CN102153673A - N-parabenzyloxycarboxymethyl chitosan quaternary ammonium salt and preparation method thereof - Google Patents
N-parabenzyloxycarboxymethyl chitosan quaternary ammonium salt and preparation method thereof Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/90—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in food processing or handling, e.g. food conservation
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Abstract
The invention discloses an N-parabenzyloxycarboxymethyl chitosan quaternary ammonium salt. The structure of the quaternary ammonium salt is shown in the specifications, wherein X is between 0.65 and 0.95, and the molecular weight is between 45 KD and 50 KD. The materialization indexes are as follows: the quaternary ammonium salt is a pale yellow powdery solid which can be dissolved in ethanol and isopropanol and be slightly dissolved in water and methylene dichloride at normal temperature; and the minimum inhibitory concentrations of the N-parabenzyloxycarboxymethyl chitosan quaternary ammonium salt for staphylococcus aureus and aspergillus niger are both up to 0.5 percent. Through modification, the antibiotic activity of chitosan is enhanced and the antibacterial range of the chitosan is expanded. The quaternary ammonium salt has high antibiotic activity on staphylococcus aureus and aspergillus niger, and can be applied to an antisepsis anticorrosive additive of foods.
Description
Technical Field
The invention relates to a chitosan chemically modified functional derivative, which is applied to the technical industry of food industry and belongs to the technical field of high molecular compounds.
Background
Chitosan is a deacetylation product of chitin, which is the only basic polysaccharide abundantly present in the biological world. Chitosan is only soluble in acids and acidic aqueous solutions due to the effect of intramolecular and intermolecular hydrogen bonds. The molecular chain of the chitosan contains a large number of modifiable groups such as hydroxyl, amino and the like, and various derivatives with special functions can be obtained through chemical modification, so that the application range of the chitosan can be expanded. For example, chitosan has excellent biodegradability, compatibility, film forming property and strong antibacterial, antiseptic and fresh-keeping capability, and is widely applied in the fields of food industry and the like. Chitosan can only be dissolved in acidic media, limiting its range of application. Usually, quaternary ammonium salt, alkyl, inorganic acid, etc. are introduced into chitosan molecules to improve the solubility or flocculation of chitosan.
Disclosure of Invention
The invention aims to overcome the defect that chitosan is insoluble in water and provide a chitosan derivative with good antibacterial effect, namely N-p-phenylmethoxy methyl chitosan quaternary ammonium salt which can be used as an antibacterial and antiseptic additive in food.
The invention also aims to provide a preparation method of the N-p-benzyloxy methyl chitosan quaternary ammonium salt.
The purpose of the invention is realized by the following technical scheme: the N-p-phenyl methoxy methyl chitosan quaternary ammonium salt is characterized in that: the structure is shown as the following formula:
wherein X is 0.65-0.95, and molecular weight is 45-50 KD. The physicochemical indexes of the compound are as follows: the solid is light yellow powder, can be dissolved in ethanol and isopropanol at normal temperature, and is slightly soluble in water and dichloromethane; the minimum inhibitory concentration of the compound on staphylococcus aureus and aspergillus niger can reach 0.5%.
The method comprises the steps of stirring chitosan and p-methoxybenzaldehyde (anisic aldehyde) in a three-neck flask for reaction to generate chitosan Schiff base, and then adding sodium borohydride for reaction to obtain alkylated chitosan; adjusting the pH value to be alkalescent by using a proper amount of sodium hydroxide, and then mixing the components in a weight ratio of 1: adding methyl iodide and sodium iodide of 1 into the solution, controlling the reaction temperature and continuously stirring, after the reaction is finished, adding acetone, standing overnight, performing suction filtration, washing with a mixed solution of ethanol and diethyl ether, and drying at constant temperature in vacuum to obtain a solid. And (3) placing the solid product in a Soxhlet extractor, performing reflux extraction by using absolute ethyl alcohol, and performing vacuum drying on the solid to constant weight to obtain the target product N-p-benzyloxy methyl chitosan quaternary ammonium salt.
