TW200920271A - Pectin-modified resistant starch, a composition containing the same and method for preparing resistant starch - Google Patents

Abstract

This invention relates to a pectin-modified resistant starch prepared by cross-linking starch with pectin by pectinesterase reaction. Such resistant starch is low amylase digestible and thus is useful in food products, including nutritional supplements, to reduce calorie content and increase fiber content. This invention also relates to a composition containing the resistant starch and a process for the preparation of the same.

Description

200920271 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種經果膠修飾之抗解澱粉，其係藉由果 膠酯酶反應將澱粉與果膠交聯製備而成，以便降低澱粉之 消化率。 【先前技術】 澱粉係為植物中之儲備營養物且為人類飲食中之重要組200920271 IX. Description of the Invention: [Technical Field] The present invention relates to a pectin-modified anti-mycorrhizal starch prepared by cross-linking starch and pectin by a pectin esterase reaction to reduce starch Digestibility. [Prior Art] Starch is a reserve nutrient in plants and is an important group in the human diet.

份，其中之消化作用係由α_澱粉酶來調節。一般而言，精 製澱粉可經由酶快速水解且實質上消化，#著由腸吸收以 充當能量來源或儲存於體内。然巾，某些澱粉可抵抗&澱 粉酶之消化。Englyst等人（1992, Eur· ; cnn.(增刊 2"33-S50)根據所攝取澱粉在活體内之可能消化率而將 其分類。他們提出三種食用澱粉類別：1}快速消化殿粉 (RDS)’其可能在人類腸道中消化；2)緩慢消化殿粉（sds)， 其可能在小腸中緩慢但完全地消化；及3)抗解殿粉⑽）， 其不可能在小腸内消化。 吾人已認識可充當抗解澱粉之經修飾澱粉，其可提供、、肖 費者低熱量之碳水化合物產品。該抗解澱粉因此可用作針 對糖尿病及前期糖尿病個體之類的食品（包括醫療食品及 滕食補充劑）中的極佳碳水化合㈣源，或為㈣㈣心 降低食物熱量或減慢殿粉消化速率之選擇。該抗解澱粉亦 二欲經由食物消耗來調節其葡萄糖反應或達成持續 能置釋放之個體。 、 文獻已說明緩慢消化殿粉 之健康相關作用 原因在於長 117795.doc 200920271 時段内之緩慢葡萄糖釋放。益處包括較長時段内之飽食感 增加（其適用於體重控制）、持續能量釋放（其適用於增強包 括耐力之運動效能）及對於注意力維持及記憶力之改良。 該緩慢消化澱粉或抗解澱粉亦可用作藥物，亦即如上文 所述用於糖尿病或前期糖尿病個體以降低疾病風險。此 外，該澱粉可用於治療高血糖症、抗胰島素症、高胰島素 血症、血脂異常及其類似病症。其亦可用於治療肥胖症。 US 6,890,571揭示一種緩慢消化澱粉產品，其係The digestive action is regulated by alpha-amylase. In general, refined starch can be rapidly hydrolyzed by an enzyme and substantially digested, absorbed by the intestine to act as a source of energy or stored in the body. However, some starches are resistant to & amylase digestion. Englyst et al. (1992, Eur.; cnn. (Supp. 2 " 33-S50) classify the ingested starch according to its possible digestibility in vivo. They propose three edible starch categories: 1} Rapid Digestive Powder (RDS) 'It may be digested in the human intestines; 2) slowly digesting the temple powder (sds), which may be slowly but completely digested in the small intestine; and 3) anti-solvent powder (10)), which is unlikely to be digested in the small intestine. We have known that modified starch, which acts as an anti-strept starch, can provide, low-calorie carbohydrate products. The anti-agglomerated starch can therefore be used as an excellent source of carbonic acid (IV) in foods (including medical foods and food supplements) for individuals with diabetes and pre-diabetes, or (4) (4) to reduce food calories or slow down the digestion of the temple powder. The choice of rate. The anti-gelatinized starch is also intended to regulate its glucose response via food consumption or to achieve sustained release of the individual. The literature has shown that the health-related role of slow digestive powder is due to the slow glucose release during the period of 117795.doc 200920271. Benefits include increased satiety over a longer period of time (which applies to weight management), sustained energy release (which is useful for enhancing exercise performance including endurance), and improvements in attention maintenance and memory. The slow-digested starch or the anti-mycorrhizal starch can also be used as a medicament, i.e., for use in a diabetic or pre-diabetic individual as described above to reduce the risk of disease. In addition, the starch can be used to treat hyperglycemia, insulin resistance, hyperinsulinemia, dyslipidemia and the like. It can also be used to treat obesity. US 6,890,571 discloses a slowly digested starch product, which is

2粉酶將低直賴粉去分枝且使所得直鏈短鏈結晶為高度 結晶形式而製備。仍6,623,943揭示一種以物理方式及化學 方式製備抗解澱粉之方法。US6，請，571之緩慢消化殿粉及 ^6,623,943之抗解澱粉皆未與果膠交聯，因此其腾食纖維 含量不如經果膠修飾之殿粉高。 在US 6,670’470之修飾澱粉（其係用於紙塗佈及上漿）係 以過乳化氫將澱粉氧化、將該氧錢粉自旨化再將該殿粉交 聯而製備。該經化學修飾之殿粉並非可食用之理想形式。 因此’需要可緩慢消化或抗消化的修飾殿粉，且其可安 全地添加至或取代食品或醫療用途中之習知碳水化合物產 ασ ° 【發明内容】 本發明係關於—種抗解殿粉，其係藉由果㈣酶之酶反 應將果膠與殿粉錢製傷而成，I中果膠及澱粉均為天然 的且屬於GRAS(普遍§忍為安全）物質。本發明之經酶修飾可 改變澱粉之物理化學特性，且產物^⑽習知經化學修飾 117795.doc 200920271 之澱粉。該抗解殿粉具有較低之消化率，因此可降低衍生 自殿粉之反水化口物中釋放葡萄糖的速率。該抗解殿粉具 有高勝食纖維含量且為天然且安全物質，且可用作天然殿 粉或習知經化學修相粉之替代品。因此，該抗解殿粉可 提供消費者持續能量釋放之低熱量碳水化合物產物。 本發明亦係關於-種組合物，其包含藉由果膠酯酶反應 將澱粉與果膠交聯製備而成之抗解澱粉。 本發明亦係關於一種製備該抗解澱粉之方法。 【實施方式】 如本文中所用之術語"抗解殺粉"意指一種不易經α_殿粉 酶完全消化之澱粉或其部分。 如本文中所用之術語"修飾澱粉，，為藉由處理澱粉或澱粉 顆粒從而部分修飾殿粉之分子結構而製備之澱粉◎修飾澱 粉在食品產品中料增簡、穩定劑或乳化劑。除食品產 品外，修飾澱粉亦可用於藥品中。 如本文中所用之術語"酶反應"意指其中藉由酶催化之反 應將製程開始時之受質分子轉化為不同分子的反應。 如本文中所用之術語”果膠，，為一種複合多醣家族，且為 咼等植物之細胞間層及細胞壁之主要組份。果膠在水果之 細胞壁中特別普遍，尤其在柑橘類水果及蘋果泥中。果膠 為雜多醣且其主要結構為半乳糖醛酸聚糖，其係由單體D_ 半乳糖醛酸紕成且藉由心丨/糖苷鍵連接，其中半乳糖醛酸 分子上超過一半之羧基與甲醇形成甲基酯鍵。