KR102044934B1 - Carnosic acid - cycloamylose complex and method for production thereof - Google Patents
Carnosic acid - cycloamylose complex and method for production thereof Download PDFInfo
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- KR102044934B1 KR102044934B1 KR1020170102441A KR20170102441A KR102044934B1 KR 102044934 B1 KR102044934 B1 KR 102044934B1 KR 1020170102441 A KR1020170102441 A KR 1020170102441A KR 20170102441 A KR20170102441 A KR 20170102441A KR 102044934 B1 KR102044934 B1 KR 102044934B1
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- carnosic acid
- cyclic amylose
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- amylose
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- QRYRORQUOLYVBU-VBKZILBWSA-N carnosic acid Chemical compound CC([C@@H]1CC2)(C)CCC[C@]1(C(O)=O)C1=C2C=C(C(C)C)C(O)=C1O QRYRORQUOLYVBU-VBKZILBWSA-N 0.000 title claims abstract description 122
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 229920000858 Cyclodextrin Polymers 0.000 title description 5
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 100
- 229920000856 Amylose Polymers 0.000 claims abstract description 98
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 10
- 229940092258 rosemary extract Drugs 0.000 claims description 43
- 235000020748 rosemary extract Nutrition 0.000 claims description 43
- 239000001233 rosmarinus officinalis l. extract Substances 0.000 claims description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 41
- 239000000243 solution Substances 0.000 claims description 21
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
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- 239000003242 anti bacterial agent Substances 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 33
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- 239000003963 antioxidant agent Substances 0.000 description 9
- 235000006708 antioxidants Nutrition 0.000 description 9
- DOUMFZQKYFQNTF-WUTVXBCWSA-N (R)-rosmarinic acid Chemical compound C([C@H](C(=O)O)OC(=O)\C=C\C=1C=C(O)C(O)=CC=1)C1=CC=C(O)C(O)=C1 DOUMFZQKYFQNTF-WUTVXBCWSA-N 0.000 description 8
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- 229920002261 Corn starch Polymers 0.000 description 4
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000008120 corn starch Substances 0.000 description 4
- 229940099112 cornstarch Drugs 0.000 description 4
- 244000005700 microbiome Species 0.000 description 4
- 108090000790 Enzymes Proteins 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 3
- 230000002292 Radical scavenging effect Effects 0.000 description 3
- ZZAFFYPNLYCDEP-HNNXBMFYSA-N Rosmarinsaeure Natural products OC(=O)[C@H](Cc1cccc(O)c1O)OC(=O)C=Cc2ccc(O)c(O)c2 ZZAFFYPNLYCDEP-HNNXBMFYSA-N 0.000 description 3
- OHDRQQURAXLVGJ-HLVWOLMTSA-N azane;(2e)-3-ethyl-2-[(e)-(3-ethyl-6-sulfo-1,3-benzothiazol-2-ylidene)hydrazinylidene]-1,3-benzothiazole-6-sulfonic acid Chemical compound [NH4+].[NH4+].S/1C2=CC(S([O-])(=O)=O)=CC=C2N(CC)C\1=N/N=C1/SC2=CC(S([O-])(=O)=O)=CC=C2N1CC OHDRQQURAXLVGJ-HLVWOLMTSA-N 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
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- 239000003205 fragrance Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- DOUMFZQKYFQNTF-MRXNPFEDSA-N rosemarinic acid Natural products C([C@H](C(=O)O)OC(=O)C=CC=1C=C(O)C(O)=CC=1)C1=CC=C(O)C(O)=C1 DOUMFZQKYFQNTF-MRXNPFEDSA-N 0.000 description 3
- TVHVQJFBWRLYOD-UHFFFAOYSA-N rosmarinic acid Natural products OC(=O)C(Cc1ccc(O)c(O)c1)OC(=Cc2ccc(O)c(O)c2)C=O TVHVQJFBWRLYOD-UHFFFAOYSA-N 0.000 description 3
- 244000063299 Bacillus subtilis Species 0.000 description 2
- XUSYGBPHQBWGAD-PJSUUKDQSA-N Carnosol Chemical compound CC([C@@H]1C2)(C)CCC[C@@]11C(=O)O[C@@H]2C2=C1C(O)=C(O)C(C(C)C)=C2 XUSYGBPHQBWGAD-PJSUUKDQSA-N 0.000 description 2
- MMFRMKXYTWBMOM-UHFFFAOYSA-N Carnosol Natural products CCc1cc2C3CC4C(C)(C)CCCC4(C(=O)O3)c2c(O)c1O MMFRMKXYTWBMOM-UHFFFAOYSA-N 0.000 description 2
- 239000001116 FEMA 4028 Substances 0.000 description 2
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- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 2
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- 235000004654 carnosol Nutrition 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 235000015097 nutrients Nutrition 0.000 description 2
- 150000008442 polyphenolic compounds Chemical class 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000007974 sodium acetate buffer Substances 0.000 description 2
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 description 1
- 108010043797 4-alpha-glucanotransferase Proteins 0.000 description 1
- 241000221832 Amorphotheca resinae Species 0.000 description 1
- 102100040894 Amylo-alpha-1,6-glucosidase Human genes 0.000 description 1
- 235000014469 Bacillus subtilis Nutrition 0.000 description 1
- 229920001503 Glucan Polymers 0.000 description 1
- 244000017020 Ipomoea batatas Species 0.000 description 1
- 235000002678 Ipomoea batatas Nutrition 0.000 description 1
- 241000589774 Pseudomonas sp. Species 0.000 description 1
- 244000178231 Rosmarinus officinalis Species 0.000 description 1
- 244000299461 Theobroma cacao Species 0.000 description 1
- 235000005764 Theobroma cacao ssp. cacao Nutrition 0.000 description 1
- 235000005767 Theobroma cacao ssp. sphaerocarpum Nutrition 0.000 description 1
- 241000589596 Thermus Species 0.000 description 1
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- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
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- 235000013824 polyphenols Nutrition 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 239000001120 potassium sulphate Substances 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 229920001592 potato starch Polymers 0.000 description 1
