JPH10195106A - Production of high-purity fucoidan from cultured itomozuku - Google Patents

Abstract

PROBLEM TO BE SOLVED: To extract and produce purely white high-quality fucoidan from cultured itomozuku, a kind of seaweed of the genus Nemacystus decipiens, by a simple and easy process. SOLUTION: Currently, fucoidan is produced from a Kombu and the like; however, since the content of fucoidan in a Kombu is low and the content of alginic acid, a polysaccharide, is high, the production process of fucoidan from a Kombu is complicated, resulting in high-price fucoidan. Moreover, fucoidan now available commercially is brown and poor in quality. Contrary to expectations, high-purity (purely white) fucoidan having a mol.wt. of 500,000 can be produced by dispersing itomozuku in an acidic soln. and stirring at room temp., though itomozuku contains alginic acid in a high content (1.5 times that of fucoidan). Because of the brown color, very low purity, and high price, a commercially available fucoidan is limited in its application; therefore, the production of high-quality fucoidan raises the value added. For producing purely white high-quality fucoidan, the use of a freeze drier is the most important.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【産業上の利用分野】 本発明は，低コレステロール
剤，抗胃潰瘍剤，抗癌剤，抗エイズウイルス剤，抗細菌
付着剤，保湿剤，および増粘剤等に利用が期待される高
純度のフコイダンの製造に関するものである．現在，昆
布類がフコイダンの供給藻であるが，含量が少なく，複
雑な工程を経て製造されているのでフコイダンが極めて
高価な素材である．イトモズクから製造したフコイダン
は硫酸含量が高いことから，上述の諸生理活性を有する
ことが考えられ，特に医薬品の分野で利用・開発の可能
性が高い．The present invention relates to a high-purity fucoidan which is expected to be used as a low-cholesterol agent, an anti-gastric ulcer agent, an anti-cancer agent, an anti-AIDS virus agent, an anti-bacterial adhesive, a humectant, a thickener and the like. It is about manufacturing. At present, kelp is the supply alga of fucoidan, but fucoidan is an extremely expensive material because it is produced through a complicated process with low content. Since fucoidan produced from Ito mozuku has a high sulfuric acid content, it is considered to have the above-mentioned various physiological activities, and it is highly likely to be used and developed especially in the field of pharmaceuticals.

【発明の背景】フコイダンは褐藻類（モズク類，昆布
類，ワカメ類，およびヒジキ類）にアルギン酸と共存す
る多糖で，従来昆布類から製造され，販売されている．
しかしながら，昆布類にはフコイダンの含量が少なく量
産化が困難であるため，フコイダンは高価な価格で販売
されている．一方，イトモズクはオキナワモズクと同
様，沖縄県で養殖により生産され，全国の需要の約１０
０％を供給している生物資源である．発明者は先に，オ
キナワモズクにに加え，イトモズクにも多量のフコイダ
ンが存在することを明らかにした．オキナワモズクから
高い純度のフコイダンを製造する方法については，現在
特許申請中である（整理番号Ｐ２２３１９Ｈ９−１）．BACKGROUND OF THE INVENTION Fucoidan is a polysaccharide that coexists with alginic acid in brown algae (mozuku, kelp, seaweed, and hijiki), and is conventionally manufactured and sold from kelp.
However, fucoidan is sold at an expensive price because it contains a small amount of fucoidan and is difficult to mass-produce. On the other hand, Ito mozuku, like Okinawa mozuku, is produced by cultivation in Okinawa Prefecture and has about 10% of the national demand.
It is a biological resource that supplies 0%. The inventor has previously shown that, in addition to Okinawa mozuku, Ito mozuku also has a large amount of fucoidan. A method for producing high-purity fucoidan from Okinawa mozuku is currently undergoing patent application (reference number P22319H9-1).

【発明の目的】イトモズクにフコイダンが存在すること
はよく知られているが，養殖イトモズクについては報告
されてない．また，市販のフコイダンは薄い褐色を呈し
ており，品質が高くない．本発明の条件で養殖イトモズ
クから抽出および精製を行うと，アルギン酸や蛋白質さ
らには褐色の色素の混入を防ぐことが出来，純白で安価
なフコイダンを製造して供給することが出来る．表１
に，イトモズクから製造したフコイダンの構成糖および
硫酸の比を示した．本フコイダンは，Ｌ−フコース，Ｄ
−ガラクトース，Ｄ−キシロース，および硫酸が１０：
１：１：３で構成する多糖である．本フコイダンは，Ｄ
−グルクロン酸を含まず，硫酸含量が著しく高いことに
特色がある． [Object of the Invention] It is well known that Fucoidan is present in Ito mozuku, but there is no report of cultured Ito mozuku. Commercially available fucoidan has a light brown color and is not of high quality. When extraction and purification are performed from cultured Ido mozuku under the conditions of the present invention, contamination with alginic acid, protein, and brown pigment can be prevented, and pure white and inexpensive fucoidan can be produced and supplied. Table 1
Figure 2 shows the ratio of the constituent sugars and sulfuric acid of fucoidan produced from Ito mozuku. This fucoidan is L-fucose, D
-Galactose, D-xylose and sulfuric acid are 10:
It is a polysaccharide composed of 1: 1: 3. This fucoidan is D
-It is characterized by not containing glucuronic acid and having a remarkably high sulfuric acid content.

