JP3647945B2 - Health food using odorless garlic - Google Patents

Description

【００１５】
ロ）ジアリルジサルファイドと糖（果糖）の水素結合
その結合様式は下記化２に示される。
【００１６】
【化２】

【００１７】
（２）イオン結合
イ）ジアリルジサルファイドとペプチドのイオン結合
その結合様式は下記化３に示される。
【００１８】
【化３】

【００１９】
（３）ジサルファイド結合
イ）アリシンとペプチドのジサルファイド結合
その結合様式は下記化４に示される。
【００２０】
【化４】

【００２１】
（４）脱水結合
イ）ジアリルジサルファイドとペプチドの脱水結合
その結合様式は下記化５に示される。
【００２２】
【化５】

【００２３】
ロ）アリシンと糖（果糖）の脱水結合
その結合様式は下記化６に示される。
【００２４】
【化６】

【００２５】
【発明の実施態様】
本発明を実施するには、にんにく球を剥皮した後、
１）水浸又は適度の加温、加熱によって、にんにく球内の酵素アリイナーゼの活動を活性化させる。
２）にんにく球を切断又は粉砕して、にんにく球内の酵素アリイナーゼを急激に活性化させる。
【００２６】
３）前記１）及び／又は２）によってアリイナーゼを活性化させ、このアリイナーゼの酵素活動により、にんにくの成分のアリインが分解されてアリシンに転換すると共に硫化物としてのにんにく臭を発生し、更に分解の進展に伴い、ジアリルジサルファイド類も発生し、特有のにんにく臭を発生するに至る。
【００２７】
４）本発明では此のアリイナーゼによる酵素分解によって分解生成した直後のアリシン及びジアリルジサルファイドなどが構造的に強固に安定せず、未だ不安定で活性を有している時期を逃さず、此の時期にペプチド又は糖質と急激にホモジナイズして両者の均一な接触を行い水素結合、ジサルファイド結合などの化学結合を行わせ硫化物を不活性な複合体として安定化させ、無臭化させる事を特徴とする。
【００２８】
５）即ち前記１）又は２）の過程で酵素アリイナーゼの活動が進んだ時点を見極め、温湯、水蒸気又は火気による加熱で酵素分解を急激に進めた直後、酵素を失活させて分解を止める。此の時、アリイナーゼによるアリインからアリシンへの酵素分解は加熱によって、その分解適正域では短時間に極めて過激な分解を起こすため、加熱開始から酵素失活までの加熱温度と時間が最も重要となる。又、此の温度と時間決定を誤るとアリシンの２次分解によるジアリルジサルファイド類の生成が多くなる。
【００２９】
６）即ち前記５）の過程に於いて、加熱によるアリイナーゼの極めて急激な酵素分解が終了に近い点を見極めつつ更に高温化してアリイナーゼを完全に失活させると同時に、あるいはその可及的直前又は直後に、ペプチド又は糖質、あるいはこれらの混合物とともに両者を均一に混合、接触せしめ（例えば急速ホモジナイズ処理）、温度、水分、ｐＨ、攪拌速度などを調整し、好適条件下で化学反応をひき起して、これらの複合体をつくらせる事によって、にんにくが酵素分解によって生じた硫化物（アリシンを始め、その２次分解によって生ずるジアリルジサルファイド、ジアリルトリサルファイドなど）のいわゆる「にんにく臭」を消去することが出来る。
【００３０】
にんにくとペプチド及び／又は糖質を急速にホモジナイズして複合体を形成させる時の反応条件として本発明では全ての反応条件に適合する範囲として、反応温度は３０℃〜９８℃、加水量は０％〜２００％、ｐＨは３．０〜９．０（好ましくは７．０を標準）、酵素アリイナーゼ反応時間は前処理段階（にんにく球の剥皮前）で５時間〜２４時間、主反応は１分間〜２０分間、尚、前処理段階を行わない場合は、主反応は１分間〜３０分間、ホモジナイズ回転速度は１０００ｒｐｍ〜１５０００ｒｐｍ（好ましくは３０００ｒｐｍ〜１００００ｒｐｍ）、複合体を形成させる反応時間は１分間〜３０分間である。
【００３１】
本発明に於いて使用されるペプチドは、魚肉由来、畜肉由来、乳由来動物性タンパク質が酵素分解されて生成したものが広く用いられるが、本発明研究に使用したイワシ由来ペプチド（例えば、特公平３−５４９５８、特開平２−１５４６９３、特開平５−２７１２９７）が上記の硫化物との化学反応及びその複合体形成には極めて良好であった。
【００３２】
魚肉由来ペプチドの例としては、イワシのほかサバ、サンマその他各種魚介類を蛋白分解酵素で処理することにより、ペプチドを生成させ、ついでこれをアルコール分画、イオン交換樹脂処理することによって分離、精製することによって得られるペプチドが挙げられる。
【００３３】
その１例であるペプチド ＤＡＮ−１００は、下記表１、表２に示される理化学的性質を有する新規物質であって、その詳細は特公平３−５４９５８号に開示されている。
【００３４】
【表１】

【００３５】
【表２】

【００３６】
また魚肉由来ペプチドの他の例としては、イワシのほかサバ、サンマその他各種魚介類を自己消化処理と蛋白分解酵素処理を同時に行って得られる分子量５００〜６，０００の機能性ペプチドが挙げられる。
【００３７】
その１例である機能性ペプチド ＥＳＰ−２は、下記表３、表４に示される理化学的性質を有する新規物質であって、その詳細は特開平２−１５４６９３号に開示されている。
【００３８】
【表３】

【００３９】
【表４】

【００４０】
また更に魚肉由来ペプチドの他の例としては、イワシのほかサバ、サンマその他各種魚介類を加熱変性せしめて自己消化酵素を失活せしめた後プロテアーゼ処理して得られるペプチドが挙げられる。
【００４１】
その１例であるペプチドα−１０００は、下記表５、表６、表７に示される理化学的性質を有する新規物質であって、その詳細は特開平５−２７１２９７号に開示されている。
【００４２】
【表５】

