CN110256607B - Anionized 2-hydroxypropyl trimethyl ammonium chloride chitosan and preparation method and application thereof - Google Patents
Anionized 2-hydroxypropyl trimethyl ammonium chloride chitosan and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the field of foods, cosmetics and biomedicine industries, in particular to anionized 2-hydroxypropyl trimethyl ammonium chloride chitosan and a preparation method and application thereof. The anionized 2-hydroxypropyl trimethyl ammonium chloride chitosan has a structural formula shown in formula (1); the invention has the advantages of simple reaction, high yield of target compounds and easy popularization and industrial application. Experiments prove that the anionized 2-hydroxypropyl trimethyl ammonium chloride chitosan has good water solubility, certain antibacterial activity and excellent moisture absorption and retention performance, and can be widely applied to the fields of food, cosmetics and biomedicine.Formula (1), whereinWherein n represents polymerization degree, and the average value range is 50-1000.
Description
Technical Field
The invention relates to the field of foods, cosmetics and biomedicine industries, in particular to anionized 2-hydroxypropyl trimethyl ammonium chloride chitosan and a preparation method and application thereof.
Background
The moisture absorption and retention capacity of the moisture absorption and retention agent mainly depends on the acting force on water molecules, and the application of the moisture absorption and retention agent mainly comprises the fields of food, daily chemicals and the like. Sodium hyaluronate is widely applied as a good moisture absorption humectant, but the preparation process of sodium hyaluronate is complex and high in cost, so that the search for a moisture absorption humectant substitute which has similar effects with wide sources and low price is an important subject. Meanwhile, the moisture absorption humectant has application in the field of food, and the hydrophilic capacity of carbohydrate is one of the most important functional properties in the aspect of food. The moisture absorption humectant with bacteriostatic activity can play a more important role in the fields of food, daily chemicals and the like.
The chitosan has biodegradability, biocompatibility, nontoxicity, film forming property, moisture absorption and retention property and antioxidant activity, so that the chitosan can be widely applied to various fields of medicine, food, agriculture, daily chemicals and the like. Although chitosan has certain biological activity, it is not enough to support the large-scale development and utilization. Researches prove that the 2-hydroxypropyl trimethyl ammonium chloride chitosan with high substitution degree has good moisture absorption and retention performance and certain antibacterial activity. Meanwhile, chloride ions in the 2-hydroxypropyl trimethyl ammonium chloride chitosan can be replaced by active molecules with high moisture absorption and retention performance and bacteriostatic activity in an ion exchange mode, so that the activity of the 2-hydroxypropyl trimethyl ammonium chloride chitosan is improved. The modified chitosan derivative has certain bacteriostatic activity and good moisture absorption and retention performance, is a good choice for replacing the traditional moisture absorption and retention agent, can be used as a functional food additive to improve the structure of food, enhance the moisture retention function of the food and adjust the water activity of the food due to the good bacteriostatic activity and the good moisture absorption and retention performance, and can also be used as a fresh-keeping material of the food to realize the fresh keeping of the food.
Disclosure of Invention
In order to solve the technical problems, the invention provides anionized 2-hydroxypropyl trimethyl ammonium chloride chitosan and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
an anionized 2-hydroxypropyl trimethyl ammonium chloride chitosan, the structural formula of the anionized 2-hydroxypropyl trimethyl ammonium chloride chitosan is shown as a formula (1):
formula (1)
In the formula (1)
Wherein n represents polymerization degree, and the average value range is 50-1000.
The preparation method of the anionized 2-hydroxypropyl trimethyl ammonium chloride chitosan comprises the following steps:
(1) dispersing chitosan in isopropanol to swell, adding a sodium hydroxide aqueous solution and a 3-chloro-2-hydroxypropyl trimethyl ammonium chloride solution, mixing, reacting in a metal bath at 55-75 ℃ for 9-12 hours, precipitating with ethanol, filtering, and drying to obtain 2-hydroxypropyl trimethyl ammonium chloride chitosan;
(2) dissolving the 2-hydroxypropyl trimethyl ammonium chloride chitosan in deionized water, adding a pyrrolidone sodium carboxylate aqueous solution, a sodium lactate aqueous solution or a betaine aqueous solution, uniformly mixing, reacting for 6-8h at room temperature, intercepting and dialyzing after reaction, and freeze-drying to obtain the anionic 2-hydroxypropyl trimethyl ammonium chloride chitosan shown in the formula (1).
