JP2010162006A - Method for producing rice bran leachate from which rice bran smell is eliminated, rice bran leachate from which rice bran smell is eliminated, and method for producing gamma-aminobutyric acid - Google Patents
Method for producing rice bran leachate from which rice bran smell is eliminated, rice bran leachate from which rice bran smell is eliminated, and method for producing gamma-aminobutyric acid Download PDFInfo
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Description
本発明は、米糠由来の糠臭が取り除かれた米糠浸出物の製造方法、当該製造方法により得られた米糠浸出物、当該米糠浸出物を用いたγ−アミノ酪酸の製造方法に関する。 The present invention relates to a method for producing a rice bran leachate from which the rice bran odor has been removed, a rice bran leachate obtained by the production method, and a method for producing γ-aminobutyric acid using the rice bran leachate.
酵素は我々の生活を支える重要な物質であり、洗剤をはじめとする日用品から医薬品の製造まで幅広く利用されている。中でも、酵素を利用して製造された食品は、化学調味料を使用して製造した食品とは異なり、種々の生理活性を有する化合物が含有されることから、近年機能性健康食品としての需要が年々増加している。例えば、グルタミン酸の酵素反応によって製造されるγ−アミノ酪酸は、降圧効果あるいはリラックスをもたらす効果があるアミノ酸として最近着目され、現在では種々の食品、サプリメントなどに添加されるに至っている。 Enzymes are important substances that support our lives, and are widely used from daily necessities such as detergents to pharmaceutical production. Among these, foods produced using enzymes, unlike foods produced using chemical seasonings, contain various physiologically active compounds, and in recent years there has been a demand for functional health foods. Increasing year by year. For example, γ-aminobutyric acid produced by an enzyme reaction of glutamic acid has recently attracted attention as an amino acid having an antihypertensive effect or an effect of relaxing, and has now been added to various foods and supplements.
一方、米を精米する過程で生じる米糠中には様々な酵素が存在し、グルタミン酸脱炭酸酵素のほか、アミラーゼなど複数の酵素の存在が報告されている。そのため、これまで廃棄物として処理されていた物質を有効に利用するという観点から、これら米糠中に存在する酵素を利用してγ−アミノ酪酸等の有用な物質を製造する手法、技術について研究されている（例えば、特許文献１−５）。 On the other hand, various enzymes exist in rice bran produced in the process of polishing rice, and in addition to glutamate decarboxylase, the presence of multiple enzymes such as amylase has been reported. Therefore, from the viewpoint of effectively using substances that have been treated as waste, research has been conducted on techniques and techniques for producing useful substances such as γ-aminobutyric acid using enzymes present in rice bran. (For example, Patent Documents 1-5).
米糠中に含まれる酵素を用いて酵素反応を行う場合、得られる溶液や生成物に米糠特有の糠臭が残ることが問題となる。そのため、当該糠臭を低減する手段が研究されている（例えば、特許文献６、７）。 When an enzyme reaction is carried out using an enzyme contained in rice bran, there is a problem that a bad smell peculiar to rice bran remains in the resulting solution or product. For this reason, means for reducing the odor have been studied (for example, Patent Documents 6 and 7).
特許文献１〜５等に記載された手法の多くは米糠に基質溶液を直接含浸してγ−アミノ酪酸を製造する方法であるが、糠臭を取り除くことについては何ら考慮されていない。また、γ−アミノ酪酸製造時に投入される米糠の固体濃度は１７質量％程度しかなく、高濃度での反応が行われていないこと、分離精製の工程が複雑であること、などの問題点がある。このような操作条件を選択せざるを得ない原因の一つとして、米糠粒子のハンドリングの難しさが考えられる。 Many of the methods described in Patent Documents 1 to 5 and the like are methods for producing γ-aminobutyric acid by directly impregnating rice bran with a substrate solution, but no consideration is given to removing the odor. In addition, the solid concentration of rice bran added during the production of γ-aminobutyric acid is only about 17% by mass, and there are problems such as that the reaction at a high concentration is not performed and the separation and purification process is complicated. is there. One of the reasons for having to select such operating conditions is the difficulty in handling rice bran particles.
米糠粒子は、玄米を機械的に研磨して生じる米の削りかすの一部であることから、その粒子径は比較的小さく、また吸湿性に富むものである。従って、米糠を水中に懸濁させると多量の水分を吸収し、粘度が高いスラリーが形成される。その結果、γ−アミノ酪酸の分離工程の際に米糠をろ過等によって除去することが困難になるばかりでなく、固体濃度が高い場合には懸濁液の撹拌さえも行うことが困難になってしまう。 Rice bran particles are a part of rice shavings produced by mechanically polishing brown rice, so that the particle diameter is relatively small and has a high hygroscopic property. Therefore, when rice bran is suspended in water, a large amount of water is absorbed and a slurry having a high viscosity is formed. As a result, it becomes difficult not only to remove rice bran by filtration during the separation step of γ-aminobutyric acid, but it is also difficult to even stir the suspension when the solid concentration is high. End up.
一方、米糠由来の糠臭は、主にリノール酸等の不飽和脂肪酸の酸化反応により生成すると考えられることから、温和な条件において酵素反応を行う場合には、酵素反応によるγ−アミノ酪酸等の生成反応と不飽和脂肪酸の液相酸化反応も同時に進行することになり、結果系内への糠臭の蓄積が生じる。従って、生成するγ−アミノ酪酸等を様々な用途に応用する場合には、酵素反応前に糠臭の原因となる脂肪酸を選択的に除去するか、又は酵素反応終了後に脂肪酸酸化物を選択的に除去する操作を必要とする。従来において、液相中において水溶性の物質を除去する場合、活性炭をはじめとするさまざまな吸着剤を利用した吸着操作が工業的に広く用いられているが、当該活性炭は吸着剤としては優れているものの、多成分が混在する系においては選択性が低く、除去対象である脂肪酸類の他、必要な酵素類まで吸着してしまい、酵素群の損失を生ずる。これに対し、特許文献６に開示されているように、乳酸発酵処理と、ガス体接触処理、超音波処理、又は放射線照射処理と、を有する製造方法とした場合、糠臭をある程度除去できるものの、製造工程が煩雑となる他、所望の粗酵素が得られない虞がある。また、超音波処理を行う場合には、超音波照射により溶液中にヒドロキシラジカルが生成することから、有機物の酸化分解が逐次的に進行し、場合によっては人体に対し毒性を示す分解中間体が生成する虞がある。放射線処理を行った場合も同様に分子鎖の断片化が生じて分解される。よって、特許文献６に開示された手段は、糠臭物質を分解処理するものであり、糠臭物質を選択的に除去するものではない。従って、食品等に応用する場合には、これらの分解生成物を除去する操作が必要となり、工程が煩雑となってしまう。一方、特許文献７に記載されたような新たに食用油を配合する製造方法としても、特許文献６と同様に、米糠由来の糠臭物質を選択的に除去できるわけではなく、より効率的に糠臭物質を選択除去できる製造方法が求められている。 On the other hand, the odor from rice bran is thought to be generated mainly by the oxidation reaction of unsaturated fatty acids such as linoleic acid. The production reaction and the liquid phase oxidation reaction of unsaturated fatty acids also proceed simultaneously, resulting in the accumulation of odor in the system. Therefore, when the produced γ-aminobutyric acid is applied to various applications, the fatty acid causing the odor is selectively removed before the enzymatic reaction, or the fatty acid oxide is selectively selected after the enzymatic reaction. Need to be removed. Conventionally, when removing water-soluble substances in a liquid phase, adsorption operations using various adsorbents including activated carbon are widely used industrially, but the activated carbon is excellent as an adsorbent. However, in a system in which multiple components are mixed, the selectivity is low, and the necessary enzymes are adsorbed in addition to the fatty acids to be removed, resulting in the loss of the enzyme group. On the other hand, as disclosed in Patent Document 6, when the production method includes a lactic acid fermentation treatment and a gas body contact treatment, an ultrasonic treatment, or a radiation irradiation treatment, the odor can be removed to some extent. In addition to the complexity of the production process, the desired crude enzyme may not be obtained. In addition, when sonication is performed, hydroxy radicals are generated in the solution by ultrasonic irradiation, so that the oxidative degradation of organic matter proceeds sequentially, and in some cases, a degradation intermediate that is toxic to the human body is produced. There is a risk of generation. Similarly, when a radiation treatment is performed, fragmentation of molecular chains occurs and is decomposed. Therefore, the means disclosed in Patent Document 6 decomposes the odor substance and does not selectively remove the odor substance. Therefore, when applying to foodstuffs etc., operation which removes these decomposition products is needed, and a process will become complicated. On the other hand, even as a production method for newly blending edible oil as described in Patent Document 7, as in Patent Document 6, it is not possible to selectively remove the odor substance derived from rice bran, and more efficiently. There is a need for a production method that can selectively remove odorous substances.
