JP5927030B2 - Inclusion complex-containing composition and method for producing inclusion complex - Google Patents
Inclusion complex-containing composition and method for producing inclusion complex Download PDFInfo
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- JP5927030B2 JP5927030B2 JP2012110671A JP2012110671A JP5927030B2 JP 5927030 B2 JP5927030 B2 JP 5927030B2 JP 2012110671 A JP2012110671 A JP 2012110671A JP 2012110671 A JP2012110671 A JP 2012110671A JP 5927030 B2 JP5927030 B2 JP 5927030B2
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- Prior art keywords
- inclusion complex
- curcumin
- polysaccharide
- acyclic
- acyclic polysaccharide
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920002674 hyaluronan Polymers 0.000 description 1
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- AIHDCSAXVMAMJH-GFBKWZILSA-N levan Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)OC[C@@H]1[C@@H](O)[C@H](O)[C@](CO)(CO[C@@H]2[C@H]([C@H](O)[C@@](O)(CO)O2)O)O1 AIHDCSAXVMAMJH-GFBKWZILSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 235000010420 locust bean gum Nutrition 0.000 description 1
- 239000000711 locust bean gum Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
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- 238000002715 modification method Methods 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 150000002772 monosaccharides Chemical group 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- KERBAAIBDHEFDD-UHFFFAOYSA-N n-ethylformamide Chemical compound CCNC=O KERBAAIBDHEFDD-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 230000026731 phosphorylation Effects 0.000 description 1
- 238000006366 phosphorylation reaction Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000009754 rhamnogalacturonan I Substances 0.000 description 1
- 239000008914 rhamnogalacturonan II Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000003865 secondary ammonium salts Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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- 238000001291 vacuum drying Methods 0.000 description 1
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- 150000004823 xylans Chemical class 0.000 description 1
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Photovoltaic Devices (AREA)
- Hybrid Cells (AREA)
Description
本発明は、非環状多糖類およびクルクミン類を含有する包接複合体およびその製造方法、並びに、包接複合体を含有する包接複合体含有組成物に関する。 The present invention relates to an inclusion complex containing an acyclic polysaccharide and curcumin, a method for producing the same, and an inclusion complex-containing composition containing an inclusion complex.
クルクミンはウコンやターメリックに含まれる色素成分であり、抗酸化作用を有することから、飲食品、健康食品等に利用されている。
また、クルクミンはβ−ジケトン構造を有しており、各種の金属イオンと配位が可能である。なお、β−ジケトン構造を導入した合成高分子は、各種の金属イオンが配位されことで、発光性を示し、高分子液晶としての特性を有することから、光電子機能材料として、従来から広く検討されている。
特許文献１においては、クルクミンを主鎖に含み、β−ジケトン構造部でルテニウムなどの金属イオンを配位させた高分子金属錯体が開示されている。
Curcumin is a pigment component contained in turmeric and turmeric, and has an antioxidant action, so it is used in foods and drinks, health foods and the like.
Curcumin has a β-diketone structure and can be coordinated with various metal ions. Synthetic polymers with a β-diketone structure have been studied extensively as optoelectronic functional materials because they exhibit luminescent properties due to coordination of various metal ions and have properties as polymer liquid crystals. Has been.
Patent Document 1 discloses a polymer metal complex containing curcumin in the main chain and coordinated with a metal ion such as ruthenium in the β-diketone structure.
特許文献１に記載されるβ−ジケトン部にルテニウムが配位した高分子金属錯体は、色素増感太陽電池の色素として使用可能であり、所定の光起電圧が達成される。
一方、近年、ルテニウムなどは希少金属であるためコスト面および供給安定面で大きな課題があると共に、地球環境負荷の低減のためには、その使用量をなるべく減らすことが求められている。
そのため、ルテニウムなどの希少金属を含まず、簡便に製造することができ、長波長領域においても優れた光吸収特性を有する色素（化合物）が望まれていた。
The polymer metal complex in which ruthenium is coordinated to the β-diketone portion described in Patent Document 1 can be used as a dye of a dye-sensitized solar cell, and a predetermined photovoltaic voltage is achieved.
On the other hand, in recent years, ruthenium and the like are rare metals, so there are major problems in terms of cost and supply stability, and in order to reduce the global environmental load, it is required to reduce the amount of use as much as possible.
Therefore, there has been a demand for a dye (compound) that does not contain a rare metal such as ruthenium, can be easily produced, and has excellent light absorption characteristics even in a long wavelength region.
また、特許文献１に記載の高分子金属錯体は、有機溶媒に対して所定の溶解性を示すものの、水への溶解性に劣る。
各種デバイス（例えば、色素増感太陽電池）に使用される色素が水に溶解できれば、有機溶媒を使用することなく各種デバイスを製造できることが期待され、環境負荷の低減につながる可能性がある。
Moreover, although the polymeric metal complex of patent document 1 shows predetermined | prescribed solubility with respect to the organic solvent, it is inferior to the solubility to water.
If the dye used in various devices (for example, dye-sensitized solar cells) can be dissolved in water, it is expected that various devices can be produced without using an organic solvent, which may lead to a reduction in environmental burden.
本発明は、上記実情に鑑みて、簡便に製造することができ、水への溶解性に優れ、長波長領域においても優れた光吸収特性を示す、クルクミンを含む包接複合体およびその製造方法を提供することを目的とする。
また、本発明は、該包接複合体を含有する包接複合体含有組成物を提供することも目的とする。
In light of the above circumstances, the present invention provides a clathrate-containing inclusion complex that can be easily produced, has excellent solubility in water, and exhibits excellent light absorption characteristics even in a long wavelength region, and a method for producing the same. The purpose is to provide.
