CN116650344A - Bicontinuous Pickering emulsion stabilized based on rough nano particles and preparation method and application thereof - Google Patents

Bicontinuous Pickering emulsion stabilized based on rough nano particles and preparation method and application thereof Download PDF

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CN116650344A
CN116650344A CN202310644102.6A CN202310644102A CN116650344A CN 116650344 A CN116650344 A CN 116650344A CN 202310644102 A CN202310644102 A CN 202310644102A CN 116650344 A CN116650344 A CN 116650344A
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bicontinuous
continuous
pickering emulsion
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emulsion composition
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李涛
陈文斌
韦智友
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Wenzhou Research Institute Of Guoke Wenzhou Institute Of Biomaterials And Engineering
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    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • A61K8/03Liquid compositions with two or more distinct layers
    • AHUMAN NECESSITIES
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    • A61K47/06Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite
    • A61K47/08Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite containing oxygen, e.g. ethers, acetals, ketones, quinones, aldehydes, peroxides
    • A61K47/10Alcohols; Phenols; Salts thereof, e.g. glycerol; Polyethylene glycols [PEG]; Poloxamers; PEG/POE alkyl ethers
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Abstract

The invention belongs to the technical field of bicontinuous emulsion, and particularly relates to a bicontinuous Pickering emulsion based on coarse nanoparticle stabilization, and a preparation method and application thereof. The invention provides a bicontinuous Pickering emulsion combinationA material comprising a continuous aqueous phase, a continuous oil phase, and a stabilizer; the stabilizer forms a protective layer at the interface of the continuous water phase and the continuous oil phase; the continuous water phase is an alcohol-water mixture, and the continuous oil phase is silicone oil; the stabilizer is silica nanoparticles; roughness R of the silica nanoparticle surface g And more than or equal to 0.75. The invention adopts the surface roughness R g The silica nano-particles with the surface roughness can be attracted to the continuous water phase-continuous oil phase interface to form a compact nano-particle protective film layer by being used as a stabilizer of the bicontinuous continuous water phase and the continuous oil phase, so that the bicontinuous Pickering emulsion composition with high system stability is formed, and the bicontinuous Pickering emulsion composition can be widely applied to the fields of medicines and cosmetics.

Description

Bicontinuous Pickering emulsion stabilized based on rough nano particles and preparation method and application thereof
Technical Field
The invention belongs to the technical field of bicontinuous emulsion, and particularly relates to a bicontinuous Pickering emulsion based on coarse nanoparticle stabilization, and a preparation method and application thereof.
Background
Bicontinuous emulsions (Bi-continuous emulsion) are emulsions in which both the continuous aqueous phase and the continuous oil phase are continuous phases in the same emulsion system, which is difficult to achieve in a fluid, and to maintain the two phase liquids in a continuous state at the same time, they are extremely high in requirements for compatibility, density, polarity, etc., and require stabilizers to firmly stabilize the liquid-liquid interface.
The two non-interfering continuous phases comprising continuous water phase and continuous oil phase in the bicontinuous emulsion can encapsulate functional substances, such as bioactive substances with reduced pharmacological activity due to interaction, if simultaneous administration is needed, the two non-interfering continuous phases can be respectively encapsulated in the two continuous phases of the bicontinuous emulsion, thereby achieving the aim of drug combination and avoiding mutual interference. The composition of the continuous water phase or the continuous oil phase is changed, so that the product can be applied to the fields of foods, medicines, cosmetics and the like, and the daily life of people is served.
The system capable of preparing bicontinuous emulsion at present generally uses a surfactant as an interface stabilizer, but emulsion stability is poor, and the system is difficult to apply to industry.
Disclosure of Invention
The invention aims to provide a bicontinuous Pickering emulsion based on coarse nano-particle stability, a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a bicontinuous Pickering emulsion composition, which comprises a continuous water phase, a continuous oil phase and a stabilizer; the stabilizer forms a protective layer at the interface of the continuous water phase and the continuous oil phase; the continuous water phase is an alcohol-water mixture, and the continuous oil phase is silicone oil; the stabilizer is silica nanoparticles; surface roughness R of the silica nanoparticles g ≥0.75。
Preferably, the surface roughness R of the silica nanoparticles g 0.75 to 3.24.
Preferably, the alcohol-water mixture is a mixture of ethanol and water;
the volume ratio of the ethanol to the water is (0.4-0.6): 1.
Preferably, the viscosity of the silicone oil is 10-100 mPas at 25 ℃.
Preferably, the volume of the silicone oil accounts for 70-75% of the total volume of the alcohol-water mixture and the silicone oil.