そこで本発明は、工程が簡略化されるとともに、有用酵素群の吸着を抑制しながら糠臭の原因物質である脂肪酸群を選択的且つ連続的に除去可能な米糠浸出物の製造方法、糠臭が取り除かれた米糠浸出物、及びγ−アミノ酪酸を含有する糠臭が取り除かれた溶液を製造する方法を提供することを課題とする。 Therefore, the present invention provides a method for producing rice bran leachables that can simplify and continuously remove the fatty acid group that is a causative substance of odor while suppressing the adsorption of useful enzymes, while simplifying the process. It is an object of the present invention to provide a method for producing a rice bran leachate from which is removed and a solution from which the odor containing γ-aminobutyric acid is removed.
本発明者らは、上記課題に鑑み、鋭意検討した結果、イオン交換反応により、有用酵素等を含む溶液から、選択的に不飽和脂肪酸等の糠臭物質を選択除去できることを知見し、本発明を完成させた。 As a result of intensive studies in view of the above problems, the present inventors have found that an odorous substance such as an unsaturated fatty acid can be selectively removed from a solution containing a useful enzyme or the like by an ion exchange reaction. Was completed.
すなわち、第一の本発明は、米糠を溶媒に含浸させ、米糠由来の粗酵素を含有する浸出液を作製する、米糠浸出液作製工程と、米糠浸出液作製工程により得られた浸出液を、イオン交換基にあらかじめ特定のイオンが吸着されたイオン交換樹脂と接触させて、当該イオン交換樹脂に糠臭物質を吸着させるとともに、糠臭物質が除去された米糠浸出物を得る、糠臭物質除去工程と、を有する、米糠浸出物の製造方法を提供して前記課題を解決するものである。 That is, the first present invention impregnates rice bran in a solvent and prepares a leachate containing a crude enzyme derived from rice bran, and the leachate obtained by the rice bran leachate preparation step using ion exchange groups. A odor substance removing step of bringing the odor substance into contact with an ion exchange resin in which specific ions have been adsorbed in advance to adsorb the odor substance and obtaining a rice bran leachate from which the odor substance has been removed. It has the manufacturing method of the rice bran leachate which has, and solves the said subject.
ここに「米糠浸出液」とは、米糠を溶媒に含浸させ、米糠から浸出する成分を含む溶液のことであり、当該溶液にコロイド等の不溶物質が含まれていてもよい概念である。「糠臭物質」とは、米糠に含まれる有用酵素以外の、米糠由来の糠臭の原因となる物質のことであり、上記不飽和脂肪酸や脂肪酸酸化物等を例示することができる。「米糠浸出物」とは、糠臭物質除去の有無に関わらず、米糠を溶媒に含浸させて得られる米糠浸出液を用いてなるものをいうが、第一の本発明においては、糠臭物質除去工程により糠臭物質が除去された米糠浸出液（以下、「糠臭除去浸出液」という場合がある。）とした後、当該糠臭除去浸出液をそのまま米糠浸出物として用いる他、糠臭除去浸出液を凍結乾燥等によって乾燥させた米糠浸出物や、糠臭除去浸出液を凍結させた氷結体の米糠浸出物等を含む概念である。また、「特定のイオン」とは、イオン交換反応により糠臭物質を選択除去可能なイオンのことをいう。例えば、反応系内がアルカリ性雰囲気とはならないような陰イオンであって、塩化物イオン、硫酸イオン、硝酸イオン等の陰イオン、又は酢酸イオン、クエン酸イオン等の有機酸由来の陰イオンのいずれかを用いることができる。このうち、食品へ適用する観点からは、塩化物イオン、硫酸イオン、又は有機酸由来の陰イオンを用いることが好ましく、食品への適用性及び糠臭物質の選択除去性を効果的に両立させる観点から、塩化物イオンを用いることが特に好ましい。尚、本願において、「糠臭物質が除去された」等の表現については、糠臭物質が低減されていればよく、必ずしも完全除去を意味しない。 Here, the “rice bran leachate” is a solution containing a component that is impregnated with rice bran in a solvent and leached from the rice bran, and is a concept that the solution may contain an insoluble substance such as a colloid. The “smelly odor substance” is a substance that causes the scent of rice bran other than useful enzymes contained in rice bran, and examples thereof include the above unsaturated fatty acids and fatty acid oxides. “Rice bran leachate” refers to a product obtained by using a rice bran leachate obtained by impregnating rice bran in a solvent regardless of whether or not a bad smell substance is removed. After making the rice bran leachate from which the malodorous substances have been removed by the process (hereinafter, sometimes referred to as “bad smell removal leachate”), in addition to using the bad smell removal leachate as it is as the rice bran leachate, the odor removal leachate is frozen. It is a concept including rice bran leachate dried by drying or the like, or frozen rice bran leachate obtained by freezing the odor removing leachate. The “specific ion” refers to an ion capable of selectively removing the odorous substance by an ion exchange reaction. For example, an anion that does not form an alkaline atmosphere in the reaction system, and anion such as chloride ion, sulfate ion, nitrate ion, or anion derived from organic acid such as acetate ion, citrate ion, etc. Can be used. Among these, from the viewpoint of application to foods, it is preferable to use chloride ions, sulfate ions, or anions derived from organic acids, which effectively balances applicability to foods and selective removal of odorous substances. From the viewpoint, it is particularly preferable to use a chloride ion. In the present application, the expression “the odorous substance has been removed” or the like is sufficient if the odorous substance is reduced, and does not necessarily mean complete removal.
第一の本発明において、イオン交換樹脂が陰イオン交換樹脂であることが好ましい。含有アミノ酸の吸着を抑制しながら糠臭物質である脂肪酸の選択吸着をより効率的に行うことができるからである。 In the first invention, the ion exchange resin is preferably an anion exchange resin. This is because the selective adsorption of fatty acids, which are odorous substances, can be performed more efficiently while suppressing the adsorption of contained amino acids.
第一の本発明において、イオン交換樹脂相のイオン交換基には、あらかじめ塩化物イオンが吸着されていることが好ましい。あらかじめイオン交換基に塩化物イオンを吸着させた後に粗酵素等を含む米糠浸出液を通液すると、含有アミノ酸の吸着を抑制しながらイオン交換反応が効率的に行われ、糠臭物質である脂肪酸をより効率的に選択吸着できるからである。 In 1st this invention, it is preferable that the chloride ion is previously adsorb | sucked to the ion exchange group of the ion exchange resin phase. Passing rice bran leachate containing crude enzyme after adsorbing chloride ions to ion exchange groups in advance, the ion exchange reaction is carried out efficiently while suppressing the adsorption of contained amino acids, and the fatty acid that is a odorous substance is removed. This is because selective adsorption can be performed more efficiently.
第一の本発明において、糠臭物質除去工程を経たイオン交換樹脂を、前処理したのち洗浄し、塩化物イオン含有溶液と接触させて、イオン交換樹脂を再生する、再生工程をさらに有することが好ましい。「前処理」としては例えば、アルカリ処理を挙げることができる。イオン交換樹脂に前処理を施した上で、洗浄と塩化物イオン含有溶液による接触とを行うことで、イオン交換樹脂を効率的に再生することができるとともに、再度イオン交換樹脂を使用するにあたり、含有アミノ酸の吸着を抑制しながらイオン交換反応を効率的に行うことができ、且つ、糠臭物質である脂肪酸をより効率的に選択吸着できる。また、吸着完了後イオン交換樹脂をいちいち取り外して再生処理する必要がなく、反応系に用いられる装置をそのまま利用できるため、製造工程が複雑化することがない。 In the first aspect of the present invention, the ion exchange resin that has been subjected to the odor substance removing step is pretreated, washed, and then brought into contact with a chloride ion-containing solution to regenerate the ion exchange resin, further comprising a regeneration step. preferable. Examples of “pretreatment” include alkali treatment. After pre-treating the ion exchange resin, it is possible to efficiently regenerate the ion exchange resin by performing washing and contact with a chloride ion-containing solution, and in using the ion exchange resin again, The ion exchange reaction can be efficiently performed while suppressing the adsorption of the contained amino acid, and the fatty acid which is a odor substance can be selectively adsorbed more efficiently. Moreover, it is not necessary to remove and regenerate the ion exchange resin after completion of the adsorption, and the apparatus used in the reaction system can be used as it is, so that the manufacturing process is not complicated.
第二の本発明は、上記第一の本発明にかかる製造方法により製造された、糠臭が取り除かれた米糠浸出物を提供して前記課題を解決するものである。 The second aspect of the present invention provides a rice bran leachate from which the odor is removed, which is produced by the production method according to the first aspect of the present invention, and solves the above problems.
第三の本発明は、上記第二の本発明にかかる米糠浸出物を、グルタミン酸を含有する溶液に添加する工程を備えてなる、γ−アミノ酪酸を含有する溶液を製造する方法を提供して前記課題を解決するものである。 The third aspect of the present invention provides a method for producing a solution containing γ-aminobutyric acid, comprising the step of adding the rice bran leachable according to the second aspect of the present invention to a solution containing glutamic acid. The problem is solved.