【００４３】
【表６】

【００４４】
【表７】

【００４５】
又、本発明に於いて使用される糖質は各種単糖類、多糖類を始め、ピリドキサールリン酸を含む抽出糖などがあげられる。中でも、果糖、ブドウ糖などの単糖が極めて良好な複合体を形成した。更にまた、蜂蜜、水あめ、液糖なども好適に使用できる。
【００４６】
又、用いられるペプチドの配合量は、にんにくの種類（産地の差）、保存期間などによって異なるが、本発明研究に於いては、にんにくの重量当たり０．５％〜３０．０％程度が適当と判断された。
【００４７】
又、糖質の配合量は単糖の場合、にんにくとの化学反応に必要な適正量の他、出来上がり製品の味覚、食感なども考慮した場合２０％〜２００％程度が良好と判断された。又、ペプチドと糖質の混合物を用いる場合も上記の各配合量とほぼ同一の配合範囲であった。
【００４８】
このようにして製造した無臭にんにくは、それ自体飲食品として使用できることはもちろんのこと、他の飲食品に混合して使用することもでき、いずれのタイプの飲食品も本発明に包含される。
【００４９】
本発明に係る無臭にんにくは、臭気成分のみが選択的に除去されているだけで、薬効成分はいささかも変化してはいないので、適宜の形態に調製して、通常の飲食品として用いることができるほか、特定保健用飲食品、機能性飲食品、健康飲食品、栄養飲食品として広く利用することができる。
【００５０】
例えば、特に糖を使用して得た無臭にんにくについては、ジャム状のペースト食品とすることができ、無臭にんにくを懸濁させたり、加水混合処理した後これを濾過ないし遠心分離して得た上清部を用いたりして液状ないし懸濁状の健康ドリンクとすることができる。また、パウダー状、タブレット状、カプセル状の健康食品とすることもできる。
【００５１】
更にまた、無臭にんにくは、それ自体及び／又は他の常用される成分を配合して、液状、ペースト状、または粉末状の調味料とすることができ、焼肉等の肉料理用その他各種の料理用の調味料として、レストランや工場のほか、家庭でも自由に使用することができる。
【００５２】
以下、本発明の製造例及び実施例について述べる。
【００５３】
【製造例１】
新鮮イワシをデボーナーで処理して採肉した。採肉した魚肉質を１０ｋｇのすり身に分割した。これを粉砕機で粉砕した後等量の水を加え、４５〜４８℃に加熱し、これを攪拌タンクに移して同温に２〜３時間保持して自己消化分解せしめた。次いでｐＨを４．１に調節した。
【００５４】
これをデナチーム（市販プロテアーゼ製剤商品名）の０．１％液を加え、４５℃に１７時間保持して酵素分解を行った。中和し、次いで１５分間煮沸して酵素を失活せしめた。
【００５５】
これをバイブスクリーン（１５０メッシュ）で濾過し、濾液を５０００ｒｐｍでジェクター処理した後、シャープレス遠心分離機で処理し（１５０００ｒｐｍ）、２０ Ｂｘとなるまで常温加熱濃縮し、そして再度シャープレス遠沈処理（１５０００ｒｐｍ）してペプチド原液（ＤＡＮ−Ｎｏ．２）を得た。
【００５６】
上記で得たペプチド原液（ｐＨ６．２２）は１８４０ｍｌとなり、これに活性炭１００ｇを加え６０分間攪拌した後濾過して濾液（ｐＨ６．１２）１５００ｍｌを得た。
濾液を１００ｍｌとり、これに冷メタノールを２０００ｍｌ加え、冷室に６０分間放置して沈殿を生ぜしめた。生じた沈殿物に水を加えて溶液（Ｅ）を得た。
【００５７】
上記溶液（Ｅ）を１００ｍｌとり、これをダウェックス５０Ｗ〔Ｈ+〕を充填したカラム（径５ｃｍ×長さ１５ｃｍ）に注入した。そして、水２０００ｍｌを用いて樹脂を水洗し、２Ｎ−ＮＨ₄ＯＨ ２５０ｍｌを用いて溶出し、得られた溶出液を常法によりアンモニア除去後凍結乾燥してペプチドＤＡＮ−１００の白色粉末を得た。
【００５８】
【製造例２】
新鮮イワシをデボーナーで処理して採肉し、得られたイワシ肉身１０ｋｇを粉砕機で粉砕した後、等量の水及びデナチーム（市販プロテアーゼ製剤商品名）１０ｇを加え、よく混合し、４５℃に４時間保持して自己消化及び酵素分解を行った。反応液をｐＨ７に中和し、次いで１５分間煮沸して酵素を失活せしめた。
【００５９】
これをバイブスクリーン（１５０メッシュ）で濾過し、濾液を５０００ｒｐｍでジェクター処理した後、シャープレス遠心分離機で処理し（１５０００ｒｐｍ）、２０ Ｂｘとなるまで常温加熱濃縮し、そして再度シャープレス遠沈処理（１５０００ｒｐｍ）した。
【００６０】
得られた清澄液を減圧濃縮機にて４倍に濃縮し、濃縮液を活性炭濾過し、次いで珪藻土濾過し、わずかに黄色を帯び透明な機能性ペプチドＥＳＰ−２の溶液を得た。
また、上記で得た機能性ペプチドＥＳＰ−２をそのまま凍結乾燥し、黄白色の機能性ペプチドＥＳＰ−２を得た。
【００６１】
【製造例３】
新鮮イワシをデボーナーで処理して採肉した。採肉した魚肉質を１０ｋｇのすり身に分割し、これを−３０℃以下で急速凍結した後、粉砕機で粉砕した後等量の水を加え、これをタンクに送り、１００℃に１０分間加熱して自己消化酵素を失活させ、熱変性させた。次いでアンモニア水を加えてｐＨを１０に調整した。
【００６２】
これに市販のアルカリプロテアーゼ製品の０．１％液を加え、４５℃に１７時間保持して酵素分解を行った。次いで１５分間煮沸して酵素を失活せしめた。
【００６３】
これをバイブスクリーン（１５０メッシュ）に通し５０００ｒｐｍでジェクター処理した後、シャープレス遠心分離機で処理し（１５０００ｒｐｍ）、珪藻土を濾過助剤として用い、濾過処理したものをペプチド原液とした。
【００６４】
上記で得たペプチド原液に活性炭を１％Ｗ／Ｖ加え、３０℃で６０分間攪拌した後濾過して濾液を得た。これを常法にしたがって減圧濃縮（２０℃）した後、常法にしたがってＵＨＴＳＴ殺菌を行って、α−１０００（液体）製品を得、これを更に常法にしたがって噴霧乾燥して粒径６０メッシュのα−１０００（粉末）製品を得、それぞれこれらの製品は冷凍保管した。
【００６５】
このようにして調製したペプチドα−１０００（粉末）について、セファデックスＧ−２５カラムを用い、下記の条件でゲル濾過した結果、分子量は２００〜１０，０００であることが判明した。カラムサイズ：径１６×９５０ｍｍ、溶出剤：０．１Ｍホスフェートバッファー（ｐＨ７．０）、分画：２ｍｌ／チューブ、流速：１０ｍｌ／ｈ、分子量マーカー：バシトラシン（分子量１４５０）。
【００６６】
上記によって得たα−１０００（液体）は、水分含量が７３．６％（減圧加熱乾燥法）であって、淡黄色を呈し、その１０％溶液のｐＨは７．５を示し、魚臭もなく苦味も認められなかった。そのアミノ酸組成についての測定を行った結果、下記する表８に示す結果が得られた。
【００６７】
【表８】

