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CN111449248A - A kind of granular starch lipid complex with low glycemic index and preparation method thereof - Google Patents

A kind of granular starch lipid complex with low glycemic index and preparation method thereof Download PDF

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CN111449248A
CN111449248A CN202010252294.2A CN202010252294A CN111449248A CN 111449248 A CN111449248 A CN 111449248A CN 202010252294 A CN202010252294 A CN 202010252294A CN 111449248 A CN111449248 A CN 111449248A
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starch
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王宏伟
刘兴丽
张艳艳
张华�
杨晓娟
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王艳
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Zhengzhou University of Light Industry
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    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
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    • A23L33/20Reducing nutritive value; Dietetic products with reduced nutritive value
    • A23L33/21Addition of substantially indigestible substances, e.g. dietary fibres
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    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
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    • A23LFOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
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    • A23L5/30Physical treatment, e.g. electrical or magnetic means, wave energy or irradiation
    • A23L5/32Physical treatment, e.g. electrical or magnetic means, wave energy or irradiation using phonon wave energy, e.g. sound or ultrasonic waves
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Abstract

本发明属于淀粉改性加工领域,具体涉及一种低血糖指数的颗粒态淀粉脂质复合物及其制备方法。本发明所述方法包括如下步骤:通过超声对淀粉和脂质的混悬液进行处理,处理的过程中维持反应混合体系的温度低于淀粉的糊化温度T0。本发明通过采用超声处理制备低血糖指数颗粒态淀粉脂质复合物,具有工艺简单、技术先进、易清洗、无污染等优点。而且用本方法制备的低血糖指数颗粒态淀粉脂质复合物产品具有复合指数高、热稳定性强、血糖生成指数低等特点,且易于实现工业化生产,可广泛应用于功能性食品、保健品等食品加工领域。The invention belongs to the field of starch modification and processing, in particular to a granular starch lipid complex with a low glycemic index and a preparation method thereof. The method of the present invention includes the following steps: processing the starch and lipid suspension by ultrasound, and maintaining the temperature of the reaction mixture system lower than the starch gelatinization temperature T 0 during the processing. The invention prepares the low-glycemic index granular starch-lipid complex by adopting ultrasonic treatment, and has the advantages of simple process, advanced technology, easy cleaning, no pollution and the like. In addition, the low-glycemic index granular starch-lipid complex product prepared by the method has the characteristics of high composite index, strong thermal stability, low glycemic index, etc., and is easy to realize industrial production, and can be widely used in functional foods and health products. and other food processing fields.

Description

一种低血糖指数的颗粒态淀粉脂质复合物及其制备方法A kind of granular starch lipid complex with low glycemic index and preparation method thereof

技术领域technical field

本发明属于淀粉改性加工领域,具体涉及一种低血糖指数的颗粒态淀粉脂质复合物及其制备方法。The invention belongs to the field of starch modification and processing, in particular to a granular starch lipid complex with a low glycemic index and a preparation method thereof.

背景技术Background technique

近年来,由于食物种类多样化程度的提高,以及膳食构成的不合理,使得人体能量的摄入与消耗不平衡,进而导致胰岛素抵抗、糖尿病、肥胖和其他相关代谢综合征的患病人群数量逐年攀升。根据美国膳食标准(USDA),碳水化合物是对人类健康至关重要的常量营养素,提供了人体45%~65%的能量需求。淀粉是植物碳水化合物的主要贮藏形式,在人类膳食中占有很大的比重,能提供人类生存所必须的能量物质,其餐后血糖应答与血糖指数(GI)呈显著正相关,其中,抗消化淀粉(RS)含量与血糖指数成线性负相关。淀粉-脂质复合物作为一类新型抗消化淀粉(resistant starch,RS5),可降低餐后血糖水平,有效控制肥胖、糖尿病等代谢性慢性疾病的发病率。In recent years, due to the increase in the diversification of food types and the unreasonable dietary composition, the energy intake and consumption of the human body are unbalanced, resulting in the number of people suffering from insulin resistance, diabetes, obesity and other related metabolic syndromes year by year. rising. According to the United States Dietary Standards (USDA), carbohydrates are macronutrients essential to human health, providing 45% to 65% of the body's energy requirements. Starch is the main storage form of plant carbohydrates. It occupies a large proportion in human diet and can provide energy substances necessary for human survival. The postprandial blood glucose response is significantly positively correlated with the glycemic index (GI). Among them, anti-digestion There was a linear negative correlation between starch (RS) content and glycemic index. Starch-lipid complexes, as a new type of resistant starch (RS5), can reduce postprandial blood glucose levels and effectively control the incidence of metabolic chronic diseases such as obesity and diabetes.

