JP2020129988A - Green tea extract composition and food/drink - Google Patents
Green tea extract composition and food/drink Download PDFInfo
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- JP2020129988A JP2020129988A JP2019024143A JP2019024143A JP2020129988A JP 2020129988 A JP2020129988 A JP 2020129988A JP 2019024143 A JP2019024143 A JP 2019024143A JP 2019024143 A JP2019024143 A JP 2019024143A JP 2020129988 A JP2020129988 A JP 2020129988A
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- cyclic
- cellooligosaccharide
- green tea
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- 229940094952 green tea extract Drugs 0.000 title abstract description 21
- 235000020688 green tea extract Nutrition 0.000 title abstract description 21
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- 230000000873 masking effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002953 preparative HPLC Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 235000021067 refined food Nutrition 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 235000021055 solid food Nutrition 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000005017 substituted alkenyl group Chemical group 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 125000005346 substituted cycloalkyl group Chemical group 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 125000001981 tert-butyldimethylsilyl group Chemical group [H]C([H])([H])[Si]([H])(C([H])([H])[H])[*]C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000002088 tosyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])S(*)(=O)=O 0.000 description 1
- 125000004665 trialkylsilyl group Chemical group 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
Abstract
Description
本発明は、緑茶抽出組成物および飲食品に関する。 The present invention relates to green tea extraction compositions and foods and drinks.
緑茶にはカテキン類が含まれている。このカテキン類には強い抗酸化力や抗菌効果が認められており、加えて、人体への生理活性効果として、動脈硬化やアレルギーの防止効果等の作用についても研究が行われている。このため、近年、飲料や加工食品等の飲食品への緑茶抽出成分の添加が検討されている。 Green tea contains catechins. These catechins have been found to have strong antioxidant and antibacterial effects, and in addition, studies have been conducted on their effects such as arteriosclerosis and allergy prevention effects as physiologically active effects on the human body. For this reason, in recent years, the addition of green tea extract components to foods and drinks such as beverages and processed foods has been studied.
しかし、上記のカテキン類のうち、特に緑茶から抽出されたものは、強い渋味、苦味を有していることから、飲食品に添加する場合に量的な制限があり、大量に添加することができないという問題がある。 However, among the above catechins, those extracted from green tea in particular have a strong astringency and bitterness, so that there is a quantitative limit when adding them to foods and drinks, and a large amount should be added. There is a problem that it cannot be done.
このような問題点に対して、各種のマスキング物質を添加して緑茶抽出物の渋味、苦味を抑制することが検討されている。 To solve such problems, it has been studied to add various masking substances to suppress the astringency and bitterness of the green tea extract.
例えば、以下の特許文献１、２には、茶の抽出物にシクロデキストリンを添加することによって包接し、カテキンのもつ苦味、渋味のマスキングを行うことが開示されている。 For example, Patent Documents 1 and 2 below disclose that the tea extract is encapsulated by adding cyclodextrin to mask the bitterness and astringency of catechin.
また、特許文献３、４には、乳由来タンパク質溶液を用いて茶を抽出することが開示されており、乳由来タンパク質溶液としてカゼインナトリウム溶液が例示されている。また、特許文献３ には、この製造方法によってタンニン成分の漏出が少なく渋味を調整できることが開示されている。 Further, Patent Documents 3 and 4 disclose that tea is extracted using a milk-derived protein solution, and a casein sodium solution is exemplified as a milk-derived protein solution. Further, Patent Document 3 discloses that the astringency can be adjusted with less leakage of the tannin component by this production method.
しかし、上記の従来技術に開示されているシクロデキストリンやカゼインは、それらを単独で添加しても、カテキン類に対する苦味、渋味の抑制効果が充分に得られなかった。このため、飲食品に対して充分な量のカテキン類を添加すると、苦味、渋味が生じて飲食品の風味が損なわれるという問題があった。また、開示されたシクロデキストリンやカゼインを多量に添加すると、それらの風味が強くなりすぎて、飲食品自体の風味が損なわれるという問題があった。 However, the cyclodextrins and caseins disclosed in the above-mentioned prior art did not sufficiently suppress the bitterness and astringency of catechins even when they were added alone. Therefore, when a sufficient amount of catechins is added to foods and drinks, there is a problem that bitterness and astringency occur and the flavor of foods and drinks is impaired. Further, when a large amount of the disclosed cyclodextrin or casein is added, the flavor thereof becomes too strong, and there is a problem that the flavor of the food or drink itself is impaired.
この発明は、上述の課題を解決するためになされたもので、その目的は、緑茶の苦味および渋味を低減した緑茶抽出組成物および飲食品を提供することである。 The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a green tea extraction composition and foods and drinks in which the bitterness and astringency of green tea are reduced.
上記課題を解決するために、本発明の緑茶抽出組成物は、下記一般式（１）で表される環状オリゴ糖と、緑茶の抽出物とを含有する。ただし、一般式（１）中、Ｒは水素原子又はその置換基を示し、複数のＲは同一でも異なってもよく、ｎは０〜３の整数を示す。 In order to solve the above problems, the green tea extraction composition of the present invention contains a cyclic oligosaccharide represented by the following general formula (1) and a green tea extract. However, in the general formula (1), R represents a hydrogen atom or a substituent thereof, and a plurality of Rs may be the same or different, and n represents an integer of 0 to 3.
本発明によれば、緑茶の苦味および渋味を低減した緑茶抽出組成物および飲食品を提供することができる。 According to the present invention, it is possible to provide a green tea extraction composition and foods and drinks in which the bitterness and astringency of green tea are reduced.
［環状セロオリゴ糖］
まず、本実施の形態に係る、上記一般式（１）により示される環状オリゴ糖（環状セロオリゴ糖とも称する）について詳細に説明する。
[Cyclic cellooligosaccharide]
First, the cyclic oligosaccharide represented by the general formula (1) (also referred to as cyclic cello-oligosaccharide) according to the present embodiment will be described in detail.
従来、環状オリゴ糖としてシクロデキストリンが知られている。シクロデキストリンは、下記一般式（×）で表されるように（式中のｍは１〜３の整数）、グルコースがα−１，４グルコシド結合により連結された環状構造を持つものであり、一般に６個のグルコースが結合したα−シクロデキストリンと、７個のグルコースが結合したβ−シクロデキストリンと、８個のグルコースが結合したγ−シクロデキストリンがある。 Conventionally, cyclodextrin is known as a cyclic oligosaccharide. Cyclodextrin has a cyclic structure in which glucose is linked by an α-1,4 glucoside bond, as represented by the following general formula (x) (m in the formula is an integer of 1 to 3). Generally, there are α-cyclodextrin in which 6 glucoses are bound, β-cyclodextrin in which 7 glucoses are bound, and γ-cyclodextrin in which 8 glucoses are bound.
これに対して、本実施形態に係る環状セロオリゴ糖は、上記一般式（１）で表される化合物であり、グルコース又はその誘導体である構成単位がβ−１，４グルコシド結合により連結された環状構造を持つ。式（１）中のｎは０〜３の整数を示し、そのため、式（１）で表される環状オリゴ糖は、上記構成単位の５量体、６量体、７量体、８量体、又はこれらの２種以上の混合物である。 On the other hand, the cyclic cellooligosaccharide according to the present embodiment is a compound represented by the above general formula (1), and the structural unit which is glucose or a derivative thereof is linked by a β-1,4 glucoside bond. Has a structure. N in the formula (1) represents an integer of 0 to 3, and therefore, the cyclic oligosaccharide represented by the formula (1) is a pentamer, hexamer, hepato, or octamer of the above-mentioned structural units. , Or a mixture of two or more of these.
本発明の実施形態に係る環状セロオリゴ糖は、たとえば、後述のように、下記一般式（２）で表されるオリゴ糖の末端のヒドロキシ基同士を結合させて環化させる等により得られる。ただし、式（２）中、Ｒは水素原子又はその置換基を示し、複数のＲは同一でも異なってもよく、ｋは３〜６の整数を示す。
The cyclic cellooligosaccharide according to the embodiment of the present invention can be obtained, for example, by binding and cyclizing the terminal hydroxy groups of the oligosaccharide represented by the following general formula (2), as described later. However, in the formula (2), R represents a hydrogen atom or a substituent thereof, and a plurality of Rs may be the same or different, and k represents an integer of 3 to 6.
式（１）中のＲが全て水素原子の場合、下記式（３）で表される、化学修飾されていない（即ち、非置換の）環状オリゴ糖である（ここで、式（３）中のｎは０〜３の整数を示す。）。 When all Rs in the formula (1) are hydrogen atoms, it is an unmodified (that is, unsubstituted) cyclic oligosaccharide represented by the following formula (3) (here, in the formula (3)). N indicates an integer from 0 to 3).
式（３）の環状オリゴ糖は、上記式（×）のシクロデキストリンとはグルコース間の連結構造がβ−１，４結合とα−１，４結合との点で異なるのみであるため、基本的に、シクロデキストリンに適用される公知の化学修飾法を用いて置換基を導入することができる。そのため、式（１）の環状オリゴ糖は、公知のシクロデキストリンの置換基と同様の置換基を持つことができる。 The cyclic oligosaccharide of the formula (3) is basically different from the cyclodextrin of the above formula (x) only in that the linking structure between glucose is β-1,4 bond and α-1,4 bond. Thus, the substituents can be introduced using known chemical modification methods applied to cyclodextrin. Therefore, the cyclic oligosaccharide of the formula (1) can have a substituent similar to that of a known cyclodextrin substituent.
式（１）中のＲは、上記のように全てが水素原子でもよく、全てが置換基でもよく、水素原子と置換基が共存してもよい。共存する場合、両者の比率は特に限定されない。例えば、ＯＲをグルコース構成単位の１級ヒドロキシ基に相当する基（ＯＲ１）と２級ヒドロキシ基に相当する基（ＯＲ２）とに区別して、式（１）を下記一般式（１−１）の通りに書き換えたとき、Ｒ１の全てが置換基でＲ２の全てが水素原子でもよく、Ｒ１の一部が置換基でＲ１の残部及びＲ２の全部が水素原子でもよく、Ｒ１の全て及びＲ２の一部が置換基でＲ２の残部が水素原子でもよい。また、Ｒ２の全てが置換基でＲ１の全てが水素原子でもよく、Ｒ２の一部が置換基でＲ２の残部及びＲ１の全部が水素原子でもよく、Ｒ２の全部及びＲ１の一部が置換基でＲ１の残部が水素原子でもよい。更には、Ｒ１とＲ２の双方で一部が置換基で残部が水素原子でもよい。 As described above, all of Rs in the formula (1) may be hydrogen atoms, all of them may be substituents, and hydrogen atoms and substituents may coexist. When coexisting, the ratio of the two is not particularly limited. For example, OR is divided into a group corresponding to a primary hydroxy group of a glucose constituent unit (OR 1 ) and a group corresponding to a secondary hydroxy group (OR 2 ), and the formula (1) is divided into the following general formula (1-1). when rewritten as described), all R 2 in all the substituents of R 1 are may be a hydrogen atom, all of the remainder and R 2 R 1 in part substituents of R 1 are may be a hydrogen atom, some all and R 2 R 2 substituents remainder of R 1 may be hydrogen atoms. Moreover, all all R 2 is R 1 in substituent may be a hydrogen atom, all of the remainder and R 1 R 2 in part substituents of R 2 are may be a hydrogen atom, all of R 2 and R A part of 1 may be a substituent and the rest of R 1 may be a hydrogen atom. Further, in both R 1 and R 2 , a part may be a substituent and the rest may be a hydrogen atom.
式（１）中のＲとして示される置換基は、グルコースのヒドロキシ水素を置換する基であり、グルコースのヒドロキシ水素から１又は複数の反応を経て誘導可能な各種の基が挙げられる。 The substituent represented by R in the formula (1) is a group that replaces the hydroxy hydrogen of glucose, and examples thereof include various groups that can be derived from the hydroxy hydrogen of glucose through one or more reactions.
