CN113527538A - Preparation method and application of cinnamic acid modified hydroxypropyl chitosan derivative - Google Patents
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Abstract
The invention discloses a preparation method and application of a cinnamic acid modified hydroxypropyl chitosan derivative, wherein the substitution degree of cinnamic acid is 0.23-0.93, and the preparation method of the cinnamic acid modified hydroxypropyl chitosan derivative comprises the steps of carrying out water-soluble chemical modification on chitosan, introducing hydroxypropyl hydrophilic groups to obtain water-soluble hydroxypropyl chitosan, introducing cinnamic acid to the hydroxypropyl chitosan, and purifying to obtain the cinnamic acid modified hydroxypropyl chitosan derivative. The preparation method is simple, the cost is low, the purification method is simple and convenient, the property is stable, the obtained cinnamic acid modified hydroxypropyl chitosan derivative has good water solubility and antibacterial activity, has good antibacterial activity on staphylococcus aureus and escherichia coli, and has good application prospects in the fields of medicines, foods, cosmetics, agriculture and the like.
Description
Technical Field
The invention belongs to the technical field of food additives, and particularly relates to a preparation method and application of a cinnamic acid modified hydroxypropyl chitosan derivative.
Background
With the development of the food industry, in order to prolong the shelf life of food and inhibit microbial contamination, the traditional physical preservation method does not meet the requirement any more, and the preservative adding method is rapidly applied due to simplicity, durability and lower cost. Abuse or overuse can pose food safety issues as chemical preservatives can have potentially cumulative toxicity. Along with the improvement of living standard and the enhancement of safety consciousness of people, some safe, nontoxic and green natural preservatives are more favored by people.
The chitosan is a natural preservative extracted from animal-related substances, is wide in distribution, simple and convenient to obtain, low in price, wide in application prospect, and capable of effectively inhibiting the growth and the reproduction of various microorganisms. However, when the pH is more than 6.5, the water solubility of chitosan is not desirable, which greatly limits the range of applications.
The cinnamic acid is a natural organic acid separated from cinnamon bark or benzoin, is safe to human bodies, has the functions of antibiosis, anti-inflammation, antioxidation and the like, can be applied to mildew prevention, corrosion prevention and sterilization of foods such as grains, vegetables, fruits and the like, is mainly used in the fields of essences and spices, food additives, medicine industry and the like, and has various cinnamic acid compounds. Cinnamic acid, however, is insoluble in water, which greatly limits its application and potential value in the food industry.
However, chitosan is a natural macromolecular product, and when used as a food preservative and antibacterial agent, the chitosan still has the defects of low antibacterial activity, poor water solubility and the like compared with the traditional common chemical preservative, so that the chitosan is not widely applied in the food industry at present.
Disclosure of Invention
This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.
The present invention has been made in view of the above and/or technical gaps in the existing food additive field.
The invention aims to provide a cinnamic acid modified hydroxypropyl chitosan derivative.
Therefore, as one aspect of the invention, the invention overcomes the defects in the prior art and provides a cinnamic acid modified hydroxypropyl chitosan derivative.
In order to solve the technical problems, the invention provides the following technical scheme: a cinnamic acid modified hydroxypropyl chitosan derivative, the chemical structural formula of which is shown as follows,
wherein DD is deacetylation degree of 80%, substitution degree of hydroxypropyl is 1.12, and substitution degree of cinnamic acid is 0.23-0.93.
As a preferable scheme of the cinnamic acid modified hydroxypropyl chitosan derivative, the cinnamic acid modified hydroxypropyl chitosan derivative comprises the following steps: the chitosan is chitosan with the molecular weight of 100kDa and the deacetylation degree of 80 percent.
