CN110292167A - A kind of preparation method for gathering hydrogen nano bubble resistant starch - Google Patents

A kind of preparation method for gathering hydrogen nano bubble resistant starch Download PDF

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Publication number
CN110292167A
CN110292167A CN201910595878.7A CN201910595878A CN110292167A CN 110292167 A CN110292167 A CN 110292167A CN 201910595878 A CN201910595878 A CN 201910595878A CN 110292167 A CN110292167 A CN 110292167A
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hydrogen
starch
resistant starch
nano bubble
nano
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CN110292167B (en
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刘东红
徐恩波
王浩
丁甜
周建伟
程焕
叶兴乾
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Zhejiang University ZJU
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Zhejiang University ZJU
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    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L29/00Foods or foodstuffs containing additives; Preparation or treatment thereof
    • A23L29/30Foods or foodstuffs containing additives; Preparation or treatment thereof containing carbohydrate syrups; containing sugars; containing sugar alcohols, e.g. xylitol; containing starch hydrolysates, e.g. dextrin
    • A23L29/35Degradation products of starch, e.g. hydrolysates, dextrins; Enzymatically modified starches
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L33/00Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
    • A23L33/10Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
    • A23L33/125Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives containing carbohydrate syrups; containing sugars; containing sugar alcohols; containing starch hydrolysates
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12PFERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P19/00Preparation of compounds containing saccharide radicals
    • C12P19/04Polysaccharides, i.e. compounds containing more than five saccharide radicals attached to each other by glycosidic bonds
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12PFERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P19/00Preparation of compounds containing saccharide radicals
    • C12P19/14Preparation of compounds containing saccharide radicals produced by the action of a carbohydrase (EC 3.2.x), e.g. by alpha-amylase, e.g. by cellulase, hemicellulase
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23VINDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
    • A23V2002/00Food compositions, function of food ingredients or processes for food or foodstuffs

Abstract

The invention discloses a kind of preparation methods for gathering hydrogen nano bubble resistant starch, belong to functional food manufacture field, starch granules is digested by this method by hydrostatic, form the porous resistant starch precursor of nanometer sheet stratiform matrix of walls, the secondary hydrophobically modified of starch granules after enzyme deactivation is living, is occurred by bottom hydrogen and ultrasonic cavitation collaboration generates accumulation hydrogen nano bubble resistant starch.The hydrogen that this method can greatly possibly dissipate by small molecule, easily is with the formal distribution of interface nano bubble in resistant starch micro-nano layer, simultaneously by nano bubble bridge active force realize bubble lock for a long time, human body relatively-high temperature (~37 DEG C) also can slow release.This method has not only widened the effective exploitation approach of starch and its derivative, but also substantially increases the utilization efficiency of hydrogen, and product has both the multiple efficacies such as anti-oxidant, anti-aging, the pernicious free radical of removal, prevention hyperglycemia.