具体的には、Ｒとして示される置換基（以下、置換基Ｒという。）としては、置換又は無置換のアルキル基、置換又は無置換のシクロアルキル基、置換又は無置換のアルケニル基、置換又は無置換のシクロアルケニル基、置換又は無置換のアリール基（例えば、フェニル基、トリル基など）、置換又は無置換のアラルキル基（例えば、ベンジル基、フェネチル基、トリチル基など）、アシル基、シリル基、スルホニル基、糖残基、置換又は非置換のポリオキシアルキレン基などが挙げられる。置換基Ｒの炭素数としては特に限定されず、例えば１〜４０でもよく、１〜３０でもよく、１〜２０でもよい。 Specifically, the substituent represented by R (hereinafter referred to as Substituent R) includes a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted group. Unsubstituted cycloalkenyl group, substituted or unsubstituted aryl group (eg, phenyl group, tolyl group, etc.), substituted or unsubstituted aralkyl group (eg, benzyl group, phenethyl group, trityl group, etc.), acyl group, silyl group. Examples include groups, sulfonyl groups, sugar residues, substituted or unsubstituted polyoxyalkylene groups and the like. The carbon number of the substituent R is not particularly limited, and may be, for example, 1 to 40, 1 to 30, or 1 to 20.
置換基Ｒの例である上記置換アルキル基、置換シクロアルキル基、置換アルケニル基、置換シクロアルケニル基、置換アリール基、置換アラルキル基としては、例えば、ヒドロキシアルキル基のように置換基としてヒドロキシ基を有するもの、スルホアルキル基又はその塩もしくはエステル基のように置換基としてスルホ基又はその誘導体基を有するもの、カルボキシメチル基又はその塩もしくはエステル基のように置換基としてカルボキシ基
又はその誘導体基を有するものなどが挙げられる。ここでのエステル基を構成する炭化水素基としては、例えば、炭素数１〜２０のアルキル基、炭素数３〜２０のシクロアルキル基が挙げられる。
Examples of the substituent R, such as the above-mentioned substituted alkyl group, substituted cycloalkyl group, substituted alkenyl group, substituted cycloalkenyl group, substituted aryl group and substituted aralkyl group, include a hydroxy group as a substituent such as a hydroxyalkyl group. Those having a sulfo group or a derivative group thereof as a substituent such as a sulfoalkyl group or a salt thereof or an ester group, and a carboxy group or a derivative group thereof as a substituent such as a carboxymethyl group or a salt or ester group thereof. Examples include those that have. Examples of the hydrocarbon group constituting the ester group here include an alkyl group having 1 to 20 carbon atoms and a cycloalkyl group having 3 to 20 carbon atoms.
置換基Ｒの例である上記アシル基としては、例えば、アセチル基やベンゾイル基のように−ＯＲ中の酸素原子とエステル結合を形成するモノカルボン酸の残基（例えば、Ｒ：−ＣＯ−Ｑ１）でもよく、また、コハク酸などのジカルボン酸の残基でもよく、ジカルボン酸残基の場合、グルコースとエステル結合していない方のカルボキシ基は酸型でも金属塩でもエステル基を形成してもよい（例えば、Ｒ：−ＣＯ−Ｑ２−ＣＯＯ−Ｑ３）。ここで、Ｑ１は、水素原子又は炭素数１〜１０（好ましくは１〜６）の有機基を示し、有機基としては、アルキル基、シクロアルキル基、アルケニル基、シクロアルケニル基、アリール基、アラルキル基が挙げられる。Ｑ２は、炭素数１〜６の炭化水素基（例えばアルカンジイル基など）を示す。Ｑ３は、水素原子、アルカリ金属又は炭素数１〜１０（好ましくは１〜６）の有機基を示し、有機基としては、アルキル基、シクロアルキル基、アルケニル基、シクロアルケニル基、アリール基、アラルキル基が挙げられる。 Examples of the acyl group, which is an example of the substituent R, include a residue of a monocarboxylic acid (for example, R: -CO-Q) that forms an ester bond with an oxygen atom in −OR, such as an acetyl group or a benzoyl group. 1 ) may be used, or a residue of a dicarboxylic acid such as succinic acid may be used. In the case of a dicarboxylic acid residue, the carboxy group that is not ester-bonded to glucose forms an ester group in either an acid form or a metal salt. It may be (for example, R: -CO-Q 2- COO-Q 3 ). Here, Q 1 represents a hydrogen atom or an organic group having 1 to 10 carbon atoms (preferably 1 to 6), and examples of the organic group include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, and an aryl group. Aralkill group can be mentioned. Q 2 is a hydrocarbon group having 1 to 6 carbon atoms (e.g., alkanediyl group). Q 3 are hydrogen atom, an organic group of alkali metal or C1-10 (preferably 1-6), examples of the organic group, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, Aralkill group can be mentioned.
置換基Ｒの例である上記シリル基としては、例えば、ｔｅｒｔ−ブチルジメチルシリル基などのトリアルキルシリル基が挙げられる。また、上記スルホニル基としては、例えば、ｐ−トルエンスルホニル基などのアリールスルホニル基などが挙げられる。更に、糖残基としては、例えば、グルコシル基、マントシル基などが挙げられる。 Examples of the silyl group as an example of the substituent R include a trialkylsilyl group such as a tert-butyldimethylsilyl group. Moreover, as the said sulfonyl group, for example, an arylsulfonyl group such as a p-toluenesulfonyl group and the like can be mentioned. Further, examples of the sugar residue include a glucosyl group and a mantosyl group.
置換基Ｒの例である上記置換又は非置換のポリオキシアルキレン基としては、ポリオキシエチレン基などの炭素数１〜４のオキシアルキレンの繰り返し単位を持つ基が挙げられ、末端のＯＨは、アミノ基やアジド基、トリチル基などの置換基で置換されていてもよい。なお、オキシアルキレン基の繰り返し数は特に限定されず、例えば２〜２０でもよい。 Examples of the substituent R as the above-mentioned substituted or unsubstituted polyoxyalkylene group include a group having a repeating unit of oxyalkylene having 1 to 4 carbon atoms such as a polyoxyethylene group, and the terminal OH is amino. It may be substituted with a substituent such as a group, an azide group, or a trityl group. The number of repetitions of the oxyalkylene group is not particularly limited, and may be, for example, 2 to 20.
以上列挙した置換基Ｒは、式（１）中の複数のＲについて、いずれか１種のみが導入されてもよく、２種以上組み合わせて導入されてもよい。 As the substituents R listed above, only one of the plurality of Rs in the formula (1) may be introduced, or two or more of them may be introduced in combination.
本実施形態に係るβ−１，４グルコシド結合を持つ環状オリゴ糖は、上記一般式（２）で表されるオリゴ糖の末端のヒドロキシ基同士を結合させて環化させる工程を経て製造することができる。式（２）中のＲは水素原子又はその置換基を示す。式（２）のＲで示される置換基としては、上述した式（１）の置換基と同様のものを例示することができ、好ましくは、Ｒはアルキル基又はアシル基であり、例えば、式（２）中のＯＲは、グルコースのヒドロキシ基をアシル化（より好ましくはアセチル化）したもの（即ち、アシルオキシ基、好ましくはアセチルオキシ基）、グルコースのヒドロキシ基をアルキル化（より好ましくはメチル化）したもの（即ち、アルコキシ基、好ましくはメトキシ基）が挙げられる。 The cyclic oligosaccharide having a β-1,4 glucoside bond according to the present embodiment is produced through a step of binding and cyclizing the hydroxy groups at the ends of the oligosaccharide represented by the above general formula (2). Can be done. R in the formula (2) represents a hydrogen atom or a substituent thereof. As the substituent represented by R in the formula (2), the same substituents as those in the above-mentioned formula (1) can be exemplified, and R is preferably an alkyl group or an acyl group, for example, the formula. The OR in (2) is an acylated (more preferably acetylated) hydroxy group of glucose (that is, an acyloxy group, preferably an acetyloxy group), and an alkylated (more preferably methylated) hydroxy group of glucose. ) (That is, an alkoxy group, preferably a methoxy group).
一実施形態に係る環状オリゴ糖としてセルロース由来の環状セロオリゴ糖を製造する方法について、図１に基づき説明する。 A method for producing a cellulose-derived cyclic cellooligosaccharide as the cyclic oligosaccharide according to the embodiment will be described with reference to FIG.
図１に示す製造方法では、まず、式（４）で表されるセルロースをアセチル化する（ここで、式中のｐはセルロースにおけるグルコース２分子分の繰り返し数に相当する数である）。セルロースは、グルコースがβ−１，４グルコシド結合により連結された構造を持ち、隣接するグルコースユニットは互いに裏返しになって一列に並び直鎖状の構造をとっている。そのため、セルロースは強固な分子内、分子間水素結合を有し、水に不溶である。かかるセルロースのヒドロキシ基をアセチル化して水素結合を消失させることで分子鎖に柔軟性を付与する。なお、部分的にアセチル化されたセルロースを出発原料として用いてもよい。 In the production method shown in FIG. 1, first, the cellulose represented by the formula (4) is acetylated (where p in the formula is a number corresponding to the number of repetitions of two glucose molecules in the cellulose). Cellulose has a structure in which glucose is linked by β-1,4 glucoside bonds, and adjacent glucose units are turned upside down and arranged in a line to form a linear structure. Therefore, cellulose has strong intramolecular and intermolecular hydrogen bonds and is insoluble in water. The hydroxy group of such cellulose is acetylated to eliminate hydrogen bonds, thereby imparting flexibility to the molecular chain. In addition, partially acetylated cellulose may be used as a starting material.
アセチル化は、例として、過塩素酸の存在下、セルロースに無水酢酸を反応させることにより行うことができる（例えば、P. Arndt et al., Cellulose,2005, 12, 317.を参照）。アセチル化により、セルロースの各構成単位の３つのヒドロキシ基を全てアセチル化した、式（５）で表される三酢酸セルロース（完全アセチル化セルロース）が得られる。 Acetylation can be carried out, for example, by reacting cellulose with acetic anhydride in the presence of perchloric acid (see, eg, P. Arndt et al., Cellulose, 2005, 12, 317.). By acetylation, cellulose triacetate (fully acetylated cellulose) represented by the formula (5) is obtained by acetylating all three hydroxy groups of each constituent unit of cellulose.
次いで、三酢酸セルロースに対してグルコシド結合の開裂を行うことで、式（６）で表される部分アセチル化セロオリゴ糖を合成する。グルコシド結合の開裂は、三酢酸セルロースに濃硫酸を加えることにより行うことができる（例えば、H. Namazi et al., J. Appl. Polym. Sci., 2008, 110, 4034.、及び、T. Kondo, D. G. Gray, J. Appl. Polym. Sci. 1992, 45, 417を参照）。そして、開裂後に分離精製することで、式（６）に示されるように、５〜８個のグルコースユニットを有し、その両末端のグルコースユニットの１位と４位にヒドロキシ基を有し、その他のヒドロキシ基は全てアセチル化された構造をもつ鎖状の部分アセチル化セロオリゴ糖が得られる。式（６）のセロオリゴ糖は、上記式（２）で表されるオリゴ糖において、−ＯＲが−Ｏ−Ａｃのものである（ここで、Ａｃはアセチル基）。 Next, the partially acetylated cellooligosaccharide represented by the formula (6) is synthesized by cleaving the glucoside bond with cellulose triacetate. Cleavage of the glucoside bond can be performed by adding concentrated sulfuric acid to cellulose triacetate (eg, H. Namazi et al., J. Appl. Polym. Sci., 2008, 110, 4034., And T. et al. See Kondo, DG Gray, J. Appl. Polym. Sci. 1992, 45, 417). Then, by separating and purifying after cleavage, as shown in the formula (6), it has 5 to 8 glucose units, and has hydroxy groups at the 1st and 4th positions of the glucose units at both ends. A chain-like partially acetylated cellooligosaccharide having an acetylated structure is obtained for all other hydroxy groups. The cellooligosaccharide of the formula (6) has an -OR of -O-Ac in the oligosaccharide represented by the above formula (2) (where Ac is an acetyl group).