【００６８】
【実施例１】
生にんにく２．０ｋｇを３０℃の温水に１０時間浸漬する。流水中で剥皮した後、沸騰水上で蒸す。最初５分間、にんにく球の品温を５０℃〜５５℃にコントロールし、その後、温度を上げ、品温が８５℃以上になるのを確認した後、直ちに取り出して、高速ホモジナイザー（８０００ｒｐｍ）内に投入すると同時に魚肉ペプチド２００ｇと混合し、両者の混合温度７０℃で５分間ホモジナイズして均一な、にんにくペーストをつくる。製品には「にんにく臭」は全くなく、これを密封後、常温及び冷蔵庫内で１２ケ月間保存後も、「にんにく臭」は認められなかった。
【００６９】
【比較実験】
脱臭効果の判定は訓練されたパネラー１５名による官能評価と、にんにくの悪臭の代表的な成分の一つであるジアリルジサルファイドの量をガスクロマトグラフにより分析する事により行った。
【００７０】
（官能評価）
官能評価は本発明による製法で製造したものと、単に、にんにくのみを処理した場合（対照品）との、にんにく臭の強度を、以下に示す基準に従って６段階評価し、１５名のパネラーを用いて両者間の比較を行なった。
０・・・にんにく臭を全く感じない。
１・・・にんにく臭をほとんど感じない。
２・・・にんにく臭を少し感じる。
３・・・にんにく臭をやや感じる。
４・・・にんにく臭を強く感じる。
５・・・にんにく臭を非常に強く感じる。
【００７１】
得られた結果を下記表９に示す。その結果から明らかなように、本発明品は、にんにく臭が脱臭されていることが示された。
【００７２】
【表９】

