阅读说明：本技术 一种三萜类化合物自乳化油包水型的稳定乳液及其制备方法 (Stable emulsion of self-emulsifying water-in-oil type triterpenoid and preparation method thereof ) 是由 曾朝喜 夏会平 刘渝港 王玉贤 易子翔 颜雨萌 杨木杨 于 2021-04-16 设计创作，主要内容包括：本发明提供了一种三萜类化合物自乳化油包水型的稳定乳液及其制备方法,所述乳液以三萜类化合物作为乳化剂,制备方法包括以下步骤：将三萜类化合物颗粒经连续搅拌在特定温度下分散于液态食用植物油中,制得三萜类化合物分散体系；将步骤1得到的三萜类化合物分散体系按一定比例与水相混合,经特定均质条件处理后得到稳定W/O乳状液,立即密封保存。本发明利用三萜类化合物作为乳化剂或凝胶剂来稳定乳液或高内相乳液凝胶,获得的稳定乳液可替代部分塑性脂肪或人造奶油等,同时还提高了三萜类化合物的生物利用度。(The invention provides a stable emulsion of self-emulsifying water-in-oil type of triterpenoid and a preparation method thereof, wherein the emulsion takes the triterpenoid as an emulsifier, and the preparation method comprises the following steps: continuously stirring the triterpenoid particles, and dispersing in liquid edible vegetable oil at a specific temperature to obtain a triterpenoid dispersion system; and (3) mixing the triterpenoid disperse system obtained in the step (1) with water according to a certain proportion, treating under a specific homogenizing condition to obtain a stable W/O emulsion, and immediately sealing and storing. The invention utilizes the triterpenes as the emulsifier or the gelling agent to stabilize the emulsion or the high internal phase emulsion gel, the obtained stable emulsion can replace part of plastic fat or artificial butter, and the like, and simultaneously, the bioavailability of the triterpenes is also improved.)

1. A preparation method of a triterpenoid self-emulsifying water-in-oil stable emulsion is characterized in that the triterpenoid is used as an emulsifier, and the preparation method comprises the following steps:

step 1, dispersing triterpenoid particles in grease, and continuously stirring to prepare a triterpenoid dispersion system;

step 2, uniformly stirring the triterpenoid dispersion system obtained in the step 1, adding the mixture into a water phase, and homogenizing to obtain a W/O emulsion;

and 3, storing the W/O emulsion prepared in the step 2 after the preparation is finished, namely the triterpenoid self-emulsifying water-in-oil stable emulsion.

2. The preparation method according to claim 1, wherein the triterpenoids include pentacyclic triterpenoids including ursolic acid, oleanolic acid and betulin.

3. The method according to claim 1, wherein the oil or fat is a liquid vegetable oil selected from the group consisting of rapeseed oil, tea oil, soybean oil, olive oil, corn oil, sunflower oil and perilla oil.

4. The preparation method according to claim 1, wherein the mass concentration of the triterpenoid particles in the step 1 is 1-20%.

5. The production method according to claim 1 or 3, wherein the stirring in step 1 is carried out under heating at a constant temperature of 60 ℃ to 120 ℃.

6. The preparation method according to claim 1, wherein the mass concentration of the triterpenoid dispersion in the water phase in the step 2 is 10-90%.

7. The method according to claim 1 or 4, wherein the homogenizing treatment in step 2 comprises high-speed homogenizing, high-pressure homogenizing, ultrasonic homogenizing, and microfluidizing homogenizing.

8. A stable emulsion of a triterpenoid compound in a self-emulsifying water-in-oil type, which is prepared by the preparation method of any one of claims 1 to 7.

9. A low-fat food product, wherein said low-fat food product is prepared from the stable emulsion of claim 8 in place of fat.

10. The low fat food product of claim 9, wherein the low fat food product comprises dairy products, bakery products and meat products prepared with the addition of solid fat.

Technical Field

The invention belongs to the technical field of grease processing, and particularly relates to a triterpenoid self-emulsifying water-in-oil stable emulsion and a preparation method thereof.

