JPWO2009044852A1 - Method for producing reduced coenzyme Q10 - Google Patents

Method for producing reduced coenzyme Q10 Download PDF

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JPWO2009044852A1
JPWO2009044852A1 JP2009536099A JP2009536099A JPWO2009044852A1 JP WO2009044852 A1 JPWO2009044852 A1 JP WO2009044852A1 JP 2009536099 A JP2009536099 A JP 2009536099A JP 2009536099 A JP2009536099 A JP 2009536099A JP WO2009044852 A1 JPWO2009044852 A1 JP WO2009044852A1
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博司 久保
博司 久保
義之 品川
義之 品川
朱華 松本
朱華 松本
尚宏 植田
尚宏 植田
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Abstract

従来、還元型補酵素Q10の製造で必要とされてきた製造設備や製造工程をことさらに必要とすることなく、簡便、安価かつ安全な、還元型補酵素Qの製造方法、及び還元型補酵素Q10を、容易に且つ効率良く補給することができる還元型補酵素Q10含有食品を提供すること。酸化型補酵素Q10を、肉類、魚介類及び/又は野菜類などの食材の共存下に加熱処理する還元型補酵素Q10の製造方法。および、該製造方法によって得られる、還元型補酵素Q10含有食品。A method for producing reduced coenzyme Q, and reduced coenzyme, which is simple, inexpensive and safe, without the need for production equipment and production steps that have been conventionally required for producing reduced coenzyme Q10. To provide a food containing reduced coenzyme Q10 that can easily and efficiently replenish Q10. A method for producing reduced coenzyme Q10, in which oxidized coenzyme Q10 is heat-treated in the presence of foods such as meat, seafood and / or vegetables. And a reduced coenzyme Q10-containing food obtained by the production method.

Description

本発明は、還元型補酵素Q10の製造方法に関する。   The present invention relates to a method for producing reduced coenzyme Q10.

広く生物界に分布することが知られているベンゾキノン誘導体である酸化型補酵素Q10は、そのビタミン様の機能からビタミンQとも呼ばれており、弱った細胞活性を健康な状態に戻す栄養源として身体を若返らせる成分である。一方、還元型補酵素Q10は、酸化型補酵素Q10の2電子還元体であり、酸化型補酵素Q10が橙色結晶であるのに対し、還元型補酵素Q10は白色結晶である。還元型補酵素Q10及び酸化型補酵素Q10は、ミトコンドリア、リソゾーム、ゴルジ体、ミクロソーム、ペルオキシソーム、或いは細胞膜などに局在し、電子伝達系の構成成分としてATP産生賦活、生体内での抗酸化作用、膜安定化に関与している生体の機能維持に必要不可欠な物質として知られている。   Oxidized coenzyme Q10, a benzoquinone derivative that is widely known in the living world, is also called vitamin Q because of its vitamin-like function, and is a nutrient source that restores weak cellular activity to a healthy state. An ingredient that rejuvenates the body. On the other hand, reduced coenzyme Q10 is a two-electron reduced form of oxidized coenzyme Q10, and oxidized coenzyme Q10 is an orange crystal, whereas reduced coenzyme Q10 is a white crystal. Reduced coenzyme Q10 and oxidized coenzyme Q10 are localized in mitochondria, lysosomes, Golgi apparatus, microsomes, peroxisomes, cell membranes, etc., ATP production activation as a component of the electron transport system, antioxidant action in vivo It is known as an indispensable substance for maintaining the functions of living bodies involved in membrane stabilization.

そのような背景のもと、酸化型補酵素Q10は、合成、発酵、天然物からの抽出等の従来公知の方法により生産され、医薬品や健康食品として使用されてきた。一方、還元型補酵素Q10も同じく、合成、発酵、天然物からの抽出等の従来公知の方法により補酵素Q10を得た後、クロマトグラフィーにより流出液中の還元型補酵素Q10区分を濃縮する方法等により得られることが知られている(特許文献1)。しかしながら、このようにして得られる還元型補酵素Q10は、必ずしも純度が高い状態では取得できず、例えば、酸化型補酵素Q10をはじめとする不純物を含有する低純度結晶や油状物、半固体状として得られやすいという問題があった。さらに、還元型補酵素Q10は酸素存在下で不安定であり、製造後の還元型補酵素Q10や還元型補酵素Q10を含む商品は、取り扱いや、保存に特段の配慮を行う必要があるという問題があった。   Under such circumstances, oxidized coenzyme Q10 has been produced by conventionally known methods such as synthesis, fermentation and extraction from natural products, and has been used as a pharmaceutical or health food. On the other hand, reduced coenzyme Q10 is similarly obtained by obtaining coenzyme Q10 by a conventionally known method such as synthesis, fermentation, extraction from natural products, etc., and then concentrates reduced coenzyme Q10 in the effluent by chromatography. It is known that it can be obtained by a method or the like (Patent Document 1). However, the reduced coenzyme Q10 obtained in this way cannot always be obtained in a high purity state. For example, low-purity crystals, oils, semisolids containing impurities such as oxidized coenzyme Q10 are not available. There was a problem that it was easy to obtain as. Furthermore, reduced coenzyme Q10 is unstable in the presence of oxygen, and products containing reduced coenzyme Q10 and reduced coenzyme Q10 after production need to be specially handled and stored. There was a problem.

本発明者らは、これらの問題を解決すべく検討した結果、高品質の還元型補酵素Q10を得るための製法及び還元型補酵素Q10を安定に保存する方法を確立し、特許出願を行っている(例えば特許文献2〜5)。これら出願に記載された製造方法は、工業的規模での製造に適した不純物の少ない高品質および/または効率的に精製された還元型補酵素Q10の製造を主な目的とした方法である。   As a result of studying to solve these problems, the present inventors established a production method for obtaining high-quality reduced coenzyme Q10 and a method for stably storing reduced coenzyme Q10, and filed a patent application. (For example, Patent Documents 2 to 5). The production methods described in these applications are methods mainly aimed at producing high-quality and / or efficiently purified reduced coenzyme Q10 with few impurities suitable for production on an industrial scale.

一方、生体に必要であるにも関わらず、減少・不足しがちな還元型補酵素Q10を好適に供給することを目的として、還元型補酵素Q10を含有する油脂組成物を食品に添加して得られる、還元型補酵素Q10富化食品に関する特許出願を行っている(特許文献6)。
特開平10−109933号公報 WO03/006408 WO03/006409 WO03/032967 WO03/062182 WO03/061395
On the other hand, an oil composition containing reduced coenzyme Q10 is added to food for the purpose of suitably supplying reduced coenzyme Q10 that tends to be decreased or deficient even though it is necessary for the living body. A patent application regarding the resulting reduced coenzyme Q10-enriched food has been filed (Patent Document 6).
JP-A-10-109933 WO03 / 006408 WO03 / 006409 WO03 / 032967 WO03 / 061822 WO03 / 061395

上記特許文献2〜5に記載の製造方法は、高品質および/または効率的に精製された還元型補酵素Q10を得ることを目的としており、特に工業的規模での製造に際しては、通常、製造設備の設計、製造工程の検討を詳細に行い、最適化する必要があるため、製造設備を新たに設立する必要があるなど、その工業化には手間と多額の費用がかかり、得られる還元型補酵素Q10は高価なものとなってしまうという課題があった。   The production methods described in Patent Documents 2 to 5 are aimed at obtaining a high-quality and / or efficiently purified reduced coenzyme Q10, and are usually produced particularly on an industrial scale. Since it is necessary to design and optimize the equipment design and manufacturing process in detail and optimize it, it is necessary to establish a new manufacturing equipment. Enzyme Q10 has a problem of becoming expensive.

上記特許文献6に記載の還元型補酵素Q10富化食品は、還元型補酵素Q10を食品に添加して得られるものであり、上述したようにわざわざ還元型補酵素Q10を別途製造するか、高価な還元型補酵素Q10を入手して利用する必要があり、手間やコストがかかるという問題がある。さらに、食品中の富化された還元型補酵素Q10はそのままでは酸化されやすく、その保存には別途何らかの工夫が必要な場合も多いという問題もあった。   The reduced coenzyme Q10-enriched food described in Patent Document 6 above is obtained by adding reduced coenzyme Q10 to food, either as described above, or separately producing reduced coenzyme Q10 separately, There is a problem that it is necessary to obtain and use an expensive reduced coenzyme Q10, which takes time and cost. Furthermore, the enriched reduced coenzyme Q10 in food is easily oxidized as it is, and there is a problem that some kind of contrivance is often required for its preservation.

一方、還元型補酵素Q10を含有する食品を購入する消費者の立場から考えた場合、摂取する還元型補酵素Q10が医薬品で要求されるような純度の高い、あるいは還元型の比率の高い、還元型補酵素Q10である必要は必ずしもなく、還元型補酵素Q10を含有する食品が安全で、かつ更に安価であり、日常的に無理なくかつ経済的に摂取できる食品であることが望まれている。しかし、現在、これらの消費者の要望に十分答えることは出来ていない。   On the other hand, when considering from the standpoint of consumers who purchase foods containing reduced coenzyme Q10, the reduced coenzyme Q10 to be ingested has a high purity as required by pharmaceuticals or a high ratio of reduced form, It is not necessarily required to be reduced coenzyme Q10, and food containing reduced coenzyme Q10 is desired to be safe and inexpensive, and can be consumed daily and economically. Yes. However, at present, these consumer demands cannot be fully answered.

