CN114349875B - Preparation method of cationic selenized nano starch - Google Patents
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Abstract
The invention relates to the technical field of starch modification, in particular to a preparation method of cationic selenized nano-starch. A preparation method of cationic selenized nano-starch comprises the following steps: (1) preparing Nano starch (Nano starch); (2) preparing sulfonated nano starch (SN-starch); (3) preparing selenized nano starch (Se-SN-starch); (4) Preparing cationic selenizing nano starch (Ca-Se-SN-starch). The Ca-Se-SN-starch has catalytic activity higher than that of Se-SN-starch under the same determination condition; the highest catalytic activity of the Ca-Se-SN-starch is 2.73 times of that of the Se-SN-starch; ca-Se-SN-starch realizes the construction of new bionic glutathione peroxidase (GPx) on a low-cost, degradable and easily popularized and applied nano starch framework, can accelerate the industrialization process of bionic GPx materials, and expands the application range of modified starch.
Description
Technical Field
The invention relates to the technical field of starch modification, in particular to a preparation method of cationic selenized nano-starch.
Background
Glutathione peroxidase (GPx) is an important antioxidant enzyme that scavenges reactive oxygen species and protects cells from oxidative damage. However, due to the defects of limited natural GPx source, poor stability and the like, the application development of the GPx is limited, so that the design and synthesis of the efficient GPx antioxidant enzyme mimics are widely concerned by academia. Based on the knowledge and understanding of the structure and the characteristics of GPx, research shows that a catalytic center, a hydrophobic microenvironment and a recognition site are important catalytic elements for constructing efficient bionic GPx, and the synergistic catalytic action of the catalytic center and the hydrophobic microenvironment plays an important role in improving the activity of the bionic GPx.
The bionic GPx selenium-rich starch prepared by taking starch as a framework can overcome the defects of natural GPx, effectively simulate the antioxidant activity of GPx, and has the catalytic activity of 1.53 multiplied by 10 of the classical micromolecule antioxidant selenase PhSePh 5 And (4) doubling. The synthesis and preparation of the selenium-rich starch can develop a new technology for developing selenium-rich functional products. Meanwhile, the nano selenium-enriched starch has a nano-scale structure, the catalytic activity of the nano selenium-enriched starch is 2.73 times that of the selenium-enriched starch, the functional characteristics are mainly attributed to the fact that the nano selenium-enriched starch has a larger surface area to mass ratio, the nano selenium-enriched starch can be loaded with more active substances, and the shape and size distribution of the nano selenium-enriched starch have important influences on the sensory characteristics of taste, texture, appearance, function and the like of food, so that the nano selenium-enriched starch is beneficial to expanding the application of the nano selenium-enriched starch in food and medicine.
Positively charged groups are functional groups that mimic the arginine recognition site in native GPx with high efficiency. Therefore, modifying the positively charged groups in the nano-selenylation starch can simulate recognition sites of natural GPx, so that the catalytic activity of the nano-selenylation starch is further improved. The hydroxyl group in the glucose residue of starch can be etherified with 2, 3-epoxypropyltrimethylammonium chloride (GTA) or 3-chloro-2-hydroxypropyltrimethylammonium Chloride (CTA) under the action of alkali catalyst. The cationic starch obtained after the reaction can show cationic characteristics under the acidic, alkaline or neutral conditions, has stable and superior performance, and can effectively improve the antioxidant catalytic activity.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention aims to provide a preparation method of selenized cationic nano-starch.