Description

A kind of preparation method for gathering hydrogen nano bubble resistant starch
Technical field
The invention belongs to functional food manufacture fields, more particularly to a kind of preparation for gathering hydrogen nano bubble resistant starch Method.
Background technique
Starch is one of most common natural biological resource, by force with from a wealth of sources, cheap, processable usability etc. Advantage.Wherein, porous-starch is most one of the method for industrial application, that is, utilizes the unformed of amylorrhexis starch granules Area inside biological corrosion particle and forms porous channel within a certain period of time.Due to enzyme action condition by temperature, moisture, pH, The many factors such as time influence, and digest the more difficult assurance of degree of porous-starch, and easily excessive hydrolysis causes particle to be disintegrated simultaneously local It is formed nanocrystal multilayered structure (i.e. resistant starch layer).So far, almost there is not the method using starch nano multilayered structure also, Mostly to waste based on the resource.
Hydrogen is that one of molecule that content is most in universe and distributed in nature are most extensive, molecule is minimum, structure is most simple Element.Hydrogen acts on existing lot of experimental data to the medical control of human body and supports, generally believes that hydrogen can selectivity now Combination high concentration pernicious free radical in ground all has certain curative effect and prophylactic function to body injury, cancer etc..However, including Directly it is perfused including hydrogen, it will as carrier using liquid (such as water, beverage) or solid-state (such as silicone oil, ceramics, calcining calcium) base-material Hydrogen is sent into human body, and utilization efficiency is all very low, and the effect for itself being enriched with and retaining hydrogen is also poor.Especially solid-state carrier shape Formula, mostly non-common food grade materials, safety it is difficult to ensure that.
Therefore, the present invention is creatively modified and utilizes the hydrophobic resistant starch in multi-layer nano gap, and is applied to It generates, enrichment, retention hydrogen nano bubble, the hydrogen that this can greatly dissipate by small molecule, easily is with the shape of interface nano bubble Formula is distributed in resistant starch micro-nano layer, while realizing that bubble locks for a long time by nano bubble bridge active force, opposite in human body High temperature (~37 DEG C) also can slow release.
Summary of the invention
The invention discloses a kind of preparation methods for gathering hydrogen nano bubble resistant starch, specifically disclose a kind of with more The hydrophobic resistant starch of layer nano gap and its generation, enrichment, retention hydrogen nano bubble processing method.
To achieve the above object, specific technical solution of the present invention is as follows: a kind of system for gathering hydrogen nano bubble resistant starch Preparation Method, starch granules digest by hydrostatic, form the porous resistant starch precursor of nanometer sheet stratiform matrix of walls, and enzyme deactivation is living The secondary hydrophobically modified of starch granules afterwards, then accumulation hydrogen nano bubble resistant starch is generated through sonic oscillation.
Further, the lamellar spacing of the porous resistant starch precursor is 30~60nm.
Further, the enzyme is high-temperatureα-amylase, mesophilicα-diastase, beta amylase, isoamylase and carbohydrase One of or it is a variety of.The mass ratio of starch and water is 1:1~3, and the content of enzyme is the 0.1%~5% of starch granules quality, institute Stating hydrostatic reaction temperature is 50~100 DEG C, 12~36h of reaction time.
Further, the porous resistant starch precursor of the nanometer sheet stratiform matrix of walls is after enzyme deactivation is living, nanoscale twins table The group of face hydrophobically modified is the groups such as grafted moiety, including hydrophobic alkyl, halogen, nitro.
Further, the lamellar spacing of the starch nano lamella of the hydrophobically modified is 10~40nm.
Further, the hydrogen occurs to include that electrode production hydrogen and conduit rush hydrogen.
Further, temperature controls between 0~20 DEG C in the hydrogen nano bubble forming process.
Further, the accumulation hydrogen nano bubble resistant starch introduces drinking water, fruit as solid-liquid type functional additive The thick state food such as dilute food liquid such as juice, milk and Yoghourt, sauce, additive amount are the 2%-10% of food quality.
Compared with prior art, the invention has the following beneficial effects: this method can be greatly possibly by small molecule, easily consumption Scattered hydrogen with the formal distribution of interface nano bubble in resistant starch micro-nano layer, while it is real by nano bubble bridge active force Existing bubble locks for a long time.This method has not only widened the effective exploitation approach of starch and its derivative, but also substantially increases hydrogen The utilization efficiency of gas, the accumulation hydrogen nano bubble resistant starch have both anti-oxidant, anti-aging, the pernicious free radical of removal, prevention height The multiple efficacies such as blood glucose can be added in a variety of lean state or thick state liquid food, wide market.
Detailed description of the invention
Fig. 1 is design flow diagram of the invention.
Fig. 2 is reaction schematic diagram of the invention.
Fig. 3 is the hydrogen nano bubble of resistant starch nano-sized hydrophobic level in the present invention.
Fig. 4 is that resistant starch particle surface is enriched with geocorona schematic diagram in the present invention.
