JP3145172B2 - Novel high melting point agarose type agar and its manufacturing method - Google Patents

Novel high melting point agarose type agar and its manufacturing method

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Publication number
JP3145172B2
JP3145172B2 JP08144592A JP8144592A JP3145172B2 JP 3145172 B2 JP3145172 B2 JP 3145172B2 JP 08144592 A JP08144592 A JP 08144592A JP 8144592 A JP8144592 A JP 8144592A JP 3145172 B2 JP3145172 B2 JP 3145172B2
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Japan
Prior art keywords
agar
agarose
novel high
melting point
high melting
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JPH05244908A (en
Inventor
三郎 原
良一 佐藤
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マルハ株式会社
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Description

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

【0001】[0001]

【産業上の利用分野】本発明は高融点を有する新規な高
融点アガロース型寒天及びその製造法に関するものであ
る。
The present invention relates to a novel high melting point agarose type agar having a high melting point and a method for producing the same.

【0002】[0002]

【従来の技術】寒天は食品として古くから知られてお
り、紅藻類の海藻から抽出される多糖類を主成分とした
物質である。寒天の化学構造は、主として3,6−アン
ヒドロ−L−ガラクトースにβ−1,4結合するD−ガ
ラクトースから成るアガロビオース残基のα−1,3結
合の反復から成るアガロースと、アガロビオース残基に
硫酸やピルビン酸が結合したアガロペクチンとから成っ
ている。このうち、D−ガラクトースの一部がメチル化
して6−メチル−D−ガラクトースとなったものも知ら
れており、紅藻類アミクサ(学名:Ceramium boydeni
i)より抽出したアガロースではD−ガラクトース対6
−メチル−D−ガラクトースの比率が3対2の割合とな
っている例がある。一方、3,6−アンヒドロ−L−ガ
ラクトースのうちの30%がメチル化して2−メチル−
3,6−アンヒドロ−L−ガラクトースとなったものが
紅藻類フジマツモ(学名:Rhodomela larix)より抽出
したアガロースに見出されている。しかしながら、構成
糖のメチル化度が50%を超えるものは未だ知られてい
ない。寒天は種々の紅藻類海藻より抽出製造されるが、
抽出温度は通常70〜100℃であり、希に100〜1
20℃の温度範囲で抽出を行う場合がある。
2. Description of the Related Art Agar has long been known as a food and is a substance mainly composed of polysaccharides extracted from seaweeds of red algae. The chemical structure of agar is mainly composed of agarose consisting of repeating α-1,3 bonds of agarobiose residues consisting of D-galactose, which is β-1,4 binding to 3,6-anhydro-L-galactose, and agarobiose residues. It consists of agaropectin to which sulfuric acid and pyruvate are bound. Among them, D-galactose which is partially methylated to form 6-methyl-D-galactose is also known, and a red alga Amixa (scientific name: Ceramium boydeni) is known.
In the agarose extracted from i), D-galactose vs. 6
There is an example in which the ratio of -methyl-D-galactose is 3 to 2. On the other hand, 30% of 3,6-anhydro-L-galactose is methylated to give 2-methyl-
3,6-Anhydro-L-galactose is found in agarose extracted from the red alga Fujimatsumo (scientific name: Rhodomela larix). However, those in which the degree of methylation of the constituent sugars exceeds 50% are not yet known. Agar is extracted and produced from various red algae seaweeds,
The extraction temperature is usually 70-100 ° C, and rarely 100-1 ° C.
The extraction may be performed in a temperature range of 20 ° C.

【0003】[0003]