The technical scheme provided by the invention is as follows:
a preparation method of cationic selenizing nano-starch comprises the following steps:
(1) Preparation of Nano starch (Nano starch): preparing 40% starch emulsion from cassava starch by using a disodium hydrogen phosphate-citric acid buffer solution, gelatinizing the starch emulsion in a boiling water bath, adding pullulanase to carry out enzymolysis for 6 hours at 60 ℃, storing supernatant for 12 hours at 4 ℃ after the enzymolysis is finished, and then washing and freeze-drying to prepare Nano starch (Nano starch);
(2) Preparation of sulfonated nano starch (SN-starch): dissolving nano starch in NaOH solution, dropwise adding acetonitrile solution of p-toluenesulfonyl chloride (p-TsCl) at 40 ℃, enabling the pH of the system to be more than 12.5 in the dropwise adding process, reacting for 6 hours, then alternately washing with ethanol and deionized water to be neutral, and freeze-drying to prepare sulfonated nano starch (SN-starch);
(3) Preparation of selenylation nano starch (Se-SN-starch): uniformly dispersing SN-starch in an absolute ethanol solution, adding sodium hydrogen selenide (NaSeH) stock solution prepared from selenium, sodium borohydride and deionized water into the SN-starch ethanol dispersion solution under the protection of nitrogen, then reacting for 6 hours at 40 ℃, filtering and washing under the atmosphere of nitrogen after the reaction is finished, and freeze-drying for 24 hours at-55 ℃ to prepare the selenylation nano starch (Se-SN-starch);
(4) Preparation of cationic selenizing nano-starch (Ca-Se-SN-starch): se-SN-starch and water/alcohol mixture solution are prepared into starch emulsion, 2, 3-epoxypropyltrimethylammonium chloride (GTA) or 3-chlorine-2-hydroxypropyl trimethyl ammonium Chloride (CTA) solution is slowly dripped into the starch emulsion, stirring reaction is carried out at 40 ℃ after dripping is finished, 75% ethanol solution is adopted for washing, filtering and freeze-drying after the reaction is finished, and then the cationic selenizing nano-starch (Ca-Se-SN-starch) is obtained.
Preferably, the pH of the disodium hydrogen phosphate-citric acid buffer in step (1) is =4.8.
Preferably, the ratio of the enzyme activity of the pullulanase in the step (1) to the mass of the starch is 50U/g.
Preferably, the concentration of NaOH in step (2) is 0.15M.
Preferably, the mass ratio of the nano starch to the p-toluenesulfonyl chloride in the step (2) is 5:1.5-3.5.
Preferably, the mass-to-volume ratio of the tosyl chloride to the acetonitrile solution in step (2) is 3g/10mL.
Preferably, the volume percentage of ethanol, methanol or isopropanol in the water/alcohol mixture solution in step (4) is 10-40%.
Preferably, in step (4) 2, 3-epoxypropyltrimethylammonium chloride or 3-chloro-2-hydroxypropyltrimethylammonium chloride is reacted with a amyloglucose unit (C) 6 H 10 O 5 ) In a molar ratio of 5-35:100.
compared with the prior art, the invention has the following beneficial effects:
(1) The Ca-Se-SN-starch has higher catalytic activity than Se-SN-starch under the same determination conditions. The highest catalytic activity of Ca-Se-SN-starch is 2.73 times of that of Se-SN-starch.
(2) The Ca-Se-SN-starch realizes the construction of a catalytic center, a hydrophobic microenvironment and a recognition site in a nano starch structure, shows obvious catalytic activity advantages, has huge application potential in the aspect of preparing nano composite materials, can be used in the aspects of biomedical equipment, biosensors or biomarkers and the like, and develops huge potential in the field of selenium-rich functional medicine foods.
Drawings
Fig. 1 is a synthetic route of cationic selenizing nano-starch;
FIG. 2 is an infrared spectrum diagram of Ca-Se-SN-starch, nano-starch, and starch;
FIG. 3 is a graph showing the change of Zeta potential in the Ca-Se-SN-starch nitrogen content;
FIG. 4 is a diagram of the catalytic activity corresponding to different etherification modified cationic selenized starches;
FIG. 5 is a diagram showing the particle size distribution of Ca-Se-SN-starch, nano-starch;
FIG. 6 is a transmission electron micrograph of Ca-Se-SN-starch during the synthesis process;
FIG. 7 shows the fixed TNB concentration of 150. Mu.M, varying the series of concentrations of CUOOH (A) and H 2 O 2 (B) Temporary Ca-Se-SN-starch and Se-SN-sthe catalytic rate of tarch; NBT was fixed at a concentration of 150. Mu.M, and CUOOH (C) and H were varied in series 2 O 2 (D) The catalytic rates of Ca-Se-SN-starch and Se-SN-starch.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1:
a preparation method of cationic selenized nano-starch (preparation route is shown in figure 1) comprises the following steps:
(1) Preparing cassava starch into 40% starch emulsion by using a disodium hydrogen phosphate-citric acid buffer solution, gelatinizing in a boiling water bath, adding pullulanase (the mass ratio of enzyme activity to starch is 50U/g) for enzymolysis at 60 ℃ for 6 hours, after the enzymolysis is finished, storing a supernatant at 4 ℃ for 12 hours, and then washing and freeze-drying to prepare Nano starch (Nano starch);