Preferably, the mass ratio of the alcohol-water mixture to the silicon dioxide nano particles is more than or equal to 50:1.
Preferably, the particle size of the silica nanoparticles is 300-500 nm.
The invention provides a preparation method of the bicontinuous Pickering emulsion composition, which comprises the following steps:
and mixing and emulsifying the continuous water phase, the continuous oil phase and the stabilizer to obtain the bicontinuous Pickering emulsion composition.
Preferably, the mixing is vortex oscillating mixing;
the emulsification is performed in a cell disruption instrument, and the power of the cell disruption instrument during emulsification is 40-50W.
The invention provides the bicontinuous Pickering emulsion composition according to the technical scheme or the application of the bicontinuous Pickering emulsion composition prepared by the preparation method according to the technical scheme in preparation of cosmetics or medicines.
The invention provides a bicontinuous leather based on coarse nano-particle stabilizationA gram (Pickering) emulsion comprising a continuous aqueous phase, a continuous oil phase and a stabilizer; the stabilizer forms a protective layer at the interface of the continuous water phase and the continuous oil phase; the continuous water phase is an alcohol-water mixture, and the continuous oil phase is silicone oil; the stabilizer is silica nanoparticles; roughness R of the silica nanoparticle surface g And more than or equal to 0.75. The invention adopts the surface roughness R g The silica nano-particles with the surface roughness can be attracted to the continuous water phase-continuous oil phase interface to form a compact nanoparticle protection film layer through the interaction of interfacial tension of silicone oil and alcohol-water mixture and the roughness of the surface of the silica nano-particles, so that the bicontinuous Pickering emulsion composition with high stability of the continuous water phase and continuous oil phase is formed, and the two continuous phases can be used for transporting and storing different kinds of functional substances, can realize multiple functions in the same product, and can be widely applied to the fields of preparation of medicines and cosmetics.
Further, in the invention, the volume ratio of the ethanol to the water is (0.4-0.6): 1, and the volume of the silicone oil accounts for 70-75% of the total volume of the ethanol-water mixture and the silicone oil. According to the invention, the volumes of ethanol, water and silicone oil are controlled within the above range, so that the bicontinuous Pickering emulsion with stable structure can be obtained, and the silicone oil has high volume fraction, belongs to bicontinuous high internal phase Pickering emulsion, improves the mass ratio of transporting and storing different kinds of functional substances, and improves the application applicability of the bicontinuous Pickering emulsion.
Further, in the present invention, the alcohol-water mixture is a mixture of ethanol and water; the volume ratio of the ethanol to the water is (0.4-0.6): 1, and the viscosity of the silicone oil at 25 ℃ is 10-100 mPas. The invention uses the polarity and viscosity of silicone oil to match the surface tension of ethanol-water mixture with volume ratio of (0.4-0.6): 1, and the roughness R of the surface g And the bicontinuous high internal phase Pickering emulsion is realized under the action of the silica nano particles of more than or equal to 0.75.
The invention provides a preparation method of the bicontinuous Pickering emulsion composition, which comprises the following steps: and mixing and emulsifying the continuous water phase, the continuous oil phase and the stabilizer to obtain the bicontinuous Pickering emulsion composition. The preparation method provided by the invention has the advantages of wide sources of raw materials and low cost, and is suitable for industrial production.
Drawings
FIG. 1 is a photograph taken by a laser confocal microscope of a bicontinuous Pickering emulsion composition prepared in example 1 of the present invention;
FIG. 2 is a TEM image of surface roughened silica nanoparticles prepared in example 1 of the present invention;
FIG. 3 is a TEM image of surface roughened silica nanoparticles prepared in example 2 of the present invention;
FIG. 4 is a TEM image of surface roughened silica nanoparticles prepared in example 3 of the present invention;
fig. 5 is a TEM image of the surface roughened silica nanoparticle prepared in comparative example 1 of the present invention.
Detailed Description
The invention provides a bicontinuous Pickering emulsion composition, which comprises a continuous water phase, a continuous oil phase and a stabilizer; the stabilizer forms a protective layer at the interface of the continuous water phase and the continuous oil phase; the continuous water phase is an alcohol-water mixture, and the continuous oil phase is silicone oil; the stabilizer is silica nanoparticles; surface roughness R of the silica nanoparticles g ≥0.75。
In the present invention, all preparation materials/components are commercially available products well known to those skilled in the art unless specified otherwise.
The bicontinuous pickering emulsion composition provided by the present invention includes a continuous aqueous phase.
In the present invention, the continuous aqueous phase is an alcohol-water mixture. The alcohol-water mixture is preferably a mixture of ethanol and water.