The molar weight of the 3-chloro-2-hydroxypropyl trimethyl ammonium chloride in the step (1) is 3-5 times that of the chitosan; the molar weight of the sodium hydroxide is 1 to 1.5 times of that of the chitosan.
And (3) after the reaction is carried out for 9-12 hours in the metal bath, carrying out alcohol precipitation on a reaction product by using ethanol, washing by using 95% of ethanol in percentage by mass, carrying out suction filtration, and drying to obtain the 2-hydroxypropyl trimethyl ammonium chloride chitosan.
The molar weight of the 2-hydroxypropyl trimethyl ammonium chloride chitosan in the step (2) is 3-5 times of that of the connected active molecules (the active molecules are sodium pyrrolidone carboxylate, sodium lactate or betaine).
And (3) transferring the reactant mixed solution after the reaction in the step (2) to a dialysis bag with the molecular weight cutoff of 500, dialyzing with deionized water for 24-48h, and freeze-drying to obtain the anionized 2-hydroxypropyl trimethyl ammonium chloride chitosan shown in the formula (1).
And (2) fully dissolving 2-hydroxypropyl trimethyl ammonium chloride chitosan in deionized water, transferring into a dialysis bag with the molecular weight cutoff of 500, adding a sodium pyrrolidone carboxylate aqueous solution, a sodium lactate aqueous solution or a betaine aqueous solution, performing dialysis reaction for 12-24 hours, dialyzing with deionized water for 24-48 hours after the reaction is finished, concentrating, and freeze-drying to obtain the anionized 2-hydroxypropyl trimethyl ammonium chloride chitosan shown in the formula (1).
The chitosan is dispersed in isopropanol, and the final concentration of the chitosan is 10-25%; the concentration of the aqueous solution obtained by dissolving the hydroxypropyl trimethyl ammonium chloride chitosan in deionized water is 5-20%.
The concentration of the sodium pyrrolidone carboxylate in the sodium pyrrolidone carboxylate aqueous solution is 5-15 wt%, the concentration of the sodium lactate in the sodium lactate aqueous solution is 5-15 wt%, and the concentration of the betaine in the betaine aqueous solution is 5-15 wt%.
The application of the anionized 2-hydroxypropyl trimethyl ammonium chloride chitosan is application of the anionized 2-hydroxypropyl trimethyl ammonium chloride chitosan as a bacteriostatic material, a moisture absorption agent or a humectant in the fields of food, cosmetics or biomedicine.
Compared with the prior art, the invention has the following beneficial technical effects:
(1) the moisture absorption humectant modified by chitosan and having antibacterial activity is superior to hyaluronic acid in antibacterial activity and moisture absorption and retention performance, and the moisture absorption humectant has good water solubility and wider application prospect.
(2) The anionic 2-hydroxypropyl trimethyl ammonium chloride chitosan prepared by the invention has the advantages of simple preparation process, high yield of target products and low cost of materials used in the reaction process, has certain antibacterial activity and excellent moisture absorption and preservation activity, is suitable for popularization and industrialization, and can be widely applied to the fields of food, cosmetics and biomedicine.
Drawings
FIG. 1 is a synthesis scheme of anionized 2-hydroxypropyl trimethylammonium chloride chitosan according to an embodiment of the present invention.
FIG. 2 is an infrared spectrum of chitosan; 3428 cm-1Is located as the hydroxyl absorption peak on the chitosan sugar ring, 2919 cm-1Saturated alkane C-H stretching vibration absorption peak of 1646 cm-1The absorption peak of the amino stretching vibration of the chitosan is shown.
