CC(O)CC1(C)C)C=CC=C(/C)C=CC2=C(C)CC(O)CC2(C)C JKQXZKUSFCKOGQ-LOFNIBRQSA-N 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000001093 anti-cancer Effects 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- -1 astaxanthin diester Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013734 beta-carotene Nutrition 0.000 description 1
- 239000011648 beta-carotene Substances 0.000 description 1
- 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 description 1
- PSQYTAPXSHCGMF-BQYQJAHWSA-N beta-ionone group Chemical group CC1=C(C(CCC1)(C)C)/C=C/C(C)=O PSQYTAPXSHCGMF-BQYQJAHWSA-N 0.000 description 1
- 229960002747 betacarotene Drugs 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 235000021466 carotenoid Nutrition 0.000 description 1
- 150000001747 carotenoids Chemical class 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 210000003169 central nervous system Anatomy 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- 235000019797 dipotassium phosphate Nutrition 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 235000012680 lutein Nutrition 0.000 description 1
- 239000001656 lutein Substances 0.000 description 1
- KBPHJBAIARWVSC-RGZFRNHPSA-N lutein Chemical compound C([C@H](O)CC=1C)C(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\[C@H]1C(C)=C[C@H](O)CC1(C)C KBPHJBAIARWVSC-RGZFRNHPSA-N 0.000 description 1
- 229960005375 lutein Drugs 0.000 description 1
- ORAKUVXRZWMARG-WZLJTJAWSA-N lutein 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=CC2C(=CC(O)CC2(C)C)C ORAKUVXRZWMARG-WZLJTJAWSA-N 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 230000000050 nutritive effect Effects 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
- FJHBOVDFOQMZRV-XQIHNALSSA-N xanthophyll Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1=C(C)CC(O)CC1(C)C)C=CC=C(/C)C=CC2C=C(C)C(O)CC2(C)C FJHBOVDFOQMZRV-XQIHNALSSA-N 0.000 description 1
- 235000010930 zeaxanthin Nutrition 0.000 description 1
- 239000001775 zeaxanthin Substances 0.000 description 1
- 229940043269 zeaxanthin Drugs 0.000 description 1
- 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 description 1
Classifications
-
- 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
- A61K31/12—Ketones
- A61K31/122—Ketones having the oxygen directly attached to a ring, e.g. quinones, vitamin K1, anthralin
-
- 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
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/11—Encapsulated compositions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/35—Ketones, e.g. benzophenone
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
- A61K9/50—Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
- A61K9/5089—Processes
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P25/00—Drugs for disorders of the nervous system
- A61P25/28—Drugs for disorders of the nervous system for treating neurodegenerative disorders of the central nervous system, e.g. nootropic agents, cognition enhancers, drugs for treating Alzheimer's disease or other forms of dementia
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P29/00—Non-central analgesic, antipyretic or antiinflammatory agents, e.g. antirheumatic agents; Non-steroidal antiinflammatory drugs [NSAID]
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P35/00—Antineoplastic agents
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P37/00—Drugs for immunological or allergic disorders
- A61P37/02—Immunomodulators
- A61P37/04—Immunostimulants
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P39/00—General protective or antinoxious agents
- A61P39/06—Free radical scavengers or antioxidants
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P9/00—Drugs for disorders of the cardiovascular system
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P9/00—Drugs for disorders of the cardiovascular system
- A61P9/10—Drugs for disorders of the cardiovascular system for treating ischaemic or atherosclerotic diseases, e.g. antianginal drugs, coronary vasodilators, drugs for myocardial infarction, retinopathy, cerebrovascula insufficiency, renal arteriosclerosis
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/08—Anti-ageing preparations
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
- A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
Abstract
The invention provides a haematococcus pluvialis astaxanthin microcapsule and a preparation method thereof, and relates to the technical field of astaxanthin microcapsule processing. The method comprises the steps of firstly blanching fresh haematococcus pluvialis and then carrying out homogenization pretreatment to obtain homogenized algae slurry; adjusting the pH value of the homogenized algae slurry to acidity, and performing enzymolysis and wall breaking treatment to obtain wall-broken haematococcus pluvialis algae slurry; and finally, adding a pH regulator into the wall-broken haematococcus pluvialis algae slurry, regulating the pH value of the algae slurry to be neutral, uniformly stirring, and performing spray drying to obtain the haematococcus pluvialis astaxanthin microcapsule. The haematococcus pluvialis astaxanthin microcapsule prepared by the invention has higher embedding rate, microcapsule yield and astaxanthin recovery rate, and the economic utilization value of haematococcus pluvialis is improved.