(2) Dissolving 5g of Nano starch (Nano starch) in NaOH (0.15M) solution, dropwise adding acetonitrile solution (3 g/10 mL) of p-toluenesulfonyl chloride (p-TsCl), reacting at 40 ℃ for 6 hours, enabling the pH of the system to be more than 12.5 in the reaction process, then alternately washing with ethanol and deionized water to be neutral, and freeze-drying to obtain sulfonated Nano starch (SN-starch);
(2) Adding deoxidized deionized water into selenium and sodium borohydride, and preparing sodium selenohydride (NaSeH) stock solution under the nitrogen protection atmosphere at room temperature; dispersing SN-starch in 50mL of absolute ethanol, adding the NaSeH stock solution into the SN-starch ethanol dispersion solution under the protection of nitrogen, then reacting for 6 hours at 40 ℃, washing under a nitrogen atmosphere after the reaction is finished, and freeze-drying to obtain the selenylation nano starch (Se-SN-starch);
(4) Se-SN-starch and a water/ethanol solution (the ethanol accounts for 35 percent of the volume ratio) are prepared into starch emulsion, then 40 percent of 2, 3-epoxypropyl trimethyl ammonium chloride aqueous solution is dripped, stirring reaction is carried out for 6 hours at 40 ℃ after the dripping is finished, and after the reaction is finished, 75 percent of ethanol solution is adopted for washing, filtering and drying, thus obtaining the cationic selenizing nano-starch (Ca-Se-SN-starch).
FIG. 2 is an infrared spectrum diagram of Ca-Se-SN-starch, nano-starch and starch.
As can be seen from FIG. 2, compared with the nano-starch, the SN-starch after sulfonation modification is 1174, 665, 552cm -1 In which sulfonic acid group-SO appears 3 Characteristic peak of H1598 cm -1 A characteristic peak of ester group-CO-was observed, 814cm -1 The characteristic peak of the bending vibration of the benzene ring-CH-appears, and proves that-SO is introduced to the glucose ring of the starch 3 H group, sulfonation reaction occurs. Compared with an SN-starch infrared spectrum, the Se-SN-starch p-toluenesulfonyl and other characteristic functional groups disappear in a reaction system, which indicates that the p-toluenesulfonyl disappears as a leaving group, and protected hydroxyl and NaSeH undergo nucleophilic substitution reaction, and the SeH is successfully modified on a nano starch skeleton. Ca-Se-SN-starch is at 1490cm in the cation etherification modification process -1 And a new characteristic peak appears, which indicates that the C-N characteristic peak of the quaternary ammonium group appears, and indicates that the quaternary ammonium group cationic group is successfully modified on the selenized starch. Compared with other starches, the cationic selenylation nano starch has the same structure, which indicates that the modified starch has the stability of the nano structure.
FIG. 3 is a graph showing the nitrogen content variation against Zeta potential for the preparation of Ca-Se-SN-starch of different degrees of etherification.
As can be seen from FIG. 3, the nitrogen content of Ca-Se-SN-starch increases with the addition of the cationic etherifying agent. The determination of the nitrogen content in the cationic selenylation starch further shows that the quaternary ammonium group of the etherifying agent is successfully modified on the selenylation starch. The Zeta potential of the cationic selenylation starch increases along with the increase of the nitrogen content, the selenylation starch shows electronegativity due to the existence of p-toluenesulfonic acid group, and the quaternary ammonium group on Se-SN-starch increases along with the increase of etherification modification degree, so that Ca-Se-SN-starch carries certain positive charge and shows electropositivity.
FIG. 4 shows that Ca-Se-SN-starch catalyzes the reduction of CUOOH or H by TNB or NBT (150. Mu.M) at 25 ℃ and pH 7.0 (50 mM PBS) 2 O 2 Catalytic Rate (v) of (250. Mu.M) 0 ). The catalytic activities corresponding to different etherification modified Ca-Se-SN-starch are shown in FIG. 4, and the oxidation resistant catalytic activity increases with the molar ratio of nitrogen to selenium (N (N)/N (Se)) increasing becauseThe Se-SN-starch is modified with quaternary ammonium groups to enable the Se-SN-starch to have positive charges, so that the Ca-Se-SN-starch can fully enrich surrounding substrates, the contact between an active center and the substrates is effectively improved, and the catalytic reaction rate is promoted. Subsequently, when the molar ratio of nitrogen to selenium (N (N)/N (Se)) is greater than 150, too much substrate accumulates around the positive charge on Ca-Se-SN-starch, resulting in most of the substrate being immobilized and difficult to diffuse so that the catalytic center is difficult to contact the substrate, resulting in a decrease in the catalytic rate.
