CN115368623B - Environment-response starch-based aerogel and preparation method and application thereof - Google Patents

Environment-response starch-based aerogel and preparation method and application thereof Download PDF

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CN115368623B
CN115368623B CN202211118336.9A CN202211118336A CN115368623B CN 115368623 B CN115368623 B CN 115368623B CN 202211118336 A CN202211118336 A CN 202211118336A CN 115368623 B CN115368623 B CN 115368623B
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缪铭
陆可钰
刘瑶
李赟高
孙雨静
张涛
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Jiangnan University
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Abstract

The application discloses an environment-responsive starch-based aerogel and a preparation method and application thereof, and belongs to the technical field of starch materials. The application relates to a preparation method of environment-responsive starch-based aerogel, which takes nano-scale starch particles as a substrate and utilizes a hydroxyl charge modifier and an enzymatic catalysis combined drying dehydration technology to obtain the environment-responsive starch-based aerogel; the method has the characteristics of high-efficiency and mild reaction, safe and controllable process, simple and environment-friendly operation and the like, and realizes the green preparation of the high-performance environment-responsive starch-based aerogel; the prepared environment-responsive starch-based aerogel has pH sensitivity, the expansion degree of the aerogel is improved by 10-60% within the pH value range of 3-10, and the environment-responsive starch-based aerogel has strong loading capacity, and can be widely applied to the fields of functional substance delivery controlled release carriers, food fresh-keeping active packages, extracellular matrix scaffolds and the like.

Description

Environment-response starch-based aerogel and preparation method and application thereof
Technical Field
The application relates to an environment response starch-based aerogel and a preparation method and application thereof, and belongs to the technical field of starch material processing.
Background
Aerogel is an emerging solid material, has unique properties of porous, ultra-high specific surface area and ultra-low density, and has wide application prospects in various industries, such as the fields of serving as a drug carrier, an adsorption material, a foam substitute, a heat insulation material, a supporting framework and the like as other functional materials. The first aerogel batch was obtained by supercritical carbon dioxide drying from Kistler at the university of stanfu, starting from rubber, silicon, cellulose derivatives and alumina, opening the research gate for aerogels. With the development of polymer synthesis technology, more and more emerging polymer materials are applied as precursor materials of aerogel, such as polysaccharide, carbon, cellulose, etc. In recent years, materials with unique properties such as graphene, cellulose nanocrystals and the like are applied to aerogels, and meanwhile, composite aerogels using various materials are also studied in a large amount to improve a certain aspect of characteristics of a single aerogel product.
Starch is an excellent material for aerogel, and is a natural high molecular compound which is green, environment-friendly, large in quantity and high in cost performance. The starch-based aerogel has the characteristics, and has better biocompatibility in application, and meanwhile, compared with cellulose, the starch-based aerogel has a cleaner synthesis process, so that the starch-based aerogel is an ideal material for preparing the aerogel by a green process.
However, starch aerogels also present some inherent bottlenecks, starch as a homopolysaccharide lacks certain charged active sites, thereby affecting the adsorption capacity for different active substances. The environmental response type aerogel prepared by taking heteropolysaccharide (sodium alginate, chitosan or carrageenan) as a raw material is reported at the present stage, for example, the sodium alginate aerogel is generally dissolved to form an aqueous solution, and then dropwise added into a salt solution containing calcium ions, so that the sodium alginate hydrogel sphere is obtained through gelation, and the structure of the aerogel is influenced by the change of pH in the gelation process, so that the aerogel structure collapses, and active substances such as vitamins, antibacterial substances and the like cannot be effectively loaded.
Aiming at the technical problems of the starch aerogel, in order to widen the application field of the starch-based aerogel and improve the added value of the starch-based aerogel, development of a processing method of the environment-responsive starch-based aerogel is urgently required.