第四の本発明は、米糠を溶媒に含浸させ、米糠由来の粗酵素を含有する浸出液を作製する、米糠浸出液作製工程と、米糠浸出液作製工程により得られた浸出液から米糠浸出物を作製する、米糠浸出物作製工程と、米糠浸出物作製工程により得られた米糠浸出物を、グルタミン酸を含有する溶液に添加して、γ−アミノ酪酸を生成させる、酵素反応工程と、酵素反応工程により得られた、γ−アミノ酪酸を含む溶液を、イオン交換基にあらかじめ特定のイオンが吸着されたイオン交換樹脂と接触させて、該イオン交換樹脂に糠臭物質を吸着させる、糠臭物質除去工程と、を有する、γ−アミノ酪酸を含有する溶液を製造する方法を提供して前記課題を解決するものである。 The fourth aspect of the present invention is to impregnate rice bran in a solvent and prepare a leachate containing a crude enzyme derived from rice bran, and prepare a rice bran leachate from the leachate obtained by the rice bran leachate preparation step and the rice bran leachate preparation step. The rice bran leachate preparation step and the rice bran leachate obtained in the rice bran leachate preparation step are added to a solution containing glutamic acid to produce γ-aminobutyric acid. Further, a odor substance removing step of bringing a solution containing γ-aminobutyric acid into contact with an ion exchange resin in which specific ions are previously adsorbed on an ion exchange group to adsorb the odor substance on the ion exchange resin; A method for producing a solution containing γ-aminobutyric acid is provided to solve the above problems.
第四の本発明において、「米糠浸出液作製工程により得られた浸出液から米糠浸出物を作製する」とは、米糠浸出液を乾燥させて粉末状の米糠浸出物とする場合や、浸出液を凍結させて氷結体の米糠浸出物とする場合の他、浸出液をそのまま用いて米糠浸出物とする場合も含む概念である。「特定のイオン」とは、上記第一の本発明における特定のイオンと同様のものが用いられる。 In the fourth aspect of the present invention, "preparing rice bran leachate from the leachate obtained in the rice bran leachate preparation step" means drying the rice bran leachate to form a powdered rice bran leachate, or freezing the leachate. It is a concept including the case of using a leachate as it is to make a rice bran leachate, in addition to the case of using a frozen rice bran leachate. The “specific ions” are the same as the specific ions in the first aspect of the present invention.
第一の本発明によれば、有用酵素群の吸着が抑制されるとともに糠臭の原因物質である脂肪酸群を選択的且つ連続的に除去しながら、酵素活性を有する米糠浸出物を製造することができる。
第二の本発明によれば、糠臭が取り除かれるとともに、高い酵素活性を有する米糠浸出物とすることができる。
第三の本発明又は第四の本発明によれば、糠臭が取り除かれたγ−アミノ酪酸を含む溶液を製造することができ、食品等に好適に用いることができる。また、米糠を直接酵素反応に用いず、米糠浸出物を用いるため、ハンドリングが容易である。
According to the first aspect of the present invention, a rice bran leachable having enzyme activity is produced while the adsorption of useful enzyme groups is suppressed and the fatty acid group which is a causative substance of odor is selectively and continuously removed. Can do.
According to the second aspect of the present invention, a rice bran leachate having a high enzymatic activity can be obtained while removing the bad smell.
According to the third aspect of the present invention or the fourth aspect of the present invention, a solution containing γ-aminobutyric acid from which the odor is removed can be produced, and can be suitably used for foods and the like. In addition, since rice bran is not directly used for enzyme reaction, but a rice bran leachate is used, handling is easy.
本発明を実施するためには、米糠浸出液、及び、イオン交換基にあらかじめイオンが吸着されたイオン交換樹脂を必須とし、任意に、イオン交換樹脂を調整するための溶液（以下、「溶液Ａ」という場合がある。）、イオン交換樹脂を再生する際の前処理用の溶液（以下、「溶液Ｂ」ということがある。）、及びイオン交換樹脂を洗浄するための溶液（以下、「溶液Ｃ」という場合がある。）を用いることが好ましい。 In order to carry out the present invention, a rice bran leachate and an ion exchange resin in which ions are previously adsorbed on an ion exchange group are essential, and optionally a solution for adjusting the ion exchange resin (hereinafter referred to as “solution A”) A solution for pretreatment when regenerating the ion exchange resin (hereinafter sometimes referred to as “solution B”), and a solution for washing the ion exchange resin (hereinafter referred to as “solution C”). Is sometimes used.) Is preferably used.
以下、本発明の一実施形態について詳述する。 Hereinafter, an embodiment of the present invention will be described in detail.
＜米糠浸出液＞
本実施形態に用いられる米糠浸出液は、米糠を溶媒に含浸させ、所定時間静置した後、固液分離操作により浸出液を回収することによって得られる。米糠を含浸させる溶媒としては特に限定されず、米糠中の酵素を浸出させることができるものであればよい。但し、食品や医薬品等を製造する場合の安全性を考慮すると、水を用いることが好ましい。米糠と溶媒の比率、含浸温度、含浸時間等については、そのパラメーターの組み合わせによって適宜最適化されるが、含浸温度については、目的の酵素が失活しない温度域となるように制御される。米糠の含浸によって酵素を浸出させたのち、米糠残渣を分離することによって酵素を含有する浸出液とされる。固液分離操作については特に制限はなく、例えば遠心分離操作や圧搾操作が挙げられる。
<Rice bran leachate>
The rice bran leachate used in the present embodiment is obtained by impregnating rice bran in a solvent, allowing it to stand for a predetermined time, and then collecting the leachate by solid-liquid separation operation. The solvent for impregnating the rice bran is not particularly limited as long as it can leach out the enzyme in the rice bran. However, it is preferable to use water in consideration of safety when producing foods, pharmaceuticals, and the like. The ratio of rice bran and solvent, the impregnation temperature, the impregnation time, and the like are optimized as appropriate depending on the combination of the parameters, but the impregnation temperature is controlled to be a temperature range in which the target enzyme is not inactivated. After the enzyme is leached by impregnation of rice bran, the rice bran residue is separated to obtain a leachate containing the enzyme. There is no restriction | limiting in particular about solid-liquid separation operation, For example, centrifugation operation and pressing operation are mentioned.
上述の米糠を溶媒に含浸する際に、あらかじめ米糠を網状の物質に内包させておくと、固液分離、抽出操作が容易となるため好ましい。網状の物質としては、例えば２００メッシュのナイロン製網などが挙げられる。溶媒に溶解せず、米糠残渣がメッシュから漏れないようなものであれば、材質、メッシュサイズはこれに限るものではない。米糠を網状の物質に内包させている場合、溶媒含浸物から米糠残渣を分離することによって浸出液を得る操作は、遠心分離による脱水操作が簡便であるが、圧搾操作による溶液の回収も可能である。得られる浸出液は、米糠残渣の分離方法にもよるが、通常、コロイド状態の微小固体物質が分散された、白濁した溶液である。 When impregnating the above-mentioned rice bran in a solvent, it is preferable to encapsulate the rice bran in a net-like substance in advance because solid-liquid separation and extraction operations become easy. Examples of the net-like substance include a 200 mesh nylon net. The material and the mesh size are not limited to this as long as they do not dissolve in the solvent and the rice bran residue does not leak from the mesh. When the rice bran is encapsulated in a net-like substance, the operation of obtaining a leachate by separating the rice bran residue from the solvent impregnated product is easy to dehydrate by centrifugation, but the solution can also be recovered by pressing. . The obtained leachate is usually a cloudy solution in which colloidal fine solid substances are dispersed, although it depends on the method for separating rice bran residue.
得られた浸出液には上記のようにコロイド状物質が含有されていることから、その溶液の塩濃度あるいはｐＨを調整することにより、コロイド状物質の析出量を増加させ、または溶解させることで、コロイド状物質の濃度を低下させてもよい。これによりタンパク質を除去する場合は、溶液のｐＨを除去の対象となるタンパク質の等電点に調整するとその除去効率が向上する。特にγ−アミノ酪酸の生成速度が速くなるｐＨ付近において等電点沈澱操作を行うと、γ−アミノ酪酸の製造を効率よく行うことができるとともに、γ−アミノ酪酸の製造時にタンパク質含有量が抑制された製品を得ることができる。この場合において、ｐＨは５以上７以下の範囲に調整されることが好ましい。米由来のタンパク質の濃度を低減することで、アレルギーのリスクを低下させ、最終製品の品質を向上させることができる。 Since the obtained leachate contains a colloidal substance as described above, by adjusting the salt concentration or pH of the solution, the precipitation amount of the colloidal substance is increased or dissolved, The concentration of colloidal material may be reduced. Thus, when removing a protein, the removal efficiency is improved by adjusting the pH of the solution to the isoelectric point of the protein to be removed. In particular, when isoelectric point precipitation is performed near pH where the production rate of γ-aminobutyric acid increases, γ-aminobutyric acid can be produced efficiently and the protein content is suppressed during the production of γ-aminobutyric acid. Product can be obtained. In this case, the pH is preferably adjusted in the range of 5 to 7. Reducing the concentration of rice-derived protein can reduce the risk of allergies and improve the quality of the final product.