果膠分子之 酯化度（DE)視植物之物種、組織及成熟情況而定，其處於 117795.doc 200920271 約 6〇%至 90〇/〇之範圍内（Van Buren, 1991，The Chemistry and Technology 〇f pectin，第 1_5頁）。 醋化度或曱基化度（DM)係定義為經甲基化之半乳糖醛 酸對於果膠分子中所有半乳糖醛酸之百分比。酯化度在理 淪上可處於〇至100。/。之範圍内。將具有大於5〇%之酯化度 (DE)之果膠稱為高甲氧基果膠（HMp)，且因此低甲氧基果 膠（LMP)具有小於 5〇%之DE(Lin，1976, Food Industry. 8(4): 1 8-22)。酯化度及其在果膠分子上之電荷對於植物細胞壁中 果膠分子之功能特性报重要^其亦顯著影響果膠製劑作為 膠凝劑或增稠劑之商業用途。 果膠酯酶為一種果膠酶，其存在於多種高等植物之根、 莖、葉、果實等中。果膠酯酶可將半乳糖醛酸之第六碳上 的甲酯鍵水解，以得到游離羧基及甲醇，因此可降低果膠 分子之酯化度。就此而言，具有高酯化度之果膠可變為具 有較低醋化度之果膠或果膠酸（Sajjaanantakul及pitifer， 1991，The Chemistry and Technology 〇f pectin，第 135_15〇 頁）。具有約60% DE值之果膠易於自天然植物來源獲得。多 數具有約30% DE值之市售果膠係藉由天然果膠之部分脫 酯化製造。 在由果膠酯酶催化果膠之反應中可能發生水解及轉醯基 反應。在水解反應中，果膠分子釋出部分甲氧基以形成果 膠酸及游離甲醇，而在轉酿基反應中，果膠分子上之一竑 醯基與果膠酯酶分子藉由第一步轉醯基反應而結合以形成 中間物，接著該中間物與另一果膠分子或一些其他受體分 117795.doc 200920271 子（諸如澱粉）上之羥基進行另一轉醯基反應以彼此交聯。該 反應之流程展示如下（Hou及Chang，1996. J. Food Biochem. 20:397-416)： PE-OH C_ HaOP~C00CH3V^ 又 P-C00-PE 中間物2 The powder enzyme is prepared by defraction of the low-branched powder and crystallization of the obtained linear short-chain into a highly crystalline form. Still 6,623,943 discloses a process for the preparation of resistant starches by physical and chemical means. US6, please, 571 of the slow digestive powder and ^6,623,943 anti-mycorrhizal starch are not cross-linked with pectin, so its dietary fiber content is not as high as the pectin-modified temple powder. The modified starch of US 6,670' 470, which is used for paper coating and sizing, is prepared by oxidizing starch with peroxygenated hydrogen, self-containing the oxygen powder, and crosslinking the powder. This chemically modified temple powder is not an ideal form for edible. Therefore, there is a need for a modified house powder which can be slowly digested or digested, and which can be safely added to or replaces the conventional carbohydrate production α σ ° in food or medical use. [Invention] The present invention relates to a kind of anti-solution powder It is made by inoculating the pectin and the temple powder by the enzyme reaction of the fruit (4) enzyme. The pectin and starch in I are natural and belong to GRAS (general § forbearance). The enzymatic modification of the present invention changes the physicochemical properties of the starch, and the product (10) is conventionally chemically modified to be a starch of 117795.doc 200920271. The anti-solution powder has a lower digestibility, thereby reducing the rate of glucose release from the counter-hydration mouth derived from the temple powder. The anti-solvent powder has a high content of dietary fiber and is a natural and safe substance, and can be used as a substitute for natural temple powder or a conventional chemical repairing powder. Therefore, the anti-solvent powder can provide a low calorie carbohydrate product that the consumer continues to release energy. The present invention is also directed to a composition comprising a starch resistant to cross-linking of starch and pectin by a pectin esterase reaction. The invention also relates to a method of preparing the anti-spelling starch. [Embodiment] The term "anti-anti-killing powder" as used herein means a starch or a part thereof which is not easily digested completely by α-houseme. The term "modified starch, as used herein, is a starch prepared by treating starch or starch granules to partially modify the molecular structure of the granules. ??? Modified starch is a material improvement, stabilizer or emulsifier in food products. In addition to food products, modified starches can also be used in pharmaceutical products. The term "enzyme reaction" as used herein means a reaction in which a substrate molecule at the beginning of a process is converted into a different molecule by an enzyme-catalyzed reaction. The term "pectin" as used herein, is a family of complex polysaccharides and is a major component of the intercellular layer and cell wall of plants such as alfalfa. Pectin is particularly prevalent in the cell wall of fruits, especially in citrus fruits and apple purees. Pectin is a heteropolysaccharide and its main structure is galacturonic acid glycoside, which is formed by the monomer D_galacturonic acid and is linked by a sputum/glycosidic bond, wherein the galacturonic acid molecule is more than half The carboxyl group forms a methyl ester bond with methanol. The degree of esterification (DE) of the pectin molecule depends on the species, organization and maturity of the plant, and is in the range of about 169795.doc 200920271 about 6〇% to 90〇/〇. (Van Buren, 1991, The Chemistry and Technology 〇f pectin, pp. 1_5). Degree of acetification or thiolation (DM) is defined as methylated galacturonic acid for all galactose in pectin molecules. Percentage of aldehyde acid. The degree of esterification can be in the range of 〇 to 100%. Pectin having a degree of esterification (DE) greater than 5% by weight is referred to as high methoxyl pectin (HMp). ), and therefore low methoxyl pectin (LMP) has less than 5% D E (Lin, 1976, Food Industry. 