In the present invention, the volume ratio of ethanol to water is preferably (0.4 to 0.6): 1, more preferably (0.45 to 0.55): 1.
The bicontinuous pickering emulsion composition provided by the invention comprises a continuous oil phase.
In the present invention, the continuous oil phase is silicone oil. The silicone oil preferably has a viscosity of 10 to 100 mPas, more preferably 10 to 80 mPas, and even more preferably 10 to 50 mPas at 25 ℃.
In the present invention, the percentage of the volume of the silicone oil to the total volume of the alcohol-water mixture and the silicone oil is preferably 70 to 75%, more preferably 72 to 74%.
The bicontinuous pickering emulsion composition provided by the invention comprises a stabilizer, wherein the stabilizer forms a protective layer at the interface of the continuous water phase and the continuous oil phase.
In the present invention, the stabilizer is silica nanoparticles; surface roughness R of the silica nanoparticles g ≥0.75。
In the present invention, the surface roughness R of the silica nanoparticles g Preferably from 0.75 to 3.24, particularly preferably from 0.75, 1.756 or 3.24.
In the present invention, the particle diameter of the silica nanoparticle is preferably 300 to 500nm, more preferably 350 to 450nm.
In the present invention, the preparation method of the silica nanoparticle comprises the steps of:
and (3) rapidly adding the solution B into the solution A under the high-speed stirring condition that the stirring speed is 500-1500 rpm, stirring at a high speed for 1-5 min, stirring at a low speed for 2-24 h, reacting at a stirring speed of 100-500 rpm, and finally centrifuging to obtain the precipitate, namely the coarse silicon spheres.
In the invention, the solution B comprises the following components in parts by volume:
8 parts of ethanol; 0.01 to 0.1 part of mercaptopropyl trimethoxysilane (MPTMS); 0.1 to 2 parts of tetraethyl silicate (TEOS).
In the invention, the solution A comprises the following components in parts by volume:
4-10 parts of ethanol; 5-10 parts of water; 0.9 to 1.8 portions of ammonia water.
In the present invention, the mass percentage of the ammonia water is preferably 28%.
In the present invention, the MPTMS is preferably premixed in the solution B as described above, or added separately after the solution A and the solution B (without MPTMS) are mixed.
In the invention, when MPTMS is added separately after mixing the solution A and the solution B (without MPTMS), the adding time of MPTMS is 1-9 min after mixing the solution B and the solution A.
In the present invention, the mass ratio of the alcohol-water mixture to the silica nanoparticles is preferably not less than 50:1, more preferably (52 to 60): 1, and most preferably 56:1.
The invention preferably takes ethanol and water as continuous water phase, and the mass ratio of the ethanol to the water is regulated to be (0.2-0.5): 1; the silicone oil is used as a continuous oil phase, and the viscosity of the silicone oil is preferably more than or equal to 50 mPas (25 ℃); meanwhile, the volume ratio of the continuous water phase to the continuous oil phase is regulated and controlled to be preferably 1 (0.7-0.75); the invention utilizes the polarity and viscosity of silicone oil and the surface tension phase balance of ethanol water mixture, thereby leading the continuous oil phase and the continuous water phase to be in continuous state at the same time; meanwhile, the interfacial tension of the silicone oil and alcohol-water mixture can attract the surface roughness R g And (3) forming a compact nanoparticle protective film layer on the water-oil interface of the silica nanoparticles which is more than or equal to 0.75, so that the stability of the continuous oil phase and the continuous water phase is improved, and the bicontinuous high internal phase Pickering emulsion is obtained. In the invention, two continuous phases can be used for transporting and storing different functional substances, and can realize multiple functions in the same product, thereby greatly expanding the application prospect of the high internal phase emulsion in the fields of medicines, cosmetics and other industries.
The invention provides a preparation method of the bicontinuous Pickering emulsion composition, which comprises the following steps:
and mixing and emulsifying the continuous water phase, the continuous oil phase and the stabilizer to obtain the bicontinuous Pickering emulsion composition.
In the present invention, the order of mixing is preferably: mixing the stabilizer with alcohol in the alcohol-water mixture, mixing the obtained mixed solution with water in the alcohol-water mixture, and finally mixing the mixed solution with silicone oil.
In the present invention, the mixing is preferably vortex-oscillating mixing, and the mixing is preferably performed in a vortex-oscillator.
In the present invention, the mixing preferably includes the following sequence: after mixing the continuous aqueous phase and the stabilizer, the continuous oil phase is added.