＜イオン交換樹脂＞
本実施形態に用いられるイオン交換樹脂は、グルタミン酸脱炭酸酵素やアミラーゼ等の酵素を選択的に吸着せず、糠臭物質である脂肪酸類を選択的に吸着するものであれば特に限定されないが、陰イオン交換樹脂を用いることが好ましい。陰イオン交換樹脂としては、例えば、強塩基性イオン交換樹脂ＤＩＡＩＯＮ ＳＡ−１０Ａ、ＳＡ−１１Ａや樹脂の豊潤収縮耐性が高いポーラスタイプのＰＡ−３０８（いずれも三菱化学社製）等を用いることができる。このようなイオン交換樹脂がカラム等の容器に充填され、上記米糠浸出液のイオン交換反応に供される。
<Ion exchange resin>
The ion exchange resin used in the present embodiment is not particularly limited as long as it does not selectively adsorb enzymes such as glutamate decarboxylase and amylase, and selectively adsorbs fatty acids that are odorous substances. It is preferable to use an anion exchange resin. As the anion exchange resin, for example, strongly basic ion exchange resins DIAION SA-10A, SA-11A, porous type PA-308 (all manufactured by Mitsubishi Chemical Corporation) having high abundant shrinkage resistance of the resin, or the like may be used. it can. Such an ion exchange resin is filled in a container such as a column and used for the ion exchange reaction of the rice bran leachate.
また、本実施形態において、酵素群の細孔内への侵入を抑制し、イオン交換基に優先的に糠臭物質である脂肪酸群を吸着させる観点からは、ゲル型のイオン交換樹脂であって比較的ミクロポアの発達したもの、あるいは塩濃度の変化による膨潤、収縮に対して高い抵抗力を有し、且つ、イオン交換反応速度が速いポーラス型の樹脂を用いることが好ましい。糖類の脱色、分子量が高い有機酸の除去等を行う場合、ハイポーラス型の吸着剤を用いることがあるが、酵素に対して細孔径が大きすぎる樹脂を用いると、条件によっては有用な酵素群の損失を生じる可能性がある。また、本実施形態において低架橋度の樹脂を用いると、塩濃度に応じてゲルの膨潤、収縮が生じるため、非イオン性物質（糖質、着色成分等）の吸着、脱着が容易となる。 Further, in the present embodiment, from the viewpoint of suppressing the penetration of the enzyme group into the pores and preferentially adsorbing the fatty acid group, which is a odor substance, to the ion exchange group, it is a gel-type ion exchange resin. It is preferable to use a porous resin having a relatively developed micropore, or a porous resin having a high resistance to swelling and shrinkage due to a change in salt concentration and having a high ion exchange reaction rate. When decolorizing saccharides, removing organic acids with high molecular weight, etc., a hyperporous adsorbent may be used, but if a resin with a pore size too large for the enzyme is used, depending on the conditions, useful enzyme groups Loss may occur. In addition, when a resin having a low degree of crosslinking is used in the present embodiment, gel swelling and shrinkage occur depending on the salt concentration, so that adsorption and desorption of nonionic substances (saccharides, coloring components, etc.) are facilitated.
＜イオン交換樹脂を調整するための溶液（溶液Ａ）＞
本実施形態においては、上記イオン交換樹脂は、溶液Ａにより調整されることで、あらかじめイオン交換基に特定のイオンが吸着された状態にある。当該イオンとしては、反応系内がアルカリ性雰囲気とはならないような陰イオンが好ましく、例えば、塩化物イオン、硫酸イオン、硝酸イオン等の陰イオン、及び酢酸イオン、クエン酸イオン等の有機酸由来の陰イオンのいずれかを用いることが好ましい。このうち、食品へ適用する観点からは、塩化物イオン、硫酸イオン、又は有機酸由来の陰イオンを用いることが好ましく、食品への適用性及び糠臭物質の選択除去性を効果的に両立させる観点から、塩化物イオンとすることが特に好ましい。これらは組み合わせて用いることもできる。このことで糠臭物質の加水分解が避けられるとともに、アミノ酸の吸着を抑制することができる。例えば、上記イオン交換樹脂に塩化ナトリウム溶液等の塩化物イオンを含む溶液を通液して、イオン交換基に塩化物イオンを吸着させる。イオン交換樹脂の樹脂相は、溶液中に含まれる糠臭物質である脂肪酸類に起因するカルボキシル基が解離しやすく、且つ、当該脂肪酸類のアルカリ加水分解反応が生じない、弱酸性から中性付近のｐＨ領域になるような物質をイオン交換させることが望ましい。具体的にはｐＨを３以上７以下とすることが好ましい。
<Solution for preparing ion exchange resin (solution A)>
In the present embodiment, the ion exchange resin is adjusted by the solution A so that specific ions are previously adsorbed on the ion exchange group. As the ion, an anion that does not form an alkaline atmosphere in the reaction system is preferable. For example, anions such as chloride ion, sulfate ion, and nitrate ion, and organic acid-derived ions such as acetate ion and citrate ion, etc. It is preferable to use any one of anions. Among these, from the viewpoint of application to foods, it is preferable to use chloride ions, sulfate ions, or anions derived from organic acids, which effectively balances applicability to foods and selective removal of odorous substances. From the viewpoint, chloride ions are particularly preferable. These can also be used in combination. As a result, hydrolysis of the odor substance can be avoided and adsorption of amino acids can be suppressed. For example, a solution containing chloride ions such as a sodium chloride solution is passed through the ion exchange resin to adsorb chloride ions to the ion exchange group. The resin phase of the ion exchange resin is weakly acidic to near neutral, in which carboxyl groups caused by fatty acids, which are odorous substances contained in the solution, are easily dissociated, and alkaline hydrolysis of the fatty acids does not occur. It is desirable to ion-exchange substances that are in the pH range. Specifically, the pH is preferably 3 or more and 7 or less.
溶液Ａの濃度、供給速度、供給時間については、イオン交換基にイオンが吸着する条件であれば特に限定されない。例えば、上記イオン交換樹脂を充填したカラム等の容器に、１Ｎ 塩化ナトリウム水溶液を、空間速度２０で、３０分通液し、樹脂相を塩化物イオン型に調整した後、同程度の空間速度、時間で蒸留水を通液することで、容器内に存在する塩化ナトリウム溶液を蒸留水で置換することにより、イオン交換樹脂が調整される。 The concentration, supply speed, and supply time of the solution A are not particularly limited as long as ions are adsorbed on the ion exchange group. For example, a 1N sodium chloride aqueous solution is passed through a container such as a column filled with the above ion exchange resin at a space velocity of 30 minutes for 30 minutes to adjust the resin phase to a chloride ion type, By passing distilled water through time, the ion exchange resin is adjusted by replacing the sodium chloride solution present in the container with distilled water.
＜イオン交換樹脂再生の際の前処理溶液（溶液Ｂ）＞
本発明に用いられる溶液Ｂとしては、下記説明するように、イオン交換樹脂にイオン化して吸着した糠臭物質を容易に脱着可能な状態へと前処理する溶液であれば特に限定されない。例えば、疎水性タンパク質の一部を分解可能なアルカリ溶液とすることが好ましい。アルカリ溶液の具体例としては、水酸化物イオンを含む溶液であることが好ましい。具体的には、水酸化ナトリウムや水酸化カリウム等のアルカリ金属塩を含む溶液、又は、水酸化カルシウムや水酸化バリウム等のアルカリ土類金属塩を含む溶液とすることが好ましく、水酸化ナトリウム水溶液とすることが特に好ましい。溶液Ｂの濃度としては、イオン交換樹脂のアルカリ処理が可能であれば特に限定されない。
<Pretreatment solution for regenerating ion exchange resin (solution B)>
As described below, the solution B used in the present invention is not particularly limited as long as it is a solution that pretreats the odorous substance ionized and adsorbed on the ion exchange resin so that it can be easily detached. For example, it is preferable to use an alkaline solution capable of decomposing a part of the hydrophobic protein. A specific example of the alkaline solution is preferably a solution containing hydroxide ions. Specifically, a solution containing an alkali metal salt such as sodium hydroxide or potassium hydroxide, or a solution containing an alkaline earth metal salt such as calcium hydroxide or barium hydroxide is preferable. It is particularly preferable that The concentration of the solution B is not particularly limited as long as alkali treatment of the ion exchange resin is possible.
＜イオン交換樹脂を洗浄するための溶液（溶液Ｃ）＞
本実施形態において用いられる溶液Ｃとしては、イオン交換樹脂を洗浄することが可能な溶液であれば特に限定されない。例えば、水（イオン交換水、蒸留水等）とすることができる。また、イオン交換樹脂を溶液Ｂ及び上記溶液Ａに交互に繰り返し接触させることで、イオン交換樹脂の再生の際、非イオン性物質の脱着と溶液Ａに含まれるイオンの吸着とを、より効率的に行うことができる。
<Solution for washing ion exchange resin (solution C)>
The solution C used in the present embodiment is not particularly limited as long as the solution can wash the ion exchange resin. For example, water (ion exchange water, distilled water, etc.) can be used. In addition, the ion exchange resin is alternately and repeatedly brought into contact with the solution B and the solution A, so that the desorption of nonionic substances and the adsorption of ions contained in the solution A can be more efficiently performed when the ion exchange resin is regenerated. Can be done.