即ち、これらの課題を総合的に解決し得る簡便、安価、安全な還元型補酵素Q10、及び還元型補酵素Q10を高含有する食品の製造方法は知られていなかった。   That is, a simple, inexpensive and safe reduced coenzyme Q10 that can comprehensively solve these problems and a method for producing a food containing a high content of reduced coenzyme Q10 have not been known.

本発明者らは上記課題を解決すべく研究した結果、酸化型補酵素Q10を、肉類、魚介類や野菜類などの食材の共存下に加熱処理することで、簡便に、還元型補酵素Q10が得られることを見出して本発明を完成させた。   As a result of studies conducted by the present inventors to solve the above-mentioned problems, reduced coenzyme Q10 can be simply and easily treated by heat-treating oxidized coenzyme Q10 in the presence of foods such as meat, seafood, and vegetables. And the present invention was completed.

即ち、本発明は以下の通りである。   That is, the present invention is as follows.

[1] 酸化型補酵素Q10(下記式1)を肉類、魚介類及び/又は野菜類共存下に加熱処理する、還元型補酵素Q10(下記式2)の製造方法

Figure 2009044852
Figure 2009044852
[1] A method for producing reduced coenzyme Q10 (following formula 2), in which oxidized coenzyme Q10 (following formula 1) is heat-treated in the presence of meat, seafood and / or vegetables.
Figure 2009044852
Figure 2009044852

[2] 酸化型補酵素Q10が外部添加されたものである[1]に記載の製造方法
[3] 加熱処理の温度条件が、100℃以上である[1]又は[2]に記載の製造方法
[4] 加熱処理の時間が、5分以上である[1]〜[3]いずれかに記載の製造方法
[5] 酸素遮断下及び/又は密閉下に加熱処理する、[1]〜[4]いずれかに記載の製造方法
[6] [1]〜[5]いずれかに記載の製造方法によって得られる、還元型補酵素Q10含有食品
[7] 食品中の補酵素Q10総量に対する還元型補酵素Q10の割合が60重量%以上である[6]に記載の食品
[2] Production method according to [1], wherein oxidized coenzyme Q10 is externally added [3] Production according to [1] or [2], wherein the temperature condition of the heat treatment is 100 ° C. or higher Method [4] The heat treatment time is 5 minutes or longer. [1] to [3] The production method [5] according to any one of [1] to [1] to [1] to [3] 4] Production method [6] according to any one of [1] to [5], wherein the reduced coenzyme Q10-containing food obtained by the production method according to any one [7] Reduced form relative to the total amount of coenzyme Q10 in the food The food according to [6], wherein the ratio of coenzyme Q10 is 60% by weight or more.

本発明によれば、従来、還元型補酵素Q10の製造で必要とされてきた製造設備や製造工程をことさらに必要とすることなく、酸化型補酵素Q10を、肉類、魚介類や野菜類などの食材の共存下で加熱処理を行うだけで、簡便、安価、安全、迅速に還元型補酵素Q10を製造できる。   According to the present invention, the oxidized coenzyme Q10 can be used for meat, seafood, vegetables, etc. without the need for production equipment and production steps that have been conventionally required for the production of reduced coenzyme Q10. The reduced coenzyme Q10 can be produced simply, inexpensively, safely and quickly simply by performing the heat treatment in the presence of the above ingredients.

さらに、本発明においては、製造された還元型補酵素Q10は、精製などの操作を行う必要もなくそのまま、製造時に共存させた肉類、魚介類や野菜類などの食材と共に、還元型補酵素Q10含有食品として摂取することが可能であり、生体に必要不可欠であるにも関わらず、減少・不足しがちな還元型補酵素Q10を、容易に且つ効率良く補給することができる還元型補酵素Q10含有食品も提供できる。   Furthermore, in the present invention, the produced reduced coenzyme Q10 is not necessary to be subjected to purification or the like, and is used as it is together with foods such as meat, seafood, vegetables and the like which are coexisted during production. Reduced coenzyme Q10 which can be ingested as a contained food and can be easily and efficiently replenished with reduced coenzyme Q10 which is indispensable to the living body and tends to decrease or lack Containing foods can also be provided.

また、本発明によれば、従来、還元型補酵素Q10の安定化や保存に際して必要とされてきた複数の成分をことさらに添加することなく、安定性および保存性に優れた還元型補酵素Q10含有食品を提供することができる。   Moreover, according to the present invention, reduced coenzyme Q10 having excellent stability and storage stability without further adding a plurality of components conventionally required for stabilizing and storing reduced coenzyme Q10. Containing foods can be provided.

以下、本発明を詳細に説明する。なお、本明細書において、単に補酵素Q10とのみ記載した場合は、酸化型、還元型を問わず、両者が混在する場合には混合物全体を表すものである。   Hereinafter, the present invention will be described in detail. In the present specification, when only coenzyme Q10 is described, it represents the entire mixture when both are present, regardless of whether they are oxidized or reduced.

本発明の製造方法は、酸化型補酵素Q10を肉類、魚介類や野菜類などの食材の共存下に加熱処理する還元型補酵素Q10の製造方法である。   The production method of the present invention is a production method of reduced coenzyme Q10 in which oxidized coenzyme Q10 is heat-treated in the presence of food such as meat, seafood, and vegetables.

本発明の製造方法において原料として使用される酸化型補酵素Q10は、肉類、魚介類や野菜類などの食材由来のものであっても良いが、外部添加されたものであるのが好ましい。酸化型補酵素Q10が外部添加されたものである場合、その由来や製造法は特に限定されないが、生体に対する安全性の観点から、天然に存在し、一般食品などに含まれるものと同じ(all-E)−異性体であるのが好ましく、酸化型補酵素Q10の製造法が発酵法に由来するものが好ましい。ここで、「発酵法に由来する」とは、好ましい上記立体異性体が発酵法に基づき得られることを意味している。本発明の製造方法においては、例えば、発酵法により得られた(all-E)−異性体の酸化型補酵素Q10を、その立体構造を保持したまま、還元型補酵素Q10を製造することができる。尚、立体異性体は常法によりHPLCにて分析される。   The oxidized coenzyme Q10 used as a raw material in the production method of the present invention may be derived from foods such as meat, seafood and vegetables, but is preferably added externally. When the oxidized coenzyme Q10 is externally added, its origin and production method are not particularly limited, but from the viewpoint of safety to the living body, it is naturally present and is the same as that contained in general foods (all -E) -isomer is preferred, and the production method of oxidized coenzyme Q10 is preferably derived from a fermentation method. Here, “derived from the fermentation method” means that the preferred stereoisomer is obtained based on the fermentation method. In the production method of the present invention, for example, the reduced coenzyme Q10 can be produced while retaining the three-dimensional structure of the (all-E) -isomer oxidized coenzyme Q10 obtained by fermentation. it can. Stereoisomers are analyzed by HPLC by a conventional method.

本発明の製造方法において、原料として使用される酸化型補酵素Q10は、酸化型補酵素Q10単独でも良く、又、還元型補酵素Q10との混合物である補酵素Q10を使用しても良い。上記酸化型補酵素Q10と還元型補酵素Q10の混合物である補酵素Q10を使用する場合、補酵素Q10の総量(すなわち、酸化型補酵素Q10及び還元型補酵素Q10の合計量)に占める酸化型補酵素Q10の割合は、添加量、形態、添加時期等、製造条件や製造方法等により異なり、一概に設定することはできないが、入手しやすく安価な酸化型補酵素Q10を利用して還元型補酵素Q10を製造するという観点からは、原料となる補酵素Q10中の酸化型補酵素Q10の割合が高いほど好ましく、例えば20重量%以上、普通40重量%以上、好ましくは60重量%以上、より好ましくは80重量%以上、とりわけ90重量%以上、なかんずく96重量%以上である。上限は100重量%であり、特に限定されないが、普通99.9重量%以下である。一方、最終的に還元型補酵素Q10比率の高い補酵素Q10、または、還元型補酵素Q10高含有食品を得るという観点では、原料となる酸化型補酵素Q10として、還元型補酵素Q10がある程度以上含まれる補酵素Q10を利用するのが好ましく、その場合の補酵素Q10の総量に占める還元型補酵素Q10の割合は、例えば20重量%以上、普通40重量%以上、好ましくは60重量%以上、より好ましくは80重量%以上、とりわけ90重量%以上、なかんずく96重量%以上である。上限は通常99.9重量%以下である。   In the production method of the present invention, the oxidized coenzyme Q10 used as a raw material may be oxidized coenzyme Q10 alone or coenzyme Q10 which is a mixture with reduced coenzyme Q10. When coenzyme Q10, which is a mixture of oxidized coenzyme Q10 and reduced coenzyme Q10, is used, oxidation accounts for the total amount of coenzyme Q10 (that is, the total amount of oxidized coenzyme Q10 and reduced coenzyme Q10). The ratio of the type coenzyme Q10 varies depending on the addition amount, form, addition timing, etc., production conditions, production method, etc., and cannot be set unconditionally, but is reduced using the easily available and inexpensive oxidized coenzyme Q10. From the viewpoint of producing type coenzyme Q10, it is preferable that the ratio of oxidized coenzyme Q10 in coenzyme Q10 as a raw material is higher, for example, 20% by weight or more, usually 40% by weight or more, preferably 60% by weight or more. More preferably, it is 80% by weight or more, especially 90% by weight or more, especially 96% by weight or more. Although an upper limit is 100 weight% and is not specifically limited, Usually, it is 99.9 weight% or less. On the other hand, from the viewpoint of finally obtaining a coenzyme Q10 having a high ratio of reduced coenzyme Q10 or a food containing a high content of reduced coenzyme Q10, reduced coenzyme Q10 is used as a raw material oxidized coenzyme Q10 to some extent. The coenzyme Q10 contained above is preferably used, and the ratio of the reduced coenzyme Q10 to the total amount of coenzyme Q10 in that case is, for example, 20% by weight or more, usually 40% by weight or more, preferably 60% by weight or more. More preferably, it is 80% by weight or more, especially 90% by weight or more, especially 96% by weight or more. The upper limit is usually 99.9% by weight or less.