目前,有关淀粉-脂质复合物的研究已成为热点,其中,颗粒态淀粉-脂质复合物具有能耗低、易清洗、操作简单、成本低等优点,对营养健康RS5型食品的创制具有重要意义。但是,当前颗粒态淀粉-脂质复合物的制备尚存在以下不足:(1)主要通过热场作用颗粒态淀粉与脂质,增强淀粉分子链段的自由体积和可移动能力,提高其与脂质分子的可接触能力,从而促进颗粒态淀粉与脂质复合反应的发生,降低淀粉-脂质复合物的消化速率。如常丰丹、D’Silva、 Nakazawa等采用热场作用协同脂质复合的方式制备颗粒态淀粉-脂质复合物,主要通过加热促进直链淀粉的逸出和支链淀粉的可移动性从而与脂质复合形成颗粒态淀粉-脂质复合物。由于脂质分子在淀粉颗粒表面的聚集,低热能对淀粉内部氢键的破坏有限且程度较低,以及淀粉超分子结构可移动能力弱,导致在制备颗粒态淀粉-脂质复合物的过程中,存在脂质分子聚集、复合程度低、稳定性弱等不足。 (2)通过物理、生物或化学修饰破坏淀粉的有序化结构和排列,使淀粉分子链(即直链和支链淀粉)得以充分释放,并与脂质进行复合反应。现有技术中大部分通过糊化、脱支、高压等加工方法处理,其有序化结构受到破坏,淀粉分子链得以释放,可与脂质复合形成具有一定抗消化性能的复合物。然而,上述制备手段工艺复杂,成本较高,不利于淀粉-脂质复合物在食品工业广泛应用。而且产品得率较低。At present, the research on starch-lipid complexes has become a hotspot. Among them, granular starch-lipid complexes have the advantages of low energy consumption, easy cleaning, simple operation, and low cost, which are very useful for the creation of nutritious and healthy RS5 food. important meaning. However, the current preparation of granular starch-lipid complexes still has the following shortcomings: (1) Mainly through the thermal field action of granular starch and lipids, the free volume and mobility of starch molecular segments are enhanced, and the ability of starch molecules to interact with lipids is enhanced. The accessibility of lipid molecules, thereby promoting the complex reaction between granular starch and lipids, and reducing the digestion rate of starch-lipid complexes. For example, Chang Fengdan, D'Silva, Nakazawa, etc. used thermal field action to synergize lipid complexes to prepare granular starch-lipid complexes, mainly by heating to promote the escape of amylose and the mobility of amylopectin to combine with Lipid complexes form granular starch-lipid complexes. Due to the aggregation of lipid molecules on the surface of starch granules, the destruction of the internal hydrogen bonds of starch by low thermal energy is limited and to a low degree, and the mobility of starch supramolecular structure is weak, resulting in the preparation of granular starch-lipid complexes in the process of , there are deficiencies such as lipid molecule aggregation, low degree of complexation, and weak stability. (2) Destroy the ordered structure and arrangement of starch through physical, biological or chemical modification, so that starch molecular chains (ie, amylose and amylopectin) can be fully released and complexed with lipids. Most of the existing technologies are processed by gelatinization, debranching, high pressure and other processing methods, the ordered structure is destroyed, the starch molecular chain is released, and it can be complexed with lipids to form a complex with certain anti-digestion properties. However, the above-mentioned preparation methods are complicated in process and high in cost, which are not conducive to the wide application of starch-lipid complexes in the food industry. And the product yield is low.

发明内容SUMMARY OF THE INVENTION

为了克服现有方法的缺点与不足,本发明提供一种利用超声处理制备低血糖指数颗粒态淀粉-脂质复合物的方法。In order to overcome the shortcomings and deficiencies of the existing methods, the present invention provides a method for preparing a low glycemic index granular starch-lipid complex by ultrasonic treatment.

本发明的方法包括如下步骤:通过超声对淀粉和脂质的混悬液进行处理,处理的过程中维持反应混合体系的温度低于淀粉的糊化温度T0The method of the present invention comprises the following steps: processing the starch and lipid suspension by ultrasonic, and maintaining the temperature of the reaction mixture system lower than the starch gelatinization temperature T 0 during the processing.

本发明发现不提前对物料进行热处理,即不使淀粉发生糊化,直接通过超声作用处理淀粉和脂质混合物,可较大程度地促进淀粉聚集态结构和链结构的运动,增加淀粉与脂质分子的可接触性,提高颗粒态淀粉-脂质复合物的复合能力,从而获得高慢消化淀粉(SDS) 和抗消化淀粉(RS)含量的颗粒态淀粉-脂质复合物。The present invention finds that without heat treatment of the material in advance, that is, without gelatinizing the starch, directly treating the starch and lipid mixture by ultrasonic action can greatly promote the movement of the starch aggregate structure and chain structure, and increase the starch and lipid Molecular accessibility improves the complexing ability of granular starch-lipid complexes, thereby obtaining granular starch-lipid complexes with high content of slowly digestible starch (SDS) and resistant starch (RS).

优选的,处理的过程中维持反应混合体系的温度为(T0-10℃) ~T0,在此温度范围内,不仅能够维持其颗粒态结构,提高其复合物得率,还可促进淀粉链结构与脂质分子间的相互作用,提高复合物复合效率与RS含量,降低其血糖指数。Preferably, the temperature of the reaction mixture system is maintained in the range of (T 0 -10° C.) to T 0 during the treatment. Within this temperature range, not only can the granular structure be maintained, the yield of the complex can be improved, but also starch can be promoted. The interaction between the chain structure and lipid molecules improves the complexation efficiency and RS content of the complex, and reduces its glycemic index.

优选的,所述淀粉和脂质的混悬液中,淀粉和脂质的质量比为1: 0.01~0.2。在此比例范围内,可促进脂质分子向淀粉颗粒内部的迁移及均匀分布,防止脂质分子聚集,从而影响复合物的制备。Preferably, in the starch and lipid suspension, the mass ratio of starch and lipid is 1:0.01-0.2. Within this ratio range, the migration and uniform distribution of lipid molecules to the interior of starch granules can be promoted, and the aggregation of lipid molecules can be prevented, thereby affecting the preparation of complexes.

优选的,所述淀粉和脂质的混悬液中,淀粉的质量分数为3~10%,淀粉在此质量范围内既可防止淀粉含量过低不容易与脂质分子发生复合反应,又可防止体系因淀粉乳浓度过高而阻碍超声波的复合作用,即链和脂质分子的可移动能力受到限制,相互之间形成复合物的几率降低。Preferably, in the suspension of starch and lipid, the mass fraction of starch is 3-10%, and within this mass range, starch can not only prevent the starch content from being too low and not easily react with lipid molecules, but also can Prevent the system from hindering the complex effect of ultrasonic waves due to the high concentration of starch milk, that is, the mobility of chains and lipid molecules is limited, and the probability of forming complexes with each other is reduced.