Specific embodiment
As illustrated in fig. 1 and 2, a kind of preparation method for gathering hydrogen nano bubble resistant starch, method particularly includes:
(1) starch granules is mixed with water according to mass ratio 1:1~3, and enzyme content is the 0.1%-5% of starch granules quality, Starch granules digests by hydrostatic, and wherein enzyme is high-temperatureα-amylase, mesophilicα-diastase, beta amylase, isoamylase With one of carbohydrase or a variety of;Hydrostatic reaction temperature is 50~100 DEG C, after 12~36h of reaction time, forms nanoscale twins The porous resistant starch precursor of shape matrix of walls.The purpose of hydrostatic enzymatic hydrolysis regulation is the amorphous region of degradable starch, to retain anti- Property crystallizing layer, as nanoscale twins, nanoscale twins gap be 30~60nm.Starch is under hydrostatic enzymolysis environment, enzyme attachment In starch surface, simultaneously inwardly selectively there is the hole that past center deepens continuously in attack amorphous region, starch surface;With enzyme The extension of time is solved, the starch chain of unformed area is converted and be dissolved in the water by enzyme, and the resistance crystal region of residual starch is caused to be protected Hold it is laminar structured, nanoscale twins gap be 30~60nm.The purpose of this process be not it is traditional enzymatic hydrolysis prepare it is porous Starch, thus " excessive " degradation ative starch particle and generality porous (1~5 μm) are needed, while in grain crystalline lamella and bone Frame stops enzyme digestion reaction before disintegrating completely, so need finely regulating reaction condition and degree.
(2) after enzyme deactivation is living, nanoscale twins surface is modified to dredge the porous resistant starch precursor of nanometer sheet stratiform matrix of walls Water base group is the groups such as grafted moiety, including hydrophobic alkyl, halogen, nitro, obtains the layer of the starch nano lamella of hydrophobically modified Gap is 10~40nm.The porous resistant starch for the nanometer sheet stratiform matrix of walls that step 1 is prepared does not have still and generates hydrogen The ability of nano bubble needs to carry out surface hydrophobicity and is modified, in nanometer layer surface, although the better resistance of crystal region, but still has The hydrophilic radicals such as hydroxyl-OH are needed through the hydrophobic groupings graft modification such as alkyl, halogen, nitro, and are formed on micro-dimension Relatively crude surface is formed to be conducive to hydrogen adsorption with nano bubble, the hydrogen of the resistant starch nano-sized hydrophobic level Nano bubble is as shown in Figure 3.
(3) it is illustrated in figure 4 resistant starch particle surface in the present invention and is enriched with geocorona schematic diagram, hydrophobically modified shallow lake Powder promotes the generation of bottom hydrogen and ultrasonic cavitation collaboration to generate accumulation hydrogen nano bubble resistant starch by sonic oscillation, and hydrogen is received Control temperature is between 0~20 DEG C in rice Bubble Formation Process.Hydrogen occurs to include that common electrode production hydrogen and conduit rush hydrogen, assists Interface hydrogen nano bubble and its fixed hydrogen microbedding are formed in starch nano lamella and surface with ultrasonication.At reaction solution bottom After portion's hydrogen occurs, hydrogen, which gradually dissolves in the rarefied zone of water and hydrophobicity surface layer contact surface first and is adsorbed on starch nano, to be dredged On water layer, to form accumulation geocorona;Gas gathers to form arc-shaped interface nano bubble in accumulation hydrogen layer, in high viscosity bubble The effect of hydrogen microfluidic is lower in the gas-liquid coupling layer and bubble of outer surface realizes Brenner-Lohse dynamic equilibrium, and inhibits to receive Rice bubble dissipates;Wherein, the gravitation of resistant starch nano-sized hydrophobic interlayer by vapor nano bubble bridge generate, while hydrophobic layer with Retained between nanometer bubble hydrogen, bubble by the nano bubble bridge locking being connected with each other;Hydrogen resistant starch particle is gathered water-soluble It is also contacted with big bubble hydrogen in liquid, and couples and to form nanometer geocorona, the effect for building up hydrogen increases.Ultrasound turns in hydrogen reaction During change, not only auxiliary promotes the generation of interface nano bubble on resistant starch nano-sized hydrophobic layer, and ultrasonic cavitation is to liquid The effect in micro- space also strengthens the dynamic transfer of hydrogen between nano bubble, and the oscillation action of ultrasound in the reaction system adds Strong gas-liquid-solid coupling, helps speed up resistant starch particle surface enrichment geocorona.
The accumulation hydrogen nano bubble resistant starch can be used as solid-liquid type functional additive and introduce drinking water, fruit juice, milk Etc. the thick state food such as dilute food liquid and Yoghourt, sauce, additive amount is the 2%-10% of food quality.
The present invention is specifically described in following example, and the following example is for illustration purposes not for limiting this hair Bright range.
Embodiment 1:
By the regulation of hydrostatic high-temperatureα-amylase enzymatic hydrolysis, (reaction temperature is 100 DEG C to starch granules, and amount of water is 3 times first Starch quality, the content of enzyme are the 5% of starch granules quality, reaction time 12h), form the porous of nanometer sheet stratiform matrix of walls Resistant starch precursor, nanoscale twins gap are 30nm, and the secondary hydrophobically modified of starch after enzyme deactivation is living, the hydrophobic grouping used is grafting Group-C6H5, it is hydrophobically modified after starch crystals layer lamellar spacing be 10nm, later by sonic oscillation (20 DEG C of temperature) produce Raw accumulation hydrogen nano bubble resistant starch adds the 2% hydrogen-rich starch and is drunk in fruit juice.