以下、本発明の一実施形態にかかる米糠浸出物の製造方法について詳述する。 Hereinafter, the manufacturing method of the rice bran leachables concerning one embodiment of the present invention is explained in full detail.
＜米糠浸出物の製造方法＞
（米糠浸出液作製工程）
本実施形態にかかる米糠浸出物の製造方法は、米糠を溶媒に含浸させて米糠浸出液を作製する工程を備える。米糠浸出液の作製方法については、上記と同様であるため省略する。
<Manufacturing method of rice bran leachate>
(Rice bran leachate preparation process)
The method for producing a rice bran leachable according to the present embodiment includes a step of impregnating rice bran with a solvent to produce a rice bran leachate. The method for preparing the rice bran leachate is the same as described above, and is therefore omitted.
（糠臭物質除去工程）
得られた米糠浸出液は、上記イオン交換樹脂を充填したカラム等の容器に供給されて、固定層連続吸着操作が行われることで、糠臭物質がイオン交換樹脂に吸着され、米糠浸出液から除去される。除去対象となる糠臭物質は主に脂肪酸類であることから、これらの物質はカルボキシル基を有し、弱酸性からアルカリ性雰囲気においては陰イオンに解離する性質を有する。従って、特に、陰イオン交換樹脂を充填し、あらかじめイオン交換基に塩化物イオンなどのイオンを吸着させた後に、米糠浸出液を通液すると、脂肪酸類はイオン交換反応により樹脂相に選択的に吸着される一方、有用酵素群はイオン交換樹脂相にほとんど吸着せずに容器から、白濁したコロイド溶液として流出する。すなわち、当該コロイド溶液が、糠臭物質である脂肪酸類が低減、除去された糠臭除去浸出液である。この糠臭除去浸出液は、溶液のまま米糠浸出物とされる他、糠臭除去浸出液を乾燥させて粉体状の米糠浸出物とすることもでき、また、糠臭除去浸出液を凍結させた米糠浸出物とすることもできる。糠臭除去浸出液を乾燥する際には、凍結乾燥を行うことが好ましく、予備冷凍として寒剤による冷凍を行うことが望ましい。使用する寒剤は溶液を凍結するのに十分な冷却能力を有するものであればどのようなものを使用してもよく、メタノール−氷程度の冷却効果を有する寒剤でも十分利用可能である。これら各形態の米糠浸出物は、高い酵素活性を有するとともに、従来よりも糠臭が低減されたものであり、γ−アミノ酪酸等を生成するための、各種酵素反応に好適に用いられる。
(Odorous substance removal process)
The obtained rice bran leachate is supplied to a container such as a column filled with the ion exchange resin, and the fixed bed continuous adsorption operation is performed, so that the odor substance is adsorbed on the ion exchange resin and removed from the rice bran leachate. The Since the odorous substances to be removed are mainly fatty acids, these substances have a carboxyl group and have the property of dissociating into anions in a weakly acidic to alkaline atmosphere. Therefore, in particular, when anion exchange resin is filled and ions such as chloride ions are adsorbed to ion exchange groups in advance and then passed through rice bran leachate, fatty acids are selectively adsorbed to the resin phase by ion exchange reaction. On the other hand, the useful enzyme group flows out from the container as a cloudy colloidal solution with little adsorption to the ion exchange resin phase. That is, the colloid solution is a odor removal leachate from which fatty acids as odor substances are reduced and removed. This odor removal leachate is used as a rice bran leachate in the form of a solution, or the odor removal leachate can be dried to form a powdered rice bran leachate, or the rice odor removal leachate can be frozen. It can also be a leachable. When drying the odor-removing leachate, it is preferable to perform freeze-drying, and it is desirable to perform freezing with a cryogen as preliminary freezing. Any cryogen may be used as long as it has a cooling capacity sufficient to freeze the solution, and a cryogen having a cooling effect equivalent to that of methanol-ice can be used sufficiently. These rice bran leachables in each form have high enzyme activity and a reduced odor than before, and are suitably used for various enzyme reactions for producing γ-aminobutyric acid and the like.
糠臭物質の吸着操作時には、時間の経過とともに樹脂相に濃い黄色から茶色の吸着帯が樹脂相上部から下部に向かって徐々に出現するが、この吸着帯が糠臭原因物質等を含む層に相当する。尚、吸着操作時の通液量は、全体の樹脂相長さに対する吸着帯の相対長さ等の指標により適宜判断され得る。 During the odor substance adsorption operation, a dark yellow to brown adsorption band gradually appears in the resin phase from the top to the bottom of the resin phase over time. Equivalent to. In addition, the liquid flow amount at the time of the adsorption operation can be appropriately determined based on an index such as the relative length of the adsorption band with respect to the entire resin phase length.
イオン交換樹脂に吸着した糠臭物質等は、上記溶液Ａ〜Ｃを用いて脱着され、イオン交換樹脂が再生される。以下、イオン交換樹脂の再生処理について説明する。 The odorous substance adsorbed on the ion exchange resin is desorbed using the solutions A to C, and the ion exchange resin is regenerated. Hereinafter, the regeneration process of the ion exchange resin will be described.
（再生工程）
まず、糠臭物質である脂肪酸類を吸着したイオン交換樹脂を、溶液Ｂにより前処理する。イオン交換樹脂に吸着した糠臭物質等の脱着の際、溶液Ｂを先に通液することにより、イオン交換樹脂上で糠臭物質を脱着し易い形態へと変え、樹脂相下部から順に溶出させる。
(Regeneration process)
First, an ion exchange resin adsorbing fatty acids, which are odorous substances, is pretreated with solution B. At the time of desorption of the odor substance adsorbed on the ion exchange resin, the solution B is first passed to change the form to easily desorb the odor substance on the ion exchange resin and elute in order from the bottom of the resin phase. .
具体的には、例えば、糠臭物質除去工程における吸着操作の後、水を供給することにより容器内を置換してから、１Ｎの水酸化ナトリウム水溶液を空間速度２０程度の速度で供給する。そして、溶液Ｂの供給を続けることで、糠臭物質の一部も脱着し、徐々に容器から流出する。 Specifically, for example, after the adsorption operation in the odor substance removing step, the inside of the container is replaced by supplying water, and then a 1N sodium hydroxide aqueous solution is supplied at a space velocity of about 20. And by continuing the supply of the solution B, a part of the odor substance is also desorbed and gradually flows out of the container.
そして、前処理の後に溶液Ｃを通液し、残存反応物質を、洗浄、溶出した後、溶液Ａを通液することで、イオン交換樹脂のイオン交換基に再度イオンが吸着された状態となる。再生工程においては、溶液Ｂによる前処理の後、溶液Ｃによる洗浄と、溶液Ａによるイオン吸着とを交互に繰り返し行うことが好ましい。このことで、イオン交換樹脂の再生の際、非イオン性物質の脱着と溶液Ａに含まれるイオンの吸着とを、より効率的に行うことができる。再生工程を経ることで、イオン交換樹脂は再生され、繰り返し粗酵素含有溶液を処理することが可能となる。 Then, after the pretreatment, the solution C is passed, the remaining reactants are washed and eluted, and then the solution A is passed, so that ions are again adsorbed on the ion exchange groups of the ion exchange resin. . In the regeneration step, after the pretreatment with the solution B, washing with the solution C and ion adsorption with the solution A are preferably performed alternately. Thus, when the ion exchange resin is regenerated, desorption of the nonionic substance and adsorption of ions contained in the solution A can be performed more efficiently. Through the regeneration step, the ion exchange resin is regenerated and the crude enzyme-containing solution can be repeatedly processed.
具体的には、例えば、容器内を蒸留水で洗浄、置換した後、１Ｎの塩化ナトリウム水溶液を空間速度２０で供給し、容器から流出する液を回収する。好ましくは蒸留水による洗浄操作と塩化ナトリウム水溶液による再生操作とを二回以上繰り返す。この際に得られる溶液は、糠臭原因物質等を含む溶液である。塩化ナトリウム水溶液を通液し、塩化物イオン型に再生された樹脂は、蒸留水により系内を置換したのち、再び米糠浸出液の吸着処理に使用される。 Specifically, for example, after washing and replacing the inside of the container with distilled water, a 1N sodium chloride aqueous solution is supplied at a space velocity of 20, and the liquid flowing out of the container is recovered. Preferably, the washing operation with distilled water and the regeneration operation with an aqueous sodium chloride solution are repeated twice or more. The solution obtained at this time is a solution containing an odor-causing substance or the like. The resin regenerated into a chloride ion type through a sodium chloride aqueous solution is used again for the adsorption treatment of the rice bran leachate after the system is replaced with distilled water.
