Temperature response type high internal phase emulsion as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of functional emulsion and food processing, and particularly relates to temperature response type high internal phase emulsion and a preparation method and application thereof. The preparation method comprises the following steps: stirring and mixing a starch aqueous solution and an OSA alcoholic solution for reaction to obtain OSA-starch; the preparation method comprises the following steps: dissolving OSA-starch in distilled water to obtain an OSA-starch solution, and then heating and uniformly mixing the OSA-starch solution with a glycyrrhizic acid solution to obtain a water-phase solution; and carrying out high-speed homogenization treatment on the obtained water-phase solution and vegetable oil to obtain the temperature-responsive high-internal-phase emulsion. According to the invention, an aqueous phase solution prepared from OSA-starch and glycyrrhizic acid is introduced into vegetable oil to form the temperature-responsive high-internal-phase emulsion, the prepared temperature-responsive high-internal-phase emulsion has high safety and good stability, rheological properties can be regulated and controlled through temperature, a solution is provided for food system individuation, and the temperature-responsive high-internal-phase emulsion has good application prospects. The method has a good application prospect in the food industry and related fields.

Description

Technical Field

[0001] The present invention belongs to the technical fields of functional emulsions and food processing, and particularly relates to a temperature-responsive high internal phase emulsion, a preparation method thereof, and an application thereof. Background Art

[0002] A high internal phase emulsion is an emulsion system with an oil phase volume fraction higher than 74%. High internal phase emulsions have characteristics such as high stability, controlled release, high loading rate, and semi-solid rheological properties, and have many potential applications in food systems: (1) It can improve food texture and structure food materials, such as preparing oil powders and oil gels, simulating margarine and butter without trans fatty acids, and simulating the preparation of plant-based cholesterol-free mayonnaise, etc.; it can also be used as a loading tool for multi-functional active ingredients or soft substances such as probiotics to achieve the protection, slow release, and even controlled release and targeted release of substances, thereby affecting the digestion and absorption of nutrients; (2) In terms of materials, it can be used to prepare 3D printing food materials and can also be used as a template for energy storage porous materials, foams, and other functional materials; (3) With its high oil phase content, high loading rate, and excellent rheological properties, high internal phase emulsions show great potential in improving dysphagia and enhancing the bioavailability of nutrients.

[0003] Responsive emulsions can be prepared by selecting appropriate responsive emulsifiers. Responsive emulsifiers are a type of emulsifier that can switch between an active state (with appropriate wettability) and an inactive state (losing appropriate wettability) under the action of external stimuli (such as temperature or pH value), and their main mechanism of action is based on non-covalent interactions. These non-covalent interactions are usually reversible, very common in nature, and are easily affected by environmental factors. Common non-covalent interactions include hydrophobic interactions, hydrogen bonds, electrostatic interactions, and van der Waals forces, among which hydrogen bond interactions are the main mechanism driving the interactions between plant active molecules. Temperature-responsive high internal phase emulsions can regulate the rheological properties of emulsions through temperature, providing solutions for the personalization of food systems.