In one aspect of the invention, the invention overcomes the defects in the prior art, and provides a preparation method of a cinnamic acid modified hydroxypropyl chitosan derivative, which comprises the steps of dissolving hydroxypropyl chitosan in ultrapure water, dissolving cinnamic acid in dimethyl sulfoxide, slowly adding a cinnamic acid solution into the hydroxypropyl chitosan solution by using a constant pressure titration funnel, adding a certain amount of 1- (3-dimethylaminopropyl) -3-ethyl carbodiimide hydrochloride, stirring and adjusting the pH value, magnetically stirring the mixed solution, dialyzing, and carrying out vacuum freeze drying to obtain the cinnamic acid modified hydroxypropyl chitosan derivative.
As a preferred scheme of the preparation method of the cinnamic acid modified hydroxypropyl chitosan derivative, the preparation method comprises the following steps: the molar ratio of the hydroxypropyl chitosan to the cinnamic acid is 2:1 to 3.
As a preferred scheme of the preparation method of the cinnamic acid modified hydroxypropyl chitosan derivative, the preparation method comprises the following steps: the pH value is adjusted to 5.5.
As a preferred scheme of the preparation method of the cinnamic acid modified hydroxypropyl chitosan derivative, the preparation method comprises the following steps: the chitosan is chitosan with the molecular weight of 100kDa and the deacetylation degree of 80 percent.
As a preferred scheme of the preparation method of the cinnamic acid modified hydroxypropyl chitosan derivative, the preparation method comprises the following steps: the mixed solution is magnetically stirred at room temperature, and the reaction time of the magnetic stirring is 24 hours.
As a preferred scheme of the preparation method of the cinnamic acid modified hydroxypropyl chitosan derivative, the preparation method comprises the following steps: and the method also comprises a purification step, wherein the mixed solution obtained after magnetic stirring is finished is dialyzed for 72 hours by ultrapure water, the cutoff molecular weight of a dialysis bag is 1000Da, and then vacuum freeze drying is carried out, so that the purified cinnamic acid modified hydroxypropyl chitosan derivative is finally obtained.
As a preferred scheme of the preparation method of the cinnamic acid modified hydroxypropyl chitosan derivative, the preparation method comprises the following steps: the preparation method of the hydroxypropyl chitosan comprises the steps of adding 50% by mass of sodium hydroxide aqueous solution into chitosan, stirring at room temperature for 3 hours to uniformly mix the chitosan, standing at-20 ℃ for 24 hours, unfreezing the chitosan, transferring the mixture into a three-neck flask containing isopropanol, violently stirring at room temperature for 30 minutes, adding 25% tetramethyl ammonium hydroxide and propylene oxide, continuously stirring at room temperature for 1 hour, refluxing at 45 ℃ for 6 hours, cooling to room temperature, dialyzing and purifying with ultrapure water, and carrying out vacuum freeze drying to obtain the hydroxypropyl chitosan.
The invention also aims to overcome the defects in the prior art and provide the application of the cinnamic acid modified hydroxypropyl chitosan derivative in the fields of medicine, food, cosmetics and agriculture.
The invention has the beneficial effects that:
(1) according to the invention, the water-soluble hydroxypropyl chitosan is obtained by carrying out water-soluble modification on chitosan, introducing a hydroxypropyl hydrophilic group, and then introducing cinnamic acid onto the hydroxypropyl chitosan to enhance the antibacterial activity of the chitosan, so that the cinnamic acid modified hydroxypropyl chitosan derivative with excellent water-solubility and antibacterial activity is prepared, and the cinnamic acid modified hydroxypropyl chitosan derivative has good application prospects in the fields of medicines, foods, cosmetics and agriculture.
(2) The cinnamic acid modified hydroxypropyl chitosan derivative has good antibacterial activity on escherichia coli and staphylococcus aureus; when the pH value of the chitosan is more than 6.5, the chitosan is poor in solubility, the cinnamic acid is not dissolved in water and is only dissolved in a plurality of organic solvents, the derivative is dissolved in an aqueous solution and a plurality of organic solvents, the water solubility of the chitosan is obviously improved by introducing the hydroxypropyl, the bacteriostatic activity of the chitosan is greatly improved by introducing the cinnamic acid, and the derivative is wider in dissolution range compared with the chitosan and the cinnamic acid; the method has simple reaction steps and higher substitution degree and yield of the product.