【発明の構成】発明者は上述の問題点に着目し，種々検
討した結果，養殖イトモズクを塩酸，硫酸，または修酸
水溶液で室温で数時間撹拌することによってフコイダン
を抽出することが出来ることを発明した．抽出液は酸性
であることから，アルカリ（水酸化ナトリウムまたは水
酸比カリウム）で中和後脱塩を行い，凍結乾燥またはア
ルコールを添加して沈殿させ粗フコイダンを製造するこ
とが出来る．特に，凍結乾燥機を使用してフコイダンを
製造する方法は養殖イトモズクに加え，養殖オキナワモ
ズクから高い純度のフコイダンを製造する際にも有用で
ある．しかしながら，養殖イトモズクから製造した粗フ
コイダンにはアルギン酸，蛋白質，および褐色の色素が
混入していた．なお，粗フコイダンの収率は０．８％
（対湿潤藻体）であった．この方法で製造した多糖を粗
フコイダンと命名する．上述の条件で製造したフコイダ
ンは，薄い褐色を呈し，相当量のアルギン酸および蛋白
質を含むことから，高品質のフコイダンを得る精製条件
を種々検討した結果，粗フコイダンを塩化バリウム溶液
に撹拌溶解後，ケイソウ土濾過を行うことによって，白
色でアルギン酸および蛋白質の混入のないフコイダンを
製造することが出来た．精製フコイダンの収率は０．６
％（対湿潤藻体）であった．なお，この様な条件で製造
したフコイダンを精製フコイダンと命名する．この様
に，本発明の特徴は，酸性（塩酸，硫酸，または修酸）
溶液でフコイダンを抽出し，凍結乾燥により粗フコイダ
ンを製造後，塩化バリウムに溶解してケイソウ土濾過を
行うことによって高い品質のフコイダンを製造すること
にある．特に，凍結乾燥法，塩化バリウム法，およびケ
イソウ土法の連結により，高い品質のフコイダンを製造
することが出来る．従って，これら３種の方法は本発明
に欠かせないものである．The present inventors have paid attention to the above problems, and as a result of various studies, it has been found that fucoidan can be extracted by stirring cultured Ito mozuku with an aqueous solution of hydrochloric acid, sulfuric acid or oxalic acid at room temperature for several hours. Invented. Since the extract is acidic, it can be neutralized with an alkali (sodium hydroxide or potassium hydroxide), desalted, freeze-dried or precipitated by adding alcohol to produce crude fucoidan. In particular, the method of producing fucoidan using a freeze-dryer is useful for producing high-purity fucoidan from cultured okinawa mozuku in addition to cultured mizumoku. However, crude fucoidan produced from cultured sweet potatoes contained alginic acid, protein, and brown pigment. The yield of crude fucoidan is 0.8%
(Vs. wet alga body). The polysaccharide produced by this method is named crude fucoidan. The fucoidan produced under the above conditions has a light brown color and contains considerable amounts of alginic acid and protein. By using diatomaceous earth filtration, fucoidan which was white and free of alginic acid and protein could be produced. Purified fucoidan yield is 0.6
% (Vs. wet alga). Fucoidan produced under such conditions is named purified fucoidan. Thus, the feature of the present invention is that acidic (hydrochloric acid, sulfuric acid, or oxalic acid)
The purpose is to extract fucoidan with a solution, produce crude fucoidan by freeze-drying, dissolve it in barium chloride and filter it with diatomaceous earth to produce high quality fucoidan. In particular, high-quality fucoidan can be produced by the freeze-drying method, the barium chloride method, and the diatomaceous earth method. Therefore, these three methods are indispensable for the present invention.