[0004] Patent CN119112713A discloses a high internal phase emulsion and its preparation and application. In this method, coconut oil is used as the oil phase, a composite nanoparticle of double protease hydrolysate and naringenin is used as the emulsifier, and water is used as the water phase to prepare the high internal phase emulsion. However, for this high internal phase emulsion, after being mixed evenly by an ultrasonic cleaner, it is homogenized by a homogenizer at 15,000 rpm. The production conditions are complex, the preparation time is long, and the production cost is high. In addition, the main purpose of this patent is to add a specific oil-water interface stabilizer, naringenin, so that walnut protein can maintain better solubility and emulsifying properties even in an environment with a pH of 5-7, improving the physical stability of the high internal phase emulsion. Moreover, this high internal phase emulsion is applied to daily chemical products to broaden the application of walnut protein in the field of daily chemicals. However, a stable temperature-responsive high internal phase emulsion has not been prepared, and the rheological properties of the temperature-responsive high internal phase emulsion regulated by temperature have not been studied. Patent CN118285479A discloses a method for applying a high internal phase emulsion based on protein-polysaccharide co-stabilization as a fat substitute to emulsified sausage. Pea protein isolate, chitosan, and vegetable oil are used as emulsion raw materials to prepare the high internal phase emulsion, and the high internal phase emulsion is used as a fat substitute to prepare emulsified sausage. This patent only explores the processing suitability of the prepared high internal phase emulsion applied to emulsified sausage products, does not prepare a temperature-responsive high internal phase emulsion, and does not study the correlation between temperature and the rheological properties of the high internal phase emulsion. Patent CN118515885A discloses a high internal phase emulsion jointly stabilized by cellulose nanocrystals, tannic acid, and calcium chloride and its preparation method. Cellulose nanocrystals, tannic acid, and an aqueous calcium chloride solution are mixed, and corn oil is added, and shear homogenization is carried out at 10,000 - 13,000 r / min for 1 - 3 min to obtain the high internal phase emulsion. This patent mainly uses the hydrogen bond of tannic acid and the "bridging" effect of calcium chloride with the negatively charged groups on the cellulose nanocrystals to regulate the interfacial properties and stability of the high internal phase emulsion. A stable temperature-responsive high internal phase emulsion has not been prepared, and the correlation between temperature and the rheological properties of the high internal phase emulsion has not been studied. Summary of the Invention

[0005] In view of the above-mentioned drawbacks and deficiencies existing in the prior art, the primary object of the present invention is to provide a preparation method for a temperature-responsive high internal phase emulsion.

[0006] Another object of the present invention is to provide a temperature-responsive high internal phase emulsion prepared by the above method.

[0007] A further object of the present invention is to provide the application of the above temperature-responsive high internal phase emulsion in food processing.

[0008] The object of the present invention is achieved by the following technical solutions:

[0009] A preparation method for a temperature-responsive high internal phase emulsion includes the following preparation steps:

[0010] (1) Dissolve starch in distilled water to obtain a starch solution;

[0011] (2) Dissolve octenyl succinic anhydride (OSA) in an alcohol solvent to obtain an OSA alcohol solution;

[0012] (3) Stir and mix the obtained starch solution and OSA alcohol solution for reaction. After the reaction is completed, centrifuge, take the solid phase, wash and dry it to obtain octenyl succinic anhydride modified starch (OSA-starch);

[0013] (4) Dissolve the obtained OSA-starch in distilled water to obtain an OSA-starch solution;

[0014] (5) Add glycyrrhizic acid powder to water, heat and stir until dissolved to obtain a glycyrrhizic acid solution;

[0015] (6) Heat, stir and mix the obtained OSA-starch solution and glycyrrhizic acid solution evenly to obtain an aqueous phase solution;

[0016] (7) Subject the obtained aqueous phase solution and vegetable oil to high-speed homogenization treatment to obtain a temperature-responsive high internal phase emulsion.

[0017] Further, the starch described in step (1) is preferably rice starch, and the mass concentration of the obtained starch solution is 20% - 40%.

[0018] Further, the alcohol solvent used in step (2) is ethanol, and the mass concentration of the obtained OSA alcohol solution is 20% - 30%.

[0019] Further, the OSA substitution degree of the OSA-starch described in step (3) is 1% - 3%.

[0020] Further, the pH of the stirring and mixing reaction described in step (3) is 8.5 - 9, the temperature is room temperature, and the time is 3 - 3.5 h.

[0021] Further, the centrifugation speed in step (3) is 2000 - 3000 rpm, and the centrifugation time is 15 - 20 min; the washing is carried out by washing with 95% ethanol and distilled water in sequence.

[0022] Further, the mass concentration of the OSA-starch solution described in step (4) is 4% - 6%.

[0023] Further, the mass concentration of the glycyrrhizic acid solution described in step (5) is 4% - 10%.

