CN115368591A - Chitosan-starch composite Janus particle and preparation method and application thereof - Google Patents
Chitosan-starch composite Janus particle and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
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- 238000002156 mixing Methods 0.000 claims description 7
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- URVNZJUYUMEJFZ-UHFFFAOYSA-N 3-tetradec-1-enyloxolane-2,5-dione Chemical compound CCCCCCCCCCCCC=CC1CC(=O)OC1=O URVNZJUYUMEJFZ-UHFFFAOYSA-N 0.000 claims description 6
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- WVRNUXJQQFPNMN-VAWYXSNFSA-N 3-[(e)-dodec-1-enyl]oxolane-2,5-dione Chemical compound CCCCCCCCCC\C=C\C1CC(=O)OC1=O WVRNUXJQQFPNMN-VAWYXSNFSA-N 0.000 claims description 3
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- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 7
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- GYSCBCSGKXNZRH-UHFFFAOYSA-N 1-benzothiophene-2-carboxamide Chemical compound C1=CC=C2SC(C(=O)N)=CC2=C1 GYSCBCSGKXNZRH-UHFFFAOYSA-N 0.000 description 2
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Images
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/16—Powdering or granulating by coagulating dispersions
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
- A23L29/30—Foods or foodstuffs containing additives; Preparation or treatment thereof containing carbohydrate syrups; containing sugars; containing sugar alcohols, e.g. xylitol; containing starch hydrolysates, e.g. dextrin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
- A61K47/36—Polysaccharides; Derivatives thereof, e.g. gums, starch, alginate, dextrin, hyaluronic acid, chitosan, inulin, agar or pectin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/02—Esters
- C08B31/04—Esters of organic acids, e.g. alkenyl-succinated starch
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
- A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2303/04—Starch derivatives
- C08J2303/06—Esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
Abstract
The invention discloses a chitosan-starch composite Janus particle and a preparation method and application thereof. The preparation method takes starch modified by succinic anhydride as a particle stabilizer of the Pickering emulsion, takes saturated fatty acid as an oil phase, and prepares the Pickering emulsion template, so that part of starch particles is locked in the oil phase of solidified fatty acid, and part of starch particles is exposed in the water phase; then, the natural polysaccharide chitosan and starch are subjected to electrostatic adsorption, so that the surfaces of the starch particles exposed in the water phase are combined with the chitosan nanoparticles to achieve the aim of asymmetric modification. The Janus particle with two polysaccharides combined is prepared for the first time, the characteristics and the advantages of two biomacromolecules can be combined, and the application of the Janus particle in the field of food or medicine is further expanded. The raw materials used by the invention are green, environment-friendly and natural polysaccharide materials with good biocompatibility, and have wide application prospect.
Description
Technical Field
The invention belongs to the technical field of modified starch, and particularly relates to a chitosan-starch composite Janus particle as well as a preparation method and application thereof.
Background
Janus particles are an emerging class of structures that describe asymmetric materials with two or more different chemical compositions or properties on the surface. To date, the versatility of synthetic polymers and inorganic materials has made them the primary raw material for the synthesis of Janus particles in the fields of material science and biomedicine. The Janus particles show unique characteristics according to binary design (such as surface activity, self-assembly, targeted release, self-propulsion and the like), but the application of the Janus particles in the fields of food and medicine is less at present, and the important reason is that in the commonly used preparation methods of the Janus particles at present, methods such as a microfluid synthesis method, a current jetting method, a template-guided self-assembly method and the like not only need special instruments and equipment, but also involve complex environments such as high temperature, an electric field, an organic solvent and the like, and certain economic pressure and environmental pollution are brought, so that further research and development are needed in the application of the Janus particles. The natural biological polymers such as polysaccharide, such as starch and chitosan, not only have low price and wide application, but also are sustainable, biodegradable, safe and edible. The chitosan is the only natural polysaccharide with positive charges in the nature, the starch is negatively charged in an aqueous phase system after esterification modification, the chitosan and the starch can be combined through electrostatic combination in the aqueous phase system, and the chitosan and the starch are not easy to be combined well to form particles due to the easy film-forming property of the pure chitosan.
Disclosure of Invention
In order to solve the related problems, the primary object of the present invention is to provide a method for preparing chitosan-starch composite Janus particles. The method comprises the steps of preparing chitosan nanoparticles by an ion gel method, and preparing polysaccharide Janus particles by combining the chitosan nanoparticles with the ODSA starch by a Pickering emulsion template method. The raw materials adopted in the method are all green, environment-friendly and pollution-free, and have good biocompatibility and biodegradability and edibility.