FIG. 5 is a particle size distribution diagram during Se-SN-starch synthesis.
As can be seen from FIG. 5, most of the starch particles are in the range of 10-1000 nm during the modification process, and are substantially in the form of nanoparticles. The particle size distribution of the SN-starch after sulfonation modification is within the range of 100-1000 nanometers, and the quantity percentage of the SN-starch within the range of 10-100 nanometers is more. After selenylation modification, the p-toluenesulfonyl group falls off, and the hydroxyl of SN-starch and sodium hydroselenide undergo nucleophilic substitution reaction. The nano starch with the grain size distribution of 100-1000 nanometers is increased, and the integral grains of Se-SN-starch are increased, and most grains are about 100-1000 nanometers. In the cationic etherification modification process, the flocculation property of Se-SN-starch is increased, aggregation is easier to occur, and the quantity percentage in the range of 100-1000 nanometers in Ca-Se-SN-starch is further increased.
FIG. 6 is a transmission electron micrograph of Ca-Se-SN-starch during the synthesis process.
As can be seen from FIG. 6A, the SN-starch particles had a particle size distribution in the range of less than 1000nm, and the particles were spherical and semispherical. The SN-starch generates nucleophilic substitution with sodium hydroselenide, starch is converged and crosslinked, and the particle size of Se-SN-starch particles is further increased and is in the range of 500-1000 nanometers. Se-SN-starch reacts with a cationic etherifying agent, and Ca-Se-SN-starch has certain flocculation property, is easy to aggregate under alkaline conditions and has larger particle size.
FIG. 7 shows the fixed TNB concentration of 150. Mu.M, varying the series of concentrations of CUOOH (A) and H 2 O 2 (B) The catalytic rates of Ca-Se-SN-starch and Se-SN-starch; NBT was fixed at a concentration of 150. Mu.M, and CUOOH (C) and H were varied in series 2 O 2 (D) The catalytic rate of Ca-Se-SN-starch.
As shown in FIG. 7, the concentration of TNB or NBT as immobilized thiophenol substrates was 150. Mu.M, and the peroxide substrate CUOOH or H was changed 2 O 2 Recording the amount of change in the absorbance of TNB or NBT, calculating the catalytic rate v 0 . As can be seen, when four different substrate combinations TNB + CUOOH, TNB + H 2 O 2 、NBT+CUOOH、NBT+H 2 O 2 When the catalytic activity is measured, the catalytic activity is increased firstly and reaches balance finally, and Ca-Se-SN-starch can show typical saturation kinetic catalytic behavior similar to natural GPx.
For evaluating the antioxidant activity of natural GPx and bionic GPx, a common evaluation method is a direct determination method based on Hilvert professor reports and related improved methods, and the antioxidant catalytic activity of the bionic material GPx can be evaluated more conveniently and effectively. Similarly, the research references the method to evaluate the antioxidant catalytic activity of Ca-Se-SN-starch. The oxidation resistant catalytic rate of Ca-Se-SN-starch is determined by taking thiophenol substrates and peroxide substrates as double substrates. The thiophenol substrate comprises two types of 3-carboxyl-4-nitrothiophenol (TNB) and 4-Nitrothiophenol (NBT), wherein the TNB has one more carboxyl than the NBT, the TNB has stronger hydrogen bond forming capability, and the NBT has stronger hydrophobicity; the peroxide substrates include cumene hydroperoxide (CUOOH) and hydrogen peroxide (H) 2 O 2 ) Two of them, in which CUOOH is in ratio of H 2 O 2 One more p-cumyl group, H 2 O 2 The capability of forming hydrogen bonds is stronger, and the CUOOH hydrophobicity is stronger. TNB + CUOOH, TNB + H are selected 2 O 2 、NBT+CUOOH、NBT+H 2 O 2 The catalytic activity measured for the four systems is shown in table 1.