[0024] Further, the heating temperature in step (6) is 55 - 65 °C, and the heating time is 5 - 10 min.

[0025] Further, the mass concentration of OSA-starch in the aqueous solution in step (6) is 2% to 3%, and the mass concentration of glycyrrhizic acid is 2% to 5%.

[0026] Further, the vegetable oil in step (7) is preferably corn oil.

[0027] Further, the volume ratio of the aqueous solution to the vegetable oil mixed in step (7) is 20 - 25:75 - 80.

[0028] Further, the homogenization speed in step (7) is 10000 - 13000 rpm, and the homogenization time is 2 - 4 min.

[0029] A temperature-responsive high internal phase emulsion is prepared by the above method.

[0030] More preferably, the temperature-responsive high internal phase emulsion solidifies below 10°C and thins and flows in the range of 47 - 59°C.

[0031] The application of the above temperature-responsive high internal phase emulsion in food processing.

[0032] The principle of the present invention is as follows: Using OSA-starch (octenyl succinic anhydride modified starch) as an emulsifier, a dense coating can be formed on the surface of oil droplets, strengthening the negative charge repulsion force between oil droplets, thereby effectively preventing coalescence; glycyrrhizic acid forms a cross-linked network with OSA-starch by enhancing non-covalent interactions under low-temperature conditions, while the non-covalent interactions weaken at high temperatures. Therefore, the OSA-starch and glycyrrhizic acid complex can not only stabilize the high internal phase emulsion, but also endow the high internal phase emulsion with good temperature responsiveness, and the rheological properties of the emulsion can be changed by regulating the temperature.

[0033] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0034] The present invention uses an aqueous solution prepared from OSA-starch and glycyrrhizic acid, introduces it into vegetable oil to form a temperature-responsive high internal phase emulsion. The preparation method is simple, the raw materials are easy to obtain, the cost is low, the prepared temperature-responsive high internal phase emulsion has high safety and good stability, and the rheological properties can be regulated by temperature, providing a solution for the personalization of food systems, and having good application prospects in the food industry and related fields. Description of the Drawings

[0035] Figure 1 It is a photograph of the appearance morphology of the temperature-responsive high internal phase emulsions obtained in Examples 1 - 18 of the present invention.

[0036] Figure 2 It is a photograph of the appearance inverted flow morphology of the temperature-responsive high internal phase emulsions obtained in Examples 1 - 7 of the present invention at low and high temperatures.

[0037] Figure 3 These are the photographs of the inverted flow morphology of the temperature-responsive high internal phase emulsions obtained in Examples 8 to 18 of the present invention at low temperatures. Detailed implementation manners

[0038] The present invention will be further described in detail below in conjunction with examples and the accompanying drawings, but the implementation manners of the present invention are not limited thereto.

[0039] Example 1

[0040] A preparation method of a temperature-responsive high internal phase emulsion includes the following preparation steps:

[0041] (1) Dissolve rice starch in distilled water to obtain a starch solution with a mass concentration of 30%.

[0042] (2) Dissolve octenyl succinic anhydride (OSA) in an ethanol solvent to obtain an OSA ethanol solution with a mass concentration of 25%.

[0043] (3) Mix the obtained starch solution and OSA ethanol solution at a mass ratio of 8:1, stir and mix them at room temperature and pH = 8.5 for 3.5 h. After the reaction is completed, centrifuge at 3000 rpm for 15 min, take the solid phase, wash it twice with 95% ethanol, wash it once with distilled water, and dry it to obtain octenyl succinic anhydride-modified rice starch (OSA-rice starch) with an OSA substitution degree of 2%.

[0044] (4) Dissolve the obtained OSA-rice starch in distilled water to obtain an OSA-rice starch solution with a mass concentration of 4%.

[0045] (5) Add glycyrrhizic acid powder to water, heat it to 80 °C, and stir until it dissolves to obtain a glycyrrhizic acid solution with a mass concentration of 4%.