In the present invention, the emulsification is preferably performed in a cell disrupter, and the power of the cell disrupter at the time of emulsification is preferably 40 to 50W, more preferably 40W. In the invention, the cell disruption instrument preferably adopts an indirect working mode, and particularly preferably circularly starts up for 1s and shuts down for 1s. In the invention, the total starting-up working time of the cell disruptor is 30s.
The invention provides the application of the bicontinuous Pickering emulsion composition or the bicontinuous Pickering emulsion composition prepared by the preparation method in cosmetics or medicines.
The technical solutions provided by the present invention are described in detail below with reference to the drawings and examples for further illustrating the present invention, but they should not be construed as limiting the scope of the present invention.
Example 1
Solution B:80mL of ethanol was mixed with 10mL of TEOS;
solution a:50mL of water was mixed with 40mL of ethanol, 18mL of aqueous ammonia (28 wt%).
Solution A is added with solution B at 1000rpm, after reaction for 1min and 30s, 0.4mL MPTMS is added, after reaction for 2min, the rotation speed is adjusted to 300rpm, and after reaction for 8 hours, the product is obtained, and the roughness of the product is 0.75. The prepared silicon sphere is shown in TEM graph in figure 2, and the surface roughness of the silicon dioxide nanometer particle can be obtained g 0.75.
With 1.0 g of water, 0.4g of ethanol (0.025 g of coarse silica nanoparticles were added to 0.4g of ethanol), and then 4.0 g of silicone oil (viscosity at 25 ℃ C.: 50 mPa.s) were added, followed by mixing with a vortex oscillator and then by action of a cell breaker with 40W power (on/off 1s/1 s) for 30s, to obtain a bicontinuous Pickering emulsion composition.
As shown in copolymer Jiao Tu of fig. 1, in the bicontinuous pickering emulsion composition prepared in this example, the black region (the region indicated by the white square) is an oil phase, composed of silicone oil, the green region (the region indicated by the red square) is an aqueous phase, composed of ethanol and water labeled with Fluorescein Isothiocyanate (FITC).
Example 2
Solution B:80mL of ethanol was mixed with 10mL of TEOS;
solution a:50mL of water was mixed with 40mL of ethanol, 18mL of aqueous ammonia (28 wt%).
Adding solution B into solution A at 1000rpm, reacting for 1min, adding 0.4mL MPTMS, reacting for 2min, adjusting the rotation speed to 300rpm, reacting for 8 hr to obtain product with product roughness R g 1.756.
1.0 g of water was used, 0.4g of ethanol (0.025 g of coarse silica nanoparticles were added to 0.4g of ethanol), 4.0 g of silicone oil (viscosity at 25 ℃ C.: 50 mPa.s) was added, and then the mixture was mixed by a vortex oscillator and then subjected to a 40W power (on/off 1s/1 s) for 30s by a cell breaker to obtain a bicontinuous Pickering emulsion composition.
The microstructure of the emulsion composition prepared in this example was the same as in example 1.
Example 3
Solution B:40mL of ethanol and 5mL of TEOS,0.4mL of MTMS were mixed;
solution a:50mL of water was mixed with 40mL of ethanol, 18mL of aqueous ammonia (28 wt%).
And adding the solution B into the solution A at the rotating speed of 1100rpm, regulating the rotating speed to 500rpm after 2min, and reacting for 6h to obtain the product. The prepared silicon sphere is shown in TEM graph in figure 4, and the surface roughness of the silicon dioxide nanometer particle can be obtained g 3.24.
1.0 g of water was used, 0.4g of ethanol (0.025 g of coarse silica nanoparticles were added to 0.4g of ethanol), 4.0 g of silicone oil (viscosity at 25 ℃ C.: 50 mPa.s) was added, and then the mixture was mixed by a vortex oscillator and then subjected to a 40W power (on/off 1s/1 s) for 30s by a cell breaker to obtain a bicontinuous Pickering emulsion composition.
The microstructure of the emulsion composition prepared in this example was the same as in example 1.
Comparative example 1
Solution A (25 mL of water, 20mL of ethanol, 9.3mL of ammonia 28wt%, mixed) and solution B (40 mL of ethanol, 5mL of TEOS mixed) were mixed at 1100rpm, and after 2min of reaction, the rotation speed was adjusted to 300rpm, and the reaction was continued for 8 hours. The sample was obtained by centrifugation at 5000rpm for 10min, and its TEM image was shown in FIG. 5 as smooth silica particles.
1.0 g of water was used, 0.4g of ethanol (0.025 g of smooth silica nanoparticles were added to 0.4g of ethanol), 4.0 g of silicone oil (viscosity at 25 ℃ C. Was 50 mPa.s) was added, and then the mixture was mixed by a vortex shaker and then subjected to a 40W power (on/off 1s/1 s) for 30s by a cell breaker, and the system was not stable and rapidly layered due to the use of smooth silica nanoparticles, and a bicontinuous Pickering emulsion composition could not be obtained.