Disclosure of Invention
In order to solve the technical defects in the prior art, the application aims to provide an environment-responsive starch-based aerogel and a preparation method and application thereof. The starch aerogel has pH sensitivity, the expansion degree of the aerogel is improved by 10-60% within the pH value range of 3-10, and the starch aerogel has stronger loading capacity; the method has the characteristics of high-efficiency and mild reaction, safe and controllable process, simple and environment-friendly operation and the like, and realizes the green preparation of the high-performance environment-responsive starch-based aerogel; the environment-responsive starch-based aerogel can be widely applied to aspects such as a functional substance delivery controlled release carrier, a food fresh-keeping active package material, an extracellular matrix bracket and the like.
A first object of the present application is to provide a method for preparing an environmentally responsive starch-based aerogel, said method comprising the steps of:
(1) Dissolving nanoscale starch particles in a buffer salt solution to prepare a substrate solution, and enabling absolute potential of the surfaces of the nanoscale starch particles to be 30-60mV through a hydroxyl charge modifier; the pH value of the buffer salt solution is 5.0-7.0;
(2) Adding a donor substance and 80-500U/g of specific enzyme of a substrate into the substrate solution subjected to the charge modification in the step (1) for reaction, and standing after the reaction is finished to obtain a gel solution;
(3) And (3) dehydrating the gel solution obtained in the step (2) under a supercritical condition to obtain the target product environment response starch-based aerogel.
In one embodiment, the source of the nanoscale starch particles of step (1): extracting endosperm of natural plants such as corn, rice, wheat, sorghum, etc.; the specific preparation process of the starch particles comprises the following steps: the grain particles are prepared by steps of crushing, partial acidolysis, extraction, classification, precipitation, drying and the like, and have the size of 30-120nm and the molecular weight of 10 7 -10 8 g/mol, amylose>10%。
In one embodiment, the nanoscale starch particles of step (1) comprise corn starch particles, potato starch particles, rice starch particles.
In one embodiment, the buffer solution of step (1) comprises any one of phosphate buffer, citrate buffer, carbonate buffer, acetate buffer, barbiturate buffer, tris salt buffer, and the like.
In one embodiment, the substrate solution of step (1) has a concentration of 10 to 40%.
In one embodiment, the hydroxyl charge modifier of step (1) comprises one or more of glucosamine, glucuronic acid, succinic anhydride, dimethylaminopropylamine, and aminoethylpiperazine.
In one embodiment, the donor molecule of step (2) comprises one or more of sucrose, linear dextrin, maltose, phosphorylated glucose derivatives.
In one embodiment, the specific enzyme of step (2) is one or more of the multifunctional amylases in hydrolase family 13, 57, 77 that can extend the alpha-1, 4 chain on the surface of the starch granule.
In one embodiment, the specific enzyme comprises one or more of a GH13 multifunctional amylosucrase, a GH57 multifunctional amylomaltase and a GH77 multifunctional starch α -transglycosylase.
In one embodiment, the donor molecule of step (2) is added in an amount of 5 to 30 times the mass of the glucosyl substrate.
In one embodiment, the reaction conditions of step (2) are: the temperature is 20-50 ℃ and the time is 2-36h.
In one embodiment, the supercritical conditions of step (3): the pressure is 7.5-12.0MPa, and the temperature is 32-45 ℃.
In one embodiment, the environmentally responsive starch-based aerogel has a density of 0.05 to 0.25g/cm 3 The porosity is 90% -95%.
It is a second object of the present application to provide an environmentally responsive starch-based aerogel prepared by the above method.
In one embodiment, the environmentally responsive starch-based aerogel has an increase in gel expansion in the range of pH3-10 of 10-60%.
The third object of the application is to provide an application of the environment-responsive starch-based aerogel in preparing a functional substance delivery controlled release carrier, a food fresh-keeping active package material and an extracellular matrix bracket.