[0046] (6) Mix the obtained OSA-rice starch solution and glycyrrhizic acid solution at a mass ratio of 1:1, and then heat it to 60 °C and stir for 5 min to obtain an aqueous solution.

[0047] (7) Mix the obtained aqueous solution and corn oil at a volume ratio of 22:78, and then perform high-speed homogenization treatment at 12000 rpm for 3 min to obtain a temperature-responsive high internal phase emulsion.

[0048] The photographs of the appearance morphology of the obtained temperature-responsive high internal phase emulsion are as Figure 1 shown.

[0049] Example 2

[0050] A preparation method of a temperature-responsive high internal phase emulsion. Compared with Example 1, the mass concentration of the glycyrrhizic acid solution in step (5) is 6%, and the rest is the same. The appearance morphology photos of the obtained temperature-responsive high internal phase emulsion are as Figure 1 shown.

[0051] Example 3

[0052] A preparation method of a temperature-responsive high internal phase emulsion. Compared with Example 1, the mass concentration of the OSA-rice starch solution in step (4) is 6%, and the mass concentration of the glycyrrhizic acid solution in step (5) is 6%, and the rest is the same. The appearance morphology photos of the obtained temperature-responsive high internal phase emulsion are as Figure 1 shown.

[0053] Example 4

[0054] A preparation method of a temperature-responsive high internal phase emulsion. Compared with Example 1, the mass concentration of the glycyrrhizic acid solution in step (5) is 8%, and the rest is the same. The appearance morphology photos of the obtained temperature-responsive high internal phase emulsion are as Figure 1 shown.

[0055] Example 5

[0056] A preparation method of a temperature-responsive high internal phase emulsion. Compared with Example 1, the mass concentration of the OSA-rice starch solution in step (4) is 6%, and the mass concentration of the glycyrrhizic acid solution in step (5) is 8%, and the rest is the same. The appearance morphology photos of the obtained temperature-responsive high internal phase emulsion are as Figure 1 shown.

[0057] Example 6

[0058] A preparation method of a temperature-responsive high internal phase emulsion. Compared with Example 1, the mass concentration of the glycyrrhizic acid solution in step (5) is 10%, and the rest is the same. The appearance morphology photos of the obtained temperature-responsive high internal phase emulsion are as Figure 1 shown.

[0059] Example 7

[0060] A preparation method of a temperature-responsive high internal phase emulsion. Compared with Example 1, the mass concentration of the OSA-rice starch solution in step (4) is 6%, and the mass concentration of the glycyrrhizic acid solution in step (5) is 10%, and the rest is the same. The appearance morphology photos of the obtained temperature-responsive high internal phase emulsion are as Figure 1 shown.

[0061] Example 8

[0062] A preparation method of a temperature-responsive high internal phase emulsion. Compared with Example 1, the rice starch in step (1) is replaced with corn starch, and the rest is the same. The appearance morphology photos of the obtained temperature-responsive high internal phase emulsion are as Figure 1 shown.

[0063] Example 9

[0064] A preparation method of a temperature-responsive high internal phase emulsion. Compared with Example 1, the rice starch in step (1) is replaced with potato starch, and the rest is the same. The appearance morphology photos of the obtained temperature-responsive high internal phase emulsion are as Figure 1 shown.

[0065] Example 10

[0066] A preparation method of a temperature-responsive high internal phase emulsion. Compared with Example 1, the rice starch in step (1) is replaced with mung bean starch, and the rest is the same. The appearance morphology photos of the obtained temperature-responsive high internal phase emulsion are as Figure 1 shown.

[0067] Example 11

[0068] A preparation method of a temperature-responsive high internal phase emulsion. Compared with Example 1, the rice starch in step (1) is replaced with glutinous rice starch, and the rest is the same. The appearance morphology photos of the obtained temperature-responsive high internal phase emulsion are as Figure 1 shown.