FIG. 3 is an infrared spectrum of 2-hydroxypropyltrimethylammonium chloride chitosan according to an embodiment of the present invention; 1478 cm-1The vibration absorption peak of the methyl group of the quaternary ammonium salt introduced into the chitosan is shown.
FIG. 4 is an infrared spectrum of the anionized 2-hydroxypropyltrimethylammonium chloride chitosan sodium pyrrolidone carboxylate of example 1 in accordance with the present invention; 1727 cm-1Vibration absorption peak of C = O in connected sodium pyrrolidone carboxylate anion, 1565 cm-1The position is the vibration absorption peak of the heterocycle in the pyrrolidone carboxylic acid sodium anion.
FIG. 5 is an infrared spectrum of sodium lactate anionized 2-hydroxypropyl trimethylammonium chloride chitosan according to example 2 of the present invention; 1416 cm-1The absorption peak of carboxylic acid anion is shown.
FIG. 6 is an infrared spectrum of betaine anionized 2-hydroxypropyl trimethylammonium chloride chitosan of example 3 according to the present invention; 1415 cm-1The absorption peak of carboxylic acid anion is shown.
Detailed Description
The following examples are presented to further illustrate embodiments of the present invention, and it should be understood that the embodiments described herein are for purposes of illustration and explanation only and are not intended to limit the invention.
The anionic 2-hydroxypropyl trimethyl ammonium chloride chitosan prepared by the invention has the advantages of simple preparation process, high yield of target products and low cost of materials used in the reaction process, has certain antibacterial activity and excellent moisture absorption and preservation activity, is suitable for popularization and industrialization, and can be widely applied to the fields of food, cosmetics and biomedicine.
The invention takes chitosan, 3-chlorine-2-hydroxypropyl trimethyl ammonium chloride, sodium hydroxide and active moisture absorption and preservation compound as raw materials to prepare the anionized 2-hydroxypropyl trimethyl ammonium chloride chitosan. Furthermore, the preparation method comprises two steps: (1) the method comprises the following steps of modifying chitosan serving as a raw material by utilizing 3-chloro-2-hydroxypropyl trimethyl ammonium chloride to obtain a reactive intermediate. (2) Based on an ion exchange mode, a series of anionic compounds with biological activity and moisture absorption and retention performances, such as sodium pyrrolidone carboxylate, sodium lactate, betaine and the like, are grafted to obtain the anionized 2-hydroxypropyl trimethyl ammonium chloride chitosan. The preparation process is simple, the yield of the target product is high, the cost of materials used in the reaction process is low, and the anionized 2-hydroxypropyl trimethyl ammonium chloride chitosan prepared by the method has certain antibacterial activity and excellent moisture absorption and preservation activity, is suitable for popularization and industrial application, and can be widely applied to the fields of food, cosmetics and biomedicine.
Example 1
FIG. 1 shows the synthesis route of anionized 2-hydroxypropyl trimethyl ammonium chloride chitosan, wherein n represents the degree of polymerization, and the average value range is 50-1000.
(1) Weighing 3.38g of chitosan (with the molecular weight of about 5 ten thousand) and dispersing in 30mL of isopropanol for swelling, dropwise adding 1.2mL of 40% sodium hydroxide aqueous solution and 19mL of 60% 3-chloro-2-hydroxypropyl trimethyl ammonium chloride solution, reacting in a metal bath reaction kettle at 55 ℃ for 9 hours, precipitating and washing with ethanol after the reaction is finished, and drying after suction filtration to obtain the 2-hydroxypropyl trimethyl ammonium chloride chitosan.
(2) Weighing 3g of the 2-hydroxypropyl trimethyl ammonium chloride chitosan, dissolving in 60mL of deionized water, then dropwise adding 30mL of pyrrolidone sodium carboxylate aqueous solution with the mass fraction of 15% to the former, reacting for 6h at room temperature, then transferring the mixed solution to a dialysis bag with the molecular weight cutoff of 500, dialyzing for 24h with deionized water, and freeze-drying to obtain the pyrrolidone sodium carboxylate anionized 2-hydroxypropyl trimethyl ammonium chloride chitosan shown in the formula I, wherein n is 300-320-.
