CN113499278A - Preparation method of water-in-water Pickering emulsion based on starch nanocrystals - Google Patents
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- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
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Abstract
The invention discloses a preparation method of a water-in-water Pickering emulsion based on starch nanocrystals. According to the method, sodium hexametaphosphate is added into a starch nanocrystal suspension, a crosslinking reaction is carried out to obtain a sodium hexametaphosphate crosslinking modified starch nanocrystal suspension, then a glucan/polyethylene glycol aqueous solution is used as a water-water system, the sodium hexametaphosphate crosslinking modified starch nanocrystal suspension is used as an emulsifier, and emulsification is carried out to obtain the water-in-water Pickering emulsion. The method has simple process, and the prepared emulsion has excellent stability and emulsibility, and the appearance of the emulsion can be adjusted by adjusting the surface property of the particles. The emulsion of the invention does not contain an oil phase, and can be used as a refreshing emulsion to be applied to cosmetics, so that the greasy feeling and the irritation are reduced, and the smooth characteristic is provided for the skin.
Description
Technical Field
The invention belongs to the technical field of emulsifiers, and relates to a preparation method of a water-in-water Pickering emulsion based on starch nanocrystals.
Background
An emulsion is a system formed by adding an emulsifier so that a certain liquid is dispersed in the form of droplets in another liquid incompatible therewith. Conventional means of stabilizing emulsions have been to add surfactants (e.g., polysorbates, phospholipids) to the emulsion. However, for emulsions of such systems, particularly in cosmetic and pharmaceutical applications, surfactants often exhibit adverse effects, such as irritation, hemolytic behavior, etc., and are susceptible to phase separation under the influence of heat and gravity.
The Pickering emulsion stabilizes the emulsion by using solid particles instead of the surfactants of conventional emulsions. The Pickering emulsion stabilized by solid particles not only retains the basic properties of the classical emulsion stabilized by a surfactant, but also has special properties such as high coalescence resistance, less harm to the environment and human bodies, less irritation, less dosage required for stabilization and the like due to the stabilization of the solid particles, and thus is widely used in foods, materials, pharmaceuticals and daily chemical products.
Starch Nanocrystals (SNCs) are one of natural polysaccharides, and high-modulus and high-strength SNCs can be obtained by removing amorphous regions of starch by acid hydrolysis or high-pressure homogenization. The starch nanocrystal can be used as an emulsifier to stabilize the emulsion. For example, wei et al hydrolyzed starch by homogeneous assisted acid hydrolysis to obtain starch nanocrystals and hydrophobically modified it with a silane coupling agent to finally obtain a highly stable paraffin/water Pickering emulsion (wei benxi. preparation, dispersion, modification and emulsification research of starch nanocrystals [ D ], university of south of the river, 2015.). Hao et al succeeded in preparing a highly stable emulsion system by succinylating the SNC octenyl obtained by acid hydrolysis (Hayachen. waxy potato starch nanocrystals, research on modification [ D ], university of south China, 2018.). Peng et al prepared highly moisturizing skin creams by using esterified starch nanoparticles instead of traditional surfactants (Peng Y. preparation of taro starch nanoparticles, esterification and their use in skin creams [ D ], Hefei university of Industrial, 2018).
Currently, the research on SNC as an emulsifier is mainly focused on oil/water systems, but rarely in water-in-water emulsion systems. Aqueous-water (W/W) systems are typically formed in multicomponent aqueous polymer solutions that exceed a critical polymer concentration. Such aqueous two-phase systems have attracted considerable attention in the fields of cell biology and biotechnology, as well as green chemistry, and are widely used in the fields of cosmetics and foods as carriers for delivery of ingredients. The W/W emulsion with stable mechanism through the Pickering emulsion has excellent biocompatibility and low toxicity, and is suitable for the field of biomedicine. Similar to the conclusions drawn in oil/water systems, the emulsion morphology and properties of water/water systems also depend strongly on particle size and topology, with lamellar particles having better physical barrier properties than spherical particles. This means that SNC in sheet form is more advantageous when used to prepare water-in-water emulsions than other polysaccharide derived nanoparticles. However, the temporal stability of stable emulsions is limited by the structure of the SNC surface polyol, and stable emulsion systems at low levels show phase separation after 2 months.