Background

Triterpene compounds are a series of natural compounds with various structures and are condensed by triterpene sapogenin and one or more glycosyl groups and/or other chemical groups, are plant-derived secondary metabolites, are widely distributed in the plant kingdom, and are mainly distributed in roots, stems, barks, leaves, seeds and fruits of plants such as Araliaceae, Leguminosae, Hippocastanaceae, Papilionaceae, Campanulaceae, Polygalaceae, Aesculaceae, Primulaceae, Sapindaceae and Theaceae, and a small amount of triterpene compounds are also derived from marine organisms and part of animal bodies. Tetracyclic triterpenes and pentacyclic triterpenes are the two most common classes of triterpenoids. Pentacyclic triterpenoids are a class of triterpenoids formed by connecting 6 isoprene structural units. Pentacyclic triterpenoids are mainly classified into four major types, namely Oleanane (Oleanane) type, Ursane (Ursane) type, Lupane (Lupane) type and Friedelane (Friedelane) type, according to the structural type. Typical representatives of the oleanane type are oleanolic acid (oleanolic acid); the most common representative of the Ursolic acid type is Ursolic acid (Ursolic acid); a representative lupane-type compound is Betulin (Betulin). At present, pentacyclic triterpenoid has been found to have wide biological activity and pharmacological activity as a secondary metabolite of plants, and has important effects such as anticancer, anti-inflammatory, antiallergic, antibacterial, leukemia treating, antivirus, blood sugar reducing, cardiovascular and cerebrovascular disease preventing and treating, and the like. Researches in recent years also show that the triterpenoids have remarkable effects in inhibiting the activity of digestive enzymes, regulating appetite, regulating lipid metabolism, increasing energy consumption, regulating intestinal microbial flora and the like.

Triterpenes can be applied to the industries of food, cosmetics, medicines and the like, but the triterpenes are mostly extremely low in water solubility and poor in bioavailability of oral preparations, and patent inventions such as ursolic acid freeze-dried powder preparations, ursolic acid sustained-release tablets, ursolic acid solid dispersible tablets, ursolic acid lipid microspheres, oleanolic acid solid dispersible tablets, and betulin-containing hair conditioners are reported at present, but the dosage forms are difficult to process, high in cost and not suitable for large-scale production and application, and reports of stable water-in-oil type emulsion or high internal phase emulsion gel of the triterpenes including ursolic acid are not available.

Plastic fat refers to a mixture of fat that appears solid at room temperature, but is actually a solid fat and a liquid oil. In general, plasticity is mainly used for processing foods such as bread and confectionery, and therefore, it is necessary to have good processability so that the food finally has creamy texture, rich flavor and soft and uniform air-filling property. At present, commercial plastic fat products in the market mainly comprise shortening, margarine, butter and other products.

Although some functional improvements can be made to this conventional liquid fat structuring process, the system based on the three-dimensional network structure formed by the crystallization of saturated fat or trans fat is not good for health, because the large intake of trans fatty acids and saturated fatty acid groups is very likely to induce nutritional safety problems such as hyperlipidemia and heart disease.

Therefore, how to improve the bioavailability of triterpenoids including ursolic acid and obtain a novel grease capable of replacing the traditional plastic fat is a problem to be solved.

Disclosure of Invention

The invention aims to provide a triterpenoid self-emulsifying water-in-oil stable emulsion and a preparation method thereof, aiming at solving the problems in the prior art.

The purpose of the invention is realized by the following technical scheme:

a preparation method of a triterpenoid self-emulsifying water-in-oil stable emulsion, which takes the triterpenoid as an emulsifier, comprises the following steps:

step 1, dispersing triterpenoid particles in grease, and continuously stirring to prepare a triterpenoid dispersion system;

step 2, uniformly stirring the triterpenoid dispersion system obtained in the step 1, adding the mixture into a water phase, and homogenizing to obtain a W/O emulsion;

and 3, immediately sealing and storing the W/O emulsion prepared in the step 2 after the preparation is finished, thus obtaining the triterpenoid self-emulsifying water-in-oil stable emulsion.

Further, the triterpenoids include pentacyclic triterpenoids including ursolic acid, betulin and oleanolic acid.

