CN113397156A - Dual Pickering emulsion and preparation method thereof - Google Patents

Dual Pickering emulsion and preparation method thereof Download PDF

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CN113397156A
CN113397156A CN202110636030.1A CN202110636030A CN113397156A CN 113397156 A CN113397156 A CN 113397156A CN 202110636030 A CN202110636030 A CN 202110636030A CN 113397156 A CN113397156 A CN 113397156A
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solution
pickering emulsion
dual
preparation
chitosan
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尹寿伟
舒欣怡
李理
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Sino Singapore International Joint Research Institute
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Sino Singapore International Joint Research Institute
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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
    • A23L29/10Foods or foodstuffs containing additives; Preparation or treatment thereof containing emulsifiers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/30Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
    • A61K47/36Polysaccharides; Derivatives thereof, e.g. gums, starch, alginate, dextrin, hyaluronic acid, chitosan, inulin, agar or pectin
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/30Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
    • A61K47/42Proteins; Polypeptides; Degradation products thereof; Derivatives thereof, e.g. albumin, gelatin or zein
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04Dispersions; Emulsions
    • A61K8/06Emulsions
    • A61K8/066Multiple emulsions, e.g. water-in-oil-in-water
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/64Proteins; Peptides; Derivatives or degradation products thereof
    • A61K8/645Proteins of vegetable origin; Derivatives or degradation products thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73Polysaccharides
    • A61K8/736Chitin; Chitosan; Derivatives thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00Medicinal preparations characterised by special physical form
    • A61K9/10Dispersions; Emulsions
    • A61K9/107Emulsions ; Emulsion preconcentrates; Micelles
    • A61K9/113Multiple emulsions, e.g. oil-in-water-in-oil
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • 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
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/10General cosmetic use
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/20Chemical, physico-chemical or functional or structural properties of the composition as a whole
    • A61K2800/30Characterized by the absence of a particular group of ingredients
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/80Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
    • A61K2800/82Preparation or application process involves sonication or ultrasonication
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/80Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
    • A61K2800/84Products or compounds obtained by lyophilisation, freeze-drying

Abstract

The invention discloses a double Pickering emulsion and a preparation method thereof. Preparing a soybean water-insoluble aggregate into a peptide dispersion liquid by adopting ultrapure water, and performing ultrasonic treatment to obtain a soybean water-insoluble aggregate solution; preparing chitosan into a solution by adopting an acetic acid aqueous solution to obtain a chitosan solution; slowly dripping the chitosan solution into the soybean water-insoluble aggregate solution which is continuously stirred, and shearing and homogenizing to obtain a composite colloid system; and adjusting the pH value of the composite colloidal particle system to 3-5, mixing with grease, and shearing and emulsifying to obtain the product. The double emulsion has high stability, can be stored for more than four months without demulsification and oil leakage, has a double structure capable of keeping more than one month, has good rheological and digestive properties, and effectively improves the green sustainable application of soybean protein enzymolysis products.

Description

Dual Pickering emulsion and preparation method thereof
Technical Field
The invention relates to a double Pickering emulsion, in particular to a double Pickering emulsion with stable soybean water-insoluble aggregates and chitosan composite colloidal particles and a preparation method thereof.
Background
The double emulsion is a relatively complex emulsion system in an emulsion system, can simultaneously exist two emulsion types of W/O and O/W, and is widely applied to multiple fields of food industry, medicines, cosmetics and the like by virtue of a unique internal structure of the double emulsion. The two main types of double emulsions are water-in-oil-in-water (W/O/W) and oil-in-water-in-oil (O/W/O).