Example 2
The difference from the embodiment 1 is that:
(1) weighing 3.38g of chitosan (with the molecular weight of about 10 ten thousand) and dispersing in 25mL of isopropanol for swelling, dropwise adding 1.4mL of 40% sodium hydroxide aqueous solution and 25mL of 60% 3-chloro-2-hydroxypropyl trimethyl ammonium chloride solution, reacting in a metal bath at 60 ℃ for 10 hours, precipitating and washing with ethanol after the reaction is finished, and drying after suction filtration to obtain the 2-hydroxypropyl trimethyl ammonium chloride chitosan.
(2) Weighing 3g of 2-hydroxypropyl trimethyl ammonium chloride chitosan, fully dissolving in 30mL of deionized water, transferring into a dialysis bag with the molecular weight cutoff of 500, dialyzing and reacting for 12 hours in a 10% sodium lactate aqueous solution, dialyzing for 24 hours by using the deionized water after the reaction is finished, concentrating, and freeze-drying to obtain the sodium lactate anionized 2-hydroxypropyl trimethyl ammonium chloride chitosan with the n being 600-630.
Example 3
The difference from the embodiment 1 is that:
(1) weighing 3.38g of chitosan (with the molecular weight of about 15 ten thousand) and dispersing in 15mL of isopropanol for swelling, dropwise adding 1.6mL of 40% sodium hydroxide aqueous solution and 30mL of 60% 3-chloro-2-hydroxypropyl trimethyl ammonium chloride solution, reacting in a metal bath at 75 ℃ for 12 hours, precipitating and washing with ethanol after the reaction is finished, and drying after suction filtration to obtain the 2-hydroxypropyl trimethyl ammonium chloride chitosan.
(2) Weighing 3g of the 2-hydroxypropyl trimethyl ammonium chloride chitosan, dissolving in 20mL of deionized water, transferring into a dialysis bag with the molecular weight cutoff of 500, carrying out dialysis reaction for 12 hours in 15% betaine aqueous solution, dialyzing for 48 hours by using the deionized water after the reaction is finished, concentrating, and carrying out freeze drying to obtain the betaine anionized 2-hydroxypropyl trimethyl ammonium chloride chitosan shown in the formula I, wherein n is 920-.
Application example 1
Measurement of moisture absorption Activity
Respectively testing the moisture absorption activity of raw material samples under the environment of saturated ammonium sulfate solution (relative humidity of 81%) and saturated sodium carbonate solution (relative humidity of 43%), wherein the raw material samples are respectively chitosan and sodium hyaluronate sold in the market, and the preparation of the example obtains pyrrolidone carboxylic acid sodium anionized 2-hydroxypropyl trimethyl ammonium chloride chitosan, sodium lactate anionized 2-hydroxypropyl trimethyl ammonium chloride chitosan, betaine anionized 2-hydroxypropyl trimethyl ammonium chloride chitosan:
drying the sample raw materials at 65 ℃ for 48h to constant weight, weighing 0.20g of the sample raw materials respectively, placing the weighed sample raw materials in a dried weighing bottle, placing the weighing bottle containing the sample raw materials in a dryer with the relative humidity of 81% and the relative humidity of 43%, weighing the mass of the weighing bottle once every other period of time, calculating the hygroscopic activity of the sample, and repeating the whole experiment once.
Moisture absorption rate (%) (W)1-W0) × 100/W0
W0And W1Mass (g) before and after sample placement
Table 1 shows the moisture absorption activity (%), when RH is 81%, of the raw material samples
Table 2 shows the moisture absorption activity (%)
Application example 2
Measurement of moisturizing Activity
The moisturizing activity of the raw material samples was tested and compared in a saturated ammonium sulfate solution (relative humidity 81%), a saturated sodium carbonate solution (relative humidity 43%) and a dry silica gel environment, respectively:
wherein the raw material samples are chitosan, commercially available sodium hyaluronate, sodium pyrrolidone carboxylate anionized 2-hydroxypropyl trimethyl ammonium chloride chitosan, sodium lactate anionized 2-hydroxypropyl trimethyl ammonium chloride chitosan, betaine anionized 2-hydroxypropyl trimethyl ammonium chloride chitosan:
after the raw material samples are dried for 48h to constant weight at 65 ℃, 0.50g of the raw material samples are weighed and placed in a dry weighing bottle respectively, 50 mu L of deionized water is added, the weighing bottle containing the samples is placed in a dryer with the relative humidity of 81 percent and the relative humidity of 43 percent and drying silica gel, the mass of the weighing bottle is weighed once every other period of time, the moisturizing activity of the samples is calculated, and all experiments are repeated once.