优选的,所述脂质为脂肪酸或甘油酯。作为食用油消费大国,植物油是人们日常生活中的重要消费品,可以提供脂肪、多不饱和脂肪酸及脂溶性维生素等多种营养元素,如玉米油、菜籽油、大豆油、油茶籽油、调和油等。植物油95%以上由甘油三酯构成,甘油三酯链上含有丰富的脂肪酸。棕榈酸(C16:0,palmtic acid,PA)、硬脂酸(C18:0,stearic acid,SA)、油酸(C18:1n-9,oleic acid,OA)、亚油酸(C18:2n-6,linoleic acid,LA)是大部分植物油的主要脂肪酸。因此,我们选择脂肪酸和甘油酯作为淀粉脂质复合物的脂质配合体,以此制备具有低GI水平的营养功能食品,同时也符合我国食品加工与饮食习惯的需求。Preferably, the lipids are fatty acids or glycerides. As a big consumer of edible oil, vegetable oil is an important consumer product in people's daily life. It can provide various nutrients such as fat, polyunsaturated fatty acids and fat-soluble vitamins, such as corn oil, rapeseed oil, soybean oil, camellia oil, blended oil etc. More than 95% of vegetable oil is composed of triglycerides, and the triglyceride chain is rich in fatty acids. Palmitic acid (C16:0, palmtic acid, PA), stearic acid (C18:0, stearic acid, SA), oleic acid (C18:1n-9, oleic acid, OA), linoleic acid (C18:2n- 6, linoleic acid, LA) is the main fatty acid of most vegetable oils. Therefore, we choose fatty acids and glycerides as lipid complexes of starch-lipid complexes to prepare nutritional functional foods with low GI levels, which also meet the needs of food processing and eating habits in my country.

进一步优选的,所述脂肪酸为月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、油酸、亚油酸、花生四烯酸或亚麻酸中的一种或几种。Further preferably, the fatty acid is one or more of lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, arachidonic acid or linolenic acid.

进一步优选的,所述甘油酯为单硬脂酸甘油酯、棕榈酸单甘油酯或三棕榈酸甘油酯中的一种或几种。Further preferably, the glyceride is one or more of glycerol monostearate, monoglyceride palmitate or glycerol tripalmitate.

优选的,所述淀粉为小麦淀粉、马铃薯淀粉、大米淀粉、玉米淀粉或绿豆淀粉中的一种或几种。Preferably, the starch is one or more of wheat starch, potato starch, rice starch, corn starch or mung bean starch.

优选的,所述超声处理的条件为频率20~45kHz,功率240~600 W,超声处理10~60min。选择此超声处理条件制备复合物,可提高复合物得率及复合效率,获得低GI水平的复合物。此外,此参数也是超声仪器通常所能满足的条件,无需进行特殊订制或要求。Preferably, the ultrasonic treatment conditions are frequency 20-45 kHz, power 240-600 W, and ultrasonic treatment for 10-60 min. Selecting this ultrasonic treatment condition to prepare the complex can improve the complex yield and complex efficiency, and obtain the complex with low GI level. In addition, this parameter is also a condition that ultrasonic instruments can usually meet without special customization or requirements.

优选的,所述淀粉和脂质的混悬液的制备方法包括如下步骤:Preferably, the preparation method of the suspension of described starch and lipid comprises the steps:

(1)将淀粉与蒸馏水充分混合,得到淀粉悬浮溶液;(1) fully mixing starch and distilled water to obtain starch suspension solution;

(2)将脂质溶于短链醇中,充分分散,将其与所述淀粉悬浮溶液混合,得到所述淀粉和脂质的混悬液;(2) lipid is dissolved in short-chain alcohol, fully dispersed, it is mixed with described starch suspension solution, obtains the suspension of described starch and lipid;

优选的,所述短链醇为乙醇、丙醇或异丙醇中的一种或几种。Preferably, the short-chain alcohol is one or more of ethanol, propanol or isopropanol.

作为优选的操作方式,所述淀粉悬浮溶液中淀粉的质量分数为 4~10%。As a preferred operation mode, the mass fraction of starch in the starch suspension solution is 4-10%.

优选的,为得到所述颗粒态淀粉脂质复合物,淀粉超声处理完后还包括如下操作:Preferably, in order to obtain the granular starch lipid complex, after the starch is ultrasonically treated, the following operations are also included:

1)将超声处理后的淀粉和脂质的混悬液冷却后离心,用乙醇- 水混合物洗涤沉淀物,得到淀粉脂质沉淀物;1) centrifugally after cooling the suspension of the starch and lipid after the ultrasonic treatment, wash the precipitate with an ethanol-water mixture to obtain a starch lipid precipitate;

2)将淀粉脂质沉淀物干燥后粉碎,即得所述颗粒态淀粉脂质复合物。2) The starch lipid precipitate is dried and then pulverized to obtain the granular starch lipid complex.

作为优选的操作方式,其具体步骤为:As a preferred mode of operation, its specific steps are:

1)将超声处理淀粉脂质混合物冷却至室温,于2800~3200r/min 条件下离心15~25min,弃上清液,用40~60%乙醇-水混合物洗涤沉淀物,抽滤,重复三次,得到淀粉脂质沉淀物;1) Cool the sonicated starch-lipid mixture to room temperature, centrifuge at 2800-3200 r/min for 15-25 min, discard the supernatant, wash the precipitate with 40-60% ethanol-water mixture, suction filtration, repeat three times, Obtain starch lipid precipitate;

2)将淀粉脂质沉淀物于40~50℃条件下干燥过夜,粉碎并过 80~120目筛即得所述颗粒态淀粉-脂质复合物。2) The starch lipid precipitate is dried at 40-50°C overnight, pulverized and passed through a 80-120 mesh sieve to obtain the granular starch-lipid complex.