The stabilization of double emulsion systems in the conventional manner usually requires that two or more surfactants are achieved by a two-step emulsification process. However, this approach is more complicated in procedure and requires additional steps or ion concentration to increase the osmotic pressure of the internal aqueous phase to prevent the external permeation of the internal aqueous phase. To overcome these drawbacks, the stabilization of double emulsions by means of a one-step emulsification process has received extensive attention. The approaches for stabilizing double emulsion by one-step emulsification method mainly include microfluidic method, block copolymer method and Pickering emulsion method. The Pickering emulsion method utilizes the colloid particles which can be adsorbed to an oil-water interface to form a firm barrier, inhibits the aggregation of internal liquid drops so as to reduce the loss of an internal water phase, can improve the overall stability of a double-emulsion system, and is more nontoxic and environment-friendly compared with a surfactant. To date, the preparation of stable dual Pickering emulsions from silica particles, graphene oxide particles, and polymer particle bound surfactants by a two-step process has been investigated. However, of these colloidal particles, the use of edible colloidal particles to stabilize double emulsions in a single step has been rarely reported. Obviously, emulsification by fully edible colloidal particles under single high shear/high pressure action is a promising efficient and safe dual Pickering emulsion production method, and its potential application advantages have been the research focus in the food industry.
Chinese patent application 2019106160134 discloses a method for preparing W/O/W dual Pickering emulsion by using modified kaolinite as emulsifier and realizing the synergistic encapsulation of catechin and curcumin. The W1/O emulsion is obtained under the condition of shearing emulsification by using emulsified oil phase (O) of medium chain triglyceride dissolved with curcumin, emulsified water phase (W1) of deionized water dissolved with catechin and using lecithin modified kaolinite with a contact angle of 130 degrees as an emulsifier. Adding deionized water dispersed with lecithin modified kaolinite with a contact angle of 88 degrees into the obtained W1/O emulsion to obtain a W2 phase, and obtaining the W1/O/W2 double Pickering emulsion in which catechin and curcumin are encapsulated in an O phase and a W1 phase simultaneously under a shearing emulsification condition. The synergistic encapsulation efficiency of the double emulsion on oil-soluble curcumin and water-soluble catechin reaches 98 percent. However, the particle emulsifier in the technology is modified kaolinite, and is a non-food grade particle emulsifier, so that the application in the food field is limited; in addition, the technology adopts a two-step method to prepare the W1/O/W2 dual Pickering emulsion, and has complex preparation method and high cost.
Disclosure of Invention
Aiming at the defects that the food-grade double Pickering emulsion is difficult to develop in the prior art and a complex two-step preparation process is adopted, the invention provides the double Pickering emulsion which can be used in the field of food and has low preparation cost and stable soybean water-insoluble aggregate-chitosan composite colloidal particles without containing a surfactant and a preparation method thereof.
Compared with the prior art, the invention mainly solves the problems that only food-grade particle emulsifier is used, the method is different from the conventional two-step emulsification method, the double Pickering emulsion is prepared by the one-step emulsification method, the raw materials are natural and safe, and the preparation method is simple. The granular emulsifier used in the invention is edible soybean water-insoluble aggregate-chitosan composite colloidal particles, and is convenient to apply in food.
For the preparation of food-grade double Pickering emulsion, the main obstacle is to find a functional and food industry allowed particle system, and the prior art is complicated to prepare by a two-step method. The soybean protein is widely applied to the food industry, and the product obtained by enzymolysis of the soybean protein also has the beneficial functional health-care characteristic for human bodies. Meanwhile, insoluble aggregates SWIA (Soy water-insoluble aggregates) generated in the enzymolysis process of the soybean protein also contain a large amount of essential amino acids with uniform components, have excellent load bearing capacity and can be widely applied to the food industry as a potential functional food ingredient. Therefore, the water-insoluble aggregate after the enzymolysis of the soybean protein is used as the base material to stabilize the double Pickering emulsion, so that the green sustainable application of the soybean protein enzymolysis product can be further improved. Chitosan CS is an alkaline cationic polysaccharide, obtained from chitin by alkaline deacetylation. It has the characteristics of rich sources, good biocompatibility, biodegradability, bacteriostasis and the like, and is widely applied to various fields.