Description
Technical Field
The invention relates to the technical field of astaxanthin microcapsule processing, in particular to haematococcus pluvialis astaxanthin microcapsules and a preparation method thereof.
Background
Astaxanthin also called astaxanthin and astaxanthin belongs to carotenoid derivatives, and the molecular structure of the astaxanthin contains 11 conjugated double bonds, 2 beta-ionone rings and hydroxyl. Astaxanthin has strong antioxidant activity 10 times higher than that of beta-carotene, zeaxanthin and lutein and 100 times higher than that of vitamin E. In addition, astaxanthin has anti-aging, anti-inflammatory, anticancer, and immunity enhancing effects, and can protect central nervous system, and be used for preventing and treating cardiovascular diseases and atherosclerosis. The astaxanthin has outstanding biological activity, so that the astaxanthin can be widely applied to the fields of food, cosmetics, aquaculture, medicines and the like.
The accumulation amount of astaxanthin in haematococcus pluvialis can reach up to 5 percent, and the haematococcus pluvialis is the best biological source of natural astaxanthin. Astaxanthin in Haematococcus pluvialis exists mainly in free and esterified forms, and astaxanthin monoester accounts for about 70%, astaxanthin diester 25%, and the rest is in free form. Besides astaxanthin, Haematococcus pluvialis also contains various amino acids, fatty acids, polysaccharides and protein nutrients. The haematococcus pluvialis protein has good oil absorption, emulsifying property and solubility, can replace other protein raw materials serving as microcapsule wall materials, and has a good embedding effect. Meanwhile, haematococcus pluvialis polysaccharide is a small molecular substance and can be used as a filler of a microcapsule wall material to play a role in supporting the wall material.
The astaxanthin microcapsule powder is prepared by compounding astaxanthin oil and a wall material solution at present and then performing high-pressure homogenization and spray drying processes, the astaxanthin oil is obtained by wall breaking, extraction, concentration and other processes, the production cost of the astaxanthin microcapsule powder is greatly increased, and polysaccharide, protein and the like in haematococcus pluvialis are denatured in the extraction process, so that the astaxanthin microcapsule powder is not effectively and comprehensively utilized.
For example, chinese patent CN 104905321 a discloses a wall-broken haematococcus pluvialis microcapsule and a preparation process thereof, the patent technology is that fresh haematococcus pluvialis is wall-broken, sugar and protein are added into a product which undergoes a maillard reaction at a high temperature, and then the wall-broken haematococcus pluvialis microcapsule is prepared through high-pressure homogenization and spray drying processes. The method has the advantages of complex process, high temperature and long time required by the Maillard reaction, inconvenient operation and damage to the nutrition system of the astaxanthin microcapsule.
Disclosure of Invention
In view of the above, the invention provides a preparation method of haematococcus pluvialis astaxanthin microcapsules, which comprises the steps of blanching haematococcus pluvialis and then carrying out homogenization pretreatment, so that effective substances in haematococcus pluvialis are fully reserved, and the emulsibility and stability of protein are improved. And then effective substances such as astaxanthin and the like in haematococcus pluvialis are effectively obtained by combining enzymolysis wall breaking treatment, and astaxanthin microcapsule powder with high nutritional value is obtained.
The preparation method of the haematococcus pluvialis astaxanthin microcapsule comprises the following steps:
1) standing and settling the collected haematococcus pluvialis fresh algae, then discharging supernatant, taking out the settled fresh algae, and performing blanching treatment;
2) homogenizing the red haematococcus pluvialis subjected to blanching treatment to obtain homogenized algae slurry;
3) adjusting the pH value of the homogenized algae slurry to acidity, and then performing enzymolysis wall breaking treatment to obtain wall-broken haematococcus pluvialis algae slurry;
4) adding a pH regulator into the wall-broken haematococcus pluvialis algae slurry, regulating the pH value of the algae slurry to 7.0-7.5, uniformly stirring, and performing spray drying to obtain the haematococcus pluvialis astaxanthin microcapsule.