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In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise. Wherein:
FIG. 1 is an infrared spectrum of chitosan;
fig. 2 is an infrared spectrum of a cinnamic acid modified hydroxypropyl chitosan derivative prepared in an example of the present invention;
FIG. 3 shows the preparation of chitosan1H nuclear magnetic resonance image;
FIG. 4 is a hydroxypropyl chitosan1H nuclear magnetic resonance image;
figure 5 shows cinnamic acid modified hydroxypropyl chitosan derivatives prepared in the examples of the present invention1H nuclear magnetic resonance image;
figure 6 is a graph comparing the apparent inhibition of staphylococcus aureus by chitosan, hydroxypropyl chitosan, cinnamic acid modified hydroxypropyl chitosan derivatives, wherein (a) the blank, (b) chitosan, (c) hydroxypropyl chitosan, (d) cinnamic acid modified hydroxypropyl chitosan derivative 1, (e) cinnamic acid modified hydroxypropyl chitosan derivative 2, (f) cinnamic acid modified hydroxypropyl chitosan derivative 3;
FIG. 7 is a graph showing the comparison of the inhibitory effect of chitosan, hydroxypropyl chitosan, and cinnamic acid-modified hydroxypropyl chitosan derivatives on E.coli, wherein (a) blank control, (b) chitosan, (c) hydroxypropyl chitosan, (d) cinnamic acid-modified hydroxypropyl chitosan derivative 1, (e) cinnamic acid-modified hydroxypropyl chitosan derivative 2, and (f) cinnamic acid-modified hydroxypropyl chitosan derivative 3;
figure 8 is a synthesis scheme for cinnamic acid modified hydroxypropyl chitosan derivatives.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with examples are described in detail below.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
The preparation method of the cinnamic acid modified hydroxypropyl chitosan derivative with good water solubility and antibacterial activity comprises the following steps:
firstly, taking chitosan and epoxypropane as raw materials, carrying out water-soluble chemical modification on the chitosan, and introducing hydroxypropyl hydrophilic groups to obtain water-soluble hydroxypropyl chitosan;
and introducing the cinnamic acid onto hydroxypropyl chitosan, and purifying to obtain the cinnamic acid modified hydroxypropyl chitosan derivative, wherein the synthetic route is shown in figure 8.
Example 1:
the preparation method of the cinnamic acid modified hydroxypropyl chitosan derivative comprises the following steps:
1. preparation of hydroxypropyl chitosan
Chitosan with molecular weight of 100kDa and deacetylation degree of 80 percent is selected.
Adding 15mL of 50% sodium hydroxide aqueous solution into 5g of chitosan, stirring for 3h at room temperature to uniformly mix, and placing in a refrigerator at-20 ℃ for 24h to fully alkalize and expand the chitosan; thawing the mixture, transferring the mixture into a three-neck flask containing 50mL of isopropanol, violently stirring for 30min at room temperature, adding 1mL of 25% tetramethylammonium hydroxide and 50mL of propylene oxide under stirring, continuously stirring for 1h at room temperature, refluxing for 6h at 45 ℃, cooling to room temperature after the reaction is finished, dialyzing and purifying for 72h with ultrapure water (the cutoff molecular weight of a dialysis bag is 1000Da), and carrying out vacuum freeze drying to obtain the hydroxypropyl chitosan.
2. Preparation of cinnamic acid modified hydroxypropyl chitosan derivative
The molar ratio of hydroxypropyl chitosan to cinnamic acid is 2: 1.
Dissolving 1mol of hydroxypropyl chitosan in 30mL of ultrapure water, dissolving 0.5mol of cinnamic acid in 30mL of dimethyl sulfoxide, slowly adding a cinnamic acid solution into the hydroxypropyl chitosan solution by using a constant-pressure titration funnel, adding 0.5mol of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, stirring, adjusting the pH value to 5.5, magnetically stirring the mixed solution at room temperature for 24 hours, dialyzing and purifying the mixed solution by using the ultrapure water for 72 hours (the cutoff molecular weight of a dialysis bag is 1000Da), and carrying out vacuum freeze drying to obtain the cinnamic acid modified hydroxypropyl chitosan derivative.
