JP5410734B2 - Process for producing refined sake enzyme - Google Patents
Process for producing refined sake enzyme Download PDFInfo
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- JP5410734B2 JP5410734B2 JP2008291777A JP2008291777A JP5410734B2 JP 5410734 B2 JP5410734 B2 JP 5410734B2 JP 2008291777 A JP2008291777 A JP 2008291777A JP 2008291777 A JP2008291777 A JP 2008291777A JP 5410734 B2 JP5410734 B2 JP 5410734B2
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- 102000004190 Enzymes Human genes 0.000 title claims description 45
- 108090000790 Enzymes Proteins 0.000 title claims description 44
- 238000000034 method Methods 0.000 title description 11
- 229940088598 enzyme Drugs 0.000 claims description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 43
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 28
- 239000008103 glucose Substances 0.000 claims description 28
- 235000019420 glucose oxidase Nutrition 0.000 claims description 25
- 238000004519 manufacturing process Methods 0.000 claims description 25
- 108010015776 Glucose oxidase Proteins 0.000 claims description 24
- 239000004366 Glucose oxidase Substances 0.000 claims description 24
- 229940116332 glucose oxidase Drugs 0.000 claims description 24
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 16
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Natural products OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 16
- 239000000174 gluconic acid Substances 0.000 claims description 16
- 235000012208 gluconic acid Nutrition 0.000 claims description 16
- 238000011282 treatment Methods 0.000 claims description 15
- WYUFTYLVLQZQNH-UHFFFAOYSA-N ethyl β-d-glucopyranoside Chemical compound CCOC1OC(CO)C(O)C(O)C1O WYUFTYLVLQZQNH-UHFFFAOYSA-N 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000002537 cosmetic Substances 0.000 description 13
- 235000013305 food Nutrition 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000012141 concentrate Substances 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000002835 absorbance Methods 0.000 description 5
- 239000004480 active ingredient Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 description 4
- 229940050410 gluconate Drugs 0.000 description 4
- 240000007594 Oryza sativa Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 239000002585 base Substances 0.000 description 3
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- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
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- 238000001914 filtration Methods 0.000 description 3
- 235000011194 food seasoning agent Nutrition 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 235000014347 soups Nutrition 0.000 description 3
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- WYUFTYLVLQZQNH-JAJWTYFOSA-N Ethyl beta-D-glucopyranoside Chemical compound CCO[C@@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O WYUFTYLVLQZQNH-JAJWTYFOSA-N 0.000 description 2
- 244000269722 Thea sinensis Species 0.000 description 2
- 235000013334 alcoholic beverage Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000000796 flavoring agent Substances 0.000 description 2
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- 239000004615 ingredient Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 235000000346 sugar Nutrition 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 235000021147 sweet food Nutrition 0.000 description 2
- 235000013616 tea Nutrition 0.000 description 2
- WYUFTYLVLQZQNH-CBQIKETKSA-N (2s,3r,4s,5s,6r)-2-ethoxy-6-(hydroxymethyl)oxane-3,4,5-triol Chemical compound CCO[C@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O WYUFTYLVLQZQNH-CBQIKETKSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 239000004475 Arginine Substances 0.000 description 1
- 241000228212 Aspergillus Species 0.000 description 1
- 241000972773 Aulopiformes Species 0.000 description 1
- 240000007154 Coffea arabica Species 0.000 description 1
- ZCLAHGAZPPEVDX-UHFFFAOYSA-N D-panose Natural products OC1C(O)C(O)C(OC(C(O)CO)C(O)C(O)C=O)OC1COC1C(O)C(O)C(O)C(CO)O1 ZCLAHGAZPPEVDX-UHFFFAOYSA-N 0.000 description 1
- 239000004278 EU approved seasoning Substances 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- AYRXSINWFIIFAE-SCLMCMATSA-N Isomaltose Natural products OC[C@H]1O[C@H](OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O)[C@@H](O)[C@@H](O)[C@@H]1O AYRXSINWFIIFAE-SCLMCMATSA-N 0.000 description 1
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 description 1
- YBHQCJILTOVLHD-YVMONPNESA-N Mirin Chemical compound S1C(N)=NC(=O)\C1=C\C1=CC=C(O)C=C1 YBHQCJILTOVLHD-YVMONPNESA-N 0.000 description 1