Disclosure of Invention
The invention aims to provide a preparation method of a water-in-water Pickering emulsion based on starch nanocrystals. According to the method, sodium hexametaphosphate is used for carrying out crosslinking modification on starch nanocrystals, and a glucan/polyethylene glycol aqueous solution is used as a water-water system to emulsify and prepare the water-in-water Pickering emulsion with stable properties.
The technical scheme for realizing the purpose of the invention is as follows:
the preparation method of the water-in-water Pickering emulsion based on the starch nanocrystals comprises the following steps:
(1) adding sodium hexametaphosphate into the starch nanocrystal suspension, adjusting the pH to 8-10, and controlling the crosslinking degree to be 4 multiplied by 10-3-7.2×10-3After the crosslinking is finished, adding water for centrifugal washing, and finally dispersing in water by ultrasonic to obtain a sodium hexametaphosphate crosslinked and modified starch nanocrystal suspension;
(2) and emulsifying three phases by taking a glucan/polyethylene glycol aqueous solution as a water-water system and taking the sodium hexametaphosphate cross-linked modified starch nanocrystal suspension as an emulsifier to prepare the water-in-water Pickering emulsion.
In the step (1), the pH is adjusted to 8-10 by adding a sodium hydroxide solution. When the pH is less than 8, the reaction proceeds in the reverse direction, resulting in a lower yield.
In the step (1), the concentration of the starch nanocrystals in the starch nanocrystal suspension is 0.04-0.06 g/mL.
In the step (1), the feeding amount of the sodium hexametaphosphate is controlledThe degree of crosslinking is made. When the feeding amount of the sodium hexametaphosphate is 0.01-0.02 g/mL, the starch nanocrystal suspension with the crosslinking degree of 4 multiplied by 10 can be realized-3～7.2×10-3。
In the step (1), the concentration of the sodium hexametaphosphate crosslinked and modified starch nanocrystal in the sodium hexametaphosphate crosslinked and modified starch nanocrystal suspension is 0.04-0.06 g/mL. When the concentration of the sodium hexametaphosphate crosslinked and modified starch nanocrystal is more than 0.06g/mL, the stability of the suspension is poor, and the starch nanocrystal exists in the suspension in a larger slurry aggregate, which is not beneficial to subsequent modification. When the concentration of the sodium hexametaphosphate crosslinked and modified starch nanocrystal is below 0.06g/mL, the sodium hexametaphosphate crosslinked and modified starch nanocrystal can be uniformly dispersed in the aqueous solution.
In the step (1), the concrete method of adding water for centrifugal washing comprises the following steps: adding water, fully mixing, centrifuging to remove supernatant, fully mixing the precipitate with water again, repeating the steps of centrifuging and mixing with water for 3-6 times, adding the precipitate of the last time into water, and performing ultrasonic dispersion to obtain the sodium hexametaphosphate cross-linked modified starch nanocrystal suspension.
In the step (1), the crosslinking time is 4 hours, and when the reaction time is too short, the yield and crosslinking degree of the reaction are too low, and when the reaction time is too long, the economic benefit is poor.
In the step (2), the water-water ratio of the glucan/polyethylene glycol aqueous solution is 9: 1-5: 5, and stable emulsion can be formed in the range. The water-water ratio refers to the mass ratio of the glucan to the polyethylene glycol. The larger the water-water ratio, the larger the droplet is, which is not favorable for emulsion stability and easy demulsification, but if the water-water content is too small, the system can generate phase inversion, which is not favorable for emulsion research.
In the step (2), the ratio of the volume of the sodium hexametaphosphate crosslinked and modified starch nanocrystal suspension to the total volume of the water-water system is 1: 0.2-0.3.