It was characterized using infrared spectroscopy and hydrogen nuclear magnetic resonance spectroscopy.
FIG. 1 is an infrared spectrum of chitosan, wherein 3440cm-1Is the stretching vibration absorption peak of O-H and N-H, 2926cm-11658cm as the absorption peak of C-H stretching vibration-1The stretching vibration absorption peak of C ═ O,1519cm-1is NH2Bending vibration absorption peak of (1), 1160cm-1And 1030cm-1Is the absorption peak of C-O stretching vibration, 893cm-1Is a ring expansion vibration absorption peak.
FIG. 2 is an infrared spectrum of the chitosan derivative of this example, in which 1519cm is compared with the raw material chitosan-1The peak of N-H stretching vibration of amino group is reduced and is 760cm-1And 687cm-1The mono-substituted absorption peak of the benzene ring in the cinnamic acid appears, which proves that the target product is successfully synthesized.
FIG. 3 shows the preparation of chitosan in this example1H NMR chart, the peak at which chemical shift occurred at 1.53ppm corresponds to-CH on the acetylamino residue3The proton peak of (1). The peak at which the chemical shift occurs at 2.50-2.82ppm corresponds to the proton peak of glucosamine N, and the multiplet at 3.82-4.91ppm is the methine hydrogen on glucosamine and acetylglucosamine.
FIG. 4 shows hydroxypropyl chitosan in this example1H NMR chart showing that, compared with chitosan, a stronger-CH of hydroxypropyl group appears at 1.59ppm3The characteristic peak proves the successful synthesis of hydroxypropyl chitosan.
Figure 5 shows the cinnamic acid modified hydroxypropyl chitosan of this example1And an H NMR chart shows that compared with hydroxypropyl chitosan, a benzene ring characteristic peak of cinnamic acid appears at 6.58-8.40ppm, which proves that the cinnamic acid is successfully introduced into the hydroxypropyl chitosan, namely the cinnamic acid modified hydroxypropyl chitosan derivative is successfully synthesized.
Example 2:
the preparation method of the cinnamic acid modified hydroxypropyl chitosan derivative comprises the following steps:
1. preparation of hydroxypropyl chitosan
Chitosan with molecular weight of 100kDa and deacetylation degree of 80 percent is selected.
Adding 15mL of 50% sodium hydroxide aqueous solution into 5g of chitosan, stirring for 3h at room temperature to uniformly mix, and placing in a refrigerator at-20 ℃ for 24h to fully alkalize and expand the chitosan; thawing the mixture, transferring the mixture into a three-neck flask containing 50mL of isopropanol, violently stirring for 30min at room temperature, adding 1mL of 25% tetramethylammonium hydroxide and 50mL of propylene oxide under stirring, continuously stirring for 1h at room temperature, refluxing for 6h at 45 ℃, cooling to room temperature after the reaction is finished, dialyzing and purifying for 72h with ultrapure water (the cutoff molecular weight of a dialysis bag is 1000Da), and carrying out vacuum freeze drying to obtain the hydroxypropyl chitosan.
2. Preparation of cinnamic acid modified hydroxypropyl chitosan derivative
The molar ratio of hydroxypropyl chitosan to cinnamic acid is 1: 1.
Dissolving 1mol of hydroxypropyl chitosan in 30mL of ultrapure water, dissolving 1mol of cinnamic acid in 30mL of dimethyl sulfoxide, slowly adding a cinnamic acid solution into the hydroxypropyl chitosan solution by using a constant pressure titration funnel, adding 1mol of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, stirring, adjusting the pH value to 5.5, magnetically stirring the mixed solution at room temperature for 24 hours, dialyzing and purifying the mixed solution by using the ultrapure water for 72 hours (the cutoff molecular weight of a dialysis bag is 1000Da), and performing vacuum freeze drying to obtain the cinnamic acid modified hydroxypropyl chitosan derivative.