- 244000061176 Nicotiana tabacum Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 241000228143 Penicillium Species 0.000 description 1
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229940061720 alpha hydroxy acid Drugs 0.000 description 1
- 150000001280 alpha hydroxy acids Chemical class 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000003579 anti-obesity Effects 0.000 description 1
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 description 1
- 235000009697 arginine Nutrition 0.000 description 1
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000014171 carbonated beverage Nutrition 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 235000015218 chewing gum Nutrition 0.000 description 1
- 235000016213 coffee Nutrition 0.000 description 1
- 235000013353 coffee beverage Nutrition 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000002016 disaccharides Chemical class 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000006911 enzymatic reaction Methods 0.000 description 1
- 238000002481 ethanol extraction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 235000015203 fruit juice Nutrition 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 235000015243 ice cream Nutrition 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- DLRVVLDZNNYCBX-RTPHMHGBSA-N isomaltose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1OC[C@@H]1[C@@H](O)[C@H](O)[C@@H](O)C(O)O1 DLRVVLDZNNYCBX-RTPHMHGBSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000009630 liquid culture Methods 0.000 description 1
- -1 liquors Chemical compound 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 235000020124 milk-based beverage Nutrition 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 238000006395 oxidase reaction Methods 0.000 description 1
- GNURASXBKKXAOM-JGWLITMVSA-N oxido-[(2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexylidene]oxidanium Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=[O+][O-] GNURASXBKKXAOM-JGWLITMVSA-N 0.000 description 1
- ZCLAHGAZPPEVDX-MQHGYYCBSA-N panose Chemical compound O[C@H]1[C@H](O)[C@@H](O)[C@@H](O[C@H]([C@H](O)CO)[C@H](O)[C@@H](O)C=O)O[C@@H]1CO[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 ZCLAHGAZPPEVDX-MQHGYYCBSA-N 0.000 description 1
- 235000020991 processed meat Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000019515 salmon Nutrition 0.000 description 1
- 235000013580 sausages Nutrition 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 235000011888 snacks Nutrition 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 235000011044 succinic acid Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000008496 α-D-glucosides Chemical class 0.000 description 1
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- General Preparation And Processing Of Foods (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Cosmetics (AREA)
Description
本発明は食品用、化粧品用などとして有用な安定性に優れた清酒酵素処理物の製造方法に関する。 The present invention relates to a method for producing a refined sake enzyme-treated product that is useful for foods, cosmetics and the like and has excellent stability.
一般的な清酒の主な成分は80%の水と15%のアルコールおよび2%のグルコースであり、残り3%にはイソマルトース,パノース,サケビオース,コージビオース,マルトース等の糖類や、グルタミン酸,プロリン,アルギニン,アラニン等のアミノ酸、乳酸,コハク酸,リンゴ酸等の有機酸など数百種類以上といわれる種々の成分が含まれており、特に、清酒の特異的な成分であるα−エチルグルコシドの効能が明らかにされるにつれて清酒の食品用、化粧品用などへの応用が広がっている(非特許文献1参照)。例えば、β−D−エチルグルコシドからなる飲食品の香味増強・改善剤(特許文献1参照)、エチル−α−D−グルコピラノシドを有効成分とするアルコール刺激臭緩和剤(特許文献2参照)、エチル−α−D−グルコシドを有効成分とする肥満抑制組成物(特許文献3参照)、エチルグルコシド、α−ヒドロキシ酸及び多価アルコールを含有する老化防止効果のある皮膚化粧料(特許文献4参照)、有機酸及びエチルグルコシドを含有する美肌組成物(特許文献5参照)などが提案されている。 The main ingredients of general sake are 80% water, 15% alcohol and 2% glucose, and the remaining 3% is sugars such as isomaltose, panose, salmon biose, cordobiose, maltose, glutamic acid, proline, Various ingredients said to be more than hundreds such as amino acids such as arginine and alanine, organic acids such as lactic acid, succinic acid and malic acid are included. Especially, the efficacy of α-ethyl glucoside which is a specific component of sake. As it becomes clear, the application of sake to foods, cosmetics, etc. is spreading (see Non-Patent Document 1). For example, a flavor enhancing / improving agent for foods and beverages comprising β-D-ethylglucoside (see Patent Document 1), an alcohol-stimulated odor mitigating agent containing ethyl-α-D-glucopyranoside as an active ingredient (see Patent Document 2), ethyl An anti-obesity composition containing α-D-glucoside as an active ingredient (see Patent Document 3), an anti-aging skin cosmetic containing ethyl glucoside, α-hydroxy acid and a polyhydric alcohol (see Patent Document 4) A skin-beautifying composition containing organic acid and ethyl glucoside (see Patent Document 5) has been proposed.