Another object of the present invention is to provide an inclusion complex-containing composition containing the inclusion complex.
本発明者らは、上記課題について鋭意検討した結果、クルクミンまたはその誘導体と非環状多糖類とを使用することにより、上記課題を解決できることを見出し、本発明を完成するに至った。
すなわち、以下に示す手段により上記課題を解決し得る。
As a result of intensive studies on the above problems, the present inventors have found that the above problems can be solved by using curcumin or a derivative thereof and an acyclic polysaccharide, and have completed the present invention.
That is, the above problems can be solved by the following means.
（１） 非プロトン性極性溶媒中において、非環状多糖類および後述する式（１）で表されるクルクミン類を混合することにより得られる、非環状多糖類と非環状多糖類により包接されたクルクミン類とを含む包接複合体を含有する包接複合体含有組成物。
（２） 非環状多糖類が、α−グルカン類またはペクチン類である、（１）に記載の包接複合体含有組成物。
（３） 非環状多糖類が直鎖状である、（１）または（２）に記載の包接複合体含有組成物。
(1) In an aprotic polar solvent, it was included by an acyclic polysaccharide and an acyclic polysaccharide obtained by mixing an acyclic polysaccharide and a curcumin represented by the formula (1) described later. An inclusion complex-containing composition comprising an inclusion complex containing curcumin.
(2) The inclusion complex-containing composition according to (1), wherein the acyclic polysaccharide is α-glucan or pectin.
(3) The inclusion complex-containing composition according to (1) or (2), wherein the acyclic polysaccharide is linear.
（４） 非環状多糖類と、非環状多糖類により包接された後述する式（１）で表されるクルクミン類とを含む包接複合体。
（５） 非環状多糖類が、α−グルカン類またはペクチン類である、（４）に記載の包接複合体。
（６） 非環状多糖類が直鎖状である、（４）または（５）に記載の包接複合体。
(4) An inclusion complex comprising an acyclic polysaccharide and a curcumin represented by the formula (1) described later, which is included by the acyclic polysaccharide.
(5) The inclusion complex according to (4), wherein the acyclic polysaccharide is α-glucan or pectin.
(6) The inclusion complex according to (4) or (5), wherein the acyclic polysaccharide is linear.
（７） 非プロトン性極性溶媒中において、非環状多糖類および後述する式（１）で表されるクルクミン類を混合することにより、非環状多糖類と非環状多糖類により包接されたクルクミン類とを含む包接複合体を製造する、包接複合体の製造方法。
（８） 非環状多糖類が、α−グルカン類またはペクチン類である、（７）に記載の包接複合体の製造方法。
（９） 非環状多糖類が直鎖状である、（７）または（８）に記載の包接複合体の製造方法。
(7) Curcumins clathrated by acyclic polysaccharide and acyclic polysaccharide by mixing acyclic polysaccharide and curcumin represented by formula (1) described later in aprotic polar solvent A method for producing an inclusion complex, comprising:
(8) The method for producing an inclusion complex according to (7), wherein the acyclic polysaccharide is α-glucan or pectin.
(9) The method for producing an inclusion complex according to (7) or (8), wherein the acyclic polysaccharide is linear.
本発明によれば、簡便に製造することができ、水への溶解性に優れ、長波長領域においても優れた光吸収特性を示す、クルクミンを含む包接複合体およびその製造方法を提供することができる。
また、本発明によれば、該包接複合体を含有する包接複合体含有組成物を提供することができる。
According to the present invention, it is possible to provide an inclusion complex containing curcumin that can be easily produced, has excellent solubility in water, and exhibits excellent light absorption characteristics even in a long wavelength region, and a method for producing the same. Can do.
Moreover, according to this invention, the inclusion complex containing composition containing this inclusion complex can be provided.
以下に、本発明の包接複合体およびその製造方法、並びに、包接複合体含有組成物の好適実施態様について説明する。
まず、本発明の従来技術と比較した特徴点について詳述する。
上述したように、本発明の特徴点の一つとしては、クルクミンまたはその誘導体と非環状多糖類とを非プロトン性極性溶媒中で混合する点が挙げられる。この処理を実施することにより、クルクミンまたはその誘導体が会合（または凝集）し、その周りを非環状多糖類が覆うことにより、内部にクルクミンまたはその誘導体が包接（内包）された包接複合体を得ることができる。
得られた包接複合体は、長波長領域（特に、５００〜７００ｎｍ）において優れた光吸収特性を示すと共に、水に対しても溶解性が優れる。一般的に、長波長領域に吸収を有する色素を得るためには、複雑な合成ステップを繰り返し実施する必要があるが、上記包接複合体は非常に簡便な方法で得ることができ、製造適性に優れる。
また、得られた包接複合体に使用されるクルクミンまたは誘導体、および、非環状多糖類は、いずれも天然由来の成分であり、いわゆるカーボンニュートラルな植物由来の化合物であるため、地球環境保全の点からも好ましい。
Hereinafter, preferred embodiments of the inclusion complex of the present invention, a method for producing the same, and the inclusion complex-containing composition will be described.
First, the feature point compared with the prior art of this invention is explained in full detail.
As described above, one of the features of the present invention is that curcumin or a derivative thereof and an acyclic polysaccharide are mixed in an aprotic polar solvent. By carrying out this treatment, an inclusion complex in which curcumin or a derivative thereof associates (or aggregates) and is surrounded by an acyclic polysaccharide so that curcumin or a derivative thereof is included (inclusion). Can be obtained.
The obtained inclusion complex exhibits excellent light absorption characteristics in a long wavelength region (particularly, 500 to 700 nm) and is excellent in solubility in water. In general, in order to obtain a dye having absorption in the long wavelength region, it is necessary to repeat a complicated synthesis step. However, the inclusion complex can be obtained by a very simple method, and is suitable for production. Excellent.