The invention develops food-grade composite colloidal particles, and further realizes the one-step preparation of the double Pickering emulsion. In the prior art, non-food-grade inorganic or polymer particles are combined with a surfactant to serve as an emulsifier of a double Pickering emulsion, and the preparation method is a two-step preparation method and is complicated in preparation process; the invention utilizes soybean protein enzymolysis by-products, namely soybean water-insoluble aggregates and chitosan to form composite colloidal particles, and the prepared composite colloidal particles can obtain stable double Pickering emulsion by a one-step emulsification method, thereby effectively improving the green sustainable application of soybean protein enzymolysis products, and having good application prospect in the fields of cosmetics, medicines, foods and health care products, including other fields. At present, no report is found on a method for preparing the double Pickering emulsion by using a food-grade colloidal particle one-step emulsification method in China.
The invention prepares the composite colloidal particles with stable structure by compounding the soybean water-insoluble aggregate SWIA and the chitosan CS, and prepares the stable double Pickering emulsion by using the composite colloidal particles as the emulsifier and utilizing a one-step homogenization method. In the invention, the double Pickering emulsion with high stability can be obtained without any surfactant and complicated procedures, and can be stored for a long time, so that the green sustainable application of the soybean protein enzymolysis product is effectively improved, and a convenient way is provided for preparing the multiple emulsions.
The purpose of the invention is realized by the following technical scheme:
the preparation method of the soybean water-insoluble aggregate-chitosan composite colloidal particle stable dual Pickering emulsion is characterized by comprising the following steps of:
preparing a soybean water-insoluble aggregate into a peptide dispersion liquid by adopting ultrapure water, and performing ultrasonic treatment to obtain a soybean water-insoluble aggregate solution; preparing chitosan into a solution by adopting an acetic acid aqueous solution to obtain a chitosan solution:
dripping the chitosan solution into the soybean water-insoluble aggregate solution which is continuously stirred, and shearing and homogenizing to obtain a system containing composite colloidal particles;
and adjusting the pH value of the composite colloidal particle system to 3-5, mixing with grease, shearing and emulsifying to obtain the double Pickering emulsion with stable soybean water-insoluble aggregate-chitosan composite colloidal particles.
In order to further achieve the purpose of the invention, preferably, the soybean water-insoluble aggregate SWIA is powder obtained by performing enzymolysis on soybean protein isolate for 12-24 hours by Protamex, and then performing freeze drying on a precipitate obtained after the enzymolysis liquid is centrifuged; the enzymatic hydrolysis condition of Protamex is set to be pH5.0-8.0, the temperature is 50 ℃, and the enzyme adding amount per gram of substrate is 000.5-0.01 ml according to the weight of the substrate. This method is commonly used in the art. In the examples, the enzyme hydrolysis was carried out for 20 hours under conditions of pH6.0 and 50 ℃ at an enzyme addition rate of 000.8 ml per gram of substrate, and the soybean water-insoluble aggregates SWIA obtained under other process conditions within the above-defined range were not substantially different.
Preferably, the mass concentration of the acetic acid aqueous solution is 1-3%.
Preferably, the dosage of the chitosan in the solution prepared by the chitosan with the acetic acid aqueous solution is 0.5-1% of the mass of the acetic acid solution;
the amount of the soybean water-insoluble aggregates in the peptide dispersion prepared from the soybean water-insoluble aggregates by adopting ultrapure water is 0.2-0.5% of the mass of water;
the volume ratio of the soybean water-insoluble aggregate solution to the chitosan solution in the continuously stirred soybean water-insoluble aggregate solution is 1: 1-2.5: 1.
Preferably, the ultrasonic power is 180W-200W, the intermittent time is 1-3 s, and the total time is 5-10 min. The ultrasonic power of the ultrasonic selection in the embodiment is 200W, the intermittent time is 2s, the total time is 8min, and the purpose of the invention can be realized by the treatment under the ultrasonic process condition.