食品、化粧品などに上記したような清酒の機能性を訴求して応用する場合には、清酒を濃縮した形態で使用されることが一般的である。しかしながら、清酒濃縮物の形態の場合、清酒中に含まれるグルコースなどの影響により経時的褐変化などに見られるように保存安定性が悪くなるなどの問題があった。そこで、酒類などをグルコースオキシダーゼで処理してグルコースをグルコン酸などへ変換させる方法が提案されている。例えば、糖質原料を醸造して得られる酒類及び甘味食品の製造工程において、グルコースオキシダーゼによるグルコース酸化物(グルコン酸など)の含有量を変化させる工程を含む酒類及び甘味食品の製造方法(特許文献6参照)、清酒にグルコースオキシダーゼを作用させてグルコン酸を多量に含み、さわやかな酸味を持ち、香味とのバランスに優れた、健康維持に効果のある清酒を製造する方法(特許文献7参照)、みりんなどの酒精含有調味料を製造する方法において、グルコースオキシダーゼを作用させ、経日的褐変増色しにくい等の特性を有する酒精含有調味料を製造する方法(特許文献8参照)などが提案されている。
上記した特許文献6、7及び8に記載されているグルコースオキシダーゼによる処理は、いずれも酒類などのアルコールが存在する状態での処理であり、反応が進まなかったり、反応効率が悪かったりなどの問題点があった。
従って、本発明の目的は、食品用、化粧品用などとして有用な保存安定性に優れた清酒酵素処理物を効率的に製造する方法を提供することである。
The treatments with glucose oxidase described in Patent Documents 6, 7 and 8 are all treatments in the presence of alcohol such as liquors, and problems such as reaction not progressing and reaction efficiency are poor. There was a point.
Accordingly, an object of the present invention is to provide a method for efficiently producing a sake enzyme-treated product having excellent storage stability useful for foods, cosmetics and the like.
本発明者らは上記のごとき課題を解決すべく、鋭意研究を行った結果、今回、清酒からエタノールを除去した後、グルコースオキシダーゼを作用させることによりグルコースからグルコン酸へ効率よく変換することができることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the problems as described above, the present inventors have been able to efficiently convert glucose to gluconic acid by removing glucose from sake and then allowing glucose oxidase to act. As a result, the present invention has been completed.
かくして、本発明によれば、清酒からエタノールを除去した後、グルコースオキシダーゼで処理することを特徴とする清酒酵素処理物の製造方法を提供することができる。
また本発明は、グルコースオキシダーゼで処理する際の清酒濃縮物のエタノール濃度が1質量%未満である前記の製造方法を提供することができる。
本発明はまた、清酒酵素処理物が実質的にグルコースを含まない前記の製造方法を提供することができる。
さらに本発明は、清酒酵素処理物中のα−エチルグルコシドの含有率が0.3質量%以上である前記の製造方法を提供することができる。
またさらに本発明は、グルコースオキシダーゼで処理した後、グルコースから変換されたグルコン酸を取り除く処理を含む前記の製造方法を提供することができる。
Thus, according to the present invention, it is possible to provide a method for producing a processed product of a sake enzyme characterized by removing ethanol from sake and then treating with glucose oxidase.
Moreover, this invention can provide the said manufacturing method whose ethanol concentration of the sake concentrate at the time of processing with glucose oxidase is less than 1 mass%.
The present invention can also provide the production method described above, wherein the sake enzyme-treated product does not substantially contain glucose.
Furthermore, this invention can provide the said manufacturing method whose content rate of (alpha) -ethyl glucoside in refined sake enzyme processed material is 0.3 mass% or more.