- 229940100486 rice starch Drugs 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/22—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients stabilising the active ingredients
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
- A01N31/08—Oxygen or sulfur directly attached to an aromatic ring system
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- 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
- A61K31/185—Acids; Anhydrides, halides or salts thereof, e.g. sulfur acids, imidic, hydrazonic or hydroximic acids
- A61K31/19—Carboxylic acids, e.g. valproic acid
- A61K31/192—Carboxylic acids, e.g. valproic acid having aromatic groups, e.g. sulindac, 2-aryl-propionic acids, ethacrynic acid
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- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
- A61K47/36—Polysaccharides; Derivatives thereof, e.g. gums, starch, alginate, dextrin, hyaluronic acid, chitosan, inulin, agar or pectin
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- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
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- A61K47/50—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates
- A61K47/69—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates the conjugate being characterised by physical or galenical forms, e.g. emulsion, particle, inclusion complex, stent or kit
- A61K47/6949—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates the conjugate being characterised by physical or galenical forms, e.g. emulsion, particle, inclusion complex, stent or kit inclusion complexes, e.g. clathrates, cavitates or fullerenes
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Abstract
본 발명은 카르노스산의 용해도 향상 및 구조 안정성이 향상된 카르노스산 내포 환형 아밀로오스 복합체 및 그 제조방법에 관한 것으로, 본 발명의 카르노스산 내포 환형 아밀로오스는 수용액에서 카르노스산의 용해도 및 안정성을 증가시켜 주며, 이는 그동안 액상 식품 및 화장품, 의약품 등에 적용하지 못했던 카르노스산의 활용도를 높여주는 효과를 발휘한다. 또한, 본 발명의 카르노스산 내포 환형 아밀로오스는 과격한 환경에서도 카르노스산의 활성을 보호해주어 카르노스산의 안정성을 증가시켜 주는 효과도 발휘한다. The present invention relates to a carnoic acid-containing cyclic amylose complex having improved solubility and structural stability of carnoic acid, and a method for preparing the same, wherein the carnoic acid-containing cyclic amylose of the present invention increases the solubility and stability of carnoic acid in an aqueous solution. It is effective in enhancing the utilization of carnosic acid, which has not been applied to liquid foods, cosmetics and medicines. In addition, the carnoic acid-containing cyclic amylose of the present invention exhibits an effect of increasing the stability of carnoic acid by protecting the activity of carnoic acid even in a harsh environment.
Description
본 발명은 카르노스산이 내포되어 있는 환형 아밀로오스 복합체 및 그 제조방법에 관한 것으로, 더욱 상세하게는 카르노스산의 용해도 및 안정성이 향상된 카르노스산 내포 환형 아밀로오스 복합체 및 그 제조방법에 관한 것이다. The present invention relates to a cyclic amylose complex containing carnosic acid, and more particularly, to a carnoic acid-containing cyclic amylose complex having improved solubility and stability of carnosic acid.
로즈마리는 허브의 한 종류로서 특유의 향을 가지고 있어 냄새를 제거하는 소취제, 향을 내는 부향제로 사용되어 왔으며, 항균 및 항산화, 항바이러스 활성 등 생리활성을 갖는 것으로 알려져 있다. Rosemary is a herb that has a distinctive fragrance and has been used as a deodorant to remove odors and as a fragrance fragrance. It is known to have physiological activities such as antibacterial and anti-oxidant and antiviral activity.
과학적 문헌에 따르면 로즈마리추출물의 항산화 활성은 카르노스산 (carnosic acid), 카르노졸 (carnosol), 로즈마린산 (rosmarinic acid)과 관련되어 있음이 밝혀졌으며, 이 중 카르노스산은 강력한 항산화 작용뿐만 아니라 항균 작용을 가지는 것으로도 알려져 있다. Scientific literature has shown that the antioxidant activity of rosemary extract is associated with carnosic acid, carnosol, and rosmarinic acid, among which carnosic acid has antibacterial activity as well as strong antioxidant activity. Also known as.
하지만, 이러한 활성 물질들은 극성이 낮고 물에 대한 용해도가 현저히 낮아 수용성 액상 식품 또는 화장품에 적용하는 데 한계가 있으며, 용액에 녹아있는 상태에서는 안정성이 매우 낮아 기능성의 유지 기간이 짧은 단점이 있다.However, these active substances have a low polarity and remarkably low solubility in water, and thus are limited in application to water-soluble liquid foods or cosmetics, and have a short stability period due to their low stability in the dissolved state.
환형 아밀로오스(cycloamylose)는 6개 내지 50개의 글루칸이 α-1,4 결합으로 연결되어 고리화 구조를 이루고 있는 당류이다. 환형 아밀로오스는 내부 공동이 상대적으로 소수성이며, 외부 표면은 친수성인 분자로서 물에 대한 용해도가 높은 특징이 있다. 이러한 이유로 난용성 또는 휘발성 게스트 분자를 내포하여 복합체를 형성할 수 있으며, 게스트 분자의 수용액 내 용해도 및 안정성을 증대시키는 용도로 사용될 수 있다.Cyclic amylose (cycloamylose) is a sugar in which 6 to 50 glucans are linked by α-1,4 bonds to form a cyclized structure. Cyclic amylose is a hydrophobic molecule whose inner cavity is relatively hydrophobic and its outer surface is hydrophilic. For this reason, complexes may be formed by containing poorly soluble or volatile guest molecules, and may be used for increasing solubility and stability of aqueous molecules in aqueous solutions.
한편, 로즈마리추출물 활성 성분의 수용액 내 용해도 향상과 빠른 산화를 방지하기 위해 고안된 방법으로, 베타 환형 덱스트린 (β-cyclodextrin)을 이용한 연구가 있으며, 활성 성분 중 로즈마린산을 베타 환형 덱스트린에 캡슐화한 시스템에서 로즈마린산의 용해도가 향상되고 저장 안정성이 증가한 것으로 보고한 바 있다. On the other hand, as a method designed to improve the solubility of the rosemary extract active ingredient in the aqueous solution and to prevent rapid oxidation, there is a study using β-cyclodextrin, rosemary acid in the system encapsulated in beta cyclic dextrin among the active ingredient It has been reported that the solubility of and improved storage stability.
베타 환형 덱스트린은 산업적으로 대량 생산이 가능하여 비용이 저렴한 장점이 있지만, 수용액에서 낮은 용해도를 가지므로 사용량에 제한이 있어 이를 해결하기 위한 대체 물질이 요구된다. Beta-cyclic dextrin has the advantage of being inexpensive because it can be industrially mass-produced, but it has a low solubility in aqueous solution, so the amount of use is limited, and alternative materials are required to solve this problem.