[0069] Example 12

[0070] A preparation method of a temperature-responsive high internal phase emulsion. Compared with Example 1, the addition amount of the OSA ethanol solution in step (3) is reduced, and the OSA substitution degree of the obtained OSA-starch is 1%, and the rest is the same. The appearance morphology photos of the obtained temperature-responsive high internal phase emulsion are as Figure 1 shown.

[0071] Example 13

[0072] A preparation method of a temperature-responsive high internal phase emulsion. Compared with Example 1, the addition amount of the OSA ethanol solution in step (3) is increased, and the OSA substitution degree of the obtained OSA-starch is 3%, and the rest is the same. The appearance morphology photos of the obtained temperature-responsive high internal phase emulsion are as Figure 1 shown.

[0073] Example 14

[0074] A preparation method of a temperature-responsive high internal phase emulsion. Compared with Example 1, the mass concentration of the OSA-rice starch solution in step (4) is 8%, and the rest is the same. The appearance morphology photos of the obtained temperature-responsive high internal phase emulsion are as Figure 1 shown.

[0075] Example 15

[0076] A preparation method of a temperature-responsive high internal phase emulsion. Compared with Example 1, in step (4), the mass concentration of the OSA-rice starch solution is 2%, and the rest is the same. The appearance morphology photos of the obtained temperature-responsive high internal phase emulsion are as Figure 1 shown.

[0077] Example 16

[0078] A preparation method of a temperature-responsive high internal phase emulsion. Compared with Example 1, in step (4), the mass concentration of the OSA-rice starch solution is 2%, and in step (5), the mass concentration of the glycyrrhizic acid solution is 6%, and the rest is the same. The appearance morphology photos of the obtained temperature-responsive high internal phase emulsion are as Figure 1 shown.

[0079] Example 17

[0080] A preparation method of a temperature-responsive high internal phase emulsion. Compared with Example 1, in step (4), the mass concentration of the OSA-rice starch solution is 2%, and in step (5), the mass concentration of the glycyrrhizic acid solution is 8%, and the rest is the same. The appearance morphology photos of the obtained temperature-responsive high internal phase emulsion are as Figure 1 shown.

[0081] Example 18

[0082] A preparation method of a temperature-responsive high internal phase emulsion. Compared with Example 1, in step (4), the mass concentration of the OSA-rice starch solution is 2%, and in step (5), the mass concentration of the glycyrrhizic acid solution is 10%, and the rest is the same. The appearance morphology photos of the obtained temperature-responsive high internal phase emulsion are as Figure 1 shown.

[0083] Temperature responsiveness tests were carried out on the samples obtained in the above examples: The samples of Examples 1-18 were refrigerated in a 10°C refrigerator. When the central temperature of the emulsion reached 10°C (low temperature), its inversion situation was observed, and the appearance of the emulsion was photographed and recorded. Then, the samples of Examples 1-7 were heated in a water bath at 47°C to 59°C (high temperature). When the temperature of the water bath reached the set temperature, the samples were put in. When the central temperature of the samples reached the set temperature, their inversion situation was observed, and the appearance of the samples was photographed and recorded.

[0084] The appearance inversion flow morphology photos of the temperature-responsive high internal phase emulsions obtained in Examples 1-7 at low and high temperatures are as Figure 2 shown. The appearance inversion flow morphology photos of the temperature-responsive high internal phase emulsions obtained in Examples 8-18 at low temperature are as Figure 3 shown. The corresponding response results of the temperature-responsive high internal phase emulsions are shown in Table 1 below.

[0085] Table 1 Temperature response test of all samples after treatment in the examples

[0086]

[0087]

[0088] Note: × indicates failed test, √ indicates passed test.