作为优选的方案,本发明包括如下步骤:As a preferred solution, the present invention comprises the steps:

(1)将小麦淀粉或大米淀粉与蒸馏水充分混合,得到淀粉悬浮溶液;(1) fully mixing wheat starch or rice starch with distilled water to obtain starch suspension solution;

(2)将脂质溶于短链醇中,充分分散,将其与所述淀粉悬浮溶液混合,得到所述淀粉和脂质的混悬液,所述淀粉和脂质的混悬液中,淀粉的质量分数为3~10%,淀粉和脂质的质量比为1:0.01~0.2;(2) lipid is dissolved in short-chain alcohol, fully dispersed, it is mixed with described starch suspension solution, obtains the suspension of described starch and lipid, in the suspension of described starch and lipid, The mass fraction of starch is 3-10%, and the mass ratio of starch and lipid is 1:0.01-0.2;

(3)通过超声对淀粉和脂质的混悬液进行处理,处理的过程中维持反应混合体系的温度低于淀粉的糊化温度(T0-10℃)~T0,超声处理的条件为频率20~45kHz,功率240~600W,超声处理10~60min。(3) The suspension of starch and lipid is processed by ultrasonic, and the temperature of the reaction mixture system is maintained below the gelatinization temperature of starch (T 0 -10° C.)~T 0 during the process, and the ultrasonic processing conditions are: Frequency 20~45kHz, power 240~600W, ultrasonic treatment for 10~60min.

本发明的另一目的是保护本发明所述的制备方法制备得到的低血糖指数的颗粒态淀粉脂质复合物。Another object of the present invention is to protect the granular starch lipid complex with low glycemic index prepared by the preparation method of the present invention.

优选的,所述低血糖指数的颗粒态淀粉脂质复合物中慢消化淀粉(SDS)和抗消化淀粉(RS)含量总和大于45%。Preferably, the total content of slowly digestible starch (SDS) and resistant starch (RS) in the granular starch lipid complex with low glycemic index is greater than 45%.

本发明具有如下有益效果:The present invention has the following beneficial effects:

1)本发明首次发现,不对淀粉颗粒预先进行热处理使其糊化,直接采用超声处理加工技术,不仅可影响淀粉颗粒的分子与超分子结构组成,还可促进脂质分子的迁移和均匀分布(脂质分子几乎不发生结构变化),制备得到一种低血糖指数的颗粒态淀粉脂质复合物。1) The present invention finds for the first time that starch granules are not subjected to heat treatment in advance to make them gelatinized, and directly adopt ultrasonic processing technology, which can not only affect the molecular and supramolecular structure composition of starch granules, but also promote the migration and uniform distribution of lipid molecules ( The lipid molecules hardly undergo structural changes), and a granular starch-lipid complex with a low glycemic index is prepared.

2)本发明制备的低血糖指数的颗粒态淀粉脂质复合物的复合指数高、热稳定性强,且慢消化淀粉(SDS)和抗消化淀粉(RS)含量高,且由于形成了低血糖指数的颗粒态淀粉脂质复合物,易于清洗纯化,制备得到的产物得率高。2) The low glycemic index granular starch-lipid complex prepared by the present invention has high composite index, strong thermal stability, and high content of slowly digestible starch (SDS) and resistant starch (RS), and due to the formation of a low glycemic index The granular starch-lipid complex is easy to clean and purify, and the prepared product has a high yield.

3)本发明所制备的低血糖指数的颗粒态淀粉脂质复合物能降低脂肪酸的氧化,所形成的复合物既具有低血糖能力,还可补充人体的必需脂肪酸,具有营养保健功能,是一种多功能的食品基料,对于营养健康食品的创制具有重要意义。3) The granular starch lipid complex with low glycemic index prepared by the present invention can reduce the oxidation of fatty acid, and the formed complex not only has the ability of low blood sugar, but also can supplement the essential fatty acids of the human body, and has the function of nutrition and health care. It is a kind of multifunctional food base material, which is of great significance for the creation of nutritious and healthy food.

4)本发明生产工艺简单,所涉及的生产设备高效、成本较低、能耗低、易清洗,制备过程对环境无污染,是一种绿色环保的新型颗粒态复合物加工方法,易于实现工业化生产。4) The production process of the present invention is simple, the involved production equipment is efficient, the cost is low, the energy consumption is low, and it is easy to clean, and the preparation process does not pollute the environment. Production.

附图说明Description of drawings

图1为实施例1中低血糖指数的颗粒态淀粉脂质复合物的13C-NMR图谱;Fig. 1 is the 13 C-NMR spectrum of the granular starch lipid complex with low glycemic index in Example 1;

图2为实施例3中颗粒态淀粉脂质复合物的X-射线衍射图谱。FIG. 2 is the X-ray diffraction pattern of the granular starch lipid complex in Example 3. FIG.

具体实施方式Detailed ways

下面结合具体实施例对本发明做出进一步地详细阐述,所述实施例只用于解释本发明,并非用于限定本发明的范围。下述实施例中所使用的实验方法,如无特殊说明,均为常规方法;所使用的材料、试剂、设备等,如无特殊说明,均可从商业途径获得。The present invention will be further elaborated below with reference to specific embodiments, which are only used to explain the present invention, but not to limit the scope of the present invention. The experimental methods used in the following examples are conventional methods unless otherwise specified; the materials, reagents, equipment, etc. used can be obtained from commercial sources unless otherwise specified.

本发明实施例和对比例中涉及的产品得率的计算方法为制备得到的低血糖指数颗粒态淀粉脂质复合物的质量与淀粉和脂质的质量和的比值。The calculation method of the product yield involved in the examples and comparative examples of the present invention is the ratio of the mass of the prepared low glycemic index granular starch-lipid complex to the mass sum of starch and lipid.