【実施例】次に，本発明の内容を具体的にするため本法
実施例をあげる．新鮮なイトモズクの乾燥体５０ｇに
０．２モルの塩酸１Ｌを加え，室温で３時間撹拌を行っ
た後，ケイソウ土の層を通して濾過を行い薄い褐色の透
過液を得た．この透過液にアルカリ（１．０モルの水酸
化ナトリウムまたは水酸化カリウム）を添加して中和を
行い，脱塩（電気透析または普通の膜透析）後，凍結乾
燥またはアルコールを添加して沈殿させ乾燥を行い粗フ
コイダン（１９ｇ）を製造した．１０ｇの粗フコイダン
を０．１モルの塩化バリウム溶液５００ｍＬに分散後，
撹拌溶解（２時間）させ，ケイソウ土の層を通して濾過
を行い，透過液に等量のアルコールを添加して脱水後，
減圧乾燥によって６．５ｇの精製フコイダンを製造し
た．この精製フコイダンはバリウム塩であるが，ナトリ
ウムまたはカリウム塩のフコイダンを製造するためには
陽イオン交換樹脂カラムを通して脱塩後，水酸化ナトリ
ウムまたは水酸化カリウム溶液で中和すれば良い．EXAMPLE Next, an example of the present method will be described in order to make the content of the present invention concrete. 1 L of 0.2 mol hydrochloric acid was added to 50 g of the dried dried freshwater sprout and stirred at room temperature for 3 hours, followed by filtration through a layer of diatomaceous earth to obtain a light brown permeate. The permeate is neutralized by adding an alkali (1.0 mol sodium hydroxide or potassium hydroxide), desalted (electrodialysis or ordinary membrane dialysis), and then lyophilized or precipitated by adding alcohol. After drying, crude fucoidan (19 g) was produced. After dispersing 10 g of crude fucoidan in 500 mL of 0.1 M barium chloride solution,
Stir and dissolve (2 hours), filter through a layer of diatomaceous earth, add an equal amount of alcohol to the permeate and dehydrate.
6.5 g of purified fucoidan was produced by drying under reduced pressure. This purified fucoidan is a barium salt, but in order to produce sodium or potassium fucoidan, desalting through a cation exchange resin column and then neutralization with a sodium hydroxide or potassium hydroxide solution may be used.

【発明の効果】以上述べた如く，本発明の方法によれ
ば，イトモズクのみならずオキナワモズクや他の褐藻類
から高品質でしかも安価なフコイダンを製造することが
可能となり，医薬品や健康食品のみならず，化粧品の分
野にも活用出来るから，藻類の有効利用，特に沖縄県で
は養殖によりイトモズクに加えオキナワモズクを生産し
ており，本県のモズク産業の活性化にもつながる産業上
極めて有用である．As described above, according to the method of the present invention, it is possible to produce high-quality and inexpensive fucoidan from not only Ito mozuku, but also Okinawa mozuku and other brown algae. However, it can also be used in the cosmetics field, so the effective use of algae, especially Okinawan mushrooms, is produced in addition to Ito mozuku by cultivation, which is extremely useful in industry, which will stimulate the mozuku industry in this prefecture. is there.

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.⁶ 識別記号 ＦＩ Ａ６１Ｋ 31/725 ＡＤＹ Ａ６１Ｋ 31/725 ＡＤＹ ＡＤＺ ＡＤＺ ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI A61K 31/725 ADY A61K 31/725 ADY ADZ ADZ

Claims (4)

【特許請求の範囲】[Claims] 【請求項１】 養殖イトモズク（Ｎｅｍａｃｙｓｔｕｓ
ｄｅｃｉｐｉｅｎｓ ＫＵＣＫ）からフコイダンを製
造する方法[Claim 1] Cultured Ito mozuku (Nemacystus)
for producing fucoidan from C. depiens (KUCK) 【請求項２】 養殖イトモズクから塩酸，硫酸，または
修酸を使用することにより，粗フコイダンを抽出する方
法．2. A method for extracting crude fucoidan from cultured cultured Izumozuku by using hydrochloric acid, sulfuric acid, or oxalic acid. 【請求項３】請求項２の条件で製造する際，粗フコイダ
ンを凍結乾燥機を使用することにより製造する方法．本
法はイトモズクに加え，オキナワモズクから高い純度の
フコイダンを製造する際にも極めて有用である．3. A method for producing crude fucoidan by using a freeze dryer when producing under the conditions of claim 2. This method is extremely useful for producing high purity fucoidan from Okinawa mozuku in addition to Ito mozuku. 【請求項４】請求項２および３の条件で製造した粗フコ
イダンを塩化バリウム溶液に溶解後，ケイソウ土を使用
することにより，高い純度のフコイダンを製造する方
法．4. A method for producing high purity fucoidan by dissolving crude fucoidan produced under the conditions of claims 2 and 3 in a barium chloride solution and using diatomaceous earth.