Preferably, the temperature of the blanching treatment in the step 1) is 85-100 ℃, and the blanching time is 10-15 min.
Preferably, the homogenizing pretreatment in the step 2) is to perform homogenizing treatment on the red haematococcus pluvialis subjected to the blanching treatment for 2-3 times under the pressure of 30-50 MPa, and the solid content of the homogenized algae slurry is 15-25%.
Preferably, the pH value of the homogenized algae slurry is adjusted to 4-6 in the step 3).
More preferably, the biological enzymes used in the enzymolysis wall-breaking treatment in step 3) are pectinase and cellulase, wherein the amount of the pectinase accounts for 0.5-2.0% of the weight of the homogenized algae slurry, and the amount of the cellulase accounts for 1.0-3.0% of the weight of the homogenized algae slurry.
Further preferably, the enzymolysis wall-breaking treatment time in the step 3) is 4-8 h.
Preferably, the stirring speed in the step 4) is 1400 r/min-1800 r/min, the stirring time is 15 min-30 min, the air inlet temperature of the spray drying is 150-170 ℃, and the air outlet temperature is 70-90 ℃.
Preferably, the pH regulator in step 4) is at least one of potassium dihydrogen phosphate, sodium dihydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, potassium citrate and sodium citrate.
Preferably, the operating temperature of the step 2), the step 3) and the step 4) is 40-60 ℃.
The invention also aims to provide a haematococcus pluvialis astaxanthin microcapsule which is obtained by the preparation method, has high nutritive value, effectively utilizes haematococcus pluvialis and improves the added value.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention effectively overcomes the problem that the cell wall fragments of the wall-broken haematococcus pluvialis are difficult to be microencapsulated, reduces the extraction process of the astaxanthin oil and greatly reduces the production cost of the haematococcus pluvialis astaxanthin microcapsule powder.
2. The invention efficiently utilizes the emulsibility and stability of the haematococcus pluvialis protein to embed the haematococcus pluvialis protein, effectively avoids the problem that the protein and algal polysaccharide cannot be directly used due to extraction, and increases the additional value of the haematococcus pluvialis.
3. The method has simple and concise process, can realize the production of the haematococcus pluvialis astaxanthin microcapsules by adopting conventional equipment, has simple operation and is easy to realize industrialization.
Detailed Description
The present invention is further illustrated by the following examples, wherein the embedding rate, microcapsule yield and astaxanthin recovery rate are calculated as follows:
the embedding rate is (1-mass of astaxanthin on the surface of microcapsule/mass of astaxanthin in the core material of microcapsule) × 100%
The yield of the microcapsule is the dry mass of the microcapsule/the dry mass of haematococcus pluvialis multiplied by 100 percent
The recovery rate of astaxanthin is microcapsule astaxanthin quality/Haematococcus pluvialis astaxanthin quality multiplied by 100%
Example 1
A preparation method of haematococcus pluvialis astaxanthin microcapsules comprises the following steps:
1) standing and settling 1000Kg of collected fresh Haematococcus pluvialis (containing astaxanthin 3.56 wt%) and discharging supernatant, taking out the settled fresh algae, and blanching at 85 deg.C for 15 min;
2) cooling the blanched haematococcus pluvialis to 40 ℃, and then carrying out three times of homogenization treatment under the pressure of 40MPa to obtain homogenized algae slurry, wherein the solid content of the homogenized algae slurry is 20%;
3) adjusting the pH value of the homogenized algae slurry to 4.5, adding pectinase and cellulase, and performing enzymolysis wall breaking at 45 deg.C for 6h, wherein the pectinase amount accounts for 1.5% of the homogenized algae slurry weight, and the cellulase amount accounts for 2.0% of the homogenized algae slurry weight, to obtain wall-broken Haematococcus pluvialis algae slurry with wall-breaking rate of 95.0%;
4) adding dipotassium hydrogen phosphate into the wall-broken haematococcus pluvialis algae pulp to adjust the pH value of the algae pulp to 7.0, stirring and mixing at the rotating speed of 1500r/min for 20min, then carrying out spray drying, controlling the air inlet temperature of the spray drying to be 165 ℃ and the air outlet temperature to be 80 ℃, producing 1.38kg of haematococcus pluvialis astaxanthin microcapsules, wherein the mass percent of the astaxanthin is 3.52%, the embedding rate of the haematococcus pluvialis astaxanthin microcapsules is 90.5%, the yield of the haematococcus pluvialis astaxanthin microcapsules is 92.0%, and the recovery rate of the astaxanthin is 90.97%.