上記説明においては、再生工程において溶液Ｂによる前処理を施すものとして説明したが、当該前処理を行わずに、溶液Ｃと溶液Ａとを用いてイオン交換樹脂を洗浄、再生することも可能といえる。但し、イオン交換樹脂に吸着した物質を容易に脱着可能な形態とするとともに、再生工程を効率的に行う観点からは、洗浄、再生処理の前に前処理を施すことが好ましい。 In the above description, the pretreatment with the solution B is performed in the regeneration step. However, the ion exchange resin can be washed and regenerated using the solution C and the solution A without performing the pretreatment. I can say that. However, it is preferable to perform pretreatment before washing and regeneration treatment from the viewpoint of making the substance adsorbed on the ion exchange resin easily removable and performing the regeneration step efficiently.
次に、上記工程により得られた米糠浸出物を用いた、γ−アミノ酪酸の製造方法について説明する。 Next, the manufacturing method of (gamma) -aminobutyric acid using the rice bran leachate obtained by the said process is demonstrated.
＜γ−アミノ酪酸の製造方法＞
上記、米糠浸出液作製工程、糠臭物質除去工程、並びに、任意に再生工程を備えることで、連続的に米糠浸出液から糠臭物質である脂肪酸類が除去され、糠臭が取り除かれた米糠浸出物が製造される。当該米糠浸出物を、グルタミン酸を含有する溶液に添加して酵素反応を行うことで、γ−アミノ酪酸を製造することができる。グルタミン酸からγ−アミノ酪酸を生成させる場合、所定の濃度、ｐＨに調製したグルタミン酸水溶液中に所定量の米糠浸出物を添加し、酵素反応の活性を示す温度域の下で所定時間反応操作を行う。反応操作は連続型、回分型いずれの反応器を用いてもよい。中でも、高濃度のγ−アミノ酪酸を得るためには回分型反応器を用いることが好ましい。また、得られるγ−アミノ酪酸の濃度は、基質として添加したグルタミン酸の濃度、該物質の添加量、反応時間等の操作条件を変えることで制御が可能である。
<Method for producing γ-aminobutyric acid>
The rice bran leachate from which the malodorous substances are continuously removed from the rice bran leachate by removing the rice bran leachate preparation process, the bad smell substance removing process, and optionally the regeneration process. Is manufactured. Γ-aminobutyric acid can be produced by adding the rice bran leachate to a solution containing glutamic acid and performing an enzyme reaction. When γ-aminobutyric acid is produced from glutamic acid, a predetermined amount of rice bran leachate is added to a glutamic acid aqueous solution adjusted to a predetermined concentration and pH, and the reaction operation is performed for a predetermined time in a temperature range showing the enzymatic reaction activity. . For the reaction operation, either a continuous type or a batch type reactor may be used. Among them, it is preferable to use a batch reactor in order to obtain a high concentration of γ-aminobutyric acid. The concentration of γ-aminobutyric acid obtained can be controlled by changing the operating conditions such as the concentration of glutamic acid added as a substrate, the amount of the substance added, and the reaction time.
本実施形態にかかる米糠浸出物を用いてγ−アミノ酪酸を生成させる際、イオン交換膜を用いた透析を行うことで、酵素反応と分離操作とを同時に行うこともできる。特に、回分型反応器とイオン交換膜を用いた透析槽からなる組み合わせ型反応器により、γ−アミノ酪酸を含む溶液を製造すると同時に分離を行うと、非常に効率よくγ−アミノ酪酸が製造できるため好ましい。また、透析操作としては、拡散透析、電気透析等が挙げられる。透析槽は単膜または複数の膜から構成される室を有する装置で、少なくとも膜の一面に米糠浸出物を分散あるいは溶解した反応溶液を供給し、また反対側には透過物質を回収する溶液を流すことが好ましい。なお用いる膜は拡散透析法の場合には陽イオン交換膜が望ましい。 When producing γ-aminobutyric acid using the rice bran leachable according to the present embodiment, dialysis using an ion exchange membrane can be performed to simultaneously perform an enzyme reaction and a separation operation. In particular, γ-aminobutyric acid is produced very efficiently when a solution containing γ-aminobutyric acid is produced at the same time as a combined reactor comprising a dialysis tank using a batch reactor and an ion exchange membrane. This is preferable because it is possible. Examples of the dialysis operation include diffusion dialysis and electrodialysis. A dialysis tank is a device having a chamber composed of a single membrane or a plurality of membranes. At least one surface of the membrane is supplied with a reaction solution in which rice bran leachate is dispersed or dissolved, and on the other side is a solution for collecting permeate. It is preferable to flow. In the case of diffusion dialysis, the membrane used is preferably a cation exchange membrane.
供給側の溶液は、酵素の機能が発現する基質を含む溶液であれば、特に固定されるものではない。また、回収側の溶液は、酸、アルカリ、中性の電解質溶液いずれの溶液でも可能であるが、透過速度、膜の選択透過性は反応溶液のｐＨさらには回収側溶液のｐＨで大きく変わるため、目的に合わせた溶質を含む溶液を選択することが望ましい。 The solution on the supply side is not particularly fixed as long as it contains a substrate that expresses the function of the enzyme. The solution on the recovery side can be any of acid, alkali, and neutral electrolyte solutions. However, the permeation rate and the selective permeability of the membrane vary greatly depending on the pH of the reaction solution and the pH of the recovery side solution. It is desirable to select a solution containing a solute suited to the purpose.
透析槽の運転は、酵素反応の反応速度、目的物質の膜透過速度を考慮した場合、反応側回収側とも回分循環方式が好ましい。十分な溶液量および膜面積を確保できる場合には連続型の運転も可能である。 The operation of the dialysis tank is preferably a batch circulation system on the reaction side recovery side in consideration of the reaction rate of the enzyme reaction and the membrane permeation rate of the target substance. If a sufficient amount of solution and membrane area can be secured, continuous operation is also possible.
上記において、γ−アミノ酪酸を含有する溶液に対し、さらに任意に固液分離処理や脱色処理を施してもよい。固液分離処理は従来公知のものが特に限定されず適用でき、例えば遠心分離操作により行われる。脱色処理についても従来公知のものが特に限定されず適用でき、例えば活性炭を用いた吸着により行われる。 In the above, the solution containing γ-aminobutyric acid may be optionally subjected to solid-liquid separation treatment or decolorization treatment. A conventionally known solid-liquid separation process can be applied without particular limitation, and is performed, for example, by a centrifugal separation operation. For the decolorization treatment, conventionally known ones can be applied without particular limitation. For example, the decolorization treatment is performed by adsorption using activated carbon.
米糠中にはグルタミン酸脱炭酸酵素の他、アミラーゼをはじめとした複数の酵素が含まれていることが知られている。従って、例えば、でんぷん含有水溶液に本実施形態にかかる米糠浸出物を添加し、酵素反応の活性を示す温度域の下で所定時間反応操作を行えば、米糠浸出物中のアミラーゼの作用により還元糖を得ることができる。この場合における好ましい反応操作や分離操作の条件は、上述のγ−アミノ酪酸の生成分離の場合と同様である。 It is known that rice bran contains a plurality of enzymes including amylase in addition to glutamate decarboxylase. Therefore, for example, when a rice bran leachate according to the present embodiment is added to a starch-containing aqueous solution and the reaction operation is performed for a predetermined time under a temperature range showing the activity of the enzyme reaction, the reducing sugar is produced by the action of amylase in the rice bran leachate Can be obtained. The preferable conditions for the reaction operation and separation operation in this case are the same as those for the production and separation of γ-aminobutyric acid described above.
また、本実施形態にかかる米糠浸出物の食品への応用を考える場合、グルタミン酸をγ−アミノ酪酸に変換すると、グルタミン酸減少による旨味の減少および、γ−アミノ酪酸の生成に伴う苦みの増加が生じ、食品の有する本来の味が変化することが考えられる。そのような場合、基質としてグルタミン酸の他に、酵素によって還元糖を生成するような、でんぷん、グリコーゲン、デキストリンなどのグルカンを主鎖とする多糖類を同時に添加、あるいはグルカンを含む穀物由来の食品に粉末を添加することで、酵素反応による還元糖の生成によりγ−アミノ酪酸の生成に伴う苦みを和らげることが可能になる。例えば、本実施形態にかかる米糠浸出物を、グルタミン酸を多く含むスープ、さらには発酵によって生成した大量のアミノ酸を含む、なれ鮨や麹漬け等の発酵食品に添加すれば、アミノ酸の含有率と種類を変えつつ、味を改善することができる。 In addition, when considering the application of rice bran leachables according to this embodiment to foods, when glutamic acid is converted to γ-aminobutyric acid, there is a decrease in umami due to glutamic acid reduction and an increase in bitterness associated with the production of γ-aminobutyric acid. It is conceivable that the original taste of the food changes. In such a case, in addition to glutamic acid as a substrate, a polysaccharide having a main chain of glucan such as starch, glycogen, dextrin, etc., which produces reducing sugar by an enzyme, is added at the same time. By adding the powder, it is possible to relieve the bitterness associated with the production of γ-aminobutyric acid by the production of reducing sugars by enzymatic reaction. For example, if the rice bran leachable according to the present embodiment is added to a soup containing a lot of glutamic acid, or a fermented food containing a large amount of amino acids generated by fermentation, such as potato or pickled rice, the content and types of amino acids The taste can be improved while changing.