Moisture retention rate (%) (100 XH)n/H0
H0、HnMass (g) of water before and after standing
Table 3 shows the moisture-retaining activity (%), when RH is 81%, of the raw material samples
Table 4 shows the moisture retaining activity (%), when RH is 43%, of the raw material samples
TABLE 5 moisture retention Activity of raw material samples on dried silica gel (%)
Application example 3
Determination of bacteriostatic Activity
The inhibition effect of the raw material sample on the botrytis cinerea is measured by adopting a hypha growth rate method. The specific operation is as follows: after the raw material samples are frozen and dried in vacuum to constant weight, water is used as a solvent to prepare 6 mg/mL sample aqueous solution, 0.2 mL, 1 mL and 2mL sample solutions are respectively added into commercial fungus culture media with the volumes of 11.8 mL, 11 mL and 10 mL, the mixture is shaken evenly and poured into a disposable culture dish with the diameter of 6 cm for cooling and solidification while the mixture is hot, and the final concentrations of the samples are 0.1 mg/mL, 0.5 mg/mL and 1.0 mg/mL. After it was completely coagulated, the cake was carefully inoculated into the center of the coagulated solid medium with sterile forceps and cultured at 28 ℃ under 60% humidity for 48 hours. An equal concentration of carbendazim was used as a positive control, and an equal volume of sterile water was used as a blank control instead of the sample. Then, the diameter of the hypha generation area is measured by a cross method, and an average value is taken. The formula for calculating the bacteriostatic rate of the sample is as follows:
bacteriostatic rate (%) < 1- (D)Sample (I)-5)/(DBlank space-5)]×100
Wherein DSample (I)The hyphal growth diameter of the sample group, DBlank spaceThe diameter of hypha growth of blank group
Wherein the raw material samples are chitosan, commercially available sodium hyaluronate, sodium pyrrolidone carboxylate anionized 2-hydroxypropyl trimethyl ammonium chloride chitosan, sodium lactate anionized 2-hydroxypropyl trimethyl ammonium chloride chitosan, betaine anionized 2-hydroxypropyl trimethyl ammonium chloride chitosan:
TABLE 6 bacteriostatic Activity of raw material samples (%)
The experimental results are as follows: the moisture absorption and retention performances of the anionized 2-hydroxypropyl trimethyl ammonium chloride chitosan, chitosan and sodium hyaluronate synthesized by the invention are shown in tables 1-5, and the antibacterial activity is shown in table 6. The study proves that the moisture absorption and retention performance of the chitosan in the experiment is far lower than that of the sodium hyaluronate, but the moisture absorption and retention performance is obviously improved after the sodium pyrrolidone carboxylate, the sodium lactate and the betaine anions are introduced, and the result shows that: the moisture absorption and retention performances of the sodium pyrrolidone carboxylate anionized 2-hydroxypropyl trimethyl ammonium chloride chitosan, the sodium lactate anionized 2-hydroxypropyl trimethyl ammonium chloride chitosan and the betaine anionized 2-hydroxypropyl trimethyl ammonium chloride chitosan are all higher than those of the sodium hyaluronate, and the moisture absorption and retention performances of the betaine anionized 2-hydroxypropyl trimethyl ammonium chloride chitosan are optimal. Meanwhile, compared with sodium hyaluronate, the moisture absorption humectant synthesized by the invention has obvious bacteriostatic activity. In addition, the cost of the target compound prepared by the method is far lower than that of sodium hyaluronate, the moisture absorption and retention activity of the target compound is obviously higher than that of sodium hyaluronate, and the target compound has certain bacteriostatic activity, so that technical support and considerable development potential are provided for development of a novel moisture absorption humectant or bacteriostatic material.