本发明实施例和对比例中涉及的颗粒态淀粉-脂质复合物的消化性能SDS和RS的计算方法为:The calculation method of the digestibility SDS and RS of the granular starch-lipid complex involved in the embodiment of the present invention and the comparative example is:

采用Sigma公司的酶,参考Englyst提出的步骤分析其快消化淀粉(RDS)、慢消化淀粉(SDS)和抗消化淀粉(RS)的含量;The enzyme of Sigma company was used to analyze the content of rapidly digestible starch (RDS), slowly digestible starch (SDS) and resistant starch (RS) with reference to the steps proposed by Englyst;

具体为:准确称取1g样品溶解于20mL pH 5.2的0.1mol/L 醋酸钠缓冲液中,搅拌均匀。然后置于沸水浴中煮沸30min,取出冷却至37℃,然后加入5mL胰α-淀粉酶和淀粉葡萄糖苷酶混合液,在37℃、190r/min震荡下进行水解。分别在20min和120 min时取0.5mL水解液,加20mL 70%乙醇灭酶,然后在4000 r/min离心10min,取0.1mL上清液,加3mL GOPOD,与45℃水中显色20min,510nm处测试吸光值。根据样品和标准葡萄糖的吸光值,分别计算快消化淀粉RDS含量、慢消化淀粉SDS含量和抗消化淀粉RS含量,公式如下:Specifically, 1 g of the sample is accurately weighed and dissolved in 20 mL of 0.1 mol/L sodium acetate buffer at pH 5.2, and stirred evenly. Then put it in a boiling water bath to boil for 30min, take it out and cool it to 37°C, then add 5mL of a mixture of pancreatic α-amylase and amyloglucosidase, and conduct hydrolysis under shaking at 37°C and 190r/min. Take 0.5mL of hydrolyzate at 20min and 120min respectively, add 20mL of 70% ethanol to inactivate the enzyme, then centrifuge at 4000 r/min for 10min, take 0.1mL of supernatant, add 3mL of GOPOD, and develop with 45℃ water for 20min, 510nm Test the absorbance value. According to the absorbance values of the sample and standard glucose, the RDS content of fast-digesting starch, the SDS content of slow-digesting starch and the RS content of resistant starch were calculated respectively. The formulas are as follows:

RDS=(G20–FG)×0.9RDS=(G 20 –FG)×0.9

SDS=(G120–G20)×0.9 (1)SDS=(G 120 -G 20 )×0.9 (1)

RS=TS–(RDS+SDS)=TS–(G120×0.9)RS=TS–(RDS+SDS)=TS–(G 120 ×0.9)

式中:G20和G120分别为酶水解20min和120min后的葡萄糖含量;FG为酶水解前样品中的葡萄糖含量(以0计);TS为总淀粉含量。In the formula: G 20 and G 120 are the glucose content after enzymatic hydrolysis for 20 min and 120 min, respectively; FG is the glucose content in the sample before enzymatic hydrolysis (calculated as 0); TS is the total starch content.

实施例1Example 1

本实施例涉及一种超声处理制备低血糖指数颗粒态淀粉脂质复合物的方法,包括如下步骤:The present embodiment relates to a method for preparing a low-glycemic index granular starch-lipid complex by ultrasonic treatment, comprising the following steps:

(1)称取100g干基小麦淀粉,与蒸馏水充分混合,得到质量分数为5%的小麦淀粉悬浮液;(1) take by weighing 100g dry base wheat starch, fully mix with distilled water, obtain the wheat starch suspension that massfraction is 5%;

(2)称取6g油酸,用2倍体积的无水乙醇分散溶解后,加入小麦淀粉悬浮液中,将小麦淀粉与油酸混合均匀,得到小麦淀粉脂质混合物;(2) take by weighing 6g oleic acid, after dispersing and dissolving with the dehydrated alcohol of 2 times of volumes, add in the wheat starch suspension, the wheat starch and oleic acid are mixed, obtain the wheat starch lipid mixture;

(3)将小麦淀粉脂质混合物置于恒温超声处理设备中进行超声处理,在40kHz、240W条件下超声处理20min,保持复合反应体系温度在(To-5)℃左右,不断搅拌,得到超声处理小麦淀粉脂质混合物;(3) place the wheat starch lipid mixture in a constant temperature ultrasonic treatment equipment for ultrasonic treatment, and ultrasonically treat it for 20 min under the conditions of 40 kHz and 240 W, keep the temperature of the composite reaction system at about (T o -5) ° C, and continuously stir to obtain ultrasonic waves. processing wheat starch lipid mixture;

(4)将超声处理小麦淀粉脂质混合物冷却至室温,于3000r/min 条件下离心20min,弃上清液,用50%乙醇-水混合物洗涤沉淀物,抽滤,重复三次,得到小麦淀粉脂质沉淀物;(4) Cool the sonicated wheat starch lipid mixture to room temperature, centrifuge at 3000 r/min for 20 min, discard the supernatant, wash the precipitate with a 50% ethanol-water mixture, perform suction filtration, and repeat three times to obtain wheat starch lipid sediment;

(5)将小麦淀粉脂质沉淀物于45℃条件下干燥过夜,粉碎并过100目筛,即得低血糖指数颗粒态-淀粉脂质复合物,最后真空包装,样品得率为94%。(5) The wheat starch lipid precipitate was dried at 45°C overnight, pulverized and passed through a 100-mesh sieve to obtain a low glycemic index granular state-starch lipid complex, which was finally vacuum-packed with a sample yield of 94%.

小麦原淀粉的SDS和RS含量分别为5.2%和2.3%,本实施例 SDS和RS含量分别为23.5%和32.7%。The SDS and RS contents of wheat native starch are 5.2% and 2.3%, respectively, and the SDS and RS contents of this example are 23.5% and 32.7%, respectively.