Comparative example 2
The surface roughened silica nanoparticles were the same as in example 1;
with 1.0 g of water, 0.4g of ethanol (0.05 g of coarse silica nanoparticles are added to 0.4g of ethanol), and then 4.0 g of silicone oil (viscosity 50 mPa.s at 25 ℃) are added, and then the mixture is mixed by a vortex oscillator and then subjected to a 40W power (on/off 1s/1 s) for 30s by a cytobreaker. In this comparative example, since the amount of coarse silica nanoparticles was twice that of example 1, the system was not stable and rapidly delaminated, and a bicontinuous pickering emulsion composition could not be obtained.
Comparative example 3
The surface roughened silica nanoparticles were the same as in example 1;
with 1.0 g of water, 0.4g of ethanol (0.025 g of coarse silica nanoparticles are added to 0.4g of ethanol), 6.0 g of silicone oil (viscosity at 25 ℃ C.: 50 mPa.s) are added, and then the mixture is mixed by a vortex oscillator and then subjected to a 40W power (on/off 1s/1 s) for 30s by a cytobreaker. The present comparative example, compared to example 1, is unable to stabilize and rapidly delaminate due to the increased mass of silicone oil, and a bicontinuous pickering emulsion composition cannot be obtained.
Comparative example 4
The surface roughened silica nanoparticles were the same as in example 1;
with 1.0 g of water, 0.4g of ethanol (0.025 g of coarse silica nanoparticles are added to 0.4g of ethanol), 4.0 g of silicone oil (viscosity at 25 ℃ C.: 50 mPa.s) and 6.0 mg of sodium dodecyl sulfate are added, and then the mixture is mixed by a vortex oscillator and then subjected to a 40W power (on/off 1s/1 s) for 30s. As a result of the inclusion of the surfactant sodium dodecyl sulfate, the system of this comparative example was not stable and rapidly delaminated, and a bicontinuous pickering emulsion composition was not obtained, as compared to example 1.
Although the foregoing embodiments have been described in some, but not all embodiments of the invention, other embodiments may be obtained according to the present embodiments without departing from the scope of the invention.

Claims (10)

1. A bicontinuous pickering emulsion composition comprising a continuous aqueous phase, a continuous oil phase, and a stabilizer; the stabilizer forms a protective layer at the interface of the continuous water phase and the continuous oil phase; the continuous water phase is an alcohol-water mixture, and the continuous oil phase is silicone oil; the stabilizer is silica nanoparticles; surface roughness R of the silica nanoparticles g ≥0.75。
2. Bicontinuous pickering emulsion composition according to claim 1, characterized in that the surface roughness R of the silica nanoparticles g 0.75 to 3.24.
3. The bicontinuous pickering emulsion composition of claim 1, wherein the alcohol-water mixture is a mixture of ethanol and water;
the volume ratio of the ethanol to the water is (0.4-0.6): 1.
4. The bicontinuous pickering emulsion composition of claim 1, wherein the silicone oil has a viscosity of 10 to 100 mPa-s at 25 ℃.
5. The bicontinuous pickering emulsion composition of any of claims 1-4, wherein the silicone oil comprises 70-75% by volume of the total volume of the alcohol-water mixture and the silicone oil.
6. A bicontinuous pickering emulsion composition according to any one of claims 1-3, wherein the mass ratio of the alcohol-water mixture to the silica nanoparticles is not less than 50:1.
7. Bicontinuous pickering emulsion composition according to claim 1 or 2, characterized in that the silica nanoparticles have a particle size of 300-500 nm.
8. A process for the preparation of a bicontinuous pickering emulsion composition as claimed in any one of claims 1 to 7, characterized by the following steps:
and mixing and emulsifying the continuous water phase, the continuous oil phase and the stabilizer to obtain the bicontinuous Pickering emulsion composition.
9. The method of preparing according to claim 8, wherein the mixing is vortex oscillating mixing;
the emulsification is performed in a cell disruption instrument, and the power of the cell disruption instrument during emulsification is 40-50W.
10. Use of the bicontinuous pickering emulsion composition of any one of claims 1-7 or the bicontinuous pickering emulsion composition prepared by the preparation method of claim 8 or 9 in the preparation of cosmetics or medicines.
CN202310644102.6A 2023-06-02 2023-06-02 Bicontinuous Pickering emulsion stabilized based on rough nano particles and preparation method and application thereof Pending CN116650344A (en)

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