The application has the following advantages:
1. the application is filled withThe nano-scale starch particles are taken as renewable resources, have the characteristics of low cost, easy obtainment, degradability and the like, are not limited by the production place and seasons, and have the size of 30-120nm and the molecular weight of 10 7 -10 8 g/mol, amylose>10%。
2. The preparation method of the application is easy to operate, the reaction condition is controllable, the cost is relatively low, and the preparation method is basically pollution-free to the environment by adopting a clean and green production process.
3. The application utilizes hydroxyl charge modification to lead the absolute potential of the surface of nano-scale starch particles to be 30-60mV, and leads starch chains on the surfaces of the particles to be assembled and aggregated to form a three-dimensional space network through enzymatic catalysis, and further combines a drying dehydration technology to obtain the high-performance environment response starch-based aerogel with the density of 0.05-0.25g/cm 3 The porosity is 90% -95%, and the gel expansion degree is improved by 10% -60% in the pH range of 3-10.
4. The product prepared by the application can protect and control the release of functional components, has slow release effect, can be applied to the aspects of food packaging, biological medicine carrying, functional medical materials and the like, has very good market prospect and wide economic benefit.
Drawings
FIG. 1 is an electron micrograph of an environmentally responsive starch-based aerogel prepared in example 1 of the present application;
FIG. 2 is a graph showing the comparison of the absorption properties of the environmentally responsive starch-based aerogel prepared in example 1 of the present application and the conventional starch aerogel prepared in comparative example 5.
Detailed Description
The application will be further elucidated with reference to the following examples, but the application is not limited to the examples.
Potential measurement: the Nano-scale starch particle potential was measured at room temperature using a Nano-ZS-potentiometer, and the refractive index of the dispersed phase and the particles were set to 1.33 and 1.53, respectively.
Density measurement: the aerogel mass M was weighed with an electronic balance, the size of the dried aerogel was measured with a vernier caliper and the volume V calculated as the density of aerogel = M/V.
Porosity measurement: as an important parameter for characterizing the aerogel structure, it is meant that the proportion of pores inside the material to the total volume of the material is calculated by using the bulk density of the sample and the true density of the starch.
Measurement of the swelling degree: 50mg of aerogel was weighed precisely, placed in 1mL of deionized water and buffer solutions of different pH, and swollen and equilibrated for 24h at a constant temperature of 40 ℃. After the supernatant was removed by centrifugation, the residual water on the surface of the swollen hydrogel was sucked off with a filter paper. Accurately weighing the mass of the hydrogel after re-swelling, and calculating the swelling degree of the hydrogel to the mass ratio of the hydrogel to the aerogel after re-swelling of the xerogel.
Adsorption capacity measurement: accurately weighing 50mg of aerogel, placing in 1mL of deionized water, adding a compound hydrogel system in a mass ratio of lysozyme to xerogel of 1:1, swelling and balancing in a water bath at 40 ℃ for 4 hours, centrifuging, taking supernatant, properly diluting, and measuring absorbance and load (M) of the supernatant at 280nm Negative pole ) The calculation formula of (2) is as follows:
wherein: m is added: the mass of lysozyme added into the system is mg; percent lysozyme release,%; c: lysozyme concentration in supernatant, mg/mL; v: supernatant volume, mL; m coagulation: aerogel powder mass, mg.
Sources of nanoscale starch particles: extracting endosperm of natural plants such as corn, rice, wheat, sorghum, etc.; the specific preparation process of the starch particles comprises the following steps: the grain particles are prepared by steps of crushing, partial acidolysis, extraction, classification, precipitation, drying and the like, and have the size of 30-120nm and the molecular weight of 10 7 -10 8 g/mol, amylose>10%。
Sources of specific hydrolase family GH13 multifunctional amylosucrase, GH57 multifunctional amylomaltase and GH77 multifunctional starch α -transglycosylase: is prepared from any one of bacillus stearothermophilus, thermophilic archaea, thermophilic thermus, and extreme thermophilic bacteria through activating culture and fermenting to generate enzyme. Available from reference (Microbial Starch-Converting Enzymes: recent Insights and per select. Ming Miao, comprehensive Reviews in Food Science and Food safety.2018), the specific hydrolase may extend the alpha-1, 4 chains on the nanoparticle surface.