【発明が解決しようとする課題】みつ豆やトコロテンの
ような寒天をゲル化させて作る食品を長期間保存しよう
とする場合、現状ではそのゲルが再溶解しない程度の温
度として約80℃の温度で殺菌が行われている。しか
し、低温度での殺菌は殺菌効果を確実成らしめるために
長時間の加熱を必要とする。また、寒天を精製したアガ
ロースは電気泳動用の支持体としてタンパク質,核酸を
研究するための手段としても広く用いられているが、そ
の構造中に酸性基である硫酸基の量が少ないものが望ま
れている。このため現在の電気泳動用アガロースの製造
に当っては、この硫酸基を取り除くための処理が必要と
なっている。そこで本発明は、高温度・短期間での加熱
殺菌が可能で、硫酸基の含量が極めて低く高品質な電気
泳動用としても使用可能な新規な高融点アガロース型寒
天及びその寒天を容易に製造できる製造法を提供するこ
とを課題とする。
When a food made by gelling agar such as bean or tocorotene is to be stored for a long period of time, at present, a temperature at which the gel does not re-dissolve at a temperature of about 80 ° C. Sterilization is taking place. However, sterilization at a low temperature requires long heating to ensure the sterilization effect. Agarose purified from agar is also widely used as a support for electrophoresis as a means for studying proteins and nucleic acids. However, it is desirable that agarose contain a small amount of acidic sulfate groups in its structure. It is rare. For this reason, in the production of current agarose for electrophoresis, a treatment for removing the sulfate group is required. Therefore, the present invention provides a novel high melting point agarose-type agar which can be sterilized by heating at a high temperature for a short period of time and has a very low content of sulfate groups and which can be used for high-quality electrophoresis, and easily produces the agar. It is an object to provide a manufacturing method which can be performed.

【0004】[0004]

【課題を解決するための手段】本発明者らは前記課題を
解決するため鋭意研究を行ってきたが、その過程におい
て紅藻類海藻リュウキュウオゴノリから第1段階で95
〜100℃の温度で熱水抽出し、第2段階で110〜1
40℃の温度で熱水抽出する2段階熱水抽出した寒天が
高い融点を持つことを見出した。本発明に係る新規な高
融点アガロース型寒天は、1,3位で結合する6−メチ
ル−D−ガラクトースと1,4位で結合する2−メチル
−3,6−アンヒドロ−L−ガラクトースとが交互に繰
り返して成るメチル化アガロース、又はこのメチル化ア
ガロースと該メチル化アガロース以外のアガロペクチン
とより主として成り、前記メチル化アガロースの割合が
総重量に対して90〜100重量%の範囲にあることを
特徴とする。
Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and in the process, the red alga seaweed Ryukyu ogonori in the first stage was 95%.
Hot water extraction at a temperature of 100100 ° C .;
It has been found that the two-stage hot water-extracted agar having a hot water extraction at a temperature of 40 ° C. has a high melting point. The novel high melting point agarose-type agar according to the present invention comprises 6-methyl-D-galactose bound at the 1,3-position and 2-methyl-3,6-anhydro-L-galactose bound at the 1,4-position. Methylated agarose alternately repeated, or mainly composed of this methylated agarose and agaropectin other than the methylated agarose, wherein the ratio of the methylated agarose is in the range of 90 to 100% by weight based on the total weight. Features.

【0005】上記本発明に係る新規な高融点アガロース
型寒天の製造に用いられる寒天原藻は、紅藻類海藻であ
るが、この中で特に好ましいのはオゴノリ属リュウキュ
ウオゴノリ(学名:Gracilaria eucheumoides)であ
る。この寒天原藻を用いて上記した本発明に係る新規な
高融点アガロース型寒天を製造するには、先ず原料であ
る寒天原藻を常温(10〜30℃)の水で5〜24時間
洗浄することにより、水溶性の塩類を除去する。次に9
5〜100℃望ましくは100℃の熱水で抽出し、その
瀘液を脱水・乾燥することにより寒天Iを得る。この寒
天Iの抽出残渣を110〜140℃の熱水で抽出し、そ
の瀘液を脱水・乾燥することにより得たこの寒天IIが本
発明に係る新規な高融点アガロース型寒天である。この
本発明に係る新規な高融点アガロース型寒天IIは、硫酸
基の含有量が0.5〜1.2%と極めて低い。
The agar protozoa used for producing the novel high-melting-point agarose-type agar according to the present invention is a red algae marine algae, and among them, particularly preferred is a species of Ryukyu ogonori (Science: Gracilaria eucheumoides). It is. In order to produce the above-mentioned novel high-melting-point agarose-type agar according to the present invention using the agar protoalga, first, the agar protozoa as a raw material is washed with water at normal temperature (10 to 30 ° C.) for 5 to 24 hours. Thereby, water-soluble salts are removed. Then 9
Agar I is obtained by extracting with hot water at 5 to 100 ° C, preferably 100 ° C, and dehydrating and drying the filtrate. Agar II obtained by extracting the extraction residue of agar I with hot water at 110 to 140 ° C. and dehydrating and drying the filtrate is the novel high melting point agarose type agar according to the present invention. The novel high melting point agarose type agar II according to the present invention has an extremely low sulfate group content of 0.5 to 1.2%.

