CN112120213B - Starch-based dextrin modified zein nano-particles and preparation method and application thereof - Google Patents

Starch-based dextrin modified zein nano-particles and preparation method and application thereof Download PDF

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CN112120213B
CN112120213B CN202011010796.0A CN202011010796A CN112120213B CN 112120213 B CN112120213 B CN 112120213B CN 202011010796 A CN202011010796 A CN 202011010796A CN 112120213 B CN112120213 B CN 112120213B
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tea polyphenol
zein
polyphenol ester
solution
dextrin
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CN112120213A (en
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章宝
孟然
李小龙
刘文杰
王毓敏
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Hefei University of Technology
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    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, 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
    • A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
    • A23L29/03—Organic compounds
    • A23L29/045—Organic compounds containing nitrogen as heteroatom
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, 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
    • A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
    • A23L29/03—Organic compounds
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, 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
    • A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
    • A23L29/03—Organic compounds
    • A23L29/035—Organic compounds containing oxygen as heteroatom
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/33—Heterocyclic compounds
    • A61K31/335—Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin
    • A61K31/35—Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin having six-membered rings with one oxygen as the only ring hetero atom
    • A61K31/352—Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin having six-membered rings with one oxygen as the only ring hetero atom condensed with carbocyclic rings, e.g. methantheline 
    • A61K31/353—3,4-Dihydrobenzopyrans, e.g. chroman, catechin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
    • A61K47/36—Polysaccharides; Derivatives thereof, e.g. gums, starch, alginate, dextrin, hyaluronic acid, chitosan, inulin, agar or pectin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
    • A61K47/42—Proteins; Polypeptides; Degradation products thereof; Derivatives thereof, e.g. albumin, gelatin or zein
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0216—Solid or semisolid forms
    • A61K8/022—Powders; Compacted Powders
    • A61K8/0225—Granulated powders
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/06—Emulsions
    • A61K8/066—Multiple emulsions, e.g. water-in-oil-in-water
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4973—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with oxygen as the only hetero atom
    • A61K8/498—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with oxygen as the only hetero atom having 6-membered rings or their condensed derivatives, e.g. coumarin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/64—Proteins; Peptides; Derivatives or degradation products thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73—Polysaccharides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/10—Dispersions; Emulsions
    • A61K9/107—Emulsions ; Emulsion preconcentrates; Micelles
    • A61K9/113—Multiple emulsions, e.g. oil-in-water-in-oil
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/14—Particulate form, e.g. powders, Processes for size reducing of pure drugs or the resulting products, Pure drug nanoparticles
    • A61K9/19—Particulate form, e.g. powders, Processes for size reducing of pure drugs or the resulting products, Pure drug nanoparticles lyophilised, i.e. freeze-dried, solutions or dispersions
    • A—HUMAN NECESSITIES
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    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P39/00—General protective or antinoxious agents
    • A61P39/06—Free radical scavengers or antioxidants
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/08—Anti-ageing preparations

Abstract

The invention discloses a starch-based dextrin modified zein nano particle and a preparation method and application thereof. The invention also discloses a W2/O2/(O1/W1) A method for preparing a multiple emulsion of the type comprising: mixing polyglycerol polyricinoleate and corn oil to form a first oil phase, mixing a mixed solution of sodium chloride and gelatin as a first water phase with the first oil phase, and performing high-pressure homogenization treatment to obtain W2/O2A type primary emulsion; mixing the second oil phase with the suspension of nanoparticles as the second aqueous phase and homogenizing under high pressure to obtain O1/W1A pickering type emulsion; then make it and the said W2/O2Mixing the primary emulsion and homogenizing under high pressure to obtain W2/O2/(O1/W1) Form multiple emulsions. The preparation method of the multiple emulsion is simple, has mild reaction conditions, is suitable for industrial production, and can be used in the fields of food, medicine, cosmetics and the like.

Description

Starch-based dextrin modified zein nano-particles and preparation method and application thereof
Technical Field
The invention belongs to the technical field of emulsification, particularly relates to a starch-based dextrin modified zein nanoparticle and a preparation method and application thereof, and particularly relates to a hollow zein-tea polyphenol ester/carboxymethyl dextrin-tea polyphenol ester nanoparticle and a preparation method thereof, and application of the hollow zein-tea polyphenol ester/carboxymethyl dextrin-tea polyphenol ester nanoparticle in preparation of W2/O2/(O1/W1) Use in multiple emulsions.
Background
Tea polyphenol ester is used as a novel antioxidant with strong free radical clearance rate, and simultaneously keeps some special physiological effects of tea polyphenol, so that the tea polyphenol ester is widely researched in the fields of foods and medicines in recent years. However, polyphenols contain multiple phenolic hydroxyl groups that make them unstable to light, high temperature and alkaline conditions, with reduced bioavailability. Many studies have shown that covalent binding of polyphenols to biopolymers may increase their physical stability, antioxidant activity and bioavailability.
The preparation of multiple emulsions is widely used in the fields of food, medicine, cosmetics, agriculture, etc. and is a hot point of research. Compared with the traditional emulsion, the multiple emulsion has unique advantages in the aspects of micro-encapsulation, slow release and low-fat food development due to the division of the internal area. Compared with the conventional emulsion, the multiple emulsion has unique advantages in application in food industry due to the division of internal structure, such as delivery vehicle of nutritional active ingredients, protective layer of sensitive active ingredients, bidirectional delivery of oil-soluble and water-soluble ingredients, controlled drug release, etc. However, the use of multiple emulsions is greatly limited due to flocculation of oil droplets, coalescence and migration of internal and external aqueous phase components which lead to the thermodynamically unstable nature of the multiple emulsions. In recent years, the research on edible particle type emulsifying agents has attracted much interest, and the edible particle type emulsifying agents can be irreversibly adsorbed on an oil-water interface to form an interface layer and endow emulsion with good stability. Replacing at least one type of surfactant molecule with edible nanoparticles provides a new approach to the stabilization of multiple emulsions. The nano particles are adsorbed on an oil-water interface to form an interface film, so that the exchange of emulsifiers at the interface and the discharge of water among liquid drop films are hindered, and the capabilities of inhibiting the coalescence of liquid drops and Ostwald curing are improved. In addition, lipid-based bioactive substances in multiple emulsions are susceptible to oxidation during storage. Research shows that the interface is the main place for the oxidation of the emulsion, and the construction of the interface with antioxidant activity is an effective way for improving the oxidation stability of the emulsion.
Therefore, how to construct the antioxidant nanoparticles and apply the antioxidant nanoparticles to the preparation of multiple emulsions is of great significance for improving the stability of multiple emulsions and the antioxidant property of lipids and expanding the application of the antioxidant nanoparticles in the fields of food, medicine and cosmetics.
Disclosure of Invention
The invention mainly aims to provide a starch-based dextrin modified zein nano particle and a preparation method and application thereof, so as to overcome the defects of the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a preparation method of starch-based dextrin modified zein nanoparticles, which comprises the following steps:
reacting a first mixed reaction system containing zein, tea polyphenol ester, sodium hydroxide, ethanol and water at 25 ℃ for 24 hours to obtain a zein-tea polyphenol ester covalent compound, and then reacting a second mixed reaction system containing the zein-tea polyphenol ester covalent compound, sodium carbonate, ethanol and water at 25 ℃ for 4 hours to obtain hollow zein-tea polyphenol ester nanoparticles;
carrying out coprecipitation reaction on a third mixed reaction system containing carboxymethyl dextrin, tea polyphenol ester, ethanol and water to obtain a carboxymethyl dextrin-tea polyphenol ester covalent complex;
and reacting a fourth mixed reaction system containing the hollow zein-tea polyphenol ester nanoparticles, the carboxymethyl dextrin-tea polyphenol ester covalent compound and water at 25 ℃ for 2 hours to obtain the hollow zein-tea polyphenol ester/carboxymethyl dextrin-tea polyphenol ester nanoparticles, namely the starch-based dextrin modified zein nanoparticles.
The embodiment of the invention also provides the starch-based dextrin modified zein nanoparticles (hollow zein-tea polyphenol ester/carboxymethyl dextrin-tea polyphenol ester nanoparticles) prepared by the method.
The embodiment of the invention also provides the application of the starch-based dextrin modified zein nanoparticles (hollow zein-tea polyphenol ester/carboxymethyl dextrin-tea polyphenol ester nanoparticles) in preparing W2/O2/(O1/W1) The use of multiple emulsions.