实施例2Example 2

一种超声处理制备低血糖指数颗粒态-淀粉脂质复合物的方法,包括如下步骤:A method for preparing a low glycemic index granular state-starch lipid complex by ultrasonic treatment, comprising the following steps:

(1)称取100g干基马铃薯淀粉,与蒸馏水充分混合,得到质量分数为6%的马铃薯淀粉悬浮液;(1) take 100g dry potato starch by weighing, fully mix with distilled water, obtain the potato starch suspension that mass fraction is 6%;

(2)称取10g油酸,用2倍体积的无水乙醇分散溶解后,加入马铃薯淀粉悬浮液中,将马铃薯淀粉与油酸混合均匀,得到马铃薯淀粉脂质混合物;(2) take by weighing 10g oleic acid, after dispersing and dissolving with the absolute ethanol of 2 times of volume, add in the potato starch suspension, potato starch and oleic acid are mixed uniformly, obtain potato starch lipid mixture;

(3)将马铃薯淀粉脂质混合物置于恒温超声处理设备中进行超声处理,在40kHz、400W条件下超声处理30min,保持复合反应体系温度在(To-10)℃左右,不断搅拌,得到超声处理马铃薯淀粉脂质混合物;(3) place the potato starch lipid mixture in a constant temperature ultrasonic treatment device for ultrasonic treatment, and ultrasonically treat it for 30 min under the conditions of 40 kHz and 400 W, keep the temperature of the composite reaction system at about (T o -10) ° C, and continuously stir to obtain ultrasonic treatment. processing potato starch lipid mixture;

(4)将超声处理马铃薯淀粉脂质混合物冷却至室温,于 3000r/min条件下离心20min,弃上清液,用50%乙醇-水混合物洗涤沉淀物,抽滤,重复三次,得到马铃薯淀粉脂质沉淀物;(4) cooling the sonicated potato starch lipid mixture to room temperature, centrifuging at 3000 r/min for 20 min, discarding the supernatant, washing the precipitate with a 50% ethanol-water mixture, suction filtration, and repeating three times to obtain potato starch lipid sediment;

(5)将马铃薯淀粉脂质沉淀物于45℃条件下干燥过夜,粉碎并过100目筛,即得低血糖指数颗粒态淀粉脂质复合物,最后真空包装,样品得率为95%。(5) The potato starch lipid precipitate was dried at 45°C overnight, pulverized and passed through a 100-mesh sieve to obtain a low glycemic index granular starch lipid complex, which was finally vacuum-packed with a sample yield of 95%.

马铃薯原淀粉的SDS和RS含量分别为13.2%和4.3%,本实施例SDS和RS含量分别为20.3%和27.7%。The SDS and RS contents of potato native starch are 13.2% and 4.3%, respectively, and the SDS and RS contents of this example are 20.3% and 27.7%, respectively.

实施例3Example 3

一种超声处理制备低血糖指数颗粒态淀粉脂质复合物的方法,包括如下步骤:A method for preparing a low glycemic index granular starch lipid complex by ultrasonic treatment, comprising the following steps:

(1)称取100g干基大米淀粉,与蒸馏水充分混合,得到质量分数为10%的大米淀粉悬浮液;(1) take by weighing 100g dry basis rice starch, fully mix with distilled water, obtain the rice starch suspension that massfraction is 10%;

(2)称取15g油酸,用3倍体积的无水乙醇分散溶解后,加入大米淀粉悬浮液中,将大米淀粉与油酸混合均匀,得到大米淀粉脂质混合物;(2) take by weighing 15g oleic acid, after dispersing and dissolving with the absolute ethanol of 3 times of volumes, add in the rice starch suspension, the rice starch and oleic acid are mixed homogeneously, obtain the rice starch lipid mixture;

(3)将大米淀粉脂质混合物置于恒温超声处理设备中进行超声处理,在20kHz、500W条件下超声处理50min,保持复合反应体系温度在(To-3)℃左右,不断搅拌,得到超声处理大米淀粉脂质混合物;(3) place the rice starch lipid mixture in a constant temperature ultrasonic treatment device for ultrasonic treatment, ultrasonically treat it for 50 min under the conditions of 20 kHz and 500 W, keep the temperature of the composite reaction system at about (T o -3) ° C, and continuously stir to obtain ultrasonic treatment. processing rice starch lipid mixture;

(4)将超声处理大米淀粉脂质混合物冷却至室温,于3000r/min 条件下离心20min,弃上清液,用50%乙醇-水混合物洗涤沉淀物,抽滤,重复三次,得到大米淀粉脂质沉淀物;(4) cooling the sonicated rice starch lipid mixture to room temperature, centrifuging at 3000 r/min for 20 min, discarding the supernatant, washing the precipitate with 50% ethanol-water mixture, suction filtration, and repeating three times to obtain rice starch lipid sediment;

(5)将大米淀粉脂质沉淀物于45℃条件下干燥过夜,粉碎并过100目筛,即得低血糖指数颗粒态淀粉脂质复合物,最后真空包装,样品得率为92%。(5) The rice starch lipid precipitate was dried at 45°C overnight, pulverized and passed through a 100-mesh sieve to obtain a low glycemic index granular starch lipid complex, which was finally vacuum-packed with a sample yield of 92%.

大米原淀粉的SDS和RS含量分别为4.3%和2.4%,本实施例 SDS和RS含量分别为21.5%和31.7%。The SDS and RS contents of rice native starch were 4.3% and 2.4%, respectively, and the SDS and RS contents of this example were 21.5% and 31.7%, respectively.

实施例4Example 4

本实施例涉及一种超声处理制备低血糖指数颗粒态淀粉脂质复合物的方法,与实施例1相比,其区别仅在于,所述超声处理反应温度在(To-2)℃左右,本实施例所得复合物样品得率为92%,SDS 含量为25.1%,RS含量为34.8%。This embodiment relates to a method for preparing a low-glycemic index granular starch-lipid complex by ultrasonic treatment. Compared with Embodiment 1, the only difference is that the ultrasonic treatment reaction temperature is about (T o -2) °C, The yield of the composite sample obtained in this example was 92%, the SDS content was 25.1%, and the RS content was 34.8%.

实施例5Example 5

本实施例涉及一种超声处理制备低血糖指数颗粒态淀粉脂质复合物的方法,与实施例2相比,其区别仅在于,所述超声处理反应温度在(To-5)℃左右,本实施例所得复合物样品得率为93%,SDS 和RS含量分别为24.3%和31.2%。This embodiment relates to a method for preparing a low-glycemic index granular starch-lipid complex by ultrasonic treatment. Compared with Embodiment 2, the only difference is that the ultrasonic treatment reaction temperature is about (T o -5) °C, The yield of the composite sample obtained in this example was 93%, and the contents of SDS and RS were 24.3% and 31.2%, respectively.