【0006】以上の方法によって得られた本発明に係る
新規な高融点アガロース型寒天IIの物理化学的性質は次
の通りである。 (1)元素分析値 測定値:C:46.5%,H:7.4%,O:45.7% 理論値:C:50.3%,H:6.6%,O:43.1% (2)平均分子量 650,000(TSK-Gel PW-5000-XLによるゲル濾過、プルラ
ンを標準とする。) (3)赤外吸収スペクトル 図1に示す。日本分光IRA-2を用いて、KBr錠剤法(1mg
/200mgKBr)による。 (4)紫外吸収スペクトル 図2の示す。日立220S型を用いて、濃度0.6%,セル長1
0mm,温度60℃(121℃で溶解後)の条件で測定。 (5)呈色反応 通常の中性糖の呈色反応(フェノール硫酸法[M. Duboi
s et al., Analyt.Chem., 28, 350(1956)],アンスロ
ン硫酸法[R. Dreywood, Ind. Eng. Chem.,18, 499(194
6)]など)及び3,6−アンヒドロガラクトース類に対
する呈色反応(レゾルシン硫酸法[W. Yaphe, Analyt.
Chem., 32, 1327-308(1960)])に陽性。 (6)物質の色 無色 (7)13C−NMRスペクトル 図3に示す。バリアン社XL-200を用いて、試料:2%溶
液(D2O),温度:80℃の条件で測定。 (8)構造式 図4に示す。1,4位で結合する6−O−メチル−D−
ガラクトピラノース残基と1,3位で結合する2−O−
メチル−3,6−アンヒドロ−L−ガラクトピラノース
残基とが交互に反復した構造。 (9)構成成分の種類,成分比 表1に示す。糖の定性分析は、本品の加水分解物をアル
ジトールアセテートに誘導体化しガスクロマトグラフィ
ー及びマススペクトルにより行った。定量は、内部標準
としてグルコースを添加して行った。硫酸基量は、ロジ
ゾン酸法[T. TTerho and K. Hartiala, Anal. Bioche
m., 41, 471(1971)]により求めた。
The physicochemical properties of the novel high melting point agarose type agar II according to the present invention obtained by the above method are as follows. (1) Elemental analysis value Measurement value: C: 46.5%, H: 7.4%, O: 45.7% Theoretical value: C: 50.3%, H: 6.6%, O: 43.1% (2) Average molecular weight 650,000 (TSK-Gel Gel filtration by PW-5000-XL and pullulan are used as standard.) (3) Infrared absorption spectrum The infrared absorption spectrum is shown in FIG. Using JASCO IRA-2, KBr tablet method (1mg
/ 200mgKBr). (4) Ultraviolet absorption spectrum Shown in FIG. Using Hitachi 220S, concentration 0.6%, cell length 1
Measured at 0 mm and at a temperature of 60 ° C (after melting at 121 ° C). (5) Color reaction The color reaction of ordinary neutral sugars (phenol sulfate method [M. Duboi
s et al., Analyt. Chem., 28, 350 (1956)], anthrone sulfate method [R. Dreywood, Ind. Eng. Chem., 18, 499 (194
6)]) and color reaction to 3,6-anhydrogalactoses (resorcinol sulfate method [W. Yaphe, Analyt.
Chem., 32, 1327-308 (1960)]). (6) Color of substance Colorless (7) 13 C-NMR spectrum Shown in FIG. Measured using a Varian XL-200 under the conditions of a sample: 2% solution (D 2 O), temperature: 80 ° C. (8) Structural formula FIG. 6-O-methyl-D- bonded at the 1,4-position
2-O- bonded to the galactopyranose residue at the 1,3-position
A structure in which methyl-3,6-anhydro-L-galactopyranose residues are alternately repeated. (9) Types and composition ratios of constituent components are shown in Table 1. The qualitative analysis of sugar was carried out by derivatizing the hydrolyzate of this product into alditol acetate and performing gas chromatography and mass spectrometry. The quantification was performed by adding glucose as an internal standard. The sulfate group content was determined by the rhodizonic acid method [T. TTerho and K. Hartiala, Anal.
m., 41, 471 (1971)].