The preparation method of the N-p-benzyloxy methyl chitosan quaternary ammonium salt comprises the following preparation steps:
adding a certain amount of chitosan into 3% glacial acetic acid with a certain volume and mass percentage according to a proportion of 20ml per gram for swelling for 30min, transferring the mixture into a three-neck flask, adding 1/2 times of anhydrous ethanol in volume of solution into the flask, and stirring at the temperature of 30-50 ℃;
adding a anisic aldehyde test solution with the same weight as that of chitosan into a constant-pressure dropping funnel, adding a certain volume of absolute ethyl alcohol according to the volume ratio of 1:20, oscillating and dissolving, slowly dropwise adding the anisic aldehyde absolute ethyl alcohol solution into the chitosan solution, and reacting for 3 hours under stirring to obtain chitosan Schiff base;
thirdly, adding sodium borohydride with the same molar weight as that of the chitosan into the beaker, adding distilled water with a certain volume according to the proportion of 30ml per gram for dissolving, slowly dropping the sodium borohydride solution into the chitosan Schiff base through a constant-pressure dropping funnel, continuously stirring until a large amount of white floccules appear, and continuously stirring for 2-3 hours to obtain the alkylated chitosan;
fourthly, slowly adding a proper amount of sodium hydroxide into the alkylated chitosan reaction solution obtained in the step three to adjust the pH to be 8-9, respectively placing a 2-time chitosan molar amount of methyl iodide reagent and sodium iodide solid into a beaker, adding a certain volume of absolute ethanol according to a proportion of 10ml per gram of sodium iodide, stirring and dissolving, slowly dropping the mixed solution into the reaction solution through a constant-pressure dropping funnel, and reacting for 3 hours under continuous stirring;
step five, adding acetone with the volume being 3 times that of the reaction liquid in the step four, standing overnight, performing suction filtration, washing with mixed liquid of ethanol and diethyl ether with the volume being 1/5 times that of the filtrate, and performing vacuum constant-temperature drying to obtain a solid;
sixthly, placing the product obtained in the step I into a Soxhlet extractor, performing reflux extraction with absolute ethyl alcohol, and drying the solid in vacuum until the weight is constant to obtain the N-p-phenylmethoxy methyl chitosan quaternary ammonium salt product.
The process conditions of stirring in the step four are: adjusting the reaction temperature to a higher rotation speed by using a constant-temperature stirrer, so that magnetons rotate at a constant speed at the bottom of the three-neck flask; the suction filtration process conditions in the step fifthly are as follows: drying in a 50-65 deg.C oven for 1-3 hr, vacuum filtering the reaction solution with a water pump at room temperature, washing, and collecting the solid.
The chitosan: anisic aldehyde: the weight ratio of the materials fed into the iodomethane is 1: (1-2): (2-3).
Methyl iodide in the fourth step: the weight ratio of sodium iodide is 1: 1.
the mixing volume ratio of the anhydrous ethanol and the anhydrous diethyl ether obtained in the step of the.
The process conditions of the Soxhlet extraction in the sixteenth step are as follows: heating in water bath at 65-75 deg.C, and extracting for 24-30 hr.
The process conditions of the vacuum drying of the sixteenth step and the sixteenth step are as follows: vacuum degree of 8 × 10 at 30-50 deg.C4Pa, drying for 12-24 hours.
The N-p-benzyloxy methyl chitosan quaternary ammonium salt is applied to preparing food preservative additives.
The novel chitosan quaternary ammonium salt synthesized by the invention has good antibacterial activity to staphylococcus aureus and aspergillus niger, enhances the antibacterial activity of chitosan, expands the antibacterial range of chitosan, and can be used as a food preservative additive.
Drawings
FIG. 1 is an infrared spectrum of chitosan.
FIG. 2 is an infrared spectrum of the prepared N-p-benzyloxy methyl chitosan quaternary ammonium salt.
FIG. 3 shows the preparation of chitosan1H NMR spectrum.
FIG. 4 shows N-p-benzyloxy methyl chitosan quaternary ammonium salt1H NMR spectrum.
FIG. 5 shows the inhibition of Staphylococcus aureus by chitosan and N-p-phenylmethoxy methyl chitosan quaternary ammonium salts at different concentrations.
FIG. 6 shows the inhibition of Aspergillus niger by chitosan and N-p-phenylmethoxy methyl chitosan quaternary ammonium salts at different concentrations.