【００７３】
（ガスクロマトグラフィー分析）
次の条件でジアリルジサルファイドを分析した。
機種 ：ガスクロ島津製作所ＧＣ−９Ａ
液相 ：ＦＡＬ−Ｍ
担体 ：Ｓｈｉｍａｌｉｔｅ ＴＰＡ
分析温度：７０℃
キャリアガス：Ｎ₂
検出器 ：ＦＰＤ
【００７４】
本発明品と対照品１０ｇを５０ｍｌ容のバイアルビンに採取し、８０℃で１５分間放置した。その後、ヘッドスペースガス５ｍｌを採取し、以上の条件下、ガスクロマトグラフィーを行なった。
【００７５】
ガスクロマトグラフィーによるジアリルジサルファイドの分析結果、図４、図５によれば、ガスクロチャート上のジアリルジサルファイドのピークが、対照品の場合（図５）は認められるのに対して、本発明品の場合（図４）は、ほとんど検出されていない。
【００７６】
ジアリルジサルファイドは、にんにく臭の中で強烈な臭いを放つ代表的な成分として、又、にんにく臭に占める比率が高いことが知られており、本試験において、モニターによる官能評価とガスクロマトグラフィーの定量結果が一致し、良好な結果が示されたことから、本発明による製法で製造したものは、明らかに、にんにく臭の脱臭が行なわれていることを裏付けた。
【００７７】
本実施例において、魚肉ペプチド（製造例３：α−１０００）にかえて製造例１及び２で製造したペプチドＤＡＮ−１００及びＥＳＰ−２を用いて同様の処理をくり返した結果、すぐれた無臭にんにくが得られた。
【００７８】
【実施例２】
生にんにく２．０ｋｇを４０℃の温水に５時間浸漬する。流水中で剥皮した後、沸騰水上で蒸す。最初５分間、にんにく球の品温を５０℃〜５５℃にコントロールして加熱した後、温度を上げ、品温が８５℃以上になるのを確認し、直ちに取り出して、高速ホモジナイザー（８０００ｒｐｍ）内に投入すると同時に、予め加温した蜂蜜１．０ｋｇと混合し、両者の混合温度７０℃で５分間ホモジナイズして均一な、にんにくペーストをつくる。製品には「にんにく臭」は全くなく、これを密封後、常温及び冷蔵庫内で１２ケ月間保存後も、「にんにく臭」は認められなかった。
【００７９】
得られたにんにくペーストはジャム状を呈し、軽い甘味を有しており、そのまま摂取したり、パンに塗って摂取したりすることが可能であった。
【００８０】
【実施例３】
生にんにく２．０ｋｇを４０℃の温水に５時間浸漬する。流水中で剥皮した後、沸騰水上で蒸す。最初から５分間、にんにく球の品温を５０℃〜５５℃にコントロールして加熱した後、温度を上げ、品温が８５℃以上になるのを確認した後、直ちに取り出して、高速ホモジナイザー（８０００ｒｐｍ）内に投入すると同時に、魚肉ペプチド２００ｇと予め加温した蜂蜜１．０ｋｇの混合物と混合し、両者の混合温度７０℃で５分間ホモジナイズして均一な、にんにくペーストをつくる。製品には「にんにく臭」は全くなく、これを密封後、常温及び冷蔵庫内で１２ケ月間保存後も、「にんにく臭」は認められなかった。
【００８１】
魚肉ペプチド（製造例３：α−１０００）として製造例１及び２で製造したペプチドＤＡＮ−１００及びＥＳＰ−２を用いて同様の処理をくり返した結果、すぐれた無臭にんにくが得られた。
【００８２】
【実施例４：ドリンク】
実施例３によって得られた、にんにくペーストに２倍量の水を加え、濾過処理後、その濾過液を用いて次の組成による健康ドリンクを作成した。
（組成）
無臭にんにく濾過液 ７０部
液糖 ２０部
ビタミンＭＩＸ ６部
香料 ２部
クエン酸Ｎａ ２部
これを１５０ｍｌの褐色ビンに詰め、殺菌した。
また、上記にんにく濾過液にかえて製造例３で得たペプチドα−１０００（液体）を用い、同様に処理して得た無臭にんにくを用いて同様に健康ドリンクを作成した。
【００８３】
【実施例５：健康食品製剤】
まず、下記原料をよく攪拌混合した。
無臭にんにく濾過液 ６０部
乳糖 ３０部
ブドウ糖 ８部
ＣＭＣ ２部
この混合物を凍結乾燥し、粉砕後、１００メッシュパス画分を各２ｇずつ分包した。
【００８４】
【実施例６：健康食品カプセル】
実施例５の粉末品９１．４部にビタミンＭＩＸ５部と酸化マグネシウム０．１部、粉末アルコール２．５部、粉末香料１．０部を加え、よく混合して、常法により内容量２５０ｍｇ／ケのカプセル製剤とした。
【００８５】
【実施例７：健康食品錠剤】
実施例５の粉末品８７．７部にビタミンＭＩＸ５部、結晶クエン酸２部、コーンスターチ４部、ステアリン酸マグネシウム１部、香料０．３部を加えて、よく混合後、常法により打錠して、錠剤を得た。
【００８６】
【実施例８：ペースト状調味料】
無臭にんにくペースト（実施例１） ８５部
食塩 ８部
粉末醤油 ４．５部
酵母エキス ２．５部
以上の原料をよく混合し、チューブに詰めて、ペースト状調味料とした。
【００８７】
【発明の効果】
本発明によって新しいにんにくの無臭化システムが開発された。本発明によって得られた無臭にんにくは、完全に脱臭されているだけでなく、安全性の面でも全く問題はなく、しかも体内に摂取した後はもとの薬効成分に戻るため、生理活性の面でも全く問題はない。
【００８８】
したがって、本発明に係る無臭にんにくは、それ自体を直接摂取できることはもとより、各種の形態に製剤したり各種タイプの飲食品にして、通常の飲食品、特定保健用食品、機能性飲食品、健康食品、栄養剤、健康ドリンク、ペースト食品、調味料等として各種用途に利用することができる。
【図面の簡単な説明】
【図１】機能性ペプチドＥＳＰ−２のゲル濾過による分子量分布を示す。
【図２】ＥＳＰ−２のＵＶスペクトルを示す。
【図３】ＥＳＰ−２のＩＲスペクトルを示す。
【図４】本発明品のガスクロマトグラムを示す。
【図５】対照品のガスクロマトグラムを示す。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a food containing odorless garlic and odorless garlic obtained by binding a sulfur component of garlic to a peptide or carbohydrate, or a mixture of both.
[0002]
[Prior art]
It is well known that garlic has been treasured since ancient times as a longevity secret medicine, as a potentiating agent, or as a specific medicine for all diseases including tuberculosis. However, despite its excellent medicinal properties, it is difficult to eliminate the unpleasant odor of garlic and it is not always effectively used.
[0003]
“Garlic odor” is a medicinal component (allysine) produced by enzymatic decomposition of alliin, which is a component of garlic, by an enzyme in garlic (allylinase), and is due to allyl sulfide compounds such as diallyl disulfide and diallyl trisulfide. It is considered. Typical garlic odor components include diallyl disulfide, diallyl trisulfide, propylallyl disulfide, diallyl monosulfide, S-allyl-2-propenethiosulfide, and other allyl sulfide compounds. These odors are intense and are perceived as unpleasant odors even when present in trace amounts.
[0004]
As described above, allicin is produced from the garlic component alliin by the enzyme alliinase. It is known that this allicin is a source of various medicinal effects of garlic. At present, the main method for non-bromating garlic is to inactivate and remove the enzyme alliinase by immersing garlic in activated silicic acid and phytic acid aqueous solution. In addition, methods such as heating garlic to inactivate the enzyme alliinase or ingesting it together with protein, vegetables, etc., have been used. However, none of the above methods inactivate the enzyme alliinase in garlic or cause sufficient enzymatic degradation activity, so the garlic component alliin is ingested without being decomposed into medicinal allicin. , Less effective in the body.