8(4): 1 8-22). The degree of esterification and its charge on the pectin molecule are important for the functional properties of pectin molecules in plant cell walls. Commercial use of a gel preparation as a gelling agent or thickener. Pectin esterase is a pectinase which is present in roots, stems, leaves, fruits, etc. of various higher plants. Pectin esterase can galactose The methyl ester bond on the sixth carbon of the acid is hydrolyzed to obtain a free carboxyl group and methanol, thereby reducing the degree of esterification of the pectin molecule. In this regard, the pectin having a high degree of esterification can be changed to have a lower acetification. Pectin or pectic acid (Sajjaanantakul and pitifer, 1991, The Chemistry and Technology 〇f pectin, pp. 135_15). Pectin with a value of about 60% DE is readily available from natural plant sources. Most have about 30% The commercially available pectin of DE value is produced by partial deesterification of natural pectin. Hydrolysis and thiol reaction may occur in the reaction of pectin catalyzed by pectin esterase. In the hydrolysis reaction, pectin molecular release Part of the methoxy group to form pectic acid and free methanol, and In the trans-branched reaction, one of the sulfhydryl groups on the pectin molecule and the pectin esterase molecule combine to form an intermediate by the first step of the thiol reaction, followed by the intermediate with another pectin molecule or some other The hydroxyl group on the receptor 117795.doc 200920271 (such as starch) undergoes another conversion thiol reaction to crosslink each other. The flow of the reaction is shown below (Hou and Chang, 1996. J. Food Biochem. 20:397-416 ): PE-OH C_ HaOP~C00CH3V^ and P-C00-PE intermediate

PE-OHPE-OH

P-C00HP-C00H

F -OH PE-〇H P-C00-Pf 如本文中所用之術語"轉醯基”意謂一種涉及醯基轉移之 化學反應。果膠酯酶不僅催化果膠分子之甲氧基的水解， 亦催化轉醯基反應，其中將半乳糖醛酸醯基轉移至果膠或 其他碳水化合物分子（諸如澱粉）之其他羥基。 在本發明中提供一種經酶修飾之澱粉，其具有低熱量及 高：維含量。藉由果膠_酶在澱粉與果膠之間之酶反應以 使匕們之間發生轉醯基反應，進而使殿粉與果朦交聯，從 :製備該修飾澱粉。該經酶修飾之澱粉對於心澱粉酶消化 具有抗性。藉由將《•澱粉酶及葡糖澱粉酶添加至殿粉或修 飾殿粉之稀釋測試樣品中，且在 ^, τ且在培養一段時間後測定溶液 中游離葡萄糖之濃度，從而量測(X-澱粉酶消化。 =際上任何㈣均可根據本文中所述之方法來修佛，其 縠物澱粉、根澱粉、塊莖搬粉、豆類殿粉、高直鏈殿 -及低直鏈澱粉”殿粉來源包括小麥、玉米、稻米、燕麥、 127795.doc -10- 200920271 木薯、綠豆、馬鈐薯、西米、甘薯、大麥、 如 夕 茶'小麥、高粱、 香蕉及其他植物來源。亦可使用物理修飾、化學修部或遺 傳修飾形式之澱粉。修飾技術包括：（1)物理轉化，諸如。 凝（再結晶）、熱處理、部分膠凝、韌化及焙燒丨（2)以化學 品及/或酶進行之處理；（3)遺傳修飾，包括基因工程改造或 染色體工程改造，諸如雜交、易位、轉化及轉形丨及（4)= 上技術之組合。 本發明之經酶修飾抗解澱粉係藉由—種涉及首先形成勺 含澱粉及果膠之溶液的方法而製造。關於形成包含澱粉2 果膠之溶液的任何已知技術均可應用於本發明。在本^明 之一較佳實施例令，包含澱粉及果膠之溶液可由以下步驟 製備： / ⑴將澱粉與選自水及乙醇溶液之溶劑預混合以獲得混人 物； ° (11)將水或驗性溶液添加至該混合物中以獲得澱粉懸浮 液； (iii)加熱該澱粉懸浮液以溶解澱粉且獲得澱粉溶液； (IV) 將水及果膠添加至該澱粉溶液中以獲得澱粉-果膠懸 浮液，及 ' (V) 加熱該澱粉-果膠懸浮液以溶解果膠且獲得包含澱粉 及果膠之溶液。 在步驟⑴中，溶劑對於澱粉之體積/重量比為約的：1 ,較 佳約20:1。若將乙醇溶液用作溶劑，則乙醇溶液可為任何 濃度，較佳為約60%至95%，且最佳為約95%。在步驟 117795.doc 200920271 中添加之水/鹼性溶液之體積 體積比為約3:1，較佳為約5:1。根據本發明，所用之驗性容 液包括（但不限於）氫氧化鈉溶液、 / ^ ^ ^ ^ ^ ^ 虱氧化鉀冷液、碳酸鈉溶 液及A錢錢。在步驟㈣中，在、物至HKTC之溫产 下加熱歷時約5至60分鐘，更佳Λ. 又 旯住為在約8〇至lOOt之溫度下 歷時約5至30分鐘，且畏枯成产 且蚨佳為在約9〇至ϊ 0(rc之溫度下歷 約5至1 0分鐘。在步驟（！）φ . 你艾驟（1V)中所添加之水的體積相對於步驟 ⑻中所添加之水/驗性溶液的體積比為約3]，較佳約Η。 在步驟⑺中’在約⑽至靖之溫度下加熱歷時約1〇至6〇 分鐘’更佳在約8(^10(rc之溫度下歷時約1〇至45分鐘且 最佳在約90至1()(^之溫度下歷時約1()至财鐘。在本發明 之最仏實施例中，係使用乙醇及/或驗性溶液促進果膠之 溶解並加速後續交聯反應。 接著將果膠酯酶添加至包含澱粉及果膠之溶液中以影響 果膠之轉醯基並使澱粉與果膠交聯。對於包含澱粉及果膠 之溶液可另外使用振盪步驟以促進酶反應。 酶反應之速率視此項技術中已知之因素而定，其包括酶 濃度、受質濃度、反應混合物之pH值、溫度及欲達成之修 飾程度（若有的話）。 本發明中所用溶液之pH值及溫度應允許果膠酯酶有效地 提供酶反應。一般而言’使用約20至80。(3之溫度，尤其為 約25至60°C。一般而言，使用此項技術中已知之技術將pH 值調節為約4.0至9·〇，尤其為約6.0至8.0。 酶反應係在水溶液中進行。一般而言，在包含澱粉及果 117795.doc 12F -OH PE-〇H P-C00-Pf The term "transalkyl" as used herein means a chemical reaction involving thiol transfer. Pectin esterase not only catalyzes the hydrolysis of the methoxy group of the pectin molecule , also catalyzes a thiol-based reaction in which a galacturonic acid thiol group is transferred to other hydroxyl groups of pectin or other carbohydrate molecules such as starch. In the present invention, an enzyme-modified starch having low calorie and High: Dimensional content: The modified starch is prepared from the pectin-enzyme in the enzymatic reaction between starch and pectin to cause a thiol reaction between the sputum and the sputum. The enzyme-modified starch is resistant to cardiac amylase digestion by adding "amylase and glucoamylase to the dilution test sample of the temple powder or the modified temple powder, and in the ^, τ and in the culture section After the time, the concentration of free glucose in the solution is measured, thereby measuring (X-amylase digestion. Any of the above (4) can be cultivated according to the method described herein, and the starch, root starch, tuber powder, Beans Palace Powder, High Straight Chain Temple - and Low Straight Chain Lake Powder sources include wheat, corn, rice, oats, 127795.doc -10- 200920271 cassava, mung bean, horse yam, sago, sweet potato, barley, yoghurt 