FIG. 7 is a diagram showing the main reaction steps involved in the present invention. Wherein,。
the chitosan infrared spectrum of 1649 cm can be seen by analyzing the two infrared spectra of FIG. 1 and FIG. 2-1The peak is small because of high deacetylation degree, 1597cm-1In the form of strong amino-NH2The absorption band. 1373 cm-11159 cm for O-H bending vibration-1And 893 cm-1Is chitosan glycosyl absorption band. 1597cm in quaternary ammonium salt infrared spectrum-1The deformation vibration absorption band of the amino group is obviously weakened, and the substitution reaction is proved to occur in-NH21511-1573 cm-1The appearance of new peak is the characteristic absorption band of quaternary ammonium salt, 1415 cm-1A sharp peak is newly introduced into-CH3and-CH2Medium C-H bending vibration, 835 cm-1The appearance of the new peak is an out-of-plane bending vibration of = C-H in the para-substituted benzene ring, 1107 cm-1The enhancement of the peak is due to the newly introduced-OCH3The characteristic absorption peak proves that the chitosan quaternary ammonium salt is successfully synthesized.
In FIGS. 3 and 4, chitosan was dissolved in CD3COOD and D2O mixture, N-p-phenylmethoxy methyl chitosan quaternary ammonium salt dissolved in D2And (4) performing measurement in O. The small peak at 2.02ppm in FIG. 3 is due to-CH in the acetamide group of chitosan3Due to the presence of (a), the peak is smaller because of the higher degree of deacetylation; while the independent peak at 2.96ppm is due to H2Presence of (a); peaks from 3.50-3.72ppm and H in chitosan3，H4，H5，H6Are completely identical; the peak at 4.67ppm is then H1The function of (1). In FIG. 4, the peak at 1.82ppm is-CH in the acetamido group3A weak peak around 2.70ppm represents-N+（CH3）2I-Middle proton resonance absorption peak, 4.66ppm is H1The multiple peak at 3.50-3.68ppm represents H3，H4，H5，H6and-OCH3Middle proton signal peak, H at 2.95ppm2Signal peak, multiplet at 6.74-7.68ppm is proton absorption peak of para-disubstituted benzene ring, -CH2InThe proton absorption peak appears at 4.32ppm, which proves the success of synthesizing the chitosan quaternary ammonium salt.
In the figure 5, chitosan and N-p-phenylmethoxy methyl chitosan quaternary ammonium salt with different concentrations have inhibition effect on staphylococcus aureus, and the bacteriostatic ability of the N-p-phenylmethoxy methyl chitosan quaternary ammonium salt is obviously higher than that of chitosan, and the minimum bacteriostatic concentration is 0.5%.
FIG. 6 is a graph showing the inhibition effect of chitosan and N-p-phenylmethoxy methyl chitosan quaternary ammonium salt at different concentrations on Aspergillus niger. When the concentration of the chitosan is lower than 0.5%, the chitosan has no inhibition effect on aspergillus niger and is beneficial to growth of the aspergillus niger. The reason may be that aspergillus niger belongs to fungi, the cell wall of the fungi contains chitosan, and the aspergillus niger has higher chitosan content, so that the aspergillus niger has certain resistance to the antibacterial performance of the chitosan, and the chitosan has no inhibition capability on the aspergillus niger, but can be used for promoting the growth and the propagation of cells. After the N-p-phenyl methoxy methyl chitosan quaternary ammonium salt is added, the dry weight of the aspergillus niger thallus is small, which shows that the product has strong inhibition capacity on the aspergillus niger, and the minimum inhibitory concentration is 0.5%.
Detailed Description
The invention is further illustrated by the following specific examples.
Example 1:
adding 1g of chitosan into 20ml of glacial acetic acid with the mass percentage of 3% for swelling for 30min, transferring the mixture into a 250ml three-neck flask, adding 10ml of absolute ethyl alcohol, stirring, slowly adding 1ml of anisic aldehyde dissolved in 20ml of absolute ethyl alcohol into a constant-pressure dropping funnel, stirring for 3h, slowly adding 0.3g of sodium borohydride solution dissolved in 10ml of distilled water into the constant-pressure dropping funnel, stirring until a large amount of white floccules appear, continuing stirring for 2h, adding sodium hydroxide into the reaction solution to adjust the pH =8-9, dissolving 0.4ml of methyl iodide and 2g of sodium iodide into 20ml of ethanol solution, uniformly stirring, slowly dropping the mixed solution into the reaction solution, controlling the reaction temperature to be 50 ℃, continuing stirring and reacting for 3h, stopping the reaction, adding 250ml of acetone into the reaction solution, standing overnight, performing suction filtration, and adding 50ml of the mixture in a volume ratio of 1: washing with ethanol and diethyl ether of 1, drying at constant temperature to obtain solid, putting the solid into a Soxhlet extractor, performing reflux extraction with absolute ethanol for 24 hours, and drying the product to constant weight to obtain the target product N-p-benzyloxy methyl chitosan quaternary ammonium salt.