한편, 로즈마린산보다 높은 항균 및 항산화 활성을 가지는 카르노스산과 카르노졸의 기능성 및 안정성 향상에 관한 연구는 현재까지 보고된 바 없으며, 난용성 게스트 물질의 용해도 및 안정성 향상을 위해 환형 아밀로오스를 호스트 물질로 사용한 예 또한 미비한 실정이다. On the other hand, studies on the functional and stability improvement of carnosic acid and carnosol having higher antimicrobial and antioxidant activity than rosmarinic acid have not been reported until now, and cyclic amylose was used as a host material to improve the solubility and stability of poorly soluble guest material. Yes is also insufficient.
본 발명은 난용성인 카르노스산의 수용액 내 용해도 및 안정성을 향상시킬 수 있는 복합체 제조 기술을 개발하여 제공하고자 한다. The present invention is to develop and provide a technology for producing a composite that can improve the solubility and stability in the aqueous solution of poorly soluble carnosic acid.
본 발명은 카르노스산(carnosic acid)이 내포되어 있는 환형 아밀로오스 복합체를 제공한다. The present invention provides a cyclic amylose complex containing carnosic acid.
본 발명의 환형 아밀로오스 복합체에 있어서, 상기 카르노스산이 내포되어 있는 환형 아밀로오스 복합체는, 바람직하게 카르노스산에 비해 수용액 상에서 용해도가 증가되어 있다.In the cyclic amylose complex of the present invention, the cyclic amylose complex containing the carnosic acid preferably has increased solubility in aqueous solution compared to carnosic acid.
본 발명은 카르노스산이 내포되어 있는 환형 아밀로오스 복합체를 포함하는 항균제를 제공한다.The present invention provides an antimicrobial agent comprising a cyclic amylose complex containing carnosic acid.
본 발명은 카르노스산 또는 카르노스산이 함유된 로즈마리추출물을 함유하는 용액과 환형 아밀로오스를 함유하는 용액을 혼합한 후, 빛을 차단한 상태로 교반하면서 반응시키는 것을 특징으로 하는 카르노스산 내포 환형 아밀로오스 복합체의 제조방법을 제공한다. According to the present invention, a solution containing a carnoic acid or a carbolic acid containing a rosemary extract and a solution containing a cyclic amylose are mixed, and then reacted while stirring while blocking light. It provides a manufacturing method.
본 발명의 카르노스산 내포 환형 아밀로오스 복합체의 제조방법에 있어서, 상기 카르노스산 또는 카르노스산이 함유된 로즈마리추출물을 함유하는 용액은, 바람직하게 카르노스산 분말 또는 카르노스산이 함유된 로즈마리추출물 분말을 에탄올, 메탄올, DMSO 중 선택되는 어느 하나의 용매에 용해시켜 제조한 것일 수 있고, 상기 환형 아밀로오스를 함유하는 용액은, 바람직하게 환형 아밀로오스를 정제수, 에탄올, 메탄올, DMSO 중 선택되는 어느 하나의 용매에 용해시켜 제조한 것일 수 있다. In the method for producing a carnoic acid-containing cyclic amylose complex of the present invention, the solution containing the carnoic acid or the rosemary extract containing the carnosic acid is preferably a carnoic acid powder or a rosemary extract powder containing the carnoic acid in ethanol or methanol. , May be prepared by dissolving in any one solvent selected from DMSO, the solution containing the cyclic amylose is preferably prepared by dissolving the cyclic amylose in any one solvent selected from purified water, ethanol, methanol, DMSO It may be one.
본 발명의 카르노스산 내포 환형 아밀로오스 복합체의 제조방법에 있어서, 상기 환형 아밀로오스는, 바람직하게 중합도가 7~41일 수 있다. In the method for producing a carnoic acid-containing cyclic amylose complex of the present invention, the cyclic amylose may preferably have a degree of polymerization of 7 to 41.
본 발명의 카르노스산 내포 환형 아밀로오스 복합체의 제조방법에 있어서, 상기 반응은, 바람직하게 20~40℃의 온도로 12~48시간 동안 수행하는 것이 좋다. In the method for producing a carnoic acid-containing cyclic amylose complex of the present invention, the reaction is preferably performed for 12 to 48 hours at a temperature of 20 ~ 40 ℃.
본 발명은 카르노스산 내포 환형 아밀로오스 복합체가 수용액에서 카르노스산의 용해도 및 안정성을 증가시켜 준다. In the present invention, the carnoic acid-containing cyclic amylose complex increases the solubility and stability of the carnoic acid in an aqueous solution.
또한, 이는 그동안 액상 식품 및 화장품, 의약품 등에 적용하지 못했던 카르노스산의 활용도를 높여주는 효과를 발휘한다.In addition, this has the effect of increasing the utilization of carnosic acid, which has not been applied to liquid food, cosmetics, and medicines.
또한, 본 발명의 카르노스산 내포 환형 아밀로오스 복합체는 과격한 환경에서도 카르노스산의 안정성을 증가시켜 카르노스산의 기능성을 보호해 주는 효과도 발휘한다. In addition, the carnotic acid-containing cyclic amylose complex of the present invention exhibits an effect of increasing the stability of carnosic acid and protecting the function of carnosic acid even in a harsh environment.
도 1은 환형 아밀로오스의 농도에 따라 로즈마리추출물과의 복합체 내에 포함되는 카르노스산의 함량을 측정한 그래프이다. 또한, 환형 아밀로오스의 각 농도에 따라 카르노스산이 복합체 내에 포함되는 데 걸리는 반응 시간을 나타낸다. 이때, 대조군은 환형 아밀로오스를 포함하지 않는 단일 로즈마리추출물의 카르노스산의 함량을 나타낸 것이다.
도 2는 환형 아밀로오스의 농도에 따라 로즈마리추출물과의 복합체를 제조하였을 때 수용액에 용해되어 있는 카르노스산의 용해도를 나타낸 그래프이다. 비교물질로 베타 환형 덱스트린과 말토덱스트린을 사용한 결과를 포함한다. 대조군인 호스트 물질 0%는 호스트 물질이 포함되지 않은 단일 로즈마리추출물에 존재하는 카르노스산의 용해도를 나타낸 것이다.
도 3은 로즈마리추출물과 환형 아밀로오스 복합체에서 환형 아밀로오스가 항산화 물질의 열안정성에 기여하는 바를 확인한 결과를 나타낸 그래프이다. 이때, 대조군은 환형 아밀로오스를 포함하지 않는 단일 로즈마리추출물을 나타낸다. 또한, 각 조성물에 열을 가하기 전의 항산화 활성을 100%로 나타내고 열을 가한 후의 항산화 활성을 상대적으로 측정하여 나타낸 것이다.