The embodiment of the invention also provides a W2/O2/(O1/W1) A method of preparing a multiple emulsion of formula (la), comprising:
providing the aforementioned starch-based dextrin-modified zein nanoparticles (hollow zein-tea polyphenol ester/carboxymethyl dextrin-tea polyphenol ester nanoparticles);
mixing polyglycerol polyricinoleate and corn oil at 65 deg.C to form first oil phase, mixing the first oil phase with mixed solution of sodium chloride and gelatin as first water phase, and homogenizing with high pressure micro jet for 3min to obtain W2/O2A type primary emulsion;
mixing the second oil phase with a suspension of starch-based dextrin-modified zein nanoparticles (hollow zein-tea polyphenol ester/carboxymethyl dextrin-tea polyphenol ester nanoparticles) as a second water phase, and homogenizing under high pressure for 3min to obtain O1/W1A pickering type emulsion;
and, making said W2/O2Type primary emulsion and O1/W1Mixing the pickering emulsion and homogenizing under high pressure for 3min to obtain W2/O2/(O1/W1) Form multiple emulsions.
The embodiment of the invention also provides W prepared by the method2/O2/(O1/W1) Form multiple emulsions.
The embodiment of the invention also provides the W2/O2/(O1/W1) The use of the multiple emulsions in the food, pharmaceutical or cosmetic field.
In the invention, compared with solid zein nanoparticles, the hollow zein nanoparticles have higher encapsulation degree on tea polyphenol ester; hollow zein stabilized W as compared to hollow zein nanoparticles2/O2/(O1/W1) Multiple emulsions are unstable and prone to aggregation and coalescence. The quinone substance in the tea polyphenol ester interacts with the nucleophilic group of the zein to form a covalent bond, so that the solubility and the emulsibility of the zein are enhanced, and the solubility and the emulsibility of the zein can be improved to a certain extentW2/O2/(O1/W1) Stabilization of multiple emulsions. The carboxymethyl dextrin serving as a polysaccharide can be electrostatically compounded with the zein to improve the hydrophobicity of the zein, improve the stability and emulsibility of zein nanoparticles, and further improve the stable W of the zein nanoparticles2/O2/(O1/W1) Stability of multiple emulsions. The tea polyphenol ester has excellent physiological effects such as antioxidant and antiaging effects. But its oral bioavailability is low due to its inherent physicochemical instability and low solubility in aqueous media. The zein is covalently bonded with the tea polyphenol ester, so that the tea polyphenol ester can be embedded to improve the solubility of the tea polyphenol ester. The spiral cavity of the carboxymethyl dextrin also has an embedding effect on the tea polyphenol ester, and has a synergistic effect with the zein in the aspects of embedding the tea polyphenol ester, improving the water solubility of the tea polyphenol ester and protecting the tea polyphenol ester from resisting environmental stress. Meanwhile, the tea polyphenol ester is embedded into the zein and the carboxymethyl dextrin at the same time, so that the antioxidant activity of the multiple emulsion can be better enhanced. Compared with the multiple emulsion stabilized by the hollow zein-tea polyphenol ester/carboxymethyl dextrin, the multiple emulsion stabilized by the hollow zein-tea polyphenol ester/carboxymethyl dextrin-tea polyphenol ester has stronger oxidation resistance. Compared with the multiple emulsion with the stable hollow zein/tea polyphenol ester, the multiple emulsion with the stable hollow zein-tea polyphenol ester/carboxymethyl dextrin-tea polyphenol ester has high stability, and is beneficial to improving the shelf life in the aspect of food application. And compared with the multiple emulsion with the stable hollow zein/tea polyphenol ester, the multiple emulsion with the stable hollow zein-tea polyphenol ester/carboxymethyl dextrin-tea polyphenol ester can improve the bioavailability of the tea polyphenol ester. The multiple emulsion has simple preparation method, is beneficial to realizing industrial production, and expands the application of the multiple emulsion in the food industry.
Compared with the prior art, the invention has the beneficial effects that:
the preparation method comprises the steps of firstly preparing hollow zein-tea polyphenol ester nano particles, and then forming the hollow zein-tea polyphenol ester nano particles and carboxymethyl dextrin-tea polyphenol ester through electrostatic complexationThe hollow zein-tea polyphenol ester/carboxymethyl dextrin-tea polyphenol ester nano particles are embedded in the zein and the carboxymethyl dextrin together, so that multiple emulsion prepared from the hollow zein-tea polyphenol ester/carboxymethyl dextrin-tea polyphenol ester nano particles has stronger oxidation resistance, and the hollow zein-tea polyphenol ester/carboxymethyl dextrin-tea polyphenol ester nano particles prepared by the method can be adsorbed on the surface of liquid drops, and can inhibit coalescence and Ostwald curing of the liquid drops by forming a compact interface film, thereby being beneficial to the stability of the multiple emulsion; in addition, the invention provides W2/O2/(O1/W1) The preparation method of the multiple emulsion is simple, the industrial production is easy to realize, and the application of the multiple emulsion in the food industry is expanded.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a graph of particle size of zein-tea polyphenol ester/CMD-tea polyphenol ester nanoparticles, zein-tea polyphenol ester/CMD nanoparticles prepared in example 2 and comparative examples 1 and 2 of the present invention;
FIG. 2 is a graph of particle size of multiple emulsions formed by different nanoparticles prepared in example 2 of the present invention and comparative examples 1 and 2;
FIG. 3 is a graph showing the variation in particle size of multiple emulsions formed at different concentrations of hollow zein-tea polyphenol ester/CMD-tea polyphenol ester nanoparticles prepared in example 1;
fig. 4 is a graph showing the antioxidant activity of multiple emulsions formed by different nanoparticles prepared in example 2 of the present invention and comparative examples 1 and 2.
Detailed Description
In view of the defects of the prior art, the inventor of the present invention has long studied and largely practiced to propose the technical solution of the present invention, which will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
One aspect of the present invention provides a method for preparing starch-based dextrin-modified zein nanoparticles, which includes:
reacting a first mixed reaction system containing zein, tea polyphenol ester, sodium hydroxide, ethanol and water at 25 ℃ for 24 hours to obtain a zein-tea polyphenol ester covalent compound, and then reacting a second mixed reaction system containing the zein-tea polyphenol ester covalent compound, sodium carbonate, ethanol and water at 25 ℃ for 4 hours to obtain hollow zein-tea polyphenol ester nanoparticles;
carrying out coprecipitation reaction on a third mixed reaction system containing carboxymethyl dextrin, tea polyphenol ester, ethanol and water to obtain a carboxymethyl dextrin-tea polyphenol ester covalent complex;
and reacting a fourth mixed reaction system containing the hollow zein-tea polyphenol ester nanoparticles, the carboxymethyl dextrin-tea polyphenol ester covalent compound and water at 25 ℃ for 2 hours to obtain the hollow zein-tea polyphenol ester/carboxymethyl dextrin-tea polyphenol ester nanoparticles, namely the starch-based dextrin modified zein nanoparticles.
In some more specific embodiments, the preparation method comprises:
dissolving zein and tea polyphenol ester in an ethanol solution to form a mixed solution, then adding a sodium hydroxide solution into the obtained mixed solution to form a first mixed reaction system and react, and then dialyzing and freeze-drying the obtained mixture to obtain the zein-tea polyphenol ester covalent compound, wherein the pH value of the first mixed reaction system is 9.0;
and dissolving the zein-tea polyphenol ester covalent compound in an ethanol solution to form a zein-tea polyphenol ester covalent compound dispersion solution, uniformly mixing the zein-tea polyphenol ester covalent compound dispersion solution with an ethanol suspension of sodium carbonate, mixing the obtained zein-tea polyphenol ester covalent compound and a mixed solution of the sodium carbonate with water to form a second mixed reaction system, and reacting to obtain the hollow zein-tea polyphenol ester nano-particles.
Further, the concentration of the zein in the first mixed reaction system is 1-2 wt%.
Further, the mass ratio of the zein to the tea polyphenol ester is 5:1-1: 1.
Further, the volume fraction of ethanol in the ethanol solution is 75-80%.
Further, the dialysis treatment comprises: after the reaction of the first mixed reaction system was completed, the obtained mixture was subjected to ultrasonic dialysis in a water bath for 24 hours.
Further, the ethanol suspension of sodium carbonate is a mixed solution of a sodium carbonate aqueous solution and absolute ethyl alcohol.
Further, the concentration of the sodium carbonate aqueous solution is 1-2 wt%.