[0005]
Therefore, the present condition is that the method of expressing efficacies without odor is not yet known. In addition, in the above method, since it is difficult to determine whether or not the enzyme in garlic has been completely inactivated, even if it can be temporarily deodorized, it can be stored, changed in temperature or humidity, or physically, chemically. At present, there is no known method for removing the “return odor” that is generated again by the generated sulfur compound due to the change.
[0006]
[Problems to be solved by the invention]
The present invention has been made for the purpose of developing a new method for deodorizing garlic and developing an effective use of the obtained odorless garlic.
[0007]
[Means for Solving the Problems]
As a result of examination from various directions to achieve the above purpose, it is desirable to prevent the production of malodorous odor components (flavor components) from garlic, but the odor component itself is a medicinal component (such as allicin). In this case, the general deodorization method loses its effectiveness, so if these can be converted into non-volatile compounds, it will be noted for the first time that it can be made non-brominated without losing its effectiveness. From this point of view, intensive research was conducted, and as a result, the present invention was completed.
[0008]
That is, according to the present invention, as a method for deodorizing garlic, the garlic sulfide compound (garlic odor) is simply and completely deodorized by combining it with peptides and / or saccharides, and the generation of a return odor over a long period of time. The present invention was completed by discovering that garlic can be stably deodorized without any problems.
[0009]
In the present invention, a sulfurized compound, which is a main odor component of garlic, is combined with a peptide and / or a carbohydrate to make it non-volatile, and the bound peptide or carbohydrate is separated by digestive action in the body, so that In addition to exerting its medicinal properties, the coexisting peptides or carbohydrates are physiologically active in the human body (such as antihypertensive activity of peptides, antihypercholesterolemic activity, mineral absorption promoting activity, and intestinal activity of carbohydrates), nutritional effects It is based on the new knowledge that it can have both.
[0010]
In addition to the above, the present invention has characteristics that can be widely applied to deodorization and deodorization of foods having a different odor common to various sulfides, allyl compounds, methyl compounds, and propenyl compounds.
[0011]
Details of the deodorization mechanism of garlic and the action mechanism of medicinal components (such as allicin) in the body according to the present invention must be studied in the future, but at present, hydrogen bonds, ions between peptides and / or carbohydrates and sulfide compounds After deodorizing by using a bond, dehydration bond, or disulfide bond, and then ingested by the body, this conjugate or complex is separated in the body and reversibly cleaves the garlic medicinal component, It is thought that the medicinal properties of garlic are exhibited by returning to the medicinal properties of garlic (intact form).
[0012]
Therefore, in the present invention, the garlic component (Alliin) is rapidly converted into a medicinal component (Allicin) by enzymatic degradation by the enzyme Alliinase, and at the same time, the medicinal component (Allicin) is further decomposed to cause malodor (diallyl disulfide). In addition, it is possible to form a conjugate of the odorous components (allicin and diallyl disulfides) with sulfides and peptides and / or carbohydrates.
The binding mode of the conjugate (complex) is as follows.
[0013]
(1) Hydrogen bond a) Hydrogen bond between allicin and peptide The bonding mode is shown in the following chemical formula 1.
[0014]
[Chemical 1]