Furthermore, the present invention can provide the above production method including a treatment for removing gluconic acid converted from glucose after treatment with glucose oxidase.
本発明の清酒酵素処理物の製造方法は、清酒中のグルコースを効率よくグルコン酸へ変換することができる。また、本発明の製造方法によって得られる清酒酵素処理物は、経時的な褐変化などの品質の劣化が抑制され保存安定性に優れている。 The method for producing a refined sake enzyme product of the present invention can efficiently convert glucose in sake into gluconic acid. In addition, the sake enzyme-treated product obtained by the production method of the present invention is excellent in storage stability because deterioration of quality such as browning over time is suppressed.
以下、本発明の清酒酵素処理物の製造方法について、さらに詳細に説明する。
本発明の清酒酵素処理物の製造方法は、清酒からエタノールを除去した後、グルコースオキシダーゼで処理することを特徴とする。本発明で使用される清酒は、普通酒、純米酒、本醸造酒、吟醸酒などに拘わらず、一般に飲用されている清酒であれば使用可能であるが、好ましくは本醸造酒や純米酒を使用することができる。特に、α−エチルグルコシドを0.3質量%以上、好ましくは0.5質量%以上含有する清酒が好適である。
Hereinafter, the manufacturing method of the sake enzyme processed material of this invention is demonstrated in detail.
The method for producing a sake enzyme-treated product of the present invention is characterized in that ethanol is removed from sake and then treated with glucose oxidase. The sake used in the present invention is not limited to ordinary sake, pure rice liquor, honjo sake, ginjo sake, etc., but can be used as long as it is generally used, but preferably brewed sake or pure rice liquor. Can be used. Particularly, sake containing 0.3% by mass or more, preferably 0.5% by mass or more of α-ethyl glucoside is suitable.
本発明における清酒からエタノールを除去する方法は特に限定されないが、清酒を濃縮する方法が好ましく例示できる。濃縮方法は特に限定されず、常圧濃縮、減圧濃縮など公知の一般的な濃縮方法を採用することができるが、清酒濃縮物中のエタノールを完全に除去し、実質的に非アルコール性の清酒濃縮物とするためには減圧濃縮が好適である。清酒濃縮物中のエタノール濃度は1質量%未満、好ましくは0.5質量%未満、さらに好ましくは0.2質量%未満である。エタノール濃度が1質量%以上の場合は、グルコースオキシダーゼによる反応が効率的に作用せず好ましくない。 Although the method of removing ethanol from sake in the present invention is not particularly limited, a method of concentrating sake can be preferably exemplified. The concentration method is not particularly limited, and a known general concentration method such as atmospheric pressure concentration or reduced pressure concentration can be adopted. However, ethanol in the sake concentrate is completely removed, and a substantially non-alcoholic sake is obtained. In order to obtain a concentrate, vacuum concentration is preferred. The ethanol concentration in the sake concentrate is less than 1% by mass, preferably less than 0.5% by mass, more preferably less than 0.2% by mass. When the ethanol concentration is 1% by mass or more, the reaction by glucose oxidase does not act efficiently, which is not preferable.
次に、上記した特定濃度に濃縮されエタノールを除去した清酒濃縮物にグルコースオキシダーゼを作用させて、濃縮物中のグルコースをグルコン酸へと変換する方法について説明する。本発明で使用されるグルコースオキシダーゼは、グルコースを酸化してグルコン酸を生成する酵素であり、例えば、アスペルギルス属、ペニシリウム属に属するカビ類由来の酵素を挙げることができる。かかる酵素は、上記した微生物の液体培養または固体培養によって得ることができ、粗製の酵素、精製された酵素のいずれでも使用することができ、また市販のグルコースオキシダーゼ酵素剤(商品名:ハイデラーゼ15(アマノエンザイム社製)、スミチームGOP(新日本化学工業社製))を使用することもできる。グルコースオキシダーゼの添加量は、使用する酵素の種類、精製度、反応条件等により異な
り一概には言えないが、通常、上記した清酒濃縮物中に混在するグルコース1gあたり10〜1000uを例示することができる。ここで1u(ユニット)とは、37℃、1分間に1μmolのグルコースを> グルコン酸に変換する酵素量をいう。
Next, a method of converting glucose in the concentrate into gluconic acid by allowing glucose oxidase to act on the sake concentrate concentrated to the above-mentioned specific concentration and from which ethanol has been removed will be described. The glucose oxidase used in the present invention is an enzyme that oxidizes glucose to produce gluconic acid, and examples thereof include enzymes derived from molds belonging to the genus Aspergillus and Penicillium. Such an enzyme can be obtained by liquid culture or solid culture of the microorganism described above, and can be used as either a crude enzyme or a purified enzyme, and a commercially available glucose oxidase enzyme agent (trade name: Hyderase 15 ( Amano Enzyme Co., Ltd.) and Sumiteam GOP (manufactured by Shin Nippon Chemical Industry Co., Ltd.)) can also be used. The amount of glucose oxidase added varies depending on the type of enzyme used, the degree of purification, the reaction conditions, etc., and cannot generally be stated, but usually 10 to 1000 u may be exemplified per 1 g of glucose mixed in the sake concentrate. it can. Here, 1 u (unit) refers to the amount of enzyme that converts 1 μmol of glucose to> gluconic acid at 37 ° C. for 1 minute.