Preferably, the rotation speed of the shearing homogenization is 15000rpm to 20000rpm, and the shearing homogenization time is 1 min to 2 min.
Preferably, the oil is corn oil.
Preferably, after the pH is adjusted to 3-5, the volume ratio of the composite colloidal particle system to the grease is 1: 1-3: 1.
Preferably, the rotation speed of the shearing emulsification is 8000 rpm-12000 rpm, and the time of the shearing emulsification is 30 s-80 s.
A soybean water-insoluble aggregate-chitosan composite colloidal particle stable double Pickering emulsion is prepared by the preparation method.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the invention utilizes the soybean water-insoluble aggregate-chitosan composite colloidal particles to stabilize the double Pickering emulsion by a one-step method for the first time, does not need more complicated procedures and does not add any surfactant.
(2) The double Pickering emulsion with stable soybean water-insoluble aggregate-chitosan composite colloidal particles has higher emulsification effect and emulsification stability, and can not be demulsified and leaked after being stored for more than four months.
(3) The soybean water-insoluble aggregate-chitosan composite colloidal particles for stabilizing the double Pickering emulsion are all natural substances, and the green sustainable application of soybean protein enzymolysis products is effectively improved, so that the soybean protein enzymolysis emulsion is healthy and nontoxic.
(4) The stable dual Pickering emulsion of the soybean water-insoluble aggregate composite colloidal particles has good rheological and digestive properties, and has good application prospects in the fields of cosmetics, medicines, foods and health products, including other fields.
Drawings
FIG. 1 is an appearance diagram of a double Pickering emulsion stabilized by freshly made SWIA-CS composite colloidal particles in an example; the double Pickering emulsion with stable composite colloidal particles of 0.25 percent SWIA-0.125 percent CS, 0.25 percent SWIA-0.25 percent CS and 0.25 percent SWIA-0.5 percent CS are sequentially arranged from left to right;
FIG. 2 is an appearance chart of a double Pickering emulsion stabilized by SWIA-CS composite colloidal particles in example 1 after being left for four months; the double Pickering emulsion with stable composite colloidal particles of 0.25 percent SWIA-0.125 percent CS, 0.25 percent SWIA-0.25 percent CS and 0.25 percent SWIA-0.5 percent CS are sequentially arranged from left to right;
FIG. 3 is a graph of the appearance of the 0.125%, 0.25% and 0.5% CS stabilized Pickering emulsions prepared in comparative example 1;
FIG. 4 is a graph of the appearance of the CS stabilized Pickering emulsions of comparative example 1 at 0.125%, 0.25%, and 0.5% after 24 hours of standing;
FIG. 5 is a microscopic image of a SWIA-CS composite colloidal particle-stabilized dual Pickering emulsion freshly prepared and left for 15 days in the examples; the double Pickering emulsion is stable with composite colloid particles of 0.25 percent SWIA-0.125 percent CS, 0.25 percent SWIA-0.25 percent CS and 0.25 percent SWIA-0.5 percent CS from top to bottom;
FIG. 6 is a microscopic image of new 0.125%, 0.25% and 0.5% CS-stabilized Pickering emulsions of comparative example 1;
FIG. 7 is a laser confocal map of the double Pickering emulsion stabilized by SWIA-CS composite colloidal particles of different CS mass concentrations in example 2; from left to right, the stable double Pickering emulsion of the composite colloidal particles of 0.25 percent SWIA-0.125 percent CS and 0.25 percent SWIA-0.25 percent CS are respectively arranged;
FIGS. 8 to 10 are respectively stress scan graphs of the composite colloidal particle stabilized dual Pickering emulsion of 0.25% SWIA-0.125% CS, 0.25% SWIA-0.25% CS, and 0.25% SWIA-0.5% CS in example 1; g 'represents an elastic modulus, and G' represents a viscous modulus;
FIGS. 11 and 12 are graphs of the changes of the stable dual Pickering emulsions of the composite colloidal particles 0.25% SWIA to 0.25% CS and 0.25% SWIA to 0.5% CS in the gastrointestinal digestion process in the examples, respectively.