Another object of the present invention is to provide chitosan-starch composite Janus particles obtained by the above preparation method. The food-grade Janus particle material is a novel food-grade Janus particle material which is purely compounded and synthesized by natural polysaccharide.
The invention further aims to provide application of the chitosan-starch composite Janus particle.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of chitosan-starch composite Janus particles comprises the following steps:
(1) Carrying out hydrophobic modification on starch by an esterifying agent to obtain hydrophobic modified starch;
(2) Taking the hydrophobically modified starch obtained in the step (1) as a solid particle stabilizer of Pickering emulsion, taking long-chain fatty acid as an oil phase, adding the long-chain fatty acid and the oil phase into water, mixing the three uniformly, and homogenizing to obtain emulsion; refrigerating the homogenized emulsion, taking out, and standing at room temperature for stabilization to obtain O/W type Pickering emulsion with solidified oil phase;
(3) Dissolving chitosan in an acetic acid aqueous solution to form a chitosan solution; stirring, adjusting the pH value to 4.5-5.2, and removing residues of insoluble particles; then preheating, stirring, adding a sodium Tripolyphosphate (TPP) aqueous solution, and reacting to obtain a chitosan nanoparticle dispersion liquid;
(4) And (3) adding the chitosan nanoparticle dispersion liquid into the Pickering emulsion obtained in the step (2), reacting to obtain a mixed system of the chitosan nanoparticle dispersion liquid and the Pickering emulsion, separating out redundant chitosan nanoparticle dispersion liquid, adding distilled water, performing ultrasonic treatment and centrifugation, repeating the steps, and pouring out the supernatant obtained by final centrifugation to obtain the chitosan-starch composite Janus particles.
Preferably, the starch in step (1) is any one or combination of quinoa starch, rice starch and amaranth starch.
Preferably, the esterifying agent in the step (1) is any one or more of octadecenyl succinic anhydride (ODSA), hexadecenyl succinic anhydride (HDSA), tetradecenyl succinic anhydride (TDSA) and dodecenyl succinic anhydride (DDSA).
Preferably, the mass range of the esterifying agent in the step (1) is 5-30% of the mass of the starch; more preferably, the mass range of the esterifying agent is 10 to 20 percent of the mass of the starch.
Preferably, step (1) is carried out at 35. + -. 5 ℃.
Preferably, the reaction time of the hydrophobic modification in the step (1) is controlled within 3 h.
Preferably, the long-chain fatty acid in the step (2) is any one or a combination of more of lauric acid, myristic acid and capric acid.
Preferably, each unit of the mixed system in the step (2) contains 30-150 mg of hydrophobic starch and 100-1500 mg of long-chain fatty acid; more preferably, the mixed system contains 50-100 mg of hydrophobic starch and 500-1000 mg of long-chain fatty acid per unit.
Preferably, the mass ratio of the long-chain fatty acid to the water in the step (2) is in the range of 1; more preferably, the mass ratio of the long-chain fatty acid to water is in the range of 1.
Preferably, the temperature condition for uniform mixing in the step (2) is 44-52 ℃; further preferably, the temperature condition for uniform mixing is 46 to 50 ℃.
Preferably, the mixing in the step (2) is realized by ultrasonic and vortex; further preferably, the time of the ultrasound is 5 to 15min.
Preferably, the rotation speed of the homogenization in the step (2) is 10000-16000 rpm, and the time is 1-5 min; more preferably, the rotation speed of the homogenizing is 13000-15000 rpm, and the time is 1-3 min.
Preferably, the refrigerating temperature in the step (2) is 0-4 ℃ and the time is 30 +/-5 min.
Preferably, the stabilizing time in step (2) is 60. + -.5 min.
Preferably, the room temperature in the present invention is 20 to 30 ℃.
Preferably, the chitosan in step (3) is any one or more of low molecular weight chitosan (MW < 50000), medium molecular weight chitosan (MW = 50000-100000), and high molecular weight chitosan (MW > 100000).
Preferably, the concentration of the acetic acid aqueous solution in the step (3) is 0.1-0.8 mg/mL; more preferably, the concentration of the aqueous acetic acid solution is 0.2 to 0.4mg/mL.