【0007】[0007]

【表1】 [Table 1]

【0008】[0008]

【実施例】以下、実施例を挙げて本発明を更に詳細に説
明する。 実施例1 紅藻類海藻リュウキュウオゴノリ1kgをその藻体が充分
に浸る大きさの容器に入れ、水道水を連続的に流しなが
ら一夜洗浄した。水切りした後、5lの熱湯を加えてか
ら加熱し沸騰後30分間の加熱を続けた。ガーゼで濾過
し、瀘液IAを得た。その濾過残渣に5lの熱湯を加え
てから再び加熱し沸騰後30分間の加熱を続けた。ガー
ゼで濾過し、瀘液IBを得た。得られた濾過残渣に5l
の熱湯を加えて高圧蒸気釜に入れ、120℃で30分間
の加圧加熱を行った。100℃まで温度が低下した後に
釜より取り出し、ガーゼで濾過して瀘液IIAを得た。こ
の濾過残渣に5lの熱湯を加えて高圧蒸気釜に入れ、1
20℃で30分間の加圧加熱を行った後、釜より取り出
してガーゼで濾過し、瀘液IIBを得た。次いで瀘液IA
及び瀘液IBを合わせて瀘液Iとし、これを凍結した後
に融解し瀘布により脱水した。これを凍結乾燥して12
gの寒天Iを得た。また、瀘液IIA及び瀘液IIBを合わ
せて瀘液IIとし、これを凍結した後に融解し瀘布により
脱水し、これを凍結乾燥して20gの寒天IIを得た。
EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. Example 1 1 kg of red algae seaweed Ryukyu ogonori was placed in a container large enough to soak the alga body, and washed overnight while continuously flowing tap water. After draining, 5 l of hot water was added and heated. After boiling, heating was continued for 30 minutes. Filtration with gauze gave filtrate IA. 5 l of hot water was added to the filtration residue, and the mixture was heated again. After boiling, heating was continued for 30 minutes. Filtration with gauze gave filtrate IB. 5 l to the obtained filtration residue
Was added to a high-pressure steam kettle and heated at 120 ° C. for 30 minutes under pressure. After the temperature dropped to 100 ° C., it was taken out of the kettle and filtered with gauze to obtain a filtrate IIA. 5 l of hot water is added to the filtration residue, and the mixture is put into a high-pressure steam kettle.
After heating under pressure at 20 ° C. for 30 minutes, it was taken out of the kettle and filtered with gauze to obtain a filtrate IIB. Then filtrate IA
The filtrate IB was combined with the filtrate IB to obtain a filtrate I, which was frozen, thawed, and dehydrated with a filter cloth. This is freeze-dried and
g of agar I was obtained. The filtrate IIA and the filtrate IIB were combined to give a filtrate II, which was frozen, thawed, dehydrated with a filter cloth, and freeze-dried to obtain 20 g of agar II.

【0009】上記工程を経て得た寒天IIの1gを100
mlの水に懸濁させ120℃20分間の加圧加熱をして溶
解させた後、円筒形の型に流し冷却してゲル化させたも
のを高さ17mmの円筒形に切断成形した。これを湯煎に
より99〜100℃に保たれた熱湯の入ったビーカー中
に投入してその形態の変化を観察した。比較対照とし
て、市販の高融点寒天のうちで最もゲル融点の高いとさ
れているものについて同様の方法で溶解成形し、全く同
じ条件で湯煎ボイルして形態の変化を観察した。その結
果を表2に示す。
[0009] 1 g of agar II obtained through the above process is added to 100 g
After suspending in 120 ml of water and dissolving it by pressurizing and heating at 120 ° C. for 20 minutes, the mixture was poured into a cylindrical mold, cooled and gelled, and cut into a cylindrical shape having a height of 17 mm. This was put into a beaker containing boiling water maintained at 99 to 100 ° C. by hot water bath, and the change in the form was observed. As a comparative control, a commercially available high melting point agar which is considered to have the highest gel melting point was melt-molded in the same manner, boiled in the same conditions, and observed for changes in form. Table 2 shows the results.

