Preparation method and application of grape cluster-like prolamin / cellulose nano-composite particles

Abstract

The invention discloses a preparation method and application of grape cluster-like prolamin / cellulose nano-composite particles. The preparation method comprises the following steps: preparing a nano-cellulose aqueous dispersion; preparing an alcohol-soluble protein alcohol-water solution; the preparation method comprises the following steps: preparing grape-cluster-shaped nano composite particles: mixing a nano cellulose aqueous dispersion with an alcohol-soluble protein alcohol-water solution, adding water into the obtained mixture to separate out and deposit alcohol-soluble protein on the surface of nano cellulose, and heating and evaporating to remove alcohol to obtain a grape-cluster-shaped alcohol-soluble protein / cellulose nano composite particle aqueous dispersion. The method is simple, the cost is low, the sustainable development requirement is met, the size and the number of the prolamin nanoparticles on the surface of the nanocellulose have certain controllability, meanwhile, the obtained nano composite particles have good emulsifying capacity, stable Pickering emulsion can be prepared, and the method is suitable for the fields of cosmetics, food, medicine and the like.

Description

Technical Field

[0001] The invention belongs to the technical field of cosmetics, food and medicine, and specifically relates to a preparation method and application of grape cluster alcohol-soluble protein / cellulose nanocomposite particles. Background Art

[0002] Compared with surfactants, emulsions prepared with solid particles, namely Pickering emulsions, have higher stability, better biocompatibility and more controllable rheological behavior, and show great application potential in the fields of cosmetics, food and medicine. In recent years, the preparation of Pickering emulsions with anisotropic solid particles as stabilizers has attracted much attention. Taking one-dimensional particles (high aspect ratio) as an example, their high interfacial adsorption energy and mutual entanglement at the liquid / liquid interface enhance the stability of droplets in the emulsion, which is better than equivalent spherical solid particles. Therefore, stabilizing droplets with anisotropic particles with high aspect ratio is an effective method for preparing Pickering emulsions.

[0003] Compared with synthetic polymer or inorganic particles, polymer particles of natural origin are considered to be ideal particle-type emulsifiers due to their advantages such as renewability, biodegradability, good biocompatibility and low cost. As a typical representative of one-dimensional particles, nanocellulose has attracted great attention from academia and industry as an emulsion stabilizer in recent years. Although nanocellulose can aggregate at the liquid / liquid interface, its overly hydrophilic properties make it difficult to achieve strong interfacial adhesion. Selective surface treatment can improve the hydrophobicity of nanocellulose and its affinity for the oil-water interface, thereby better adsorbing at the oil-water interface and even significantly reducing the interfacial tension between the two phases.

[0004] However, surface chemical or physical modification of nanocellulose often involves the use of harmful chemicals, which affects its natural properties and is not in line with the requirements of sustainable development. Summary of the invention

[0005] The purpose of this section is to summarize some aspects of embodiments of the present invention and briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section and the specification abstract and the invention title of this application to avoid blurring the purpose of this section, the specification abstract and the invention title, and such simplifications or omissions cannot be used to limit the scope of the present invention.

[0006] In view of the above problems and / or the problems existing in the prior art, the present invention is proposed.

[0007] Therefore, the purpose of the present invention is to overcome the deficiencies in the prior art and provide a method for preparing grape cluster prolamin / cellulose nanocomposite particles.

[0008] In order to solve the above technical problems, the present invention provides the following technical solutions: a method for preparing grape cluster prolamin / cellulose nanocomposite particles, comprising:

[0009] preparing a nanocellulose aqueous dispersion;

[0010] preparing an alcohol solution of prolamin;

[0011] Preparation of grape cluster nanocomposite particles: mixing nanocellulose aqueous dispersion with alcohol protein aqueous solution, adding water to the obtained mixture to precipitate the alcohol protein and deposit it on the surface of nanocellulose, heating and evaporating to remove ethanol to obtain grape cluster alcohol protein / cellulose nanocomposite particle aqueous dispersion.

[0012] As a preferred embodiment of the preparation method of the present invention, the alcohol-soluble protein is one or more of zein, wheat alcohol-soluble protein or kaffir protein;

[0013] The nanocellulose is derived from one or more of plants, fungi, algae, arthropod shells and extracellular products of bacteria.

[0014] As a preferred embodiment of the preparation method of the present invention, the alcohol in the alcohol aqueous solution includes one or more of methanol, ethanol, n-butanol and isopropanol.