Detailed Description
For a better understanding of the present invention, the present invention is further described below with reference to the accompanying drawings and examples, but the embodiments of the present invention are not limited thereto.
Comparative example 1
The preparation method of the chitosan stable dual Pickering emulsion comprises the following steps:
(1) accurately weighing 0.0125g, 0.025g and 0.05g of chitosan CS, and dissolving in 10mL of acetic acid solution with the mass concentration of 1% to obtain CS solutions with the mass concentrations of 0.125%, 0.25% and 0.5%, respectively;
(2) and (3) mixing the solution obtained in the step (1) with 3mL of corn oil, and performing shearing emulsification at the rotating speed of 15000rpm/min for 2min to obtain the Pickering emulsion with stable chitosan.
Examples 1 to 3
A preparation method of a soybean water-insoluble aggregate-chitosan one-step stable dual Pickering emulsion comprises the following steps:
(1) accurately weighing 0.05g of soybean water insoluble aggregate SWIA (obtained by enzymolysis of soybean protein) generated in the soybean enzymolysis process, dissolving the soybean water insoluble aggregate SWIA in 10mL of ultrapure water, performing ultrasonic treatment after overnight hydration to obtain a SWIA solution with the mass concentration of 0.5%;
(2) accurately weighing 0.1g of chitosan CS, and dissolving in 10mL of acetic acid solution with the mass concentration of 1% to obtain a CS solution with the mass concentration of 1%;
(3) slowly dripping the CS solution obtained in the step (2) into the SWIA solution obtained in the step (1), and shearing and homogenizing to obtain composite colloidal particles with the mass concentration of 0.25-0.5% of SWIA;
(4) and (3) mixing the solution obtained in the step (3) with 3mL of corn oil, and performing shearing emulsification at the rotating speed of 15000rpm/min for 2min to obtain the soybean water-insoluble aggregate-chitosan stable dual Pickering emulsion.
In this example, a gradient test was performed on the mass concentration of CS in step (2), and the mass concentrations of CS prepared were 0.125%, 0.25%, and 0.5%, respectively, to obtain dual Pickering emulsions with stable SWIA-CS composite colloidal particles of different mass concentrations of CS, specifically, dual Pickering emulsions with stable SWIA-0.125% of SWIA, 0.25% of SWIA-0.25% of CS, and 0.25% of SWIA-0.5% of CS composite colloidal particles, respectively.
As can be seen from the examples, compared with the common double Pickering emulsion in the prior art, the product obtained by the invention has the advantages that the particle emulsifier is a natural and safe food raw material and is prepared by a one-step emulsification method.
The obtained double emulsion structure is proved by microscope observation; the soybean water-insoluble aggregate-chitosan stable double Pickering emulsion product is characterized by the unchanged structure of the double emulsion through microscopic observation in the storage process and the combination of appearance stability; the double Pickering emulsion is W/O/W type as proved by the detection result of a laser confocal microscope by carrying out fluorescent dyeing on particles and grease.