[0015]
B) Hydrogen bonding between diallyl disulfide and sugar (fructose) The bonding mode is shown in the following chemical formula 2.
[0016]
[Chemical formula 2]

[0017]
(2) Ion bond a) Ially bond between diallyl disulfide and peptide The bond mode is shown in the following chemical formula 3.
[0018]
[Chemical 3]

[0019]
(3) Disulfide binding a) Disulfide binding between allicin and peptide The binding mode is shown in the following chemical formula 4.
[0020]
[Formula 4]

[0021]
(4) Dehydration bond (i) Dehydration bond between diallyl disulfide and peptide.
[0022]
[Chemical formula 5]

[0023]
B) Dehydration bond between allicin and sugar (fructose).
[0024]
[Chemical 6]

[0025]
DETAILED DESCRIPTION OF THE INVENTION
To carry out the present invention, after peeling the garlic balls,
1) The activity of the enzyme alliinase in garlic spheres is activated by water immersion or moderate heating and heating.
2) Cutting or crushing the garlic spheres to rapidly activate the enzyme alliinase in the garlic spheres.
[0026]
3) The alliinase is activated by the above 1) and / or 2), and by the enzymatic activity of this alliinase, alliin of the garlic component is decomposed and converted into allicin, and a garlic odor as a sulfide is generated and further decomposed. As this progresses, diallyl disulfides are also generated, leading to the generation of a unique garlic odor.
[0027]
4) In the present invention, allicin and diallyl disulfide, etc. immediately after being decomposed and produced by enzymatic decomposition with this alliinase are not structurally strongly stable and do not miss the time when they are still unstable and active. To homogenize rapidly with peptides or carbohydrates at the same time to make uniform contact between them and perform chemical bonds such as hydrogen bonds and disulfide bonds to stabilize sulfides as inert complexes and to make them non-bromide Features.
[0028]
5) That is, determine the time when the activity of the enzyme alliinase has progressed in the process of 1) or 2), and immediately after the enzymatic decomposition is rapidly advanced by heating with hot water, steam or fire, the enzyme is deactivated to stop the decomposition. At this time, the enzymatic degradation from alliin to allicin by alliinase is caused by heating, causing extremely extreme degradation in a short time in the appropriate decomposition range, so the heating temperature and time from the start of heating to enzyme deactivation are the most important. . Moreover, if the temperature and time are determined incorrectly, the production of diallyl disulfides by secondary decomposition of allicin increases.
[0029]
6) That is, in the process of 5), the temperature is further increased and the alliinase is completely deactivated at the same time as it is determined that the extremely rapid enzymatic degradation of alliinase by heating is close to completion, or immediately before that or Immediately afterwards, the peptide or carbohydrate or a mixture thereof is mixed and brought into contact with each other uniformly (for example, rapid homogenization), and the temperature, moisture, pH, stirring speed, etc. are adjusted to cause a chemical reaction under suitable conditions. By forming these complexes, the so-called “garlic odor” of sulfides (such as allicin, diallyl disulfide, diallyl trisulfide, etc.) generated by secondary decomposition of garlic is eliminated by making these complexes. I can do it.
[0030]
In the present invention, as a reaction condition when a complex is formed by rapidly homogenizing a garlic and a peptide and / or carbohydrate, the reaction temperature is 30 ° C. to 98 ° C., and the amount of water added is 0. % To 200%, pH is 3.0 to 9.0 (preferably 7.0 is standard), enzyme alliinase reaction time is 5 to 24 hours in the pretreatment stage (before garlic peeling), main reaction is 1 If the pretreatment stage is not performed, the main reaction is 1 minute to 30 minutes, the homogenization rotation speed is 1000 rpm to 15000 rpm (preferably 3000 rpm to 10,000 rpm), and the reaction time for forming the complex is 1 minute ~ 30 minutes.
[0031]
Peptides used in the present invention are widely used peptides produced by enzymatic degradation of fish-derived, livestock-derived, or milk-derived animal proteins. 3-54958, JP-A-2-154893, and JP-A-5-271297) were very good for chemical reaction with the above sulfide and formation of a complex thereof.
[0032]
Examples of fish-derived peptides include sardines, mackerel, saury, and other fish and shellfishes treated with proteolytic enzymes to produce peptides, which are then separated and purified by alcohol fractionation and ion-exchange resin treatment. The peptide obtained by doing is mentioned.
[0033]
Peptide DAN-100 as an example thereof is a novel substance having physicochemical properties shown in Tables 1 and 2 below, and details thereof are disclosed in Japanese Patent Publication No. 3-54958.
[0034]
[Table 1]