本発明に記載の酸化型補酵素Q10を外部添加する際の酸化型補酵素Q10の形態については、特に限定されず、酸化型補酵素Q10原末(粉末)の他、既知の技術を利用した加工品、例えば、エマルジョンやリポソームやシクロデキストリン包摂などの水溶液、顆粒製剤粉末、油などに溶解又は分散させたものが挙げられる。また、添加する酸化型補酵素Q10として、酸化型補酵素Q10を高含有する天然品や加工品を利用することもでき、例えば、酸化型補酵素Q10含有酵母などの酸化型補酵素Q10含有菌体やその加工物も利用できる。   The form of oxidized coenzyme Q10 when the oxidized coenzyme Q10 described in the present invention is externally added is not particularly limited, and known techniques are used in addition to oxidized coenzyme Q10 bulk powder (powder). Processed products, for example, emulsions, liposomes, aqueous solutions such as cyclodextrin inclusions, granular preparation powders, oils and the like dissolved or dispersed. Further, as the oxidized coenzyme Q10 to be added, a natural product or a processed product containing a high amount of oxidized coenzyme Q10 can be used. For example, a bacterium containing oxidized coenzyme Q10 such as yeast containing oxidized coenzyme Q10. The body and its work can also be used.

本発明の製造方法において使用される肉類としては、食用可能な肉類であれば特に限定されず、具体的には、牛肉、豚肉、鶏肉、イノシシ肉、馬肉、羊肉、ヤギ肉、ウサギ肉、鯨肉などが挙げられ、さらに、それぞれの部位別にモモ、肩、ムネ、ハラミ、肝臓、心臓などが挙げられる。本発明における肉類としては、肉類由来の動物性タンパク質も含む。本発明の製造方法において使用される魚介類としては、食用可能な魚介類であれば特に限定されず、具体的には、さば、いわし、アジ、サケ、タラ、カレイ、マグロ、ブリ、ハマチ、タイ、サンマ、ホタテ、カキ、イカ、タコ、エビ、シジミ、タニシ類、ハマグリ・アサリ類、アワビ類、サザエ類、カニ、ウニ、ナマコなどが挙げられ、さらには、スケトウダラ、シシャモの卵巣及び卵、キャビア、イクラなどの魚卵類も含まれる。また、本発明における魚介類には、魚肉を始めとした動物性タンパク質も含まれる。本発明の製造において使用される野菜類としては、食用可能な野菜類であれば特に限定されないが、例えば、茎菜類(具体的には、アスパラガス、タケノコ、ジャガイモ、サトイモなど)、果菜類(具体的には、コーン、豆類(例えば、グリンピース、大豆、小豆)、カボチャ、トマトなど)、根菜類(具体的には、人参、ゴボウ、サツマイモなど)、葉菜類(具体的には、タマネギ、キャベツ、ホウレンソウ、パセリなど)、及びキノコ類(具体的には、マッシュルーム、エリンギ、ブナシメジ、シイタケ、キクラゲ、ナメコなど)が挙げられる。また、本発明においては、上記肉類、魚介類及び/又は野菜類を適宜組み合わせて使用することもでき、また、これら食材を複数用いたシチュー、カレー等の加工食品の形態も本発明の肉類、魚介類及び/又は野菜類の食材に含まれる。   The meat used in the production method of the present invention is not particularly limited as long as it is edible meat, and specifically, beef, pork, chicken, boar meat, horse meat, mutton, goat meat, rabbit meat, whale. Meat, etc., and peaches, shoulders, mune, harami, liver, heart, etc. are listed for each part. The meat in the present invention includes animal protein derived from meat. The seafood used in the production method of the present invention is not particularly limited as long as it is an edible seafood. Specifically, mackerel, sardine, horse mackerel, salmon, cod, flounder, tuna, yellowtail, hamachi, Thailand, saury, scallops, oysters, squid, octopus, shrimp, swordfish, snails, clams and clams, abalone, turban shells, crabs, sea urchins, sea cucumbers, etc. Fish eggs such as caviar and salmon roe are also included. In addition, the seafood in the present invention includes animal proteins including fish meat. The vegetables used in the production of the present invention are not particularly limited as long as they are edible vegetables. For example, stem vegetables (specifically, asparagus, bamboo shoots, potatoes, taros, etc.), fruit vegetables (Specifically, corn, beans (eg, green peas, soybeans, red beans), pumpkins, tomatoes, etc.), root vegetables (specifically, carrots, burdock, sweet potatoes, etc.), leaf vegetables (specifically, onions, And cabbage, spinach, parsley, etc.) and mushrooms (specifically, mushrooms, eringi, beech shimeji mushroom, shiitake mushroom, jellyfish, nameko, etc.). Further, in the present invention, the meat, seafood and / or vegetables can be used in appropriate combination, and the form of processed food such as stew and curry using a plurality of these ingredients is also the meat of the present invention. Included in seafood and / or vegetable ingredients.

本発明での製造方法において使用される上記肉類、魚介類及び野菜類は、熱加工等を行っていない生鮮食材の状態で使用するのが好ましいが、その食品的性格を著しく変更させることなく物理的、あるいは微生物学的な処理を行った一次加工品であっても構わない。   The meat, seafood and vegetables used in the production method of the present invention are preferably used in the state of fresh food that has not been subjected to heat processing or the like. It may be a primary processed product that has been subjected to target or microbiological treatment.

本発明の製造方法においては、酸化型補酵素Q10を肉類、魚介類及び/又は野菜類と、共存下に加熱処理することによって、還元型補酵素Q10とすることを特徴とする。ここでいう「共存下」とは、加熱処理時、または加熱処理前後において、還元型補酵素Q10を生成し得る範囲で酸化型補酵素Q10と肉類、魚介類及び/又は野菜類が同一空間内に存在する状態を意味する。従って、本発明における共存下とは、酸化型補酵素Q10と肉類、魚介類及び/又は野菜類が必ずしも完全に接触または混合している必要はなく、同一空間内で共有された雰囲気を介して還元型補酵素Q10が生成可能な範囲に存在した状態をも含むものである。即ち、例えば加熱処理する際に、酸化型補酵素Q10と肉類、魚介類及び/又は野菜類を別の容器に入れた状態のものを同一の空間を共有できるように外側から包装した状態で還元型補酵素Q10を生成し得る場合も共存下であると定義できる。なお、本発明の還元型補酵素Q10の製造に際して、酸化型補酵素Q10と肉類、魚介類及び/又は野菜類の共存下状態の作出と加熱処理の実施の順序は特に限定されない。なお、本発明における、好ましい共存下条件は、加熱処理時に、酸化型補酵素Q10と肉類、魚介類及び/又は野菜類が接触または十分均一に混合している状態である。   The production method of the present invention is characterized in that reduced coenzyme Q10 is obtained by subjecting oxidized coenzyme Q10 to heat treatment in the presence of meat, seafood, and / or vegetables. The term “in the presence of coexistence” as used herein means that oxidized coenzyme Q10 and meat, seafood and / or vegetables are in the same space as long as reduced coenzyme Q10 can be produced during or before heat treatment. Means a state that exists. Therefore, coexistence in the present invention does not necessarily mean that oxidized coenzyme Q10 and meat, fish and shellfish and / or vegetables are in complete contact or mixing, but via an atmosphere shared in the same space. This includes a state in which reduced coenzyme Q10 exists in a range where it can be produced. That is, for example, when heat-treated, the oxidized coenzyme Q10 and meat, seafood and / or vegetables in a separate container are reduced in a state of being packaged from the outside so that the same space can be shared. When the coenzyme Q10 can be produced, it can be defined as coexisting. In the production of reduced coenzyme Q10 of the present invention, the order in which the oxidized coenzyme Q10 and meat, fish and / or vegetables coexist and the heat treatment is performed is not particularly limited. In the present invention, preferable coexistence conditions are conditions in which oxidized coenzyme Q10 and meat, fish and shellfish and / or vegetables are in contact or sufficiently uniformly mixed during the heat treatment.

本発明の製造方法における加熱処理とは、酸化型補酵素Q10と、肉類、魚介類及び/又は野菜類を、共存下に、何らかの手段で加温処理することを意味し、その方法は限定されない。本発明の製造方法における加熱処理には、湿熱処理と乾熱処理の何れを選択することも可能である。加熱処理の具体的な方法としては、例えば、温水、水蒸気、ドライエアー、直火、加熱ロールに酸化型補酵素Q10と、肉類、魚介類及び/又は野菜類を接触させる方法や、マイクロ波加熱処理、通電加熱処理などがある。本発明の加熱処理に際しては、何れの方法を単独、または組み合わせて用いても良い。   The heat treatment in the production method of the present invention means that the oxidized coenzyme Q10 and meat, seafood and / or vegetables are heated by some means in the presence of coexistence, and the method is not limited. . For the heat treatment in the production method of the present invention, either wet heat treatment or dry heat treatment can be selected. Specific methods for the heat treatment include, for example, a method in which oxidized coenzyme Q10 and meat, seafood and / or vegetables are brought into contact with hot water, water vapor, dry air, direct fire, a heating roll, or microwave heating. Treatment, electric heating treatment, and the like. In the heat treatment of the present invention, any method may be used alone or in combination.