次いで、式（６）で表される部分アセチル化セロオリゴ糖の両末端のヒドロキシ基同士を結合させて環化させる。環化方法は、特に限定されず、例えば式（６）で表される部分アセチル化セロオリゴ糖の末端の１位ヒドロキシ基をトリクロロアセトイミデート化してから環化反応させてもよい。トリクロロアセトイミデート化は、部分アセチル化セロオリゴ糖にトリクロロアセトニトリルを反応させることで行うことができ、次いで、トリクロロアセトイミデート化した部分アセチル化セロオリゴ糖に、三フッ化ホウ素ジエチルエーテル錯体を加えて反応させることにより、両末端のグルコースユニットがβ−１，４グルコシド結合により連結されて環状になる。 Next, the hydroxy groups at both ends of the partially acetylated cellooligosaccharide represented by the formula (6) are bonded to each other for cyclization. The cyclization method is not particularly limited, and for example, the 1-position hydroxy group at the terminal of the partially acetylated cellooligosaccharide represented by the formula (6) may be trichloroacetoimidate and then undergo a cyclization reaction. Trichloroacetoimidate can be performed by reacting partially acetylated cellooligosaccharide with trichloroacetonitrile, and then adding boron trifluoride diethyl ether complex to trichloroacetoimidate partially acetylated cellooligosaccharide. By reacting, the glucose units at both ends are linked by β-1,4 glucoside bonds to form a ring.
なお、トリクロロアセトイミデート化することなく、部分アセチル化セロオリゴ糖に三フッ化ホウ素ジエチルエーテル錯体を加えて反応させることにより、両末端のグルコースユニットをβ−１，４グルコシド結合により連結して環状にしてもよい。 By adding a boron trifluoride diethyl ether complex to a partially acetylated cellooligosaccharide and reacting it without trichloroacetoimidate, the glucose units at both ends are linked by β-1,4 glucoside bonds and cyclic. It may be.
これにより、式（７）で表されるアセチル化環状セロオリゴ糖が得られる。式（７）のアセチル化環状セロオリゴ糖は、上記式（１）で表される環状オリゴ糖において、−ＯＲが全て−Ｏ−Ａｃのものである。 As a result, the acetylated cyclic cellooligosaccharide represented by the formula (7) is obtained. The acetylated cyclic cellooligosaccharide of the formula (7) is a cyclic oligosaccharide represented by the above formula (1) and has all -OR of -O-Ac.
次いで、式（７）で表されるアセチル化環状セロオリゴ糖のアセチルオキシ基を、例えば塩基触媒（水酸化ナトリウム、トリエチルアミンなど）を用いて加水分解することにより、上記の式（３）で表される環状オリゴ糖が得られる。 Next, the acetyloxy group of the acetylated cyclic cellooligosaccharide represented by the formula (7) is hydrolyzed using, for example, a base catalyst (sodium hydroxide, triethylamine, etc.) to be represented by the above formula (3). Cyclic oligosaccharides are obtained.
図２は、他の実施形態に係る環状オリゴ糖の合成ステップを示した図である。図２の例では、セルロースのヒドロキシ基が部分的にメチル化された、式（１０）で表される部分メチル化セルロースを出発原料として用いて、式（１３）で表されるメチル化環状セロオリゴ糖を合成する。 FIG. 2 is a diagram showing a step of synthesizing a cyclic oligosaccharide according to another embodiment. In the example of FIG. 2, the partially methylated cellulose represented by the formula (10) in which the hydroxy group of the cellulose is partially methylated is used as a starting material, and the methylated cyclic cellooligoe represented by the formula (13) is used as a starting material. Synthesize sugar.
図２に示す製造方法では、まず、部分メチル化セルロースをメチル化して完全メチル化セルロースを合成する。メチル化は、例として、部分メチル化セルロースに水素化ナトリウムとヨードメタンを反応させることにより行うことができる（例えば、J. N. Bemiller, Earle E. Allen, JR., J. Polym. Sci. 1967, 5, 2133.を参照）。これにより、セルロースの各構成単位の３つのヒドロキシ基を全てメチル化した、式（１１）で表される完全メチル化セルロースが得られる。 In the production method shown in FIG. 2, first, partially methylated cellulose is methylated to synthesize fully methylated cellulose. Methylation can be carried out, for example, by reacting partially methylated cellulose with sodium hydride and iodomethane (eg, JN Bemiller, Earle E. Allen, JR., J. Polym. Sci. 1967, 5, 2133.). As a result, fully methylated cellulose represented by the formula (11) is obtained in which all three hydroxy groups of each structural unit of cellulose are methylated.
次いで、完全メチル化セルロースに対してグルコシド結合の開裂を行うことで、式（１２）で表される部分メチル化セロオリゴ糖を合成する。グルコシド結合の開裂は、図１の場合と同様である。そして、開裂後に分離精製することで、式（１２）に示されるように、５〜８個のグルコースユニットを有し、その両末端のグルコースユニットの１位と４位にヒドロキシ基を有し、その他のヒドロキシ基は全てメチル化された構造をもつ鎖状の部分メチル化セロオリゴ糖が得られる。式（１２）のセロオリゴ糖は、上記式（２）で表されるオリゴ糖において、−ＯＲが−Ｏ−Ｍｅのものである（ここで、Ｍｅはメチル基を示す）。 Next, the partially methylated cellooligosaccharide represented by the formula (12) is synthesized by cleaving the glucoside bond to the fully methylated cellulose. Cleavage of the glucoside bond is the same as in FIG. Then, by separation and purification after cleavage, as shown in the formula (12), it has 5 to 8 glucose units, and has hydroxy groups at the 1st and 4th positions of the glucose units at both ends. A chain partially methylated cellooligosaccharide having a structure in which all other hydroxy groups are methylated can be obtained. The cellooligosaccharide of the formula (12) has an -OR of -O-Me in the oligosaccharide represented by the above formula (2) (where Me represents a methyl group).
次いで、式（１２）で表される部分アセチル化セロオリゴ糖の両末端のヒドロキシ基同士を結合させて環化させる。環化方法は、特に限定されず、例えば、部分メチル化セロオリゴ糖にトリフルオロメタンスルホン酸無水物（Ｔｆ２Ｏ）と２，６−ジ−ｔｅｒｔ−ブチルピリジン（ＤＢＰ）を反応させることにより行うことができる。これにより、両末端のグルコースユニットがβ−１，４グルコシド結合により連結されて環状になり、式（１３）で表されるメチル化環状セロオリゴ糖が得られる。このメチル化環状セロオリゴ糖は、上記式（１）で表される環状オリゴ糖において、−ＯＲが全て−Ｏ−Ｍｅのものである。 Next, the hydroxy groups at both ends of the partially acetylated cellooligosaccharide represented by the formula (12) are bonded to each other for cyclization. The cyclization method is not particularly limited, and is, for example, carried out by reacting a partially methylated cellooligosaccharide with trifluoromethanesulfonic anhydride (Tf 2 O) and 2,6-di-tert-butyl pyridine (DBP). Can be done. As a result, the glucose units at both ends are linked by β-1,4 glucoside bonds to form a ring, and a methylated cyclic cellooligosaccharide represented by the formula (13) is obtained. This methylated cyclic cello-oligosaccharide is a cyclic oligosaccharide represented by the above formula (1) and has all -OR of -O-Me.
式（１）で表される環状オリゴ糖において、式中のＲの置換基は、上記のように、基本的にはシクロデキストリンに適用される公知の化学修飾法を用いて導入することができる。例えば、−ＯＲとしてメトキシ基などのアルコキシ基を導入するには、特開昭６１−２００１０１号公報に記載のヒドロキシ基をアルキル化する方法を利用してもよい。また、Ｒが置換アルキル基の場合としてスルホアルキル基やカルボキシメチルエステル基を、エーテル酸素を介して導入するには、特開平１１−６０６１０号公報や特開２０１３−２８７４４号公報に記載の方法を利用してもよい。また、Ｒがアシル基の場合としてコハク酸などのジカルボン酸の残基を導入するには、特開平４−８１４０３号公報に記載の方法を利用してもよい。また、Ｒがスルホニル基の場合としてトシル基をエーテル酸素を介して導入するには、特開２０１６−６９６５２号公報に記載の方法を利用してもよい。 In the cyclic oligosaccharide represented by the formula (1), the substituent of R in the formula can be introduced by using a known chemical modification method basically applied to cyclodextrin as described above. .. For example, in order to introduce an alkoxy group such as a methoxy group as -OR, the method of alkylating a hydroxy group described in JP-A-61-200101 may be used. Further, in order to introduce a sulfoalkyl group or a carboxymethyl ester group via ether oxygen as the case where R is a substituted alkyl group, the method described in JP-A-11-60610 and JP-A-2013-288444 is used. You may use it. Further, in order to introduce a residue of a dicarboxylic acid such as succinic acid when R is an acyl group, the method described in JP-A-4-81403 may be used. Further, in the case where R is a sulfonyl group, in order to introduce a tosyl group via ether oxygen, the method described in JP-A-2016-69652 may be used.
なお、置換基を導入する方法としては、上記のようにアセチル化環状セロオリゴ糖を合成した後、一旦加水分解により式（３）の環状オリゴ糖にしてから置換基を導入することは必ずしも要せず、環化した後、そのまま他の置換基に変換してもよい。 As a method for introducing a substituent, it is not always necessary to synthesize an acetylated cyclic cellooligosaccharide as described above, and then hydrolyze the cyclic oligosaccharide of the formula (3) before introducing the substituent. Instead, after cyclization, it may be directly converted to another substituent.
本実施形態に係る環状オリゴ糖は、上記のように、地球上で最も多量に存在する有機化合物であって再生可能な非食用植物資源であるセルロースから合成することができるので、資源の有効活用を図ることができる。 As described above, the cyclic oligosaccharide according to the present embodiment can be synthesized from cellulose, which is an organic compound present in the largest amount on the earth and is a recyclable non-edible plant resource, and therefore effective utilization of the resource. Can be planned.
また、本実施形態に係る環状オリゴ糖とシクロデキストリンとの分子構造を比較した場合、本実施形態に係る環状オリゴ糖は、シクロデキストリンよりも空孔内の疎水性が高い。詳細には、式（×）で表されるシクロデキストリンの分子構造が図４に示す通りであるのに対し、式（３）で表される環状オリゴ糖の分子構造は図３に示す通りである。図３及び図４において、白色の原子が水素原子、黒色の原子が炭素原子、その間のグレーの原子が酸素原子を示す。 Further, when the molecular structures of the cyclic oligosaccharide according to the present embodiment and cyclodextrin are compared, the cyclic oligosaccharide according to the present embodiment has higher hydrophobicity in the pores than cyclodextrin. Specifically, the molecular structure of the cyclodextrin represented by the formula (x) is as shown in FIG. 4, whereas the molecular structure of the cyclic oligosaccharide represented by the formula (3) is as shown in FIG. is there. In FIGS. 3 and 4, a white atom indicates a hydrogen atom, a black atom indicates a carbon atom, and a gray atom in between indicates an oxygen atom.
図４に示すように、シクロデキストリンでは、グルコースユニット間を連結しているグルコシド酸素が空孔の内側に向いており、そのため、空孔内はエーテル程度の疎水性環境にある。これに対し、図３に示すように、本実施形態に係る環状オリゴ糖では、グルコシド酸素が外側を向いており、空孔の内側に酸素原子が向いていない。そのため、本実施形態に係る環状オリゴ糖では、空孔内がシクロデキストリンよりも疎水性の高い環境にあり、疎水性の高い物質の取り込みが可能である。これにより、例えば水中において、より高いゲスト包接能とゲスト選択性を持つことが期待できる。 As shown in FIG. 4, in cyclodextrin, the glucoside oxygen connecting the glucose units faces the inside of the pores, and therefore, the inside of the pores is in a hydrophobic environment as much as ether. On the other hand, as shown in FIG. 3, in the cyclic oligosaccharide according to the present embodiment, the glucoside oxygen faces outward, and the oxygen atom does not face inside the pores. Therefore, in the cyclic oligosaccharide according to the present embodiment, the pores are in an environment having a higher hydrophobicity than cyclodextrin, and a substance having a higher hydrophobicity can be taken in. As a result, it can be expected to have higher guest inclusion ability and guest selectivity, for example, in water.