The storage stability of the dual Pickering emulsions was characterized by observing their state after various periods of time. FIG. 1 is an appearance diagram of a double Pickering emulsion stabilized by freshly made SWIA-CS composite colloidal particles in an example; the double Pickering emulsion with stable composite colloidal particles of 0.25 percent SWIA-0.125 percent CS, 0.25 percent SWIA-0.25 percent CS and 0.25 percent SWIA-0.5 percent CS are sequentially arranged from left to right; FIG. 2 is an appearance chart of a double Pickering emulsion stabilized by SWIA-CS composite colloidal particles in example 1 after being left for four months; the double Pickering emulsion with stable composite colloidal particles of 0.25 percent SWIA-0.125 percent CS, 0.25 percent SWIA-0.25 percent CS and 0.25 percent SWIA-0.5 percent CS are sequentially arranged from left to right; FIG. 5 is a microscopic image of a SWIA-CS composite colloidal particle-stabilized dual Pickering emulsion freshly prepared and left for 15 days in the examples; the stable double Pickering emulsion is composed of composite colloid particles of 0.25 percent SWIA-0.125 percent CS, 0.25 percent SWIA-0.25 percent CS and 0.25 percent SWIA-0.5 percent CS from top to bottom. As can be seen from FIGS. 1 and 2, the dual Pickering emulsions stabilized by the composite colloidal particles of 0.25% SWIA-0.125% CS, 0.25% SWIA-0.25% CS, and 0.25% SWIA-0.5% CS, respectively, were stable for up to 4 months when stored without breaking emulsions. As can be seen from FIG. 5, the double emulsion structure of the emulsion remained and was stable after 15 days of storage.
FIG. 3 is a graph of the appearance of the 0.125%, 0.25% and 0.5% CS stabilized Pickering emulsions prepared in comparative example 1; FIG. 4 is a graph of the appearance of the CS stabilized Pickering emulsions of comparative example 1 at 0.125%, 0.25%, and 0.5% after 24 hours of standing; FIG. 6 is a microscopic image of new 0.125%, 0.25% and 0.5% CS-stabilized Pickering emulsions of comparative example 1. As can be seen from fig. 3 and 4, in the comparative examples, when new 0.125%, 0.25% and 0.5% CS-stabilized Pickering emulsions were left for 24 hours, the oil layer was completely separated, a distinct demulsification state was seen, and micrographs of the new emulsions demonstrated no double emulsion structure. Pickering emulsions stabilized with CS of 0.125%, 0.25% and 0.5% are not stable and cannot be prepared as double emulsions. As can be seen from fig. 3 and 4, the Pickering emulsions prepared with different chitosan concentrations in comparative example 1 are unstable and completely demulsified after being left for 24 hours, and it can be clearly seen from fig. 6 that the chitosan solution alone cannot prepare double emulsions. It can be seen that the stable dual Pickering emulsion can not be prepared by one-step method by using CS alone with mass concentrations of 0.125%, 0.25% and 0.5%, and the stable dual Pickering emulsion can be prepared by one-step method by using the composite colloidal particles formed by CS and SWIA.
Adding Nile red, Nile blue and a fluorescent whitening agent into a fresh emulsion sample to respectively dye grease, protein and chitosan, and observing by a laser confocal microscope. The excitation wavelength of Nile blue is 633nm, the excitation wavelength of Nile red is 488nm, and the fluorescence white excitation wavelength is 405 nm. Fig. 7 is a laser confocal plot of a swaa-CS composite colloidal particle stabilized dual Pickering emulsion at different CS mass concentrations. As can be clearly seen from FIG. 7, the O/W emulsion droplets in all the soybean water-insoluble aggregate-chitosan stabilized dual Pickering emulsions contained a large number of W/O small emulsion droplets, indicating that the soybean water-insoluble aggregate-chitosan composite colloidal particles can be homogenized into the W/O/W dual Pickering emulsions by a simple one-step method. In the figure, blue and red are the distribution of soybean water-insoluble aggregates and chitosan in the double emulsion, and the composite particles can be seen to be uniformly adsorbed on an oil interface, so that the formation of the double Pickering emulsion is further confirmed, a firm barrier is formed on the interface, internal phases are independent from each other, and the coalescence phenomenon is inhibited.