Example 2
A preparation method of haematococcus pluvialis astaxanthin microcapsules comprises the following steps:
1) standing and settling 1000Kg of collected fresh Haematococcus pluvialis (containing astaxanthin 3.56 wt%) and discharging supernatant, taking out the settled fresh algae, and blanching at 85 deg.C for 15 min;
2) cooling the blanched haematococcus pluvialis to 40 ℃, and then carrying out three times of homogenization treatment under the pressure of 40MPa to obtain homogenized algae slurry, wherein the solid content of the homogenized algae slurry is 20%;
3) adjusting the pH value of the homogenized algae slurry to 4.5, adding pectinase and cellulase, and performing enzymolysis wall breaking at 45 deg.C for 8h, wherein the amount of pectinase accounts for 1.5% of the homogenized algae slurry, and the amount of cellulase accounts for 2.0% of the homogenized algae slurry, to obtain wall-broken Haematococcus pluvialis algae slurry with wall-breaking rate of 97.0%;
4) adding dipotassium hydrogen phosphate into the wall-broken haematococcus pluvialis algae pulp to adjust the pH value of the algae pulp to 7.0, stirring and mixing at the rotating speed of 1500r/min for 20min, then carrying out spray drying, controlling the air inlet temperature of the spray drying to be 165 ℃ and the air outlet temperature to be 80 ℃, producing 1.41kg of haematococcus pluvialis astaxanthin microcapsules, wherein the mass percent of the astaxanthin is 3.50%, the embedding rate of the haematococcus pluvialis astaxanthin microcapsules is 95.1%, the yield of the haematococcus pluvialis astaxanthin microcapsules is 94.0%, and the recovery rate of the astaxanthin is 92.42%.
Example 3
A preparation method of haematococcus pluvialis astaxanthin microcapsules comprises the following steps:
1) standing and settling 1000Kg of collected fresh Haematococcus pluvialis (containing astaxanthin 3.56 wt%) and discharging supernatant, taking out the settled fresh algae, and blanching at 85 deg.C for 15 min;
2) cooling the blanched haematococcus pluvialis to 40 ℃, and then carrying out three times of homogenization treatment under the pressure of 40MPa to obtain homogenized algae slurry, wherein the solid content of the homogenized algae slurry is 20%;
3) adjusting the pH value of the homogenized algae slurry to 4.5, adding pectinase and cellulase, and performing enzymolysis wall breaking at 45 deg.C for 6h, wherein the pectinase amount accounts for 0.8% of the homogenized algae slurry weight, and the cellulase amount accounts for 1.5% of the homogenized algae slurry weight, to obtain wall-broken Haematococcus pluvialis algae slurry with wall-breaking rate of 90.8%;
4) adding dipotassium hydrogen phosphate into the wall-broken haematococcus pluvialis algae pulp to adjust the pH value of the algae pulp to 7.0, then stirring and mixing at the rotating speed of 1500r/min for 20min, and then carrying out spray drying, wherein the air inlet temperature of the spray drying is 165 ℃, the air outlet temperature is 80 ℃, 1.44kg of haematococcus pluvialis astaxanthin microcapsules are produced, the mass percentage of the astaxanthin is 3.50%, the embedding rate of the haematococcus pluvialis astaxanthin microcapsules is 93.7%, the yield of the haematococcus pluvialis astaxanthin microcapsules is 86.6%, and the recovery rate of the astaxanthin is 94.38%.