なお、加温処理方法として湿熱処理を選択する場合は、熱伝導効率の点から水蒸気による加熱であることが好ましく、熱容量が大きい気流式過熱水蒸気や、さらに低酸素状態となる過熱飽和水蒸気による加温処理方法が好ましい。また、加温処理方法として乾熱処理を選択する場合は、効率よくしかもより均一に処理する事が可能な、回転式あるいは撹拌翼付の加熱装置を用いるのが好ましい。   When wet heat treatment is selected as the heating treatment method, heating with steam is preferable from the viewpoint of heat conduction efficiency, and heating with airflow-type superheated steam having a large heat capacity or superheated saturated steam that becomes a low oxygen state is preferable. A temperature treatment method is preferred. Further, when a dry heat treatment is selected as the heating treatment method, it is preferable to use a heating device with a rotary type or a stirring blade that can be efficiently and more uniformly treated.

本発明の製造方法によって得られた、還元型補酵素Q10を、その製造に使用した肉類、魚介類及び/又は野菜類とともに食品等として摂取する場合は、その製造過程における加熱処理において、食品としての風味だけでなく品質の劣化や物性に与える影響も考慮した加熱処理条件の選択が必要である。また、還元型補酵素Q10の製造のための加熱処理と、食品の製造工程としての殺菌処理をあわせて実施しても良い。この場合、各温度で微生物の死滅する速度と組成物中の成分の分解や劣化等の品質の低下する速度を比較し、温度と処理時間を設定する等の最適化を行っても良い。例えば、湿熱処理の場合、通常、50〜120℃前後で数秒〜数十分での加熱処理で十分な殺菌効果を得ることが出来る。一方、乾熱処理の場合、殺菌処理のためには180℃で数時間の加熱処理が必要な場合もある。   When the reduced coenzyme Q10 obtained by the production method of the present invention is ingested as a food together with meat, seafood and / or vegetables used in the production, in the heat treatment in the production process, as a food It is necessary to select heat treatment conditions that take into account not only the flavor of but also the effects on quality degradation and physical properties. Moreover, you may implement together the heat processing for manufacture of reduced coenzyme Q10, and the sterilization process as a manufacturing process of foodstuffs. In this case, optimization such as setting the temperature and processing time may be performed by comparing the rate at which microorganisms die at each temperature with the rate at which quality decreases such as decomposition or degradation of components in the composition. For example, in the case of wet heat treatment, a sufficient bactericidal effect can be usually obtained by heat treatment at around 50 to 120 ° C. for several seconds to several tens of minutes. On the other hand, in the case of dry heat treatment, heat treatment at 180 ° C. for several hours may be required for sterilization treatment.

本発明の製造方法において、還元型補酵素Q10を高効率に製造するためには、上記加温処理は、酸素遮断雰囲気下または密閉下で実施するのが好ましい。酸素遮断雰囲気は、不活性ガスによる置換、減圧、沸騰やこれらを組み合わせることにより達成でき、上述した過熱飽和水蒸気下での処理によっても達成しうる。少なくとも、不活性ガスによる置換、即ち、不活性ガス雰囲気を用いるのが好適である。上記不活性ガスとしては、例えば、窒素ガス、水蒸気、ヘリウムガス、アルゴンガス、水素ガス、炭酸ガス等を挙げることができ、好ましくは窒素ガス又は水蒸気である。なお、本発明における酸素遮断雰囲気下とは、加熱処理時に厳密に酸素を非存在とする必要はなく、通常の大気条件よりは酸素濃度が低い場合や、加熱処理時に酸化型補酵素Q10や肉類、魚介類及び/又は野菜類に自由に酸素が供給されない状態も含む。そのような観点から、不活性ガスにより置換を行わず、単に密閉条件下で加熱処理を行うのもまた、本発明の製造方法の好ましい態様である。この場合の密閉条件下とは、例えば、酸化型補酵素Q10と肉類、魚介類及び/又は野菜類を、缶や瓶などの密閉容器にいれて封入した瓶詰めや缶詰の状態、レトルトパウチされた状態などが挙げられる。また、酸素遮断雰囲気下、例えば不活性ガスに置換し更に密閉した条件で加熱処理するのもまた、本発明の好ましい態様である。   In the production method of the present invention, in order to produce reduced coenzyme Q10 with high efficiency, the heating treatment is preferably carried out in an oxygen-blocked atmosphere or sealed. The oxygen barrier atmosphere can be achieved by substitution with an inert gas, reduced pressure, boiling, or a combination thereof, and can also be achieved by the above-described treatment under superheated saturated steam. It is preferable to use at least substitution with an inert gas, that is, an inert gas atmosphere. Examples of the inert gas include nitrogen gas, water vapor, helium gas, argon gas, hydrogen gas, carbon dioxide gas, and the like, preferably nitrogen gas or water vapor. Note that the oxygen-blocked atmosphere in the present invention does not require oxygen to be strictly absent during the heat treatment, and when the oxygen concentration is lower than normal atmospheric conditions, or when the oxidized coenzyme Q10 and meat are used during the heat treatment. In addition, a state where oxygen is not freely supplied to seafood and / or vegetables is also included. From such a viewpoint, it is also a preferred embodiment of the production method of the present invention that the heat treatment is simply performed under sealed conditions without replacing with an inert gas. The sealed condition in this case is, for example, a bottled or canned state in which oxidized coenzyme Q10 and meat, seafood and / or vegetables are placed in a sealed container such as a can or a bottle, and a retort pouch is used. The state etc. are mentioned. Moreover, it is also a preferable aspect of the present invention to perform heat treatment under an oxygen-blocking atmosphere, for example, by replacing with an inert gas and further sealing.

本発明の製造方法における加熱処理工程において昇温過程を有する場合、その昇温速度は、特に制限されないが、一般的に、加温処理にかかる時間および経済性も考慮して、少なくとも0.1℃/分以上、普通1℃/分以上、好ましくは3℃/分以上、より好ましくは5℃/分以上、さらに好ましくは10℃/分以上の条件で実施される。昇温速度の上限は、特に制限されないが、普通600℃/分以内である。   In the case where the heating process in the production method of the present invention has a temperature rising process, the temperature rising rate is not particularly limited, but is generally at least 0.1 ° C./in consideration of the time and economy required for the heating process. Min. Or more, usually 1 ° C./min or more, preferably 3 ° C./min or more, more preferably 5 ° C./min or more, and further preferably 10 ° C./min or more. The upper limit of the heating rate is not particularly limited, but is usually within 600 ° C./min.

本発明の製造方法における加熱処理時の温度条件は、加熱処理方法および加熱処理時間等にもよるが、例えば、室温以上〜200℃の範囲内、普通、室温以上〜180℃の範囲内、好ましくは80〜160℃の範囲内である。その中でも、より好ましくは100℃以上、さらには110℃以上、特に120℃以上の条件で加熱処理するのが好ましい。加熱処理時の温度の上限としては150℃以下がより好ましく、さらに130℃以下が好ましい。   The temperature condition during the heat treatment in the production method of the present invention depends on the heat treatment method and the heat treatment time, but is, for example, in the range of room temperature to 200 ° C, usually in the range of room temperature to 180 ° C, preferably Is in the range of 80-160 ° C. Among them, the heat treatment is more preferably performed at 100 ° C. or higher, more preferably 110 ° C. or higher, and particularly preferably 120 ° C. or higher. The upper limit of the temperature during the heat treatment is more preferably 150 ° C. or less, and further preferably 130 ° C. or less.

本発明の加温処理時の圧力としては、加温処理条件、工程、方法により大きく異なるが、例えば、0〜20Mpaの範囲内、普通、100hpa〜10Mpaの範囲内で実施できる。本発明においては、加圧条件下で加熱処理するのが好ましく、その場合、好ましい圧力条件は1015hpa以上、更に好ましくは1800hpa以上である。加圧方法としては特に限定されないが、例えば、高圧蒸気滅菌装置や圧力釜などが使用できる。なかでも高圧蒸気滅菌装置を使用した場合、上述したように過熱飽和水蒸気雰囲気で加熱処理が行えるという点で特に好ましい。   The pressure during the heat treatment of the present invention varies greatly depending on the heat treatment conditions, steps, and methods, but can be, for example, in the range of 0 to 20 MPa, usually in the range of 100 hpa to 10 MPa. In the present invention, the heat treatment is preferably performed under a pressurized condition. In that case, the preferred pressure condition is 1015 hpa or more, more preferably 1800 hpa or more. Although it does not specifically limit as a pressurization method, For example, a high pressure steam sterilizer, a pressure cooker, etc. can be used. In particular, when a high-pressure steam sterilizer is used, it is particularly preferable in that heat treatment can be performed in an overheated saturated steam atmosphere as described above.

本発明の加温処理時の酸化型補酵素Q10と肉類、魚介類及び/又は野菜類およびその周辺の雰囲気下のpHは、使用する食材の種類、加温処理条件、工程、方法により大きく異なり限定されないが、例えば、1〜13の範囲内、普通、2〜12の範囲内、好ましくは3〜11、より好ましくは4〜10の範囲内、さらに好ましくは5〜9の範囲内であることが望ましい。   The oxidized coenzyme Q10 and the pH of the meat, seafood and / or vegetables and the surrounding atmosphere during the heat treatment of the present invention vary greatly depending on the type of food used, the heat treatment conditions, the process and the method. Although it is not limited, for example, it is within the range of 1 to 13, usually within the range of 2 to 12, preferably within the range of 3 to 11, more preferably within the range of 4 to 10, and further preferably within the range of 5 to 9. Is desirable.