In addition, curcumin or derivatives and acyclic polysaccharides used in the resulting inclusion complex are naturally derived components, so-called carbon neutral plant-derived compounds, It is preferable also from a point.
以下では、まず、包接複合体の製造方法で使用される材料（非環状多糖類、クルクミン類、非プロトン性極性溶媒など）について詳述し、その後、製造方法の手順、および、得られた包接複合体について詳述する。 In the following, first, materials (acyclic polysaccharide, curcumin, aprotic polar solvent, etc.) used in the production method of the inclusion complex will be described in detail, and then the procedure of the production method and the obtained The inclusion complex will be described in detail.
＜非環状多糖類＞
非環状多糖類は、環状でない多糖類である。より具体的には、直鎖状または分岐鎖状の多糖類を意図し、シクロデキストリンなどの環状の多糖類は含まれない。このような非環状多糖類であれば、クルクミン類を内部に包接することができ、その包接複合体自体の安定性にも優れる。
なかでも、包接複合体の諸特性（光吸収特性および水への溶解性）がより優れる点で、直鎖状の多糖類が好ましい。
<Acyclic polysaccharide>
Acyclic polysaccharides are polysaccharides that are not cyclic. More specifically, a linear or branched polysaccharide is intended, and cyclic polysaccharides such as cyclodextrins are not included. With such a non-cyclic polysaccharide, curcumin can be included inside and the stability of the inclusion complex itself is excellent.
Among these, linear polysaccharides are preferred in that the various characteristics (light absorption characteristics and water solubility) of the inclusion complex are more excellent.
非環状多糖類としては、単糖類反復単位を含む骨格を有する直鎖状または分岐鎖状のポリマーであり、ホモ多糖類でもヘテロ多糖類であってもよい。例えば、キチン、キトサン等のキチン質類、アミロース、グリコーゲン、アミロペクチン、キサンタンガム等のα−グルカン類、例えば、ラミナラン、カードラン、セルロース等のβ−グルカン類、ローカストビーンガム、グアーガム、フェヌグリークガム等のガラクトマンナン類、ラムナン硫酸、コンドロイチン硫酸、デルタマン硫酸、ヘパラン硫酸、フコイダン、ケラタン硫酸、ヒアルロン酸等のようなグリコサミノグリカン類（ムコ多糖類）、イヌリン、レバン等のフルクタン類、ポリガラクツロン酸、ホモガラクツロナン、ラムノガラクツロナン−I、ラムノガラクツロナン−II等のペクチン類、キシラン、アラビノキシラン、キシログルカン等のヘミセルロース類などが挙げられる。なかでも、包接複合体の光吸収特性および水への溶解性がより優れる点で、α−グルカン類またはペクチン類が好ましく、アミロースまたはポリガラクツロン酸がより好ましい。 The acyclic polysaccharide is a linear or branched polymer having a skeleton containing a monosaccharide repeating unit, and may be a homopolysaccharide or a heteropolysaccharide. For example, chitins such as chitin and chitosan, α-glucans such as amylose, glycogen, amylopectin and xanthan gum, for example, β-glucans such as laminaran, curdlan and cellulose, locust bean gum, guar gum, fenugreek gum and the like Galactomannans, rhamnan sulfate, chondroitin sulfate, deltaman sulfate, heparan sulfate, fucoidan, keratan sulfate, hyaluronic acid, etc. glycosaminoglycans (mucopolysaccharides), fructans such as inulin, levan, polygalacturonic acid, Examples include pectins such as homogalacturonan, rhamnogalacturonan-I and rhamnogalacturonan-II, and hemicelluloses such as xylan, arabinoxylan and xyloglucan. Of these, α-glucans or pectins are preferable, and amylose or polygalacturonic acid is more preferable in terms of more excellent light absorption characteristics and water solubility of the inclusion complex.
また、本発明で使用される非環状多糖類は、上記例示のとおり、変性されていないものであってもよく、置換基等を導入した変性物であってもよい。変性された非環状多糖類としては、例えば、変性デンプン、変性アミロペクチン、変性アミロース、変性セルロース、変性ガラクトマンナン、変性グルコマンナン、変性キサンタンガム、変性カラギーナン等が挙げられる。これらの変性物を得るための変性手法としては、各非環状多糖類のアセチル化処理等のエステル化、カルボキシアルキル化等のエーテル化、リン酸化、酸化、硫酸化、リン酸架橋、アジピン酸架橋、酵素処理およびそれらの組み合わせにより得られるものである。 In addition, the non-cyclic polysaccharide used in the present invention may be unmodified as described above, or may be a modified product into which a substituent or the like is introduced. Examples of the modified acyclic polysaccharide include modified starch, modified amylopectin, modified amylose, modified cellulose, modified galactomannan, modified glucomannan, modified xanthan gum, and modified carrageenan. Modification methods for obtaining these modified products include esterification such as acetylation treatment of each acyclic polysaccharide, etherification such as carboxyalkylation, phosphorylation, oxidation, sulfation, phosphoric acid crosslinking, adipic acid crosslinking , Obtained by enzyme treatment and combinations thereof.
非環状多糖類の質量平均分子量は特に制限されないが、取扱い性により優れる点で、５００以上が好ましく、１０００以上がより好ましく、２０００以上がさらに好ましく、５０００以上が特に好ましく、１００００以上が最も好ましい。また、その上限は特に限定されないが、１０００万以下が好ましく、８００万以下がさらに好ましく、５００万以下が特に好ましい。
なお、非環状多糖類は、単独で使用しても二種類以上を混合使用してもよい。
The mass average molecular weight of the acyclic polysaccharide is not particularly limited, but is preferably 500 or more, more preferably 1000 or more, further preferably 2000 or more, particularly preferably 5000 or more, and most preferably 10,000 or more in terms of superior handling properties. The upper limit is not particularly limited, but is preferably 10 million or less, more preferably 8 million or less, and particularly preferably 5 million or less.