尚、上記説明においては、米糠浸出物の製造段階において、糠臭物質除去工程を備える一実施形態について説明した。しかしながら、糠臭が取り除かれたγ−アミノ酪酸等を含む溶液を製造する場合、必ずしもこの形態に限定されない。例えば、上記米糠浸出液作製工程から、糠臭物質が残存したままの当該米糠浸出液を用いて米糠浸出物を得て（米糠浸出物作製工程）、グルタミン酸含有溶液に添加して酵素反応を行うことでγ−アミノ酪酸を含む溶液を製造し、その後、当該γ−アミノ酪酸を含む溶液について、上記糠臭物質除去工程を行うことで、糠臭物質を取り除く形態としてもよい。尚、この実施形態において用いられる米糠浸出物についても、上記と同様に溶液状、粉体状、氷結体状等、形態を問わない。 In addition, in the said description, one Embodiment provided with a malodorous substance removal process in the manufacture stage of the rice bran leachables was demonstrated. However, when a solution containing γ-aminobutyric acid or the like from which the odor is removed is not necessarily limited to this form. For example, from the rice bran leachate preparation step, a rice bran leachate is obtained using the rice bran leachate with the odor substance remaining (rice bran leachate preparation step) and added to the glutamic acid-containing solution to perform an enzyme reaction. A solution containing γ-aminobutyric acid may be manufactured, and then the odorous substance may be removed by performing the above-mentioned odorant removing process for the solution containing γ-aminobutyric acid. In addition, the rice bran leachate used in this embodiment may be in any form such as a solution, a powder, or an iced body as in the above.
以下、上記工程により得られる種々の物質の特性を示すデータに基づき、本発明にかかる実施例について説明する。 Hereinafter, examples according to the present invention will be described based on data indicating characteristics of various substances obtained by the above-described steps.
図１に、塩化物イオン型に調整した陰イオン交換樹脂を充填したカラムに、米糠浸出液を流して、イオン交換処理を行った溶液、及び未処理の溶液のそれぞれを乾燥して乾燥粉末とし、当該各乾燥粉末を水に溶解して、水溶性の物質について蛍光検出する逆相ＨＰＬＣにより分析を行った結果を示す。図中の線Ａは、イオン交換処理を行わない物質の測定結果、線Ｂはイオン交換処理を行った物質を測定した結果である。図より、イオン交換処理を行わない物質は２．５〜５分までの間に３つのピークが観測されているが、イオン交換処理を行った物質については、５分までの全体ピーク面積が減少するとともに、未処理物質に現れている最初のピークに相当するピークが消失していることが分かる。また、７分以降のＨＰＬＣクロマトグラムには、イオン交換処理を行った物質と未処理物質とで、大きな違いが見られない。このことから、イオン交換処理を行った物質について、７分程度までに現れる全体ピーク面積が減少したのは、イオン交換によって樹脂相に糠臭物質が吸着されたためであると考えられる。 In FIG. 1, a rice bran leachate is poured into a column packed with an anion exchange resin adjusted to a chloride ion type, and each of the solution subjected to the ion exchange treatment and the untreated solution is dried to obtain a dry powder. The result of having analyzed each said dry powder in water and analyzed by the reverse phase HPLC which carries out the fluorescence detection about the water-soluble substance is shown. A line A in the figure is a measurement result of a substance not subjected to ion exchange treatment, and a line B is a result of measurement of a substance subjected to ion exchange treatment. From the figure, three peaks are observed between 2.5 and 5 minutes for substances that are not subjected to ion exchange treatment, but the overall peak area is reduced to 5 minutes for substances that have undergone ion exchange treatment. In addition, it can be seen that the peak corresponding to the first peak appearing in the untreated substance has disappeared. Further, in the HPLC chromatogram after 7 minutes, there is no significant difference between the substance subjected to the ion exchange treatment and the untreated substance. From this, it can be considered that the total peak area that appears in about 7 minutes for the substance subjected to the ion exchange treatment decreased because the odor substance was adsorbed on the resin phase by ion exchange.
図２に、吸着操作の後、イオン交換樹脂に水酸化ナトリウム水溶液を滴下して、前処理した後、塩化ナトリウム水溶液を用いてイオン交換樹脂に吸着している物質を脱着させた際に得られる溶液を、蛍光検出器を有する逆相ＨＰＬＣにより分析を行った結果を示す。図中の線Ｃが、前処理や塩化ナトリウムによるイオン交換により溶出した物質を分析した結果である。図中の線Ａ、Ｂについては、図１と同様である。この場合、各時間における線Ａ、Ｂのピーク面積差は、樹脂相に吸着した物質量に相当する。また、水酸化ナトリウムによる化学変化を伴わないものとすると、線Ｃの分析結果は、線Ａ、Ｂのピーク面積差に対応して増減することとなる。図２によれば、水酸化ナトリウムによる前処理を行った後に塩化ナトリウム水溶液で流出させた液においては、線Ａの一つめのピークに相当するピーク１（線Ｂにおいてイオン交換処理により消失したピーク）に相当する物質が確認された。また、線Ａの二つめ、三つめのピーク２、３に相当する物質は明確には確認されなかったが、保持時間が短時間側と長時間側にシフトした物質二種類が確認された。
In FIG. 2, after the adsorption operation, a sodium hydroxide aqueous solution is dropped onto the ion exchange resin, and after pretreatment, the substance adsorbed on the ion exchange resin is desorbed using the sodium chloride aqueous solution. The result of having analyzed the solution by the reverse phase HPLC which has a fluorescence detector is shown. The line C in the figure is the result of analyzing the substance eluted by pretreatment or ion exchange with sodium chloride. The lines A and B in the figure are the same as those in FIG. In this case, the peak area difference between the lines A and B at each time corresponds to the amount of the substance adsorbed on the resin phase. If the chemical change caused by sodium hydroxide is not involved, the analysis result of the line C increases or decreases corresponding to the peak area difference between the lines A and B. According to FIG. 2, in the solution that was pretreated with sodium hydroxide and then flowed out with an aqueous sodium chloride solution, peak 1 corresponding to the first peak of line A (peak disappeared by ion exchange treatment in line B) ) Was confirmed. Further, although the substances corresponding to the second and
図３に、イオン交換処理を行った乾燥粉末を用いてグルタミン酸を基質としてＧＡＢＡの生成実験を行った結果を示す。実験は４０℃、ｐＨ５．５の下で行い、グルタミン酸の濃度を２ｍｏｌ／ｍ３とし、粉末添加量を０．７５、１．５ｗｔ／ｖｏｌ％として、１８０分反応操作を行った。図より、いずれの実験においても、グルタミン酸からＧＡＢＡが生成しており、イオン交換処理を行った場合でも米糠浸出物の酵素を高い収率で回収できたことが分かる。また、実験終了後の溶液を煮沸した溶液には、糠臭、糠の味がほとんど感じられず、イオン交換処理の効果が認められた。 FIG. 3 shows the results of a GABA production experiment using glutamic acid as a substrate using the ion-exchanged dry powder. The experiment was performed at 40 ° C. and pH 5.5, and the reaction was performed for 180 minutes with the glutamic acid concentration of 2 mol / m 3 , the powder addition amount of 0.75 and 1.5 wt / vol%. From the figure, it can be seen that in any experiment, GABA was produced from glutamic acid, and the rice bran leachate enzyme could be recovered in high yield even when ion exchange treatment was performed. Moreover, in the solution which boiled the solution after completion | finish of experiment, the bad smell and the taste of a strawberry were hardly felt, and the effect of the ion exchange process was recognized.
図４に、５０ｇの米糠を１００ｍｌの蒸留水で水浸出した溶液を用い、温度４０℃、ｐＨ５．５の下でグルタミン酸の濃度を２ｍｏｌ／ｍ３とした溶液５００ｍｌを用いてＧＡＢＡの生成反応を１８０分行った場合の、溶液中のアミノ酪酸のクロマトグラムを示す（線Ｄ）。尚、図中には、実験終了後の溶液を塩化物イオン型の陰イオン交換樹脂で処理した場合の結果（線Ｅ）も併せて示す。図より、酵素反応終了後の溶液についてイオン交換処理を行うと、１０分までに出現するアミノ酸群に関するピークの減少が若干確認されるものの、他のピークはイオン交換処理の有無に関わらずほぼ同じ強度を示すことが分かる。しかし、イオン交換処理を行った溶液からは糠臭、糠味はほとんど感じられず、塩化物イオン型の陰イオン交換樹脂を用いることで、反応終了後の溶液からアミノ酸群の損失を抑制しながら、糠臭物質を選択的に除去することができることが分かった。 FIG. 4 shows a GABA production reaction using 500 ml of a solution obtained by leaching 50 g of rice bran with 100 ml of distilled water and having a glutamic acid concentration of 2 mol / m 3 at a temperature of 40 ° C. and a pH of 5.5. A chromatogram of aminobutyric acid in the solution after 180 minutes is shown (line D). In the figure, the result (line E) when the solution after the experiment is treated with a chloride ion type anion exchange resin is also shown. From the figure, when ion exchange treatment is performed on the solution after completion of the enzyme reaction, although a slight decrease in peaks related to amino acid groups appearing by 10 minutes is confirmed, the other peaks are almost the same regardless of whether or not ion exchange treatment is performed. It can be seen that it shows strength. However, the odor and taste are hardly felt from the solution subjected to the ion exchange treatment, and by using a chloride ion type anion exchange resin, the loss of the amino acid group is suppressed from the solution after the reaction is completed. It was found that odorous substances can be selectively removed.