'wheat, sorghum, banana and other plant sources. It is also possible to use starches in physical, chemical or genetically modified forms. Modification techniques include: (1) physical transformation, such as condensation (recrystallization), heat treatment, partial gelation, toughening and calcination (2) with chemistry Treatment with products and/or enzymes; (3) genetic modification, including genetic engineering or chromosomal engineering, such as hybridization, translocation, transformation and transformation, and (4) = combination of the above techniques. Modified anti-mycorrhizal starch is produced by a method involving first forming a solution containing starch and pectin in a spoon. Any known technique for forming a solution containing starch 2 pectin can be applied to the present invention. In a preferred embodiment, the solution comprising starch and pectin can be prepared by the following steps: / (1) premixing the starch with a solvent selected from the group consisting of water and ethanol to obtain a mixed character; ° (11) water or testability a liquid is added to the mixture to obtain a starch suspension; (iii) heating the starch suspension to dissolve the starch and obtaining a starch solution; (IV) adding water and pectin to the starch solution to obtain a starch-pectin suspension And '(V) heating the starch-pectin suspension to dissolve the pectin and obtaining a solution comprising starch and pectin. In step (1), the volume/weight ratio of solvent to starch is about: 1, preferably about 20: 1. If an ethanol solution is used as the solvent, the ethanol solution may be any concentration, preferably about 60% to 95%, and most preferably about 95%. Water/base added in step 117795.doc 200920271 The volumetric volume ratio of the solution is about 3:1, preferably about 5: 1. According to the present invention, the assay liquid used includes, but is not limited to, sodium hydroxide solution, / ^ ^ ^ ^ ^ ^ 虱 oxidation Potassium cold liquid, sodium carbonate solution and A money. In the step (4), the heating is carried out at a temperature of HKTC for about 5 to 60 minutes, more preferably. The yield is preferably about 9 to 10 (the temperature of rc is about 5 to 10 minutes. In step (!) φ. The volume of water added in your step (1V) is relative to step (8). The volume ratio of the added water/test solution is about 3], preferably about Η. In step (7), 'heating at about (10) to the temperature of Jing for about 1 〇 to 6 〇 minutes is more preferably about 8 (^) 10 (at a temperature of rc for about 1 to 45 minutes and preferably at about 90 to 1 () at a temperature of about 1 () to the clock. In the last embodiment of the invention, ethanol is used. And/or the test solution promotes the dissolution of the pectin and accelerates the subsequent cross-linking reaction. Next, the pectin esterase is added to the solution containing starch and pectin to affect the conversion of the pectin and cross-link the starch with the pectin. An additional oscillating step can be used to promote the enzymatic reaction for solutions comprising starch and pectin. The rate of enzymatic reaction depends on factors known in the art, including enzyme concentrations. The concentration of the substrate, the pH of the reaction mixture, the temperature and the degree of modification desired, if any. The pH and temperature of the solution used in the present invention should allow the pectin esterase to efficiently provide an enzymatic reaction. Use from about 20 to 80. (3 temperatures, especially about 25 to 60 ° C. In general, the pH is adjusted to about 4.0 to 9 Torr, especially about 6.0 to 8.0, using techniques known in the art. The enzymatic reaction is carried out in an aqueous solution. In general, it contains starch and fruit 117795.doc 12

200920271 1溶液中澱粉與果谬之重量比為約2Q:i，較佳為約ι〇ι， 且=為約1:1。所添加之轉㈣量為每毫升最終溶液約 1至3 0個爭位，齡/去么益 較佳為母毫升最終溶液約1至1 0個單位。 酶反應持續至抗解殿粉的獲得，且其持續時間視殿粉修 飾之所要程度而定。反料間亦視利澱粉及果膠之類型 、、為果膠之ga化度）及反應參數（諸如pH值及溫度）而 定。一般而言，酶反應需要約〇.5至12〇小時，更佳為約^至 96小時。戶斤有酯化度之果膠均適用於本發明。然而，果膠 酯化度越高，則反應產生抗解澱粉之潛力越高。在一實施 例中，係以具有高於3〇%酯化度之果膠進行酶反應。在一 較佳實施例中，使用具有高於6〇%酯化度之果膠進行酶反 應0 接著視情況藉由離心且接著在習知烘箱、濕熱加熱器、 蒸汽噴射蒸箱及/或噴霧乾燥器中乾燥沈澱物來回收溶液 中之產物。 本發明之抗解澱粉亦可在果膠與澱粉交聯之前或之後經 進一步修飾。該修飾可為此項技術中已知之物理修飾、酶 修飾或化學修飾中之任一種。 本文中所揭示之抗解澱粉可用於具有高膳食纖維含量、 低脂肪含量及/或低熱量之組合物（諸如食品組合物）中。舉 例而言’可將抗解澱粉併入食品產品中，其包括（但不限於） 小甜餅、餅乾、麵包、披薩、布丁、麵食、麵條、冰淇淋、 優格、蛋糕及其類似物。將抗解澱粉併入食品產品中可獲 得最終產品之膳食纖維要求。可按照由熟習此項技術者確 117795.doc -13· 200920271 定之程度併人修飾殿粉，以製造具有低熱量之食品。 除食品組合物外’該抗解丨殿粉亦可用於營養食品及飲料 產品中’其包括腾食補充劑、糖尿病患者食品及飲料產品， 及其類似物。 1可按獲得組合物之功能性所要或必需之任何量添加抗解 殿粕 般而5，可按照以組合物之重量計約0. 〇 1 %至 100%、尤其約1%至5G%之量添加殿粉。可按照與任何其他 澱粉相同之方式將抗解澱粉添加至食品或飲料中，通常係 藉由直接混合至產品中或將其添加至水溶液中。 以下實例Μ述根據本文中所報導之手段特定經酶修飾之 抗解澱粉，卩及製備該修飾澱粉之方&。應瞭解該等實例 僅以說明之方式提供，且不應將其中任何内容視為對於隨 後申請專利範圍所界定之本發明範疇的限制。 實例 實例1經果膝修飾之直鏈殺粉 1.樣品製備 (1)直鏈澱粉溶液（直鏈澱粉，Α) 將直鍵殿粉（50mg，in型，來自馬鈴薯，SigmaChemical Co.，Germany)與1 ml乙醇（95%)在圓底燒瓶中預混合，接 著將5 ml氫氧化鈉溶液（〇.5 N)添加至燒瓶中。