도 4는 '로즈마리추출물과 환형 아밀로오스의 복합체'와 '로즈마리추출물과 말토덱스트린 복합체'의 열안정성을 비교한 그래프이다. 농도별 환형 아밀로오스를 사용한 것과 비교물질로 농도별 말토덱스트린을 사용한 복합체에 열을 가한지 24시간 째 항산화 활성을 나타낸 것이다.1 is a graph measuring the content of carnosic acid contained in the complex with rosemary extract according to the concentration of cyclic amylose. In addition, the reaction time taken for the carnosic acid to be included in the complex according to each concentration of the cyclic amylose. At this time, the control group shows the content of carnosic acid of a single rosemary extract that does not contain cyclic amylose.
2 is a graph showing the solubility of carnosic acid dissolved in an aqueous solution when a complex with rosemary extract was prepared according to the concentration of cyclic amylose. The results include the use of beta cyclic dextrins and maltodextrins as comparables. The
3 is a graph showing the results confirming that the cyclic amylose contributes to the thermal stability of the antioxidant substance in the rosemary extract and the cyclic amylose complex. At this time, the control group represents a single rosemary extract containing no cyclic amylose. In addition, the antioxidant activity before adding heat to each composition is represented by 100%, and the antioxidant activity after applying heat is measured and shown relatively.
Figure 4 is a graph comparing the thermal stability of the 'rosemary extract and cyclic amylose complex' and 'rosemary extract and maltodextrin complex'. Antioxidant activity was shown 24 hours after heat was applied to the complex using the concentration of cyclic amylose by concentration and maltodextrin by concentration.
본 발명은 카르노스산(carnosic acid)이 내포되어 있는 환형 아밀로오스 복합체를 제공한다. 본 발명은 카르노스산이 내포되어 있는 환형 아밀로오스 복합체를 포함하는 항균제를 제공한다. 또한, 본 발명은 카르노스산 또는 카르노스산이 함유된 로즈마리추출물을 함유하는 용액과 환형 아밀로오스를 함유하는 용액을 혼합한 후, 빛을 차단한 상태로 교반하면서 반응시키는 것을 특징으로 하는 카르노스산 내포 환형 아밀로오스 복합체의 제조방법을 제공한다. The present invention provides a cyclic amylose complex containing carnosic acid. The present invention provides an antimicrobial agent comprising a cyclic amylose complex containing carnosic acid. In addition, the present invention is mixed with a solution containing a carnoic acid or a rosemary extract containing carnosic acid and a solution containing a cyclic amylose, and then reacted while stirring while blocking the light, carnosic acid-containing cyclic amylose It provides a method for producing a composite.
이상과 같이 제조한 본 발명의 카르노스산 내포 환형 아밀로오스 복합체는 카르노스산에 비해 수용액 상에서 용해도가 증가되어 있다. 또한, 복합체 내 카르노산의 안정성도 증가되어 있는 특징도 있다. Carnoic acid-containing cyclic amylose complex of the present invention prepared as described above has increased solubility in aqueous solution compared to carnosic acid. In addition, there is also a feature that the stability of carnoic acid in the complex is also increased.
본 발명에서는 시판중인 환형 아밀로오스를 사용할 수 있는데, 바람직하게 중합도가 7~41인 것을 사용하는 것이 좋다. 또한, 필요에 따라 전분으로부터 환형 아밀로오스를 제조하여 사용할 수도 있다. 환형 아밀로오스를 제조하기 위해서는 일 예로 쌀전분, 고구마전분 또는 옥수수전분을 사용할 수 있다. 바람직하게는 아밀로오스 함량이 높은 전분을 사용하는 것이며, 가장 바람직하게는 아밀로오스 함량이 60% 이상인 고아밀로오스 옥수수전분을 사용하는 것이다. 상기의 전분으로부터 환형 아밀로오스를 제조하는 구체적인 방법은 당업계에 알려진 공지의 기술을 사용할 수 있으므로, 이에 관한 구체적 기재는 생략하기로 한다. In the present invention, a commercially available cyclic amylose can be used, but it is preferable to use one having a polymerization degree of 7 to 41. If necessary, cyclic amylose can also be produced from starch. To prepare cyclic amylose, for example, rice starch, sweet potato starch or corn starch may be used. Preferably, starch with a high amylose content is used, and most preferably, high amylose corn starch having an amylose content of 60% or more. Since the specific method for preparing the cyclic amylose from the starch may use a technique known in the art, a detailed description thereof will be omitted.
한편, 본 발명에서는 카르노스산 또는 카르노스산이 함유된 로즈마리추출물을 사용하는데, 카르노스산이 함유된 로즈마리추출물의 경우 바람직하게 카르노스산을 50~70% 정도 함유되어 있는 것을 사용할 수 있다. On the other hand, in the present invention, a carnoic acid or a rosemary extract containing carnosic acid is used, but in the case of a rosemary extract containing carnosic acid, one containing about 50 to 70% of carnosic acid can be preferably used.
본 발명의 카르노스산 내포 환형 아밀로오스 복합체 제조 시, 카르노스산 또는 로즈마리추출물 용액의 제조를 위해 사용되는 용매는 일 예로 에탄올, 메탄올, DMSO 등을 사용할 수 있다. 가장 바람직하게는 80% 이상의 에탄올을 사용하는 것이다. 또한, 환형 아밀로오스 용액의 제조를 위해 사용되는 용매는 일 예로, 정제수, 에탄올, 메탄올, DMSO 등을 사용할 수 있다. 바람직하게는 50% 이하의 에탄올이며, 가장 바람직하게는 정제수이다.When preparing the carnoic acid-containing cyclic amylose complex of the present invention, a solvent used for preparing a carnoic acid or a rosemary extract solution may be, for example, ethanol, methanol, DMSO, or the like. Most preferably, at least 80% ethanol is used. In addition, the solvent used for the preparation of the cyclic amylose solution may be, for example, purified water, ethanol, methanol, DMSO and the like. Preferably it is 50% or less of ethanol, and most preferably purified water.