以上、現時点において、もっとも、実践的であり、かつ、好ましいと思われる実施形態に関連して本発明を説明したが、本発明は、本願明細書中に開示された実施形態に限定されるものではなく、請求の範囲および明細書全体から読み取れる発明の要旨或いは思想に反しない範囲で適宜変更可能であり、そのような変更を伴う糠臭が取り除かれた米糠浸出物の製造方法、糠臭が取り除かれた米糠浸出物、及びγ−アミノ酪酸の製造方法もまた本発明の技術的範囲に包含されるものとして理解されなければならない。 While the present invention has been described in connection with embodiments that are presently the most practical and preferred, the present invention is not limited to the embodiments disclosed herein. Rather, it can be changed as appropriate without departing from the spirit or idea of the invention that can be read from the claims and the entire specification, and the method for producing rice bran leachate from which the odor accompanied with such changes has been removed, The rice bran leachate removed and the process for producing γ-aminobutyric acid should also be understood as being within the scope of the present invention.
本発明によれば、高い酵素活性を有するとともに、米糠由来の特有の糠臭、糠味が除去された米糠浸出物を製造することができる。また、本発明によれば、糠臭、糠味が除去されたγ−アミノ酪酸、還元糖等を製造することができる。よって、本発明は、γ−アミノ酪酸、還元糖等が効果的に生成されるとともに、糠臭、糠味が除去されている機能性健康食品を製造する場合に特に好適に用いられる。 According to the present invention, it is possible to produce a rice bran leachate that has high enzyme activity and from which the peculiar odor and taste of rice bran are removed. In addition, according to the present invention, γ-aminobutyric acid, reducing sugar and the like from which the odor and taste are removed can be produced. Therefore, the present invention is particularly preferably used in the case of producing a functional health food from which γ-aminobutyric acid, reducing sugar, etc. are effectively produced and the odor and taste are removed.
Claims (7)
前記米糠浸出液作製工程により得られた前記浸出液を、イオン交換基にあらかじめ特定のイオンが吸着されたイオン交換樹脂と接触させて、該イオン交換樹脂に糠臭物質を吸着させるとともに、該糠臭物質が除去された米糠浸出物を得る、糠臭物質除去工程と、
を有する、糠臭が取り除かれた米糠浸出物の製造方法。 A rice bran leachate preparation step of impregnating rice bran in a solvent to prepare a leachate containing a crude enzyme derived from rice bran;
The leachate obtained by the rice bran leachate preparation step is brought into contact with an ion exchange resin in which specific ions are adsorbed in advance on an ion exchange group to adsorb the odor substance on the ion exchange resin, and the odor substance To obtain a rice bran leachate from which the odor has been removed,
A method for producing a rice bran leachate from which a bad smell is removed.
前記米糠浸出液作製工程により得られた前記浸出液から米糠浸出物を作製する、米糠浸出物作製工程と、
前記米糠浸出物作製工程により得られた前記米糠浸出物を、グルタミン酸を含有する溶液に添加して、γ−アミノ酪酸を生成させる、酵素反応工程と、
前記酵素反応工程により得られた、前記γ−アミノ酪酸を含む溶液を、イオン交換基にあらかじめ特定のイオンが吸着されたイオン交換樹脂と接触させて、該イオン交換樹脂に糠臭物質を吸着させる、糠臭物質除去工程と、
を有する、γ−アミノ酪酸を含有する溶液を製造する方法。 A rice bran leachate preparation step of impregnating rice bran in a solvent to prepare a leachate containing a crude enzyme derived from rice bran;
A rice bran leachate preparation step for preparing a rice bran leachate from the leachate obtained by the rice bran leachate preparation step;
An enzyme reaction step of adding the rice bran leachate obtained in the rice bran leachate preparation step to a solution containing glutamic acid to produce γ-aminobutyric acid;
The solution containing the γ-aminobutyric acid obtained by the enzyme reaction step is brought into contact with an ion exchange resin in which specific ions are adsorbed in advance on an ion exchange group, thereby adsorbing a odor substance on the ion exchange resin. , Odor substance removal process,
A method for producing a solution containing γ-aminobutyric acid.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107326052A (en) * | 2017-06-28 | 2017-11-07 | 岭南师范学院 | A kind of method that glutamate decarboxylase activity is improved with D101 macroporous absorbent resins |
| CN115477592A (en) * | 2022-09-30 | 2022-12-16 | 西安萃源生物科技有限公司 | Crystallization method of gamma-aminobutyric acid |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61227543A (en) * | 1985-03-30 | 1986-10-09 | Nippon Oil & Fats Co Ltd | Separation of higher alcohol |
| JPS6274300A (en) * | 1985-09-25 | 1987-04-06 | 帝人エンジニアリング株式会社 | Method for purifying rice bran saccharification solution |
| JPS6372392A (en) * | 1986-09-17 | 1988-04-02 | Japan Organo Co Ltd | Ion exchange apparatus for removing nitrate ion in drinking water and method for sampling nitrate ion removed treated water |
| JPH08280341A (en) * | 1995-04-13 | 1996-10-29 | Kano Shiyoujiyuan:Kk | Production of fermented liquid containing lactic acid |
| JPH0947761A (en) * | 1995-08-11 | 1997-02-18 | Mitsubishi Rayon Co Ltd | Water purifier |
| JP2001333728A (en) * | 2000-05-25 | 2001-12-04 | Nisshin Sugar Mfg Co Ltd | Sweetener including mulberry leaf extract and method of producing the same |
| WO2002076919A1 (en) * | 2001-03-26 | 2002-10-03 | Nippon Shokubai Co., Ltd. | Method of reaction with soluble metallic catalyst and anion-exchange resin, method of recovering the soluble metallic catalyst, and method of recycling |
| JP2007185156A (en) * | 2006-01-16 | 2007-07-26 | Sunstar Inc | Method for producing deodorized rice bran, and food mixed with the same |
| WO2007129674A1 (en) * | 2006-05-02 | 2007-11-15 | Toyo Hakko Co., Ltd. | Fermented product composition, cosmetic composition and method of producing the same |
-
2009
- 2009-01-19 JP JP2009009223A patent/JP4537486B2/en not_active Expired - Fee Related
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61227543A (en) * | 1985-03-30 | 1986-10-09 | Nippon Oil & Fats Co Ltd | Separation of higher alcohol |
| JPS6274300A (en) * | 1985-09-25 | 1987-04-06 | 帝人エンジニアリング株式会社 | Method for purifying rice bran saccharification solution |
| JPS6372392A (en) * | 1986-09-17 | 1988-04-02 | Japan Organo Co Ltd | Ion exchange apparatus for removing nitrate ion in drinking water and method for sampling nitrate ion removed treated water |
| JPH08280341A (en) * | 1995-04-13 | 1996-10-29 | Kano Shiyoujiyuan:Kk | Production of fermented liquid containing lactic acid |
| JPH0947761A (en) * | 1995-08-11 | 1997-02-18 | Mitsubishi Rayon Co Ltd | Water purifier |
| JP2001333728A (en) * | 2000-05-25 | 2001-12-04 | Nisshin Sugar Mfg Co Ltd | Sweetener including mulberry leaf extract and method of producing the same |
| WO2002076919A1 (en) * | 2001-03-26 | 2002-10-03 | Nippon Shokubai Co., Ltd. | Method of reaction with soluble metallic catalyst and anion-exchange resin, method of recovering the soluble metallic catalyst, and method of recycling |
| JP2007185156A (en) * | 2006-01-16 | 2007-07-26 | Sunstar Inc | Method for producing deodorized rice bran, and food mixed with the same |
| WO2007129674A1 (en) * | 2006-05-02 | 2007-11-15 | Toyo Hakko Co., Ltd. | Fermented product composition, cosmetic composition and method of producing the same |
Non-Patent Citations (2)
| Title |
|---|
| 化学工学会秋季大会研究発表講演要旨集, vol. 39, JPN6010003141, 13 August 2007 (2007-08-13), pages 123, ISSN: 0001616472 * |
| 化学工学会秋季大会研究発表講演要旨集, vol. 40, JPN6010003138, 24 August 2008 (2008-08-24), pages 171, ISSN: 0001616471 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107326052A (en) * | 2017-06-28 | 2017-11-07 | 岭南师范学院 | A kind of method that glutamate decarboxylase activity is improved with D101 macroporous absorbent resins |
| CN107326052B (en) * | 2017-06-28 | 2020-12-22 | 岭南师范学院 | Method for improving glutamate decarboxylase activity by using D101 macroporous adsorption resin |
| CN115477592A (en) * | 2022-09-30 | 2022-12-16 | 西安萃源生物科技有限公司 | Crystallization method of gamma-aminobutyric acid |
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