Further, the volume ratio of the sodium carbonate aqueous solution to the absolute ethyl alcohol is 3: 7.
Further, the volume ratio of the zein-tea polyphenol ester covalent compound dispersion liquid to the sodium carbonate ethanol suspension liquid is 1: 1.
Further, the volume ratio of the mixed solution of the zein-tea polyphenol ester covalent compound and the sodium carbonate to water is 1:1-1: 6.
In some more specific embodiments, the preparation method specifically comprises:
sequentially carrying out gelatinization, debranching and enzyme deactivation on waxy corn starch to obtain linear dextrin;
and carrying out alkalization reaction on the obtained linear dextrin at 30 ℃ for 4h, then adding monochloroacetic acid into the obtained mixed solution, and carrying out etherification reaction for 7h under the conditions of pH value of 4 and temperature of 40 ℃ to obtain the carboxymethyl dextrin.
Further, the preparation method of the carboxymethyl dextrin (CMD) comprises the following steps:
adding 20g of waxy corn starch into 400ml of phosphoric acid buffer solution (0.01mol/L, pH value of 5.5), and stirring for 1h at 99 ℃ to completely gelatinize the waxy corn starch; cooling the completely gelatinized starch to 55 ℃, placing the completely gelatinized starch in a 55 ℃ water bath, adding pullulanase (100U/g) into the starch paste for enzymolysis for 24 hours, and carrying out debranching treatment. After the reaction is finished, the solution is subjected to enzyme inactivation in boiling water bath for 10min, and then centrifuged at 4500rpm for 15min to obtain a supernatant. Vacuum freeze drying the supernatant to obtain Linear Dextrin (LD);
10g of LD and 6g of sodium hydroxide were added to 100ml of 90% ethanol solution and stirred at 30 ℃ for 1 hour, after which 6g of chloroacetic acid was added to the mixed solution and stirred at 40 ℃ for 4 hours, then the above solution was adjusted to pH 4 using 7.0mol/L hydrochloric acid and centrifuged at 3500rpm for 15 minutes to obtain a precipitate, the precipitate was washed several times with 85% ethanol solution until chloride ions were washed off, and then washed several times with absolute ethanol, and the above precipitate was dried in an oven at 45 ℃ for 24 hours and ground to obtain CMD.
Further, the degree of substitution of the carboxymethyl dextrin was 0.315.
In some more specific embodiments, the preparation method comprises: and (3) treating the aqueous solution of the carboxymethyl dextrin in a boiling water bath for 20min, mixing the aqueous solution of the carboxymethyl dextrin with the ethanol solution of the tea polyphenol ester to form the third mixed reaction system, and stirring and reacting at 80 ℃ for 2h to obtain the carboxymethyl dextrin-tea polyphenol ester covalent compound.
In some more specific embodiments, the preparation method comprises:
respectively dissolving the hollow zein-tea polyphenol ester nanoparticles and the carboxymethyl dextrin-tea polyphenol ester covalent compound in water to form a hollow zein-tea polyphenol ester nanoparticle solution and a carboxymethyl dextrin-tea polyphenol ester covalent compound solution, then dropwise adding the hollow zein-tea polyphenol ester nanoparticle solution into the carboxymethyl dextrin-tea polyphenol ester covalent compound solution to form a fourth mixed reaction system, and reacting to obtain the hollow zein-tea polyphenol ester/carboxymethyl dextrin-tea polyphenol ester nanoparticles.
Further, the preparation method further comprises the following steps: after the reaction of the fourth mixed reaction system was completed, the pH of the obtained mixture was adjusted to 4.0.
Further, the mass ratio of the hollow zein-tea polyphenol ester nanoparticles to the carboxymethyl dextrin-tea polyphenol ester covalent compound is 4: 1-1: 4, and preferably any one of 4:1, 2:1, 1:2 and 1: 4.
As a preferred embodiment of the present invention, the method for preparing the starch-based dextrin-modified zein nanoparticles (hollow zein-tea polyphenol ester/carboxymethyl dextrin-tea polyphenol ester nanoparticles) specifically comprises:
(1) preparation of hollow zein-tea polyphenol ester nanoparticles
Respectively dissolving zein and tea polyphenol ester in 80% (v/v) ethanol solution, mixing, adjusting the pH value to 9.0 by using 0.1mol/L sodium hydroxide solution, continuously stirring at 25 ℃ for reaction for 24h, after the reaction is finished, carrying out ultrasonic dialysis on the obtained mixed solution in water bath for 24h, replacing dialyzate for 8 times during the ultrasonic dialysis to remove free tea polyphenol ester, and finally carrying out freeze drying treatment on the solution to obtain the zein-tea polyphenol ester covalent compound;
dissolving 2g of zein-tea polyphenol ester covalent compound in 100mL of ethanol solution (volume fraction is 80%), stirring at 800rpm for 2h, standing until the zein-tea polyphenol ester covalent compound is completely dissolved, simultaneously uniformly mixing 2wt% of sodium carbonate aqueous solution with absolute ethanol according to the volume ratio of 3:7 to form ethanol suspension of sodium carbonate, mixing the suspension with the zein-tea polyphenol ester covalent compound solution according to the volume ratio of 1:1, coating sodium carbonate particles with the zein-tea polyphenol ester covalent compound, slowly adding the mixed solution of the zein-tea polyphenol ester covalent compound and the sodium carbonate into distilled water according to the volume ratio of 1:6, stirring at 800rpm for reaction for 4h, and performing freeze drying to obtain the hollow zein-tea polyphenol ester nano particles.
(2) Preparation of carboxymethyl dextrin (CMD)
Adding 20g of waxy corn starch into 400ml of phosphoric acid buffer solution (0.01M, pH value is 5.5), stirring at 99 ℃ for 1h to completely gelatinize the waxy corn starch, cooling the completely gelatinized starch to the temperature, then adding pullulanase (100U/g) into the gelatinized starch, carrying out enzymolysis at 55 ℃ for 24h for debranching treatment, after the reaction is finished, placing the obtained solution in a boiling water bath for 10min to carry out enzyme deactivation treatment, then centrifuging at the rotating speed of 4500rpm for 15min, and carrying out vacuum freeze drying treatment on the centrifuged supernatant to prepare Linear Dextrin (LD);
mixing 10g of LD, 6g of sodium hydroxide and 100ml of ethanol solution (volume fraction is 90%), stirring and reacting at 30 ℃ for 1h, then adding 6g of chloroacetic acid into the mixed solution, stirring and reacting at 40 ℃ for 4h, then adjusting the pH value of the reacted solution to 4 by using 7.0M hydrochloric acid, centrifuging at 3500rpm for 15min to obtain a precipitate, washing the precipitate for several times by using 85% ethanol solution until chloride ions are washed, washing the precipitate for several times by using absolute ethanol, finally drying the precipitate in an oven at 45 ℃ for 24h, and grinding the precipitate to obtain the CMD.
(3) Preparation of CMD-tea polyphenol ester covalent complex
Preparing CMD-tea polyphenol ester covalent complex by adopting a coprecipitation method, dissolving 0.2g of tea polyphenol ester in 50ml of absolute ethyl alcohol to form a tea polyphenol ester solution, simultaneously dissolving 1g of carboxymethyl dextrin in 100ml of distilled water, stirring in a boiling water bath for 20min to promote molecular chain development, and then cooling to 80 ℃; and then adding 50ml of tea polyphenol ester solution into the cooled solution, continuously stirring and reacting for 2h, standing the mixture overnight to ensure complete mixing, centrifuging at 8000rpm for 25min to obtain a precipitate, washing with 50% absolute ethyl alcohol for 3 times, and drying in an oven at 40 ℃ to obtain the carboxymethyl dextrin-tea polyphenol ester covalent complex.
(4) Preparation of hollow zein-tea polyphenol ester/CMD-tea polyphenol ester nanoparticles
Dissolving 1g of hollow zein-tea polyphenol ester nanoparticles in 50ml of distilled water, stirring at 800rpm for 2 hours to form a hollow zein-tea polyphenol ester nanoparticle solution, simultaneously dissolving a carboxymethyl dextrin-tea polyphenol ester covalent complex in 200ml of deionized water, and continuously stirring at 800rpm for 4 hours to form a carboxymethyl dextrin-tea polyphenol ester covalent complex solution; then, 50ml of the hollow zein-tea polyphenol ester nanoparticle solution is dropwise added into 200ml of the CMD-tea polyphenol ester solution, the mixture is stirred at 800rpm for reaction for 2 hours, and meanwhile, the pH value of the system is adjusted to 4, so that the hollow zein-tea polyphenol ester/CMD-tea polyphenol ester nanoparticles with different mass ratios are obtained.