본 발명에서 일 예로 에탄올에 녹인 카르노스산 함유 로즈마리추출물의 농도는 건조 중량 기준으로 10% 이상부터 최대 용해될 수 있는 양까지 용해시킬 수 있으며, 바람직하게는 20% 이상부터 최대 용해될 수 있는 양까지 용해시킬 수 있다. 또한, 일 예로 정제수에 녹인 환형 아밀로오스의 농도는 건조 중량 기준으로 0.5~30% 용해시켜 사용할 수 있으며 바람직하게는 5~30% 용해시켜 사용할 수 있다. 이상과 같이 제조한 에탄올에 녹인 카르노스산 함유 로즈마리추출물과 정제수에 녹인 환형 아밀로오스를 혼합하여 5~20% 에탄올에 카르노스산 함유 로즈마리추출물과 환형 아밀로오스가 포함되도록 제조된다. 이후, 빛을 차단한 상태로 교반하면서 반응시키면 카르노스산이 내포된 환형 아밀로오스 복합체가 제조된다. 교반은 항온 수조에서 일정하게 교반하는 것이 좋다.In the present invention, for example, the concentration of carnosic acid-containing rosemary extract dissolved in ethanol may be dissolved from 10% or more to the maximum solubilizable amount, based on dry weight, preferably from 20% or more to the maximum soluble amount. Can be dissolved. In addition, as an example, the concentration of the cyclic amylose dissolved in purified water may be used by dissolving 0.5-30% on a dry weight basis, and preferably by dissolving 5-30%. The carnoic acid-containing rosemary extract dissolved in ethanol prepared as described above and cyclic amylose dissolved in purified water are mixed to prepare the carnoic acid-containing rosemary extract and cyclic amylose in 5-20% ethanol. Thereafter, the reaction is carried out while stirring in a light-blocking state to prepare a cyclic amylose complex containing carnosic acid. Stirring is preferably stirred constantly in a constant temperature water bath.
한편, 본 발명에서 카르노스산 내포 환형 아밀로오스 복합체의 제조 시, 반응시간은 12~48시간인 것이 바람직하다. 가장 바람직하게는 24~48시간 반응시키는 것이 좋다. 또한, 반응온도는 20~40℃ 사이인 것이 좋고, 바람직하게는 25~37℃인 것이 좋다. On the other hand, in the preparation of the carnoic acid-containing cyclic amylose complex in the present invention, the reaction time is preferably 12 to 48 hours. Most preferably, the reaction is carried out for 24 to 48 hours. Moreover, it is good that reaction temperature is between 20-40 degreeC, Preferably it is 25-37 degreeC.
한편, 이상과 같이 제조한 본 발명의 카르노스산 내포 환형 아밀로오스 복합체는 동결건조하여 분말화할 수 있다.On the other hand, the carnotic acid-containing cyclic amylose complex of the present invention prepared as described above can be lyophilized and powdered.
이하, 본 발명의 이해를 돕기 위해 바람직한 실시예 및 실험예를 제시한다. 다만, 하기 실시예 및 실험예는 본 발명의 이해를 돕기 위하여 제시되는 것일 뿐 본 발명이 하기 실시예 및 실험예로 한정되는 것은 아니다.Hereinafter, preferred examples and experimental examples are presented to help understand the present invention. However, the following Examples and Experimental Examples are only presented to aid the understanding of the present invention, and the present invention is not limited to the following Examples and Experimental Examples.
[[ 실시예Example 1: 본 발명의 1: of the present invention 고아밀로오스Goamylose 옥수수전분으로부터 환형 아밀로오스 제조] Cyclic Amylose Production from Corn Starch]
환형 아밀로오스를 제조하기 위하여, 건조 중량 1%의 고아밀로오스 옥수수전분 (Hylon Ⅶ, National Starch and Chemical Company) 을 50mM 소듐 아세테이트 완충액 (sodium acetate buffer, pH 4.5) 에 완전히 용해시켜 호화 과정을 거친 후 이소아밀레이즈 (Pseudomonas sp ., 280U/mg, Megazyme) 5U/g을 40℃에서 8시간 반응시켰다. To prepare cyclic amylose, 1% dry amylose cornstarch (Hylon Ⅶ, National Starch and Chemical Company) was completely dissolved in 50 mM sodium acetate buffer (pH 4.5), subjected to gelatinization and isoamyl. Raise ( Pseudomonas sp . , 280U / mg, Megazyme) 5U / g was reacted at 40 ° C for 8 hours.
반응이 끝난 후 10분간 끓여 효소를 불활성화시키고, 5배가량의 95% 에탄올을 첨가하여 원심분리하고 탈분지화된 전분을 회수한 후 건조시켰다. 탈분지화된 전분 1% (w/v) 를 소량의 90% (v/v) 다이메틸설폭사이드 (dimethyl sulfoxide, DMSO) 에 완전히 용해시킨 후 50mM 트리스-염산 완충액 (Tris-HCl buffer, pH 7.5 ) 을 첨가하여 테르무스 아쿠아티쿠스 (Thermus aquaticus) 유래의 4-α-글루카노트랜스퍼레이즈 (TAαGTase) 10U/g을 가해 75℃에서 14시간 반응시켰다. 반응이 끝난 후 10분간 끓여 효소를 불활성화시키고 5배 가량의 95% 에탄올을 첨가하여 원심분리하였다. After the reaction, the reaction was boiled for 10 minutes to inactivate the enzyme, centrifuged by adding 5 times 95% ethanol, and the dried starch was recovered after drying. 1% (w / v) of debranched starch was completely dissolved in a small amount of 90% (v / v) dimethyl sulfoxide (DMSO), followed by 50 mM Tris-HCl buffer (pH 7.5). ) By adding Termus Aquaticus ( Thermus) aquaticus ) -derived 4-α-glucanotransferase (TAαGTase) 10 U / g was added and reacted at 75 ° C. for 14 hours. After the reaction, the reaction was boiled for 10 minutes to inactivate the enzyme and centrifuged by adding 5 times 95% ethanol.
침전된 반응물을 50mM 소듐 아세테이트 완충액 (pH 4.5) 에 용해시키고 50U/g의 글루카노트랜스퍼레이즈 (Hormoconis resinae, 64 U/mg, Megazyme) 를 가하여 40℃에서 10시간 이상 반응시켰다. 반응이 끝난 후, 10분간 끓여 효소를 불활성화시키고, 5배가량의 95% 에탄올과 80% 에탄올을 차례로 첨가하여 원심분리하여 침전된 환형 아밀로오스를 회수하고, 소량의 증류수에 녹인 후 동결건조하여 분말 제형의 환형 아밀로오스를 제조하였다.The precipitated reaction was dissolved in 50 mM sodium acetate buffer (pH 4.5) and 50 U / g glucanotransferase ( Hormoconis resinae , 64 U / mg, Megazyme) were added and reacted for 10 hours at 40 ° C. After the reaction, boil for 10 minutes to inactivate the enzyme, centrifuged by adding about 5 times 95% ethanol and 80% ethanol in order to recover the precipitated cyclic amylose, dissolved in a small amount of distilled water and then lyophilized to powder Cyclic amylose of the formulation was prepared.