[0015] As a preferred embodiment of the preparation method of the present invention, the concentration of the alcohol solution of prolamin in g / mL is 0.0025-0.1 g / mL; the volume fraction of alcohol in the alcohol solution is 55-90 vol%.

[0016] As a preferred embodiment of the preparation method of the present invention, the mass ratio of the alcohol-soluble protein to the nanocellulose is 10:1 to 1:2.

[0017] As a preferred embodiment of the preparation method of the present invention, the pH of the nanocellulose aqueous dispersion and the alcohol solution of prolamin after mixing is 3-9.

[0018] Another object of the present invention is to overcome the deficiencies in the prior art and provide an application of grape cluster prolamin / cellulose nanocomposite particles in the preparation of Pickering emulsions, comprising:

[0019] The grape cluster prolamin / cellulose nanocomposite particle aqueous dispersion is mixed with the oil phase and homogenized to obtain a stable Pickering emulsion.

[0020] As a preferred embodiment of the application of the present invention, the amount of the grape cluster alcohol-soluble protein / cellulose nanocomposite particles is 0.25-2.5 wt %;

[0021] The volume fraction of the oil phase is 10 to 80 vol%;

[0022] The homogenization is carried out at 6000-18000 rpm for 1-10 minutes;

[0023] The oil phase includes one or more of alkanes, esters, aromatic hydrocarbons, silicone oils, and vegetable oils.

[0024] As a preferred embodiment of the application of the present invention, the alkane includes isododecane, n-hexane, liquid paraffin, and hexadecane;

[0025] The esters include caprylic / capric triglyceride and ethylhexyl palmitate; the aromatic hydrocarbons include toluene and styrene;

[0026] The silicone oil includes decamethylcyclopentasiloxane and polydimethylsiloxane;

[0027] The vegetable oils include soybean oil and sunflower oil.

[0028] Another object of the present invention is to overcome the deficiencies in the prior art and provide a grape cluster prolamin / cellulose nanocomposite particle for use in cosmetics, food and medicine.

[0029] Beneficial effects of the present invention:

[0030] (1) The grape cluster alcohol-soluble protein / cellulose nanocomposite particles prepared by the present invention use renewable plant components as the matrix raw materials, which are not only abundant and renewable in source but also low in cost; the alcohol-soluble protein nanoparticles and the nanocellulose are bound by non-covalent interactions, and the two do not need any chemical treatment, so the preparation process is simple, meets the requirements of green chemistry, and is easy to industrialize.

[0031] (2) The grape cluster alcohol-soluble protein / cellulose nanocomposite particles prepared by the present invention have the advantages of good biocompatibility and biodegradability, and can be uniformly adsorbed on the oil-water interface, reducing the interfacial tension between oil and water, and forming a long-term stable Pickering emulsion. Interestingly, using alcohol-soluble protein nanoparticles or nanocellulose alone cannot prepare a long-term stable emulsion. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following briefly introduces the drawings required for describing the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without creative labor. Among them:

[0033] Figure 1are scanning electron microscope photographs of the embodiments of the present invention, wherein, (left) is a scanning electron microscope photograph of the alcohol-soluble zein nanoparticles prepared in step B1 of comparative example 1, (middle) is a scanning electron microscope photograph of the alcohol-soluble zein / cellulose nanocomposite particles prepared in step b1 of embodiment 1 of the present invention, and (right) is a scanning electron microscope photograph of the nanocellulose prepared in A2 of comparative example 2 of the present invention.

[0034] Figure 2 : are appearance pictures of the emulsions prepared in the examples of the present invention, wherein (left) is the appearance picture of the emulsion prepared by alcohol-soluble zein nanoparticles in step C1 of comparative example 1, (middle) is the appearance picture of the emulsion prepared by alcohol-soluble zein / cellulose nanocomposite particles in step c1 of example 1, and (right) is the appearance picture of the emulsion prepared by nanocellulose in step B2 of comparative example 2.

[0035] Figure 3 This is a scanning electron microscope photograph of the alcohol-soluble zein / cellulose nanocomposite particles prepared in step b2 of Example 2 of the present invention.

[0036] Figure 4 This is a microscope photograph of the alcohol-soluble zein / cellulose nanocomposite particle stabilized emulsion in step c2 of Example 2 of the present invention.

[0037] Figure 5 This is a scanning electron microscope photograph of the alcohol-soluble zein / cellulose nanocomposite particles prepared in step b3 of Example 3 of the present invention.