Preferably, the dosage of the water-soluble chitosan in the step (3) is calculated according to the concentration of the water-soluble chitosan in the system of 0.1-1.0 mg/mL; further preferably, the dosage of the water-soluble chitosan is calculated by the concentration of the water-soluble chitosan in the system being 0.3-0.8 mg/mL.
Preferably, the stirring time in the step (3) is 1-18 h; more preferably, the stirring time is 3 to 12 hours.
Preferably, the pH adjustment in step (3) is 4.7 to 4.8.
Preferably, the reagent used for the adjustment in the step (3) is sodium hydroxide solution; further preferably, the concentration of the sodium hydroxide solution is 10% (m/v).
Preferably, the removal of the residue of insoluble particles in step (3) is achieved by means of a syringe filter; further preferably, the pore size of the syringe filter is 0.45 μm.
Preferably, the preheating temperature in the step (3) is 25-70 ℃, and the time is 5-40 min; further preferably, the preheating temperature is 40-60 ℃ and the time is 10-20 min; still further preferably, the preheating is effected by means of a water bath.
Preferably, the rotation speed of the preheated stirring in the step (3) is 200-1000 rpm; more preferably, the rotation speed is 600 to 800rpm.
Preferably, the concentration of the sodium tripolyphosphate aqueous solution in the step (3) is 0.1-1.0 mg/mL; further preferably, the concentration of the sodium tripolyphosphate aqueous solution is 0.3-0.8 mg/mL; still more preferably, the aqueous solution of sodium tripolyphosphate is passed through a syringe filter before use, the pore size of the syringe filter being 0.22 μm.
Preferably, in the step (3), the addition amount of the sodium tripolyphosphate aqueous solution is 2-10 mL based on the volume of the chitosan solution from which the residues of the insoluble particles are removed being 20 mL; more preferably, the addition amount of the sodium tripolyphosphate aqueous solution is 4-6 mL.
Preferably, the reaction time in the step (3) is 5-60 min; more preferably, the reaction time is 10 to 30min.
Preferably, the chitosan nanoparticle dispersion liquid in the step (4) is diluted by 3.3 to 100 times before use; more preferably, the chitosan nanoparticle dispersion is diluted 5 to 50 times before use.
Preferably, the volume ratio of the chitosan nanoparticle dispersion liquid to the Pickering emulsion in the step (4) is 1; further preferably, the volume ratio of the chitosan nanoparticle dispersion to the Pickering emulsion is 2.
Preferably, the reaction time in the step (4) is 5-60 min; more preferably, the reaction time is 10 to 30min.
Preferably, the separation of the redundant chitosan nanoparticle dispersion liquid in the step (4) is realized by centrifugation; further preferably, the time of centrifugation is 1-7 min; more preferably, the time for centrifugation is 3 to 5min.
Preferably, the repetition frequency in the step (4) is 1 to 7 times; more preferably, the number of repetitions is 3 to 5.
A chitosan-starch composite Janus particle is prepared by the preparation method.
The chitosan-starch composite Janus particle is applied to the field of food or medicine.
The invention is based on the following:
(1) The small-particle quinoa starch with the particle size of 1-3 mu m can well stabilize the Pickering emulsion, and can be more stably adsorbed on an oil-water interface of the Pickering emulsion through hydrophobic modification of succinic anhydride.
(2) The selected long-chain fatty acid as the oil phase is non-toxic and harmless, is solid at normal temperature, has the melting point higher than the gelatinization temperature of starch, is heated to the melting point to be changed into liquid, is prepared into O/W emulsion, is stabilized at the room temperature, is solidified, and is locked by the solidified oil phase, and is still exposed in the water phase, so that the possibility of asymmetric modification is provided.
(3) The chitosan nanoparticles are prepared, and the electropositivity of the natural polysaccharide chitosan and the electronegativity of the starch are combined through electrostatic interaction, so that the asymmetric modification of the chitosan nanoparticles on the surface of the starch exposed on one side of the water phase is completed.
(4) After finishing modification, the solidified oil phase is heated to a melting point and becomes liquid again, and after successful demulsification, the starch granules are conveniently extracted from the oil phase, so that the chitosan-starch composite Janus particles are obtained.