[[ 실시예Example 2: 본 발명 ' 2: present invention '' 로즈마리추출물과Rosemary Extract 환형 아밀로오스 복합체'의 제조] Preparation of Cyclic Amylose Complexes]
로즈마리추출물 분말 0.5g을 95% 에탄올 2.5mL에 완전히 용해시키고, 환형 아밀로오스는 농도별로 각각 0.25g, 0.5g, 2.5g, 5g, 10g, 15g을 증류수 47.5mL에 용해시켜 각각 준비하였다 (이들 환형 아밀로오스의 농도별 샘플들이 도 1 내지 도 4에 기재한 CA 0.5, 1, 5, 10, 20, 30% 샘플을 각각 의미함). 0.5 g of rosemary extract powder was completely dissolved in 2.5 mL of 95% ethanol, and cyclic amylose was prepared by dissolving 0.25 g, 0.5 g, 2.5 g, 5 g, 10 g, and 15 g in 47.5 mL of distilled water, respectively. Concentrations of samples refer to CA 0.5, 1, 5, 10, 20, 30% samples described in Figures 1 to 4, respectively).
이상과 같이 준비한 로즈마리추출물 용액과 환형 아밀로오스 용액을 1:19의 부피 비율로 혼합한 후 빛을 차단한 상태로 25℃에서 48시간 동안 교반하였다. 48시간 후, 로즈마리추출물과 환형 아밀로오스 복합 조성물을 0.45㎛ 필터로 여과한 후 72시간 동안 동결건조하여 분말화된 복합체를 제조하였다.The rosemary extract solution and the cyclic amylose solution prepared as described above were mixed at a volume ratio of 1:19, and then stirred at 25 ° C. for 48 hours while blocking light. After 48 hours, the rosemary extract and the cyclic amylose complex composition were filtered through a 0.45 μm filter, and then lyophilized for 72 hours to prepare a powdered complex.
[[ 실험예Experimental Example 1: 본 발명의 1: of the present invention 로즈마리추출물과Rosemary Extract 환형 아밀로오스 복합체 제조 조건] Cyclic Amylose Complex Production Conditions]
실시예 2의 방법에 따라 각 조성물의 복합체를 제조하고 8시간, 24시간, 48시간에 각 샘플을 취하여 0.45㎛ 필터로 여과한 후 285nm에서 흡광도를 측정하여 로즈마리추출물과 환형 아밀로오스 복합체에 존재하는 카르노스산의 농도를 정량하였다. The composite of each composition was prepared according to the method of Example 2, each sample was taken at 8 hours, 24 hours, and 48 hours, filtered through a 0.45 μm filter, and the absorbance was measured at 285 nm. Carnos present in the rosemary extract and the cyclic amylose complex. The concentration of the acid was quantified.
로즈마리추출물에 존재하는 카르노스산을 정량화하기 위해 카르노스산 표준물질 (Sigma, USA) 을 95% 에탄올에 녹인 후 200~600nm 범위에서 분광광도계를 이용하여 흡광도 스펙트럼을 측정하였다. 측정된 흡광 파장 범위에서 카르노스산 표준물질의 농도별 (0~0.015 wt.%) 흡광도를 측정하여 표준곡선을 그린 후, 로즈마리추출물 내의 카르노스산 또는 복합체 내의 카르노스산의 흡광도 값을 표준곡선으로부터 얻은 수식에 대입하여 역으로 계산하여 정량하였다.In order to quantify carnosic acid in rosemary extract, carnosic acid standard (Sigma, USA) was dissolved in 95% ethanol and absorbance spectra were measured using a spectrophotometer in the range of 200-600 nm. After measuring the absorbance for each concentration of carnosic acid standard (0 ~ 0.015 wt.%) In the measured absorption wavelength range, draw the standard curve, and then calculate the absorbance value of carnosic acid in the rosemary extract or carnosic acid in the complex from the standard curve. Substituted in the reverse calculation and quantified.
도 1은 환형 아밀로오스 농도와 교반 시간에 따른 복합체에 포함된 카르노스산의 농도를 구한 결과를 나타낸다. 단일 카르노스산인 대조구는 수용액에서 존재하는 농도가 가장 낮았으며, 환형 아밀로오스의 농도가 증가할수록 복합체를 형성하는 카르노스산의 농도도 증가하였다. 또한, 10% 이상의 환형 아밀로오스와 카르노스산이 복합체를 형성하기 위해서는 24시간 이상의 시간이 소요되는 것으로 나타났다.Figure 1 shows the results obtained by calculating the concentration of carnoic acid contained in the complex according to the cyclic amylose concentration and the stirring time. The control group, which is a single carnosic acid, had the lowest concentration in the aqueous solution, and as the concentration of the cyclic amylose increased, the concentration of the carnosic acid forming the complex also increased. In addition, more than 10% of cyclic amylose and carnosic acid were found to take more than 24 hours to form a complex.
[실험예 2: 본 발명의 로즈마리추출물과 환형 아밀로오스 복합체의 수용액에서의 용해도 평가]Experimental Example 2: Evaluation of Solubility in Aqueous Solution of Rosemary Extract of the Present Invention and Cyclic Amylose Complex
실시예 2에 따라 로즈마리추출물과 환형 아밀로오스 복합체를 제조하고, 48시간 후, 각 샘플을 0.45㎛ 필터로 여과한 후 분광광도계를 이용하여 285nm에서 흡광도를 측정하여 복합체 용액에 존재하는 카르노스산의 농도를 구하였다. 이때, 환형 아밀로오스의 비교물질로 베타 환형 덱스트린과 중합도 8~12를 가지는 말토덱스트린 (maltodextrin, MD)을 사용하여 같은 조건으로 복합체를 제조하였다. 카르노스산의 농도는 상기 실험예 1의 방법으로 측정하였다. According to Example 2, a rosemary extract and a cyclic amylose complex were prepared, and after 48 hours, each sample was filtered with a 0.45 μm filter, and then absorbance was measured at 285 nm using a spectrophotometer to determine the concentration of carnosic acid present in the complex solution. Obtained. At this time, the composite was prepared under the same conditions by using beta cyclic dextrin and maltodextrin (maltodextrin, MD) having a polymerization degree of 8 to 12 as comparative substances of cyclic amylose. Carnosic acid concentration was measured by the method of Experimental Example 1.