Hydrophobic dye rhodamine 6G is added in the above-mentioned hydrogen-rich starch being prepared and reversely indicates hydrogen, in super-resolution The micro- sem observation distribution of rate confocal laser;In hydrogen-rich starch surface doping nano fluorescent cadmiumsulfide quantum dot, further look at Distribution;Starch nano crystallizing layer is removed in liquid body phase simultaneously and is measured by atomic force microscope.The result shows that: hydrogen exists Densely distributed in starch crystals layer, bubble aperture is less than 10nm.
Embodiment 2:
By hydrostatic mesophilicα-diastase and the regulation of glucoamylase enzyme solution, (reaction temperature is 70 DEG C to starch granules, adds water first Amount is 3 times of starch qualities, and the content of enzyme is the 2% of starch granules quality, is stirred to react the time for 24 hours), form nanometer sheet stratiform base The porous resistant starch precursor of matter wall, nanoscale twins gap are 60nm, the secondary hydrophobically modified of starch after enzyme deactivation is living, use it is hydrophobic Group is grafted moiety-C=CH2, it is hydrophobically modified after starch crystals layer lamellar spacing be 30nm, later by ultrasound vibration It swings (0 DEG C of temperature) and generates accumulation hydrogen nano bubble resistant starch, the 6% hydrogen-rich starch is added in milk and is drunk.
Hydrogen is reversely indicated by hydrophobic dye rhodamine 6G is added in the above-mentioned hydrogen-rich starch being prepared, in superelevation point The micro- sem observation distribution of resolution confocal laser;In hydrogen-rich starch surface doping nano fluorescent cadmiumsulfide quantum dot, further see Examine distribution;Starch nano crystallizing layer is removed in liquid body phase simultaneously and is measured by atomic force microscope.The result shows that: hydrogen Densely distributed in starch crystals layer, bubble aperture is less than 30nm.
Embodiment 3:
By hydrostatic mesophilicα-diastase and the regulation of glucoamylase enzyme solution, (reaction temperature is 70 DEG C to starch granules, adds water first Amount is 3 times of starch qualities, and the content of enzyme is the 4% of starch granules quality, is stirred to react the time for 24 hours), form nanometer sheet stratiform base The porous resistant starch precursor of matter wall, nanoscale twins gap are 60nm, the secondary hydrophobically modified of starch after enzyme deactivation is living, use it is hydrophobic Group be grafted moiety-Cl, it is hydrophobically modified after starch crystals layer lamellar spacing be 30nm, later by sonic oscillation (temperature 0 DEG C of degree) hydrogen-rich nano bubble resistant starch is generated, the 8% hydrogen-rich starch is added in milk and is drunk.
Hydrophobic dye rhodamine 6G is added in the above-mentioned hydrogen-rich starch being prepared and reversely indicates hydrogen, in super-resolution The micro- sem observation distribution of rate confocal laser;In hydrogen-rich starch surface doping nano fluorescent cadmiumsulfide quantum dot, further look at Distribution;Starch nano crystallizing layer is removed in liquid body phase simultaneously and is measured by atomic force microscope.The result shows that: hydrogen exists Densely distributed in starch crystals layer, bubble aperture is less than 30nm.
Embodiment 4:
By hydrostatic beta amylase and the regulation of isoamylase enzymatic hydrolysis, (reaction temperature is 50 DEG C to starch granules, amount of water first For 1 times of starch quality, the content of enzyme is the 0.1% of starch granules quality, is stirred to react time 36h), form nanometer sheet stratiform base The porous resistant starch precursor of matter wall, nanoscale twins gap are 50nm, and the secondary hydrophobically modified of starch uses hydrophobic after enzyme deactivation is living Group is grafted moiety-NO2, it is hydrophobically modified after starch crystals layer lamellar spacing in 40nm, later pass through sonic oscillation (10 DEG C of temperature) generates hydrogen-rich nano bubble resistant starch, and the 10% hydrogen-rich starch is added in Yoghourt and is eaten.
Hydrophobic dye rhodamine 6G is added in the above-mentioned hydrogen-rich starch being prepared and reversely indicates hydrogen, in super-resolution The micro- sem observation distribution of rate confocal laser;In hydrogen-rich starch surface doping nano fluorescent cadmiumsulfide quantum dot, further look at Distribution;Starch nano crystallizing layer is removed in liquid body phase simultaneously and is measured by atomic force microscope.The result shows that: hydrogen exists Densely distributed in starch crystals layer, bubble aperture is less than 40nm.
Above-mentioned accumulation hydrogen starch has both the multiple efficacies such as anti-oxidant, anti-aging, the pernicious free radical of removal, prevention hyperglycemia, Its products made thereby without bad mouthfeel, to release hydrogen effect good.
To sum up, above-mentioned general explanatory note and specific embodiment have made detailed description to the present invention, but in the present invention The starch (or similar organism-based raw material) with nanometer multilayer of preparation can make some improvement or raising with hydrogen-rich product, this is to this It is for the technical staff of field it will be apparent that therefore also falling within the scope of the claimed invention.