In addition, an acyclic polysaccharide may be used individually or may be used in mixture of 2 or more types.
＜クルクミン類＞
クルクミン類は、式（１）で表される。
<Curcumin>
Curcumin is represented by Formula (1).
式（１）中、Ｒ1およびＲ2は、それぞれ独立に、水素原子、または、アルコキシ基を表す。
アルコキシ基中のアルキル部分の炭素数は特に制限されないが、包接複合体の各種特性（光吸収特性、水への溶解性）がより優れる点より、炭素数１〜６が好ましく、例えば、メチル、エチル、プロピル、イソプロピル、ブチル、ｓｅｃ−ブチル、ｔｅｒｔ−ブチル、ペンチル、ヘキシルが挙げられる。
Ｌ1およびＬ2は、それぞれ独立に、−Ｃ＝Ｃ−または−ＣＨ2ＣＨ2−を表す。
なかでも、包接複合体の各種特性（光吸収特性、水への溶解性）がより優れる点より、Ｌ1およびＬ2が、−Ｃ＝Ｃ−であることが好ましい。
In formula (1), R 1 and R 2 each independently represents a hydrogen atom or an alkoxy group.
The number of carbon atoms of the alkyl moiety in the alkoxy group is not particularly limited, but is preferably 1 to 6 carbon atoms from the viewpoint that the various properties of the inclusion complex (light absorption characteristics, solubility in water) are more excellent. , Ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl.
L 1 and L 2 each independently represent —C═C— or —CH 2 CH 2 —.
Among them, various characteristics (light absorption properties, solubility in water) of the inclusion complex than that more excellent, L 1 and L 2 are preferably -C = a C-.
上記式で表されるクルクミン類としては、例えば、テトラヒドロクルクミン、テトラヒドロジメトキシクルクミン、ビスジメトキシクルクミン、テトラヒドロビスジメトキシクルクミンなどが挙げられる。 Examples of the curcumin represented by the above formula include tetrahydrocurcumin, tetrahydrodimethoxycurcumin, bisdimethoxycurcumin, and tetrahydrobisdimethoxycurcumin.
＜非プロトン性極性溶媒＞
非プロトン性極性溶媒としては公知の溶媒を使用することができ、例えば、エーテル類（ジエチルエーテル、ジイソプロピルエーテル、テトラヒドロフラン、１，２−ジオキサンなど）、カーボネート類（エチレンカーボネート、エチルメチルカーボネート、ジエチルカーボネート、ジメチルカーボネート、プロピレンカーボネート、ブチレンカーボネートなど）、アミド類（ホルムアミド、Ｎ−メチルホルムアミド、Ｎ−メチルアセトアミド、Ｎ−エチルホルムアミド、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジエチルホルムアミド、アセトアミド、Ｎ−メチルアセトアミド、Ｎ−エチルアセトアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジエチルアセトアミド、Ｎ−メチル−２−ピロリドン、Ｎ−エチル−２−ピロリドン、ピペリドン、Ｎ−メチルピペリドン、Ｎ−エチルピペリドン、ヘキサメチルホスホリックトリアミド、１，３−ジメチル−２−イミダゾリジノン、メチルオキサゾリジノン、エチルオキサゾリジノンなど）、スルホキシド類（ジメチルスルホキシドなど）、スルホン類（テトラメチレンスルホンなど）、イオン性液体などを挙げることができる。
<Aprotic polar solvent>
As the aprotic polar solvent, known solvents can be used. For example, ethers (diethyl ether, diisopropyl ether, tetrahydrofuran, 1,2-dioxane, etc.), carbonates (ethylene carbonate, ethyl methyl carbonate, diethyl carbonate) Dimethyl carbonate, propylene carbonate, butylene carbonate, etc.), amides (formamide, N-methylformamide, N-methylacetamide, N-ethylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N- Methylacetamide, N-ethylacetamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, pipette Don, N-methylpiperidone, N-ethylpiperidone, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone, methyl oxazolidinone, ethyl oxazolidinone, sulfoxides (dimethyl sulfoxide, etc.), sulfones (tetramethylene) Sulfone and the like) and ionic liquids.
なお、イオン性液体とは、イオンのみ（アニオン、カチオン）から構成される塩であり、通常、常温で液体状であるという性質を持つ。
例えば、大野弘幸編「イオン性液体−開発の最前線と未来−」ＣＭＣ出版（２００３）、「イオン性液体の機能創製と応用」エヌ・ティー・エス（２００４）等に記載されている第４級アンモニウム塩類、イミダゾリウム塩類、ピリジニウム塩類、ピロリジニウム塩類、ピペリジニウム塩類等を使用することができる。
The ionic liquid is a salt composed of only ions (anions and cations) and usually has a property of being liquid at room temperature.
For example, the fourth described in Hiroyuki Ohno, “Ionic Liquids—Development Frontiers and Future”, CMC Publishing (2003), “Functional Creation and Application of Ionic Liquids” NTS (2004), etc. Secondary ammonium salts, imidazolium salts, pyridinium salts, pyrrolidinium salts, piperidinium salts, and the like can be used.