In the step (2), the rotating speed in the emulsification is 2000-10000 r/min, and the emulsification time is 1-2 min. The larger the emulsification rate is, the smaller the liquid drop is, the more stable the emulsion is, and meanwhile, from the viewpoint of energy conservation, the upper limit of the emulsification speed is set to 10000r/min, and the time is preferably 1-2 min.
Compared with the prior art, the invention has the following advantages:
(1) according to the invention, sodium hexametaphosphate is adopted to perform crosslinking modification on the starch nanocrystal, and the modified starch nanocrystal has different particle size and surface properties, but the capability of stabilizing a water-water system is improved.
(2) The Pickering emulsion prepared by using the glucan/polyethylene glycol aqueous solution as a water-water system and the sodium hexametaphosphate cross-linked modified starch nanocrystal suspension as an emulsifier has excellent stability and emulsifying property. In practical application, the water-water ratio, the content of the starch nanocrystal and the content of the modified starch nanocrystal can be adjusted as required to prepare Pickering emulsions with different droplet sizes. The emulsion of the invention does not contain an oil phase, and can be used as a refreshing emulsion to be applied to cosmetics, so that the greasy feeling and the irritation are reduced, and the smooth characteristic is provided for the skin.
Drawings
FIG. 1 is a physical representation of the emulsions prepared in examples 1-4 and comparative examples 1-2.
FIG. 2 is an optical microscope photograph of emulsions prepared in examples 1-4 and comparative examples 1-2.
FIG. 3 is a graph of the steady state rheological characteristics of the emulsions prepared in examples 1-4, comparative examples 1-2.
Detailed Description
The present invention will be described in more detail with reference to the following examples and the accompanying drawings.
In the following examples, starch nanocrystals were prepared by existing methods, for example, by acid hydrolysis, refer to patent documents such as cn201310264825.x, CN201310352678.1, CN201610162973.4, and the like. The method comprises the following specific steps:
the method comprises the steps of preparing starch nanocrystals from corn starch by a sulfuric acid hydrolysis method, mixing the starch nanocrystals with water, centrifuging, pouring back to remove supernatant, and repeating the operation for 6 times to gradually remove acid in the starch nanocrystal dispersion liquid. And after the starch nanocrystal precipitate is centrifuged to be neutral, adding deionized water into the starch nanocrystal precipitate for the last time, and performing ultrasonic dispersion to obtain a starch nanocrystal suspension. Under the action of ultrasound, the starch nanocrystals can form a stable suspension for subsequent steps. The starch nanocrystal does not need to be dried, and the agglomeration in the drying process is completely avoided.
Example 1
The preparation method of the water-in-water Pickering emulsion based on the starch nanocrystals comprises the following steps:
(1) mixing 100mL of starch nanocrystal suspension with sodium hexametaphosphate under an alkaline condition, wherein the feeding amount of the sodium hexametaphosphate is 1 g; the reaction pH was controlled to 8 by sodium hydroxide solution. Fully mixing the obtained cross-linked modified starch nanocrystal with water, centrifuging, pouring out supernatant, fully mixing the precipitate with water again, centrifuging, pouring out supernatant, repeating the operation for 6 times, adding water into the precipitate at the last time, and performing ultrasonic dispersion to obtain sodium hexametaphosphate modified starch nanocrystal suspension with the cross-linking degree of (4.0 +/-0.1) multiplied by 10-3The reaction time is 4 hours; by controlling the water content, the concentration of the sodium hexametaphosphate modified starch nanocrystal in the obtained suspension is 0.04 g/mL.
(2) Taking a glucan/polyethylene glycol aqueous solution as a water-water system, taking a crosslinked modified starch nanocrystal suspension as an emulsifier, wherein the dosage ratio of the total volume of the selected crosslinked modified starch nanocrystal suspension to the water-water system is 0.2:1, and the water-water ratio is 7: 3; the rotation speed of the emulsifying machine is 10000r/min, the emulsifying time is 2min, and three phases are emulsified at high speed by the emulsifying machine to prepare Pickering emulsion.