藉由在95亡 下加熱5分鐘使懸浮液中之直鏈澱粉溶解，接著將去離子水 (Miin-QPFP1US，16.7至18佰萬歐/公分，Mimp〇re，Fr_e) 添加至溶液中，達到50 ml之最終體積。 (2)包含直鍵殿粉及果膠之溶液（直鏈激粉+果朦，Αρ) 117795.doc • 14- 200920271 將直鏈澱粉（50 11^)與1 mi乙醇（95%)在圓底燒瓶中預混 合，接著將5 ml氫氧化鈉溶液（〇·5 N)添加至燒瓶中。藉由 在95C下加熱5分鐘使懸浮液中之直鏈澱粉溶解，接著將去 離子水添加至溶液中，達到4〇 ml之體積。將果膠（50 ， 來自蘋果，DE>60，Sigma Chemical Co.，Germany)添加至 該溶液中。藉由在95°C下加熱20分鐘使溶液中之果膠溶 解，接著將去離子水添加至該溶液中，達到5〇⑹之最終體 積。 (3)直鏈殿粉、果膠及果膠酯酶之混合溶液（直鏈澱粉+果 膠+果勝酯酶，ape) 將直鏈澱粉（50 mg)與i ml乙醇（95%)在圓底燒瓶中預混 合，接著將5 ml氫氧化鈉溶液（0·5 N)添加至燒瓶中。藉由 在95 C下加熱5分鐘使懸浮液中之直鏈澱粉溶解，接著將去 離子水添加至溶液中，達到4〇 ml之體積。將果膠（5〇 mg) 添加至該溶液中，接著藉由在95°C下加熱20分鐘而溶解。 藉由添加0·1 N鹽酸溶液（37%，Merck，Germany)w該溶液 之pH值調節為約7 5。將果膠酯酶（8〇1單位/毫升，〇 l ， EC 3_l_l.li ’ 來自橘皮，Sigma Chemical &，Germany)及 去離子水添加至該溶液中，達到5〇 ml之最終體積。以丨5〇 rpm之速率將混合物振盪24至72小時。 2,消化率測試 將去離子水添加至如上所製備之各樣品中，達到250 ml 之體積’接著將各溶液之pH值調節為約5.8至6.5。將熱穩 疋型 α-澱粉酶（13000 Lj/g，0.1 ml，KLEISTASE T10S， 117795.doc 200920271 DAIWA KASEI Κ·Κ.，Japan)添加至各溶液中，且將該等溶 液在100°C水浴中加熱5分鐘以進行酶反應。在反應後，將 溶液之pH值調節為約4，接著將去離子水添加至各溶液中， 達到25 0 ml之體積。接著將葡糠澱粉酶（225 GAU/ml，0.3 ml 5 OPIMAX 7525HP 5 Genencor Division » Danisco US. Inc.，U.S.A.)添加至各溶液中，以在55至60°C之水浴中與受 質反應10分鐘。再次將去離子水添加至各溶液中，達到2000 ml之體積。藉由使用RQ flex® plus測試條（Merck，Germany) 來測定各溶液中葡萄糖之濃度。藉由將測試條中所讀取之 值乘以稀釋倍數來計算各樣品中葡萄糖之濃度。根據以下 方程式來計算各樣品之消化率，且在表1中展示結果。 xlOO% 消化率=-T 1叫…0〜他/又 直鏈澱粉溶液中葡萄糖之 表1 :樣品之消化率 A AP APE 消化率(％) 100 92.8±6.1 34.8±4.0 A :直鏈澱粉 AP :直鏈澱粉+果膠 APE :直鏈澱粉+果膠+果膠酯酶 實例2經果膠修飾之小麥澱粉 1.樣品製備 (1)小麥澱粉溶液（小麥澱粉，S) 將小麥殿粉（50 mg，頂級 Al，Crop star，Australia)與 1 ml 水在圓底燒瓶中預混合，接著將5 ml氫氧化鈉溶液（0.5 N) 117795.doc • 16· 200920271 添加至燒&中。藉由在95t下加熱5分鐘使懸浮液中之小麥 澱粉溶解，接著將去離子水添加至溶液中，達到4〇mi之體 積。將該溶液之pH值調節為約7.^將去離子水添加至該溶 液中，達到50 ml之最終體積。在使用前將該溶液於3〇。〇下 靜置1小時。 (2)小麥澱粉與果膠之混合溶液（小麥澱粉+果膠，sp) (i) 熱處理及驗處理 將小麥殿粉（5〇1^，頂級八卜以〇1)_，入11价_)與11111 水在圓底燒瓶中預混合，接著將5 ml氫氧化鈉溶液（〇5 N) 添加至燒瓶中。藉由在95°C下加熱5分鐘使懸浮液中之小麥 澱粉溶解，接著將去離子水添加至溶液中，達到4〇 ml之體 積。將果膠（50 mg，來自蘋果，DE>6〇，Sigma chemical d，200920271 1 The weight ratio of starch to fruit in solution is about 2Q:i, preferably about ι〇ι, and = about 1:1. The amount of the added (four) added is about 1 to 30 points per ml of the final solution, and the age/de-bene is preferably about 1 to 10 units of the final solution of the mother milliliter. The enzymatic reaction continues until the anti-resolving powder is obtained, and its duration depends on the degree of the temple powder modification. Depending on the type of starch and pectin, the degree of pectin, and the reaction parameters (such as pH and temperature). In general, the enzymatic reaction requires about 5 to 12 hours, more preferably about 2 to 96 hours. Pectin having a degree of esterification is suitable for use in the present invention. However, the higher the degree of esterification of the pectin, the higher the potential of the reaction to produce anti-starch. In one embodiment, the enzymatic reaction is carried out with pectin having a degree of esterification of greater than 3% by weight. In a preferred embodiment, the enzymatic reaction is carried out using pectin having a degree of esterification of greater than 6% by weight. 0 followed by centrifugation followed by a conventional oven, a moist heat heater, a steam jet steamer and/or a spray. The precipitate is dried in a desiccator to recover the product in the solution. The anti-starch starch of the present invention may also be further modified before or after the pectin is crosslinked with the starch. The modification can be any of physical, enzymatic or chemical modifications known in the art. The anti-paste starch disclosed herein can be used in compositions (such as food compositions) having high dietary fiber content, low fat content, and/or low calorie content. For example, anti-decomposition starch can be incorporated into food products including, but not limited to, cookies, biscuits, bread, pizza, pudding, pasta, noodles, ice cream, yogurt, cakes, and the like. The incorporation of the anti-gelatinized starch into the food product provides the dietary fiber requirements of the final product. Foods with low calorie can be made according to the degree to which the skilled artisan can determine the degree of 117795.doc -13. 200920271. In addition to the food composition, the anti-allergic powder can also be used in nutraceutical foods and beverage products, which include food supplements, food and beverage products for diabetic patients, and the like. 1 may be added in any amount required or necessary to obtain the functionality of the composition, and may be added in an amount of from about 0.1% to about 100%, especially from about 1% to about 5% by weight based on the weight of the composition. Temple powder. The anti-gelatinized starch can be added to the food or beverage in the same manner as any other starch, usually by direct mixing into the product or added to the aqueous solution. The following examples describe specific enzyme-modified anti-sludge