上記イオン性液体のカチオンとしては、例えば、ピリジニウム系カチオン、イミダゾリウム系カチオン、アンモニウム系カチオン、ピロリジニウム系カチオン、ピペリジニウム系カチオン、ホスホニウム系カチオンなどが挙げられる。 Examples of the cation of the ionic liquid include a pyridinium cation, an imidazolium cation, an ammonium cation, a pyrrolidinium cation, a piperidinium cation, and a phosphonium cation.
一方、上記イオン性液体が有するアニオンとしては、具体的には、Ｉ-、Ｂｒ-、ＡｌＣｌ4 -、Ａｌ2Ｃｌ7 -、ＮＯ3 -、ＢＦ4 -、ＰＦ6 -、ＣＨ3ＣＯＯ-、ＣＦ3ＣＯＯ-、ＣＦ3ＳＯ3 -、（ＣＮ）4Ｂ-、ＳＣＮ-、（ＣＦ3ＳＯ2）2Ｎ-、（ＦＳＯ2）2Ｎ-、（ＣＮ）2Ｎ-、（ＣＦ3ＳＯ2）3Ｃ-、（ＣＮ）3Ｃ-、ＡｓＦ6 -、ＳｂＦ6 -、Ｆ（ＨＦ）n -、ＣＦ3ＣＦ2ＣＦ2ＣＦ2ＳＯ3 -、（ＣＦ3ＣＦ2ＳＯ2）2Ｎ-、ＣＦ3ＣＦ2ＣＦ2ＣＯＯ-などが好適に例示される。 On the other hand, specific examples of the anion of the ionic liquid include I − , Br − , AlCl 4 − , Al 2 Cl 7 − , NO 3 − , BF 4 − , PF 6 − , CH 3 COO − , CF 3 COO − , CF 3 SO 3 − , (CN) 4 B − , SCN − , (CF 3 SO 2 ) 2 N − , (FSO 2 ) 2 N − , (CN) 2 N − , (CF 3 SO 2 ) 3 C − , (CN) 3 C − , AsF 6 − , SbF 6 − , F (HF) n − , CF 3 CF 2 CF 2 CF 2 SO 3 − , (CF 3 CF 2 SO 2 ) 2 N -, CF 3 CF 2 CF 2 COO - , etc. can be preferably exemplified.
＜包接複合体の製造方法＞
本発明の包接複合体の製造方法は、非プロトン性極性溶媒中において、上述した非環状多糖類および式（１）で表されるクルクミン類（以後、単にクルクミン類とも称する）を混合する工程を備える。非プロトン性極性溶媒中で２種の化合物を混合することにより、クルクミン類が非環状多糖類で包接（内包）された包接複合体が得られる。
以下に、工程の手順について詳述する。
<Method for producing inclusion complex>
The method for producing an inclusion complex of the present invention comprises a step of mixing the acyclic polysaccharide and the curcumin represented by the formula (1) (hereinafter also simply referred to as curcumin) in an aprotic polar solvent. Is provided. By mixing two compounds in an aprotic polar solvent, an inclusion complex in which curcumin is included (encapsulated) with an acyclic polysaccharide is obtained.
Below, the procedure of a process is explained in full detail.
本工程で使用される非環状多糖類とクルクミン類との混合モル比は特に制限されないが、包接複合体の各種特性（光吸収特性、水への溶解性）がより優れる点で、混合モル比（非環状多糖類の繰り返し単位のモル数／クルクミン類のモル数）は０．１〜１００が好ましく、１〜５０がより好ましく、１．５〜１０がさらに好ましい。 The mixing molar ratio of the acyclic polysaccharide and curcumin used in this step is not particularly limited, but the mixing mole is that the various characteristics (light absorption characteristics, solubility in water) of the inclusion complex are more excellent. The ratio (number of moles of repeating unit of acyclic polysaccharide / number of moles of curcumin) is preferably from 0.1 to 100, more preferably from 1 to 50, and even more preferably from 1.5 to 10.
本工程で使用される非プロトン性極性溶媒中におけるクルクミン類の濃度は特に制限されないが、包接複合体の各種特性（光吸収特性、水への溶解性）がより優れる点で、０．０１〜１００ｍＭが好ましく、０．１〜５０ｍＭがより好ましく、０．５〜１０ｍＭがさらに好ましい。 The concentration of curcumin in the aprotic polar solvent used in this step is not particularly limited, but it is 0.01 in that the various characteristics (light absorption characteristics, water solubility) of the inclusion complex are more excellent. -100 mM is preferable, 0.1-50 mM is more preferable, and 0.5-10 mM is further more preferable.
非環状多糖類とクルクミン類とを混合する手順は特に制限されず、例えば、非プロトン性極性溶媒中に非環状多糖類とクルクミン類とを添加して、混合する方法が挙げられる。非プロトン性極性溶媒中への化合物の添加順は特に制限されず、非環状多糖類とクルクミン類とを同時に添加してもよく、非環状多糖類およびクルクミン類のいずれか一方を先に添加して、所定時間経過後に他方を添加してもよい。 The procedure for mixing the acyclic polysaccharide and curcumin is not particularly limited, and examples thereof include a method in which the acyclic polysaccharide and curcumin are added and mixed in an aprotic polar solvent. The order of addition of the compound in the aprotic polar solvent is not particularly limited, and the acyclic polysaccharide and curcumin may be added at the same time, and either the acyclic polysaccharide or curcumin is added first. The other may be added after a predetermined time has elapsed.