本発明の製造方法における加熱処理時間としては、加熱処理温度、加熱処理方法等にもよるが、例えば、1秒〜24時間の範囲内、普通、20秒〜12時間の範囲内、好ましくは30秒〜5時間の範囲内、より好ましくは1分〜3時間の範囲内、さらに好ましくは5分〜2時間の範囲内であることが望ましい。すなわち、加熱処理時間としては、例えば1秒以上、普通20秒以上、好ましくは30秒以上、より好ましくは1分以上、さらに好ましくは5分以上であり、その上限としては、例えば24時間以内、普通12時間以内、好ましくは5時間以内、より好ましくは3時間以内、さらに好ましくは2時間以内である。その中でも、過熱飽和水蒸気下での加熱処理を行った場合、30分以上の加熱処理を行うのが最も好ましい。   The heat treatment time in the production method of the present invention depends on the heat treatment temperature, the heat treatment method, etc., but is, for example, in the range of 1 second to 24 hours, usually in the range of 20 seconds to 12 hours, preferably 30. It is desirable to be within the range of seconds to 5 hours, more preferably within the range of 1 minute to 3 hours, and even more preferably within the range of 5 minutes to 2 hours. That is, the heat treatment time is, for example, 1 second or more, usually 20 seconds or more, preferably 30 seconds or more, more preferably 1 minute or more, further preferably 5 minutes or more, and the upper limit thereof is, for example, within 24 hours, Usually, it is within 12 hours, preferably within 5 hours, more preferably within 3 hours, and even more preferably within 2 hours. Among these, when heat treatment is performed under superheated saturated steam, it is most preferable to perform heat treatment for 30 minutes or more.

なお、上記の種々の加熱処理条件は、本発明の効果を損なわない範囲で、多段階加熱法など加熱処理工程や加熱方法など適宜最適な条件を選択しても良い。また、必要であれば、冷却処理を加熱処理の前後に実施しても良い。   Note that the various heat treatment conditions described above may be appropriately selected as appropriate such as a heat treatment step such as a multistage heating method or a heating method within a range not impairing the effects of the present invention. If necessary, the cooling process may be performed before and after the heat treatment.

本発明の製造方法における、還元型補酵素Q10の収率は特に限定されず、原料として使用した酸化型補酵素Q10の全量ではなくその一部が還元型補酵素Q10への変換された態様も、本発明の製造方法の範囲内である。すなわち、本発明の製造方法は、酸化型補酵素Q10を含有する補酵素Q10を、肉類、魚介類及び/又は野菜類共存下に加熱処理することを特徴とする、還元型補酵素Q10の比率を高める方法でもある。その場合の、補酵素Q10の総量に占める還元型補酵素Q10の割合は高いほど好ましく、例えば20重量%以上、普通40重量%以上、好ましくは60重量%以上、さらに好ましくは70重量%以上、より好ましくは80重量%以上、とりわけ90重量%以上、なかんずく96重量%以上である。上限はいうまでもなく100重量%であるが、99.9重量%程度でも差し支えない。   In the production method of the present invention, the yield of reduced coenzyme Q10 is not particularly limited, and there is also an embodiment in which a part of the oxidized coenzyme Q10 used as a raw material is converted into reduced coenzyme Q10 instead of the total amount. Within the scope of the production method of the present invention. That is, in the production method of the present invention, the ratio of reduced coenzyme Q10 is characterized in that coenzyme Q10 containing oxidized coenzyme Q10 is heat-treated in the presence of meat, seafood and / or vegetables. It is also a way to increase In this case, the ratio of reduced coenzyme Q10 to the total amount of coenzyme Q10 is preferably as high as possible, for example, 20% by weight or more, usually 40% by weight or more, preferably 60% by weight or more, more preferably 70% by weight or more, More preferably, it is 80% by weight or more, especially 90% by weight or more, especially 96% by weight or more. Needless to say, the upper limit is 100% by weight, but it may be about 99.9% by weight.

上述したように、本発明の製造方法によって得られる、還元型補酵素Q10と、その製造に利用した肉類、魚介類及び/又は野菜類は、そのまま、還元型補酵素Q10含有食品、好ましくは還元型補酵素Q10含有加工食品として利用できる。   As described above, the reduced coenzyme Q10 obtained by the production method of the present invention and the meat, seafood and / or vegetables used for the production are directly used as the reduced coenzyme Q10-containing food, preferably reduced. It can be used as a processed food containing type coenzyme Q10.

このようにして得られる還元型補酵素Q10含有食品中の還元型補酵素Q10の含有濃度は、製造時に使用した酸化型補酵素Q10の量にもよるが還元型補酵素Q10の含有量がある程度高いほど好ましく、例えば20μg/g以上、普通30μg/g以上、好ましくは50μg/g以上、さらに好ましくは100μg/g以上、より好ましくは500μg/g以上、とりわけ1mg/g以上、なかんずく3mg/g以上である。上限は特に限定されないが、コスト等の点から例えば500mg/gであり、好ましくは300mg/gである。また、還元型補酵素Q10含有食品中の補酵素Q10の総量に占める還元型補酵素Q10の割合も高いほど好ましく、例えば20重量%以上、普通40重量%以上、好ましくは60重量%以上、より好ましくは80重量%以上、とりわけ90重量%以上、なかんずく96重量%以上である。上限はいうまでもなく100重量%であるが、99.9重量%程度でも差し支えない。   The content of reduced coenzyme Q10 in the reduced coenzyme Q10-containing food obtained in this way depends on the amount of oxidized coenzyme Q10 used during production, but the content of reduced coenzyme Q10 is somewhat. Higher is preferable, for example, 20 μg / g or more, usually 30 μg / g or more, preferably 50 μg / g or more, more preferably 100 μg / g or more, more preferably 500 μg / g or more, especially 1 mg / g or more, especially 3 mg / g or more. It is. The upper limit is not particularly limited, but is, for example, 500 mg / g, preferably 300 mg / g from the viewpoint of cost. Further, the ratio of reduced coenzyme Q10 to the total amount of coenzyme Q10 in the reduced coenzyme Q10-containing food is preferably higher, for example, 20% by weight or more, usually 40% by weight or more, preferably 60% by weight or more. Preferably it is 80% by weight or more, especially 90% by weight or more, especially 96% by weight or more. Needless to say, the upper limit is 100% by weight, but it may be about 99.9% by weight.

上記還元型補酵素Q10含有加工食品の好ましい形態として、耐熱性、耐衝撃性、および既存の製造設備の使用および汎用性、流通性、コストの観点から、缶詰、瓶詰め、およびレトルトパック等が挙げられる。また、この際の還元型補酵素Q10含有食品は脱酸素雰囲気下条件となる加工によって得られるのが品質保持の観点から好ましい。さらに好ましくは、上記製造方法において、例えば、酸化型補酵素Q10と肉類、魚介類及び/又は野菜類を、酸素遮断雰囲気下、瓶詰めや缶詰、またはレトルトパウチされた状態で、密閉し、加熱処理して得られたものをそのまま、上記還元型補酵素Q10含有加工食品として利用したものである。   Preferred forms of the reduced coenzyme Q10-containing processed food include canned food, bottling, retort pack, and the like from the viewpoints of heat resistance, impact resistance, and use and versatility of existing manufacturing equipment, distribution, and cost. It is done. In this case, the reduced coenzyme Q10-containing food is preferably obtained by processing under conditions in a deoxygenated atmosphere from the viewpoint of maintaining quality. More preferably, in the above production method, for example, the oxidized coenzyme Q10 and meat, fish and shellfish and / or vegetables are sealed in a bottled or canned or retorted pouch in an oxygen-blocking atmosphere, and heat-treated. The product obtained as described above is used as it is as a processed food containing the reduced coenzyme Q10.

また、本発明の製造方法または本発明の製造方法により得られる還元型補酵素Q10含有食品中には、薬学的、製剤学的、各国の食品規制に許容される物質を、本発明の効果を損なわない範囲で自由に使用または添加することが出来る。その様な物質としては、ビタミン類、抗酸化剤、微量元素等が挙げられる。   In addition, in the production method of the present invention or the reduced coenzyme Q10-containing food obtained by the production method of the present invention, a substance that is permitted by pharmacological, pharmaceutical, and food regulations in each country can be used for the effect of the present invention. It can be used or added freely as long as it is not impaired. Such substances include vitamins, antioxidants, trace elements and the like.

本発明に記載の製造法により得られる還元型補酵素Q10含有食品は消費者にとって魅力的である。よって、本発明の方法に従い製造される還元型補酵素Q10含有食品の有用性に関して、商品のラベルに文言、還元型補酵素Q10比率、還元型補酵素Q10含量等を記載することは、ビジネス上有益な手段であり、本発明の還元型補酵素Q10含有食品と不可分の同一の属性を有するものである。また、本発明に記載の還元型補酵素Q10含有食品の有用性をパンプレットやインターネットを通じた発信、提供することも同様に本件特許の態様の一つであり、発明の一部である。さらに、医師、薬剤師、および栄養師などの社会的に信用される人物を介した、本発明の方法により製造される還元型補酵素Q10含有食品のあらゆる販売促進、啓蒙活動は、本発明により製造されて初めて成し得る事柄であることから、同様に本発明の製造方法および還元型補酵素Q10含有食品と不可分の同一の属性を有する本発明の一部である。   The reduced coenzyme Q10-containing food obtained by the production method described in the present invention is attractive to consumers. Therefore, regarding the usefulness of the reduced coenzyme Q10-containing food produced according to the method of the present invention, describing the wording, the reduced coenzyme Q10 ratio, the reduced coenzyme Q10 content, etc. It is a useful means and has the same attribute that is inseparable from the reduced coenzyme Q10-containing food of the present invention. In addition, transmission and provision of the usefulness of the reduced coenzyme Q10-containing food described in the present invention via a brochure or the Internet is also one aspect of the present patent and is part of the invention. Furthermore, all sales promotion and enlightenment activities of reduced coenzyme Q10-containing foods produced by the method of the present invention through socially trusted persons such as doctors, pharmacists, and nutritionists are manufactured according to the present invention. Therefore, it is a part of the present invention having the same attributes that are inseparable from the production method of the present invention and the reduced coenzyme Q10-containing food.