Comparative example 1
A preparation method of haematococcus pluvialis astaxanthin microcapsules comprises the following steps:
1) standing and settling 1000Kg of collected fresh Haematococcus pluvialis (containing astaxanthin 3.56 wt%) and discharging supernatant, taking out the settled fresh algae, and blanching at 85 deg.C for 15 min;
2) cooling the blanched haematococcus pluvialis to 40 ℃, and then carrying out three times of homogenization treatment under the pressure of 40MPa to obtain homogenized algae slurry, wherein the solid content of the homogenized algae slurry is 20%;
3) adjusting the pH value of the homogenized algae slurry to 2.0, adding pectinase and cellulase, and performing enzymolysis wall breaking at 45 deg.C for 6h, wherein the pectinase amount accounts for 1.5% of the homogenized algae slurry weight, and the cellulase amount accounts for 2.0% of the homogenized algae slurry weight, to obtain wall-broken Haematococcus pluvialis algae slurry with wall-breaking rate of 25.6%;
4) adding dipotassium hydrogen phosphate into the wall-broken haematococcus pluvialis algae pulp to adjust the pH value of the algae pulp to 7.0, stirring and mixing at the rotating speed of 1500r/min for 20min, then carrying out spray drying, controlling the air inlet temperature of the spray drying to be 165 ℃ and the air outlet temperature to be 80 ℃, producing 1.35kg of haematococcus pluvialis astaxanthin microcapsules, wherein the mass percent of the astaxanthin is 0.91%, the embedding rate of the haematococcus pluvialis astaxanthin microcapsules is 95.8%, the yield of the haematococcus pluvialis astaxanthin microcapsules is 90.0%, and the recovery rate of the astaxanthin is 23.0%.
Comparative example 2
A preparation method of haematococcus pluvialis astaxanthin microcapsules comprises the following steps:
1) standing and settling 1000Kg of collected fresh Haematococcus pluvialis (containing astaxanthin 3.56 wt%) and discharging supernatant, taking out the settled fresh algae, and blanching at 85 deg.C for 15 min;
2) cooling the blanched haematococcus pluvialis to 40 ℃, and then carrying out three times of homogenization treatment under the pressure of 40MPa to obtain homogenized algae slurry, wherein the solid content of the homogenized algae slurry is 20%;
3) adjusting the pH value of the homogenized algae slurry to 4.5, adding pectinase and cellulase, and performing enzymolysis wall breaking at 45 deg.C for 6h, wherein the pectinase amount accounts for 0.2% of the homogenized algae slurry weight, and the cellulase amount accounts for 0.5% of the homogenized algae slurry weight, to obtain wall-broken Haematococcus pluvialis algae slurry with wall-breaking rate of 28.7%;
4) adding dipotassium hydrogen phosphate into the wall-broken haematococcus pluvialis algae slurry to adjust the pH value of the algae slurry to 7.0, then stirring and mixing at the rotating speed of 1500r/min for 20min, and then carrying out spray drying, wherein the air inlet temperature of the spray drying is 165 ℃, the air outlet temperature is 80 ℃, 1.31kg of haematococcus pluvialis astaxanthin microcapsules are produced, the mass percent of the astaxanthin is 1.02%, the embedding rate of the haematococcus pluvialis astaxanthin microcapsules is 96.2%, the yield of the haematococcus pluvialis astaxanthin microcapsules is 87.3%, and the recovery rate of the astaxanthin is 14.58%.
Comparative example 3
A preparation method of haematococcus pluvialis astaxanthin microcapsules comprises the following steps:
1) standing and settling 1000Kg of collected fresh Haematococcus pluvialis (containing astaxanthin 3.56 wt%) and discharging supernatant, taking out the settled fresh algae, and blanching at 85 deg.C for 15 min;
2) cooling the blanched haematococcus pluvialis to 40 ℃, and then carrying out three times of homogenization treatment under the pressure of 40MPa to obtain homogenized algae slurry, wherein the solid content of the homogenized algae slurry is 20%;
3) adjusting the pH value of the homogenized algae slurry to 2.0, adding pectinase and cellulase, and performing enzymolysis wall breaking at 15 deg.C for 6h, wherein the pectinase amount accounts for 1.5% of the homogenized algae slurry weight, and the cellulase amount accounts for 2.0% of the homogenized algae slurry weight, to obtain wall-broken Haematococcus pluvialis algae slurry with wall-breaking rate of 30.4%;
4) adding dipotassium phosphate into the wall-broken haematococcus pluvialis algae pulp to adjust the pH value of the algae pulp to 7.0, stirring and mixing at the rotating speed of 1500r/min for 20min, then carrying out spray drying, controlling the air inlet temperature of the spray drying to be 165 ℃ and the air outlet temperature to be 80 ℃, producing 1.39kg of haematococcus pluvialis astaxanthin microcapsules, wherein the mass percent of the astaxanthin is 1.12%, the embedding rate of the haematococcus pluvialis astaxanthin microcapsules is 96.2%, the yield of the haematococcus pluvialis astaxanthin microcapsules is 90.0%, and the recovery rate of the astaxanthin is 29.15%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of haematococcus pluvialis astaxanthin microcapsules is characterized by comprising the following steps:
1) standing and settling the collected haematococcus pluvialis fresh algae, then discharging supernatant, taking out the settled fresh algae, and performing blanching treatment;
2) homogenizing the red haematococcus pluvialis subjected to blanching treatment to obtain homogenized algae slurry;
3) adjusting the pH value of the homogenized algae slurry to acidity, and then performing enzymolysis wall breaking treatment to obtain wall-broken haematococcus pluvialis algae slurry;
4) adding a pH regulator into the wall-broken haematococcus pluvialis algae slurry, regulating the pH value of the algae slurry to 7.0-7.5, uniformly stirring, and performing spray drying to obtain the haematococcus pluvialis astaxanthin microcapsule.