starches, oxime and the preparation of the modified starches according to the means reported herein. It is to be understood that the examples are provided by way of illustration only and should not be construed as limiting the scope of the invention as defined by the scope of the claims. EXAMPLES Example 1 Straight-chain powder-killing modified by the knee 1. Sample preparation (1) Amylose solution (amylose, Α) Direct-bonded powder (50 mg, in-type, from potato, Sigma Chemical Co., Germany) Premixed with 1 ml of ethanol (95%) in a round bottom flask, followed by 5 ml of sodium hydroxide solution (〇.5 N) was added to the flask. The amylose in the suspension was dissolved by heating at 95 minutes for 5 minutes, and then deionized water (Miin-QPFP1US, 16.7 to 180,000 ohms/cm, Mimp〇re, Fr_e) was added to the solution to reach Final volume of 50 ml. (2) A solution containing a direct bond powder and pectin (linear chain powder + fruit 朦, Αρ) 117795.doc • 14- 200920271 Amylose (50 11^) and 1 mi of ethanol (95%) in a circle The bottom flask was premixed, and then 5 ml of sodium hydroxide solution (〇·5 N) was added to the flask. The amylose in the suspension was dissolved by heating at 95 C for 5 minutes, and then deionized water was added to the solution to a volume of 4 〇 ml. Pectin (50 from Apple, DE > 60, Sigma Chemical Co., Germany) was added to the solution. The pectin in the solution was dissolved by heating at 95 ° C for 20 minutes, and then deionized water was added to the solution to reach a final volume of 5 〇 (6). (3) Mixed solution of linear hall powder, pectin and pectin esterase (amylose + pectin + fruit esterase, ape) Amylose (50 mg) and i ml of ethanol (95%) The round bottom flask was premixed and then 5 ml of sodium hydroxide solution (0.5 N) was added to the flask. The amylose in the suspension was dissolved by heating at 95 C for 5 minutes, and then deionized water was added to the solution to a volume of 4 〇 ml. Pectin (5 〇 mg) was added to the solution, followed by dissolution by heating at 95 ° C for 20 minutes. The pH of the solution was adjusted to about 75 by the addition of 0.1 N hydrochloric acid solution (37%, Merck, Germany). Pectin esterase (8 〇 1 unit/ml, 〇 l , EC 3_l_l.li 'from orange peel, Sigma Chemical &, Germany) and deionized water were added to the solution to a final volume of 5 〇 ml. The mixture was shaken at a rate of 〇5 rpm for 24 to 72 hours. 2. Digestibility test Deionized water was added to each sample prepared as above to a volume of 250 ml. Then, the pH of each solution was adjusted to about 5.8 to 6.5. Heat-stable α-amylase (13,000 Lj/g, 0.1 ml, KLEISTASE T10S, 117795.doc 200920271 DAIWA KASEI Κ·Κ., Japan) was added to each solution, and the solutions were bathed at 100 ° C. The medium was heated for 5 minutes to carry out an enzyme reaction. After the reaction, the pH of the solution was adjusted to about 4, and then deionized water was added to each solution to a volume of 250 ml. Then, glucoside amylase (225 GAU/ml, 0.3 ml 5 OPIMAX 7525HP 5 Genencor Division » Danisco US. Inc., USA) was added to each solution to react with the substrate in a water bath of 55 to 60 ° C. minute. Deionized water was again added to each solution to a volume of 2000 ml. The concentration of glucose in each solution was determined by using an RQ flex® plus test strip (Merck, Germany). The concentration of glucose in each sample was calculated by multiplying the value read in the test strip by the dilution factor. The digestibility of each sample was calculated according to the following equation, and the results are shown in Table 1. XlOO% digestibility = -T 1 is called...0~he/and glucose in amylose solution Table 1: Digestibility of sample A AP APE Digestibility (%) 100 92.8±6.1 34.8±4.0 A : Amylose AP : Amylose + Pectin APE : Amylose + Pectin + Pectin Esterase Example 2 Wheat starch modified by pectin 1. Sample preparation (1) Wheat starch solution (wheat starch, S) Wheat house powder ( 50 mg, top grade Al, Crop star, Australia) was premixed with 1 ml of water in a round bottom flask, followed by 5 ml of sodium hydroxide solution (0.5 N) 117795.doc • 16· 200920271 added to the Burn & The wheat starch in the suspension was dissolved by heating at 95 t for 5 minutes, and then deionized water was added to the solution to reach a volume of 4 〇mi. The pH of the solution was adjusted to about 7. The deionized water was added to the solution to a final volume of 50 ml. The solution was applied to 3 Torr before use. Underarm, let stand for 1 hour. (2) Mixed solution of wheat starch and pectin (wheat starch + pectin, sp) (i) Heat treatment and treatment will be wheat powder (5〇1^, top eight 〇1)_, into 11 price _ ) Premixed with 11111 water in a round bottom flask, followed by the addition of 5 ml of sodium hydroxide solution (〇5 N) to the flask. The wheat starch in the suspension was dissolved by heating at 95 ° C for 5 minutes, and then deionized water was added to the solution to a volume of 4 〇 ml. Pectin (50 mg from apple, DE > 6 〇, Sigma chemical d,