以下に製造例、実施例を挙げて本発明をさらに詳しく説明するが、本発明はこれらに限定されるものではない。   Hereinafter, the present invention will be described in more detail with reference to production examples and examples, but the present invention is not limited thereto.

(実施例1)
<実験方法>
ハサミを用いてマグロの切り身を細切した。次に細切したマグロ肉(魚肉)の一部を量り取り、6つのサンプル(試料)に分け、各サンプルの魚肉に酸化型補酵素Q10粉末(株式会社 カネカ製)を50μg/g魚肉となるように添加し、ヘラを用いて酸化型補酵素Q10を魚肉に練りこみミンチ状の魚肉とした。その後、酸化型補酵素Q10を添加した魚肉を下記及び表1に示す条件で処理した。その後、各試料50mg当たり2-プロパノールを1.95mL加え、ポリトロン型ホモジナイザーを用いてサンプルのホモジナイズを行った。その後、ホモジナイズした試料を、日立工機株式会社製 卓上微量高速遠心機himac CT−13Rを用いて16,000×g、4℃の条件で遠心分離処理し、上清中の還元型補酵素Q10量および酸化型補酵素Q10量を、下記条件でHPLC−ECDを用いて分析した。
Example 1
<Experiment method>
The tuna fillet was shredded with scissors. Next, a portion of the minced tuna meat (fish meat) is weighed and divided into 6 samples (samples), and the oxidized coenzyme Q10 powder (manufactured by Kaneka Corporation) is 50 μg / g fish meat in the fish meat of each sample. The oxidized coenzyme Q10 was kneaded into the fish meat using a spatula to obtain a minced fish meat. Then, the fish meat to which oxidized coenzyme Q10 was added was treated under the conditions shown below and in Table 1. Thereafter, 1.95 mL of 2-propanol was added per 50 mg of each sample, and the samples were homogenized using a polytron homogenizer. Thereafter, the homogenized sample was centrifuged at 16,000 × g, 4 ° C. using a tabletop micro high-speed centrifuge himac CT-13R manufactured by Hitachi Koki Co., Ltd., and the amount of reduced coenzyme Q10 in the supernatant and The amount of oxidized coenzyme Q10 was analyzed using HPLC-ECD under the following conditions.

カラム:YMC−PACK ODS−A303(250mm×4.6mm、5-μm particle size)、還元触媒カラムRC-10(株式会社 資生堂製)、カラム温度:40℃、移動相:21.06g NaClO4・H2O in 2640mL CH3OH/360mL Hexane、流速:1mL/分、還元型補酵素Q10の保持時間;17.5分、酸化型補酵素Q10の保持時間;27.5分、電気化学検出器:Nanospace SI-2(株式会社 資生堂製、印加電圧:600mV)。Column: YMC-PACK ODS-A303 (250 mm × 4.6 mm, 5-μm particle size), reduction catalyst column RC-10 (manufactured by Shiseido Co., Ltd.), column temperature: 40 ° C., mobile phase: 21.06 g NaClO 4 · H 2 O in 2640 mL CH 3 OH / 360 mL Hexane, flow rate: 1 mL / min, retention time of reduced coenzyme Q10; 17.5 minutes, retention time of oxidized coenzyme Q10; 27.5 minutes, electrochemical detector: Nanospace SI-2 (manufactured by Shiseido Co., Ltd., applied voltage: 600mV).

また、試料中の還元型補酵素Q10比率(%)は、以下の式より算出した。   Further, the reduced coenzyme Q10 ratio (%) in the sample was calculated from the following equation.

還元型補酵素Q10比率(%)=還元型補酵素Q10量×100/総補酵素Q10量
総補酵素Q10量=還元型補酵素Q10量+酸化型補酵素Q10量
<処理方法>
・試料1:細切したマグロ肉に酸化型補酵素Q10を添加混合したもの(非加熱処理、非保存)
・試料2:酸化型補酵素Q10を添加した魚肉をアルミ製容器に入れ、容器内を窒素ガスにより置換後、密栓した。次に、サクラ精機株式会社製 ネオクレーブ ASV-3022を用いて121℃、30分、1961hpa(2kgf/cm)の条件で加熱処理し、その後、4℃で一晩保存
・試料3:酸化型補酵素Q10を添加した魚肉をアルミ製容器に入れ、容器内はガス置換を行わず、空気で満たした状態で密栓した。次に試料2と同条件で加熱処理をし、その後、4℃で一晩保存
・試料4:酸化型補酵素Q10を添加した魚肉をレトルト用フードパック(品名:R-1420H、明和産商株式会社製)に入れた。魚肉を入れたレトルト用フードパックをシャープ株式会社製 業務用卓上バキュームシーラー SQ-202にセットし脱気した後、ラミネート密栓した。次に試料2と同条件で加熱処理をし、その後、4℃で一晩保存
・試料5:酸化型補酵素Q10を添加した魚肉をアルミ製容器に入れ、容器内を窒素ガスにより置換後、密栓した。その後、加熱処理は行わず、4℃で一晩保存
・試料6:酸化型補酵素Q10を添加した魚肉をレトルト用フードパックに入れ、試料4と同様に、脱気した後、ラミネート密栓した。その後、加熱処理は行わず、4℃で一晩保存
<結果>
上記、試料1〜6の各処理条件および処理後の還元型補酵素Q10比率を表1に示す。

Figure 2009044852
Reduced coenzyme Q10 ratio (%) = reduced coenzyme Q10 amount × 100 / total coenzyme Q10 amount Total coenzyme Q10 amount = reduced coenzyme Q10 amount + oxidized coenzyme Q10 amount <Treatment Method>
Sample 1: A mixture of minced tuna meat added with oxidized coenzyme Q10 (non-heat treated, non-preserved)
Sample 2: Fish meat added with oxidized coenzyme Q10 was placed in an aluminum container, the inside of the container was replaced with nitrogen gas, and the container was sealed. Next, heat treatment was carried out using a Neoclave ASV-3022 made by Sakura Seiki Co., Ltd. under conditions of 121 ° C, 30 minutes, 1961hpa (2kgf / cm 2 ), and then stored overnight at 4 ° C. Sample 3: oxidized type supplement The fish meat to which the enzyme Q10 was added was placed in an aluminum container, and the container was sealed without being replaced with gas and filled with air. Next, heat-treat under the same conditions as Sample 2, and then store overnight at 4 ° C. Sample 4: Fish meat with oxidized coenzyme Q10 added to retort food pack (Product name: R-1420H, Meiwa Sansho Co., Ltd.) (Made by company). A retort food pack containing fish meat was set on a SQ-202 commercial desk top vacuum sealer manufactured by Sharp Corporation, deaerated, and then sealed with a laminate. Next, heat treatment was performed under the same conditions as Sample 2, and then stored overnight at 4 ° C. Sample 5: Fish meat added with oxidized coenzyme Q10 was placed in an aluminum container, and the inside of the container was replaced with nitrogen gas. Sealed. Thereafter, heat treatment was not performed, and the sample was stored overnight at 4 ° C. Sample 6: Fish meat added with oxidized coenzyme Q10 was placed in a retort food pack, degassed in the same manner as Sample 4, and then sealed with a laminate. Then, heat treatment is not performed, and it is stored overnight at 4 ° C. <Result>
Table 1 shows the respective treatment conditions for samples 1 to 6 and the reduced coenzyme Q10 ratio after the treatment.
Figure 2009044852

上記結果より、酸化型補酵素Q10と魚肉を共存下に加熱処理をした試料2〜4の補酵素Q10総量に対する還元型補酵素Q10比率は、いずれも、酸化型補酵素Q10を魚肉に添加混合させただけの試料1や酸化型補酵素Q10を魚肉に添加混合させ加熱せず一晩保存した試料5及び6の還元型補酵素Q10比率と比較して、著しく高いことが示された。すなわち、酸化型補酵素Q10と魚肉を共存下に加熱処理することで、還元型補酵素Q10比率が高くなり、還元型補酵素Q10が富化された魚肉食品を製造できることが確認された。   From the above results, the ratio of reduced coenzyme Q10 to the total amount of coenzyme Q10 in samples 2 to 4 subjected to heat treatment in the presence of oxidized coenzyme Q10 and fish meat was added and mixed with oxidized coenzyme Q10 in fish meat. It was shown that it was significantly higher than the ratio of reduced coenzyme Q10 of samples 5 and 6 in which sample 1 and oxidized coenzyme Q10 were simply added to fish meat and stored overnight without heating. That is, it was confirmed that by performing heat treatment in the presence of oxidized coenzyme Q10 and fish meat, the ratio of reduced coenzyme Q10 is increased, and a fish food product enriched in reduced coenzyme Q10 can be produced.