非環状多糖類とクルクミン類との混合時間は特に制限されず、使用される非プロトン性極性溶媒の種類などに応じて適宜最適な条件が選択されるが、生産性・収率などの観点から、１０〜３６０分であることが好ましく、３０〜１２０分であることがより好ましい。
また、非環状多糖類とクルクミン類とを混合する際に、加熱処理を施してもよい。加熱処理を施すことにより、両者の化合物の溶解がより進行し、包接複合体の製造が促進される。加熱温度は特に制限されず、使用される非プロトン性極性溶媒の種類などに応じて適宜最適な条件が選択されるが、生産性・収率などの観点から、３０〜１００℃であることが好ましく、４０〜８０℃であることがより好ましい。
The mixing time of the acyclic polysaccharide and curcumin is not particularly limited, and optimal conditions are appropriately selected according to the type of aprotic polar solvent used, but from the viewpoint of productivity, yield, etc. 10 to 360 minutes, and more preferably 30 to 120 minutes.
Moreover, you may heat-process, when mixing acyclic polysaccharide and curcumin. By performing the heat treatment, the dissolution of both compounds further proceeds, and the production of the inclusion complex is promoted. The heating temperature is not particularly limited, and optimal conditions are appropriately selected according to the type of aprotic polar solvent used, but from the viewpoint of productivity and yield, it should be 30 to 100 ° C. Preferably, it is 40-80 degreeC.
＜包接複合体、包接複合体含有組成物＞
上記工程を経ることにより、非環状多糖類と非環状多糖類により包接されたクルクミン類とを含む包接複合体を含む組成物が得られる。
包接複合体は長波長領域（特に、５００〜７００ｎｍ）において優れた光吸収特性を示すと共に、水への溶解性が優れ、水への再分散が可能である。
組成物中の包接複合体には、その内部にクルクミン類が含まれ、クルクミン類を包む（内包する）ように非環状多糖類が配置される。包接複合体が長波長領域に優れた光吸収特性を示す理由は不明だが、包接複合体内部で複数（２つ以上）のクルクミン類が会合（または凝集）して会合体（または凝集体）を形成することにより、クルクミン類間で相互作用が生じ、長波長領域での吸収が生じたと考えられる。
<Inclusion complex, inclusion complex-containing composition>
By passing through the said process, the composition containing the inclusion complex containing the acyclic polysaccharide and the curcumin included by the acyclic polysaccharide is obtained.
The inclusion complex exhibits excellent light absorption characteristics in a long wavelength region (particularly, 500 to 700 nm), has excellent solubility in water, and can be redispersed in water.
The inclusion complex in the composition contains curcumin therein, and an acyclic polysaccharide is disposed so as to enclose (enclose) the curcumin. The reason why the inclusion complex exhibits excellent light absorption characteristics in the long wavelength region is unclear, but multiple (two or more) curcumins associate (or aggregate) within the inclusion complex to form an aggregate (or aggregate). ) Is considered to cause an interaction between curcumins and absorption in a long wavelength region.
包接複合体および包接複合体含有組成物は種々の用途に使用することができ、例えば、光電子機能素子（例えば、太陽電池（特に、色素増感太陽電池や有機薄膜太陽電池））の材料、触媒（例えば、水の光分解による水素発生触媒）などへの利用が可能である。特に、色素増感太陽電池の色素として有用である。 The inclusion complex and the inclusion complex-containing composition can be used for various applications, for example, materials for optoelectronic functional elements (for example, solar cells (particularly dye-sensitized solar cells and organic thin film solar cells)). And can be used as a catalyst (for example, a hydrogen generation catalyst by photolysis of water). It is particularly useful as a dye for dye-sensitized solar cells.
また、包接複合体中のクルクミン類に含まれるβ−ジケトン構造部は金属イオンの配位部位として利用可能である。つまり、包接複合体には、さらに金属イオンが含まれていてもよい。
β−ジケトン構造部に配位可能な金属イオンの金属種としては、例えば、Ｒｕ、Ｃｒ、Ｆｅ、Ｃｕ、Ｂ、Ｏｓ、Ｉｒ、Ｐｔ、Ｅｕ、ＴｂおよびＴｉなどが挙げられる。
また、クルクミン類のβ−ジケトン構造部に金属イオンが配位する場合、他の公知の配位子を合わせて使用してもよい。公知の配位子としては、例えば、アセチルアセトンなどのジケトン化合物、ジフェニルホスフィノエタン、ジフェニルホスフィノプロパン、ジフェニルホスフィノブタンなどのホスフィン系化合物、フェナントロリン、ビスビピリジル、ターピリジル、ピリジン、フェニルピリジン、２−アリールピリジンなどのアリール系置換基を有するピリジン、イミダゾール、トリアゾール、インドール、ピリミジン、キノリン、ピラゾール、チアゾール、オキサゾール、ベンゾイミダゾール、ベンゾオキサゾール、ベンゾチアゾールなどが挙げられる。
Moreover, the β-diketone structure part contained in the curcumins in the inclusion complex can be used as a coordination site for metal ions. That is, the clathrate complex may further contain a metal ion.
Examples of metal species of metal ions that can be coordinated to the β-diketone structure include Ru, Cr, Fe, Cu, B, Os, Ir, Pt, Eu, Tb, and Ti.
Moreover, when a metal ion coordinates to the β-diketone structure part of curcumin, other known ligands may be used in combination. Known ligands include, for example, diketone compounds such as acetylacetone, phosphine compounds such as diphenylphosphinoethane, diphenylphosphinopropane, diphenylphosphinobutane, phenanthroline, bisbipyridyl, terpyridyl, pyridine, phenylpyridine, 2- Examples include pyridine having an aryl substituent such as arylpyridine, imidazole, triazole, indole, pyrimidine, quinoline, pyrazole, thiazole, oxazole, benzimidazole, benzoxazole, and benzothiazole.