Further, the concentration of the zein in the step (1) is 2 wt%.
Further, the mass ratio of the zein to the tea polyphenol ester in the step (1) is 5: 1.
Further, the degree of substitution of the carboxymethyl dextrin obtained in the step (2) was 0.315.
Further, in the step (4), the mass ratio of the hollow zein-tea polyphenol ester nanoparticles to the carboxymethyl dextrin-tea polyphenol ester covalent compound is any one of 4:1, 2:1, 1:2 and 1: 4.
Yet another aspect of an embodiment of the present invention provides starch-based dextrin-modified zein nanoparticles (hollow zein-tea polyphenol ester/carboxymethyl dextrin-tea polyphenol ester nanoparticles) prepared by the foregoing method.
In another aspect of the embodiments of the present invention, the application of the starch-based dextrin-modified zein nanoparticle (hollow zein-tea polyphenol ester/carboxymethyl dextrin-tea polyphenol ester nanoparticle) in preparing W2/O2/(O1/W1) The use of multiple emulsions.
Another aspect of the embodiments of the present invention also provides a W2/O2/(O1/W1) A method of preparing a multiple emulsion of formula (la), comprising:
providing the aforementioned starch-based dextrin-modified zein nanoparticles (hollow zein-tea polyphenol ester/carboxymethyl dextrin-tea polyphenol ester nanoparticles);
mixing polyglycerol polyricinoleate and corn oil at 65 ℃ to form a first oil phase, and then chlorinating as a first water phaseMixing the mixed solution of sodium and gelatin with the obtained first oil phase, and homogenizing with high pressure micro jet for 3min to obtain W2/O2A type primary emulsion;
mixing the second oil phase with the suspension of the starch-based dextrin-modified zein nanoparticles (hollow zein-tea polyphenol ester/carboxymethyl dextrin-tea polyphenol ester nanoparticles) as the second water phase, and homogenizing under high pressure for 3min to obtain O1/W1Type pickering emulsion;
and, making said W2/O2Type primary emulsion and O1/W1Mixing the pickering emulsion and homogenizing under high pressure for 3min to obtain W2/O2/(O1/W1) Form multiple emulsions.
In some more specific embodiments, the mass ratio of polyglycerol ricinoleate to corn oil is 5: 100.
Further, the volume ratio of the first water phase to the first oil phase is 1:9-5: 5.
Further, said O1/W1The concentration of the starch-based dextrin modified zein nanoparticles (hollow zein-tea polyphenol ester/carboxymethyl dextrin-tea polyphenol ester nanoparticles) of the pickering emulsion is 0.1-2.0 wt%.
Further, in the first water phase, the concentration of NaCl is 3% (w/v), and the concentration of gelatin is 0-7 wt%.
Further, the second oil phase is corn oil, and is not limited thereto.
Further, the volume ratio of the second oil phase to the second water phase is 2:8-5: 5.
Further, said W2/O2Type primary emulsion and O1/W1The volume ratio of the pickering emulsion is 1:9-5: 5.
The invention utilizes a three-step emulsification method to prepare W2/O2/(O1/W1) Multiple emulsions of type, comprising in particular:
(1) preparation of W2/O2Type I primary emulsion: mixing with NaCl and gelatinPreparing W by high pressure micro-jet method with corn oil containing polyglycerol polyricinoleate as first oil phase2/O2Forming an emulsion; (2) preparation of O1/W1Type pickering emulsion: adopting high-pressure homogenization technology to uniformly mix corn oil (second oil phase) and the hollow zein-tea polyphenol ester/carboxymethyl dextrin-tea polyphenol ester nanoparticle suspension (second oil phase) to obtain O1/W1A pickering type emulsion; (3) preparation of W2/O2/(O1/W1) Type multiple emulsion: will W2/O2The type primary emulsion is added to the emulsion containing O1/W1The stable W is obtained by high-pressure homogenization in the water phase of the Pickering emulsion2/O2/(O1/W1) Multiple emulsions.
As one of the preferred embodiments of the present invention, said W2/O2/(O1/W1) The preparation method of the multiple emulsion can comprise the following steps:
(1)W2/O2preparation of type Primary emulsion
Mixing and stirring polyglycerol polyricinoleate and corn oil at 65 ℃, and obtaining a first oil phase after complete dissolution; mixing the first oil phase with mixed solution containing NaCl and gelatin as first water phase, homogenizing the obtained mixture with high pressure micro jet for 3min to obtain W2/O2A type primary emulsion;
(2)O1/W1preparation of pickering emulsion
Adding corn oil (second oil phase) into starch-based dextrin modified zein nanoparticle (hollow zein-tea polyphenol ester/carboxymethyl dextrin-tea polyphenol ester nanoparticle) suspension (second water phase), and homogenizing under high pressure for 3min to obtain O1/W1A pickering type emulsion;
(3)W2/O2/(O1/W1) Preparation of multiple emulsions
Will W2/O2Addition of type Primary emulsion to O1/W1In the pickering emulsion, homogenizing under high pressureObtaining stable W2/O2/(O1/W1) Multiple emulsions.
Further, the addition mass of the polyglycerol polyricinoleate is 5 wt% of the mass of the corn oil.
Further, in the first water phase, the concentration of NaCl is 3% (w/v), and the concentration of gelatin is 0-7 wt%.
Further, said W2/O2Type Primary emulsion Medium aqueous phase (W)2) And an oil phase (O)2) The volume ratio of the components is 1:9-5: 5.
Further, said O1/W1The concentration of the starch-based dextrin-modified zein nanoparticles (hollow zein-tea polyphenol ester/CMD-tea polyphenol ester nanoparticles) in the primary emulsion is 0.1-2 wt%.
Further, said O1/W1Aqueous phase (W) in pickering emulsion1) And an oil phase (O)1) The volume ratio of the components is 1:9-5: 5.
In another aspect of embodiments of the present invention there is also provided W prepared by the foregoing method2/O2/(O1/W1) Form multiple emulsions.
In another aspect of the embodiments of the present invention, there is also provided the aforementioned W2/O2/(O1/W1) The use of the multiple emulsions in the food, pharmaceutical or cosmetic field.
The technical solutions of the present invention are further described in detail below with reference to several preferred embodiments and the accompanying drawings, which are implemented on the premise of the technical solutions of the present invention, and a detailed implementation manner and a specific operation process are provided, but the scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples used below were all available from conventional biochemical reagents companies, unless otherwise specified.
Example 1
(1) Preparation of hollow zein-tea polyphenol ester nano-particles
Respectively dissolving zein and tea polyphenol ester in 80% (v/v) ethanol solution, mixing, adjusting the pH value to 9.0 by using 0.1mol/L sodium hydroxide solution, continuously stirring at 25 ℃ for reaction for 24h, after the reaction is finished, carrying out ultrasonic dialysis on the obtained mixed solution in water bath for 24h, replacing dialyzate for 8 times during the ultrasonic dialysis to remove free tea polyphenol ester, and finally carrying out freeze drying treatment on the solution to obtain the zein-tea polyphenol ester covalent compound;
dissolving 2g zein-tea polyphenol ester covalent complex in 100mL ethanol solution (volume fraction 80%), stirring at 800rpm for 2h, standing until completely dissolved, simultaneously, uniformly mixing 2wt% of sodium carbonate aqueous solution with absolute ethyl alcohol according to the volume ratio of 3:7 to form sodium carbonate ethanol suspension, mixing the suspension with zein-tea polyphenol ester covalent compound solution according to the volume ratio of 1:1, the method comprises the steps of coating sodium carbonate particles with the zein-tea polyphenol ester covalent compound, slowly adding the mixed solution of the zein-tea polyphenol ester covalent compound and the sodium carbonate into distilled water according to the volume ratio of 1:6, stirring at 800rpm for 4h, and freeze drying to obtain hollow zein-tea polyphenol ester nanoparticles (zein-tea polyphenol ester nanoparticles).