2. The preparation method according to claim 1, wherein the temperature of the blanching treatment in the step 1) is 85-100 ℃, and the blanching time is 10-15 min.
3. The preparation method according to claim 1, wherein the homogenizing pretreatment in step 2) is to homogenize the blanched Haematococcus pluvialis at a pressure of 30MPa to 50MPa for 2 to 3 times, and the solid content of the homogenized algae slurry is 15% to 25%.
4. The preparation method according to claim 1, wherein the pH value of the homogenized algae slurry in the step 3) is adjusted to 4-6.
5. The preparation method according to claim 4, wherein the biological enzymes used in the enzymolysis wall-breaking treatment in step 3) are pectinase and cellulase, wherein the pectinase accounts for 0.5-2.0 wt% of the homogenized algae slurry, and the cellulase accounts for 1.0-3.0 wt% of the homogenized algae slurry.
6. The preparation method of claim 5, wherein the time of the enzymolysis wall-breaking treatment in the step 3) is 4-8 h.
7. The preparation method according to claim 1, wherein the stirring speed in the step 4) is 1400 r/min-1800 r/min, the stirring time is 15 min-30 min, the air inlet temperature of the spray drying is 150 ℃ to 170 ℃, and the air outlet temperature is 70 ℃ to 90 ℃.
8. The method according to claim 1, wherein the pH adjusting agent in step 4) is at least one of potassium dihydrogen phosphate, sodium dihydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, potassium citrate, and sodium citrate.
9. The method according to claim 1, wherein the operating temperatures of step 2), step 3) and step 4) are 40 ℃ to 60 ℃.
10. A Haematococcus pluvialis astaxanthin microcapsule characterized by being obtained by the production method according to any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110411084.8A CN113081869B (en) | 2021-04-16 | 2021-04-16 | Haematococcus pluvialis astaxanthin microcapsule and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110411084.8A CN113081869B (en) | 2021-04-16 | 2021-04-16 | Haematococcus pluvialis astaxanthin microcapsule and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113081869A true CN113081869A (en) | 2021-07-09 |
| CN113081869B CN113081869B (en) | 2022-06-03 |
Family
ID=76678336
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110411084.8A Active CN113081869B (en) | 2021-04-16 | 2021-04-16 | Haematococcus pluvialis astaxanthin microcapsule and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113081869B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116622797A (en) * | 2023-04-03 | 2023-08-22 | 广州优卡思农业技术有限公司 | Method for extracting astaxanthin from haematococcus pluvialis |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006176449A (en) * | 2004-12-22 | 2006-07-06 | Yamachu:Kk | Composition for cosmetic against ultraviolet |
| CN104905321A (en) * | 2015-05-27 | 2015-09-16 | 中国科学院天津工业生物技术研究所 | Wall-breaking Haematoccoccus Pluvialis powder microcapsules and preparation process thereof |
| CN105483009A (en) * | 2015-11-20 | 2016-04-13 | 晨光生物科技集团股份有限公司 | Method for producing wall-broken haematococcus pluvialis powder |
| CN110713450A (en) * | 2019-10-17 | 2020-01-21 | 福建启元堂生物技术有限公司 | Astaxanthin extraction method based on haematococcus pluvialis |
| CN111875528A (en) * | 2020-08-30 | 2020-11-03 | 云南爱尔康生物技术有限公司 | Method for preparing astaxanthin oil from haematococcus pluvialis |
-
2021
- 2021-04-16 CN CN202110411084.8A patent/CN113081869B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006176449A (en) * | 2004-12-22 | 2006-07-06 | Yamachu:Kk | Composition for cosmetic against ultraviolet |
| CN104905321A (en) * | 2015-05-27 | 2015-09-16 | 中国科学院天津工业生物技术研究所 | Wall-breaking Haematoccoccus Pluvialis powder microcapsules and preparation process thereof |