[0035]
[Table 2]

[0036]
Other examples of fish-derived peptides include functional peptides having a molecular weight of 500 to 6,000, which are obtained by simultaneously carrying out self-digestion treatment and proteolytic enzyme treatment of mackerel, mackerel and other fish and shellfish in addition to sardines.
[0037]
Functional peptide ESP-2, which is one example thereof, is a novel substance having physicochemical properties shown in Tables 3 and 4 below, and details thereof are disclosed in JP-A-2-154893.
[0038]
[Table 3]

[0039]
[Table 4]

[0040]
Furthermore, other examples of fish-derived peptides include peptides obtained by subjecting sardines, mackerel, saury, and other various seafoods to heat to inactivate self-digesting enzymes, followed by protease treatment.
[0041]
Peptide α-1000 as one example is a novel substance having physicochemical properties shown in the following Table 5, Table 6, and Table 7, and details thereof are disclosed in JP-A-5-271297.
[0042]
[Table 5]

[0043]
[Table 6]

[0044]
[Table 7]

[0045]
Examples of the saccharide used in the present invention include various monosaccharides and polysaccharides, and extracted sugars containing pyridoxal phosphate. Among them, monosaccharides such as fructose and glucose formed a very good complex. Furthermore, honey, syrup, liquid sugar, etc. can be used suitably.
[0046]
The amount of peptide to be used varies depending on the type of garlic (difference in production area), storage period, etc., but in the present invention, about 0.5% to 30.0% per garlic weight is appropriate. It was judged.
[0047]
In addition, in the case of monosaccharides, the amount of carbohydrate added was determined to be about 20% to 200% in consideration of the proper amount necessary for the chemical reaction with garlic, as well as the taste and texture of the finished product. . In addition, when a mixture of peptide and carbohydrate was used, the blending range was almost the same as the above blending amounts.
[0048]
The odorless garlic produced as described above can be used as a food or drink per se, or can be used by mixing with other food or drink, and any type of food or drink is included in the present invention.
[0049]
In the odorless garlic according to the present invention, only the odor component is selectively removed, and the medicinal component is not slightly changed, so it can be prepared in an appropriate form and used as a normal food or drink. In addition, it can be widely used as specific health foods, functional foods, health foods, and nutritional foods.
[0050]
For example, especially for odorless garlic obtained by using sugar, it can be made into a jam-like paste food, obtained by suspending odorless garlic or subjecting it to water mixing and filtering or centrifuging it. A liquid or suspended health drink can be obtained by using Kiyobe. Moreover, it can also be set as the health food of a powder form, a tablet form, and a capsule form.
[0051]
Furthermore, odorless garlic can be blended with itself and / or other commonly used ingredients to make liquid, paste, or powder seasonings, and various other dishes for meat dishes such as yakiniku. As a seasoning, it can be used freely in restaurants, factories, and even at home.
[0052]
Hereinafter, production examples and examples of the present invention will be described.
[0053]
[Production Example 1]
Fresh sardines were processed with a deboner and minced. The minced fish quality was divided into 10 kg surimi. After pulverizing this with a pulverizer, an equal amount of water was added and heated to 45 to 48 ° C., transferred to a stirring tank, and kept at the same temperature for 2 to 3 hours for self-digestion decomposition. The pH was then adjusted to 4.1.
[0054]
A 0.1% solution of Denateam (commercial name of commercial protease preparation) was added thereto, and kept at 45 ° C. for 17 hours for enzymatic degradation. Neutralized and then boiled for 15 minutes to deactivate the enzyme.
[0055]
This is filtered through a vibe screen (150 mesh), the filtrate is treated with a jet at 5000 rpm, then treated with a sharp press centrifuge (15000 rpm), concentrated at room temperature to 20 Bx, and again subjected to a sharp press centrifuge treatment. (15000 rpm) to obtain a peptide stock solution (DAN-No. 2).
[0056]
The peptide stock solution (pH 6.22) obtained above was 1840 ml. To this was added 100 g of activated carbon, and the mixture was stirred for 60 minutes and filtered to obtain 1500 ml of a filtrate (pH 6.12).
100 ml of the filtrate was taken, 2000 ml of cold methanol was added thereto, and left in a cold room for 60 minutes to cause precipitation. Water was added to the resulting precipitate to obtain a solution (E).
[0057]
100 ml of the solution (E) was taken and injected into a column (diameter 5 cm × length 15 cm) packed with Dowex 50W [H +]. The resin was washed with 2000 ml of water and eluted with 250 ml of 2N-NH ₄ OH. The obtained eluate was lyophilized after removing ammonia by a conventional method to obtain a white powder of peptide DAN-100. .
[0058]
[Production Example 2]
After processing fresh sardines with a deboner and collecting meat, 10 kg of the obtained sardine meat was pulverized with a pulverizer, and then added with an equal amount of water and 10 g of Denateam (commercial product name of commercial protease preparation), mixed well, and heated to 45 ° C Auto-digestion and enzymatic degradation were carried out for 4 hours. The reaction was neutralized to pH 7 and then boiled for 15 minutes to deactivate the enzyme.
[0059]
This is filtered through a vibe screen (150 mesh), the filtrate is treated with a jet at 5000 rpm, then treated with a sharp press centrifuge (15000 rpm), concentrated at room temperature to 20 Bx, and again subjected to a sharp press centrifuge treatment. (15000 rpm).
[0060]
The obtained clarified liquid was concentrated 4 times with a vacuum concentrator, the concentrated liquid was subjected to activated carbon filtration, and then diatomaceous earth filtration to obtain a slightly yellowish transparent functional peptide ESP-2 solution.
Moreover, the functional peptide ESP-2 obtained above was lyophilized as it was to obtain a yellowish white functional peptide ESP-2.
[0061]
[Production Example 3]
Fresh sardines were processed with a deboner and minced. Divided fish meat is divided into 10kg surimi, rapidly frozen at -30 ° C or lower, crushed with a pulverizer, added with an equal amount of water, sent to a tank, and heated to 100 ° C for 10 minutes Then, the autolytic enzyme was inactivated and heat denatured. Subsequently, aqueous ammonia was added to adjust the pH to 10.
[0062]
A 0.1% solution of a commercially available alkaline protease product was added thereto, and the mixture was kept at 45 ° C. for 17 hours for enzymatic degradation. The enzyme was then inactivated by boiling for 15 minutes.
[0063]
This was passed through a vibrator screen (150 mesh), treated with a jet at 5000 rpm, then treated with a sharp press centrifuge (15000 rpm), and filtered using diatomaceous earth as a filter aid to obtain a peptide stock solution.
[0064]
1% W / V of activated carbon was added to the peptide stock solution obtained above, and the mixture was stirred at 30 ° C. for 60 minutes and filtered to obtain a filtrate. This was concentrated under reduced pressure (20 ° C.) according to a conventional method and then UHTST sterilized according to a conventional method to obtain an α-1000 (liquid) product, which was further spray-dried according to a conventional method to obtain a particle size of 60 mesh. Α-1000 (powder) products were obtained and each of these products was stored frozen.
[0065]
The peptide α-1000 (powder) thus prepared was subjected to gel filtration under the following conditions using a Sephadex G-25 column. As a result, it was found that the molecular weight was 200 to 10,000. Column size: diameter 16 × 950 mm, eluent: 0.1 M phosphate buffer (pH 7.0), fraction: 2 ml / tube, flow rate: 10 ml / h, molecular weight marker: bacitracin (molecular weight 1450).
[0066]
The α-1000 (liquid) obtained as described above has a water content of 73.6% (vacuum drying method), is light yellow, and the 10% solution has a pH of 7.5 and fish odor There was no bitterness. As a result of measuring the amino acid composition, the results shown in Table 8 below were obtained.
[0067]
[Table 8]

[0068]
[Example 1]
Soak 2.0 kg of raw garlic in warm water at 30 ° C. for 10 hours. After peeling in running water, steam over boiling water. For the first 5 minutes, the temperature of the garlic balls is controlled to 50 ° C. to 55 ° C., and then the temperature is raised. After confirming that the product temperature is 85 ° C. or higher, immediately remove the garlic balls and place them in a high speed homogenizer (8000 rpm). At the same time, the mixture is mixed with 200 g of fish peptide and homogenized at a mixing temperature of 70 ° C. for 5 minutes to form a uniform garlic paste. There was no “garlic odor” in the product, and no “garlic odor” was observed after sealing it and storing it at room temperature and in a refrigerator for 12 months.
[0069]
[Comparison experiment]
The determination of the deodorizing effect was performed by sensory evaluation by 15 trained panelists and analyzing the amount of diallyl disulfide, which is one of the representative components of garlic malodor, by gas chromatography.
[0070]
(sensory evaluation)
In sensory evaluation, the intensity of garlic odor between the product produced by the method according to the present invention and the case where only garlic was treated (control product) was evaluated in 6 stages according to the criteria shown below, and 15 panelists were used. A comparison was made between the two.
0 ... No garlic odor at all.
1 ... Almost no garlic odor.
2 ... I feel a little garlic odor.
3 ... Slightly smells of garlic.
4 ... Strongly smells of garlic.
5 ... The garlic odor is very strong.
[0071]
The obtained results are shown in Table 9 below. As is apparent from the results, it was shown that the garlic odor was deodorized in the product of the present invention.
[0072]
[Table 9]