[0038] Figure 6 This is a microscope photograph of the alcohol-soluble zein / cellulose nanocomposite particle stabilized emulsion in step c3 of Example 3 of the present invention.

[0039] Figure 7 This is a scanning electron microscope photograph of the product prepared in step B3 of comparative example 3 of the present invention. DETAILED DESCRIPTION

[0040] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, the specific implementation methods of the present invention are described in detail below in conjunction with the embodiments of the specification.

[0041] In the following description, many specific details are set forth to facilitate a full understanding of the present invention, but the present invention may also be implemented in other ways different from those described herein, and those skilled in the art may make similar generalizations without violating the connotation of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed below.

[0042] Secondly, the term "one embodiment" or "embodiment" as used herein refers to a specific feature, structure or characteristic that may be included in at least one implementation of the present invention. The term "in one embodiment" that appears in different places in this specification does not refer to the same embodiment, nor is it a separate or selective embodiment that is mutually exclusive with other embodiments. The experimental materials in the present invention are all common commercially available products.

[0043] Example 1

[0044] Step a1: dispersing 10 g of nanocellulose into 115 g of deionized water to obtain an 8 wt % nanocellulose aqueous dispersion;

[0045] Dissolve 1 g of alcohol-soluble zein in 40 mL of 60 vol% ethanol aqueous solution to obtain a 2.5 wt% alcohol-soluble zein solution;

[0046] The alcohol-soluble zein solution was mixed with a portion of the nanocellulose aqueous dispersion, wherein the mass ratio of the alcohol-soluble zein to the nanocellulose was 5:1, and the pH value of the mixture was adjusted to 3 using 1M hydrochloric acid.

[0047] Step b1: 120 mL of deionized water was added to the mixture obtained in step a1, and after stirring for 1.5 h, ethanol was evaporated in a 40° C. water bath to obtain an aqueous dispersion of grape cluster alcohol-soluble zein / cellulose nanocomposite particles.

[0048] Step c1: dilute the grape cluster alcohol-soluble zein / cellulose nanocomposite particle aqueous dispersion obtained in step b1 to 1 wt %, take 3 mL of the aqueous dispersion and mix it with 3 mL of decamethylcyclopentasiloxane (D5), and homogenize it at 17000 rpm for 2 min to obtain a grape cluster alcohol-soluble zein / cellulose nanocomposite particle stabilized Pickering emulsion.

[0049] Figure 1 (Middle) is a scanning electron microscope photograph of the grape cluster alcohol-soluble zein / cellulose nanocomposite particles prepared in step b1. Figure 2 (Middle) is a photograph of the appearance of the Pickering emulsion prepared in step c1 after being stored for 1 month.

[0050] Example 2

[0051] Step a2: dispersing 10 g of nanocellulose into 115 g of deionized water to obtain an 8 wt % nanocellulose aqueous dispersion;

[0052] Dissolve 1 g of alcohol-soluble zein in 40 mL of 60 vol% ethanol aqueous solution to obtain a 2.5 wt% alcohol-soluble zein solution;

[0053] The alcohol-soluble zein solution was mixed with a portion of the nanocellulose aqueous dispersion, wherein the mass ratio of the alcohol-soluble zein to the nanocellulose was 1:1, and the pH value of the mixture was adjusted to 3 using 1M hydrochloric acid.

[0054] Step b2: 120 mL of deionized water was added to the mixture obtained in step a1, and after stirring for 1.5 h, ethanol was evaporated in a 40° C. water bath to obtain an aqueous dispersion of grape cluster alcohol-soluble zein / cellulose nanocomposite particles.

[0055] Step c2: dilute the grape cluster alcohol-soluble zein / cellulose nanocomposite particle aqueous dispersion obtained in step b1 to 1 wt %, take 3 mL of the aqueous dispersion and mix it with 3 mL of decamethylcyclopentasiloxane (D5), and homogenize it at 17000 rpm for 2 min to obtain a grape cluster alcohol-soluble zein / cellulose nanocomposite particle stabilized Pickering emulsion.

[0056] Figure 3 is a scanning electron microscope photograph of the grape cluster alcohol-soluble zein / cellulose nanocomposite particles prepared in step b2;

[0057] Figure 4 is the Pickering emulsion prepared in step c2.