(実施例2)
<実験方法>
ハサミを用いて豚肉の切り身を細切した後、さらにヘラを用いて豚肉をミンチ状にし、4つのサンプル(試料)にわけた。2mgの酸化型補酵素Q10(株式会社 カネカ製)に200mgの食用油(日清ライトブレンド油、日清オイリオ株式会社製)を添加し、約60℃の加温条件下で酸化型補酵素Q10を溶解、混合した。その後、得られた酸化型補酵素Q10/油溶液に蒸留水を加え、総量10mLとし、約60℃の加温条件下で超音波処理を行い、乳化溶液を調製した。この酸化型補酵素Q10を含む乳化液を、先のミンチ状にした豚肉のサンプルのうち2つのサンプルに加え、酸化型補酵素Q10の添加量が20μg/g豚肉となるようにした。その後、25℃以下の条件で、酸化型補酵素Q10を添加したミンチ状の豚肉を十分に混合し、ペースト状の豚肉試料とした。その後、酸化型補酵素Q10非添加、または添加した試料を下記及び表2に示す条件で処理した。その後、実施例1と同様に、豚肉中の補酵素Q10の抽出と、HPLC−ECD(電気化学検出器)を用いた含量分析を行い、試料中の還元型補酵素Q10比率を算出した。
(Example 2)
<Experiment method>
After cutting the pork fillet with scissors, the pork was minced with a spatula and divided into four samples. 200 mg of edible oil (Nisshin Light Blend Oil, Nisshin Oilio Co., Ltd.) is added to 2 mg of oxidized coenzyme Q10 (manufactured by Kaneka Corporation), and oxidized coenzyme Q10 is heated at about 60 ° C. Was dissolved and mixed. Thereafter, distilled water was added to the obtained oxidized coenzyme Q10 / oil solution to make a total volume of 10 mL, and sonication was performed under a heating condition of about 60 ° C. to prepare an emulsified solution. This emulsion containing oxidized coenzyme Q10 was added to two samples of the minced pork sample so that the added amount of oxidized coenzyme Q10 was 20 μg / g pork. Thereafter, minced pork to which oxidized coenzyme Q10 was added was thoroughly mixed under a condition of 25 ° C. or lower to obtain a pasty pork sample. Thereafter, the oxidized coenzyme Q10 was not added, or the added sample was treated under the conditions shown below and Table 2. Thereafter, extraction of coenzyme Q10 in pork and content analysis using HPLC-ECD (electrochemical detector) were performed in the same manner as in Example 1 to calculate the reduced coenzyme Q10 ratio in the sample.

<処理方法>
・試料7:細切した豚肉そのまま(酸化型補酵素Q10非添加、非加熱処理、非保存)。
<Processing method>
Sample 7: Shredded pork as it is (oxidized coenzyme Q10 not added, non-heat treated, non-preserved).

・試料8:細切した豚肉に酸化型補酵素Q10を添加混合し、ペースト状にしたもの(非加熱処理、非保存)。 Sample 8: Oxidized coenzyme Q10 added to and mixed into minced pork and pasted (non-heated, non-preserved).

・試料9:酸化型補酵素Q10を添加していない豚肉を、レトルト用フードパック(品名:R−1420H、明和産商株式会社製)に入れ、試料4と同様に、脱気した後、ラミネート密栓し、サクラ精機株式会社製 ネオクレーブ ASV−3022を用いて121℃、30分、1961hpa(2kgf/cm)の条件で加熱処理した。その後、4℃で一晩保存(酸化型補酵素Q10非添加)
・試料10:酸化型補酵素Q10を添加した豚肉をレトルト用フードパックに入れ、試料9と同様に、脱気した後、ラミネート密栓した。次に試料9と同条件で加熱処理を行い、その後、4℃で一晩保存
<結果>
上記、試料7〜10の各処理条件および処理後の試料の還元型補酵素Q10比率を表2に示す。
Sample 9: Put pork not added with oxidized coenzyme Q10 into a retort food pack (product name: R-1420H, manufactured by Meiwa Sansho Co., Ltd.), degassed in the same manner as sample 4, and then laminate Sealed and heat-treated using a Neoclave ASV-3022 manufactured by Sakura Seiki Co., Ltd. under the conditions of 121 ° C., 30 minutes, 1961 hpa (2 kgf / cm 2 ). Then store overnight at 4 ° C (without oxidized coenzyme Q10)
Sample 10: Pork to which oxidized coenzyme Q10 was added was placed in a retort food pack, degassed in the same manner as sample 9, and then sealed with a laminate. Next, heat treatment is performed under the same conditions as Sample 9, and then stored overnight at 4 ° C. <Results>
Table 2 shows the treatment conditions for the samples 7 to 10 and the reduced coenzyme Q10 ratio of the treated sample.

また、試料8、9、および10中の処理後の還元型補酵素Q10濃度、酸化型補酵素Q10濃度、総補酵素Q10濃度を表3に示す。

Figure 2009044852
Figure 2009044852
Table 3 shows the reduced coenzyme Q10 concentration, oxidized coenzyme Q10 concentration, and total coenzyme Q10 concentration after treatment in Samples 8, 9, and 10.
Figure 2009044852
Figure 2009044852

上記結果より、酸化型補酵素Q10と豚肉を共存下に加熱処理することによって、補酵素Q10総量に対する還元型補酵素Q10比率を高められることが確認された。   From the above results, it was confirmed that the ratio of reduced coenzyme Q10 to the total amount of coenzyme Q10 can be increased by heat-treating oxidized coenzyme Q10 and pork in the coexistence.

また表3の結果より、単に酸化型補酵素Q10を豚肉に混合させただけでは得られる食品中の還元型補酵素Q10濃度は増加せず、酸化型補酵素Q10を添加した食品の還元型補酵素Q10濃度を増加させる、すなわち酸化型補酵素Q10を利用して還元型補酵素Q10が富化された食品を得る、ためには、加熱処理が必須であることが確認された。   Further, from the results of Table 3, the concentration of reduced coenzyme Q10 in the food obtained by simply mixing oxidized coenzyme Q10 with pork does not increase, but the reduced coenzyme Q10 of food to which oxidized coenzyme Q10 has been added is not increased. In order to increase the concentration of enzyme Q10, that is, to obtain food enriched with reduced coenzyme Q10 using oxidized coenzyme Q10, it was confirmed that heat treatment was essential.

(実施例3)
<実験方法>
ハサミを用いて約20gのミニアスパラガスを細切した。4mgの酸化型補酵素Q10(株式会社 カネカ製)に200mgの大豆油を添加し、約60℃の加温条件下で酸化型補酵素Q10を溶解、混合した。その後、得られた酸化型補酵素Q10/油溶液に蒸留水を加え、総量10mLとし、約60℃の加温条件下で超音波処理を行い、乳化液を調製した。この酸化型補酵素Q10を含む乳化液を、細切にしたミニアスパラガスに加え、十分に混合し、酸化型補酵素Q10添加ミニアスパラガス試料とした。この試料の一部(約200mg程度)を試料11とした。残り(約15g程度)をアルミ缶に入れて密栓し、サクラ精機株式会社製 ネオクレーブ ASV-3022を用いて121℃、30分、1961hpa(2kgf/cm)の条件で加熱処理し、得られた試料を試料12とした。試料11および12について、実施例1と同様に補酵素Qの抽出と、HPLC−ECD(電気化学検出器)を用いた含量分析を行い、試料中の還元型補酵素Q10濃度、酸化型補酵素Q10濃度、総補酵素Q10濃度および還元型補酵素Q10比率を算出した。
(Example 3)
<Experiment method>
About 20g of mini asparagus was chopped with scissors. 200 mg of soybean oil was added to 4 mg of oxidized coenzyme Q10 (manufactured by Kaneka Corporation), and oxidized coenzyme Q10 was dissolved and mixed under a heating condition of about 60 ° C. Thereafter, distilled water was added to the obtained oxidized coenzyme Q10 / oil solution to make a total volume of 10 mL, and sonication was performed under a heating condition of about 60 ° C. to prepare an emulsion. The emulsion containing oxidized coenzyme Q10 was added to the minced mini asparagus and mixed well to obtain an oxidized coenzyme Q10-added mini asparagus sample. A part of this sample (about 200 mg) was designated as Sample 11. The remaining (about about 15 g) was sealed and put into aluminum cans, 121 ° C. using a Sakura Seiki Co., Ltd. Neokurebu ASV-3022, 30 min, heat treatment under the conditions of 1961hpa (2kgf / cm 2), the resulting The sample was designated as sample 12. Samples 11 and 12 were subjected to extraction of coenzyme Q and content analysis using HPLC-ECD (electrochemical detector) in the same manner as in Example 1, and reduced coenzyme Q10 concentration in sample and oxidized coenzyme. Q10 concentration, total coenzyme Q10 concentration and reduced coenzyme Q10 ratio were calculated.

<結果>
上記、試料11、12中の還元型補酵素Q10濃度、酸化型補酵素Q10濃度、総補酵素Q10濃度および還元型補酵素Q10比率を表4に示す。

Figure 2009044852
<Result>
Table 4 shows the reduced coenzyme Q10 concentration, oxidized coenzyme Q10 concentration, total coenzyme Q10 concentration, and reduced coenzyme Q10 ratio in Samples 11 and 12.
Figure 2009044852

上記結果より、酸化型補酵素Q10とミニアスパラガスを共存下に加熱処理することによって、補酵素Q10総量に対する還元型補酵素Q10比率を高められることが確認された。   From the above results, it was confirmed that the ratio of reduced coenzyme Q10 to the total amount of coenzyme Q10 can be increased by heat treatment in the presence of oxidized coenzyme Q10 and mini asparagus.