And (3) respectively taking 1mL of the stable double Pickering emulsion of the SWIA-CS composite colloidal particles with different CS mass concentrations to perform rheological property test, wherein the temperature is 25 ℃, and the stress scanning frequency is set to be 1Hz, so as to obtain a stress scanning graph. FIGS. 8 to 10 are stress scan graphs of dual Pickering emulsions stabilized by composite colloidal particles of 0.25% SWIA-0.125% CS, 0.25% SWIA-0.25% CS, and 0.25% SWIA-0.5% CS, respectively. As can be seen, the elastic modulus G 'is greater than the viscous modulus G', indicating that the emulsion in this state exhibits gel properties dominated by viscoelasticity.
FIGS. 11 and 12 are periodic microscopic observations of emulsions of 0.25% SWIA-0.25% CS and 0.25% SWIA-0.5% CS, respectively, composite colloidal particle stabilized Pickering double emulsions during intestinal and gastric digestion, respectively. Fats and oils exist in a wide variety of forms in foods, and their digestion, absorption and metabolism play a very important role in directing food formulations. As can be seen in fig. 11 and 12, during gastric digestion, the internal aqueous phase of the dual Pickering emulsion facilitates the transfer of a portion of the internal aqueous phase from the internal phase of low salt concentration to the environment of relatively high salt concentration digestive juices due to the high salt environment of the digestive juices. However, partial internal water phase of emulsion droplets still exists after the gastric digestion is finished, and the size of oil droplets is not substantially changed in the whole gastric digestion process, which preliminarily shows that the dual Pickering emulsion prepared from the composite colloid particles can keep the integrity of an interface structure in the gastric digestion process and is beneficial to conveying fat-soluble active substances to the intestinal digestion.
The soybean water-insoluble aggregate-chitosan composite colloidal particle stable double Pickering emulsion can be used as an active ingredient conveying carrier with hydrophobicity, photosensitivity and intolerance to environmental influence in the fields of food, medicine, cosmetics and other fields, and can be used as a double emulsion template prepared by porous microspheres; the dual Pickering emulsions of the prior art are stabilized by inorganic particles and are prepared in two steps: first form W1Preparation of W after the emulsion1/O/W2Emulsion (CN 110302156A; 20319; Yongchun, Wangqingyun, Baiqingling, Lizhen, Jia legend. double Pickering emulsion template method for preparing inorganic-organic composite hollow microsphere [ J]The chemical journal of higher schools, 2018,39(07): 1462-; the particle emulsifier used in the invention is green and natural food-grade soybean water-insoluble aggregate-chitosan composite colloidal particles, and the preparation method of the invention is a one-step method for preparing W1/O/W2The double Pickering emulsion meets the requirements of the industrial fields of food, medicine and the like on natural, safe and nontoxic raw materials, and has simple and efficient preparation process. The soybean water-insoluble aggregate-chitosan composite colloidal particle stable double Pickering emulsion can be used as an active ingredient conveying carrier with hydrophobicity, photosensitivity and intolerance to environmental influence in the fields of food, medicines and cosmetics, and can be used as a double emulsion template prepared from porous microspheres.
In the prior art, non-food-grade inorganic or polymer particles are combined with a surfactant to serve as an emulsifier of a double Pickering emulsion, and the preparation method is a two-step preparation method and is complicated in preparation process; the invention develops food-grade composite colloidal particles, realizes one-step preparation of the double Pickering emulsion, and provides good technical support for large-scale production.
The embodiments of the present invention are not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents and are included in the scope of the present invention.

Claims (10)

1. A preparation method of a dual Pickering emulsion is characterized by comprising the following steps:
preparing a soybean water-insoluble aggregate into a peptide dispersion liquid by adopting ultrapure water, and performing ultrasonic treatment to obtain a soybean water-insoluble aggregate solution; preparing chitosan into a solution by adopting an acetic acid aqueous solution to obtain a chitosan solution:
dripping the chitosan solution into the soybean water-insoluble aggregate solution which is continuously stirred, and shearing and homogenizing to obtain a system containing composite colloidal particles;
and adjusting the pH value of the composite colloidal particle system to 3-5, mixing with grease, shearing and emulsifying to obtain the double Pickering emulsion with stable soybean water-insoluble aggregate-chitosan composite colloidal particles.