Example 2
The preparation method of the water-in-water Pickering emulsion based on the starch nanocrystals comprises the following steps:
(1) mixing 100mL of starch nanocrystal suspension with sodium hexametaphosphate under an alkaline condition, wherein the feeding amount of the sodium hexametaphosphate is 1.5 g; controlling the reaction pH to 8 by sodium hydroxide solution to obtain crosslinked modified starch nanocrystal, fully mixing with water, centrifuging, pouring off supernatant, fully mixing precipitate with water, centrifuging, pouring off supernatant, repeating the operation for 6 times, adding water into the precipitate for the last time, and ultrasonically dispersing to obtain sodium hexametaphosphate modified starch nanocrystal suspension with crosslinking degree of (5.9 + -0.1) x 10-3The reaction time is 4 hours; by controlling the water content, the obtained suspension is made to be the sodium hexametaphosphate modified starch nanocrystalThe concentration was 0.04 g/mL.
(2) Taking a glucan/polyethylene glycol aqueous solution as a water-water system, taking a crosslinked modified starch nanocrystal suspension as an emulsifier, wherein the dosage ratio of the total volume of the selected crosslinked modified starch nanocrystal suspension to the water-water system is 0.2:1, and the water-water ratio is 7: 3; the rotation speed of the emulsifying machine is 10000r/min, the emulsifying time is 2min, and three phases are emulsified at high speed by the emulsifying machine to prepare Pickering emulsion.
Example 3
The preparation method of the water-in-water Pickering emulsion based on the starch nanocrystals comprises the following steps:
(1) mixing 100mL of starch nanocrystal suspension with sodium hexametaphosphate under an alkaline condition, wherein the feed amount of the sodium hexametaphosphate is 2 g; controlling the pH value of the reaction to be 8 by sodium hydroxide solution, fully mixing the obtained cross-linked modified starch nanocrystal with water, centrifuging, pouring out supernatant, fully mixing the precipitate with water again, centrifuging, pouring out supernatant, repeating the operation for 6 times, adding water into the precipitate at the last time, and performing ultrasonic dispersion to obtain sodium hexametaphosphate modified starch nanocrystal suspension with the cross-linking degree of (7.2 +/-0.1) multiplied by 10-3The reaction time is 4 hours; by controlling the water content, the concentration of the sodium hexametaphosphate modified starch nanocrystal in the obtained suspension is 0.04 g/mL.
(2) Taking a glucan/polyethylene glycol aqueous solution as a water-water system, taking an acylation modified starch nanocrystal suspension as an emulsifier, wherein the dosage ratio of the total volume of the selected acylation modified starch nanocrystal suspension to the water-water system is 0.2:1, and the water-water ratio is 7: 3; the rotating speed of the emulsifying machine is 8000r/min, the emulsifying time is 1.5min, and three phases are emulsified at high speed by the emulsifying machine to prepare the Pickering emulsion.
Example 4
The preparation method of the water-in-water Pickering emulsion based on the starch nanocrystals comprises the following steps:
(1) mixing 100mL of starch nanocrystal suspension with sodium hexametaphosphate under an alkaline condition, wherein the feed amount of the sodium hexametaphosphate is 2 g; controlling the pH value of the reaction to be 8 by sodium hydroxide solution, fully mixing the obtained cross-linked modified starch nanocrystal with water, centrifuging, then pouring out supernatant, and precipitating againMixing with water, centrifuging, removing supernatant, repeating the operation for 6 times, adding water into the precipitate, and ultrasonically dispersing to obtain sodium hexametaphosphate modified starch nanocrystal suspension with crosslinking degree of (7.2 + -0.1) x 10-3The reaction time is 4 hours; by controlling the water content, the concentration of the sodium hexametaphosphate modified starch nanocrystal in the obtained suspension is 0.04 g/mL.