Compared with the prior art, the invention has the following advantages and effects:
1) The Pickering emulsion is used as a template to synthesize Janus particles, the conditions are mild, and the operation is simple and convenient;
2) The selected oil phase is long-chain fatty acid, so that the emulsion is non-toxic and harmless, toxic hazard and pollution caused by taking the traditional emulsion organic phase as the oil phase are avoided, and the emulsion is more environment-friendly, so that the technology can be used in food;
3) The Janus particle with two polysaccharides combined is prepared for the first time, the characteristics and advantages of two biomacromolecules can be combined, and the application of the Janus particle in the field of food or medicine is further expanded.
Drawings
FIG. 1 is a confocal microscope showing the combination of chitosan nanoparticles and Pickering latex obtained in example 1; wherein A is a picture taken at an excitation wavelength of 488 nm; B. c is a picture shot after two channels with excitation wavelengths of 488nm and 633nm are superposed, chitosan nanoparticles appear green after excitation, and starch appears red after excitation;
FIG. 2 is a scanning electron microscope image of Janus particles compounded by two kinds of chitosan nanoparticle modified starch-based polysaccharides obtained in example 1; wherein A, B and C are Janus particles prepared from chitosan nanoparticles and Pickering emulsion at a volume ratio of 2, 5, 3 and 10.
FIG. 3 is a confocal microscope of Janus particles composited by two types of chitosan nanoparticle-modified starch-based polysaccharides obtained in example 1; wherein, A (0-5 μm scale) and B (0-2.5 μm scale) are pictures shot under different magnification factors after two channels with excitation wavelengths of 488nm and 633nm are superposed, chitosan nanoparticles appear green after excitation, and starch appears red after excitation;
FIG. 4 is a TG thermogram of three kinds of particles obtained in example 1.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
Example 1
The preparation method of the chitosan-starch composite Janus particle comprises the following specific steps:
(1) Carrying out hydrophobic modification on quinoa starch by taking octadecenyl succinic anhydride (ODSA) as an esterifying agent at 35 ℃, wherein the mass of the esterifying agent is 15% of that of the starch, and the reaction time is controlled within 3h, so as to prepare the ODSA modified ODSA starch.
(2) Adding 75mg of ODSA starch as a solid particle stabilizer of Pickering emulsion and 750mg of lauric acid as an oil phase into 5mL of water, ultrasonically dispersing the whole system under the water bath condition of 46 ℃ for 10min, integrally swirling to uniformly mix the three, and homogenizing at 14000rpm for 2min by using a homogenizer under the water bath condition of 46 ℃. And (3) vertically placing the homogenized emulsion in the upper layer of a refrigerator for refrigeration at 0-4 ℃ for 30min, then taking out and placing at room temperature for stabilization for 1h to obtain the O/W type Pickering emulsion with the lauric acid oil phase solidified.
(3) Low molecular weight chitosan was dissolved in aqueous acetic acid to form a 0.5mg/mL chitosan solution with an acetic acid concentration of 0.3mg/mL. The chitosan solution was stirred at room temperature for 6h using magnetic stirring and the pH was adjusted to 4.7-4.8 with 10% sodium hydroxide solution, then the chitosan solution was passed through a syringe filter (pore size 0.45 μm) to remove the residue of insoluble particles. TPP (sodium tripolyphosphate) was dissolved in distilled water at a concentration of 0.5mg/mL and passed through a syringe filter (pore size 0.22 μm). Preheating 20mL of chitosan solution in a 100mL beaker in a 50 ℃ water bath for 15min, then stirring the beaker at 700rpm, adding 5mL of TPP solution into the chitosan solution, and reacting for 20min to obtain the chitosan nanoparticle dispersion.
(4) And adding the 30-fold diluted chitosan nanoparticle dispersion liquid into the Pickering emulsion according to the volume ratio of the chitosan nanoparticle dispersion liquid to the Pickering emulsion of 10, and reacting for 20min to obtain a mixed system of the chitosan nanoparticle dispersion liquid and the Pickering emulsion. The confocal microscopy of chitosan nanoparticles in combination with Pickering latex is shown in FIG. 1. As can be seen from the figure, after the oil phase of the Pickering emulsion template is solidified, one part of the surface of the starch particle is locked in the oil phase, and the other part of the surface is exposed in the water phase, at the moment, the chitosan nanoparticle is only modified with the surface of the starch particle exposed in the water phase, and does not go deep into the oil phase, so that the aim of asymmetric modification is fulfilled.