Further, the oil comprises rapeseed oil, tea oil, soybean oil, olive oil, corn oil, sunflower seed oil and perilla oil.

Further, the mass concentration of the triterpenoid particles in the step 1 is 1-20%.

Further, the stirring in the step 1 is carried out under the condition of heating at a constant temperature, and the temperature is 60-120 ℃.

Further, the mass concentration of the triterpenoid dispersion system in the water phase in the step 2 is 10-90%.

Further, the homogenizing treatment in the step 2 comprises high-speed homogenizing, high-pressure homogenizing, ultrasonic homogenizing and micro-jet homogenizing.

Further, the W/O emulsion in the step 3 is sealed and stored at room temperature.

Another aspect of the invention:

a stable emulsion of triterpenoid in water in self-emulsifying oil is prepared by the preparation method.

Another aspect of the invention:

a low-fat food is prepared from the triterpene compound self-emulsifying water-in-oil stable emulsion instead of fat.

Further, the low-fat food comprises dairy products, baked products and meat products prepared by adding solid fat.

Compared with the prior art, the invention has the beneficial effects that:

1. the natural triterpenoid is a substance formed by connecting a plurality of isoprene end to end after hydroxyl is removed. Triterpenoids are common in nature and can be isolated from animals and plants, with one part being in a free state and called triterpene sapogenin, and the other part being in a form of glycoside combined with sugar and called triterpene saponin. The common sapogenins are mostly tetracyclic triterpenes and pentacyclic triterpenes, and consist of 6 isoprene units and contain 30 carbon atoms. The triterpene components are widely distributed in nature. At present, triterpene saponin becomes one of the most active and fastest-developing fields in the research of natural products, and has a plurality of important biological activities and wide pharmacological actions, such as anticancer, anti-inflammatory, antiallergic, leukemia treatment, antivirus, blood sugar reduction, cardiovascular and cerebrovascular disease prevention and treatment and the like; the invention takes the natural triterpenoid as the emulsifier, is applied to the preparation of the water-in-oil type stable emulsion, and the preparation of the water-in-oil type stable emulsion, so that the natural triterpenoid can replace part of plastic fat or artificial butter and the like, and simultaneously, the bioavailability of the triterpenoid is also improved;

2. the ursolic acid, a representative of three pentacyclic triterpenoid compounds, has wide pharmacological effects of hepatitis resistance, tumor resistance, inflammation resistance, virus resistance, blood fat reduction, atherosclerosis resistance, immunity enhancement and the like, and is low in toxicity and few in adverse reaction, the ursolic acid self-emulsifying water-in-oil stable emulsion takes the ursolic acid (UA, UOOLICACID) as an emulsifier or a gel, various oils can be wetted by utilizing the hydrophobicity of UA particles, the interfacial tension of the oil and water is only reduced in a small degree after the UA is added, a Pickering stabilizing mechanism exists in the system, the obtained emulsion is good in storage stability and rheological property, easy to store, and free of aggregation, precipitation and other phenomena in the normal-temperature storage process;

3. W/O type emulsions are more difficult to form than O/W type emulsions, mainly due to poor emulsion stability due to the high mobility of the water droplets and the low conductivity of the oil phase resulting in an emulsion without electrostatic repulsion mechanism. Thus, few emulsifiers are currently used to stabilize W/O emulsions, particularly stabilizers of natural origin;

4. compared with the traditional plastic fat product, the self-emulsifying water-in-oil stable emulsion of the triterpenoid is higher in nutritive value, can replace the traditional water-in-oil emulsion prepared by a hydrogenation method, and opens up a more healthy and convenient new path for the production of hydrogenated oil such as artificial butter; meanwhile, the emulsion is also used as a carrier of the triterpenoid, so that the solubility of the triterpenoid is obviously improved, the bioavailability of the triterpenoid can be improved, the oxidation can be delayed, the stability can be improved, and the triterpenoid can be applied to the preparation of low-fat foods and functional foods;

5. the preparation method of the self-emulsifying water-in-oil stable emulsion of the triterpenoid is simple, efficient, green and environment-friendly, and has wide application prospect.