Example 3:
the preparation method of the cinnamic acid modified hydroxypropyl chitosan derivative comprises the following steps:
1. preparation of hydroxypropyl chitosan
Chitosan with molecular weight of 100kDa and deacetylation degree of 80 percent is selected.
Adding 15mL of 50% sodium hydroxide aqueous solution into 5g of chitosan, stirring for 3h at room temperature to uniformly mix, and placing in a refrigerator at-20 ℃ for 24h to fully alkalize and expand the chitosan; thawing the mixture, transferring the mixture into a three-neck flask containing 50mL of isopropanol, violently stirring for 30min at room temperature, adding 1mL of 25% tetramethylammonium hydroxide and 50mL of propylene oxide under stirring, continuously stirring for 1h at room temperature, refluxing for 6h at 45 ℃, cooling to room temperature after the reaction is finished, dialyzing and purifying for 72h with ultrapure water (the cutoff molecular weight of a dialysis bag is 1000Da), and carrying out vacuum freeze drying to obtain the hydroxypropyl chitosan.
2. Preparation of cinnamic acid modified hydroxypropyl chitosan derivative
The molar ratio of hydroxypropyl chitosan to cinnamic acid is 2: 3.
Dissolving 1mol of hydroxypropyl chitosan in 30mL of ultrapure water, dissolving 1.5mol of cinnamic acid in 30mL of dimethyl sulfoxide, slowly adding a cinnamic acid solution into the hydroxypropyl chitosan solution by using a constant-pressure titration funnel, adding 1.5mol of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, stirring, adjusting the pH value to 5.5, magnetically stirring the mixed solution at room temperature for 24 hours, dialyzing and purifying the mixed solution by using the ultrapure water for 72 hours (the cutoff molecular weight of a dialysis bag is 1000Da), and carrying out vacuum freeze drying to obtain the cinnamic acid modified hydroxypropyl chitosan derivative.
Example 4:
the cinnamic acid-modified hydroxypropyl chitosan derivatives obtained in examples 1 to 3 (designated as HPCS-CA1, HPCS-CA2, and HPCS-CA3, respectively) were used.
According to the element analysis result, the yield and the substitution degree of the cinnamic acid modified hydroxypropyl chitosan derivative are calculated by the following formulas:
DD＝1-DA
in the formula (I), the compound is shown in the specification,
DA-acetyl degree of chitosan;
DD-degree of deacetylation of chitosan;
RC/N-mass percent of carbon nitrogen in chitosan;
MNrelative to the original nitrogen atomA sub-mass;
MC-carbon atom relative atomic mass;
DS' -degree of substitution of hydroxypropyl chitosan;
R'C/N-mass percent of carbon nitrogen in hydroxypropyl chitosan;
DS' -degree of substitution of cinnamic acid modified hydroxypropyl chitosan derivative;
R”C/Nmass percent of carbon and nitrogen in the cinnamic acid modified hydroxypropyl chitosan derivative.
The elemental analysis results are shown below in table 1.
TABLE 1
Example 5:
the solubility of the cinnamic acid-modified hydroxypropyl chitosan derivatives, chitosan, hydroxypropyl chitosan, and cinnamic acid prepared in examples 1 to 3 of the present invention in water having a pH of 7.0 was measured, and the results are shown in Table 2.
TABLE 2
Example 6:
the antibacterial activity of the cinnamic acid modified hydroxypropyl chitosan derivative is as follows:
gram-negative and gram-positive bacteria (E.coli and S.aureus) were selected as test bacteria. Selecting strains, growing in LB culture medium for the second generation, culturing to obtain a strain solution with turbidity equivalent to 0.5 McLeod turbidimetric tube, and diluting with MH liquid culture medium to about 100 times to desired level (about 10 times)6CFU/mL) of bacteria.