本実施形態に係る環状オリゴ糖は、空孔内に疎水性のゲスト分子またはその一部を包接する性質を有しているため、シクロデキストリンと同様、揮発性物質の不揮発化及び徐放、不安定物質の安定化、難溶性物質の可溶化などを目的として、食品、化粧品、トイレタリー製品、医薬品等の用途に用いることができる。 Since the cyclic oligosaccharide according to the present embodiment has the property of encapsulating a hydrophobic guest molecule or a part thereof in the pores, it is non-volatile, sustained-release, and non-volatile as in the case of cyclodextrin. It can be used in foods, cosmetics, toiletry products, pharmaceuticals, etc. for the purpose of stabilizing stable substances and solubilizing poorly soluble substances.
［緑茶抽出組成物および飲食品］
本実施形態の緑茶抽出組成物は、緑茶の抽出液（抽出物）と、環状セロオリゴ糖とを含む。以下、緑茶抽出組成物の製造工程に沿って説明する。
[Green tea extract composition and food and drink]
The green tea extract composition of the present embodiment contains a green tea extract (extract) and a cyclic cellooligosaccharide. Hereinafter, the process of producing the green tea extraction composition will be described.
まず、原料となる茶葉を抽出して緑茶抽出液を得る。原料の茶葉としては緑茶であればよく特に限定されない。 First, tea leaves as a raw material are extracted to obtain a green tea extract. The raw material tea leaves are not particularly limited as long as they are green tea.
抽出方法は特に限定されないが、従来公知の熱水抽出が好ましく用いられる。抽出条件は適宜設定でき、例えば、茶葉１００質量部に対して、５００〜２００００質量部の９０〜１００℃の熱水で１〜３０分間行うことができる。抽出後の茶葉は、例えば１００メッシュ程度のフィルター等で自然ろ過し茶葉を回収することができる。 The extraction method is not particularly limited, but conventionally known hot water extraction is preferably used. The extraction conditions can be set as appropriate, and for example, 100 parts by mass of tea leaves can be subjected to 500 to 20000 parts by mass of hot water at 90 to 100 ° C. for 1 to 30 minutes. The tea leaves after extraction can be naturally filtered with a filter of about 100 mesh or the like to collect the tea leaves.
なお、上記の抽出を効率的に行うためには、抽出後の茶葉を再度あらたな熱水に投入して、繰り返し抽出することが好ましい。これにより、一般的に３回の抽出を行うことで、茶葉のカテキン類のほぼ全量を抽出することができる。 In order to efficiently perform the above extraction, it is preferable to put the extracted tea leaves into new hot water again and repeatedly extract the tea leaves. As a result, it is generally possible to extract almost the entire amount of catechins in tea leaves by performing the extraction three times.
得られた抽出液は水分量が多いため濃縮することが好ましい。濃縮手段としては特に限定されず、減圧濃縮、加熱濃縮、凍結濃縮などの常法が適宜選択できるが、減圧濃縮または凍結濃縮がより好ましい。濃縮条件としては、例えば、２００〜４００Ｔｏｒｒの減圧下で、７０〜８０℃、２〜４時間の条件で濃縮することができる。濃縮液は緑茶固形分が５〜３０％となるように行うことが好ましく、１５〜２０％がより好ましい。なお、本実施形態においては上記の濃縮は必ずしも行う必要はなく、例えば、後述する飲食品が飲料等の場合には行わなくてもよい。 Since the obtained extract has a large amount of water, it is preferable to concentrate it. The concentrating means is not particularly limited, and conventional methods such as vacuum concentration, heat concentration, and freeze concentration can be appropriately selected, but vacuum concentration or freeze concentration is more preferable. As the concentration conditions, for example, it can be concentrated under a reduced pressure of 200 to 400 Torr at 70 to 80 ° C. for 2 to 4 hours. The concentrate is preferably carried out so that the green tea solid content is 5 to 30%, more preferably 15 to 20%. In this embodiment, the above concentration does not necessarily have to be performed, and for example, it may not be performed when the food or drink described later is a beverage or the like.
濃縮終了後、環状セロオリゴ糖を添加混合して緑茶抽出組成物を得る。 After completion of concentration, cyclic cellooligosaccharide is added and mixed to obtain a green tea extraction composition.
本実施の形態に係る緑茶抽出組成物は、さらにカゼインを含んでも良い。これにより、緑茶抽出組成物の渋みおよび苦味をより抑えることができる。 The green tea extraction composition according to the present embodiment may further contain casein. Thereby, the astringency and bitterness of the green tea extraction composition can be further suppressed.
カゼインとしては、カゼインナトリウム（カゼインＮａ）、カゼインカルシウム（カゼインＣａ）等が好ましく用いられる。カゼインＮａは水溶性であり、カゼインＣａは不溶性であるが、いずれも好適に用いることができる。なお、後述する飲食品が飲料である場合には、沈殿を防止するためにカゼインＮａ等の水溶性塩類を用いることが好ましい。 As the casein, sodium casein (Na casein), calcium casein (casein Ca) and the like are preferably used. Casein Na is water-soluble and casein Ca is insoluble, but any of them can be preferably used. When the food or drink described later is a beverage, it is preferable to use water-soluble salts such as casein Na in order to prevent precipitation.
カゼインと環状セロオリゴ糖との配合割合は、カゼイン１００質量部に対して環状セロオリゴ糖を５〜２０００質量部配合することが好ましく、１０〜１０００質量部配合することがより好ましい。カゼイン１００質量部に対する環状セロオリゴ糖の配合量が５質量部未満又は２０００質量部を超えると、カゼインと環状セロオリゴ糖との相乗効果が得られず、苦味、渋味抑制効果が不充分となるので好ましくない。 The mixing ratio of casein and cyclic cellooligosaccharide is preferably 5 to 2000 parts by mass, and more preferably 10 to 1000 parts by mass, based on 100 parts by mass of casein. If the amount of the cyclic cellooligosaccharide compounded with respect to 100 parts by mass of casein is less than 5 parts by mass or exceeds 2000 parts by mass, the synergistic effect of casein and the cyclic cellooligosaccharide cannot be obtained, and the bitterness and astringency suppressing effect becomes insufficient. Not preferred.
緑茶抽出液中の固形分に対する、カゼイン及び環状セロオリゴ糖の合計量の配合割合は、緑茶抽出液中の固形分１００質量部に対して、カゼイン及び環状セロオリゴ糖を１０〜９００質量部含有することが好ましく、３０〜３００質量部含有することがより好ましく、５０〜２００質量部含有することが特に好ましい。 The mixing ratio of the total amount of casein and cyclic cellooligosaccharide to the solid content in the green tea extract is 10 to 900 parts by mass of casein and cyclic cellooligosaccharide with respect to 100 parts by mass of the solid content in the green tea extract. Is preferable, and it is more preferably contained in an amount of 30 to 300 parts by mass, and particularly preferably contained in an amount of 50 to 200 parts by mass.
カゼイン及び環状セロオリゴ糖の合計量の配合割合が１０質量部未満であると、苦味、渋味抑制効果が不充分となるので好ましくない。また、９００質量部を超えると、カゼインの風味が強くなり、飲食品本来の持つ風味が損なわれるので好ましくない。 If the total amount of casein and cyclic cellooligosaccharide is less than 10 parts by mass, the effect of suppressing bitterness and astringency becomes insufficient, which is not preferable. On the other hand, if it exceeds 900 parts by mass, the flavor of casein becomes strong and the original flavor of food and drink is impaired, which is not preferable.
カゼイン及び環状セロオリゴ糖の添加方法は通常用いられる方法より適宜選択できる。たとえば濃縮液を撹拌しながらカゼイン及び環状セロオリゴ糖を添加していけばよい。なお、上記の濃縮を行う場合には、カゼイン及び環状セロオリゴ糖の添加は濃縮前に添加してもよい。 The method for adding casein and cyclic cellooligosaccharide can be appropriately selected from the commonly used methods. For example, casein and cyclic cellooligosaccharide may be added while stirring the concentrated solution. When performing the above concentration, casein and cyclic cellooligosaccharide may be added before the concentration.
上記の濃縮液は、飲料などに使用する場合は濃縮液のまま使用できるが、その他の固形食品等に配合する場合には、乾燥粉末化することが好ましい。乾燥粉末化は、従来公知の噴霧乾燥、凍結乾燥、ドラムドライなどの方法から適宜選択できる。例えば噴霧乾燥機としては、大川原化工機社製のＣＬ−８型等が使用でき、例えば、入り口温度１６０度、出口温度９５〜９８℃条件で、乾燥粉末化できる。噴霧乾燥の方式としては、例えば、スプレー方式はアトマイザー方式、粉末回収方法はサイクロン１点回収方式が使用できる。 The above concentrate can be used as it is when used for beverages and the like, but it is preferably made into a dry powder when blended with other solid foods and the like. The dry powdering can be appropriately selected from conventionally known methods such as spray drying, freeze drying, and drum drying. For example, as the spray dryer, CL-8 type manufactured by Okawara Kakoki Co., Ltd. can be used, and for example, it can be dried and powdered under the conditions of an inlet temperature of 160 ° C. and an outlet temperature of 95 to 98 ° C. As the spray drying method, for example, an atomizer method can be used as the spray method, and a cyclone one-point recovery method can be used as the powder recovery method.
次に、本実施の形態に係る緑茶抽出組成物を含有する飲食品について説明する。飲食品としては特に限定されないが、飲料、飲料用粉末、ゼリー、キャンディー、焼き菓子、チョコレート、まんじゅう、アイスクリーム、冷菓、打錠菓子等が挙げられる。 Next, foods and drinks containing the green tea extraction composition according to the present embodiment will be described. The food and drink is not particularly limited, and examples thereof include beverages, beverage powders, jellies, candies, baked goods, chocolates, steamed buns, ice cream, frozen desserts, and tableted sweets.
緑茶抽出組成物の上記の飲食品への添加は、上記のような濃縮液の状態で添加してもよく、未濃縮液の状態で添加してもよく、乾燥粉末の状態で添加してもよく、飲食品の種類に応じて適宜選択できる。 The green tea extract composition may be added to the above-mentioned food and drink in the state of a concentrated solution as described above, in the state of an unconcentrated solution, or in the state of a dry powder. Often, it can be appropriately selected according to the type of food and drink.
本実施の形態に係る飲食品は、緑茶抽出組成物が添加されたものであっても良いし、緑茶の抽出物および環状セロオリゴ糖が別々に添加されたものであってもよい。また、当該飲食品は、カゼインを添加されても良い。 The food or drink according to the present embodiment may be one to which the green tea extract composition is added, or the one to which the green tea extract and the cyclic cellooligosaccharide are separately added. In addition, casein may be added to the food or drink.
緑茶抽出組成物の飲食品への添加量は、目的とする食品によって適宜選択可能であるが、飲食品全体１００ｇあたり０．１〜１０ｇとなるように配合することが好ましい。 The amount of the green tea extract composition added to the food or drink can be appropriately selected depending on the target food, but it is preferably blended so as to be 0.1 to 10 g per 100 g of the whole food or drink.
具体的には、例えば、キャンディーや錠菓の場合には、上記の緑茶抽出組成物の固形分換算で、食品１００ｇあたり０．４〜８ｇ配合することが好ましく、１〜４ｇ配合することがより好ましい。また、焼き菓子の場合には、上記の緑茶抽出組成物の固形分換算で、食品１００ｇあたり０．４〜５ｇ配合することが好ましく、１〜４ｇ配合することがより好ましい。更に、緑茶飲料等の飲料の場合には、上記の緑茶抽出組成物の固形分換算で、飲料１００ｇあたり０．１〜１ｇ配合することが好ましく、０．２〜０．５ｇ配合することがより好ましい。 Specifically, for example, in the case of candy and tablet confectionery, it is preferable to add 0.4 to 8 g per 100 g of food in terms of solid content of the above green tea extraction composition, and it is more preferable to add 1 to 4 g. preferable. Further, in the case of baked confectionery, it is preferable to add 0.4 to 5 g per 100 g of food, and more preferably 1 to 4 g in terms of solid content of the above green tea extraction composition. Further, in the case of a beverage such as a green tea beverage, it is preferable to add 0.1 to 1 g per 100 g of the beverage in terms of the solid content of the above green tea extraction composition, and 0.2 to 0.5 g is more preferable. preferable.