Claims (8)

1. a kind of preparation method for gathering hydrogen nano bubble resistant starch, it is characterised in that: starch granules is digested by hydrostatic and adjusted It is super to form the porous resistant starch precursor of nanometer sheet stratiform matrix of walls, the secondary hydrophobically modified of starch granules after enzyme deactivation is living, then warp for control Sound oscillation generates accumulation hydrogen nano bubble resistant starch.
2. method according to claim 1, which is characterized in that the lamellar spacing of the porous resistant starch precursor be 30~ 60nm。
3. method according to claim 1 or claim 2, which is characterized in that the enzyme be high-temperatureα-amylase, mesophilicα-diastase, One of beta amylase, isoamylase and carbohydrase are a variety of.The mass ratio of starch and water is 1:1~3, and the content of enzyme is to form sediment The 0.1%~5% of powder particles quality, the hydrostatic reaction temperature are 50~100 DEG C, 12~36h of reaction time.
4. method according to claim 1, which is characterized in that the porous resistant starch precursor of the nanometer sheet stratiform matrix of walls After enzyme deactivation is living, the modified group of nanoscale twins surface hydrophobicity is the groups such as grafted moiety, including hydrophobic alkyl, halogen, nitro.
5. according to claim 1 or 4 the methods, which is characterized in that the lamellar spacing of the starch nano lamella of the hydrophobically modified For 10~40nm.
6. method according to claim 1, which is characterized in that the hydrogen occurs to include that electrode production hydrogen and conduit rush hydrogen.
7. method according to claim 1 or 6, which is characterized in that temperature control is 0 in the hydrogen nano bubble forming process Between~20 DEG C.
8. any one of -7 the method according to claim 1, which is characterized in that the accumulation hydrogen nano bubble resistant starch conduct Solid-liquid type functional additive introduces the thick state food such as dilute food liquid and Yoghourt, sauce such as drinking water, fruit juice, milk, addition Amount is the 2%-10% of food quality.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113068808A (en) * 2021-05-06 2021-07-06 福建农林大学 Processing method for improving quality of fried fish cake

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Publication number Priority date Publication date Assignee Title
US5935826A (en) * 1997-10-31 1999-08-10 National Starch And Chemical Investment Holding Corporation Glucoamylase converted starch derivatives and their use as emulsifying and encapsulating agents
CN106235301A (en) * 2016-08-31 2016-12-21 华南理工大学 A kind of functional starch and its preparation method and application

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