(2) Taking a glucan/polyethylene glycol aqueous solution as a water-water system, taking an acylation modified starch nanocrystal suspension as an emulsifier, wherein the dosage ratio of the total volume of the selected acylation modified starch nanocrystal suspension to the water-water system is 0.3:1, and the water-water ratio is 7: 3; the rotating speed of the emulsifying machine is 8000r/min, the emulsifying time is 1.5min, and three phases are emulsified at high speed by the emulsifying machine to prepare the Pickering emulsion.
Comparative example 1
(1) Taking 50g of commercial corn starch as a raw material, carrying out sulfuric acid hydrolysis for 5 days, then fully mixing the raw material with water, centrifuging, then pouring out supernatant, fully mixing the precipitate with water again, centrifuging, pouring out the supernatant, repeating the operation for 6 times, adding water into the precipitate at the last time, and then carrying out ultrasonic dispersion to obtain the starch nanocrystal suspension. The concentration of the starch nanocrystal in the starch nanocrystal suspension is controlled to be 0.04g/mL by adding the amount of water.
(2) Taking a glucan/polyethylene glycol aqueous solution as a water-water system, taking an unmodified starch nanocrystal suspension as an emulsifier, wherein the dosage ratio of the total volume of the selected starch nanocrystal suspension to the water-water system is 0.2:1, and the water-water ratio is 7: 3; the rotation speed of the emulsifying machine is 10000r/min, the emulsifying time is 2min, and three phases are emulsified at high speed by the emulsifying machine to prepare Pickering emulsion.
Comparative example 2
(1) Mixing 100mL of starch nanocrystal suspension with sodium hexametaphosphate under an alkaline condition, wherein the feed amount of the sodium hexametaphosphate is 0.3 g; controlling the pH value of the reaction to be 8 by sodium hydroxide solution, fully mixing the obtained cross-linked modified starch nanocrystal with water, centrifuging, pouring out supernatant, fully mixing the precipitate with water again, centrifuging, pouring out the supernatant, repeating the operation for 6 times, adding water into the precipitate at the last time, and performing ultrasonic dispersion to obtain sodium hexametaphosphate modified starch nanocrystal suspensionLiquid, degree of crosslinking being (1.8. + -. 0.1). times.10-4The reaction time is 4 hours; by controlling the water content, the concentration of the sodium hexametaphosphate modified starch nanocrystal in the obtained suspension is 0.04 g/mL.
(2) Taking a glucan/polyethylene glycol aqueous solution as a water-water system, taking a crosslinked modified starch nanocrystal suspension as an emulsifier, wherein the dosage ratio of the total volume of the selected crosslinked modified starch nanocrystal suspension to the water-water system is 0.2:1, and the water-water ratio is 7: 3; the rotation speed of the emulsifying machine is 10000r/min, the emulsifying time is 2min, and three phases are emulsified at high speed by the emulsifying machine to prepare Pickering emulsion
FIG. 1 is a physical diagram of the emulsions prepared in examples 1-4 and comparative examples 1-2, and it can be seen from the figure that unmodified and low crosslinking degree starch nanocrystals can emulsify water-water system, but the emulsion is unstable and the droplets are easy to aggregate and settle. The comparison shows that under the condition of adding the emulsifying agent with the same mass, the addition of the modified starch nanocrystal can stabilize the emulsion to a greater extent, and the proportion of the emulsion layer is larger along with the increase of the addition amount of the sodium hexametaphosphate in the modification process. The reason is that the size of the starch nanocrystalline solid particles is slightly increased after crosslinking modification, and according to a particle desorption formula, the generation of a particle aggregate structure is favorable for the emulsification of the particle aggregate structure on an interface. It was also found that an increase in the particle content also contributes to the stability of the emulsion, since the more particles are added, the more complete the surface coating of the droplets and the better the stability of the emulsion.