Claims (10)
2. The method of preparing anionized 2-hydroxypropyltrimethylammonium chloride chitosan according to claim 1, wherein:
(1) dispersing chitosan in isopropanol to swell, adding a sodium hydroxide aqueous solution and a 3-chloro-2-hydroxypropyl trimethyl ammonium chloride solution, mixing, reacting in a metal bath at 55-75 ℃ for 9-12 hours, precipitating with ethanol, filtering, and drying to obtain 2-hydroxypropyl trimethyl ammonium chloride chitosan;
(2) dissolving the 2-hydroxypropyl trimethyl ammonium chloride chitosan in deionized water, adding a betaine water solution, uniformly mixing, reacting for 6-8h at room temperature, intercepting and dialyzing after reaction, and freeze-drying to obtain the anionized 2-hydroxypropyl trimethyl ammonium chloride chitosan shown in the formula (1).
3. The method of claim 2, wherein the anionized 2-hydroxypropyltrimethylammonium chloride chitosan is prepared by: the molar weight of the 3-chloro-2-hydroxypropyl trimethyl ammonium chloride in the step (1) is 3-5 times that of the chitosan; the molar weight of the sodium hydroxide is 1 to 1.5 times of that of the chitosan.
4. The method of claim 2, wherein the anionized 2-hydroxypropyltrimethylammonium chloride chitosan is prepared by: and (3) after the reaction is carried out for 9-12 hours in the metal bath, carrying out alcohol precipitation on a reaction product by using ethanol, washing by using 95% of ethanol in percentage by mass, carrying out suction filtration, and drying to obtain the 2-hydroxypropyl trimethyl ammonium chloride chitosan.
5. The method of claim 2, wherein the anionized 2-hydroxypropyltrimethylammonium chloride chitosan is prepared by: the molar weight of the 2-hydroxypropyl trimethyl ammonium chloride chitosan in the step (2) is 3-5 times of that of the connected active molecules.
6. The method of claim 2, wherein the anionized 2-hydroxypropyltrimethylammonium chloride chitosan is prepared by: and (3) transferring the reactant mixed solution after the reaction in the step (2) to a dialysis bag with the molecular weight cutoff of 500, dialyzing with deionized water for 24-48h, and freeze-drying to obtain the anionized 2-hydroxypropyl trimethyl ammonium chloride chitosan shown in the formula (1).
7. The method for preparing anionized 2-hydroxypropyltrimethylammonium chloride chitosan according to claim 2 or 6, wherein: and (2) the step (2) can be replaced by fully dissolving 2-hydroxypropyl trimethyl ammonium chloride chitosan in deionized water, transferring the solution into a dialysis bag with the molecular weight cutoff of 500, then adding a betaine aqueous solution for carrying out dialysis reaction for 12-24 hours, dialyzing the solution for 24-48 hours by using the deionized water after the reaction is finished, and carrying out freeze drying after concentration to obtain the anionized 2-hydroxypropyl trimethyl ammonium chloride chitosan shown in the formula (1).
8. The method of claim 2, wherein the anionized 2-hydroxypropyltrimethylammonium chloride chitosan is prepared by: the chitosan is dispersed in isopropanol, and the final concentration of the chitosan is 10-25%; the concentration of the aqueous solution obtained by dissolving the hydroxypropyl trimethyl ammonium chloride chitosan in deionized water is 5-20%.
9. The method of claim 2, wherein the anionized 2-hydroxypropyltrimethylammonium chloride chitosan is prepared by: the concentration of betaine in the betaine aqueous solution is 5-15 wt%.
10. The anionized 2-hydroxypropyltrimethylammonium chloride chitosan according to claim 1, wherein: the anionic 2-hydroxypropyl trimethyl ammonium chloride chitosan is applied as a bacteriostatic material, a moisture absorption agent or a humectant in the fields of food, cosmetics or biomedicine.
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