[0058] Example 3

[0059] Step a3: Disperse 10g of nanocellulose into 115g of deionized water to obtain an 8wt% nanocellulose aqueous dispersion; dissolve 1g of alcohol-soluble zein in 40mL of 90vol% ethanol aqueous solution to obtain a 2.5wt% alcohol-soluble zein solution; mix the above alcohol-soluble zein solution with the nanocellulose aqueous dispersion, wherein the mass ratio of alcohol-soluble zein to part of the nanocellulose is 5:1, and adjust the pH value of the mixture to 3 using 1M hydrochloric acid.

[0060] Step b3: 120 mL of deionized water was added to the mixture obtained in step a1, and after stirring for 1.5 h, ethanol was evaporated in a 40° C. water bath to obtain an aqueous dispersion of grape cluster alcohol-soluble zein / cellulose nanocomposite particles.

[0061] Step c3: dilute the grape cluster alcohol-soluble zein / cellulose nanocomposite particle aqueous dispersion obtained in step b1 to 1 wt %, take 3 mL of the aqueous dispersion and mix it with 3 mL of decamethylcyclopentasiloxane (D5), and homogenize it at 17000 rpm for 2 min to obtain a Pickering emulsion stabilized by grape cluster alcohol-soluble zein / cellulose nanocomposite particles.

[0062] Figure 5This is a scanning electron microscope photograph of the grape cluster alcohol-soluble zein / cellulose nanocomposite particles prepared in step b3.

[0063] Figure 6 is the Pickering emulsion prepared in step c3.

[0064] Comparative Example 1

[0065] Step A1: Add 1.5 g alcohol-soluble protein into 40 mL of 75 vol% ethanol aqueous solution, stir for 0.5 h to fully dissolve it, and obtain alcohol-soluble corn protein ethanol aqueous solution.

[0066] Step B1: Add 120 mL of deionized water to the alcohol-soluble protein ethanol aqueous solution obtained in step A1, and then evaporate and remove ethanol in a 40° C. water bath to obtain an alcohol-soluble zein nanoparticle dispersion.

[0067] Step C1: dilute the alcohol-soluble zein nanoparticle dispersion obtained in step B1 to 1 wt %, take 3 mL of the aqueous dispersion and mix it with 3 mL of decamethylcyclopentasiloxane (D5), and homogenize it at 17000 rpm for 2 min to obtain a Pickering emulsion stabilized by alcohol-soluble zein nanoparticles.

[0068] Figure 1 (Left) is the alcohol-soluble zein nanoparticles prepared in step B1, Figure 2 (Left) is a photograph of the Pickering emulsion prepared in step C1 after being left for 7 days.

[0069] Comparative Example 2

[0070] Step A2: dilute the nanocellulose aqueous dispersion prepared in Comparative Example 1 to 1 wt %

[0071] Step B2: 3 mL of the aqueous nanocellulose dispersion obtained in A2 was mixed with 3 mL of decamethylcyclopentasiloxane (D5), and homogenized at 17,000 rpm for 2 min to obtain a Pickering emulsion.

[0072] Figure 1 (Right) is a scanning electron microscope photo of the nanocellulose obtained in step A2. Figure 2 (Right) is a photograph of the Pickering emulsion prepared in step B2, which cannot form an emulsion.

[0073] Comparative Example 3

[0074] Step A3: dispersing 10 g of nanocellulose into 115 g of deionized water to obtain an 8 wt % nanocellulose aqueous dispersion;

[0075] Dissolve 1 g of alcohol-soluble zein in 40 mL of 60 vol% ethanol aqueous solution to obtain a 2.5 wt% alcohol-soluble zein solution;

[0076] The alcohol-soluble zein solution was mixed with a portion of the nanocellulose aqueous dispersion, wherein the mass ratio of the alcohol-soluble zein to the nanocellulose was 5:1, and the pH value of the mixture was adjusted to 6 using 1M hydrochloric acid.

[0077] Step B3: 120 mL of deionized water was added to the mixture obtained in step a1, and after stirring for 1.5 h, ethanol was evaporated in a 40° C. water bath to obtain an aqueous dispersion of the product.

[0078] Figure 7 This is a scanning electron microscope image of the product prepared in step B3.

[0079] In summary, the present invention prepares typical grape cluster-shaped prolamin / nanocellulose nanocomposite particles, and the structure has excellent emulsifying ability.

[0080] from Figure 1 It can be seen that Example 1 obviously has a grape cluster structure compared with Comparative Examples 1 and 2, and this structure plays a unique role in stabilizing the oil-water interface.