实施例6Example 6

本实施例涉及一种超声处理制备低血糖指数颗粒态淀粉脂质复合物的方法,与实施例3相比,其区别仅在于,所述超声处理反应温度在(To-8)℃左右,本实施例所得复合物样品得率为94%,SDS 和RS含量分别为18.2%和28.4%。This embodiment relates to a method for preparing a low-glycemic index granular starch-lipid complex by ultrasonic treatment. Compared with Embodiment 3, the only difference is that the ultrasonic treatment reaction temperature is about (T o -8) °C, The yield of the composite sample obtained in this example was 94%, and the contents of SDS and RS were 18.2% and 28.4%, respectively.

实施例7Example 7

与实施例1相比,其区别在于,所述超声的条件为在40kHz、 400W条件下超声处理20min,反应温度在(To-5)℃左右,本实施例所得复合物样品得率为92%,SDS和RS含量分别为27.4%和 34.2%。Compared with Example 1, the difference is that the ultrasonic conditions are ultrasonic treatment for 20min under the condition of 40kHz and 400W, the reaction temperature is about (T o -5) ℃, and the yield of the composite sample obtained in this example is 92. %, SDS and RS contents were 27.4% and 34.2%, respectively.

实施例8Example 8

与实施例1相比,其区别在于,所述超声的条件为在40kHz、 400W条件下超声处理15min,反应温度在(To-10)℃左右。本实施例所得复合物样品得率为94%,SDS和RS含量分别为17.8%和23.6%。Compared with Example 1, the difference lies in that the ultrasonic conditions are ultrasonic treatment at 40 kHz and 400 W for 15 min, and the reaction temperature is about ( To -10)°C. The yield of the composite sample obtained in this example was 94%, and the contents of SDS and RS were 17.8% and 23.6%, respectively.

实施例9Example 9

与实施例1相比,其区别在于,所述超声的条件为在30kHz、 500W条件下超声处理50min,反应温度为(To-3)℃左右。本实施例所得复合物样品得率为89%,SDS和RS含量分别为24.2%和 33.9%。Compared with Example 1, the difference lies in that the ultrasonic conditions are ultrasonic treatment at 30 kHz and 500 W for 50 min, and the reaction temperature is about ( To -3)°C. The yield of the composite sample obtained in this example was 89%, and the contents of SDS and RS were 24.2% and 33.9%, respectively.

实施例10Example 10

与实施例1、2、3相比,其区别在于,所述步骤(3)在超声处理的过程中控制反应的温度为(To-15)℃。在此条件下制备的复合物的复合效率低,产品得率为92%、93%和95%,SDS的含量为17.2%、 15.4%和16.3%,RS含量为12.5%、14.2%和13.8%。Compared with Examples 1, 2, and 3, the difference lies in that, in the step (3), the temperature of the reaction is controlled to be (T o -15)° C. during the ultrasonic treatment. The complexes prepared under this condition had low compounding efficiency, with product yields of 92%, 93% and 95%, SDS contents of 17.2%, 15.4% and 16.3%, and RS contents of 12.5%, 14.2% and 13.8% .

对比例1Comparative Example 1

与实施例1、2、3相比,其区别在于,所述步骤(3)在超声处理的过程中控制反应的温度为(To+10)℃。在此条件下制备的小麦、马铃薯、大米复合物产品得率为82%,84%和78%,SDS的含量分别为27.1%、22.4%和24.1%,RS含量为33.6%,28.3%和33.7%。Compared with Examples 1, 2, and 3, the difference lies in that, in the step (3), the temperature of the reaction is controlled to be (T o +10)° C. during the ultrasonic treatment. The yields of wheat, potato and rice composite products prepared under this condition were 82%, 84% and 78%, the contents of SDS were 27.1%, 22.4% and 24.1%, and the contents of RS were 33.6%, 28.3% and 33.7%, respectively. %.

对比例2Comparative Example 2

与实施例1、2和3的制备方法相比,其区别在于,采用超声法处理淀粉颗粒,但并未添加脂质分子。在此条件下制备的超声处理淀粉的SDS含量分别为3.7%、10.7%和2.8%,RS含量为1.5%、 2.5%和1.5%。Compared with the preparation methods of Examples 1, 2 and 3, the difference is that the starch granules are treated by ultrasonic method, but no lipid molecules are added. The SDS contents of the sonicated starch prepared under this condition were 3.7%, 10.7% and 2.8%, and the RS contents were 1.5%, 2.5% and 1.5%, respectively.

对比例3Comparative Example 3

与实施例1、2和3的制备方法相比,其区别在于,未经超声处理,反应温度相一致,即采用热加工方式制备颗粒态复合物。在此条件下制备的颗粒态淀粉复合物的SDS含量分别为11.6%、16.6%和14.6%,RS含量分别为20.4%、17.4%和16.4%。Compared with the preparation methods of Examples 1, 2 and 3, the difference lies in that, without ultrasonic treatment, the reaction temperature is the same, that is, the granular composite is prepared by thermal processing. The SDS contents of the granular starch complexes prepared under this condition were 11.6%, 16.6% and 14.6%, and the RS contents were 20.4%, 17.4% and 16.4%, respectively.

实验例1Experimental example 1

本实施例涉及对得到的低血糖颗粒态淀粉脂质复合物的微观表征。This example relates to the microscopic characterization of the resulting hypoglycemic granular starch lipid complexes.