GH13 amylosaccharifying enzyme: the aspergillus strain is prepared by deep fermentation and extraction, so that starch can be rapidly liquefied to generate low-molecular dextrin, and the commercial product of the enzyme can be purchased from known companies such as Norwestine and DuPont.
Example 1
The preparation method of the environment-responsive starch-based aerogel specifically comprises the following steps:
100g of nanoscale maize starch particles (particle size 52nm, molecular weight 5.2X10 were weighed out 7 g/mol and 17% of amylose content) are dissolved in Tris-hydrochloric acid buffer solution with pH of 7.0 to prepare substrate solution with 10%, succinic anhydride with mass concentration of 3% is added into the substrate solution, the pH value of a reaction system is regulated to 8.5, and the reaction is carried out for 5 hours at 42 ℃ to ensure that the absolute potential of the surface of the nanoscale starch particles is 36mV; continuously adding linear dextrin with the mass 10 times of that of the substrate and GH57 maltose to glucose transferase with the mass 100U/g of the substrate, then placing the mixture at 30 ℃ for reaction for 6 hours, and then standing the mixture for treatment to obtain gel; and (3) dehydrating the obtained gel under the supercritical condition of 35 ℃ and 8.0MPa to obtain the target product environment response starch-based aerogel.
As can be seen from analysis and measurement, the density of the environment-responsive starch-based aerogel is 0.11g/cm 3 The porosity is 92%, the water absorption expansion degree of the gel is improved by 29% under the condition of pH3-10, and the capacity of absorbing load substances of the gel three-dimensional structure is improved by 38%.
Example 2
100g of nanoscale potato starch particles (particle size 73nm, molecular weight 9.5X10 were weighed out 7 g/mol and 23% of amylose) are dissolved in an acetic acid buffer salt solution with pH of 5.4 to prepare a substrate solution with 25%, glucuronic acid with mass concentration of 5% is added into the substrate solution, the pH value of a reaction system is regulated to 9.0, and the reaction is carried out for 6 hours at 38 ℃ so that the absolute potential of the surface of the nanoscale starch particles is 42mV; continuing to add 20 times of the substrateAfter sucrose and GH13 amylosucrase with 240U/g substrate, placing the mixture at 20 ℃ for reaction for 12 hours, and then standing the mixture for treatment to obtain gel; and (3) dehydrating the obtained gel under the supercritical condition of 40 ℃ and 12.0MPa to obtain the target product environment response starch-based aerogel.
As can be seen from analysis and measurement, the density of the environment-responsive starch-based aerogel is 0.08g/cm 3 The porosity is 94%, the gel expansion degree is improved by 32% at pH3-10, and the capacity (i.e. adsorption performance) of the gel three-dimensional space junction for adsorbing the loaded substances is improved by 45%.
Example 3
100g of nano-scale rice starch particles (particle size 41nm, molecular weight 3.4X10 were weighed out 7 g/mol and 15% of amylose are dissolved in phosphate buffer salt solution with pH of 6.8 to prepare substrate solution with 40%, glucosamine with mass concentration of 3.5% is added into the substrate solution, the pH value of a reaction system is regulated to 8.5, and the reaction is carried out for 3.5 hours at 40 ℃ to ensure that the absolute potential of the surface of the nanoscale starch particles is 31mV; continuously adding phosphorylated glucose with the mass of 5 times of that of the substrate and GH57 maltose transglucosidase with the mass of 100U/g of the substrate, then placing the mixture at 35 ℃ for reaction for 4 hours, and then standing the mixture for treatment to obtain gel; and (3) dehydrating the obtained gel under the supercritical condition of 45 ℃ and 8.5MPa to obtain the target product environment response starch-based aerogel.