[0089] From the above results, it can be seen that among the starch types and degrees of substitution, the high internal phase emulsion prepared with rice starch having an OSA degree of substitution of 2% has the temperature response characteristics of solidifying at 10°C and flowing at high temperatures of 47°C to 59°C. In the aqueous solution, when the concentration of OSA-rice starch is in the range of 2% to 3% and the concentration of glycyrrhizic acid is in the range of 2% to 5%, good temperature response effects can be achieved through synergistic effects. Further, through Figures 1 to 3 it can be more intuitively observed the temperature response effects of OSA-rice starch and glycyrrhizic acid on the temperature-responsive high internal phase emulsion. It can effectively solidify when the central temperature reaches 10°C and thin and flow when the central temperature reaches 47 to 59°C, and this temperature response characteristic is reversible. In summary, OSA-rice starch and glycyrrhizic acid can prepare a temperature-responsive high internal phase emulsion that solidifies below 10°C and can thin and flow in the range of 47 to 59°C.

[0090] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications made without departing from the spirit and principle of the present invention shall be equivalent replacement methods and are all included in the protection scope of the present invention.

Claims

1. A method for preparing a temperature-responsive high internal phase emulsion, characterized in that: The method comprises the following preparation steps: (1) dissolving starch in distilled water to obtain a starch solution; (2) dissolving OSA in an alcohol solvent to obtain an OSA alcohol solution; (3) stirring and mixing the obtained starch solution with the OSA alcohol solution for reaction, centrifuging after the reaction is completed, washing and drying the solid phase to obtain OSA-starch; (4) dissolving the obtained OSA-starch in distilled water to obtain an OSA-starch solution; (5) adding glycyrrhizic acid powder to water, heating and stirring until dissolved, to obtain a glycyrrhizic acid solution; (6) heating and stirring the obtained OSA-starch solution and the glycyrrhizic acid solution to mix evenly to obtain an aqueous phase solution; (7) The obtained aqueous phase solution and vegetable oil are subjected to high-speed homogenization to obtain a temperature-responsive high internal phase emulsion.

2. The method for preparing a temperature-responsive high internal phase emulsion according to claim 1, characterized in that: The starch in step (1) is rice starch, and the mass concentration of the obtained starch solution is 20% to 40%; the alcohol solvent in step (2) is ethanol, and the mass concentration of the obtained OSA alcohol solution is 20% to 30%.

3. The method for preparing a temperature-responsive high internal phase emulsion according to claim 1, characterized in that: The OSA substitution degree of the OSA-starch in step (3) is 1% to 3%.

4. The method for preparing a temperature-responsive high internal phase emulsion according to claim 1, characterized in that: The pH of the stirring and mixing reaction in step (3) is 8.5-9, the temperature is room temperature, and the time is 3-3.5 hours; the centrifugal speed is 2000-3000 rpm, and the centrifugal time is 15-20 minutes; the washing is carried out using 95% ethanol and distilled water in sequence.

5. The method for preparing a temperature-responsive high internal phase emulsion according to claim 1, characterized in that: The mass concentration of the OSA-starch solution in step (4) is 4% to 6%; the mass concentration of the glycyrrhizic acid solution in step (5) is 4% to 10%.

6. The method for preparing a temperature-responsive high internal phase emulsion according to claim 1, characterized in that: The heating temperature in step (6) is 55-65° C., and the heating time is 5-10 min. The mass concentration of OSA-starch in the aqueous phase solution is 2%-3%, and the mass concentration of glycyrrhizic acid is 2%-5%.

7. The method for preparing a temperature-responsive high internal phase emulsion according to claim 1, characterized in that: The vegetable oil in step (7) is corn oil; the volume ratio of the aqueous solution to the vegetable oil is 20-25:75-80; the homogenization speed is 10000-13000 rpm, and the homogenization time is 2-4 min.

8. A temperature-responsive high internal phase emulsion, characterized in that: It is prepared by the method according to any one of claims 1 to 7.

9. A temperature-responsive high internal phase emulsion according to claim 8, characterized in that: The temperature-responsive high internal phase emulsion solidifies below 10°C and thins and flows within the range of 47 to 59°C.

10. Use of the temperature-responsive high internal phase emulsion according to claim 8 or 9 in food processing.

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