以下、実施例により更に詳細に説明するが、本発明はこれらに限定されるものではない。なお、以下の実施例において「％」は特に断らない限り「質量％」を意味する。 Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. In the following examples, "%" means "mass%" unless otherwise specified.
［環状セロオリゴ糖］
以下、本実施例で使用する環状セロオリゴ糖の合成等について示す。分析及び測定方法は以下の通りである。
[Cyclic cellooligosaccharide]
Hereinafter, the synthesis and the like of the cyclic cellooligosaccharide used in this example will be described. The analysis and measurement methods are as follows.
（赤外吸収スペクトル（ＦＴ−ＩＲ））
フーリエ変換赤外分光光度計（日本分光（株）製「ＦＴ／ＩＲ４７００ＳＴ型」）により測定（ＡＴＲ法）。
(Infrared absorption spectrum (FT-IR))
Measured by Fourier transform infrared spectrophotometer ("FT / IR4700ST type" manufactured by JASCO Corporation) (ATR method).
（ＮＭＲ）
日本電子（株）製「ＪＮＭ−ＥＣＳ４００」により測定。
(NMR)
Measured by "JNM-ECS400" manufactured by JEOL Ltd.
（質量分析）
マトリックス支援レーザー脱離イオン化飛行時間型質量分析計（ＭＡＬＤＩ−ＴＯＦ ＭＳ）（日本パーセプティブリミテッド製「ＶｏｙａｇｅｒＴＭ ＲＰ」）により測定。
(Mass spectrometry)
Measured by a matrix-assisted laser desorption / ionization time-of-flight mass spectrometer (MALDI-TOF MS) (“Voyager TM RP” manufactured by Japan Perceptive Limited).
（ＨＰＬＣ）
カラム：ＯＤＳ（和光純薬工業株式会社製「Wakosil 5C18 AR」、内径４．６ｍｍ、長さ１５０ｍｍ）
移動相：アセトニトリル／水＝８／２（体積比）
流速：１．０ｍＬ／分
温度：３０℃
検出：ＥＬＳＤ（米国SofTA社製「Model400 ELSD」）。
(HPLC)
Column: ODS ("Wakosil 5C18 AR" manufactured by Wako Pure Chemical Industries, Ltd., inner diameter 4.6 mm, length 150 mm)
Mobile phase: Acetonitrile / water = 8/2 (volume ratio)
Flow velocity: 1.0 mL / min Temperature: 30 ° C
Detection: ELSD ("Model 400 ELSD" manufactured by SofTA, USA).
（ＴＬＣ）
展開溶媒：メタノール／クロロホルム＝１／４０（体積比）。
(TLC)
Developing solvent: Methanol / chloroform = 1/40 (volume ratio).
＜合成例１．メチル化環状セロオリゴ糖の合成＞
まず、本実施の形態にかかる環状セロオリゴ糖の一態様であるメチル化環状セロオリゴ糖の合成ついて説明する。
<Synthesis example 1. Synthesis of methylated cyclic cellooligosaccharides>
First, the synthesis of methylated cyclic cellooligosaccharide, which is one aspect of the cyclic cellooligosaccharide according to the present embodiment, will be described.
（１−１ 部分メチル化セルロースからの完全メチル化セルロースの合成）
J.N. Bemiller, Earle E. Allen, JR., J.Polym. Sci. 1967, 5, 2133.に記載の方法に
従い行った。反応式及び合成方法の詳細は以下の通りである。
(Synthesis of fully methylated cellulose from 1-1 partially methylated cellulose)
The procedure was described in JN Bemiller, Earle E. Allen, JR., J. Polym. Sci. 1967, 5, 2133. Details of the reaction formula and the synthesis method are as follows.
８０℃で一晩、真空乾燥を行った部分メチル化セルロース(２．０１ｇ、５．０３×１０−５ｍｏｌ、Sigma-Aldrich製「酢酸セルロース（Ｍｎ〜30,000）」)を、窒素雰囲気下でＤＭＳＯ（１１０ｍＬ）に溶解させた。この溶液を水素化ナトリウム（含量：６０％、１．８１ｇ、４．５３×１０−２ｍｏｌ）に加え、５０℃で１６時間撹拌した。ここにヨードメタン(２．９５ｍＬ、４．７４×１０−２ｍｏｌ)を３０分かけて滴下し、５０℃で２４時間撹拌した。系中にメタノール（３．８５ｍＬ）を加えて未反応の水素化ナトリウムを失活させ、得られた溶液を水（３５０ｍＬ）に加え再沈殿させた。生じた固体を遠心分離により分離し、６０℃で真空乾燥させて生成物（白色粉末状固体）を得た（収量１．９０ｇ、収率９５％）。 Partially methylated cellulose (2.01 g, 5.03 × 10-5 mol, “cellulose acetate (Mn ~ 30,000)” manufactured by Sigma-Aldrich) that has been vacuum dried overnight at 80 ° C. is DMSO in a nitrogen atmosphere. It was dissolved in (110 mL). The solution of sodium hydride (content: 60%, 1.81g, 4.53 × 10 -2 mol) was added, and the mixture was stirred for 16 hours at 50 ° C.. Here iodomethane was added dropwise over (2.95mL, 4.74 × 10 -2 mol ) of 30 min and stirred at 50 ° C. 24 hours. Methanol (3.85 mL) was added to the system to inactivate unreacted sodium hydride, and the resulting solution was added to water (350 mL) for reprecipitation. The resulting solid was separated by centrifugation and vacuum dried at 60 ° C. to give the product (white powder solid) (yield 1.90 g, yield 95%).
生成物のＦＴ−ＩＲスペクトルを、原料の部分メチル化セルロースのＦＴ−ＩＲスペクトルとともに図５に示す。原料の部分メチル化セルロースでは、図５（ａ）に示されるように３４００ｃｍ−１付近にＯＨ伸縮振動に基づく吸収ピークが観測された。これに対し、生成物のＦＴ−ＩＲスペクトルでは、図５（ｂ）に示されるように、２９１５、１４５５、１０５０ｃｍ−１に吸収ピークが観測されたが、３４００ｃｍ−１付近のＯＨ伸縮振動に基づく吸収ピークは消失しており、すべてのヒドロキシ基がメチル化されたことを確認した。 The FT-IR spectrum of the product is shown in FIG. 5 together with the FT-IR spectrum of the raw material partially methylated cellulose. In the raw material partially methylated cellulose, an absorption peak based on OH expansion and contraction vibration was observed near 3400 cm -1 as shown in FIG. 5 (a). In contrast, in the FT-IR spectrum of the product, as shown in FIG. 5 (b), an absorption peak at 2915,1455,1050Cm -1 was observed, based on the OH stretching vibration near 3400 cm -1 It was confirmed that the absorption peak had disappeared and all the hydroxy groups were methylated.
生成物の１Ｈ−ＮＭＲ分析の結果を以下に示すとともに、ＮＭＲスペクトルを図６に示す。
1H-NMR (400MHz, chloroform-d): δ 2.92 (t, 1H), 3.19 (t, 1H),3.27(m,1H),3.37 (s, 3H), 3.52 (s,3H),3.56 (s, 3H), 3.69-3.61 (m, 2H),3.75 (m, 1H), 4.31 (d, 1H)。
The results of 1 H-NMR analysis of the product are shown below, and the NMR spectrum is shown in FIG.
1 H-NMR (400MHz, chloroform-d): δ 2.92 (t, 1H), 3.19 (t, 1H), 3.27 (m, 1H), 3.37 (s, 3H), 3.52 (s, 3H), 3.56 ( s, 3H), 3.69-3.61 (m, 2H), 3.75 (m, 1H), 4.31 (d, 1H).
以上より、生成物が完全メチル化セルロースであることを確認した。 From the above, it was confirmed that the product was fully methylated cellulose.
（１−２ 完全メチル化セルロースからの部分メチル化セロオリゴ糖の合成）
T.Kondo, D. G. Gray, J. Appl. Polym.Sci. 1992, 45, 417に記載の方法を参考にして、完全メチル化セルロースから部分メチル化セロオリゴ糖（５〜８グルコースユニット）の合成を行った。反応式及び合成方法の詳細は以下の通りである。
(1-2 Synthesis of partially methylated cellooligosaccharides from fully methylated cellulose)
Partially methylated cellooligosaccharides (5-8 glucose units) were synthesized from fully methylated cellulose by referring to the method described in T.Kondo, DG Gray, J. Appl. Polym.Sci. 1992, 45, 417. It was. Details of the reaction formula and the synthesis method are as follows.
８０℃で真空乾燥を行った完全メチル化セルロース（０．５５ｇ、１．２×１０−２ｍｍｏｌ）を、窒素雰囲気下で脱水ジクロロメタン（３０ｍＬ）に溶解させた。ここに三フッ化ホウ素ジエチルエーテル錯塩（７．２ｍＬ、５６ｍｍｏｌ、和光純薬工業（株）製、含量：４６．０〜４９．０％（ＢＦ３））を添加し、室温で６時間撹拌した。得られた溶液に飽和炭酸水素ナトリウム水溶液（１５ｍＬ）を加えて反応を終了させた。ジクロロメタン（３０ｍＬ）で２回抽出し、集めたジクロロメタン溶液を無水硫酸マグネシウムで乾燥後、溶媒留去し褐色粘性液体を得た（粗収量０．５２ｇ、粗収率９３％）。 Fully methylated cellulose (0.55 g, 1.2 × 10-2 mmol) vacuum dried at 80 ° C. was dissolved in dehydrated dichloromethane (30 mL) under a nitrogen atmosphere. Boron trifluoride diethyl ether complex salt (7.2 mL, 56 mmol, manufactured by Wako Pure Chemical Industries, Ltd., content: 46.0-49.0% (BF 3 )) was added thereto, and the mixture was stirred at room temperature for 6 hours. .. A saturated aqueous sodium hydrogen carbonate solution (15 mL) was added to the obtained solution to terminate the reaction. Extraction was performed twice with dichloromethane (30 mL), the collected dichloromethane solution was dried with anhydrous magnesium sulfate, and the solvent was distilled off to obtain a brown viscous liquid (crude yield 0.52 g, crude yield 93%).
ＭＡＬＤＩ−ＴＯＦ−ＭＳ測定より、得られた生成物は２〜１１グルコースユニットからなる部分メチル化セロオリゴ糖の混合物であることがわかった。これをサイズ排除クロマトグラフィーにかけて５〜８グルコースユニットからなる部分メチル化セロオリゴ糖を分離した（収量８８ｍｇ、収率１６％）。 MALDI-TOF-MS measurements revealed that the product obtained was a mixture of partially methylated cellooligosaccharides consisting of 2-11 glucose units. This was subjected to size exclusion chromatography to separate partially methylated cellooligosaccharides consisting of 5-8 glucose units (yield 88 mg, yield 16%).
サイズ排除クロマトグラフィーは、分離装置として以下のものを用いた。
・装置：日本分析工業（株）製、リサイクル分取ＨＰＬＣ ＬＣ−９２１０ ＮＥ×Ｔ・カラム：日本分析工業（株）製、ＪＡＩＧＥＬ−２ＨＲ（排除限界分子量５，０００）×２本
・流速：９．５ｍＬ／分
・溶離液：クロロホルム
・１回あたりの注入量：６７ｍｇ（クロロホルム１ｍＬ）
・検出器：日本分析工業（株）製、ＲＩ−７００ ＩＩ ＮＥ×Ｔ。
For size exclusion chromatography, the following was used as the separation device.