Germany)添加至該溶液中且藉由在95<t下加熱2〇分鐘而溶 解’接著將去離子水添加至該溶液中，達到4〇 ml之體積。 將該溶液之pH值調節為約7.5。將去離子水添加至該溶液 中，達到50 ml之最終體積。在使用前將該溶液於3〇它下靜 置1小時。 (ii) 熱處理 將小麥澱粉（50 mg)與1 ml水在圓底燒瓶中預混合，接著 將5 ml水添加至燒瓶中。藉由在95。〇下加熱5分鐘使懸浮液 中之小麥澱:粉溶解’接著將去離子水添加至溶液中，達到 40 ml之體積。將果膠（50 mg)添加至該溶液中且藉由在9 5。^ 下加熱20分鐘而溶解。將該溶液之ρίί值調節為約7,5。將去 離子水添加至該溶液中，達到50 ml之最終體積。在使用^Germany) was added to the solution and dissolved by heating at 95 < t for 2 Torr. Then, deionized water was added to the solution to a volume of 4 〇 ml. The pH of the solution was adjusted to about 7.5. Deionized water was added to the solution to a final volume of 50 ml. The solution was allowed to stand under 3 Torr for 1 hour before use. (ii) Heat treatment Wheat starch (50 mg) was premixed with 1 ml of water in a round bottom flask, and then 5 ml of water was added to the flask. By at 95. The wheat leaves in the suspension were heated for 5 minutes under the armpit: the powder was dissolved. Then deionized water was added to the solution to a volume of 40 ml. Pectin (50 mg) was added to the solution and at 95. ^ Dissolve by heating for 20 minutes. The ρίί value of the solution was adjusted to about 7,5. Deionized water was added to the solution to a final volume of 50 ml. In use ^

/ 月’J 117795.doc •17- 200920271 將該溶液於3 0 °C下靜置1小時。 (3)小麥殿粉、果膠及果膠酯酶之混合溶液（小麥澱粉+果 膠+果膠醋酶，SPE) (i)熱處理及驗處理 將小麥澱粉（50 mg)與1 ml水在圓底燒瓶中預混合，接著 將5 ml氫氧化鈉溶液（〇5 N)添加至燒瓶中。藉由在95。〇下 加熱5分鐘使懸浮液中之小麥澱粉溶解’接著將去離子水添 加至溶液中’達到40 ml之體積。將果膠（50 mg)添加至該溶 液中且藉由在95°C下加熱20分鐘而溶解。將該溶液之1)^1值 調節為約7.5。將去離子水添加至該溶液中，達到5〇 mi之最 終體積。將果膠酯酶（8〇1單位/毫升，〇.丨ml)添加至該溶液 中。在使用前將該溶液於3CTC下靜置1小時。 (ii)熱處理 將小麥殿粉（50 mg)與i ml水在圓底燒瓶中預混合，接著 將5 ml水添加至燒瓶中。藉由在95。〇下加熱5分鐘使懸浮液 中之小麥澱粉溶解，接著將去離子水添加至溶液中，達到 40 ml之體積。將果膠（50 mg)添加至該溶液中且藉由在％ 下加熱20分鐘而溶解。將該溶液之pH值調節為約7.5。將去 離子水添加至該溶液中，達到5〇 ml之最終體積。在使用前 將該溶液於30°C下靜置1小時◊將果膠酯酶（8〇1單位/毫升， 0.1 ml)添加至該溶液中。在使用前將該溶液於3〇它下靜置工 小時。 2·消化率測試 將去離子水添加至如上所製備之各樣品中，達到25〇 Μ H7795.doc -18- 200920271 之體積，接著將各溶液之pH值調節為約5.8至6.5。將熱穩 定型α-澱粉酶（13000 Lj/g，0.1 ml)添加至各溶液中，且將 該等溶液在1 〇〇°C水浴中加熱5分鐘以進行酶反應。在反應 後，將溶液之pH值調節為約4，接著將去離子水添加至各溶 液中，達到250 ml之體積。接著將葡糖澱粉酶（225 GAU/ml，0.3 ml)添加至各溶液中，以在55至60°C之水浴中 與受質反應10分鐘。再次將去離子水添加至各溶液中，達 到2000 ml之體積。藉由使用RQ flex® plus測試條來測定各 溶液中葡萄糖之濃度。藉由將測試條中所讀取之值乘以稀 釋倍數來計算各樣品中葡萄糖之濃度。根據以下方程式來 計算各樣品之消化率，且在表2中展示結果。 xlOO% :肖化率= 樣品中葡萄糖之濃度 '~ _小麥澱粉溶液中葡萄糖之濃度 表2 :樣品之消化率 S SP SPE HA treatment H treatment HA treatment H treatment 消化率(％) 100 100 100 73.3±5.8 75.8±9.0 S :小麥澱粉 SP :小麥澱粉+果膠 SPE :小麥澱粉+果膠+果膠酯酶 HA treatment :熱處理及驗處理 H treatment :熱處理 117795.doc -19-/ month 'J 117795.doc • 17- 200920271 The solution was allowed to stand at 30 ° C for 1 hour. (3) Mixed solution of wheat house powder, pectin and pectin esterase (wheat starch + pectin + pectin vinegar, SPE) (i) heat treatment and treatment treatment of wheat starch (50 mg) with 1 ml of water The round bottom flask was premixed and then 5 ml of sodium hydroxide solution (〇5 N) was added to the flask. By at 95. The wheat starch in the suspension was dissolved by heating under the arm for 5 minutes and then deionized water was added to the solution to a volume of 40 ml. Pectin (50 mg) was added to the solution and dissolved by heating at 95 ° C for 20 minutes. The value of 1) was adjusted to about 7.5. Deionized water was added to the solution to a final volume of 5 〇 mi. Pectin esterase (8〇1 unit/ml, 〇.丨ml) was added to the solution. The solution was allowed to stand at 3 CTC for 1 hour before use. (ii) Heat treatment Wheat house powder (50 mg) was premixed with i ml of water in a round bottom flask, and then 5 ml of water was added to the flask. By at 95. The wheat starch in the suspension was dissolved by heating under the arm for 5 minutes, and then deionized water was added to the solution to a volume of 40 ml. Pectin (50 mg) was added to the solution and dissolved by heating at % for 20 minutes. The pH of the solution was adjusted to about 7.5. Deionized water was added to the solution to a final volume of 5 〇 ml. The solution was allowed to stand at 30 ° C for 1 hour before use, and pectin esterase (8 〇 1 unit / ml, 0.1 ml) was added to the solution. The solution was allowed to stand under 3 Torr for a few hours before use. 2. Digestibility test Deionized water was added to each sample prepared as above to a volume of 25 〇 H7795.doc -18-200920271, and then the pH of each solution was adjusted to about 5.8 to 6.5. A heat-stable α-amylase (13,000 Lj/g, 0.1 ml) was added to each solution, and the solutions were heated in a 1 ° C water bath for 5 minutes to carry out an enzymatic reaction. After the reaction, the pH of the solution was adjusted to about 4, and then deionized water was added to each solution to a volume of 250 ml. Glucoamylase (225 GAU/ml, 0.3 ml) was then added to each