例えば、Ｒｕの配位子としては、ビスビピリジルなどが用いられ、Ｉｒの配位子としては、フェニルピリジン等が用いられ、Ｅｕの配位子としてはビピリジル、Ｔｂの配位子としては、アセチルアセトンなどが用いられる。Ｐｔの配位子としては、ピリジン、フェニルピリジン、イミダゾール、トリアゾール、インドール、ピリミジン、キノリン、ピラゾール、チアゾール、オキサゾール、ベンゾイミダゾール、ベンゾオキサゾール、ベンゾチアゾールなどの単座配位子が用いられる。 For example, bisbipyridyl and the like are used as the Ru ligand, phenylpyridine and the like are used as the Ir ligand, bipyridyl as the Eu ligand, and acetylacetone as the Tb ligand. Etc. are used. As the ligand for Pt, monodentate ligands such as pyridine, phenylpyridine, imidazole, triazole, indole, pyrimidine, quinoline, pyrazole, thiazole, oxazole, benzimidazole, benzoxazole, and benzothiazole are used.
包接複合体に金属イオンを含有させる方法は特に制限されず、例えば、上記工程で得られた包接複合体含有組成物中に所定の金属イオンを加えて、混合させ、クルクミン類のβ−ジケトン構造部に金属イオンを配位させる方法や、金属イオンが配位したクルクミン類を用いて上記工程を実施して、包接複合体を得る方法などが挙げられる。 The method for adding metal ions to the inclusion complex is not particularly limited. For example, a predetermined metal ion is added to and mixed with the inclusion complex-containing composition obtained in the above step, and β- Examples thereof include a method of coordinating metal ions to the diketone structure, and a method of obtaining an inclusion complex by carrying out the above steps using curcumins coordinated with metal ions.
以下、実施例により、本発明について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。 EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.
＜実施例１＞
ジメチルスルホキシド（以後、ＤＭＳＯとも称する）（１０ｍｌ）中に、クルクミン（濃度：４ｍＭ）およびアミロース（アミロースの繰り返し単位のユニット換算モル濃度：１０ｍＭ、SIGMA; Amylose from potato）を加え、７０℃で１２０分間攪拌した。反応溶液は、攪拌と共に、溶液の色が黄色から黒色に変化していき、包接複合体が形成されていることが確認された。得られた反応溶液の紫外・可視吸収スペクトル測定を行ったところ、５００〜７００ｎｍに付近にクルクミン類の会合体（または凝集体）由来と推測される新たな吸収ピークが生じていることが確認された（図１参照）。
なお、その後７０℃でＤＭＳＯを減圧留去後、７０℃で加熱真空乾燥し黒色の固体である包接複合体を得た。得られた包接複合体を水中に添加したところ、可溶した。結果を表１にまとめて示す。
<Example 1>
Curcumin (concentration: 4 mM) and amylose (unit conversion molar concentration of amylose repeating unit: 10 mM, SIGMA; Amylose from potato) were added to dimethyl sulfoxide (hereinafter also referred to as DMSO) (10 ml) at 70 ° C. for 120 minutes. Stir. As the reaction solution stirred, the color of the solution changed from yellow to black, confirming the formation of an inclusion complex. When the obtained reaction solution was subjected to ultraviolet / visible absorption spectrum measurement, it was confirmed that a new absorption peak presumed to be derived from an aggregate (or aggregate) of curcumin was generated in the vicinity of 500 to 700 nm. (See FIG. 1).
After that, DMSO was distilled off under reduced pressure at 70 ° C., followed by heating and vacuum drying at 70 ° C. to obtain an inclusion complex as a black solid. When the resulting inclusion complex was added to water, it was soluble. The results are summarized in Table 1.
＜実施例２＞
アミロースの繰り返し単位のユニット換算モル濃度を１０ｍＭから２０ｍＭに変更した以外は、実施例１と同様の手順に従って、包接複合体を製造した。各種測定結果を表１にまとめて示す。
<Example 2>
An inclusion complex was produced according to the same procedure as in Example 1 except that the unit conversion molar concentration of the repeating unit of amylose was changed from 10 mM to 20 mM. Various measurement results are summarized in Table 1.
＜実施例３＞
アミロースの繰り返し単位のユニット換算モル濃度を１０ｍＭから３０ｍＭに変更した以外は、実施例１と同様の手順に従って、包接複合体を製造した。各種測定結果を表１にまとめて示す。
<Example 3>
An inclusion complex was produced according to the same procedure as in Example 1 except that the unit conversion molar concentration of the repeating unit of amylose was changed from 10 mM to 30 mM. Various measurement results are summarized in Table 1.
＜比較例１＞
アミロースを使用せずに実施例１と同様の手順に従って、クルクミン類をジメチルスルホキシドに添加して混合した。得られた溶液では、長波長領域に新たなピークの上昇は見られたが、ジメチルスルホキシドを除去して得られた粉末は水に溶解しなかった。
<Comparative Example 1>
According to the same procedure as in Example 1 without using amylose, curcumins were added to dimethyl sulfoxide and mixed. In the obtained solution, an increase in a new peak was observed in the long wavelength region, but the powder obtained by removing dimethyl sulfoxide did not dissolve in water.
＜比較例２＞
ジメチルスルホキシドの代わりにメタノールを使用した以外は、比較例１の手順に従って、クルクミン類を添加した。得られた溶液では、長波長領域に新たなピークは見られなかった。
<Comparative Example 2>
Curcumins were added according to the procedure of Comparative Example 1 except that methanol was used instead of dimethyl sulfoxide. In the obtained solution, no new peak was observed in the long wavelength region.
＜比較例３＞
ジメチルスルホキシドの代わりにメタノールを使用した以外は、実施例１の手順に従って、クルクミン類およびアミロースを添加したが、アミロースがメタノールに溶解しなかった。
<Comparative Example 3>
Curcumin and amylose were added according to the procedure of Example 1 except that methanol was used instead of dimethyl sulfoxide, but amylose was not dissolved in methanol.