TABLE 1 catalysis Rate (v) for Ca-Se-SN-starch catalysis of reduction of superoxide (ROOH, 250 μ M) by thiophenol (ArSH, 150 μ M) at pH 7.0 (50 mM PBS) 0 )
As can be seen from Table 1, ca-Se-SN-starch has a catalytic activity higher than that of Se-SN-starch under the same measurement conditions. The highest catalytic activity of Ca-Se-SN-starch is 2.73 times of that of Se-SN-starch and 4.24 times of that of selenized starch (Se-starch). The Ca-Se-SN-starch shows obvious catalytic activity advantage, and meanwhile, the nano structure of the Ca-Se-SN-starch makes the Ca-Se-SN-starch have more potential in the field of development of selenium-enriched functional medicine foods and cosmetics.
The foregoing descriptions of specific exemplary embodiments of the present invention have been presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain certain principles of the invention and its practical application to enable one skilled in the art to make and use various exemplary embodiments of the invention and various alternatives and modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (8)
1. A preparation method of cationic selenized nano-starch is characterized by comprising the following steps:
(1) Preparation of Nano starch (Nano starch): preparing cassava starch into starch emulsion by using a disodium hydrogen phosphate-citric acid buffer solution, gelatinizing the cassava starch in a boiling water bath, adding pullulanase, performing enzymolysis for 6 hours at 60 ℃, storing supernate for 12 hours at 4 ℃ after the enzymolysis is finished, and then washing and freeze-drying to prepare Nano starch (Nano starch);
(2) Preparation of sulfonated nano starch (SN-starch): dissolving nano starch in NaOH solution, and dripping p-toluenesulfonyl chloride (P) (at 40 ℃)p-TsCl) in acetonitrile, the pH of the system being adjusted during the dropwise addition>12.5, reacting for 6 hours, then alternately washing with ethanol and deionized water to be neutral, and freeze-drying to prepare the sulfonated nano starch (SN-starch);
(3) Preparation of selenylation nano starch (Se-SN-starch): uniformly dispersing SN-starch in an absolute ethanol solution, adding sodium hydrogen selenide (NaSeH) stock solution prepared from selenium, sodium borohydride and deionized water into the SN-starch ethanol dispersion solution under the protection of nitrogen, then reacting for 6 hours at 40 ℃, filtering and washing under the atmosphere of nitrogen after the reaction is finished, and freeze-drying for 24 hours at-55 ℃ to prepare the selenylation nano starch (Se-SN-starch);
(4) Preparation of cationic selenizing nano-starch (Ca-Se-SN-starch): se-SN-starch and water/alcohol mixture solution are prepared into starch emulsion, 2, 3-epoxypropyltrimethylammonium chloride (GTA) or 3-chlorine-2-hydroxypropyl trimethyl ammonium Chloride (CTA) solution is slowly dripped into the starch emulsion, stirring reaction is carried out at 40 ℃ after dripping is finished, 75% ethanol solution is adopted for washing, filtering and freeze-drying after the reaction is finished, and then the cationic selenizing nano-starch (Ca-Se-SN-starch) is obtained.
2. The method for preparing cationic selenized nano-starch of claim 1, wherein the pH of the disodium hydrogen phosphate-citric acid buffer solution in the step (1) is =4.8.
3. The method for preparing cationic selenizing nano-starch according to claim 1, wherein the mass ratio of the enzyme activity of the pullulanase in the step (1) to the starch is 50U/g.
4. The method for preparing cationic selenized nano-starch of claim 1, wherein the concentration of NaOH in step (2) is 0.15M.
5. The preparation method of cationic selenized nano-starch as claimed in claim 1, wherein the mass ratio of nano-starch to p-toluenesulfonyl chloride in step (2) is 5:1.5-3.5.
6. The preparation method of cationic selenized nano-starch of claim 1, wherein the mass-to-volume ratio of the p-toluenesulfonyl chloride to the acetonitrile solution in step (2) is 3g/10mL.
7. The method for preparing cationic selenized nano-starch as claimed in claim 1, wherein the volume percentage of ethanol, methanol or isopropanol in the water/alcohol mixture solution in step (4) is 10-40%.
8. The method for preparing cationic selenized nano-starch of claim 1, wherein in the step (4), 2, 3-epoxypropyltrimethylammonium chloride or 3-chloro-2-hydroxypropyltrimethylammonium chloride is mixed with glucose unit (C) of starch 6 H 10 O 5 ) In a molar ratio of 5 to 35:100.
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| CN113135998A (en) * | 2021-04-02 | 2021-07-20 | 北部湾大学 | Preparation method of selenium-rich starch |
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