(2) Preparation of carboxymethyl dextrin (CMD)
Adding 20g of waxy corn starch into 400ml of phosphoric acid buffer solution (0.01M, pH value is 5.5), stirring at 99 ℃ for 1h to completely gelatinize the waxy corn starch, cooling the completely gelatinized starch to the temperature, then adding pullulanase (100U/g) into the gelatinized starch, carrying out enzymolysis at 55 ℃ for 24h for debranching treatment, after the reaction is finished, placing the obtained solution in a boiling water bath for 10min to carry out enzyme deactivation treatment, then centrifuging at the rotating speed of 4500rpm for 15min, and carrying out vacuum freeze drying treatment on the centrifuged supernatant to prepare Linear Dextrin (LD);
mixing 10g of LD, 6g of sodium hydroxide and 100ml of ethanol solution (volume fraction is 90%), stirring and reacting at 30 ℃ for 1h, then adding 6g of chloroacetic acid into the mixed solution, stirring and reacting at 40 ℃ for 4h, then adjusting the pH value of the reacted solution to 4 by using 7.0M hydrochloric acid, centrifuging at 3500rpm for 15min to obtain a precipitate, washing the precipitate for several times by using 85% ethanol solution until chloride ions are washed, washing the precipitate for several times by using absolute ethanol, finally drying the precipitate in an oven at 45 ℃ for 24h, and grinding the precipitate to obtain the CMD.
(3) Preparation of carboxymethyl dextrin-tea polyphenol ester (CMD-tea polyphenol ester) covalent Complex
Preparing CMD-tea polyphenol ester covalent complex by adopting a coprecipitation method, dissolving 0.2g of tea polyphenol ester in 50ml of absolute ethyl alcohol to form a tea polyphenol ester solution, simultaneously dissolving 1g of carboxymethyl dextrin in 100ml of distilled water, stirring in a boiling water bath for 20min to promote molecular chain development, and then cooling to 80 ℃; and then adding 50ml of tea polyphenol ester solution into the cooled solution, continuously stirring for reacting for 2 hours, standing the mixture overnight to ensure complete mixing, centrifuging at 8000rpm for 25min to obtain a precipitate, washing with 50% absolute ethyl alcohol for 3 times, and drying in a 40 ℃ oven to obtain the carboxymethyl dextrin-tea polyphenol ester covalent complex.
(4) Preparation of hollow zein-tea polyphenol ester/CMD-tea polyphenol ester nanoparticles
Dissolving 1g of hollow zein-tea polyphenol ester nanoparticles in 50ml of distilled water, stirring at 800rpm for 2 hours to form a hollow zein-tea polyphenol ester nanoparticle solution, simultaneously dissolving a carboxymethyl dextrin-tea polyphenol ester covalent complex in 200ml of deionized water, and continuously stirring at 800rpm for 4 hours to form a carboxymethyl dextrin-tea polyphenol ester covalent complex solution; and then, dropwise adding 50ml of hollow zein-tea polyphenol ester nanoparticle solution into 200ml of CMD-tea polyphenol ester solution, stirring at 800rpm for reaction for 2 hours, and simultaneously adjusting the pH value of the system to be 4, wherein the mass ratio of the hollow zein-tea polyphenol ester nanoparticles to the CMD-tea polyphenol ester is 2:1, so as to prepare hollow zein-tea polyphenol ester/CMD-tea polyphenol ester nanoparticles (zein-tea polyphenol ester/CMD-tea polyphenol ester nanoparticles).
(5)W2/O2/(O1/W1) Preparation of multiple emulsions
3g of gelatin are dispersed in a 3% (W/v) aqueous NaCl solution to form a first aqueous phase W2Simultaneously mixing 5% polyglycerol polyricinoleate and corn oil at 65 DEG CStirring for 15min to form a first oil phase O2Then the first aqueous phase W2And a first oil phase O2Mixing at a ratio of 3:7, immediately homogenizing for 3min by high pressure microjet to obtain W2/O2A type primary emulsion;
adding corn oil into suspension of hollow zein-tea polyphenol ester/CMD-tea polyphenol ester nanoparticles, and homogenizing under high pressure for 3min to obtain O1/W1Pickering emulsion, wherein the concentration of emulsifier (hollow zein-tea polyphenol ester/CMD-tea polyphenol ester nanoparticles) is 1.0 wt%;
w is to be2/O2Addition of type Primary emulsion O1/W1Homogenizing under high pressure for 3min to obtain W2/O2/(O1/W1) Multiple emulsion of which W2/O2Type primary emulsion and O1/W1The volume ratio of the pickering emulsion is 4: 6.
In the embodiment, the particle size of the double emulsion prepared from the hollow zein-tea polyphenol ester/CMD-tea polyphenol ester nano particles is 30-70 microns, the nano particles can be irreversibly adsorbed and anchored at an oil/water interface to form a compact layer, so that the steric hindrance effect is increased, the stability of the emulsion is increased, the coalescence resistance and Ostwald curing resistance of the emulsion are obviously improved, and the stability of the multiple emulsion is facilitated.
Example 2
(1) Preparation of hollow zein-tea polyphenol ester nano-particles
Respectively dissolving zein and tea polyphenol ester in 80% (v/v) ethanol solution, mixing, adjusting the pH value to 9.0 by using 0.1mol/L sodium hydroxide solution, continuously stirring at 25 ℃ for reaction for 24h, after the reaction is finished, carrying out ultrasonic dialysis on the obtained mixed solution in water bath for 24h, replacing dialyzate for 8 times during the ultrasonic dialysis to remove free tea polyphenol ester, and finally carrying out freeze drying treatment on the solution to obtain the zein-tea polyphenol ester covalent compound;
dissolving 2g zein-tea polyphenol ester covalent complex in 100mL ethanol solution (volume fraction 80%), stirring at 800rpm for 2h, standing until completely dissolved, simultaneously, uniformly mixing 2wt% of sodium carbonate aqueous solution with absolute ethyl alcohol according to the volume ratio of 3:7 to form sodium carbonate ethanol suspension, mixing the suspension with zein-tea polyphenol ester covalent compound solution according to the volume ratio of 1:1, the method comprises the steps of coating sodium carbonate particles with zein-tea polyphenol ester covalent compound, slowly adding a mixed solution of the zein-tea polyphenol ester covalent compound and the sodium carbonate into distilled water according to the volume ratio of 1:6, stirring at 800rpm for 4h, and freeze drying to obtain hollow zein-tea polyphenol ester nanoparticles (zein-tea polyphenol ester nanoparticles).
(2) Preparation of carboxymethyl dextrin (CMD)
Adding 20g of waxy corn starch into 400ml of phosphoric acid buffer solution (0.01M, pH value is 5.5), stirring at 99 ℃ for 1h to completely gelatinize the waxy corn starch, cooling the completely gelatinized starch to the temperature, then adding pullulanase (100U/g) into the gelatinized starch, carrying out enzymolysis at 55 ℃ for 24h for debranching treatment, after the reaction is finished, placing the obtained solution in a boiling water bath for 10min to carry out enzyme deactivation treatment, then centrifuging at the rotating speed of 4500rpm for 15min, and carrying out vacuum freeze drying treatment on the centrifuged supernatant to prepare Linear Dextrin (LD);
mixing 10g of LD, 6g of sodium hydroxide and 100ml of ethanol solution (volume fraction is 90%), stirring at 30 ℃ for 1h, adding 6g of chloroacetic acid into the mixed solution, stirring at 40 ℃ for 4h, adjusting the pH value of the reacted solution to 4 by using 7.0M hydrochloric acid, centrifuging at 3500rpm for 15min to obtain a precipitate, washing the precipitate with 85% ethanol solution for several times until chloride ions are washed, washing with absolute ethanol for several times, drying the precipitate in an oven at 45 ℃ for 24h, and grinding to obtain the CMD.
(3) Preparation of carboxymethyl dextrin-tea polyphenol ester (CMD-tea polyphenol ester) covalent Complex
Preparing CMD-tea polyphenol ester covalent complex by adopting a coprecipitation method, dissolving 0.2g of tea polyphenol ester in 50ml of absolute ethyl alcohol to form a tea polyphenol ester solution, simultaneously dissolving 1g of carboxymethyl dextrin in 100ml of distilled water, stirring in a boiling water bath for 20min to promote molecular chain development, and then cooling to 80 ℃; and then adding 50ml of tea polyphenol ester solution into the cooled solution, continuously stirring and reacting for 2h, standing the mixture overnight to ensure complete mixing, centrifuging at 8000rpm for 25min to obtain a precipitate, washing with 50% absolute ethyl alcohol for 3 times, and drying in an oven at 40 ℃ to obtain the carboxymethyl dextrin-tea polyphenol ester covalent complex.