【0010】[0010]

【表2】 [Table 2]

【0011】実施例2 実施例1に掲げた寒天IIのゲルの形状をトコロテン突き
で押出し成形してトコロテン状としたものについて、同
様のボイル条件でその変化を観察した。その結果、寒天
IIのトコロテン状ゲルは60分後まで元の形を保って
いた。
Example 2 The shape of the gel of agar II listed in Example 1 was extruded with a tocorotene extruder to form a tocorotene, and the change was observed under the same boiling conditions. As a result, the tocorotene-like gel of Agar II maintained its original shape until 60 minutes later.

【0012】実施例4 実施例2に掲げた寒天IIのトコロテン状ゲル50gを椀
に入れ、そこに沸騰した出し汁250mlを注いでトコロ
テン入りのお吸い物を作った。このときトコロテンは溶
けたり、型崩れすることなく、寒天特有の食感を持った
お吸い物が出来た。
Example 4 50 g of the agar II tocorotene-like gel described in Example 2 was placed in a bowl, and 250 ml of boiling broth was poured into the bowl to make a tocorotene-containing soup. At this time, the tocorotene did not melt or lose its shape, and a soup with a texture unique to agar was formed.

【0013】[0013]

【発明の効果】以上に詳述した如く、本発明に係る新規
な高融点アガロース型寒天は、これから作ったゲルの溶
解温度が従来の寒天と比較して高いため、トコロテンや
みつ豆のような寒天をゲル化させて作る食品を長時間保
存しようとする目的で加熱殺菌する場合により高い温度
での加熱が可能になり、殺菌時間の短縮による効率化の
みならず、殺菌効力が上がることによる保存可能期間の
延長などの効果がある。又、寒天をゲル化させて作る食
品は、従来は冷やして食べるのが通常であったが、本発
明に係る新規な高融点アガロース型寒天を用いれば、上
記トコロテンをお吸い物,鍋料理等の温かい料理に利用
することが可能になる。更に、本発明に係る新規な高融
点アガロース型寒天の成分中には硫酸基が極めて少ない
という特徴を利用して、タンパク質や核酸を研究するた
めの手段としての電気泳動用の支持体に用いれば、従来
よりも高温度での電気泳動操作が可能となる。このよう
な種々の利点を有する本発明の工業的価値は非常に大き
なものである。
As described in detail above, the novel high melting point agarose-type agar according to the present invention has a higher gel dissolution temperature than conventional agar, so that agar such as tocorotene and honey bean can be obtained. In the case of heat sterilization for the purpose of preserving food made by gelling for a long time, it is possible to heat at higher temperature, not only to improve efficiency by shortening the sterilization time, but also to preserve by increasing the sterilization effect This has the effect of extending the period. In addition, foods made by gelling agar have conventionally been usually cooled and eaten. However, if the novel high melting point agarose-type agar according to the present invention is used, the above-mentioned tocorotene can be used as a soup, a cooking pot, etc. It can be used for hot dishes. Furthermore, by using the feature that the components of the novel high melting point agarose-type agar according to the present invention have an extremely small number of sulfate groups, they can be used as a support for electrophoresis as a means for studying proteins and nucleic acids. Thus, the electrophoresis operation at a higher temperature than before can be performed. The industrial value of the present invention having such various advantages is very large.

【図面の簡単な説明】[Brief description of the drawings]

【図1】実施例1で製造した寒天IIの赤外吸収スペクト
ルを示す図である。
FIG. 1 is a view showing an infrared absorption spectrum of agar II produced in Example 1.

【図2】実施例1で製造した寒天IIの紫外吸収スペクト
ルを示す図である。
FIG. 2 is a view showing an ultraviolet absorption spectrum of agar II produced in Example 1.