(実施例4)
<実験方法>
ハサミを用いて約20gのマグロの切り身を細切した。40mgの補酵素Q10(還元型:酸化型=96:4)に400mgの大豆油を添加し、約60℃の加温条件下で溶解、混合した。その後、得られた油溶液に蒸留水を加え、総量10mLとし、約60℃の加温条件下で超音波処理を行い、補酵素Q10(還元型:酸化型=96:4)の乳化液を調製した。この補酵素Q10を含む乳化液を、細切にしたマグロ切り身に加え、十分に混合し、補酵素Q10(還元型:酸化型=96:4)添加マグロ切り身試料とした。この試料の一部(約200mg程度)を試料13とした。残り(約15g程度)をアルミ缶に入れて密栓し、サクラ精機株式会社製 ネオクレーブ ASV-3022を用いて121℃、30分、1961hpa(2kgf/cm)の条件で加熱処理し、得られた試料を試料14とした。試料13および14について、実施例1と同様に補酵素Q10の抽出と、HPLC−ECD(電気化学検出器)を用いた含量分析を行い、試料中の還元型補酵素Q10比率を算出した。
Example 4
<Experiment method>
About 20g of tuna fillet was chopped with scissors. 400 mg of soybean oil was added to 40 mg of coenzyme Q10 (reduced type: oxidized type = 96: 4), and dissolved and mixed under heating conditions of about 60 ° C. Thereafter, distilled water is added to the obtained oil solution to make a total volume of 10 mL, and sonication is performed under a heating condition of about 60 ° C. to obtain an emulsion of coenzyme Q10 (reduced type: oxidized type = 96: 4). Prepared. The emulsion containing coenzyme Q10 was added to the minced tuna fillet and mixed well to obtain a tuna fillet sample added with coenzyme Q10 (reduced type: oxidized type = 96: 4). A part of this sample (about 200 mg) was designated as Sample 13. The remaining (about about 15 g) was sealed and put into aluminum cans, 121 ° C. using a Sakura Seiki Co., Ltd. Neokurebu ASV-3022, 30 min, heat treatment under the conditions of 1961hpa (2kgf / cm 2), the resulting The sample was designated as sample 14. Samples 13 and 14 were subjected to extraction of coenzyme Q10 and content analysis using HPLC-ECD (electrochemical detector) in the same manner as in Example 1, and the reduced coenzyme Q10 ratio in the sample was calculated.

<結果>
上記、試料13、14中の還元型補酵素Q10比率を表5に示す。

Figure 2009044852
<Result>
Table 5 shows the ratio of reduced coenzyme Q10 in Samples 13 and 14.
Figure 2009044852

(実施例5)
<実験方法>
ハサミを用いて約20gの豚肉を細切した。40mgの補酵素Q10(還元型:酸化型=96:4)に400mgの大豆油を添加し、約60℃の加温条件下で溶解、混合した。その後、得られた油溶液に蒸留水を加え、総量10mLとし、約60℃の加温条件下で超音波処理を行い、補酵素Q10(還元型:酸化型=96:4)の乳化液を調製した。この補酵素Q10を含む乳化液を、細切にしたマグロ切り身に加え、十分に混合し、補酵素Q10(還元型:酸化型=96:4)添加豚肉試料とした。この試料の一部(約200mg程度)を試料15とした。残り(約15g程度)をアルミ缶に入れて密栓し、サクラ精機株式会社製 ネオクレーブ ASV−3022を用いて121℃、30分、1961hpa(2kgf/cm)の条件で加熱処理し、得られた試料を試料16とした。試料15および16について、実施例1と同様に補酵素Q10の抽出と、HPLC−ECD(電気化学検出器)を用いた含量分析を行い、試料中の還元型補酵素Q10比率を算出した。
(Example 5)
<Experiment method>
About 20 g of pork was chopped with scissors. 400 mg of soybean oil was added to 40 mg of coenzyme Q10 (reduced type: oxidized type = 96: 4), and dissolved and mixed under heating conditions of about 60 ° C. Thereafter, distilled water is added to the obtained oil solution to make a total volume of 10 mL, and sonication is performed under a heating condition of about 60 ° C. to obtain an emulsion of coenzyme Q10 (reduced type: oxidized type = 96: 4). Prepared. This emulsified liquid containing coenzyme Q10 was added to the minced tuna fillet and mixed well to prepare a pork sample with coenzyme Q10 (reduced type: oxidized type = 96: 4) added. A part of this sample (about 200 mg) was designated as Sample 15. The rest (about 15g) was put in an aluminum can and sealed, and heat-treated under the conditions of 1961hpa (2kgf / cm 2 ) at 121 ° C for 30 minutes using a Neoclave ASV-3022 manufactured by Sakura Seiki Co., Ltd. The sample was designated as Sample 16. For samples 15 and 16, extraction of coenzyme Q10 and content analysis using HPLC-ECD (electrochemical detector) were performed in the same manner as in Example 1, and the reduced coenzyme Q10 ratio in the sample was calculated.

<結果>
上記、試料15、16中の還元型補酵素Q10比率を表6に示す。

Figure 2009044852
<Result>
The ratio of reduced coenzyme Q10 in samples 15 and 16 is shown in Table 6.
Figure 2009044852

本明細書は本願の優先権の基礎である日本国特許出願2007-262101号の明細書および/または図面に記載される内容を包含する。   This specification includes the contents described in the specification and / or drawings of Japanese Patent Application No. 2007-262101, which is the basis of the priority of the present application.

本明細書で引用した全ての刊行物、特許および特許出願をそのまま参考として本明細書にとり入れるものとする。   All publications, patents and patent applications cited herein are incorporated herein by reference in their entirety.

Claims (7)

酸化型補酵素Q10(下記式1)を肉類、魚介類及び/又は野菜類共存下に加熱処理する、還元型補酵素Q10(下記式2)の製造方法
Figure 2009044852
Figure 2009044852
A process for producing reduced coenzyme Q10 (formula 2 below), wherein oxidized coenzyme Q10 (formula 1 below) is heat-treated in the presence of meat, seafood and / or vegetables.
Figure 2009044852
Figure 2009044852
酸化型補酵素Q10が外部添加されたものである請求項1に記載の製造方法   The production method according to claim 1, wherein oxidized coenzyme Q10 is externally added. 加熱処理の温度条件が、100℃以上である請求項1、又は2に記載の製造方法   The manufacturing method according to claim 1, wherein the temperature condition of the heat treatment is 100 ° C. or more. 加熱処理の時間が、5分以上である請求項1〜3いずれか1項に記載の製造方法   The time of heat processing is 5 minutes or more, The manufacturing method of any one of Claims 1-3 酸素遮断下及び/又は密閉下に加熱処理する、請求項1〜4いずれか1項に記載の製造方法   The manufacturing method of any one of Claims 1-4 which heat-processes under oxygen interruption | blocking and / or sealing. 請求項1〜5いずれか1項に記載の製造方法によって得られる、還元型補酵素Q10含有食品   A reduced coenzyme Q10-containing food obtained by the production method according to any one of claims 1 to 5. 食品中の補酵素Q10総量に対する還元型補酵素Q10の割合が60重量%以上である請求項6に記載の食品   The food according to claim 6, wherein the ratio of reduced coenzyme Q10 to the total amount of coenzyme Q10 in the food is 60% by weight or more.
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10109933A (en) * 1996-08-16 1998-04-28 Kanegafuchi Chem Ind Co Ltd Pharmaceutical composition
WO2001052822A1 (en) * 2000-01-20 2001-07-26 Chopra Raj K Reduced form of coenzyme q in high bioavailability stable dosage forms and related applications
WO2003006409A1 (en) * 2001-07-13 2003-01-23 Kaneka Corporation Method of producing reduced coenzyme q10 crystals with excellent handling properties
WO2003006408A1 (en) * 2001-07-13 2003-01-23 Kaneka Corporation Method of producing reduced coenzyme q10 using solvent with high oxidation-protective effect
WO2003032967A1 (en) * 2001-10-10 2003-04-24 Kaneka Corporation Method of stabilizing reduced coenzyme q10
WO2004066988A1 (en) * 2003-01-31 2004-08-12 Kaneka Corporation Fatigue reducing agent
EP1474991A1 (en) * 2002-01-18 2004-11-10 Kaneka Corporation Ubiquinol-enriched fat-containing foods
WO2009025277A1 (en) * 2007-08-22 2009-02-26 Kaneka Corporation Method of producing reduced coenzyme q10 and method of stabilizing the same

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10109933A (en) * 1996-08-16 1998-04-28 Kanegafuchi Chem Ind Co Ltd Pharmaceutical composition
WO2001052822A1 (en) * 2000-01-20 2001-07-26 Chopra Raj K Reduced form of coenzyme q in high bioavailability stable dosage forms and related applications
WO2003006409A1 (en) * 2001-07-13 2003-01-23 Kaneka Corporation Method of producing reduced coenzyme q10 crystals with excellent handling properties
WO2003006408A1 (en) * 2001-07-13 2003-01-23 Kaneka Corporation Method of producing reduced coenzyme q10 using solvent with high oxidation-protective effect
WO2003032967A1 (en) * 2001-10-10 2003-04-24 Kaneka Corporation Method of stabilizing reduced coenzyme q10
EP1474991A1 (en) * 2002-01-18 2004-11-10 Kaneka Corporation Ubiquinol-enriched fat-containing foods
WO2004066988A1 (en) * 2003-01-31 2004-08-12 Kaneka Corporation Fatigue reducing agent
WO2009025277A1 (en) * 2007-08-22 2009-02-26 Kaneka Corporation Method of producing reduced coenzyme q10 and method of stabilizing the same

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