・ Equipment: Nippon Analytical Industry Co., Ltd., recycled preparative HPLC LC-9210 NE × T ・ Column: Nippon Analytical Industry Co., Ltd., JAIGEL-2HR (exclusion limit molecular weight 5,000) × 2 ・ Flow velocity: 9 .5 mL / min ・ Eluent: Chloroform ・ Injection amount per injection: 67 mg (1 mL of chloroform)
-Detector: RI-700 II NE × T manufactured by Nippon Analytical Industry Co., Ltd.
（１−３ 部分メチル化セロオリゴ糖からのメチル化環状セロオリゴ糖の合成） (Synthesis of methylated cyclic cellooligosaccharides from 1-3 partially methylated cellooligosaccharides)
窒素雰囲気下、上記１−２で得られた部分メチル化セロオリゴ糖（７５ｍｇ、５．２×１０−５ｍｏｌ）をトルエン（１８ｍＬ）に溶解させた。ここに、トルエン（３ｍＬ）に溶解させたトリフルオロメタンスルホン酸無水物（Ｔｆ２Ｏ）（１５μＬ、９．０×１０−５ｍｏｌ）を滴下し室温で１時間撹拌した。その後、トルエン（３ｍＬ）に溶解させた２，６−ジｔｅｒｔ−ブチルピリジン（ＤＢＰ）（１８５μＬ、８．４×１０−４ｍｏｌ）を滴下し室温で１７時間撹拌した。その後、飽和炭酸水素ナトリウム水溶液（５０ｍＬ）を加えて、トルエン（１００ｍＬ）で抽出した。トルエン層を無水硫酸マグネシウムで乾燥後、溶媒留去し、得られた粗生成物（白色固体）をサイズ排除クロマトグラフィーにかけ、さらに中圧カラムクロマトグラフィーにかけて精製しメチル化環状セロオリゴ糖（６量体）を得た（収量１ｍｇ、収率１．５％、白色固体）。反応式は上記の通りである。 Under a nitrogen atmosphere, the partially methylated cellooligosaccharide (75 mg, 5.2 × 10-5 mol) obtained in 1-2 above was dissolved in toluene (18 mL). Trifluoromethanesulfonic anhydride (Tf 2 O) (15 μL, 9.0 × 10-5 mol) dissolved in toluene (3 mL) was added dropwise thereto, and the mixture was stirred at room temperature for 1 hour. Then, 2,6-ditert-butyl pyridine (DBP) (185 μL, 8.4 × 10 -4 mol) dissolved in toluene (3 mL) was added dropwise, and the mixture was stirred at room temperature for 17 hours. Then, saturated aqueous sodium hydrogen carbonate solution (50 mL) was added, and the mixture was extracted with toluene (100 mL). The toluene layer is dried over anhydrous magnesium sulfate, the solvent is distilled off, and the obtained crude product (white solid) is subjected to size exclusion chromatography and further purified by medium pressure column chromatography to be a methylated cyclic cellooligosaccharide (hexameric). ) (Yield 1 mg, yield 1.5%, white solid). The reaction formula is as described above.
サイズ排除クロマトグラフィーは上記１−２と同様に行った。中圧カラムクロマトグラフィーによる分離条件は以下の通りである。
・カラム：ＯＤＳ（山善株式会社製「ユニバーサルカラムＯＤＳ」、内径２０ｍｍ、長さ８４ｍｍ）
・移動相：アセトニトリル／水＝８／２（体積比）。
Size exclusion chromatography was performed in the same manner as in 1-2 above. The separation conditions by medium pressure column chromatography are as follows.
-Column: ODS ("Universal column ODS" manufactured by Yamazen Corporation, inner diameter 20 mm, length 84 mm)
-Mobile phase: acetonitrile / water = 8/2 (volume ratio).
６量体に精製する前の粗生成物についての質量分析（ＭＡＬＤＩ−ＴＯＦ ＭＳ）の結果を図７に示す。図７に示すように、５〜８量体のメチル化環状セロオリゴ糖に相当するピークが見られた。 The result of mass spectrometry (MALDI-TOF MS) on the crude product before purification into a hexamer is shown in FIG. As shown in FIG. 7, a peak corresponding to the methylated cyclic cellooligosaccharide of 5 to 8 was observed.
精製後の生成物（６量体）の１Ｈ−ＮＭＲ分析の結果を以下に示すとともに、ＮＭＲスペクトルを図８に示す。
1H NMR (400 MHz, chloroform-d)：5.08 (d, J = 2.3 Hz, 6H),4.33 (dd, J = 2.3, 7.7 Hz, 6H), 4.20 (ddd, J = 2.3, 4.5, 7.3 Hz, 6H), 4.03 (dd,J = 2.3, 6.8 Hz, 6H), 3.96 (dd, J = 6.8, 7.7 Hz, 6H), 3.67 (dd, J = 8.2, 9.9Hz, 6H), 3.50 (dd, J = 4.5, 9.5 Hz, 6H), 3.42 (s, 18H), 3.40 (s, 18H), 3.32 (s,18H) ppm。
The results of 1 H-NMR analysis of the purified product (hexameric) are shown below, and the NMR spectrum is shown in FIG.
1 1 H NMR (400 MHz, chloroform-d): 5.08 (d, J = 2.3 Hz, 6H), 4.33 (dd, J = 2.3, 7.7 Hz, 6H), 4.20 (ddd, J = 2.3, 4.5, 7.3 Hz , 6H), 4.03 (dd, J = 2.3, 6.8 Hz, 6H), 3.96 (dd, J = 6.8, 7.7 Hz, 6H), 3.67 (dd, J = 8.2, 9.9Hz, 6H), 3.50 (dd, J = 4.5, 9.5 Hz, 6H), 3.42 (s, 18H), 3.40 (s, 18H), 3.32 (s, 18H) ppm.
また、生成物のＮＯＥＳＹスペクトルを図９に示し、そのうち、グルコースユニットの１位の炭素に結合した水素（Ｈ１）付近の拡大図を図１０に示す。 The NOESY spectrum of the product is shown in FIG. 9, and an enlarged view of the vicinity of hydrogen (H 1 ) bonded to the carbon at the 1-position of the glucose unit is shown in FIG.
生成物の１３Ｃ−ＮＭＲ分析の結果を以下に示すとともに、ＮＭＲスペクトルを図１１に示す。
13C NMR (400 MHz, chloroform-d)：105.38, 90.72, 87.34,79.27, 74.20, 72.59, 59.11, 58.86, 57.69 ppm。
The results of 13 C-NMR analysis of the product are shown below, and the NMR spectrum is shown in FIG.
13 C NMR (400 MHz, chloroform-d): 105.38, 90.72, 87.34, 79.27, 74.20, 72.59, 59.11, 58.86, 57.69 ppm.
生成物の質量分析（ＭＡＬＤＩ−ＴＯＦ ＭＳ）の結果を以下に示すとともに、そのスペクトルを図１２に示す。
MALDI-TOF MS (m/z)：1246 [M+Na]+。
The results of mass spectrometry (MALDI-TOF MS) of the product are shown below, and the spectrum thereof is shown in FIG.
MALDI-TOF MS (m / z): 1246 [M + Na] + .
生成物のＴＬＣの結果は、Ｒｆ値＝０．４８であった。 The result of TLC of the product was Rf value = 0.48.
生成物のＨＰＬＣの結果（図１３（ａ））を、完全メチル化α−シクロデキストリン（α−シクロデキストリンのヒドロキシ基を全てメチル化したもの）の測定結果（図１３（ｂ））とともに図１３に示す。 The result of HPLC of the product (FIG. 13 (a)) is shown in FIG. 13 together with the measurement result (FIG. 13 (b)) of fully methylated α-cyclodextrin (all methylated hydroxy groups of α-cyclodextrin). Shown in.
ＭＳスペクトルとＨＰＬＣの結果より、本生成物は完全メチル化α−シクロデキストリンと同じ分子量を持つが、それとは異なる化合物であることがわかる。また、１Ｈ−ＮＭＲスペクトルと１３Ｃ−ＮＭＲスペクトルより、本生成物は２位、３位、６位の水酸基がメチル化されたグルコースユニットから構成されている、対称性の高い化合物であると考えられる。さらに、ＮＯＥＳＹスペクトル（図９、図１０）より、グルコースユニットの１位プロトンが２位、３位、５位、６位プロトンとは相関を示すのに対して４位のプロトンとは相間を示さないことから、１位プロトンと４位プロトンは距離が離れており、グルコースユニット間はβ―１，４結合でつながっていると考えられる。このようなことから、メチル化環状セロオリゴ糖の化学構造が式（１）（Ｒ＝メチル基、ｎ＝１）に示したものであると同定できる。 From the MS spectrum and the results of HPLC, it can be seen that this product has the same molecular weight as fully methylated α-cyclodextrin, but is a different compound. Further, from the 1 H-NMR spectrum and the 13 C-NMR spectrum, it was found that this product is a highly symmetric compound composed of glucose units in which the hydroxyl groups at the 2-position, 3-position and 6-position are methylated. Conceivable. Furthermore, from the NOESY spectrum (FIGS. 9 and 10), the 1-position proton of the glucose unit shows a correlation with the 2-position, 3-position, 5-position, and 6-position protons, while the phase interval with the 4-position proton. Since there is no such thing, it is considered that the 1-position proton and the 4-position proton are separated from each other, and the glucose units are connected by β-1,4 bonds. From these facts, it can be identified that the chemical structure of the methylated cyclic cellooligosaccharide is as shown in the formula (1) (R = methyl group, n = 1).
以下、このようにして得られたメチル化環状セロオリゴ糖を「環状セロオリゴ糖１」とも称する。 Hereinafter, the methylated cyclic cellooligosaccharide thus obtained is also referred to as “cyclic cellooligosaccharide 1”.
＜合成例２．環状セロオリゴ糖の合成＞
次に、本実施の形態に係る環状セロオリゴ糖の他の態様である環状セロオリゴ糖（式（１）中のＲ＝水素原子）の合成について説明する。
<Synthesis example 2. Synthesis of cyclic cellooligosaccharide>
Next, the synthesis of a cyclic cellooligosaccharide (R = hydrogen atom in the formula (1)), which is another embodiment of the cyclic cellooligosaccharide according to the present embodiment, will be described.
（２−１ 部分アセチル化セルロースからの完全アセチル化セルロースの合成）
P.Arndt et al., Cellulose, 2005, 12, 317.に記載の方法に従い、完全アセチル化セ
ルロースの合成を行った。反応式及び合成方法の詳細は以下の通りである。
(2-1 Synthesis of fully acetylated cellulose from partially acetylated cellulose)
Fully acetylated cellulose was synthesized according to the method described in P. Arndt et al., Cellulose, 2005, 12, 317. Details of the reaction formula and the synthesis method are as follows.
部分アセチル化セルロース（Ｓｉｇｍａ−Ａｌｄｒｉｃｈ製、Ｍｎ＝３００００、アセチル化度＝１．４８）（４．０ｇ、９．３×１０−５ｍｏｌ）を酢酸（８０ｍＬ）に溶解させ、無水酢酸（２６ｍＬ、２．７×１０−１ｍｏｌ）と過塩素酸（１．６ｍＬ、２．８×１０−２ｍｏｌ）を加えて室温で２時間撹拌した。反応混合物を水（１００ｍＬ）中に注ぎ、生じた固体を吸引ろ過により回収した。これを飽和炭酸水素ナトリウム水溶液（５００ｍＬ）、次に水（５００ｍＬ）で洗浄し、この洗浄操作をさら１回行った後、固体を７０℃で真空乾燥させ、白色粉末状固体を得た（収量３．９ｇ、収率８０％）。 Partially acetylated cellulose (manufactured by Sigma-Aldrich, Mn = 30,000, degree of acetylation = 1.48) (4.0 g, 9.3 × 10-5 mol) was dissolved in acetic acid (80 mL) and acetic anhydride (26 mL, 2.7 × 10 -1 mol) and perchloric acid (1.6 mL, 2.8 × 10 -2 mol) were added, and the mixture was stirred at room temperature for 2 hours. The reaction mixture was poured into water (100 mL) and the resulting solid was collected by suction filtration. This was washed with saturated aqueous sodium hydrogen carbonate solution (500 mL) and then with water (500 mL), and after performing this washing operation once more, the solid was vacuum dried at 70 ° C. to obtain a white powdery solid (yield). 3.9 g, yield 80%).