As can be seen from analysis and measurement, the density of the environment-responsive starch-based aerogel is 0.16g/cm 3 The porosity is 92%, the gel expansion degree is improved by 15% at pH3-10, and the capacity of adsorbing load substances of the gel three-dimensional space junction is improved by 32%.
Comparative example 1
Referring to example 1, the modification of hydroxyl charge is changed to make the absolute potential of the surface of the nano-scale starch particles be 13mV, and other conditions are unchanged, so that the target product is prepared. The results of the obtained products are shown in Table 1.
Comparative example 2
Referring to example 1, the target product was prepared by replacing the amount of GH57 maltogenic transglucosylase with 10U/g substrate and 1000U/g substrate, respectively, under the same conditions. The results of the obtained products are shown in Table 1.
Comparative example 3
Referring to example 1, the nano-scale starch particles were replaced with common corn starch, and the other conditions were unchanged, to prepare the target product. The results of the obtained products are shown in Table 1.
TABLE 1 Property results of the products obtained in comparative examples 1 to 3
Comparative example 4
Compared with the example 1, the target product is prepared by replacing GH13 amylase with unchanged other conditions. The resulting product was degraded and failed to form a gel structure.
Comparative example 5
Referring to example 1, the target product was prepared without using a charge modifier means of hydroxyl-bonded glucosamine, with other conditions unchanged; the adsorption performance results of the obtained product are shown in FIG. 2.
The specific embodiments of the application described are intended to be illustrative only of the spirit and part of the experiments. Those skilled in the art to which the application relates may make various modifications or additions to the specific embodiments described or substitutions in a similar manner without departing from the spirit of the application or exceeding the scope of the application as defined in the accompanying claims.

Claims (8)

1. A method for preparing an environmentally responsive starch-based aerogel, said method comprising the steps of:
(1) Dissolving nanoscale starch particles in a buffer salt solution to prepare a substrate solution, and enabling absolute potential of the surfaces of the nanoscale starch particles to be 30-60mV through a hydroxyl charge modifier; the pH value of the buffer salt solution is 5.0-7.0; the hydroxyl charge modifier is one or more of glucosamine, glucuronic acid, succinic anhydride, dimethylaminopropylamine and aminoethylpiperazine;
(2) Adding a donor substance and 80-500U/g of specific enzyme of a substrate into the substrate solution subjected to the charge modification in the step (1) for reaction, and standing after the reaction is finished to obtain a gel solution; the specific enzyme is one or more of GH13 multifunctional amylosucrase, GH57 multifunctional amylomaltase and GH77 multifunctional starch alpha-transglycosylase; the donor substance is one or more of sucrose, linear dextrin, maltose and phosphorylated glucose derivatives;
(3) And (3) dehydrating the gel solution obtained in the step (2) under a supercritical condition to obtain the target product environment response starch-based aerogel.
2. The method according to claim 1, wherein the mass addition amount of the donor substance in step (2) is 5 to 30 times the mass of the substrate solution.
3. The method of claim 1, wherein the reaction conditions of step (2) are: the temperature is 20-50 ℃ and the time is 2-36h.
4. The method of claim 1, wherein the supercritical conditions of step (3): the pressure is 7.5-12.0MPa, and the temperature is 32-45 ℃.
5. The method of claim 1, wherein the nanoscale starch particles of step (1) are corn starch particles, potato starch particles, rice starch particles.
6. The method according to claim 1, wherein the nano-scale starch particles have a size of 30-120nm and a molecular weight of 10 7 -10 8 g/mol, amylose>10%。
7. An environmentally responsive starch-based aerogel prepared by the method of any of claims 1-6.
8. The use of the environmentally-responsive starch-based aerogel of claim 7 in the preparation of a controlled release carrier for delivering functional substances, a food preservative active package material, and an extracellular matrix scaffold.
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