Dissolving chitosan, hydroxypropyl chitosan and cinnamic acid modified hydroxypropyl chitosan derivative in 1% acetic acid aqueous solution by volume fraction, adjusting pH value to 6.0 with 1mol/L sodium hydroxide aqueous solution to make initial concentration of sample 4096 μ g/mL, and determining Minimum Inhibitory Concentration (MIC) and Minimum Bactericidal Concentration (MBC) of sample by double dilution method.
Adding 200 mu L of antibacterial sample liquid into the first hole of each row of a 96-well plate, taking 100 mu L to the second hole, adding 100 mu L of sterile physiological saline into the second hole, uniformly mixing, sucking 100 mu L to the third hole, repeating the steps, continuously diluting to the eighth hole, discarding the last 100 mu L, and finally obtaining the sample with the concentration of 4096, 2048, 1024, 512, 256, 128, 64 and 32 mu g/mL respectively.
To each well of the 96-well plate, 100. mu.L of the bacterial solution was added, and 3 sets of each sample were set in parallel with a blank of sterile physiological saline, and the experiment was repeated 3 times.
After being mixed evenly, the mixture is placed in an incubator at 37 ℃ for 24 hours. The minimum concentration in visually clear wells was recorded as the MIC value for this sample, and the minimum concentration of colonies grown after pipetting 100 μ L of all visually clear wells on MH solid medium plates and incubating at 37 ℃ for 24h was recorded as the MBC value.
The results of MIC and MBC values are shown in Table 3.
TABLE 3
The antibacterial activity of chitosan, hydroxypropyl chitosan, cinnamic acid modified hydroxypropyl chitosan derivatives against staphylococcus aureus and escherichia coli is shown in fig. 6 and 7, respectively. Compared with a blank control, the chitosan (b), the hydroxypropyl chitosan (c) and the cinnamic acid modified hydroxypropyl chitosan derivative (d, e, f) can inhibit the growth of escherichia coli and staphylococcus aureus to different degrees, and the modified material is proved to have better antibacterial activity.
The invention provides a preparation method of cinnamic acid modified hydroxypropyl chitosan derivatives, which comprises the steps of taking chitosan and propylene oxide as raw materials, carrying out water-soluble chemical modification on chitosan, and introducing hydroxypropyl hydrophilic groups to obtain water-soluble hydroxypropyl chitosan; introducing cinnamic acid onto hydroxypropyl chitosan, and purifying to obtain cinnamic acid modified hydroxypropyl chitosan derivative; the analysis of the derivative by infrared spectroscopy and nuclear magnetic resonance hydrogen spectroscopy confirms that the cinnamic acid is effectively combined with hydroxypropyl chitosan, and the substitution degree of hydroxypropyl of the derivative is 1.124 and the substitution degree of cinnamic acid is 0.232-0.933 obtained by elemental analysis.
The preparation method is simple, the cost is low, the purification method is simple and convenient, the property is stable, the obtained cinnamic acid modified hydroxypropyl chitosan derivative has good water solubility and antibacterial activity, has good antibacterial activity on staphylococcus aureus and escherichia coli, and has good application prospects in the fields of medicines, foods, cosmetics, agriculture and the like.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (10)
1. A cinnamic acid modified hydroxypropyl chitosan derivative is characterized in that: the chemical structural formula of the cinnamic acid modified hydroxypropyl chitosan derivative is as follows:
wherein DD is deacetylation degree of 80%, substitution degree of hydroxypropyl is 1.12, and substitution degree of cinnamic acid is 0.23-0.93.
2. The cinnamic acid-modified hydroxypropyl chitosan derivative of claim 1, wherein: the chitosan is chitosan with the molecular weight of 100kDa and the deacetylation degree of 80 percent.