得られた固体の赤外吸収スペクトルでは、カルボニル基の吸収ピーク（１７３５ｃｍ−１）の存在、及び、原料で見られたヒドロキシ基の吸収ピーク（３４００ｃｍ−１付近）の消失が確認された。 The obtained infrared absorption spectrum of the solid, the presence of absorption peak of a carbonyl group (1735 cm -1), and the disappearance of the absorption peak of hydroxyl groups was observed in the raw material (3400 cm around -1) was confirmed.
（２−２ 完全アセチル化セルロースからの部分アセチル化セロオリゴ糖の合成）
T. Kondo, D. G. Gray, J. Appl. Polym. Sci.1992, 45, 417に記載の方法を参考にして、完全アセチル化セルロースから部分アセチル化セロオリゴ糖の合成を行った。反応式及び合成方法の詳細は以下の通りである。
(2-2 Synthesis of partially acetylated cellooligosaccharide from fully acetylated cellulose)
Partially acetylated cellooligosaccharides were synthesized from fully acetylated cellulose with reference to the method described in T. Kondo, DG Gray, J. Appl. Polym. Sci. 1992, 45, 417. Details of the reaction formula and the synthesis method are as follows.
上記２−１で合成した完全アセチル化セルロース（０．４５ｇ、８．３×１０−６ｍｏｌ）を酢酸（９．０ｍＬ）中に８０℃で溶解させ、無水酢酸（１５０μＬ、１．６×１０−３ｍｏｌ）、濃硫酸（３５μＬ、６．５×１０−４ｍｏｌ）、水（５４μＬ、３．０×１０−３ｍｏｌ）を順次加えて８０℃で１６時間撹拌した。反応溶液を室温まで放冷し、２０％酢酸マグネシウム水溶液(７０μＬ)を添加後、反応混合物をジエチルエーテル（１００ｍＬ）中に注ぎ、生じた固体を吸引ろ過により回収し、水（１００ｍＬ）で洗浄後真空乾燥した（収量０．１６ｇ）。 The fully acetylated cellulose (0.45 g, 8.3 × 10-6 mol) synthesized in 2-1 above was dissolved in acetic acid (9.0 mL) at 80 ° C. and acetic anhydride (150 μL, 1.6 × 10). -3 mol), concentrated sulfuric acid (35 μL, 6.5 × 10 -4 mol), and water (54 μL, 3.0 × 10 -3 mol) were sequentially added, and the mixture was stirred at 80 ° C. for 16 hours. The reaction solution is allowed to cool to room temperature, a 20% aqueous magnesium acetate solution (70 μL) is added, the reaction mixture is poured into diethyl ether (100 mL), the resulting solid is collected by suction filtration, and washed with water (100 mL). It was vacuum dried (yield 0.16 g).
ＭＡＬＤＩ−ＴＯＦ−ＭＳ測定により、得られた生成物は２〜１３グルコースユニットからなる部分アセチル化セロオリゴ糖の混合物であることがわかった（図１４参照）。 MALDI-TOF-MS measurements revealed that the product obtained was a mixture of partially acetylated cellooligosaccharides consisting of 2 to 13 glucose units (see FIG. 14).
（２−３ 部分アセチル化セロオリゴ糖からのアセチル化環状セロオリゴ糖の合成） (2-3 Synthesis of acetylated cyclic cellooligosaccharides from partially acetylated cellooligosaccharides)
上記２−２で得られた部分アセチル化セロオリゴ糖（５００ｍｇ、２．０×１０−４ｍｏｌ）を脱水ジクロロメタン（２７ｍＬ）と脱水トルエン（３．０ｍＬ）の混合溶液に溶解させた。ここに三フッ化ホウ素ジエチルエーテル錯体（８００μＬ、７．０×１０−３ｍｏｌ、和光純薬工業（株）製、含量：４６．０〜４９．０％（ＢＦ３））を加え、４０℃で１５時間撹拌した。その後、飽和炭酸水素ナトリウム水溶液（５０ｍＬ）を添加し、
クロロホルム１００ｍＬで抽出後、溶媒を留去して茶黄白色固体（２００ｍｇ）を得た。これを脱水ピリジン（３．０ｍＬ）に溶解させ、無水酢酸（１．５ｍＬ，１．５×１０−２ｍｏｌ）を加えて室温で２４時間撹拌することで遊離した水酸基のアセチル化を行った。飽和食塩水（１００ｍＬ）とクロロホルム（１００ｍＬ）で抽出し、クロロホルム層から溶媒を留去して茶黄白色固体（２５０ｍｇ）を得た。シリカゲルカラムクロマトグラフィーを２回行い（１回目の移動層：メタノール／クロロホルム（１／９９）、２回目の移動層：メタノール／クロロホルム（１／１５０））、粗生成物（６ｍｇ）を得た。反応式は上記の通りである。
The partially acetylated cellooligosaccharide (500 mg, 2.0 × 10 -4 mol) obtained in 2-2 above was dissolved in a mixed solution of dehydrated dichloromethane (27 mL) and dehydrated toluene (3.0 mL). Boron trifluoride diethyl ether complex (800 μL, 7.0 × 10 -3 mol, manufactured by Wako Pure Chemical Industries, Ltd., content: 46.0-49.0% (BF 3 )) was added thereto, and the temperature was 40 ° C. Was stirred for 15 hours. Then, saturated aqueous sodium hydrogen carbonate solution (50 mL) was added.
After extraction with 100 mL of chloroform, the solvent was distilled off to obtain a brownish yellowish white solid (200 mg). This was dissolved in dehydrated pyridine (3.0 mL), acetic anhydride (1.5 mL, 1.5 × 10-2 mol) was added, and the mixture was stirred at room temperature for 24 hours to acetylate the liberated hydroxyl groups. Extraction was performed with saturated brine (100 mL) and chloroform (100 mL), and the solvent was distilled off from the chloroform layer to obtain a brown-yellowish white solid (250 mg). Silica gel column chromatography was performed twice (first mobile layer: methanol / chloroform (1/99), second mobile layer: methanol / chloroform (1/150)) to obtain a crude product (6 mg). The reaction formula is as described above.
得られた粗生成物についてＭＡＬＤＩ−ＴＯＦ−ＭＳ測定を行った。その結果を図１５に示す。図１５に示すように、合成例１のメチル化体の場合と同様、５〜８量体の環状体に相当するピークが見られた。詳細には、合成例２では、環状化されていない直鎖状の６〜８量体に相当するピークとともに、５〜８量体のアセチル化環状セロオリゴ糖に相当するピークが見られた。 MALDI-TOF-MS measurement was performed on the obtained crude product. The result is shown in FIG. As shown in FIG. 15, as in the case of the methylated product of Synthesis Example 1, a peak corresponding to a 5-octameric cyclic body was observed. Specifically, in Synthesis Example 2, a peak corresponding to a non-cyclized linear 6 to 8 mer and a peak corresponding to a 5 to 8 acetylated cyclic cellooligosaccharide were observed.
（２−４ アセチル化環状セロオリゴ糖からの環状セロオリゴ糖の合成） (2-4 Synthesis of cyclic cellooligosaccharides from acetylated cyclic cellooligosaccharides)
アセチル化環状セロオリゴ糖（４．０ｍｇ）をメタノール（１．２ｍＬ）に溶解させ、ここに水（０．８ｍＬ）を加えた。さらにトリエチルアミン（０．８ｍＬ、５．５×１０−３ｍｏｌ）を加え、４０℃で２４時間撹拌した。溶媒を留去して粗生成物（４ｍｇ）を得た。反応式は上記の通りである。 Acetylated cyclic cellooligosaccharide (4.0 mg) was dissolved in methanol (1.2 mL), and water (0.8 mL) was added thereto. Further, triethylamine (0.8 mL, 5.5 × 10 -3 mol) was added, and the mixture was stirred at 40 ° C. for 24 hours. The solvent was distilled off to obtain a crude product (4 mg). The reaction formula is as described above.
得られた粗生成物についてＭＡＬＤＩ−ＴＯＦ−ＭＳ測定を行った。その結果を図１６に示す。図１６に示すように、６〜８量体の直鎖状セロオリゴ糖に相当するピークとともに、６〜８量体の環状セロオリゴ糖に相当するピークが見られた。 MALDI-TOF-MS measurement was performed on the obtained crude product. The result is shown in FIG. As shown in FIG. 16, a peak corresponding to a 6 to 8 mer linear sero-oligosaccharide and a peak corresponding to a 6 to 8 mer cyclic sero-oligosaccharide were observed.
以下、このようにして得られた環状セロオリゴ糖を「環状セロオリゴ糖２」とも称する。 Hereinafter, the cyclic cellooligosaccharide thus obtained is also referred to as “cyclic cellooligosaccharide 2”.
［緑茶抽出組成物］ [Green tea extraction composition]
以下、実施例を挙げて本発明をさらに具体的に説明する。
実施例１（緑茶抽出組成物の製造）
茶葉１００ｇを、２リットルの９５℃の熱水に投入し、９５℃に保ちながら５分間撹拌後、１００メッシュのフィルターで自然ろ過し茶葉を回収した。より効率的に抽出するため、抽出後の茶葉をあらたな熱水に投入し、同様に計３回抽出を行い、６リットルの抽出液を得た。得られた抽出液は、凍結乾燥機（ＤＦ−０１０Ｈ型：日本真空技術（株）社製）を用い、０．２Ｔｏｒｒ、品温２０℃の条件で凍結乾燥して粉末化した。
Hereinafter, the present invention will be described in more detail with reference to examples.
Example 1 (Production of Green Tea Extraction Composition)
100 g of tea leaves were put into 2 liters of hot water at 95 ° C., stirred for 5 minutes while maintaining at 95 ° C., and then naturally filtered through a 100 mesh filter to recover the tea leaves. In order to extract more efficiently, the tea leaves after extraction were put into fresh hot water and extracted three times in the same manner to obtain 6 liters of an extract. The obtained extract was freeze-dried and powdered using a freeze-dryer (DF-010H type: manufactured by Nippon Vacuum Technology Co., Ltd.) under the conditions of 0.2 Torr and a product temperature of 20 ° C.
上記の粉末を３．６ｍｇ／ｍｌの濃度で水に溶かし、環状セロオリゴ糖１とカゼインＮａの１：１混合物を、それぞれ１．３ｍｇ／ｍｌ、４ｍｇ／ｍｌ、８ｍｇ／ｍｌ、１２ｍｇ／ｍｌになるように添加し溶解させ、４種類の濃度の実施例１の緑茶抽出組成物を得た。 The above powder is dissolved in water at a concentration of 3.6 mg / ml, and a 1: 1 mixture of cyclic cellooligosaccharide 1 and casein Na is adjusted to 1.3 mg / ml, 4 mg / ml, 8 mg / ml, and 12 mg / ml, respectively. To obtain the green tea extraction composition of Example 1 having four different concentrations.
実施例２
環状セロオリゴ糖２とカゼインＮａの１：１混合物を、それぞれ１．３ｍｇ／ｍｌ、４ｍｇ／ｍｌ、８ｍｇ／ｍｌ、１２ｍｇ／ｍｌになるように添加し溶解させた以外は、実施例１と同様にして、４種類の濃度の実施例２の緑茶抽出組成物を得た。
Example 2
The same as in Example 1 except that a 1: 1 mixture of cyclic cellooligosaccharide 2 and casein Na was added and dissolved so as to be 1.3 mg / ml, 4 mg / ml, 8 mg / ml, and 12 mg / ml, respectively. The green tea extraction composition of Example 2 having four kinds of concentrations was obtained.