[0073]
(Gas chromatography analysis)
Diallyl disulfide was analyzed under the following conditions.
Model: Gaskuro Shimadzu Corporation GC-9A
Liquid phase: FAL-M
Carrier: Shimalite TPA
Analysis temperature: 70 ° C
Carrier gas: N ₂
Detector: FPD
[0074]
10 g of the product of the present invention and the control product were collected in a 50 ml vial and left at 80 ° C. for 15 minutes. Thereafter, 5 ml of headspace gas was collected and subjected to gas chromatography under the above conditions.
[0075]
According to the results of analysis of diallyl disulfide by gas chromatography, FIGS. 4 and 5, the peak of diallyl disulfide on the gas chromatograph is observed in the control product (FIG. 5), whereas the product of the present invention. In the case of FIG. 4 (FIG. 4), it is hardly detected.
[0076]
Diallyl disulfide is known as a representative component that emits a strong odor among garlic odors, and is also known to have a high proportion of garlic odors. In this test, sensory evaluation and gas chromatography Since the quantitative results were consistent and showed good results, it was clearly confirmed that the garlic odor was deodorized by the production method according to the present invention.
[0077]
In this example, the same treatment was repeated using the peptides DAN-100 and ESP-2 produced in Production Examples 1 and 2 instead of fish peptide (Production Example 3: α-1000). As a result, excellent odorless garlic was obtained. was gotten.
[0078]
[Example 2]
Soak 2.0 kg of raw garlic in warm water at 40 ° C. for 5 hours. After peeling in running water, steam over boiling water. First, heat the garlic balls at a temperature of 50 ° C to 55 ° C for 5 minutes, raise the temperature, confirm that the product temperature is 85 ° C or higher, take it out immediately, and place it in a high-speed homogenizer (8000 rpm). At the same time, it is mixed with 1.0 kg of pre-warmed honey and homogenized for 5 minutes at a mixing temperature of 70 ° C. to make a uniform garlic paste. There was no “garlic odor” in the product, and no “garlic odor” was observed after sealing it and storing it at room temperature and in a refrigerator for 12 months.
[0079]
The obtained garlic paste was jam-like and had a light sweetness and could be ingested as it was or applied to bread.
[0080]
[Example 3]
Soak 2.0 kg of raw garlic in warm water at 40 ° C. for 5 hours. After peeling in running water, steam over boiling water. For 5 minutes from the beginning, the product temperature of the garlic balls was controlled to 50 ° C. to 55 ° C. and then heated. After confirming that the product temperature reached 85 ° C. or higher, the product was taken out immediately and a high-speed homogenizer (8000 rpm) At the same time, the mixture is mixed with 200 g of fish peptide and 1.0 kg of pre-warmed honey, and homogenized for 5 minutes at a mixing temperature of 70 ° C. to make a uniform garlic paste. There was no “garlic odor” in the product, and no “garlic odor” was observed after sealing it and storing it at room temperature and in a refrigerator for 12 months.
[0081]
As a result of repeating the same treatment using the peptides DAN-100 and ESP-2 produced in Production Examples 1 and 2 as fish peptide (Production Example 3: α-1000), excellent odorless garlic was obtained.
[0082]
[Example 4: Drink]
Two times the amount of water was added to the garlic paste obtained in Example 3, and after filtration, a healthy drink having the following composition was prepared using the filtrate.
(composition)
Odorless garlic filtrate 70 parts Liquid sugar 20 parts Vitamin MIX 6 parts Fragrance 2 parts Na citrate 2 parts This was packed in a 150 ml brown bottle and sterilized.
In addition, using the peptide α-1000 (liquid) obtained in Production Example 3 instead of the garlic filtrate, a health drink was similarly prepared using odorless garlic obtained by the same treatment.
[0083]
[Example 5: Health food preparation]
First, the following raw materials were thoroughly stirred and mixed.
Odorless garlic filtrate 60 parts Lactose 30 parts Glucose 8 parts CMC 2 parts This mixture was freeze-dried and ground, and then 2 g each of 100 mesh pass fractions were packaged.
[0084]
[Example 6: Health food capsule]
Add 5 parts of vitamin MIX, 0.1 part of magnesium oxide, 2.5 parts of powdered alcohol and 1.0 part of powdered fragrance to 91.4 parts of the powder product of Example 5 and mix well. This was a capsule preparation.
[0085]
[Example 7: Health food tablet]
Add 5 parts of vitamin MIX, 2 parts of crystalline citric acid, 4 parts of corn starch, 1 part of magnesium stearate and 0.3 part of fragrance to 87.7 parts of the powder product of Example 5 and mix well. A tablet was obtained.
[0086]
[Example 8: Pasty seasoning]
Odorless garlic paste (Example 1) 85 parts salt 8 parts powder soy sauce 4.5 parts yeast extract 2.5 parts or more of ingredients were mixed well and packed in a tube to give a paste-like seasoning.
[0087]
【The invention's effect】
A new garlic-free bromide system has been developed by the present invention. The odorless garlic obtained by the present invention is not only completely deodorized, but also has no problem in terms of safety, and since it returns to its original medicinal component after ingestion, it is physiologically active. But there is no problem at all.
[0088]
Therefore, the odorless garlic according to the present invention can be directly ingested itself, formulated into various forms or made into various types of foods and drinks, normal foods and drinks, specified health foods, functional foods and drinks, health It can be used for various purposes as food, nutrients, health drinks, paste foods, seasonings and the like.
[Brief description of the drawings]
FIG. 1 shows the molecular weight distribution of functional peptide ESP-2 by gel filtration.
FIG. 2 shows the UV spectrum of ESP-2.
FIG. 3 shows an IR spectrum of ESP-2.
FIG. 4 shows a gas chromatogram of the product of the present invention.
FIG. 5 shows a gas chromatogram of a control product.

Claims (6)

  Activate alliinase in garlic to promote enzymatic degradation to produce sulfurized components of garlic, increase the temperature at or near the end of enzymatic degradation and deactivate the enzyme at the same time or immediately before or immediately as possible, Odorless garlic, which is obtained by adding and mixing peptides and / or carbohydrates and bringing them into contact uniformly and combining them to make them non-volatile.   A food or drink comprising the odorless garlic according to claim 1.   The food / beverage product according to claim 2, wherein the food / beverage product is a jam-like paste food.   The food or drink according to claim 2, wherein the food or drink is a health drink in the form of a solution and / or a suspension.   The food / beverage product according to claim 2, wherein the food / beverage product is a powder, tablet, and / or capsule health food.   The food / beverage product according to claim 2, wherein the food / beverage product is a liquid, pasty and / or powdery seasoning.

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