[0081] Figure 2 The appearance of the emulsions prepared in Example 1 and Comparative Examples 1 and 2 is shown. Alcohol-soluble zein nanoparticles and nanocellulose alone cannot stabilize the oil-water interface for a long time, while alcohol-soluble zein / cellulose nanocomposite particles can prepare relatively stable emulsions.

[0082] Figure 3 , Figure 5 and Figure 7 It was demonstrated that alcohol-soluble zein / cellulose nanocomposite particles with different morphologies can be obtained by regulating factors such as the mass ratio of alcohol-soluble zein and nanocellulose, pH conditions and ethanol volume fraction.

[0083] Figure 4 and Figure 6 The purpose of regulating the microstructure of the emulsion can be explained by changing the morphology of alcohol-soluble zein / cellulose nanocomposite particles.

[0084] Therefore, the present invention proposes a simple and efficient method, using anti-solvent technology, using two food-grade raw materials, prolamin and nanocellulose, to prepare grape cluster-shaped prolamin / cellulose nanocomposite particles with good interfacial activity and structural stability. The method does not require complex operations and harsh reaction conditions, achieves efficient, low-cost, and controllable preparation, and also ensures the biocompatibility and biodegradability of the product, showing broad application prospects in the fields of food, medicine, and cosmetics.

[0085] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present invention can be modified or replaced by equivalents without departing from the spirit and scope of the technical solutions of the present invention, which should all be included in the scope of the present invention.

Claims

1. A method for preparing grape cluster prolamin / cellulose nanocomposite particles, characterized in that: include, preparing a nanocellulose aqueous dispersion; preparing an alcohol solution of prolamin; Preparation of grape cluster nanocomposite particles: mixing a nanocellulose aqueous dispersion with an alcohol-soluble protein solution, adding water to the resulting mixture to precipitate the alcohol-soluble protein and deposit it on the surface of the nanocellulose, and heating and evaporating to remove ethanol to obtain a grape cluster alcohol-soluble protein / cellulose nanocomposite particle aqueous dispersion.

2. The preparation method according to claim 1, characterized in that: The alcohol-soluble protein is one or more of zein, wheat alcohol-soluble protein or kaorinin; The nanocellulose is derived from one or more of plants, fungi, algae, arthropod shells and extracellular products of bacteria.

3. The preparation method according to claim 1 or 2, characterized in that: The alcohol in the alcohol aqueous solution includes one or more of methanol, ethanol, n-butanol and isopropanol.

4. The preparation method according to claim 3, characterized in that: The alcohol solution of prolamin has a concentration of 0.0025 to 0.1 g / mL in g / mL; the volume fraction of alcohol in the alcohol solution is 55 to 90 vol%.

5. The preparation method according to claim 4, characterized in that: The mass ratio of the alcohol-soluble protein to the nanocellulose is 10:1 to 1:

2.

6. The preparation method according to any one of claims 1, 2, 4 or 5, characterized in that: After the nanocellulose aqueous dispersion and the alcohol solution of prolamin are mixed, the pH value thereof is 3-9.

7. Use of grape cluster prolamin / cellulose nanocomposite particles prepared by the preparation method according to any one of claims 1 to 6 in the preparation of Pickering emulsion, characterized in that: include, The grape cluster prolamin / cellulose nanocomposite particle aqueous dispersion is mixed with the oil phase and homogenized to obtain a stable Pickering emulsion.

8. The use according to claim 7, characterized in that: The grape cluster prolamin / cellulose nanocomposite particles are used in an amount of 0.25 to 2.5 wt %; The volume fraction of the oil phase is 10 to 80 vol%; The homogenization is carried out at 6000-18000 rpm for 1-10 minutes; The oil phase includes one or more of alkanes, esters, aromatic hydrocarbons, silicone oils, and vegetable oils.

9. The use according to claim 8, characterized in that: The alkanes include isododecane, n-hexane, liquid paraffin, and hexadecane; The esters include caprylic / capric triglyceride and ethylhexyl palmitate; the aromatic hydrocarbons include toluene and styrene; The silicone oil includes decamethylcyclopentasiloxane and polydimethylsiloxane; The vegetable oils include soybean oil and sunflower oil.

10. Use of grape cluster prolamin / cellulose nanocomposite particles prepared by the preparation method according to any one of claims 1 to 6 in cosmetics, food and medicine.

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