酵素反応条件は、特に制限されず、使用するグルコースオキシダーゼの種類などにより異なり一概には言えないが、通常、20〜60℃の温度範囲で、pH4〜9にて、通気攪拌による酸素供給下で、5〜24時間程度である。本発明では、前述したグルコースオキシダーゼで処理する際に、塩類の存在下に行うことが好ましい。塩類の存在下にグルコースオキシダーゼで処理することにより、反応の進行に伴い、生成するグルコン酸による反応液のpHの変化を抑制し、反応効率を上げることができるため好ましい。かかる塩類としては、特に制限されるものではなく広い範囲の塩類を使用することができ、例えば、炭酸カルシウム、炭酸マグネシウムなどを挙げることができ、また、グルコン酸の生成に伴うpHの低下を水酸化ナトリウムなどのアルカリを供給してpHをコントロールすることが好ましい。塩類の使用量は特に限定されず反応条件等により異なり一概には言えないが、生成するグルコン酸の量に見合った量、あるいは過剰に添加することができる。以上の方法により得られる清酒酵素処理物は、グルコースが効率的にグルコン酸へと変換されているため、実質的にグルコースを含んでいない。尚、ここで言う実質的にグルコースを含まないとは、清酒酵素処理物中のクルコース含有量が0.2質量%以下をいい、好ましくは0.1質量%以下、更に好ましくは0.05質量%以下をいう。 The enzyme reaction conditions are not particularly limited and vary depending on the type of glucose oxidase to be used. , About 5 to 24 hours. In the present invention, the treatment with glucose oxidase described above is preferably performed in the presence of salts. Treatment with glucose oxidase in the presence of salts is preferable because the reaction efficiency can be increased by suppressing the change in pH of the reaction solution due to gluconic acid produced as the reaction proceeds. Such salts are not particularly limited, and a wide range of salts can be used. Examples thereof include calcium carbonate, magnesium carbonate, and the like. It is preferable to control the pH by supplying an alkali such as sodium oxide. The amount of the salt used is not particularly limited and varies depending on the reaction conditions and cannot be generally specified. The sake enzyme-treated product obtained by the above method contains substantially no glucose because glucose is efficiently converted into gluconic acid. Incidentally, the phrase “substantially free of glucose” as used herein means that the kurcose content in the processed sake enzyme product is 0.2% by mass or less, preferably 0.1% by mass or less, more preferably 0.05% by mass. % Or less.
また上記の方法にて得られた清酒酵素処理物は、グルコースが効率的にグルコン酸へ変換されているため、α−エチルグルコシドについては上記処理を行う前と実質的に同量含まれている。実質的に同量含まれているとは、上記処理後のα−エチルグルコシドの含有量が処理前の同含有量に比べ90%以上含有していることをいう。α−エチルグルコシドは食品、化粧品へ非常に有用な成分となるため、本清酒酵素処理物の製造方法において得られる清酒酵素処理物中のα−エチルグルコシドの含有量は0.3質量%以上であることが好ましく、0.5質量%以上である事が最も好ましい。 Also, the sake enzyme-treated product obtained by the above method contains substantially the same amount of α-ethylglucoside as before the above treatment because glucose is efficiently converted to gluconic acid. . “Substantially the same amount is contained” means that the content of α-ethyl glucoside after the treatment is 90% or more than the same content before the treatment. Since α-ethyl glucoside is a very useful ingredient for foods and cosmetics, the content of α-ethyl glucoside in the sake enzyme-treated product obtained in the method for producing a product of this sake enzyme is 0.3% by mass or more. It is preferable that it is 0.5 mass% or more.