FIG. 2 is an optical microscope photograph of emulsions prepared in examples 1-4 and comparative examples 1-2. It can be seen from the figure that, under the condition of adding an emulsifier with equal mass, the size of the stable water-water emulsion liquid drop of the unmodified starch nanocrystal is very large, and the particle size of the liquid drop is smaller along with the increase of the addition amount of ammonium hexametaphosphate and the increase of particle content in the modification process, because the modified starch nanocrystal introduces charged groups, the charged amount is increased, the dispersibility is stronger, and the particle utilization rate is high. In addition, the increase of the particles also leads to the formation of a network between the particles, so that the particle size of the formed emulsion is small and the emulsion is stable.
FIG. 3 is a graph of the steady state rheological characteristics of the emulsions prepared in examples 1-4, comparative examples 1-2. All emulsions have typical non-newtonian pseudoplastic behavior. The comparison shows that the emulsion viscosity of unmodified starch nanocrystal is the lowest, the emulsion viscosity of particles with higher crosslinking degree is the highest under larger particle concentration, according to Stokes' theorem, the rising rate of liquid drops can be slowed down by increasing the emulsion viscosity, the probability of continuous mutual collision is reduced, the separation tendency of emulsion-like liquid is reduced, the generation of chromatography of emulsion is inhibited, and the emulsion is more stable.
Claims (10)
1. The preparation method of the water-in-water Pickering emulsion based on the starch nanocrystals is characterized by comprising the following steps:
(1) adding sodium hexametaphosphate into the starch nanocrystal suspension, adjusting the pH to 8-10, and controlling the crosslinking degree to be 4 multiplied by 10-3-7.2×10-3After the crosslinking is finished, adding water for centrifugal washing, and finally dispersing in water by ultrasonic to obtain a sodium hexametaphosphate crosslinked and modified starch nanocrystal suspension;
(2) and emulsifying three phases by taking a glucan/polyethylene glycol aqueous solution as a water-water system and taking the sodium hexametaphosphate cross-linked modified starch nanocrystal suspension as an emulsifier to prepare the water-in-water Pickering emulsion.
2. The method according to claim 1, wherein in the step (1), the pH is adjusted to 8 to 10 by adding a sodium hydroxide solution.
3. The preparation method according to claim 1, wherein in the step (1), the concentration of the starch nanocrystals in the starch nanocrystal suspension is 0.04-0.06 g/mL.
4. The preparation method according to claim 1, wherein in the step (1), the feeding amount of the sodium hexametaphosphate is 0.01-0.02 g/mL of the starch nanocrystal suspension.
5. The preparation method according to claim 1, wherein in the step (1), the concentration of the sodium hexametaphosphate crosslinked and modified starch nanocrystal in the sodium hexametaphosphate crosslinked and modified starch nanocrystal suspension is 0.04-0.06 g/mL.
6. The preparation method according to claim 1, wherein in the step (1), the water is added for centrifugal washing by a specific method comprising: adding water, fully mixing, centrifuging to remove supernatant, fully mixing the precipitate with water again, repeating the steps of centrifuging and mixing with water for 3-6 times, adding the precipitate of the last time into water, and performing ultrasonic dispersion to obtain the sodium hexametaphosphate cross-linked modified starch nanocrystal suspension.
7. The production method according to claim 1, wherein in the step (1), the crosslinking time is 4 hours.
8. The method according to claim 1, wherein in the step (2), the ratio of water to water in the aqueous solution of dextran/polyethylene glycol is 9:1 to 5: 5.
9. The preparation method according to claim 1, wherein in the step (2), the ratio of the volume of the sodium hexametaphosphate crosslinked and modified starch nanocrystal suspension to the total volume of the water-water system is 1: 0.2-0.3.
10. The method according to claim 1, wherein in the step (2), the rotation speed in the emulsification is 2000 to 10000r/min, and the emulsification time is 1 to 2 min.
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| CN105601757A (en) * | 2016-03-22 | 2016-05-25 | 中南林业科技大学 | Preparation method of drug carrier crosslinking-modified rice starch nanocrystals |
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