(4) Preparation of hollow zein-tea polyphenol ester/CMD-tea polyphenol ester nanoparticles
Dissolving 1g of hollow zein-tea polyphenol ester nanoparticles in 50ml of distilled water, stirring at 800rpm for 2 hours to form a hollow zein-tea polyphenol ester nanoparticle solution, simultaneously dissolving a carboxymethyl dextrin-tea polyphenol ester covalent complex in 200ml of deionized water, and continuously stirring at 800rpm for 4 hours to form a carboxymethyl dextrin-tea polyphenol ester covalent complex solution; then, 50ml of hollow zein-tea polyphenol ester nanoparticle solution is dropwise added into 200ml of CMD-tea polyphenol ester solution, the mixture is stirred at 800rpm for reaction for 2 hours, and meanwhile, the pH value of the system is adjusted to 4, wherein the mass ratio of the hollow zein-tea polyphenol ester nanoparticles to the CMD-tea polyphenol ester is 1:1, and the hollow zein-tea polyphenol ester/CMD-tea polyphenol ester nanoparticles (zein-tea polyphenol ester/CMD-tea polyphenol ester nanoparticles) are prepared.
(5)W2/O2/(O1/W1) Preparation of multiple emulsions
2g of gelatin are dispersed in a 3% (W/v) aqueous NaCl solution to form a first aqueous phase W2Simultaneously mixing 5% polyglycerol polyricinoleate and corn oil at 65 deg.C, stirring for 15min to form a first oil phase O2Then the first aqueous phase W2And a first oil phase O2Mixing at a ratio of 2:8, immediately homogenizing for 3min by high pressure microjet to obtain W2/O2A type primary emulsion;
adding corn oil into suspension of hollow zein-tea polyphenol ester/CMD-tea polyphenol ester nanoparticles, and homogenizing under high pressure for 3min to obtain O1/W1Pickering emulsion, wherein the emulsifier (hollow zein)The concentrations of the soluble protein-tea polyphenol ester/CMD-tea polyphenol ester nanoparticles) were all 2.0 wt%;
w is to be2/O2Addition of type Primary emulsion O1/W1Homogenizing under high pressure for 3min to obtain W2/O2/(O1/W1) Multiple emulsion of which W2/O2Type Primary emulsion and O1/W1The volume ratio of the pickering emulsion is 4: 6.
In the embodiment, the particle size of the double emulsion prepared from the hollow zein-tea polyphenol ester/CMD-tea polyphenol ester nano particles is 30-70 microns, the nano particles can be irreversibly adsorbed and anchored at an oil/water interface to form a compact layer, so that the steric hindrance effect is increased, the stability of the emulsion is increased, the coalescence resistance and Ostwald curing resistance of the emulsion are obviously improved, and the stability of the multiple emulsion is facilitated.
Example 3
(1) Preparation of hollow zein-tea polyphenol ester nano-particles
Respectively dissolving zein and tea polyphenol ester in 80% (v/v) ethanol solution, mixing, adjusting the pH value to 9.0 by using 0.1mol/L sodium hydroxide solution, continuously stirring at 25 ℃ for reaction for 24h, after the reaction is finished, carrying out ultrasonic dialysis on the obtained mixed solution in water bath for 24h, replacing dialyzate for 8 times during the ultrasonic dialysis to remove free tea polyphenol ester, and finally carrying out freeze drying treatment on the solution to obtain the zein-tea polyphenol ester covalent compound;
dissolving 2g zein-tea polyphenol ester covalent complex in 100mL ethanol solution (volume fraction 80%), stirring at 800rpm for 2h, standing until completely dissolved, simultaneously, uniformly mixing 2wt% of sodium carbonate aqueous solution with absolute ethyl alcohol according to the volume ratio of 3:7 to form sodium carbonate ethanol suspension, mixing the suspension with zein-tea polyphenol ester covalent compound solution according to the volume ratio of 1:1, the method comprises the steps of coating sodium carbonate particles with zein-tea polyphenol ester covalent compound, slowly adding a mixed solution of the zein-tea polyphenol ester covalent compound and the sodium carbonate into distilled water according to the volume ratio of 1:6, stirring at 800rpm for 4h, and freeze drying to obtain hollow zein-tea polyphenol ester nanoparticles (zein-tea polyphenol ester nanoparticles).
(2) Preparation of carboxymethyl dextrin (CMD)
Adding 20g of waxy corn starch into 400ml of phosphoric acid buffer solution (0.01M, pH value is 5.5), stirring at 99 ℃ for 1h to completely gelatinize the waxy corn starch, cooling the completely gelatinized starch to the temperature, then adding pullulanase (100U/g) into the gelatinized starch, carrying out enzymolysis at 55 ℃ for 24h for debranching treatment, after the reaction is finished, placing the obtained solution in a boiling water bath for 10min to carry out enzyme deactivation treatment, then centrifuging at the rotating speed of 4500rpm for 15min, and carrying out vacuum freeze drying treatment on the centrifuged supernatant to prepare Linear Dextrin (LD);
mixing 10g of LD, 6g of sodium hydroxide and 100ml of ethanol solution (volume fraction is 90%), stirring and reacting at 30 ℃ for 1h, then adding 6g of chloroacetic acid into the mixed solution, stirring and reacting at 40 ℃ for 4h, then adjusting the pH value of the reacted solution to 4 by using 7.0M hydrochloric acid, centrifuging at 3500rpm for 15min to obtain a precipitate, washing the precipitate for several times by using 85% ethanol solution until chloride ions are washed, washing the precipitate for several times by using absolute ethanol, finally drying the precipitate in an oven at 45 ℃ for 24h, and grinding the precipitate to obtain the CMD.
(3) Preparation of carboxymethyl dextrin-tea polyphenol ester (CMD-tea polyphenol ester) covalent Complex
Preparing CMD-tea polyphenol ester covalent complex by adopting a coprecipitation method, dissolving 0.2g of tea polyphenol ester in 50ml of absolute ethyl alcohol to form a tea polyphenol ester solution, simultaneously dissolving 1g of carboxymethyl dextrin in 100ml of distilled water, stirring in a boiling water bath for 20min to promote molecular chain development, and then cooling to 80 ℃; and then adding 50ml of tea polyphenol ester solution into the cooled solution, continuously stirring and reacting for 2h, standing the mixture overnight to ensure complete mixing, centrifuging at 8000rpm for 25min to obtain a precipitate, washing with 50% absolute ethyl alcohol for 3 times, and drying in an oven at 40 ℃ to obtain the carboxymethyl dextrin-tea polyphenol ester covalent complex.
(4) Preparation of hollow zein-tea polyphenol ester/CMD-tea polyphenol ester nanoparticles
Dissolving 1g of hollow zein-tea polyphenol ester nanoparticles in 50ml of distilled water, stirring at 800rpm for 2h to form a hollow zein-tea polyphenol ester nanoparticle solution, simultaneously dissolving the carboxymethyl dextrin-tea polyphenol ester covalent complex in 200ml of deionized water, and continuously stirring at 800rpm for 4h to form a carboxymethyl dextrin-tea polyphenol ester covalent complex solution; then, 50ml of hollow zein-tea polyphenol ester nanoparticle solution is dropwise added into 200ml of CMD-tea polyphenol ester solution, the mixture is stirred at 800rpm for reaction for 2 hours, and meanwhile, the pH value of the system is adjusted to 4, wherein the mass ratio of the hollow zein-tea polyphenol ester nanoparticles to the CMD-tea polyphenol ester is 1:2, and the hollow zein-tea polyphenol ester/CMD-tea polyphenol ester nanoparticles (zein-tea polyphenol ester/CMD-tea polyphenol ester nanoparticles) are prepared.
(5)W2/O2/(O1/W1) Preparation of multiple emulsions
5g of gelatin are dispersed in a 3% (W/v) aqueous NaCl solution to form a first aqueous phase W2Simultaneously mixing 5% polyglycerol polyricinoleate and corn oil at 65 deg.C, stirring for 15min to form a first oil phase O2Then the first aqueous phase W2And a first oil phase O2Mixing at a ratio of 5:5, immediately homogenizing for 3min by high pressure microjet to obtain W2/O2A type primary emulsion;
adding corn oil into suspension of hollow zein-tea polyphenol ester/CMD-tea polyphenol ester nanoparticles, and homogenizing under high pressure for 3min to obtain product O1/W1Pickering emulsion, wherein the concentration of emulsifier (hollow zein-tea polyphenol ester/CMD-tea polyphenol ester nanoparticles) is 0.5 wt%;
w is to be2/O2Addition of type Primary emulsion O1/W1Homogenizing under high pressure for 3min to obtain W2/O2/(O1/W1) Multiple emulsion of which W2/O2Type primary emulsion and O1/W1The volume ratio of the pickering emulsion is 5: 5.