本清酒酵素処理物は反応終了後、エタノール抽出、イオン交換樹脂処理、活性炭処理などの適宜な精製手段によって処理することにより清酒酵素処理物中の有効成分を精製することもできる。
例えば本発明の清酒酵素処理物中にはグルコースから生成した過剰なグルコン酸(グルコン酸塩)を含有するため、上記反応終了後、残存する塩類を濾過などの適宜な分離操作により分離した後、減圧濃縮などの適宜な濃縮手段を採用して水分を除去し、グルコン酸塩を不溶化する溶媒(エタノール等)を添加してグルコン酸塩を濾過などの適宜な分離手段により分離した後、所望により減圧濃縮などの適宜な濃縮手段を採用して溶媒を回収することにより、化粧料等への応用に際して肌への刺激を緩和させる効果等が期待できる製剤とすることが可能である。
さらに上記の如く得られた清酒酵素処理物に低級アルコールや多価アルコールを含有することにより各種製剤としての汎用性を高めることが可能となる。
After completion of the reaction, the treated product of the sake enzyme can be purified by an appropriate purification means such as ethanol extraction, ion exchange resin treatment, activated carbon treatment, etc. to purify the active ingredient in the sake enzyme treated product.
For example, since the sake enzyme-treated product of the present invention contains excess gluconic acid (gluconate) generated from glucose, after the reaction is completed, the remaining salts are separated by an appropriate separation operation such as filtration, Water is removed using an appropriate concentration means such as vacuum concentration, a gluconate insoluble solvent (such as ethanol) is added, and the gluconate is separated by an appropriate separation means such as filtration. By recovering the solvent by employing an appropriate concentration means such as vacuum concentration, it is possible to obtain a preparation that can be expected to reduce the irritation to the skin when applied to cosmetics and the like.
Furthermore, the versatility as various preparations can be improved by including a lower alcohol or a polyhydric alcohol in the sake enzyme-treated product obtained as described above.
本発明により得られる清酒酵素処理物は、グルコースがグルコン酸へと変換され、実質的にグルコースを含まないため、清酒酵素処理物の経時的な褐変化などの劣化が抑制され、保存安定性に優れており、食品用、化粧品用などとして幅広く応用することができる。例えば、炭酸飲料、果汁飲料、果実酒飲料類、乳飲料などの飲料類;アイスクリーム類、シャーベット類、アイスキャンディー類などの冷菓類;和・洋菓子、チューインガム類、パン類、コーヒー、紅茶、お茶、タバコなどの嗜好品類;和風スープ類、洋風スープ類などのスープ類;ハム、ソーセージなどの畜肉加工品;風味調味料、各種インスタント飲料ないし食品類、各種のスナック類などに、本発明の清酒酵素処理物の適当量を添加することにより、清酒酵素処理物に含まれる有効成分が賦与された飲食品類を提供することができる。また、例えば、シャンプー類、ヘアクリーム類、その他の毛髪化粧料基剤;オシロイ、口紅、その他の化粧用基剤や化粧用洗剤類基剤などに、本発明の清酒酵素処理物の適当量を添加することにより、清酒酵素処理物に含まれる有効成分が賦与された化粧品類を提供することができる。 In the sake enzyme-treated product obtained according to the present invention, glucose is converted into gluconic acid and substantially free of glucose, so that degradation of the sake enzyme-treated product over time such as browning is suppressed, and storage stability is improved. It is excellent and can be widely applied to foods and cosmetics. For example, beverages such as carbonated drinks, fruit juice drinks, fruit liquor drinks, milk drinks; frozen confectionery such as ice creams, sherbets, ice candy; Japanese / Western confectionery, chewing gums, breads, coffee, tea, tea Refined products such as tobacco, soups such as Japanese-style soups and Western-style soups; processed meat products such as ham and sausages; flavored seasonings, various instant beverages and foods, various snacks, etc. By adding an appropriate amount of the enzyme-treated product, foods and drinks to which the active ingredients contained in the sake-enzyme-treated product are added can be provided. In addition, for example, shampoos, hair creams, other hair cosmetic bases; siroy, lipstick, other cosmetic bases and cosmetic detergent bases, etc. By adding, it is possible to provide cosmetics to which the active ingredient contained in the processed enzyme product of sake is added.