実施例３
環状セロオリゴ糖１のみを、それぞれ１．３ｍｇ／ｍｌ、４ｍｇ／ｍｌ、８ｍｇ／ｍｌ、１２ｍｇ／ｍｌになるように添加し溶解させた以外は、実施例１と同様にして、４種類の濃度の実施例３の緑茶抽出組成物を得た。
Example 3
4 different concentrations in the same manner as in Example 1 except that only cyclic cellooligosaccharide 1 was added and dissolved so as to be 1.3 mg / ml, 4 mg / ml, 8 mg / ml, and 12 mg / ml, respectively. The green tea extraction composition of Example 3 was obtained.
実施例４
環状セロオリゴ糖２のみを、それぞれ１．３ｍｇ／ｍｌ、４ｍｇ／ｍｌ、８ｍｇ／ｍｌ、１２ｍｇ／ｍｌになるように添加し溶解させた以外は、実施例４と同様にして、４種類の濃度の実施例４の緑茶抽出組成物を得た。
Example 4
4 different concentrations in the same manner as in Example 4 except that only cyclic cellooligosaccharide 2 was added and dissolved so as to be 1.3 mg / ml, 4 mg / ml, 8 mg / ml, and 12 mg / ml, respectively. The green tea extraction composition of Example 4 was obtained.
試験例１（等価濃度試験法による相乗効果の確認）
実施例１、比較例１、２の緑茶抽出組成物について、以下の等価濃度試験法によって苦味、渋味の評価を行った。
Test Example 1 (Confirmation of synergistic effect by equivalent concentration test method)
The green tea extraction compositions of Example 1 and Comparative Examples 1 and 2 were evaluated for bitterness and astringency by the following equivalent concentration test method.
等価濃度試験法は、上記の緑茶抽出液を凍結乾燥した粉末（環状セロオリゴ糖１，２、カゼインＮａは未添加）を規定の濃度（３．６ｍｇ／ｍｌ、２．１ｍｇ／ｍｌ、１．２ｍｇ／ｍｌ）で水に溶かし、等価濃度試験法の標準液とした。 In the equivalent concentration test method, the above green tea extract is lyophilized and dried (cyclic cellooligosaccharides 1 and 2 and casein Na are not added) at a specified concentration (3.6 mg / ml, 2.1 mg / ml, 1.2 mg). / Ml) was dissolved in water to prepare a standard solution for the equivalent concentration test method.
３．６ｍｇ／ｍｌの濃度の標準液の苦味および渋みのレベルすなわち苦味等レベルを「５」とし、２．１ｍｇ／ｍｌの濃度の標準液の苦味等レベルを「３」とし、１．２ｍｇ／ｍｌの濃度の標準液の苦味等レベルを「１」とした。 The bitterness and astringency level of the standard solution having a concentration of 3.6 mg / ml, that is, the bitterness level is set to "5", and the bitterness level of the standard solution having a concentration of 2.1 mg / ml is set to "3", 1.2 mg / ml. The bitterness level of the standard solution having a concentration of ml was set to "1".
実施例１〜４の各緑茶抽出組成物と各標準液とを飲み比べ、サンプルの苦味および渋味がどの苦味等レベルに相当するかを判定した。 Each green tea extraction composition of Examples 1 to 4 was drank and compared with each standard solution, and it was determined which level of bitterness and astringency of the sample corresponded to.
その結果を表１に示す。具体的には、表１では、苦味等レベルが５の標準液と同程度の苦味等を有するサンプルを「５」と示し、苦味等レベルが３の標準液と同程度の苦味等を有するサンプルを「３」と示し、苦味等レベルが「１」標準液と同程度の苦味等を有するサンプルを「１」と示す。つまり、表１中の各実施例および比較例に係る数値は、苦味および渋みの程度を表し、数値が大きいサンプルほど苦味および渋みが強い。 The results are shown in Table 1. Specifically, in Table 1, a sample having the same bitterness as the standard solution having a bitterness level of 5 is shown as “5”, and a sample having the same bitterness as the standard solution having a bitterness level of 3 is shown as “5”. Is indicated as "3", and a sample having a bitterness and the like having a bitterness and the like level similar to that of the standard solution is indicated as "1". That is, the numerical values related to each of the Examples and Comparative Examples in Table 1 represent the degree of bitterness and astringency, and the larger the numerical value, the stronger the bitterness and astringency.
表１の結果より、環状セロオリゴ糖１を単独で用いた実施例３および環状セロオリゴ糖２を単独で用いた実施例４は、ともに、苦味、渋味が低減されていることが分かる。また、環状セロオリゴ糖１とカゼインＮａとを併用した実施例１、環状セロオリゴ糖２とカゼインＮａとを併用した実施例２においては、実施例３、４に比べて、苦味、渋味がさらに低減されていることが分かる。なお、カゼインを単独で使用した場合も苦味、渋味が低減されることが確認できたが、実施例１〜４と比べると、苦味、渋味の低減の程度は低かった。 From the results in Table 1, it can be seen that the bitterness and astringency were reduced in both Example 3 in which the cyclic cellooligosaccharide 1 was used alone and Example 4 in which the cyclic cellooligosaccharide 2 was used alone. Further, in Example 1 in which cyclic cellooligosaccharide 1 and casein Na were used in combination, and in Example 2 in which cyclic cellooligosaccharide 2 and casein Na were used in combination, bitterness and astringency were further reduced as compared with Examples 3 and 4. You can see that it has been done. It was confirmed that bitterness and astringency were reduced even when casein was used alone, but the degree of reduction in bitterness and astringency was lower than in Examples 1 to 4.
実施例５（飲食品（キャンディー）の製造）
下記の表２の配合で、常法により、本発明の緑茶抽出組成物を含有するキャンディーを製造した。なお、緑茶抽出組成物としては、上記の緑茶抽出液を凍結乾燥した粉末の１００質量部に対して、環状セロオリゴ糖１とカゼインＮａの１：１混合物を、２００質量部添加したものを用いた。この結果、このキャンディーにおいては、効果的に苦味、渋味が抑制されることが、パネラー５名による官能検査により確認できた。
Example 5 (Manufacturing of food and drink (candy))
A candy containing the green tea extraction composition of the present invention was produced by a conventional method with the formulation shown in Table 2 below. As the green tea extraction composition, 200 parts by mass of a 1: 1 mixture of cyclic cellooligosaccharide 1 and casein Na was added to 100 parts by mass of the powder obtained by freeze-drying the above green tea extract. .. As a result, it was confirmed by a sensory test by five panelists that bitterness and astringency were effectively suppressed in this candy.
実施例６（飲食品（焼き菓子）の製造）
下記の表３の配合で、常法により、本発明の緑茶抽出組成物を含有する焼き菓子を製造した。なお、緑茶抽出組成物としては、上記の緑茶抽出液を凍結乾燥した粉末の１００質量部に対して、環状セロオリゴ糖１とカゼインＮａの１：１混合物を、１００質量部添加したものを用いた。この結果、この焼き菓子においては、効果的に苦味、渋味が抑制されることが、パネラー５名による官能検査により確認できた。
Example 6 (Manufacturing of food and drink (baked confectionery))
A baked confectionery containing the green tea extraction composition of the present invention was produced by a conventional method with the formulation shown in Table 3 below. As the green tea extraction composition, 100 parts by mass of a 1: 1 mixture of cyclic cellooligosaccharide 1 and casein Na was added to 100 parts by mass of the powder obtained by freeze-drying the above green tea extract. .. As a result, it was confirmed by a sensory test by five panelists that the bitterness and astringency were effectively suppressed in this baked confectionery.
実施例７（飲食品（オレンジ飲料）の製造）
下記の表４の配合で、常法により、本発明の緑茶抽出組成物を含有するオレンジ飲料を製造した。なお、緑茶抽出組成物としては、上記の緑茶抽出液の濃縮液（固形分２０％）の固形分１００質量部に対して、環状セロオリゴ糖１とカゼインＮａの１：１混合物を、２００質量部添加したものを用いた。この結果、このオレンジ飲料においては、効果的に苦味、渋味が抑制されることが、パネラー５名による官能検査により確認できた。
Example 7 (Manufacturing of food and drink (orange beverage))
An orange beverage containing the green tea extraction composition of the present invention was produced by a conventional method with the formulation shown in Table 4 below. As the green tea extraction composition, 200 parts by mass of a 1: 1 mixture of cyclic cellooligosaccharide 1 and casein Na with respect to 100 parts by mass of the solid content of the concentrated solution (solid content 20%) of the above green tea extract. The added one was used. As a result, it was confirmed by a sensory test by five panelists that bitterness and astringency were effectively suppressed in this orange beverage.
実施例８（飲食品（緑茶飲料）の製造）
下記の表５の配合で、常法により、本発明の緑茶抽出組成物を含有する緑茶飲料を製造した。なお、緑茶抽出組成物としては、上記の緑茶抽出液の濃縮液（固形分２０％）の固形分１００質量部に対して、環状セロオリゴ糖１とカゼインＮａの１：１混合物を、２００質量部添加したものを用いた。この結果、この緑茶飲料においては、効果的に苦味、渋味が抑制されることが、パネラー５名による官能検査により確認できた。
Example 8 (Manufacturing of food and drink (green tea beverage))
A green tea beverage containing the green tea extraction composition of the present invention was produced by a conventional method with the formulation shown in Table 5 below. As the green tea extraction composition, 200 parts by mass of a 1: 1 mixture of cyclic cellooligosaccharide 1 and casein Na with respect to 100 parts by mass of the solid content of the concentrated solution (solid content 20%) of the above green tea extract. The added one was used. As a result, it was confirmed by a sensory test by five panelists that bitterness and astringency were effectively suppressed in this green tea beverage.
また、実施例４〜８のそれぞれにおいて、環状セロオリゴ糖１とカゼインＮａの１：１混合物の代わりに、環状セロオリゴ糖１のみを用いた場合においても、苦味、渋味が抑制されることが、パネラー５名による官能検査により確認できた。 Further, in each of Examples 4 to 8, bitterness and astringency can be suppressed even when only cyclic cellooligosaccharide 1 is used instead of the 1: 1 mixture of cyclic cellooligosaccharide 1 and casein Na. It was confirmed by a sensory test by 5 panelists.
また、実施例４〜８のそれぞれにおいて、環状セロオリゴ糖１とカゼインＮａの１：１混合物の代わりに、環状セロオリゴ糖２のみを用いた場合においても、苦味、渋味が抑制されることが、パネラー５名による官能検査により確認できた。 Further, in each of Examples 4 to 8, bitterness and astringency are suppressed even when only cyclic cellooligosaccharide 2 is used instead of the 1: 1 mixture of cyclic cellooligosaccharide 1 and casein Na. It was confirmed by a sensory test by 5 panelists.
また、実施例４〜８のそれぞれにおいて、環状セロオリゴ糖１とカゼインＮａの１：１混合物の代わりに、環状セロオリゴ糖２とカゼインＮａの１：１混合物を用いた場合においても、効果的に苦味、渋味が抑制されることが、パネラー５名による官能検査により確認できた。 Further, in each of Examples 4 to 8, even when a 1: 1 mixture of cyclic cellooligosaccharide 2 and casein Na is used instead of the 1: 1 mixture of cyclic cellooligosaccharide 1 and casein Na, the bitterness is effectively used. It was confirmed by a sensory test by 5 panelists that the astringency was suppressed.
以上、本発明のいくつかの実施形態を説明したが、これら実施形態は、例として提示したものであり、発明の範囲を限定することは意図していない。これら実施形態は、その他の様々な形態で実施されることが可能であり、発明の要旨を逸脱しない範囲で、種々の省略、置き換え、変更を行うことができる。これら実施形態やその省略、置き換え、変更などは、発明の範囲や要旨に含まれると同様に、特許請求の範囲に記載された発明とその均等の範囲に含まれるものである。
Although some embodiments of the present invention have been described above, these embodiments are presented as examples and are not intended to limit the scope of the invention. These embodiments can be implemented in various other forms, and various omissions, replacements, and changes can be made without departing from the gist of the invention. These embodiments, omissions, replacements, changes, etc. thereof are included in the scope and gist of the invention, as well as in the scope of the invention described in the claims and the equivalent scope thereof.
Claims (3)
A food or drink containing the cyclic oligosaccharide according to claim 1 and an extract of green tea.
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