In the embodiment, the particle size of the double emulsion prepared from the hollow zein-tea polyphenol ester/CMD-tea polyphenol ester nano particles is 30-70 microns, the nano particles can be irreversibly adsorbed and anchored at an oil/water interface to form a compact layer, so that the steric hindrance effect is increased, the stability of the emulsion is increased, the coalescence resistance and Ostwald curing resistance of the emulsion are obviously improved, and the stability of the multiple emulsion is facilitated.
Comparative example 1: multiple emulsion prepared from hollow zein-tea polyphenol ester nanoparticles
(1) Preparation of hollow zein-tea polyphenol ester nano-particles
Respectively dissolving zein and tea polyphenol ester in 80% (v/v) ethanol solution, mixing, adjusting the pH value to 9.0 by using 0.1mol/L sodium hydroxide solution, continuously stirring at 25 ℃ for reaction for 24h, after the reaction is finished, carrying out ultrasonic dialysis on the obtained mixed solution in water bath for 24h, replacing dialyzate for 8 times during the ultrasonic dialysis to remove free tea polyphenol ester, and finally carrying out freeze drying treatment on the solution to obtain the zein-tea polyphenol ester covalent compound;
dissolving 2g zein-tea polyphenol ester covalent complex in 100mL ethanol solution (volume fraction 80%), stirring at 800rpm for 2h, standing until completely dissolved, simultaneously, uniformly mixing 2wt% of sodium carbonate aqueous solution with absolute ethyl alcohol according to the volume ratio of 3:7 to form sodium carbonate ethanol suspension, mixing the suspension with zein-tea polyphenol ester covalent compound solution according to the volume ratio of 1:1, the method comprises the steps of coating sodium carbonate particles with zein-tea polyphenol ester covalent compound, slowly adding a mixed solution of the zein-tea polyphenol ester covalent compound and the sodium carbonate into distilled water according to the volume ratio of 1:6, stirring at 800rpm for 4h, and freeze drying to obtain hollow zein-tea polyphenol ester nanoparticles (zein-tea polyphenol ester nanoparticles).
(2) Preparation of hollow zein-tea polyphenol ester nanoparticle (zein-tea polyphenol ester nanoparticle) multiple emulsion
2g of gelatin are dispersed in a 3% (W/v) aqueous NaCl solution to form a first aqueous phase W2Simultaneously, 5 percent of polyglycerol polyricinoleate and corn are mixed at 65 DEG CMixing the oils, stirring for 15min to form a first oil phase O2Then the first aqueous phase W2And a first oil phase O2Mixing at a ratio of 2:8, immediately homogenizing for 3min by high pressure microjet to obtain W2/O2A type primary emulsion;
adding corn oil into the suspension of zein-tea polyphenol ester nanoparticles, and homogenizing under high pressure for 3min to obtain O1/W1Pickering emulsion, wherein the concentration of the emulsifier (zein-tea polyphenol ester nano particles) is 2.0 wt%;
w is to be2/O2Addition of type Primary emulsion O1/W1Homogenizing under high pressure for 3min to obtain W2/O2/(O1/W1) Multiple emulsion of which W2/O2Type primary emulsion and O1/W1The volume ratio of the pickering emulsion is 4: 6.
Comparative example 2: multiple emulsion prepared from hollow zein-tea polyphenol ester/carboxymethyl dextrin nanoparticles
(1) Preparation of hollow zein-tea polyphenol ester nano-particles
Respectively dissolving zein and tea polyphenol ester in 80% (v/v) ethanol solution, mixing, adjusting the pH value to 9.0 by using 0.1mol/L sodium hydroxide solution, continuously stirring at 25 ℃ for reaction for 24h, after the reaction is finished, carrying out ultrasonic dialysis on the obtained mixed solution in water bath for 24h, replacing dialyzate for 8 times during the ultrasonic dialysis to remove free tea polyphenol ester, and finally carrying out freeze drying treatment on the solution to obtain the zein-tea polyphenol ester covalent compound;
dissolving 2g zein-tea polyphenol ester covalent complex in 100mL ethanol solution (volume fraction 80%), stirring at 800rpm for 2h, standing until completely dissolved, simultaneously, uniformly mixing 2wt% of sodium carbonate aqueous solution with absolute ethyl alcohol according to the volume ratio of 3:7 to form sodium carbonate ethanol suspension, mixing the suspension with zein-tea polyphenol ester covalent compound solution according to the volume ratio of 1:1, the method comprises the steps of coating sodium carbonate particles with zein-tea polyphenol ester covalent compound, slowly adding a mixed solution of the zein-tea polyphenol ester covalent compound and the sodium carbonate into distilled water according to the volume ratio of 1:6, stirring at 800rpm for 4h, and freeze drying to obtain hollow zein-tea polyphenol ester nanoparticles (zein-tea polyphenol ester nanoparticles);
(2) preparation of carboxymethyl dextrin (CMD)
Adding 20g of waxy corn starch into 400ml of phosphoric acid buffer solution (0.01M, pH value is 5.5), stirring at 99 ℃ for 1h to completely gelatinize the waxy corn starch, cooling the completely gelatinized starch to the temperature, then adding pullulanase (100U/g) into the gelatinized starch, carrying out enzymolysis at 55 ℃ for 24h for debranching treatment, after the reaction is finished, placing the obtained solution in a boiling water bath for 10min to carry out enzyme deactivation treatment, then centrifuging at the rotating speed of 4500rpm for 15min, and carrying out vacuum freeze drying treatment on the centrifuged supernatant to prepare Linear Dextrin (LD);
mixing 10g of LD, 6g of sodium hydroxide and 100ml of ethanol solution (volume fraction is 90%), stirring and reacting at 30 ℃ for 1h, then adding 6g of chloroacetic acid into the mixed solution, stirring and reacting at 40 ℃ for 4h, then adjusting the pH value of the reacted solution to 4 by using 7.0M hydrochloric acid, centrifuging at 3500rpm for 15min to obtain a precipitate, washing the precipitate for several times by using 85% ethanol solution until chloride ions are washed, washing the precipitate for several times by using absolute ethanol, finally drying the precipitate in an oven at 45 ℃ for 24h, and grinding the precipitate to obtain the CMD.
(3) Preparation of hollow zein-tea polyphenol ester/carboxymethyl dextrin nanoparticles
1g of hollow zein-tea polyphenol ester nanoparticles was added to 50ml of distilled water solution and stirred at 800rpm for 2 hours. CMD was dissolved in 200ml of deionized water and stirred continuously at 800rpm for 4 h. Then, 50ml of the zein-tea polyphenol ester nanoparticle solution was added dropwise to 200ml of the CMD solution, and stirred at 800rpm for 2 h. Adjusting the pH value of the dispersion system to 4, wherein the mass ratio of the hollow zein-tea polyphenol ester nano particles to the CMD is 1: 2;
(4) preparing a hollow zein-tea polyphenol ester/CMD nanoparticle (zein-tea polyphenol ester/CMD nanoparticle) multiple emulsion;
2g of gelatin are dispersed in a 3% (W/v) aqueous NaCl solution to form a first aqueous phase W2Simultaneously mixing 5% polyglycerol polyricinoleate and corn oil at 65 deg.C, stirring for 15min to form a first oil phase O2Then the first aqueous phase W2And a first oil phase O2Mixing at a ratio of 2:8, immediately homogenizing for 3min by high pressure microjet to obtain W2/O2A type primary emulsion;
adding corn oil to the zein-tea polyphenol ester/CMD nanoparticle suspension, and homogenizing under high pressure for 3min to obtain O1/W1Pickering emulsion, wherein the concentration of emulsifier (zein-tea polyphenol ester/CMD nano particles) is 2.0 wt%;
w is to be2/O2Addition of type Primary emulsion O1/W1Homogenizing under high pressure for 3min to obtain W2/O2/(O1/W1) Multiple emulsion of which W2/O2Type primary emulsion and O1/W1The volume ratio of the pickering emulsion is 4: 6.