2. The process for the preparation of a dual Pickering emulsion as claimed in claim 1, characterized in that: the soybean water-insoluble aggregate is powder obtained by performing freeze drying on a precipitate obtained after centrifuging an enzymolysis liquid after performing enzymolysis on soybean protein isolate for 12-24 hours by Protamex; the enzymatic hydrolysis condition of Protamex is set to be pH5.0-8.0, the temperature is 50 ℃, and the enzyme adding amount per gram of substrate is 000.5-0.01 ml according to the weight of the substrate.
3. The process for the preparation of a dual Pickering emulsion as claimed in claim 1, characterized in that: the mass concentration of the acetic acid aqueous solution is 1-3%.
4. The process for the preparation of a dual Pickering emulsion as claimed in claim 1, characterized in that: the dosage of the chitosan in the solution prepared by the chitosan with the acetic acid aqueous solution is 0.5-1% of the mass of the acetic acid solution;
the amount of the soybean water-insoluble aggregates in the peptide dispersion prepared from the soybean water-insoluble aggregates by adopting ultrapure water is 0.2-0.5% of the mass of water;
the volume ratio of the soybean water-insoluble aggregate solution to the chitosan solution in the continuously stirred soybean water-insoluble aggregate solution is 1: 1-2.5: 1.
5. The process for the preparation of a dual Pickering emulsion as claimed in claim 1, characterized in that: the ultrasonic power is 180W-200W, the intermittent time is 1-3 s, and the total time is 5-10 min.
6. The process for the preparation of a dual Pickering emulsion as claimed in claim 1, characterized in that: the rotating speed of the shearing homogenization is 15000rpm to 20000rpm, and the shearing homogenization time is 1 min to 2 min.
7. The process for the preparation of a dual Pickering emulsion as claimed in claim 1, characterized in that: the oil is corn oil.
8. The process for the preparation of a dual Pickering emulsion as claimed in claim 1, characterized in that: after the pH is adjusted to be 3-5, the volume ratio of the composite colloidal particle system to the grease is 1: 1-3: 1.
9. The process for the preparation of a dual Pickering emulsion as claimed in claim 1, characterized in that: the rotating speed of the shearing emulsification is 8000 rpm-12000 rpm, and the time of the shearing emulsification is 30 s-80 s.
10. A dual Pickering emulsion is characterized in that: which is obtained by the process according to claims 1-9.
CN202110636030.1A 2021-06-08 2021-06-08 Dual Pickering emulsion and preparation method thereof Pending CN113397156A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114424820A (en) * 2021-12-13 2022-05-03 东北农业大学 Preparation method of low-fat perilla oil flavored salad sauce
CN115428934A (en) * 2022-07-21 2022-12-06 中国农业科学院农产品加工研究所 Bicontinuous emulsion applied to food and medicine fields and preparation method thereof
CN116268368A (en) * 2023-04-03 2023-06-23 东北农业大学 Preparation method of curcumin Pickering emulsion loaded by soybean isolate protein-chitosan

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114424820A (en) * 2021-12-13 2022-05-03 东北农业大学 Preparation method of low-fat perilla oil flavored salad sauce
CN115428934A (en) * 2022-07-21 2022-12-06 中国农业科学院农产品加工研究所 Bicontinuous emulsion applied to food and medicine fields and preparation method thereof
CN115428934B (en) * 2022-07-21 2023-10-03 中国农业科学院农产品加工研究所 Bicontinuous emulsion applied to fields of food and medicine and preparation method thereof
CN116268368A (en) * 2023-04-03 2023-06-23 东北农业大学 Preparation method of curcumin Pickering emulsion loaded by soybean isolate protein-chitosan

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