(5) And (3) centrifuging the mixed system of the chitosan nanoparticle and the chitosan nanoparticle to separate redundant chitosan nanoparticle dispersion liquid, adding distilled water, performing ultrasonic treatment at 50 ℃ for 10min, centrifuging at 4000rpm for 4min, repeating the steps for 4 times, and pouring out the supernatant obtained by final centrifugation to obtain the chitosan-starch composite Janus particles. A photograph under a laser confocal microscope of the prepared Janus particles is shown in fig. 3. As can be seen from the figure, only a part of the surface of the finally obtained chitosan-starch Janus particle is covered with the chitosan nanoparticle, and further an auxiliary scanning electron microscope picture verifies the successful preparation of the asymmetric chitosan-starch Janus particle. Scanning electron microscope results of Janus particles prepared at different volume ratios are shown in FIG. 2.
The TG thermogravimetric curves of the three particles obtained in this example are shown in FIG. 4. As can be seen from the figure, the mass retention rates of the original ODSA starch, the Janus ODSA starch and the full-coverage ODSA starch at the temperature of 500 ℃ are respectively 12.78%, 23.77% and 27.31%, which proves that only a part of chitosan-starch Janus particles are attached with chitosan nanoparticles, so that the final mass retention rate is between the two.
The results of DSC data of the three particles obtained in this example are shown in Table 1. As can be seen from the table, with the binding of chitosan nanoparticles to ODSA starch, the endothermic enthalpy of the particles increases significantly and the endothermic enthalpy of Janus particles is between that of the original ODSA starch and the full-covered starch, demonstrating the asymmetric structure of Janus particles.
TABLE 1 DSC data results for three particles
Example 2
The preparation method of the chitosan-starch composite Janus particle comprises the following specific steps:
(1) Carrying out hydrophobic modification on quinoa starch at 35 ℃ by taking hexadecenyl succinic anhydride (HDSA) as an esterifying agent, wherein the mass of the esterifying agent is 10% of that of the starch, and the reaction time is controlled within 3h, so as to prepare HDSA modified HDSA starch;
(2) Taking 50mg of HDSA starch as a solid particle stabilizer of Pickering emulsion, taking 500mg of decanoic acid as an oil phase, adding the two solids into 5mL of water, then ultrasonically dispersing the whole system under the water bath condition of 48 ℃ for 10min, integrally swirling to uniformly mix the two solids, and homogenizing for 1min at 13000rpm by using a homogenizer under the water bath condition of 48 ℃. And (3) vertically placing the homogenized emulsion in the upper layer of a refrigerator for refrigeration for 30min at the temperature of 0-4 ℃, then taking out the emulsion and placing the emulsion at room temperature for stabilization for 1h to obtain O/W type Pickering emulsion after the decanoic acid oil phase is solidified.
(3) The medium molecular weight chitosan was dissolved in aqueous acetic acid to form a 0.3mg/mL chitosan solution with an acetic acid concentration of 0.2mg/mL. The chitosan solution was stirred at room temperature for 3h using magnetic stirring and the pH was adjusted to 4.7-4.8 with 10% sodium hydroxide solution, then the chitosan solution was passed through a syringe filter (pore size 0.45 μm) to remove the residue of insoluble particles. TPP (sodium tripolyphosphate) was dissolved in distilled water at a concentration of 0.3mg/mL and passed through a syringe filter (pore size 0.22 μm). Preheating 20mL of chitosan solution in a 100mL beaker in a water bath at 40 ℃ for 10min, then stirring the beaker at 600rpm, adding 4mL of TPP solution into the chitosan solution, and reacting for 10min to obtain the chitosan nanoparticle dispersion.
(4) Adding the chitosan nanoparticle dispersion liquid diluted by 50 times and the Pickering emulsion in a volume ratio of 2.
(5) And (3) centrifuging the mixed system of the chitosan nanoparticle and the chitosan nanoparticle to separate redundant chitosan nanoparticle dispersion liquid, adding distilled water, performing ultrasonic treatment at 35 ℃ for 10min, centrifuging at 4000rpm for 3min, repeating the steps for 3 times, and pouring the supernatant obtained by final centrifugation to obtain the chitosan-starch composite Janus particles.