도 2는 환형 아밀로오스의 농도가 증가함에 따라 수용액에 용해되어 있는 카르노스산의 함량이 증가한 결과를 나타낸다. 난용성의 카르노스산이 환형 아밀로오스와 복합체를 형성함으로써 물에 대한 용해도가 향상된 것으로 보여진다. Figure 2 shows the result of increasing the content of carnoic acid dissolved in the aqueous solution as the concentration of the cyclic amylose increases. It has been shown that solubility in water is enhanced by the insoluble carnosic acid complexing with cyclic amylose.
비교물질로 사용된 베타 환형 덱스트린은 낮은 농도에서 카르노스산의 용해도를 증가시키는 역할을 하나, 높은 농도에서는 자체의 낮은 용해도로 인해 카르노스산의 용해도를 오히려 감소시키는 결과를 나타내었다. The beta cyclic dextrin used as a comparator increases the solubility of carnoic acid at low concentrations, but at higher concentrations, the solubility of carnoic acid is rather reduced due to its low solubility.
또 다른 비교물질로 사용된 말토덱스트린은 농도가 증가할수록 카르노스산의 용해도를 증가시켜 주었으나, 환형 아밀로오스와 비교해서 더 높은 용해도를 나타내지는 못하였다. 즉, 카르노스산의 물에 대한 용해도는 환형 아밀로오스, 말토덱스트린, 베타 환형 덱스트린 순으로 기여도가 높았다. Maltodextrin, used as another comparator, increased the solubility of carnosic acid with increasing concentration, but did not show higher solubility compared to cyclic amylose. In other words, the solubility of carnosic acid in water was the highest in order of cyclic amylose, maltodextrin, and beta cyclic dextrin.
[실험예 3: 본 발명 로즈마리추출물과 환형 아밀로오스 복합체의 수용액에서 항균력 측정]Experimental Example 3: Measurement of Antimicrobial Activity in an Aqueous Solution of the Invention of Rosemary Extract and Cyclic Amylose Complex
실시예 2에서 제조한 로즈마리추출물과 환형 아밀로오스 복합체의 미생물에 대한 항균력을 평가하였다. 항균력 시험에 사용된 미생물은 그람 양성균인 바실러스 서브틸리스 (Bacillus subtilis ATCC 6633) 균주이고, 항균력을 평가하는 방법은 미생물의 최소생육저해농도 (MIC, Minimal Inhibitory Concentration) 를 측정하는 방법을 사용하였다. The antimicrobial activity of the rosemary extract prepared in Example 2 and the cyclic amylose complex against microorganisms was evaluated. The microorganism used in the antimicrobial activity test was a Gram-positive bacterium Bacillus subtilis ATCC 6633 (microbial strain), and the method of evaluating the antimicrobial activity was measured by measuring the minimum inhibitory concentration (MIC).
미생물은 영양 배지 (Nutrient broth, DifcoTM, USA) 에서 30℃ 온도에서 24시간 전배양하여 활성화시킨 후, 이를 105-6 CFU/㎖ 의 농도가 되도록 희석하여 준비하였다. 각 농도별 환형 아밀로오스와 로즈마리추출물 복합체에 포함된 카르노스산의 농도를 분광광도계를 이용하여 정량화하였고, 각 샘플을 96 웰 플레이트 (96 well plate) 에 200㎕ 씩 분주한 후 배지를 이용하여 단계희석하였다. 준비한 미생물을 각 well에 100㎕ 씩 분주하고 30℃에서 24시간 배양한 후 MIC 결과를 확인하였다. 그 결과는 하기 표 1에 나타내었다.The microorganisms were prepared by activating by preculture in a nutrient medium (Nutrient broth, DifcoTM, USA) for 24 hours at 30 ℃ temperature, diluted to a concentration of 10 5-6 CFU / ㎖. The concentration of carnosic acid in the cyclic amylose and rosemary extract complex at each concentration was quantified using a spectrophotometer, and 200 μl of each sample was placed in a 96 well plate, followed by step dilution using a medium. . 100 μl of the prepared microorganisms were dispensed into each well and incubated at 30 ° C. for 24 hours to confirm MIC results. The results are shown in Table 1 below.
상기 표 1에 나타난 바와 같이, 로즈마리추출물과 환형 아밀로오스 복합체의 항균 활성을 측정한 결과, 환형 아밀로오스의 농도가 증가할수록 항균 활성이 향상되는 것을 확인할 수 있다. As shown in Table 1, as a result of measuring the antimicrobial activity of the rosemary extract and the cyclic amylose complex, it can be seen that the antimicrobial activity is improved as the concentration of the cyclic amylose increases.
이는 수용액에서 불안정한 카르노스산이 환형 아밀로오스와 복합체를 형성함으로써 안정성이 증대되어 항균 활성에 영향을 미치는 것으로 보여진다.It is shown that unstable carnosic acid in aqueous solution forms a complex with cyclic amylose, which increases stability and affects antimicrobial activity.
[실험예 4: 로즈마리추출물과 환형 아밀로오스 복합체의 열 안정성 측정을 위한 열 가속실험]Experimental Example 4: Thermal Acceleration Test for Measurement of Thermal Stability of Rosemary Extract and Cyclic Amylose Complex
실시예 2에서 제조한 로즈마리추출물과 환형 아밀로오스 복합체의 열 안정성을 평가하였다. 이때, 비교 물질로 8~12의 중합도를 가지는 말토덱스트린 (MD)을 사용하여 복합체를 제조하였다. The thermal stability of the rosemary extract and the cyclic amylose complex prepared in Example 2 was evaluated. At this time, the composite was prepared using maltodextrin (MD) having a polymerization degree of 8 to 12 as a comparative material.
각 조성물 (실시예 2 및 말토덱스트린을 사용한 비교 물질)을 90℃ 항온수조에서 24시간 동안 열처리하였고, 2시간 간격으로 샘플링하여 복합체의 항산화 활성을 평가하였다. 항산화 활성 측정은 ABTS 라디칼 소거능 측정 방법을 이용하였고, 이 방법은 ABTS가 포타슘 펄설페이트 (potassium persulfate) 와의 반응에 의해 생성된 ABTS 양이온이 시료 내의 항산화 물질에 의해 제거되어 탈색되는 것을 이용한 항산화능 측정 방법이다. Each composition (Example 2 and comparative material using maltodextrin) was heat-treated in a 90 ° C. constant temperature water bath for 24 hours and sampled at 2 hour intervals to evaluate the antioxidant activity of the complex. Antioxidant activity was measured using the ABTS radical scavenging method, which is an ABTS cation that reacts with potassium persulfate to remove the ABTS cation by the antioxidant in the sample. to be.