solution to react with the substrate for 10 minutes in a water bath at 55 to 60 °C. Deionized water was again added to each solution to a volume of 2000 ml. The concentration of glucose in each solution was determined by using the RQ flex® plus test strip. The concentration of glucose in each sample was calculated by multiplying the value read in the test strip by the dilution factor. The digestibility of each sample was calculated according to the following equation, and the results are shown in Table 2. XlOO%: Xiaohuan rate = concentration of glucose in the sample '~ _ glucose concentration in wheat starch solution Table 2: Digestibility of sample S SP SPE HA treatment H treatment HA treatment H treatment Digestibility (%) 100 100 100 73.3± 5.8 75.8±9.0 S: wheat starch SP: wheat starch + pectin SPE: wheat starch + pectin + pectin esterase HA treatment: heat treatment and treatment H treatment : heat treatment 117795.doc -19-

Claims (1)

200920271 十、申請專利範圍： 種抗解澱粉，其係藉由經果膠酯酶反應將澱粉與果膠 交聯製備而成。 2.種組合物’其包含如請求項1之抗解澱粉。 3 _如叫求項2之組合物，其為食品組合物或醫藥組合物。 4. 種用於製備抗解殿粉之方法，其包含： 1 (a)製備包含澱粉及果膠之溶液；且 (b)藉由果膠酯酶反應將澱粉與果膠交聯。 5. 如請求項4之方法，其中步驟（b)中之交聯反應係在約20 至8 0 °C之溫度下進行。 6. 如請求項4之方法，其中步驟（b)中之交聯反應係在約4〇 至9.0之pH值下進行。 7_如凊求項4至6中任一項之方法，其中該包含澱粉及果膠 之溶液係由以下步驟製備： (1)將該澱粉與選自水及乙醇溶液之溶劑預混合以獲得 * 混合物； t (丨丨）將水或驗性溶液添加至該混合物♦以獲得澱粉懸浮 液； (iii) 力口熱該澱粉懸浮液以溶解該殿粉且獲得殿粉溶液； (iv) 將水及果膠添加至該澱粉溶液中以獲得澱粉_果膠 懸浮液； 及 (v) 加熱該殿粉-果膠懸浮液以溶解該果膠且獲得包含 殿粉及果膠之溶液。 117795.doc 200920271 8 · 如清求Jg 7 士 只/之方法，其中步驟⑴中所使用之溶劑為乙醇溶 液。 月求項8之方法，其中該乙醇溶液之濃度為約95%。 10.如請求 I -,ι 之方法’其中在步驟（ii)中添加該鹼性溶液。 如二求項7之方*，其中在步驟（iii)中之加熱係在約60至 1 〇〇 C之溫度下進行約5至60分鐘。 12·如叫求項7之方法，其中該果膠具有高於30之酯化度（dE) 值。 13·如切求項12之方法，其中該果膠具有高於60之DE值。 月求項7之方法’其中在步驛（v)中之加熱係在約60至 i〇〇c之溫度下進行約1〇至6〇分鐘。 如3求項7之方法，其進一步包含步驟（vi)以用於藉由離 心回收該抗解澱粉。 16.如叫求項μ之方法，其進一步包含步驟（^丨丨）以用於乾燥該 經回收之抗解澱粉。 1 7. —種抗解澱粉，其係藉由如請求項4至丨6中任一項之方法 而製備。 18. —種組合物，其包含如請求項17之抗解澱粉。 19. 如請求項18之組合物’其為食品組合物或醫藥組合物。 117795.doc 200920271 七、指定代表圖： (一) 本案指定代表圖為：第（）圖。 (二) 本代表圖之元件符號簡單說明： 八、本案若有化學式時，請揭示最能顯示發明特徵的化學式： f 117795.doc200920271 X. Patent application scope: A kind of anti-mycorrhizal starch, which is prepared by cross-linking starch and pectin by pectin esterase reaction. 2. A composition comprising the anti-starch as claimed in claim 1. A composition according to claim 2 which is a food composition or a pharmaceutical composition. 4. A method for preparing an anti-resolved powder comprising: 1 (a) preparing a solution comprising starch and pectin; and (b) crosslinking the starch with pectin by a pectin esterase reaction. 5. The method of claim 4, wherein the crosslinking reaction in step (b) is carried out at a temperature of from about 20 to 80 °C. 6. The method of claim 4, wherein the crosslinking reaction in step (b) is carried out at a pH of from about 4 Torr to 9.0. The method of any one of items 4 to 6, wherein the solution comprising starch and pectin is prepared by the following steps: (1) premixing the starch with a solvent selected from the group consisting of water and ethanol solutions to obtain * mixture; t (丨丨) adding water or an assay solution to the mixture ♦ to obtain a starch suspension; (iii) heat the starch suspension to dissolve the powder and obtain a powder solution; (iv) Water and pectin are added to the starch solution to obtain a starch-pectin suspension; and (v) the temple powder-pectin suspension is heated to dissolve the pectin and a solution containing the temple powder and pectin is obtained. 117795.doc 200920271 8 · For the method of purifying Jg 7 only, the solvent used in the step (1) is an ethanol solution. The method of claim 8, wherein the concentration of the ethanol solution is about 95%. 10. A method of requesting I -, ι' wherein the alkaline solution is added in step (ii). The method of claim 7 is wherein the heating in step (iii) is carried out at a temperature of about 60 to 1 〇〇 C for about 5 to 60 minutes. 12. The method of claim 7, wherein the pectin has a degree of esterification (dE) greater than 30. 13. The method of claim 12, wherein the pectin has a DE value above 60. The method of claim 7 wherein the heating in step (v) is carried out at a temperature of about 60 to i〇〇c for about 1 to 6 minutes. The method of claim 7, further comprising the step (vi) for recovering the anti-paste starch by centrifugation. 16. The method of claim μ, further comprising the step of drying the recovered anti-paste starch. 1 7. An anti-gelatinized starch prepared by the method of any one of claims 4 to 6. 18. A composition comprising the anti-starch as claimed in claim 17. 19. The composition of claim 18 which is a food composition or a pharmaceutical composition. 117795.doc 200920271 VII. Designated representative map: (1) The representative representative of the case is: (). (2) A brief description of the symbol of the representative figure: 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: f 117795.doc