以下の、表１中、「アミロース」欄では、溶媒中でのアミロースの繰り返し単位のモル濃度を表す。
表１中、「長波長領域での吸収ピーク」欄は、紫外・可視吸収スペクトル測定において５００〜７００ｎｍの領域に新たなピークが確認された場合を「○」、確認されなかった場合を「×」として示す。
表１中、「水への溶解性」欄は、反応溶液から溶媒を除去して得られた粉末が水に溶解（可溶）する場合を「○」、溶解しない、または、一部粉末が残る場合を「×」として示す。
In Table 1 below, the “amylose” column represents the molar concentration of repeating units of amylose in the solvent.
In Table 1, the “absorption peak in the long wavelength region” column indicates “○” when a new peak is confirmed in the region of 500 to 700 nm in the ultraviolet / visible absorption spectrum measurement, and “×” when it is not confirmed. ".
In Table 1, the column “Solubility in water” is “O” when the powder obtained by removing the solvent from the reaction solution is soluble (soluble), not dissolved, or part of the powder is The remaining case is indicated as “x”.
表１に示すように、実施例１〜３において、アミロースとクルクミンとを非プロトン性極性溶媒中で混合することにより得られる包接複合体は、長波長領域における光吸収特性に優れると共に、水への溶解性にも優れていた。
一方、アミロースを使用していない比較例１においては、長波長領域での吸収ピークの上昇はみられるものの、得られた固形分は水への溶解性を示さなかった。これは、ＤＭＳＯ溶液中ではクルクミンの会合（または凝集）が生じているが、ＤＭＳＯを除去して得られる固体（クルクミン）は非環状多糖に内包されていないので、水への溶解性に劣ると推測される。
また、比較例２および３に示すように、非プロトン性極性溶媒を使用しなかった場合は、長波長領域での吸収特性の改善は見られなかった。
As shown in Table 1, in Examples 1 to 3, the inclusion complex obtained by mixing amylose and curcumin in an aprotic polar solvent has excellent light absorption characteristics in the long wavelength region, and water It was also excellent in solubility.
On the other hand, in Comparative Example 1 in which amylose was not used, although the absorption peak increased in the long wavelength region, the obtained solid content did not exhibit solubility in water. This is because the association (or aggregation) of curcumin occurs in the DMSO solution, but the solid (curcumin) obtained by removing DMSO is not encapsulated in the non-cyclic polysaccharide, so that the solubility in water is poor. Guessed.
Further, as shown in Comparative Examples 2 and 3, when no aprotic polar solvent was used, no improvement in absorption characteristics in the long wavelength region was observed.
＜実施例４＞
１−ブチル−３−メチルイミダゾリウムブロミドを溶媒として使用し、この溶媒中にアミロース（アミロースの繰り返し単位のユニット換算モル濃度：２０ｍＭ、SIGMA; Amylose from potato）を加えて、６０℃で加熱撹拌し溶解させた。その後、得られた溶液にクルクミン（４ｍＭ）を加えて、６０℃で１時間加熱撹拌して混合したところ、実施例１と同様に、溶液の色が黄色から黒色に変化していき、包接複合体が形成されていることが確認された。
得られた反応溶液の紫外・可視吸収スペクトル測定を行ったところ、５００〜９００ｎｍに付近にクルクミン類の会合体（または凝集体）由来と推測される新たな吸収ピークが生じていることが確認された（図２参照）。
<Example 4>
1-Butyl-3-methylimidazolium bromide was used as a solvent, amylose (unit conversion molar concentration of amylose repeating unit: 20 mM, SIGMA; Amylose from potato) was added to this solvent, and the mixture was heated and stirred at 60 ° C. Dissolved. Thereafter, curcumin (4 mM) was added to the resulting solution, and the mixture was heated and stirred at 60 ° C. for 1 hour, and mixed. As in Example 1, the color of the solution changed from yellow to black. It was confirmed that a complex was formed.
When the obtained reaction solution was subjected to ultraviolet / visible absorption spectrum measurement, it was confirmed that a new absorption peak presumed to be derived from an aggregate (or aggregate) of curcumin was generated in the vicinity of 500 to 900 nm. (See FIG. 2).
Claims (6)
（式（１）中、Ｒ1およびＲ2は、それぞれ独立に、水素原子、または、アルコキシ基を表す。Ｌ1およびＬ2は、それぞれ独立に、−Ｃ＝Ｃ−または−ＣＨ2ＣＨ2−を表す。） An inclusion complex containing an acyclic polysaccharide and a curcumin represented by the formula (1) enclosed by the acyclic polysaccharide, and an inclusion complex-containing composition containing an aprotic polar solvent .
(In formula (1), R 1 and R 2 each independently represents a hydrogen atom or an alkoxy group. L 1 and L 2 each independently represent —C═C— or —CH 2 CH 2. Represents-)
（式（１）中、Ｒ1およびＲ2は、それぞれ独立に、水素原子、または、アルコキシ基を表す。Ｌ1およびＬ2は、それぞれ独立に、−Ｃ＝Ｃ−または−ＣＨ2ＣＨ2−を表す。） By mixing the acyclic polysaccharide and the curcumin represented by the formula (1) in an aprotic polar solvent, the acyclic polysaccharide and the curcumin included by the acyclic polysaccharide are included. A method for producing an inclusion complex, which comprises producing an inclusion complex.
(In formula (1), R 1 and R 2 each independently represents a hydrogen atom or an alkoxy group. L 1 and L 2 each independently represent —C═C— or —CH 2 CH 2. Represents-)
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