图1是实施例1中颗粒态淀粉-脂质复合物的13C-NMR图谱,其中颗粒态复合物为实施例1制备得到的产品,超声淀粉为对比例2 所述方法制备得到的淀粉。从图1可知,超声处理能够促进小麦淀粉与油酸形成颗粒态淀粉-脂质复合物,复合物在31.7ppm处出现新的化学位移峰。研究表明脂肪酸链中的亚甲基在30~32ppm范围内会产生化学位移峰,为V型淀粉-脂肪酸复合物的特征标志,而不是简单的物理混合。1 is the 13 C-NMR spectrum of the granular starch-lipid complex in Example 1, wherein the granular complex is the product prepared in Example 1, and the ultrasonic starch is the starch prepared by the method described in Comparative Example 2. It can be seen from Figure 1 that ultrasonic treatment can promote the formation of granular starch-lipid complexes between wheat starch and oleic acid, and the complexes have a new chemical shift peak at 31.7 ppm. Studies have shown that the methylene groups in the fatty acid chain will produce chemical shift peaks in the range of 30-32 ppm, which are characteristic signs of V-starch-fatty acid complexes, rather than simple physical mixing.

图2为实施例3中颗粒态淀粉-脂质复合物的X-射线衍射图谱。其中颗粒态复合物为实施例3制备得到的产品,超声淀粉为对比例2 所述方法制备得到的淀粉。由图2可知,超声处理未改变大米淀粉的A-型晶型,但其在2theta角为19.8°处的峰增强,表明亚油酸的加入,使其形成了更多的V-型复合物。FIG. 2 is the X-ray diffraction pattern of the granular starch-lipid complex in Example 3. FIG. The granular composite is the product prepared in Example 3, and the ultrasonic starch is the starch prepared by the method described in Comparative Example 2. It can be seen from Figure 2 that ultrasonic treatment did not change the A-type crystal form of rice starch, but its peak at 2theta angle of 19.8° was enhanced, indicating that the addition of linoleic acid made it form more V-type complexes. .

实验例2Experimental example 2

本实施例涉及本发明所述颗粒在降低血糖指数方面的研究,根据实施例2中消化性的测定方法,分别测定不同时间段的水解曲线(0 min、20min、30min、60min、90min、120min、180min、240min),然后与白面包的水解曲线面积进行比较,获得水解指数HI,随之计算其血糖指数:This example relates to the research on reducing the glycemic index of the granules of the present invention. According to the digestion method in Example 2, the hydrolysis curves of different time periods (0 min, 20 min, 30 min, 60 min, 90 min, 120 min, 180min, 240min), then compare with the hydrolysis curve area of white bread to obtain the hydrolysis index HI, and then calculate its glycemic index:

eGI=8.198+0.862HI (1)。eGI=8.198+0.862HI (1).

不同淀粉及其复合物的具体血糖指数见表1。The specific glycemic indices of different starches and their complexes are shown in Table 1.

表1不同淀粉及其复合的GI水平Table 1 GI levels of different starches and their complexes

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Figure DEST_PATH_IMAGE001

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Figure DEST_PATH_IMAGE002

由以上数据可知,本发明所述淀粉脂质复合物确实可降低血糖水平。From the above data, it can be known that the starch-lipid complex of the present invention can indeed reduce the blood sugar level.

虽然,上文中已经用一般性说明、具体实施方式及试验,对本发明作了详尽的描述,但在本发明基础上,可以对之作一些修改或改进,这对本领域技术人员而言是显而易见的。因此,在不偏离本发明精神的基础上所做的这些修改或改进,均属于本发明要求保护的范围。Although the present invention has been described in detail above with general description, specific embodiments and tests, some modifications or improvements can be made on the basis of the present invention, which is obvious to those skilled in the art . Therefore, these modifications or improvements made without departing from the spirit of the present invention fall within the scope of the claimed protection of the present invention.

Claims (10)

1. A method for preparing granular starch lipid complex with low glycemic index is characterized in that suspension of starch and lipid is treated by ultrasound, and the temperature of a reaction mixing system is kept lower than the gelatinization temperature T of starch in the treatment process0
2. The method according to claim 1, wherein the temperature of the reaction mixture system is maintained at (T) during the treatment0-10℃)~T0
3. The method according to claim 1 or 2, wherein the starch and lipid suspension has a starch to lipid mass ratio of 1: 0.01 to 0.2.
4. The method according to claim 3, wherein the starch is present in an amount of 3 to 10% by mass of the suspension of starch and lipid.
5. The production method according to claim 1 or 4, wherein the lipid is a fatty acid or a glyceride;
preferably, the fatty acid is one or more of lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, arachidonic acid, or linolenic acid.
And/or the glyceride is one or more of glyceryl monostearate, palmitic acid monoglyceride or tripalmitin.
6. The method according to claim 5, wherein the starch is one or more of wheat starch, potato starch, rice starch, corn starch, and mung bean starch.
7. The preparation method according to any one of claims 1 to 6, wherein the ultrasonic treatment is carried out under the conditions of frequency of 20 to 45kHz, power of 240 to 600W and ultrasonic treatment time of 10 to 60 min.
8. The method of any one of claims 1 to 7, wherein the method of preparing the suspension of starch and lipid comprises the steps of:
(1) fully mixing starch with distilled water to obtain a starch suspension solution;
(2) dissolving lipid in short chain alcohol, fully dispersing, and mixing with the starch suspension solution to obtain the starch and lipid suspension.
Preferably, the short-chain alcohol is one or more of ethanol, isopropanol or propanol.
9. The method according to any one of claims 1 to 8, further comprising the following steps after the completion of the ultrasonic treatment:
1) cooling the suspension of the starch and the lipid after the ultrasonic treatment, centrifuging, and washing the precipitate by using an ethanol-water mixture to obtain a starch lipid precipitate;
2) and drying and crushing the starch lipid precipitate to obtain the granular starch lipid compound with low glycemic index.
10. A granular starch lipid complex with low glycemic index prepared by the preparation method of any one of claims 1 to 9; preferably, the low-glycemic-index granular starch lipid complex has a total content of Slowly Digestible Starch (SDS) and resistant digestible starch (RS) of more than 45%.
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