以下、実施例により本発明をさらに具体的に説明する。 Hereinafter, the present invention will be described more specifically with reference to examples.
<脱エタノール清酒の調製>
市販の清酒(純米酒:以下、清酒Aという)1000gを2倍程度に減圧濃縮して濃縮清酒462.2gを得た。この濃縮清酒に流出液量と同量(537.8g)のイオン交換水を添加して脱エタノール清酒B1000gを調製した。清酒Aおよび脱エタノール清酒Bそれぞれの分析値を表1に示す。
<Preparation of ethanol-free sake>
1000 g of commercially available sake (pure rice sake: hereinafter referred to as “Sake Sake A”) was concentrated under reduced pressure approximately twice to obtain 462.2 g of concentrated sake. To this concentrated sake was added ion exchange water in the same amount as the effluent (537.8 g) to prepare 1000 g of deethanol sake B. The analytical values of sake A and deethanol sake B are shown in Table 1.
清酒Aおよび脱エタノール清酒Bを使用して、下記の実施例1および比較例1で、グルコースオキシダーゼによる脱グルコースにおけるエタノールの影響について検討した。 Using sake A and deethanol sake B, in Example 1 and Comparative Example 1 below, the influence of ethanol on deglucose by glucose oxidase was examined.
<実施例1>
上記の如く調製した脱エタノール清酒B800gを2L容ミニジャーに仕込み、30質量%NaOH水溶液にてpH4.5に調整した後、ハイデラーゼ15(アマノエンザイム社製のグルコースオキシダーゼの商品名)0.78g(1170u)をイオン交換水10.0gで溶解して加え、40℃で通気攪拌(通気量:0.2L/min,攪拌:600rpm)した。なお、反応液のpHが4.2±0.2となるように30質量%NaOH水溶液にて調整しながら反応した。反応1時間、4時間、5時間および20時間目の反応液の分析値を表2に示し、残存グルコース量の変化を図1に示す。
<Example 1>
After adding 800 g of deethanol sake B prepared as described above to a 2 L mini jar and adjusting the pH to 4.5 with a 30% by mass NaOH aqueous solution, 0.78 g (1170 u) of Hyderase 15 (trade name of glucose oxidase manufactured by Amano Enzyme) ) Was added after dissolving in 10.0 g of ion-exchanged water, and aerated and stirred at 40 ° C. (aeration rate: 0.2 L / min, stirring: 600 rpm). In addition, it reacted, adjusting with 30 mass% NaOH aqueous solution so that pH of a reaction liquid might be 4.2 +/- 0.2. Analytical values of the reaction solutions at 1 hour, 4 hours, 5 hours and 20 hours of reaction are shown in Table 2, and the change in the amount of residual glucose is shown in FIG.
<比較例1>
実施例1において、脱エタノール清酒Bに代えて清酒Aを使用する以外は実施例1と同様に反応した。反応1時間、2時間、3時間、4時間、18時間、19時間および20時間目の反応液の分析値を表3に示し、残存グルコース量の変化を図1に示す。
<Comparative Example 1>
In Example 1, it reacted like Example 1 except using sake A instead of deethanol sake B. The analysis values of the reaction solutions at 1 hour, 2 hours, 3 hours, 4 hours, 18 hours, 19 hours and 20 hours of reaction are shown in Table 3, and the change in the amount of residual glucose is shown in FIG.