Example 3
The preparation method of the chitosan-starch composite Janus particle comprises the following specific steps:
(1) Carrying out hydrophobic modification on quinoa starch by using tetradecenyl succinic anhydride (TDSA) as an esterifying agent at 35 ℃, wherein the mass of the esterifying agent is 20% of that of the starch, and the reaction time is controlled within 3h, so as to prepare TDSA modified TDSA starch;
(2) 100mg of TDSA starch is used as a solid particle stabilizer of Pickering emulsion, 1000mg of myristic acid is used as an oil phase, the two solids are added into 5mL of water, then the whole system is ultrasonically dispersed uniformly for 10min under the water bath condition of 50 ℃, then the whole system is swirled to be uniformly mixed with each other, and then the mixture is homogenized for 3min at the rotating speed of 15000rpm by using a homogenizer under the water bath condition of 50 ℃. And (3) placing the homogenized emulsion immediately on the upper layer of a refrigerator for refrigeration at 0-4 ℃ for 30min, then taking out and placing at room temperature for stabilization for 1h to obtain the O/W type Pickering emulsion after the myristic acid oil phase is solidified.
(3) High molecular weight chitosan was dissolved in aqueous acetic acid to form a 0.8mg/mL chitosan solution at a concentration of 0.4mg/mL. The chitosan solution was stirred at room temperature for 12h using magnetic stirring and the pH was adjusted to 4.7-4.8 with 10% sodium hydroxide solution, then the chitosan solution was passed through a syringe filter (pore size 0.45 μm) to remove the residue of insoluble particles. TPP (sodium tripolyphosphate) was dissolved in distilled water at a concentration of 0.8mg/mL and passed through a syringe filter (pore size 0.22 μm). Preheating 20mL of chitosan solution in a 100mL beaker in a water bath at 60 ℃ for 20min, then stirring the beaker at 800rpm, adding 6mL of TPP solution into the chitosan solution, and reacting for 30min to obtain the chitosan nanoparticle dispersion.
(4) Adding the chitosan nanoparticle dispersion liquid diluted by 5 times and the Pickering emulsion in a volume ratio of 20.
(5) And (3) centrifuging the mixed system of the chitosan nanoparticle and the chitosan nanoparticle to separate redundant chitosan nanoparticle dispersion liquid, adding distilled water, performing ultrasonic treatment at 52 ℃ for 10min, centrifuging at 4000rpm for 5min, repeating the step for 5 times, and pouring the supernatant obtained by final centrifugation to obtain the chitosan-starch composite Janus particles.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of chitosan-starch composite Janus particles is characterized by comprising the following steps: the method comprises the following steps:
(1) Carrying out hydrophobic modification on starch by an esterifying agent to obtain hydrophobic modified starch;
(2) Taking the hydrophobically modified starch obtained in the step (1) as a solid particle stabilizer of Pickering emulsion, taking long-chain fatty acid as an oil phase, adding the long-chain fatty acid and the oil phase into water, mixing the three uniformly, and homogenizing to obtain emulsion; refrigerating the homogenized emulsion, taking out, and standing at room temperature for stabilization to obtain O/W type Pickering emulsion with solidified oil phase;
(3) Dissolving chitosan in an acetic acid aqueous solution to form a chitosan solution; stirring, adjusting the pH value to 4.5-5.2, and removing residues of insoluble particles; then preheating, stirring, adding sodium tripolyphosphate aqueous solution, and reacting to obtain chitosan nanoparticle dispersion liquid;
(4) And (3) adding the chitosan nanoparticle dispersion liquid into the Pickering emulsion obtained in the step (2), reacting to obtain a mixed system of the chitosan nanoparticle dispersion liquid and the Pickering emulsion, separating out redundant chitosan nanoparticle dispersion liquid, adding distilled water, performing ultrasonic treatment and centrifugation, repeating the steps, and pouring out the supernatant obtained by final centrifugation to obtain the chitosan-starch composite Janus particles.
2. The method of preparing chitosan-starch composite Janus particles of claim 1, wherein:
the starch in the step (1) is any one or combination of multiple of quinoa starch, rice starch and amaranth starch;
the esterifying agent in the step (1) is any one or combination of octadecenyl succinic anhydride, hexadecenyl succinic anhydride, tetradecenyl succinic anhydride and dodecenyl succinic anhydride;
the mass range of the esterifying agent in the step (1) is 5-30% of the mass of the starch.
3. The method of preparing chitosan-starch composite Janus particles of claim 1, wherein:
in the step (2), the long-chain fatty acid is any one or combination of more of lauric acid, myristic acid and capric acid;
in the step (2), each unit of the mixed system contains 30-150 mg of hydrophobic starch and 100-1500 mg of long-chain fatty acid;
the mass ratio of the long-chain fatty acid to the water in the step (2) is 1.
4. The method of preparing chitosan-starch composite Janus particles of claim 2 or 3, wherein:
in the step (1), the mass range of the esterifying agent is 10-20% of the mass of the starch;
in the step (2), each unit of the mixed system contains 50-100 mg of hydrophobic starch and 500-1000 mg of long-chain fatty acid;
the mass ratio range of the long-chain fatty acid to the water in the step (2) is 1;
the step (1) is carried out at 35 +/-5 ℃;
the reaction time of the hydrophobic modification in the step (1) is controlled within 3 h;
the temperature condition for uniform mixing in the step (2) is 44-52 ℃;
the uniform mixing in the step (2) is realized by ultrasound and vortex; the ultrasonic time is 5-15 min;
the rotation speed of the homogenization in the step (2) is 10000-16000 rpm, and the time is 1-5 min;
the refrigeration temperature in the step (2) is 0-4 ℃, and the time is 30 +/-5 min;
the stabilizing time in the step (2) is 60 +/-5 min.
5. The method of preparing chitosan-starch composite Janus particles of claim 1, wherein:
the chitosan in the step (3) is any one or combination of a plurality of low molecular weight chitosan, medium molecular weight chitosan and high molecular weight chitosan;
the concentration of the acetic acid aqueous solution in the step (3) is 0.1-0.8 mg/mL;
the dosage of the water-soluble chitosan in the step (3) is calculated according to the concentration of the water-soluble chitosan in a system of 0.1-1.0 mg/mL;
the preheating temperature in the step (3) is 25-70 ℃, and the time is 5-40 min;
the concentration of the sodium tripolyphosphate aqueous solution in the step (3) is 0.1-1.0 mg/mL;
in the step (3), the addition amount of the sodium tripolyphosphate aqueous solution is 2-10 mL according to the volume of the chitosan solution for removing the residues of the insoluble particles is 20 mL;
the reaction time in the step (3) is 5-60 min.
6. The method of preparing chitosan-starch composite Janus particles of claim 5, wherein:
the concentration of the acetic acid aqueous solution in the step (3) is 0.2-0.4 mg/mL;
the dosage of the water-soluble chitosan in the step (3) is calculated according to the concentration of the water-soluble chitosan in a system of 0.3-0.8 mg/mL;
the preheating temperature in the step (3) is 40-60 ℃, and the time is 10-20 min;
the concentration of the sodium tripolyphosphate aqueous solution in the step (3) is 0.3-0.8 mg/mL;
in the step (3), the addition amount of the sodium tripolyphosphate aqueous solution is 4-6 mL according to the volume of the chitosan solution from which the residues of the insoluble particles are removed being 20 mL;
the reaction time in the step (3) is 10-30 min
The stirring time in the step (3) is 1-18 h;
adjusting the pH value to 4.7-4.8 in the step (3);
the reagent used for adjusting in the step (3) is sodium hydroxide solution;
the rotation speed of the preheated stirring in the step (3) is 200-1000 rpm.
7. The method of preparing chitosan-starch composite Janus particles of claim 1, wherein:
diluting the chitosan nanoparticle dispersion liquid by 3.3-100 times before use in the step (4);
the volume ratio of the chitosan nanoparticle dispersion liquid to the Pickering emulsion in the step (4) is 1;
the reaction time in the step (4) is 5-60 min.
8. The method of preparing chitosan-starch composite Janus particles of claim 7, wherein:
diluting the chitosan nanoparticle dispersion liquid by 5-50 times before use in the step (4);
the volume ratio of the chitosan nanoparticle dispersion liquid to the Pickering emulsion in the step (4) is 2-20;
the reaction time in the step (4) is 10-30 min;
the separation of redundant chitosan nanoparticle dispersion liquid in the step (4) is realized by centrifugation; the centrifugation time is 1-7 min;
the repetition frequency in the step (4) is 1 to 7 times.
9. A chitosan-starch composite Janus particle, which is characterized in that: obtained by the production method described in any one of claims 1 to 8.
10. Use of the chitosan-starch composite Janus particle as claimed in claim 9 in the food or pharmaceutical field.
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