Drawings

The invention is further illustrated by the following examples in conjunction with the accompanying drawings:

FIG. 1 is a graph showing the particle size results of emulsions prepared under different UA particle mass concentrations as described in example 1;

FIG. 2 is a graph showing particle size results of emulsions prepared according to example 1 under different oil-water ratios;

FIG. 3 is a photograph showing the state of an emulsion prepared under the condition of different UA particles mass concentrations described in example 1;

FIG. 4 is a photograph showing the state of emulsions prepared under different oil-water ratios as described in example 1;

FIG. 5 is a graph showing the rheological results of emulsions prepared according to example 1 under different UA particle mass concentrations and different oil-water ratios;

FIG. 6 is a photograph showing the appearance of emulsion gel prepared under the condition of different mass concentrations of oleanolic acid particles described in example 4;

FIG. 7 is an optical microscope photograph of emulsion gels prepared according to example 4 with different concentrations by mass of oleanolic acid particles;

FIG. 8 is a graph showing the rheological results of emulsion gels prepared under the different oleanolic acid particle mass concentrations described in example 4.

Detailed Description

The present invention is further described with reference to the following examples, which are only for illustrating the present invention and are not intended to limit the scope of the present invention.

Example 1

The embodiment provides a preparation method of ursolic acid self-emulsifying water-in-oil stable emulsion, wherein the emulsion takes ursolic acid as an emulsifier, and the preparation method comprises the following steps:

step 1, dispersing ursolic acid particles in rapeseed oil, and continuously stirring for 20min under the condition of 80 ℃ constant-temperature water bath to prepare an ursolic acid dispersion system;

in order to explore the influence of the UA concentration on the particle size, storage stability, rheological property and the like of formed emulsion, the mass concentrations of the prepared UA particles are respectively 1%, 3% and 5%;

step 2, uniformly stirring the ursolic acid dispersion system obtained in the step 1, adding the ursolic acid dispersion system into a water phase, and homogenizing in a digital display high-speed dispersion machine to obtain a W/O emulsion;

homogenizing at 13600rpm for 2 min;

in order to explore the influence of oil-water ratio on the particle size, storage stability, rheological property and the like of the formed emulsion, the mass concentrations of the ursolic acid dispersoid in water are respectively 60%, 70%, 80% and 90%;

and 3, after the W/O emulsion in the step 2 is prepared, immediately sealing and storing in a 20ml serum bottle, and storing at room temperature to obtain the ursolic acid self-emulsifying water-in-oil stable emulsion.

As shown in fig. 1 and 2, the particle diameters of the emulsions prepared under the conditions of different mass concentrations of UA particles and different oil-water ratios are shown. The results show that: the UA concentration and different oil-water ratios have smaller influence on the emulsion particle size, but the UA concentration is increased or the water phase proportion is increased, so that the emulsion droplet uniformity is improved. And the particle size of the freshly prepared emulsion is maintained at 6-7 mu m. After one week of storage time, the droplets may coalesce to form larger sized droplets and the interfacial area increases.

As shown in fig. 3 and 4, photographs of the state of the emulsion prepared under different UA particle mass concentrations and different oil-water ratios are shown, respectively, indicating the storage stability of the solution under different conditions. The appearance chart shows that the stability of the formed emulsion is poor except for the emulsion formed under the extreme oil-water ratio (9:1) and the extreme UA concentration value (1%), the stability of the rest emulsions is good, and the phenomenon of obvious oil-water separation does not occur.

As shown in fig. 5, the rheological properties of the prepared emulsion are shown under different UA particle mass concentrations and different oil-water ratios. The emulsion as a whole exhibits a fluid morphology (G "> G') which is highly frequency dependent and belongs to a pseudoplastic fluid with shear thinning. By increasing the UA concentration or increasing the proportion of aqueous phase, both the elastic properties (G') and the shear viscosity of the emulsion are increased.