3. A method for preparing the cinnamic acid modified hydroxypropyl chitosan derivative of claim 1 or 2, wherein: comprises the steps of (a) preparing a mixture of a plurality of raw materials,
dissolving hydroxypropyl chitosan in ultrapure water, dissolving cinnamic acid in dimethyl sulfoxide, slowly adding the cinnamic acid solution into the hydroxypropyl chitosan solution by using a constant pressure titration funnel, adding a certain amount of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, stirring and adjusting the pH value;
and magnetically stirring the mixed solution, dialyzing, and carrying out vacuum freeze drying to obtain the cinnamic acid modified hydroxypropyl chitosan derivative.
4. A method for preparing the cinnamic acid modified hydroxypropyl chitosan derivative of claim 3, wherein: the molar ratio of hydroxypropyl chitosan to cinnamic acid is 2:1 to 3.
5. A method for preparing the cinnamic acid modified hydroxypropyl chitosan derivative of claim 3, wherein: the pH value is adjusted to 5.5.
6. A method for preparing the cinnamic acid modified hydroxypropyl chitosan derivative of claim 3, wherein: the chitosan is chitosan with the molecular weight of 100kDa and the deacetylation degree of 80 percent.
7. A method for preparing the cinnamic acid modified hydroxypropyl chitosan derivative of claim 3, wherein: and magnetically stirring the mixed solution at room temperature, wherein the reaction time of the magnetic stirring is 24 hours.
8. The method for preparing a cinnamic acid-modified hydroxypropyl chitosan derivative according to claim 3, wherein: and the method also comprises a purification step, wherein the mixed solution obtained after magnetic stirring is finished is dialyzed for 72 hours by ultrapure water, the cutoff molecular weight of a dialysis bag is 1000Da, and then vacuum freeze drying is carried out, so that the purified cinnamic acid modified hydroxypropyl chitosan derivative is finally obtained.
9. A method for preparing the cinnamic acid modified hydroxypropyl chitosan derivative according to any one of claims 3 to 8, wherein the method comprises the following steps: the preparation method of the hydroxypropyl chitosan comprises the steps of adding 50% by mass of sodium hydroxide aqueous solution into chitosan, stirring at room temperature for 3 hours to uniformly mix the chitosan, standing at-20 ℃ for 24 hours, unfreezing the chitosan, transferring the mixture into a three-neck flask containing isopropanol, violently stirring at room temperature for 30 minutes, adding 25% tetramethyl ammonium hydroxide and propylene oxide, continuously stirring at room temperature for 1 hour, refluxing at 45 ℃ for 6 hours, cooling to room temperature, dialyzing and purifying with ultrapure water, and carrying out vacuum freeze drying to obtain the hydroxypropyl chitosan.
10. The use of the cinnamic acid modified hydroxypropyl chitosan derivative of any one of claims 1 to 9 in the fields of medicine, food, cosmetics and agriculture.
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| CN113880996A (en) * | 2021-10-27 | 2022-01-04 | 大连理工大学 | Multifunctional marine antifouling coating resin and preparation method thereof |
| CN114982822A (en) * | 2022-05-17 | 2022-09-02 | 华南理工大学 | Chitosan oligosaccharide cinnamate and preparation method and application thereof |
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| CN111732674A (en) * | 2020-07-31 | 2020-10-02 | 江南大学 | Chitosan oligosaccharide-M-cinnamyl alcohol derivative, preparation method and application thereof |
| CN112062869A (en) * | 2020-09-21 | 2020-12-11 | 江苏澳新生物工程有限公司 | Industrial preparation method of O-hydroxypropyl chitosan |
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| CN113880996A (en) * | 2021-10-27 | 2022-01-04 | 大连理工大学 | Multifunctional marine antifouling coating resin and preparation method thereof |
| CN113880996B (en) * | 2021-10-27 | 2024-02-13 | 大连理工大学 | Multifunctional marine antifouling paint resin and preparation method thereof |
| CN114982822A (en) * | 2022-05-17 | 2022-09-02 | 华南理工大学 | Chitosan oligosaccharide cinnamate and preparation method and application thereof |
| CN114982822B (en) * | 2022-05-17 | 2024-02-23 | 华南理工大学 | Chitosan oligosaccharide cinnamic acid ester and preparation method and application thereof |
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