7mM ABTS와 2.45mM 포타슘 펄설페이트를 혼합하고, 상온에서 24시간 반응시킨 후 ABTS 양이온을 형성시켰다. ABTS 양이온이 포함된 용액을 증류수로 희석하여 734nm에서 흡광도 값이 0.7이 되도록 준비하였다. ABTS 양이온 용액 1㎖에 샘플 10㎕를 가하여 상온에서 20분 동안 방치 후에 흡광도를 측정하였다. 항산화 활성은 샘플을 녹인 용매인 5% 에탄올을 대조군으로 사용하여 다음의 수학식 1로 라디칼 소거능을 상대적인 백분율로 나타내었다. 7 mM ABTS and 2.45 mM potassium sulphate were mixed and reacted at room temperature for 24 hours to form ABTS cations. The solution containing the ABTS cation was diluted with distilled water to prepare an absorbance value of 0.7 at 734 nm. 10 μl of sample was added to 1 ml of ABTS cation solution, and the absorbance was measured after standing at room temperature for 20 minutes. Antioxidant activity was expressed as a relative percentage of radical scavenging ability by the following equation (1) using 5% ethanol, the solvent in which the sample was dissolved, as a control.
[수학식 1][Equation 1]
ABTS radical scavenging activity = (1 - Atest/ Acontrol) x 100ABTS radical scavenging activity = (1-A test / A control ) x 100
도 3은 열을 가해 항산화 활성을 감속시키는 환경에서 환형 아밀로오스가 항산화 물질의 안정성에 영향을 주는 결과를 나타낸 것이다. 환형 아밀로오스가 포함되어 있지 않은 단일 로즈마리추출물은 열을 가하는 24시간 동안 항산화 활성이 크게 감소하는 반면, 환형 아밀로오스와의 복합체는 항산화 활성이 덜 감소하는 것을 확인할 수 있으며, 특히 환형 아밀로오스의 농도가 5% 이상에서는 항산화 활성에 큰 차이가 없는 것을 확인할 수 있다. 이 결과는 환형 아밀로오스가 로즈마리추출물과 복합체를 형성하여 항산화 물질의 열안정성에 기여하는 것으로 보여진다.Figure 3 shows the results of the effect of the cyclic amylose on the stability of the antioxidant substances in the environment to reduce the antioxidant activity by applying heat. Single rosemary extract containing no cyclic amylose significantly reduced antioxidant activity during the 24 hours of heating, whereas the complex with cyclic amylose showed less antioxidant activity, in particular the concentration of cyclic amylose was 5%. In the above it can be seen that there is no significant difference in the antioxidant activity. These results show that cyclic amylose complexes with rosemary extract and contributes to the thermal stability of antioxidants.
도 4는 환형 아밀로오스의 비교물질로 말토덱스트린을 사용하여 열을 가해준 지 24시간 째의 복합체의 항산화 활성을 측정하여 나타낸 것이다. 그 결과, 0.5~1%의 환형 아밀로오스와 말토덱스트린 사이에는 큰 차이가 없으나, 5% 이상의 환형 아밀로오스와 말토덱스트린의 경우 큰 차이가 있음을 확인할 수 있었다. 말토덱스트린은 높은 농도에서도 항산화 활성이 크게 감소한 것으로 보아 항산화 물질의 열안정성에 크게 기여하지 않는 것으로 보여진다.Figure 4 shows the antioxidant activity of the complex at 24 hours after heat was applied using maltodextrin as a comparative substance of cyclic amylose. As a result, there was no significant difference between 0.5-1% of cyclic amylose and maltodextrin, but more than 5% of cyclic amylose and maltodextrin was confirmed to have a big difference. Maltodextrin does not appear to contribute significantly to the thermal stability of antioxidants due to the significant decrease in antioxidant activity even at high concentrations.
Claims (7)
상기 카르노스산 내포 환형 아밀로오스 복합체는 카르노스산에 비해 수용액 상에서 용해도가 증가되어 있는 것을 특징으로 하는 항균제의 제조방법.
After mixing a solution containing carnosic acid or a rosemary extract containing carnosic acid and a solution containing cyclic amylose at a concentration of 5 to 30% (w / v), the solution is stirred at 20 to 40 Reacting for 12 to 48 hours at a temperature to produce a carnosic acid-containing cyclic amylose complex,
The carnosic acid-containing cyclic amylose complex is a method for producing an antimicrobial agent, characterized in that the solubility is increased in aqueous solution compared to carnosic acid.
상기 카르노스산 또는 카르노스산이 함유된 로즈마리추출물을 함유하는 용액은,
카르노스산 분말 또는 카르노스산이 함유된 로즈마리추출물 분말을 에탄올, 메탄올, DMSO 중 선택되는 어느 하나의 용매에 용해시켜 제조한 것을 특징으로 하고,
상기 환형 아밀로오스를 함유하는 용액은,
환형 아밀로오스를 정제수, 에탄올, 메탄올, DMSO 중 선택되는 어느 하나의 용매에 용해시켜 제조한 것을 특징으로 하는 항균제의 제조방법.
The method of claim 4, wherein
The solution containing the rosemary extract containing the carnosic acid or carnosic acid,
Characterized in that it was prepared by dissolving carnosic acid powder or rosemary extract powder containing carnosic acid in any one solvent selected from ethanol, methanol, DMSO,
The solution containing the cyclic amylose,
A method for producing an antimicrobial agent, characterized in that it is prepared by dissolving cyclic amylose in any one solvent selected from purified water, ethanol, methanol, and DMSO.
상기 환형 아밀로오스는,
중합도가 7~41인 것을 특징으로 하는 항균제의 제조방법.
The method of claim 4, wherein
The cyclic amylose is,
A method for producing an antibacterial agent, characterized in that the degree of polymerization is 7 to 41.
상기 카르노스산 내포 환형 아밀로오스 복합체는 카르노스산에 비해 수용액 상에서 용해도가 증가되어 있는 것을 특징으로 하는 항산화제의 제조방법.After mixing a solution containing carnosic acid or a rosemary extract containing carnosic acid and a solution containing cyclic amylose at a concentration of 5 to 30% (w / v), the solution is stirred at 20 to 40 Reacting for 12 to 48 hours at a temperature to produce a carnosic acid-containing cyclic amylose complex,
The carnosic acid-containing cyclic amylose complex has an increased solubility in aqueous solution compared to carnosic acid.
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