Example 2

The embodiment provides a preparation method of ursolic acid self-emulsifying water-in-oil type stable emulsion gel, wherein the emulsion gel takes ursolic acid as an emulsifier, and the preparation method comprises the following steps:

step 1, dispersing ursolic acid particles in soybean oil, and continuously stirring for 5min under the condition of a constant-temperature oil bath at 120 ℃ to prepare an ursolic acid dispersion system;

in order to explore the influence of the UA concentration on the particle size, storage stability, rheological property and the like of formed emulsion gel, the mass concentrations of the prepared UA particles are 4%, 7% and 10% respectively;

step 2, uniformly stirring the ursolic acid dispersion system obtained in the step 1, adding the ursolic acid dispersion system into a water phase, and performing ultrasonic homogenization treatment to obtain W/O emulsion gel;

the ultrasonic homogenization treatment conditions are that the power is 300W, the ultrasonic is turned on for 3s and turned off for 5s, and the total time is 5 min;

in order to explore the influence of oil-water ratio on the particle size, storage stability, rheological property and the like of the formed emulsion gel, the mass concentrations of the ursolic acid dispersoid in water are respectively 10%, 20%, 30% and 40%;

and 3, after the W/O emulsion gel in the step 2 is prepared, immediately sealing and storing in a 20ml centrifugal tube, and storing at room temperature to obtain the ursolic acid self-emulsifying water-in-oil stable emulsion gel.

Example 3

This example provides a method for preparing a betulin self-emulsifying water-in-oil stable emulsion, which uses betulin as an emulsifier, and includes the following steps:

step 1, dispersing betulin particles in olive oil, and continuously stirring for 20min under the condition of a constant-temperature water bath at 80 ℃ to prepare a betulin dispersion system;

wherein, the mass concentration of the betulin particles in the olive oil is 3 percent;

step 2, uniformly stirring the betulin dispersion system obtained in the step 1, adding the mixture into a water phase, and homogenizing in a digital display high-speed disperser to obtain a W/O emulsion;

homogenizing at 13600rpm for 2 min;

wherein the mass concentration of the betulin dispersion system in water is 70 percent;

and 3, after the W/O emulsion in the step 2 is prepared, immediately sealing and storing in a 20ml serum bottle, and storing at room temperature to obtain the betulin self-emulsifying water-in-oil stable emulsion.

Example 4

This example provides a method for preparing an oleanolic acid self-emulsifying water-in-oil high internal phase emulsion gel using oleanolic acid as an emulsifier, comprising the steps of:

step 1, dispersing oleanolic acid particles in rapeseed oil, and continuously stirring for 20min under the condition of 80 ℃ constant-temperature water bath to prepare an ursolic acid dispersion system;

in order to explore the influence of the concentration of oleanolic acid on the particle size, storage stability, rheological property and the like of the formed emulsion gel, the mass concentration of the prepared oleanolic acid particles is respectively 1%, 3% and 5%;

step 2, uniformly stirring the oleanolic acid dispersion system obtained in the step 1, adding the mixture into a water phase, and homogenizing in a digital display high-speed disperser to obtain a W/O emulsion;

homogenizing at 13600rpm for 15 min;

and 3, after the W/O emulsion in the step 2 is prepared, immediately sealing and storing in a 20ml serum bottle, and storing at room temperature to obtain the oleanolic acid self-emulsifying water-in-oil type high internal phase emulsion gel.

As shown in FIG. 6, photographs of the state of emulsion gel prepared under different mass concentration conditions of oleanolic acid particles are shown. From the appearance texture of the emulsion gel, the texture of the sample became more viscous, more similar to the morphology of solid cream, after increasing the oleanolic acid concentration. Indicating that increasing the amount of emulsifier is required to achieve a better emulsion gel product.

Fig. 7 shows the electron microscope result of the prepared emulsion gel under the condition of different mass concentrations of oleanolic acid particles, and the particle size and storage stability of the emulsion gel are reflected.

Fig. 8 shows the rheological properties of the emulsion gel prepared under different oleanolic acid particle mass concentrations.

Finally, it should be noted that the above only illustrates the technical solution of the present invention, but not limited thereto, and although the present invention has been described in detail with reference to the preferred arrangement, it will be understood by those skilled in the art that modifications or equivalent substitutions may be made thereto without departing from the spirit and scope of the technical solution of the present invention.