And (3) performance characterization:
FIG. 1 is a graph of particle size for zein-tea polyphenol ester/CMD-tea polyphenol ester nanoparticles, zein-tea polyphenol ester/CMD nanoparticles prepared in example 2 and comparative examples 1, 2;
FIG. 2 is a graph of the particle size of multiple emulsions formed by different nanoparticles prepared in example 2 and comparative examples 1 and 2. from FIG. 2, it can be seen that the multiple emulsion prepared from hollow zein-tea polyphenol ester/CMD-tea polyphenol ester nanoparticles has the smallest particle size, the emulsion drop is 31.7 μm, and after one month of storage, there is no significant change in particle size, indicating that it has good stability, where the multiple emulsion prepared from hollow zein nanoparticles alone coalesces and therefore cannot be measured for its stable emulsion particle size;
fig. 3 is a graph showing the variation of the particle size of multiple emulsions formed by zein-tea polyphenol ester/CMD-tea polyphenol ester nanoparticles prepared in example 1 at different concentrations. As can be seen from fig. 3, the concentration of the hollow zein-tea polyphenol ester/CMD-tea polyphenol ester nanoparticles is 2wt%, the minimum formed emulsion droplet is 31.7um, and the particle size does not change significantly after one month of storage, indicating that it has good stability.
Fig. 4 shows the antioxidant activity of multiple emulsions formed by different nanoparticles prepared in example 2 and comparative examples 1 and 2. it can be seen from fig. 4 that the multiple emulsions stabilized by hollow zein-tea polyphenol ester/CMD-tea polyphenol ester nanoparticles have the highest antioxidant activity.
In addition, the inventors of the present invention have also made experiments with other raw materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.
Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.
It should be understood that the order of steps or order in which certain actions are performed is not critical, so long as the present teachings remain operable. Further, two or more steps or actions may be performed simultaneously.
Although the present invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.

Claims (12)

1. A preparation method of starch-based dextrin modified zein nanoparticles is characterized by comprising the following steps:
reacting a first mixed reaction system containing zein, tea polyphenol ester, sodium hydroxide, ethanol and water at 25 ℃ for 24 hours to obtain a zein-tea polyphenol ester covalent compound, and then reacting a second mixed reaction system containing the zein-tea polyphenol ester covalent compound, sodium carbonate, ethanol and water at 25 ℃ for 4 hours to obtain hollow zein-tea polyphenol ester nanoparticles;
carrying out coprecipitation reaction on a third mixed reaction system containing carboxymethyl dextrin, tea polyphenol ester, ethanol and water to obtain a carboxymethyl dextrin-tea polyphenol ester covalent complex;
and reacting a fourth mixed reaction system containing the hollow zein-tea polyphenol ester nanoparticles, the carboxymethyl dextrin-tea polyphenol ester covalent compound and water at 25 ℃ for 2 hours to obtain the hollow zein-tea polyphenol ester/carboxymethyl dextrin-tea polyphenol ester nanoparticles, namely the starch-based dextrin modified zein nanoparticles.
2. The production method according to claim 1, characterized by comprising:
dissolving zein and tea polyphenol ester in an ethanol solution to form a mixed solution, then adding a sodium hydroxide solution into the obtained mixed solution to form a first mixed reaction system and react, and then dialyzing and freeze-drying the obtained mixture to obtain the zein-tea polyphenol ester covalent compound, wherein the pH value of the first mixed reaction system is 9.0;
dissolving the zein-tea polyphenol ester covalent compound in an ethanol solution to form a zein-tea polyphenol ester covalent compound dispersion solution, uniformly mixing the zein-tea polyphenol ester covalent compound dispersion solution with an ethanol suspension of sodium carbonate, mixing the obtained zein-tea polyphenol ester covalent compound and a mixed solution of sodium carbonate with water to form a second mixed reaction system, and reacting to obtain the hollow zein-tea polyphenol ester nano-particles;
wherein the concentration of the zein in the first mixed reaction system is 1-2 wt%;
the mass ratio of the zein to the tea polyphenol ester is 5:1-1: 1;
the volume fraction of ethanol in the ethanol solution is 75-80%;
the dialysis treatment comprises: after the reaction of the first mixed reaction system is finished, carrying out ultrasonic dialysis treatment on the obtained mixture in a water bath for 24 hours;
the ethanol suspension of the sodium carbonate is a mixed solution of a sodium carbonate aqueous solution and absolute ethyl alcohol; the concentration of the sodium carbonate aqueous solution is 1-2 wt%; the volume ratio of the sodium carbonate aqueous solution to the absolute ethyl alcohol is 3: 7;
the volume ratio of the dispersion liquid of the zein-tea polyphenol ester covalent compound to the ethanol suspension of the sodium carbonate is 1: 1;
the volume ratio of the mixed liquid of the zein-tea polyphenol ester covalent compound and the sodium carbonate to water is 1:1-1: 6.
3. The method according to claim 1, comprising:
sequentially carrying out gelatinization, debranching and enzyme deactivation on waxy corn starch to obtain linear dextrin;
mixing the obtained linear dextrin, sodium hydroxide and ethanol solution, stirring and reacting for 1h at 30 ℃, then adding chloroacetic acid into the obtained mixed solution, stirring and reacting for 4h at 40 ℃, and then adjusting the pH value of the obtained solution to 4 by using hydrochloric acid to obtain the carboxymethyl dextrin;
wherein the degree of substitution of the carboxymethyl dextrin is 0.315.
4. The method according to claim 1, comprising: and (3) treating the aqueous solution of the carboxymethyl dextrin in a boiling water bath for 20min, mixing the aqueous solution of the carboxymethyl dextrin with the ethanol solution of the tea polyphenol ester to form the third mixed reaction system, and stirring and reacting at 80 ℃ for 2h to obtain the carboxymethyl dextrin-tea polyphenol ester covalent compound.
5. The production method according to claim 1, characterized by comprising: respectively dissolving the hollow zein-tea polyphenol ester nanoparticles and the carboxymethyl dextrin-tea polyphenol ester covalent compound in water to form a hollow zein-tea polyphenol ester nanoparticle solution and a carboxymethyl dextrin-tea polyphenol ester covalent compound solution, then dropwise adding the hollow zein-tea polyphenol ester nanoparticle solution into the carboxymethyl dextrin-tea polyphenol ester covalent compound solution to form a fourth mixed reaction system and react, and adjusting the pH value of the obtained mixture to be 4.0 after the reaction is finished to obtain the hollow zein-tea polyphenol ester/carboxymethyl dextrin-tea polyphenol ester nanoparticles;
the mass ratio of the hollow zein-tea polyphenol ester nanoparticles to the carboxymethyl dextrin-tea polyphenol ester covalent compound is 4: 1-1: 4.
6. The method of claim 5, wherein: the mass ratio of the hollow zein-tea polyphenol ester nano particles to the carboxymethyl dextrin-tea polyphenol ester covalent compound is any one of 4:1, 2:1, 1:2 and 1: 4.
7. Starch-based dextrin-modified zein nanoparticles prepared by the method of any one of claims 1-6.
8. Use of the starch-based dextrin-modified zein nanoparticles of claim 7 in the preparation of W2/O2/(O1/W1) Use in multiple emulsions.
9. W2/O2/(O1/W1) A method for preparing a multiple emulsion, comprising:
providing the starch-based dextrin-modified zein nanoparticles of claim 7;
mixing polyglycerol polyricinoleate and corn oil at 65 deg.C to form first oil phase, mixing the first oil phase with mixed solution of sodium chloride and gelatin as first water phase, and homogenizing with high pressure micro jet for 3min to obtain W2/O2A type primary emulsion;
mixing the second oil phase with the suspension of the starch-based dextrin-modified zein nanoparticles as the second water phase, and homogenizing under high pressure for 3min to obtain O1/W1A pickering type emulsion;
and, making said W2/O2Type primary emulsion and O1/W1Mixing the pickering emulsion and homogenizing under high pressure for 3min to obtain W2/O2/(O1/W1) Form multiple emulsions.
10. The method of claim 9, wherein: the mass ratio of the polyglycerol polyricinoleate to the corn oil is 5: 100;
the volume ratio of the first water phase to the first oil phase is 1:9-5: 5;
said O is1/W1The concentration of the starch-based dextrin modified zein nanoparticles in the pickering emulsion is 0.1-2.0 wt%;
the second oil phase is corn oil;
the volume ratio of the second oil phase to the second water phase is 2:8-5: 5;
the W is2/O2Type primary emulsion and O1/W1The volume ratio of the pickering emulsion is 1:9-5: 5.
11. W prepared by the process of any one of claims 9 or 102/O2/(O1/W1) Form multiple emulsions.
12. W according to claim 112/O2/(O1/W1) Use of multiple emulsions of formula (I) for the preparation of a food product, a pharmaceutical or a cosmetic product.
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