図1の結果から明らかなように、脱エタノール清酒Bを使用してグルコースオキシダーゼで処理した本発明の製造方法による清酒酵素処理物(実施例1)は、反応5時間目でほとんどグルコースが残存していないのに比較して、清酒Aを使用した清酒酵素処理物(比較例1)は、反応20時間目においても反応前のグルコース量の約22%が残存していた。また本発明の製造方法によっても、α−エチルグルコシドの含有量はほとんど変化していない事が判る(脱エタノール清酒Bをグルコースコキシダーゼ処理した実施例1では20時間後でもα−エチルグルコシドが0.37質量%残存(処理前は0.37質量%;表1参照),清酒Aをグルコースオキシダーゼ処理した比較例1では20時間後0.36質量%が残存(処理前は0.38質量%;表1参照)していた)。 As is clear from the results of FIG. 1, the sake enzyme-treated product (Example 1) produced by the production method of the present invention treated with glucose oxidase using deethanol sake B had almost no glucose remaining in the reaction at 5 hours. In contrast, the sake enzyme-treated product using Sake A (Comparative Example 1) had about 22% of the glucose amount before the reaction even after 20 hours of the reaction. Also, it can be seen that the content of α-ethyl glucoside is hardly changed even by the production method of the present invention (in Example 1 in which deethanolized sake B was treated with glucose coxidase, α-ethyl glucoside was 0 even after 20 hours. 37% by weight remaining (0.37% by weight before treatment; see Table 1), and in Comparative Example 1 in which sake A was treated with glucose oxidase, 0.36% by weight remained after 20 hours (0.38% by weight before treatment) ; See Table 1)).
<本発明の製造方法による清酒酵素処理物(実施例1によるもの;以降、「発明実施品1」と称す。)と比較品の清酒酵素処理物(比較例1によるもの;以降、「比較品1」と称す。)の安定性比較試験>
発明実施品1と比較品1を濾過して残存する塩類を除去し、減圧下(45℃、50mmHg)で水を除去した。その後エタノールを加えてグルコン酸塩を濾過により除去し、再度減圧下にてそれぞれ10倍濃縮(質量として1/10になるまで)し、水分およびアルコール分を除去する。それぞれ60℃の恒温槽に保存し、時間の経過による着色度合いを加速的に観察した。着色の評価方法としては、紫外・可視分光光度計を用い、測定波長を430nmとして吸光度を測定し、以下の算出式により吸光度の変化量を求め、その結果を表4に示す。
算出式: 吸光度の変化量=(X日目の吸光度)−(初期の吸光度)
<Sake enzyme-treated product according to the production method of the present invention (according to Example 1; hereinafter referred to as “Invention Product 1”) and a comparative product of sake enzyme-treated product (Comparative Example 1; hereinafter referred to as “Comparative Product”) 1)) stability comparison test>
Invention product 1 and comparative product 1 were filtered to remove residual salts, and water was removed under reduced pressure (45 ° C., 50 mmHg). Thereafter, ethanol is added and the gluconate is removed by filtration, and each is concentrated again 10 times under reduced pressure (until the mass becomes 1/10) to remove moisture and alcohol. Each was stored in a constant temperature bath at 60 ° C., and the degree of coloring over time was observed at an accelerated rate. As a coloring evaluation method, an ultraviolet / visible spectrophotometer was used, the absorbance was measured at a measurement wavelength of 430 nm, the amount of change in absorbance was determined by the following calculation formula, and the results are shown in Table 4.
Calculation formula: Amount of change in absorbance = (absorbance on day X)-(initial absorbance)
表4より明らかな通り、本発明製造方法による発明実施品1の方が、比較品1よりも着色度合いの進行が低く、安定性の面で優れているといえる。 As is apparent from Table 4, it can be said that the inventive product 1 produced by the production method of the present invention has a lower degree of coloring than the comparative product 1 and is superior in terms of stability.
本発明の清酒酵素処理物の製造方法により、清酒中のグルコースを効率よくグルコン酸へ変換することができるため、得られる清酒酵素処理物は、経時的な褐変化などの品質の劣化が抑制され保存安定性に優れている。そのため食品用、化粧品用等、様々な分野への応用が期待できる。
Since the method for producing an enzyme-treated product of sake of the present invention can efficiently convert glucose in sake to gluconic acid, the resulting enzyme-treated product of purified sake has suppressed degradation of quality such as browning over time. Excellent storage stability. Therefore, application to various fields such as for foods and cosmetics can be expected.
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