【図3】実施例1で製造した寒天IIの13C−NMRスペ
クトルを示す図である。
FIG. 3 is a view showing a 13 C-NMR spectrum of agar II produced in Example 1.

【図4】実施例1で製造した寒天IIの1,4位で結合す
る6−O−メチル−D−ガラクトピラノース残基と1,
3位で結合する2−O−メチル−3,6−アンヒドロ−
L−ガラクトピラノース残基とが交互に反復した構造の
構造式である。
FIG. 4 shows a 6-O-methyl-D-galactopyranose residue bonded at the 1,4-position of agar II prepared in Example 1 and 1,
2-O-methyl-3,6-anhydro- bonded at the 3-position
1 is a structural formula of a structure in which L-galactopyranose residues are alternately repeated.

───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7,DB名) A23L 1/337 CA(STN) REGISTRY(STN)──────────────────────────────────────────────────続 き Continued on the front page (58) Fields surveyed (Int. Cl. 7 , DB name) A23L 1/337 CA (STN) REGISTRY (STN)

Claims (3)

(57)【特許請求の範囲】(57) [Claims] 【請求項1】 1,3位で結合する6−メチル−D−ガ
ラクトースと1,4位で結合する2−メチル−3,6−
アンヒドロ−L−ガラクトースとが交互に繰り返して成
るメチル化アガロース、又は該メチル化アガロースと該
メチル化アガロース以外のアガロペクチンとより主とし
て成り、前記メチル化アガロースの割合が90〜100
重量%の範囲にあることを特徴とする新規な高融点アガ
ロース型寒天。
1. A 6-methyl-D-galactose bonded at the 1,3-position and a 2-methyl-3,6-bonded at the 1,4-position.
Anhydro-L-galactose alternately repeats methylated agarose, or is mainly composed of the methylated agarose and the agaropectin other than the methylated agarose, and the ratio of the methylated agarose is 90 to 100.
A novel high melting point agarose-type agar characterized in the range of weight percent.
【請求項2】 寒天原藻を温度95〜100℃にて熱水
抽出した後に、その残渣を110〜140℃にて熱水抽
出することを特徴とする新規な高融点アガロース型寒天
の製造法。
2. A method for producing a novel high-melting-point agarose-type agar, which comprises extracting hot water from agar algae at a temperature of 95 to 100 ° C. and then extracting the residue with hot water at 110 to 140 ° C. .
【請求項3】 寒天原藻が、紅藻類オゴノリ属リュウキ
ュウオゴノリ(学名:Gracilaria eucheumoides)であ
る請求項2に記載の新規な高融点アガロース型寒天の製
造法。
3. The method for producing a novel high-melting-point agarose-type agar according to claim 2, wherein the agar-producing algae is a red alga, Ryukyu ogonori (scientific name: Gracilaria eucheumoides).
JP08144592A 1992-03-04 1992-03-04 Novel high melting point agarose type agar and its manufacturing method Expired - Fee Related JP3145172B2 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001089322A1 (en) * 2000-05-19 2001-11-29 Hershey Foods Corporation Process utilizing agar-agar in a high temperature, short time processing of high solids confectionery products
US6783790B1 (en) 2000-05-19 2004-08-31 Hershey Foods Corporation Process utilizing agar-agar in a high temperature, short time processing of high solids confectionery products
JP5525775B2 (en) * 2009-07-27 2014-06-18 イーエヌ大塚製薬株式会社 Softening method and softened vegetable food
US8704019B2 (en) 2010-12-13 2014-04-22 Exxonmobil Research And Engineering Company Catalyst recovery in hydrothermal treatment of biomass
US8624070B2 (en) 2010-12-13 2014-01-07 Exxonmobil Research And Engineering Company Phosphorus recovery from hydrothermal treatment of biomass
US8704020B2 (en) 2010-12-13 2014-04-22 Exxonmobil Research And Engineering Company Catalytic hydrothermal treatment of biomass
US8487148B2 (en) 2010-12-13 2013-07-16 Exxonmobil Research And Engineering Company Hydrothermal treatment of biomass with heterogeneous catalyst

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