| CN105483009A (en) * | 2015-11-20 | 2016-04-13 | 晨光生物科技集团股份有限公司 | Method for producing wall-broken haematococcus pluvialis powder |
| CN110713450A (en) * | 2019-10-17 | 2020-01-21 | 福建启元堂生物技术有限公司 | Astaxanthin extraction method based on haematococcus pluvialis |
| CN111875528A (en) * | 2020-08-30 | 2020-11-03 | 云南爱尔康生物技术有限公司 | Method for preparing astaxanthin oil from haematococcus pluvialis |
Non-Patent Citations (2)
| Title |
|---|
| 余绍蕾等: "酶解结合物理法对雨生红球藻破壁处理的工艺研究", 《食品工程》 * |
| 贺青华等: "雨生红球藻虾青素的制备及生物活性研究进展", 《中国酿造》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116622797A (en) * | 2023-04-03 | 2023-08-22 | 广州优卡思农业技术有限公司 | Method for extracting astaxanthin from haematococcus pluvialis |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113081869B (en) | 2022-06-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105949163A (en) | Method for extracting and purifying anthocyanin in pomace of aronia melanocarpa | |
| CN101948897A (en) | Method for extracting shinyleaf yellowhorn oil, shinyleaf yellowhorn polysaccharide and shinyleaf yellowhorn protolysate peptide from shinyleaf yellowhorn | |
| CN107988011B (en) | Black glutinous rice wine and preparation method thereof | |
| CN113081869B (en) | Haematococcus pluvialis astaxanthin microcapsule and preparation method thereof | |
| Rodríguez-Sifuentes et al. | Importance of downstream processing of natural astaxanthin for pharmaceutical application | |
| CN107427055A (en) | The device of subtle powder smash Red Ginseng is manufactured, for being decomposed by biochemical fermentation and enzyme and the Red Ginseng concentrate of red ginseng active ingredient uptake ratio and the preparation method of red ginseng liquid of maximizing by physics mode | |
| CN103073914B (en) | Method for extracting maize yellow pigment from maize protein | |
| CN112011585A (en) | Preparation method of pumpkin seed polypeptide | |
| CN106699625B (en) | The method that zeaxanthin is prepared from Chinese wolfberry fruit dregs | |
| CN108771061A (en) | Rocket ram jet concentration stock solution with anticancer function and preparation method thereof | |
| CN108034685A (en) | A kind of preparation method of ginseng polypeptide | |
| CN1792274A (en) | Method for preparing blackberry mixed juice by using enzymatic engineering tech. | |
| CN110679934A (en) | Lutein-containing enzyme capable of clearing liver and improving eyesight and preparation method thereof | |
| CN101946882A (en) | Processing method of tomato powder | |
| CN107951860A (en) | The method that lycopene oil-in-water microemulsion prepares microcapsules | |
| CN107821923A (en) | The preparation method of microcapsules containing lycopene | |
| CN106046845A (en) | Method for preparing Cordyceps militaris flavochrome powder | |
| Lavecchia et al. | Cellulase applications in pigment and bioactive compound extraction | |
| CN111869738A (en) | Preparation method of pineapple-flavored nut milk beverage | |
| Anisuzzaman et al. | Optimisation of spray drying operating conditions of tomato slurry using response surface methodology | |
| Hu et al. | The influence of different product process on the effect ingredient content of Ningxia Lycium barbarum | |
| CN108530939B (en) | Microcapsule of astaxanthin in haematococcus pluvialis prepared by foam spray drying method and preparation method thereof | |
| JP2002112712A (en) | Stable carotenoid-containing powder and method for producing the same | |
| CN104448911A (en) | Extraction process for corn yellow pigment | |
| CN114209006A (en) | Production method of dehyrogenized black rice fermentation liquor for improving total flavone content |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |