CN115746172A - Preparation method and fresh-keeping application of pH-sensitive starch-based carrier - Google Patents
Preparation method and fresh-keeping application of pH-sensitive starch-based carrier Download PDFInfo
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- CN115746172A CN115746172A CN202211511837.3A CN202211511837A CN115746172A CN 115746172 A CN115746172 A CN 115746172A CN 202211511837 A CN202211511837 A CN 202211511837A CN 115746172 A CN115746172 A CN 115746172A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 139
- 229940109262 curcumin Drugs 0.000 claims abstract description 104
- 239000004148 curcumin Substances 0.000 claims abstract description 98
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- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims abstract description 50
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Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/90—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in food processing or handling, e.g. food conservation
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- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention belongs to the technical field of modified starch. A preparation method of a pH-sensitive starch-based carrier is characterized by comprising the following steps: selecting carboxymethyl starch, potassium persulfate, methacrylic acid and sodium hydroxide; adding distilled water and carboxymethyl starch into a three-neck flask, and gelatinizing to obtain gelatinized carboxymethyl starch; adding potassium persulfate solution for activation; adding methacrylic acid neutralizing solution to obtain grafted starch; and step two, weighing the grafted starch and the beta-cyclodextrin, placing the grafted starch and the beta-cyclodextrin in an alkali liquor prepared from sodium hydroxide, slowly stirring the mixture at 40 ℃, and adding a cross-linking agent sodium trimetaphosphate to obtain the pH-sensitive starch-based carrier. The method takes carboxymethyl starch as a raw material, has certain pH sensitivity and embedding function through double modification, realizes the functionalization of the carrier, has simple preparation flow and low cost, and is convenient for mass production; the invention uses the carrier to embed the curcumin as the food preservative, and solves the problems that the curcumin is not easy to use and is sensitive to the environment.
Description
Technical Field
The invention belongs to the technical field of modified starch, and particularly relates to a preparation method of a pH-sensitive starch-based carrier and application thereof in the technical field of preservation.
Background
The starch has the advantages of wide source range, low cost, degradability, reproducibility, high safety and biocompatibility, and has great development potential in the field of carrier material application, but the natural starch has poor hydrophobicity and low resistance and is difficult to meet the condition of serving as a fat-soluble functional factor carrier. The alpha-D-glucopyranose is a basic unit for forming the starch, and the 2, 3 and 6 positions of the alpha-D-glucopyranose have hydroxyl groups with higher activity, so that the molecular structure of the starch is easy to modify and regulate. By modifying starch, the starch has the potential of being used as a carrier, the application performance of the starch is improved, and the embedding effect of functional factors is improved. The carboxymethyl starch is an anionic starch derivative soluble in cold water, and has the advantages of wide source, low production cost, simple process and the like. At present, the research mostly uses carboxymethyl starch as raw material, and produces graft products with acrylic acid, acrylamide, styrene and the like through free radical graft copolymerization. The copolymerization principle of the grafted starch can be divided into three types of free radical initiation, ionic interaction and condensation addition, and the invention adopts the first mode to modify carboxymethyl starch by the free radical initiation to obtain the grafted modified starch. The beta-cyclodextrin is an oligomer consisting of seven glucopyranoses, has an external hydrophilic and internal hydrophobic cavity structure, can form an inclusion compound with some hydrophobic organic molecules through the action of a host and an object, and has certain adsorption characteristics. Cyclodextrin polymers have a large number of hydroxyl groups on the molecule which can be combined with other materials by cross-linking agents or other chemical actions to give cross-linked cyclodextrin polymers. The invention combines grafted starch and beta-cyclodextrin by a cross-linking agent to obtain the composite modified starch.
Curcumin is a green and natural food preservative, is non-toxic and harmless, has certain physiological effects of resisting oxidation, cancer, inflammation and the like, but has poor water solubility, low bioavailability and poor self stability, is sensitive to external factors such as ultraviolet rays, oxygen and temperature, and seriously restricts the application field of curcumin. At present, a plurality of documents report that different types of delivery systems are applied to improving the bioavailability of curcumin, but still have some problems to be solved, such as difficult control of the release rate of curcumin in vivo, easy metabolism in intestinal environment and environmental sensitivity, thereby influencing the application of curcumin.
Based on the current situation of low curcumin bioavailability, the carboxymethyl starch is subjected to graft-crosslinking double modification, the molecular structure of the starch is regulated, the pH-sensitive modified starch is prepared, and the starch-curcumin compound is constructed. The starch-based carrier has corresponding pH sensitivity through process optimization, the modified starch is subjected to infrared characterization to ensure synthesis, and finally the problems of poor water solubility, poor stability and low bioavailability of curcumin are solved by embedding curcumin.
Disclosure of Invention
The invention aims to provide a preparation method of a pH-sensitive starch-based carrier, which takes carboxymethyl starch as a raw material, has certain pH sensitivity and embedding function through double modification, realizes carrier functionalization, has simple preparation process and low cost, and is convenient for mass production; the other purpose of the invention is to embed the curcumin as the food preservative by utilizing the carrier, thereby solving the problems that the curcumin is not easy to utilize and is sensitive to the environment.
In order to realize the purpose, the invention adopts the following scheme: a preparation method of a pH-sensitive starch-based carrier is characterized by comprising the following steps:
step one, (1) raw material selection: according to the mass ratio of potassium persulfate to methacrylic acid of 2-10%, according to the weight ratio of carboxymethyl starch: the mass of the methacrylic acid is 1:2 to 1:6, selecting carboxymethyl starch, potassium persulfate, methacrylic acid and sodium hydroxide for later use according to the mass ratio (neutralization degree) of the sodium hydroxide to the methacrylic acid of 10-30%;
(2) methacrylic acid neutralizing solution: weighing sodium hydroxide, dissolving the sodium hydroxide in 10mL of distilled water to prepare a sodium hydroxide solution, and mixing the sodium hydroxide solution with methacrylic acid to obtain a neutralized solution for later use;
(3) potassium persulfate solution: preparing a potassium persulfate solution by using 20mL of distilled water for later use;
(4) according to the weight ratio of carboxymethyl starch: the mass ratio of the distilled water is 1: 10-1: 50, adding distilled water and carboxymethyl starch (namely sodium carboxymethyl starch, CMS) into a three-neck flask, and magnetically stirring to uniformly disperse the carboxymethyl starch; placing the mixture in a water bath kettle to be gelatinized for 0.5 to 1 hour at the temperature of between 50 and 90 ℃, cooling the gelatinized mixture to the reaction temperature (the reaction temperature is between 50 and 80 ℃) to obtain gelatinized carboxymethyl starch;
(5) adding potassium persulfate solution (initiator) into the gelatinized carboxymethyl starch to activate the hydroxyl of the starch to generate free radicals, wherein the activation time is 0.5-1 h, and the reaction temperature is 50-80 ℃;
(6) slowly adding methacrylic acid neutralized liquid (PMAA) after activation, carrying out free radical graft copolymerization reaction under the catalysis of potassium persulfate solution (initiator), introducing nitrogen to the whole reaction system to remove oxygen interference, wherein the reaction temperature is 50-80 ℃, and the reaction time is 1-3 h; precipitating and filtering the product after reaction by deionized water and ethanol in sequence to remove monomers and homopolymers, drying and sieving the product to obtain the grafted starch (CMS-PMAA);
step two, crosslinking the grafted starch (CMS-PMAA) obtained in the step one with beta-cyclodextrin (beta-CD): according to the mass ratio of the beta-cyclodextrin to the grafted starch of 1:10 to 1:2, grafting starch: lye = 0.1-0.2 g:1mL (namely the ratio of the grafted starch to the alkali liquor is 0.1-0.2 g/mL), and the mass ratio of the sodium trimetaphosphate to the grafted starch is 1: 10-3: 10; weighing grafted starch and beta-cyclodextrin, placing the grafted starch and the beta-cyclodextrin in an alkali liquor prepared from sodium hydroxide, slowly stirring the mixture at 40 ℃, slowly adding a cross-linking agent sodium trimetaphosphate, reacting the mixture for 1 to 2 hours to obtain massive gel, crushing the massive gel, sequentially washing the massive gel with deionized water, ethanol and acetone, drying the crushed gel, and sieving the crushed gel to obtain the pH-sensitive starch-based carrier { or named as: grafted cross-linked starch (CMS-PMAA-. Beta. -CD) }.
Further, the concentration of the sodium hydroxide solution in the step one is 0.1-0.3 g/mL.
Further, the concentration of the potassium persulfate solution in the step one is 0.004-0.048 g/mL.
Further, the degree of substitution of the carboxymethyl starch selected in the first step is 0.2.
Further, the gelatinization temperature in the first step is 90 ℃.
Further, drying and sieving the product in the step one: the drying temperature is 40 ℃, and the mixture is sieved by a 200-mesh sieve.
Further, the concentration of the sodium hydroxide in the alkali liquor in the second step is 0.01-0.02 g/mL (the solvent is distilled water).
And further, drying and sieving in the step two: drying at 40 deg.C, and sieving with 200 mesh sieve.
The application of the pH-sensitive starch-based carrier obtained by the preparation method { embedded curcumin (Cur) } is characterized by comprising the following steps: step 1), preparing a curcumin/ethanol solution; step 2), adding a pH-sensitive starch-based carrier { or: preparing a carrier solution by using the grafted crosslinked starch (CMS-PMAA-beta-CD) } and deionized water, and stirring and pasting for 30-60 min in a boiling water bath; cooling to 40-50 ℃ after gelatinization, and adjusting the pH value of the solution to 7-9 to obtain a carrier suspension; according to the mass ratio of the curcumin to the pH sensitive starch-based carrier of 1: 50-1: and 10, dropwise adding the curcumin/ethanol solution into the carrier suspension under water bath heating, stirring for 2-5h, keeping out of the sun in the whole reaction process, removing ethanol by rotary evaporation after the reaction is finished, centrifuging to remove the non-embedded curcumin, and freeze-drying the supernatant to obtain the starch-curcumin composite (St-Cur).
Further, the concentration of the curcumin/ethanol solution in the step 1) is 2.5mg/mL.
Further, the concentration of the carrier suspension in the step 2) is 10-20 mg/mL.
Further, in the step 2), the rotary evaporation time is 0.5h, the temperature is 40 ℃, the centrifugal speed is 1000r/min, and the centrifugal time is 10min.
The invention has the following beneficial effects:
1. the aim of pH sensitivity is achieved by grafting methacrylic acid with carboxymethyl starch, and a corresponding pH sensitive interval is achieved by changing experimental conditions, so that the sensitive interval of the carrier can be conveniently and subsequently applied to different carrier fields.
2. The embedding rate of the starch carrier is increased by crosslinking beta-cyclodextrin through sodium trimetaphosphate, the beta-cyclodextrin has a cavity structure, the functionalization of the carrier is realized by combining the pH sensitivity of the carrier, and the curcumin of the food preservative is embedded by utilizing the carrier, so that the curcumin has different release characteristics under different pH values.
3. According to the invention, the pH sensitivity of the starch carrier is improved by adopting methacrylic acid, the embedding rate and the controlled release effect of the product are increased by crosslinking beta-cyclodextrin, and the problems of poor water solubility, low utilization rate, instability and easy decomposition of curcumin of the natural food preservative are solved. The invention provides theoretical guidance for improving the bioavailability of lipid soluble functional factors of curcumin and has good application prospect in the field of food.
4. The loss rate of the starch-curcumin complex after embedding is obviously reduced.
Drawings
FIG. 1 is a graph showing the effect of different experimental conditions (ratio of CMS to PMAA, B: neutralization degree of methacrylic acid neutralized solution, C: initiator concentration, D: reaction temperature, E: reaction time) on the swelling degree of starch at different pH values according to the present invention.
FIG. 2 is a Fourier infrared spectrum of the raw material and modified starch of the present invention.
FIG. 3 is a graph showing the effect of different experimental conditions (A: ratio, B: pH, C: time) on the curcumin embedding rate and loading of starch embedding.
Fig. 4 is a graph showing the release behavior of the starch-curcumin complex (a) and the β -cyclodextrin-curcumin complex (B) at different pH values.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of a pH-sensitive starch-based carrier comprises the following steps:
step one, (1) selection of raw materials: according to the mass ratio of potassium persulfate to methacrylic acid of 2 percent, according to the weight ratio of carboxymethyl starch: the mass of the methacrylic acid is 1:2, selecting 2g of carboxymethyl starch, 0.08g of potassium persulfate, 4g of methacrylic acid and 1.2g of sodium hydroxide for later use according to the mass ratio (neutralization degree) of the sodium hydroxide to the methacrylic acid being 30%;
(2) methacrylic acid neutralizing solution: weighing 1.2g of sodium hydroxide, dissolving the sodium hydroxide in 10mL of distilled water to prepare a sodium hydroxide solution, and mixing the sodium hydroxide solution with 4g of methacrylic acid to obtain a neutralized solution for later use;
(3) potassium persulfate solution: weighing 0.08g of potassium persulfate, and preparing a potassium persulfate solution by using 20mL of distilled water for later use;
(4) adding 100mL of distilled water and 2g of carboxymethyl starch (the mass ratio of the carboxymethyl starch to the distilled water is 1: 50) into a three-neck flask, magnetically stirring to uniformly disperse the starch, placing the mixture into a water bath kettle to gelatinize at 70 ℃ for 0.5h, and cooling to the reaction temperature of 50 ℃ after gelatinization to obtain gelatinized carboxymethyl starch;
(5) adding a potassium persulfate solution (initiator) into the gelatinized carboxymethyl starch to activate starch hydroxyl to generate free radicals, wherein the activation time is 0.5h, and the reaction temperature is 50 ℃;
(6) slowly adding methacrylic acid neutralized liquid (PMAA) after activation, carrying out free radical graft copolymerization reaction under the catalysis of potassium persulfate solution (initiator), introducing nitrogen to the whole reaction system to remove oxygen interference, wherein the reaction temperature is 50 ℃, and the reaction time is 1h; precipitating and filtering the reaction product with deionized water and ethanol in sequence to remove monomers and homopolymers, drying and sieving the product to obtain the grafted starch (CMS-PMAA);
step two, weighing 10g of grafted starch and 1g of beta-cyclodextrin (the mass ratio of the beta-cyclodextrin to the grafted starch is 1: grafted cross-linked starch (CMS-PMAA-. Beta. -CD) }.
The application of the pH-sensitive starch-based carrier obtained by the preparation method { embedded curcumin (Cur) } comprises the following steps: step 1), preparing a curcumin/ethanol solution of 2.5 mg/mL; step 2), preparing a carrier solution with the concentration of 10mg/mL by using deionized water for the pH sensitive starch-based carrier, and stirring and pasting for 30min in a boiling water bath; cooling to 40 ℃ after gelatinization, and adjusting the pH value of the solution to 8 to obtain a carrier suspension; according to the mass ratio of the curcumin to the pH sensitive starch-based carrier of 1:50, dropwise adding the curcumin/ethanol solution into the carrier suspension under the heating of a water bath, stirring for 2 hours, keeping out of the sun in the whole reaction process, performing rotary evaporation to remove ethanol after the reaction is finished (the rotary evaporation time is 0.5 hour, the temperature is 40 ℃, the centrifugal rotation speed is 1000r/min, and the centrifugal time is 10 min), centrifuging to remove the non-embedded curcumin, and freeze-drying the supernatant to obtain the starch-curcumin composite (St-Cur).
Example 2
A preparation method of a pH-sensitive starch-based carrier comprises the following steps:
step one, (1) selection of raw materials: according to the mass ratio of potassium persulfate to methacrylic acid of 4 percent, the weight ratio of carboxymethyl starch: the mass of the methacrylic acid is 1:4, selecting 2g of carboxymethyl starch, 0.32g of potassium persulfate, 8g of methacrylic acid and 1.6g of sodium hydroxide for later use according to the mass ratio (neutralization degree) of the sodium hydroxide to the methacrylic acid of 20 percent;
(2) methacrylic acid neutralizing solution: weighing 1.6g of sodium hydroxide, dissolving the sodium hydroxide in 10mL of distilled water to prepare a sodium hydroxide solution, and mixing the sodium hydroxide solution with 8g of methacrylic acid to obtain a neutralized solution for later use;
(3) potassium persulfate solution: weighing 0.32g of potassium persulfate, and preparing a potassium persulfate solution by using 20mL of distilled water for later use;
(4) adding 100mL of distilled water and 2g of carboxymethyl starch into a three-neck flask, magnetically stirring to uniformly disperse the starch, placing the mixture into a water bath kettle to gelatinize at 80 ℃ for 1h, and cooling to the reaction temperature of 60 ℃ after gelatinization to obtain gelatinized carboxymethyl starch;
(5) adding a potassium persulfate solution (initiator) into the gelatinized carboxymethyl starch to activate starch hydroxyl to generate free radicals, wherein the activation time is 1h, and the reaction temperature is 60 ℃;
(6) slowly adding methacrylic acid neutralized liquid (PMAA) after activation, carrying out free radical graft copolymerization reaction under the catalysis of potassium persulfate solution (initiator), introducing nitrogen to the whole reaction system to remove oxygen interference, wherein the reaction temperature is 60 ℃, and the reaction time is 2 hours; precipitating and filtering the reaction product with deionized water and ethanol in sequence to remove monomers and homopolymers, drying and sieving the product to obtain the grafted starch (CMS-PMAA);
step two, weighing 10g of grafted starch and 2g of beta-cyclodextrin (the mass ratio of the beta-cyclodextrin to the grafted starch is 1: grafted cross-linked starch (CMS-PMAA-. Beta. -CD) }.
The application of the pH-sensitive starch-based carrier obtained by the preparation method { embedded curcumin (Cur) } comprises the following steps: step 1), preparing a curcumin/ethanol solution of 2.5 mg/mL; step 2), preparing a carrier solution with the concentration of 10mg/mL by using deionized water for the pH sensitive starch-based carrier, and stirring and pasting for 30min in a boiling water bath; cooling to 40 ℃ after gelatinization, and adjusting the pH value of the solution to 9 to obtain a carrier suspension; according to the mass ratio of the curcumin to the pH sensitive starch-based carrier of 1:40, dropwise adding the curcumin/ethanol solution into the carrier suspension under the heating of water bath, stirring for 3 hours in a reaction manner, keeping out of the sun in the whole process, performing rotary evaporation to remove ethanol after the reaction is finished (the rotary evaporation time is 0.5 hour, the temperature is 40 ℃, the centrifugal rotation speed is 1000r/min, and the centrifugal time is 10 min), centrifuging to remove the non-embedded curcumin, and freeze-drying the supernatant to obtain the starch-curcumin composite (St-Cur).
Example 3
A preparation method of a pH-sensitive starch-based carrier comprises the following steps:
step one, (1) selection of raw materials: according to the mass ratio of potassium persulfate to methacrylic acid of 8 percent, the weight ratio of carboxymethyl starch: the mass of the methacrylic acid is 1: selecting 2g of carboxymethyl starch, 0.96g of potassium persulfate, 12g of methacrylic acid and 2.4g of sodium hydroxide for later use according to the mass ratio (neutralization degree) of the sodium hydroxide to the methacrylic acid of 20 percent;
(2) methacrylic acid neutralizing solution: weighing 2.4g of sodium hydroxide, dissolving the sodium hydroxide in 10mL of distilled water to prepare a sodium hydroxide solution, and mixing the sodium hydroxide solution with 12g of methacrylic acid to obtain a neutralized solution for later use;
(3) potassium persulfate solution: weighing 0.96g of potassium persulfate, and preparing a potassium persulfate solution by using 20mL of distilled water for later use;
(4) adding 100mL of distilled water and 2g of carboxymethyl starch into a three-neck flask, magnetically stirring to uniformly disperse the starch, placing the mixture into a water bath kettle to gelatinize for 1h at 60 ℃, and cooling to the reaction temperature of 80 ℃ after gelatinization to obtain gelatinized carboxymethyl starch;
(5) adding a potassium persulfate solution (initiator) into the gelatinized carboxymethyl starch to activate the hydroxyl of the starch to generate free radicals, wherein the activation time is 1h, and the reaction temperature is 80 ℃;
(6) slowly adding methacrylic acid neutralized liquid (PMAA) after activation, carrying out free radical graft copolymerization reaction under the catalysis of potassium persulfate solution (initiator), introducing nitrogen to the whole reaction system to remove oxygen interference, wherein the reaction temperature is 70 ℃, and the reaction time is 3 hours; precipitating and filtering the reaction product with deionized water and ethanol in sequence to remove monomers and homopolymers, drying and sieving the product to obtain the grafted starch (CMS-PMAA);
step two, weighing 10g of grafted starch and 3g of beta-cyclodextrin (the mass ratio of the beta-cyclodextrin to the grafted starch is 3: grafted cross-linked starch (CMS-PMAA-. Beta. -CD) }.
The application of the pH-sensitive starch-based carrier obtained by the preparation method { embedded curcumin (Cur) } comprises the following steps: step 1), preparing a curcumin/ethanol solution of 2.5 mg/mL; step 2), preparing a carrier solution with the concentration of 10mg/mL by using deionized water for the pH sensitive starch-based carrier, and stirring and pasting for 30min in a boiling water bath; cooling to 40 ℃ after gelatinization, and adjusting the pH value of the solution to 7 to obtain a carrier suspension; according to the mass ratio of the curcumin to the pH sensitive starch-based carrier of 1: and 20, dropwise adding the curcumin/ethanol solution into the carrier suspension under the heating of a water bath, stirring for 4 hours during the reaction, keeping out of the sun in the whole process, performing rotary evaporation to remove ethanol after the reaction is finished (the rotary evaporation time is 0.5 hour, the temperature is 40 ℃, the centrifugal rotation speed is 1000r/min, and the centrifugal time is 10 min), performing centrifugal removal to remove the non-embedded curcumin, and freeze-drying the supernatant to obtain the starch-curcumin composite (St-Cur).
Example 4
A preparation method of a pH-sensitive starch-based carrier comprises the following steps:
step one, (1) selection of raw materials: according to the mass ratio of potassium persulfate to methacrylic acid of 8 percent, the weight ratio of carboxymethyl starch: the mass of the methacrylic acid is 1:5, selecting 2g of carboxymethyl starch, 0.8g of potassium persulfate, 10g of methacrylic acid and 1g of sodium hydroxide for later use according to the mass ratio (neutralization degree) of the sodium hydroxide to the methacrylic acid of 10%;
(2) methacrylic acid neutralizing solution: weighing 1g of sodium hydroxide, dissolving the sodium hydroxide in 10mL of distilled water to prepare a sodium hydroxide solution, and mixing the sodium hydroxide solution with 10g of methacrylic acid to obtain a neutralization solution for later use;
(3) potassium persulfate solution: weighing 0.8g of potassium persulfate, and preparing a potassium persulfate solution by using 20mL of distilled water for later use;
(4) adding 100mL of distilled water and 2g of carboxymethyl starch (the mass ratio of the carboxymethyl starch to the distilled water is 1: 50) into a three-neck flask, magnetically stirring to uniformly disperse the starch, placing the mixture into a water bath kettle to gelatinize at 90 ℃ for 0.5h, and cooling to the reaction temperature of 70 ℃ after gelatinization to obtain gelatinized carboxymethyl starch;
(5) adding a potassium persulfate solution (initiator) into the gelatinized carboxymethyl starch to activate the hydroxyl of the starch to generate free radicals, wherein the activation time is 0.5h, and the reaction temperature is 70 ℃;
(6) slowly adding methacrylic acid neutralization solution (PMAA) after activation, carrying out free radical graft copolymerization reaction under the catalysis of an initiator (potassium persulfate solution), introducing nitrogen to remove oxygen interference in the whole reaction system, wherein the reaction temperature is 70 ℃, and the reaction time is 2 hours; precipitating and filtering the reaction product with deionized water and ethanol in sequence to remove monomers and homopolymers, drying and sieving the product to obtain the grafted starch (CMS-PMAA);
step two, weighing 10g of grafted starch and 2g of beta-cyclodextrin, placing the grafted starch and 2g of beta-cyclodextrin in 50mL of alkali liquor, slowly stirring the mixture at 40 ℃ (the concentration of the grafted starch is 0.2g/mL, and the concentration of sodium hydroxide in the alkali liquor is 0.01 g/mL), slowly adding 2g of cross-linking agent sodium trimetaphosphate, reacting for 1h to obtain blocky gel, crushing the whole piece of gel, cleaning and drying the blocky gel by using deionized water, ethanol and acetone in sequence, and then sieving the blocky gel (the drying temperature is 40 ℃, and sieving the blocky gel by a 200-mesh sieve) to obtain a pH sensitive starch-based carrier { or: grafted cross-linked starch (CMS-PMAA-. Beta. -CD) }.
The application of the pH-sensitive starch-based carrier obtained by the preparation method { embedded curcumin (Cur) } comprises the following steps: step 1), preparing a curcumin/ethanol solution of 2.5 mg/mL; step 2), preparing a carrier solution with the concentration of 10mg/mL by using deionized water for the pH sensitive starch-based carrier, and stirring and pasting for 30min in a boiling water bath; cooling to 40 ℃ after gelatinization, and adjusting the pH value of the solution to 8 to obtain a carrier suspension; according to the mass ratio of the curcumin to the pH sensitive starch-based carrier of 1: and 10, dropwise adding the curcumin/ethanol solution into the carrier suspension under the heating of a water bath, stirring for 3 hours, keeping out of the sun in the whole reaction process, performing rotary evaporation to remove ethanol after the reaction is finished (the rotary evaporation time is 0.5 hour, the temperature is 40 ℃, the centrifugal rotation speed is 1000r/min, and the centrifugal time is 10 min), centrifuging to remove the non-embedded curcumin, and freeze-drying the supernatant to obtain the starch-curcumin composite (St-Cur).
Example 5
A method for preparing a pH-sensitive starch-based carrier, which is different from example 1 in that:
in the step one (4), 20mL of distilled water and 2g of carboxymethyl starch (the mass ratio of the carboxymethyl starch to the distilled water is 1;
weighing 2g of grafted starch, 1g of beta-cyclodextrin (the mass ratio of the beta-cyclodextrin to the grafted starch is 1;
otherwise, as in example 1, a pH-sensitive starch-based carrier { or: grafted cross-linked starch (CMS-PMAA-. Beta. -CD) }.
The application of the pH-sensitive starch-based carrier obtained by the preparation method { embedded curcumin (Cur) } comprises the following steps: step 1), preparing a curcumin/ethanol solution of 2.5 mg/mL; step 2), preparing a carrier solution with the concentration of 20mg/mL by using deionized water for the pH sensitive starch-based carrier, and stirring and pasting for 60min in a boiling water bath; cooling to 50 ℃ after gelatinization, and adjusting the pH value of the solution to 7 to obtain a carrier suspension; according to the mass ratio of the curcumin to the pH sensitive starch-based carrier of 1:50, dropwise adding the curcumin/ethanol solution into the carrier suspension under the heating of a water bath, stirring for 5 hours, keeping out of the sun in the whole reaction process, performing rotary evaporation to remove ethanol after the reaction is finished (the rotary evaporation time is 0.5 hour, the temperature is 40 ℃, the centrifugal rotation speed is 1000r/min, and the centrifugal time is 10 min), centrifuging to remove the non-embedded curcumin, and freeze-drying the supernatant to obtain the starch-curcumin composite (St-Cur).
The influence of experimental conditions on the pH sensitivity of the grafted product and the grafted and crosslinked product is shown in FIG. 1, carboxymethyl starch grafted methacrylic acid is a free radical polymerization reaction, and the ratio of starch to methacrylic acid, the concentration of an initiator, the neutralization degree of methacrylic acid, the reaction temperature and the reaction time all influence the grafting reaction, so that the pH sensitivity is changed. At the same time, the cross-linked beta-CD has a certain influence on the carboxyl content. The product obtained in example 4 is the best synthesis condition due to the best pH sensitivity. The following data are based on the product obtained in example 4.
FIG. 2 is an IR spectrum of raw material and modified starch, CMS-PMAA at 1692cm -1 A strong absorption appeared, corresponding to a carbonyl absorption peak of PMAA, 1257cm -1 The success of grafting can be preliminarily proved by the stretching vibration of acrylic acid, the property change of a combined product and an infrared spectrum. The CMS-PMAA-beta-CD carbonyl absorption peak is shifted to the right of 1729cm compared with CMS-PMAA -1 The beta-CD is crosslinked with the graft product at 1600cm -1 The new peak is a typical absorption peak of beta-CD and is 1257cm -1 The stretching vibration of acrylic acid is weakened, the hydroxyl peak is shifted to the right and widened to 2932cm -1 The peak of the-CH 2 is stronger than that of CMS-PMAA, which indicates that more-CH 2 is introduced into the cross-linked cyclodextrin, and the introduced beta-CD provides more hydroxyl, and the combination of the infrared spectrogram change indicates that the product is successfully synthesized.
Fig. 3 is the influence of experimental conditions on the curcumin embedding rate and the loading capacity, the embedding rate is reduced and the loading capacity is increased as the addition amount of curcumin is increased, 1: when 10 hours, the maximum loading capacity is 51.16ug/mg, and the embedding rate is 76.88 percent; the embedding rate is greatly influenced by the reaction pH and the reaction time, and the embedding rate and the loading capacity are highest when the pH is 6.5 and the reaction time is 3 hours.
The stability change before and after the curcumin is embedded is shown in table 1, the curcumin loss rate is continuously increased along with the increase of storage time and temperature, because the curcumin is unstable in air and can be decomposed when meeting oxygen and high temperature, the loss rate of the embedded starch-curcumin compound is obviously reduced, the curcumin loss rate is 9.84 percent after being stored for 288h, the starch-curcumin is only 1.88 percent, the curcumin loss rate is 10.64 percent when the temperature is increased to 80 ℃, the starch-curcumin is 2.03 percent, the thermal stability and the storage time stability of the curcumin after being embedded are both improved, and the curcumin loss rate is low, which indicates that the modified starch can be used as an embedding agent, provides a physical barrier for the curcumin, and protects the curcumin from being decomposed by light, oxygen and the like.
TABLE 1 curcumin stability Change before and after encapsulation
Comparative example 1
Preparing 2.5mg/mL curcumin/ethanol solution, preparing carrier suspension with the concentration of 10mg/mL beta-cyclodextrin by using deionized water, and stirring and pasting for 30min in a boiling water bath. Cooling to 40 ℃ after gelatinization, adjusting the pH value of the solution to 7, dropwise adding a curcumin/ethanol solution into the carrier suspension under water bath heating, wherein the mass ratio of curcumin to the carrier is 1: and 20, stirring for 2 hours in the reaction process, keeping out of the sun in the whole process, removing ethanol by rotary evaporation after the reaction is finished, centrifuging to remove unencapsulated curcumin, and freeze-drying the supernatant to obtain the beta-cyclodextrin-curcumin compound.
FIG. 4 shows the release behavior of the products of example 4 and comparative example 1 at different pH values (A: starch-curcumin complex:, B: beta-cyclodextrin-curcumin complex), the starch-curcumin complex has pH sensitive release behavior, the release rate increases with the increase of pH, the release rate of the complex at pH 6, 6.5, 7, 7.5 and 8 is respectively 27.87%, 42.06%, 51.57%, 55.68% and 56.76%, because the starch swells at different pH values, the swelling degree is higher under alkaline condition, and the curcumin release rate is also higher. The release rate of the beta-cyclodextrin-curcumin complex is obviously higher than that of the starch-curcumin complex because the beta-cyclodextrin and the curcumin are simple host-guest actions, and besides the host-guest actions, hydrogen bonds or other actions exist between curcumin molecules and starch when the curcumin is embedded in the starch, so that the structure is tighter, and the release rate is lower. The release rate of the beta-cyclodextrin-curcumin complex under alkaline conditions is higher than that of the beta-cyclodextrin-curcumin complex under acidic conditions, the release rates of the beta-cyclodextrin-curcumin complex under pH 6, 6.5, 7, 7.5 and 8 are 73.46%, 75.68%, 82.26%, 83.64% and 85.12% respectively, and the release rate under alkaline conditions is higher because curcumin molecules have two phenolic hydroxyl groups and can be ionized under alkaline conditions to promote curcumin dissolution, but the carrier has no pH sensitivity.
The above examples are only preferred embodiments of the present invention, and do not limit the scope of the claims of the present invention, and it is obvious to other researchers in the field that the present invention can be modified and changed each set of experimental conditions. Any modification or improvement made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (10)
1. A preparation method of a pH-sensitive starch-based carrier is characterized by comprising the following steps:
step one, (1) raw material selection: according to the mass ratio of potassium persulfate to methacrylic acid of 2-10%, according to the weight ratio of carboxymethyl starch: the mass of the methacrylic acid is 1:2 to 1:6, selecting carboxymethyl starch, potassium persulfate, methacrylic acid and sodium hydroxide for later use according to the mass ratio of 10-30 percent of sodium hydroxide to methacrylic acid;
(2) methacrylic acid neutralizing solution: weighing sodium hydroxide, dissolving the sodium hydroxide in 10mL of distilled water to prepare a sodium hydroxide solution, and mixing the sodium hydroxide solution with methacrylic acid to obtain a neutralized solution for later use;
(3) potassium persulfate solution: preparing a potassium persulfate solution by using 20mL of distilled water for later use;
(4) according to the weight ratio of carboxymethyl starch: the mass ratio of the distilled water is 1: 10-1: 50, adding distilled water and carboxymethyl starch into a three-neck flask, and uniformly dispersing the carboxymethyl starch by magnetic stirring; placing the mixture in a water bath kettle, gelatinizing the mixture for 0.5 to 1 hour at the temperature of between 50 and 90 ℃, and cooling the gelatinized mixture to the reaction temperature to obtain gelatinized carboxymethyl starch;
(5) adding potassium persulfate solution into the gelatinized carboxymethyl starch to activate the hydroxyl of the starch to generate free radicals, wherein the activation time is 0.5-1 h, and the reaction temperature is 50-80 ℃;
(6) slowly adding methacrylic acid neutralized liquid after activation, carrying out free radical graft copolymerization reaction under the catalysis of potassium persulfate solution, introducing nitrogen into the whole reaction system to remove oxygen interference, wherein the reaction temperature is 50-80 ℃, and the reaction time is 1-3 h; precipitating and filtering the product after reaction by deionized water and ethanol in sequence to remove monomers and homopolymers, drying and sieving the product to obtain grafted starch;
step two, crosslinking the grafted starch obtained in the step one with beta-cyclodextrin: according to the mass ratio of the beta-cyclodextrin to the grafted starch of 1: 10-1: 2, grafting starch: lye = 0.1-0.2 g:1mL, wherein the mass ratio of the sodium trimetaphosphate to the grafted starch is 1:10 to 3:10; weighing grafted starch and beta-cyclodextrin, placing the grafted starch and the beta-cyclodextrin in an alkali liquor prepared from sodium hydroxide, stirring at 40 ℃, adding a cross-linking agent sodium trimetaphosphate, reacting for 1-2 h to obtain blocky gel, crushing the whole piece of gel, cleaning and drying the blocky gel by using deionized water, ethanol and acetone in sequence, and sieving to obtain the pH sensitive starch-based carrier.
2. The method for preparing a pH-sensitive starch-based carrier according to claim 1, wherein the concentration of the sodium hydroxide solution in the first step is 0.1 to 0.3g/mL; the concentration of the potassium persulfate solution in the first step is 0.004-0.048 g/mL.
3. The method for preparing a pH-sensitive starch-based carrier according to claim 1, wherein the product obtained in the first step is dried and sieved: drying at 40 deg.C, and sieving with 200 mesh sieve.
4. The method for preparing the pH sensitive starch-based carrier according to claim 1, wherein the concentration of the sodium hydroxide in the alkali solution in the second step is 0.01-0.02 g/mL.
5. The method for preparing a pH-sensitive starch-based carrier according to claim 1, wherein the reaction pH in the second step is 8 to 9.
6. The method for preparing the pH sensitive starch-based carrier according to claim 1, wherein the drying and sieving in the second step are as follows: drying at 40 deg.C, and sieving with 200 mesh sieve.
7. Use of a pH sensitive starch based carrier according to the preparation method of claim 1, comprising the steps of: step 1), preparing a curcumin/ethanol solution; step 2), preparing a carrier solution from the pH-sensitive starch-based carrier by using deionized water, and stirring and pasting for 30-60 min in a boiling water bath; cooling to 40-50 ℃ after gelatinization, and adjusting the pH value of the solution to 7-9 to obtain a carrier suspension; according to the mass ratio of the curcumin to the pH sensitive starch-based carrier of 1: 50-1: and 10, heating in a water bath, dropwise adding a curcumin/ethanol solution into the carrier suspension, reacting and stirring for 2-5 hours, keeping out of the sun in the whole reaction process, performing rotary evaporation to remove ethanol after the reaction is finished, centrifuging to remove the non-embedded curcumin, and freeze-drying the supernatant to obtain the starch-curcumin composite.
8. The use as claimed in claim 7, wherein the concentration of curcumin/ethanol solution in step 1) is 2.5mg/mL.
9. The use according to claim 7, wherein the carrier suspension in step 2) has a concentration of 10 to 20mg/mL.
10. The use of claim 7, wherein in step 2) the spin-steaming time is 0.5h, the temperature is 40 ℃, the centrifugation speed is 1000r/min, and the centrifugation time is 10min.
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