Example 2:
the N-p-phenylmethoxy methyl chitosan quaternary ammonium salt and the bacteriostasis rate (%) of chitosan to staphylococcus aureus of the invention
Example 3:
the antibacterial rate (%) of the N-p-benzyloxy methyl chitosan quaternary ammonium salt and the chitosan on the Aspergillus niger
And (3) determining the bacteriostatic rate: preparing chitosan solution and chitosan quaternary ammonium salt solution with different mass fractions (0.5% acetic acid solution is used as solvent). Respectively and uniformly coating 0.1 mL of bacterial suspension and 0.1 mL of sample solution with different concentrations on a culture medium flat plate, wherein the blank is the bacterial suspension without the sample solution. All plates were incubated in a 37 ℃ incubator for 24h, taken out and observed for bacterial growth on each plate, and the inhibition rate was calculated:
I = (n1-n2)/ n1×100%
wherein n is1And n2The number of colonies on the blank and sample coated plates, respectively.
The bacteriostatic efficiency of the chitosan and the derivatives is determined by a dry weight method for Aspergillus niger. Preparing chitosan solution and chitosan quaternary ammonium salt solution with different mass fractions (0.5% acetic acid solution is used as solvent). Respectively adding 1mL of aspergillus niger suspension and 2 mL of sample solutions with different concentrations into a Sabouraud's medium, culturing the blank in a constant-temperature oscillation incubator at 28 ℃ for 48 h without adding the sample solution, performing suction filtration, drying and weighing the dry weight of thalli, and calculating the bacteriostasis rate:
I = (m1-m2)/ m 1×100%
wherein m is1And m2The dry weight of the mycelia in the culture medium without sample addition and in the culture medium with sample addition were measured.
Those skilled in the art will appreciate that modifications, additions and substitutions are possible, without departing from the scope of the invention as disclosed in the accompanying claims.
Claims (9)
1. The N-p-phenylmethoxy methyl chitosan quaternary ammonium salt is characterized in that: the structure of the compound is shown as the following formula:
wherein X is 0.65-0.95, and molecular weight is 45-50 KD.
2. The method for preparing N-p-phenylmethoxy methyl chitosan quaternary ammonium salt as claimed in claim 1, which is characterized in that: the preparation steps are as follows:
adding a certain amount of chitosan into 3% glacial acetic acid with a certain volume and mass percentage according to a proportion of 20ml per gram for swelling for 30min, transferring the mixture into a three-neck flask, adding 1/2 times of anhydrous ethanol in volume of solution into the flask, and stirring at the temperature of 30-50 ℃;
adding a anisic aldehyde test solution with the same weight as that of chitosan into a constant-pressure dropping funnel, adding a certain volume of absolute ethyl alcohol according to the volume ratio of 1:20, oscillating and dissolving, slowly dropwise adding the anisic aldehyde absolute ethyl alcohol solution into the chitosan solution, and reacting for 3 hours under stirring to obtain chitosan Schiff base;
thirdly, adding sodium borohydride with the same molar weight as that of the chitosan into the beaker, adding distilled water with a certain volume according to the proportion of 30ml per gram for dissolving, slowly dropping the sodium borohydride solution into the chitosan Schiff base through a constant-pressure dropping funnel, continuously stirring until a large amount of white floccules appear, and continuously stirring for 2-3 hours to obtain the alkylated chitosan;
fourthly, slowly adding a proper amount of sodium hydroxide into the alkylated chitosan reaction solution obtained in the step three to adjust the pH to be 8-9, respectively placing a methyl iodide reagent and sodium iodide solids which are 2 times of the chitosan molar weight into a beaker, adding a certain volume of absolute ethanol according to a proportion of 10ml per gram of sodium iodide, stirring and dissolving, slowly dripping the mixed solution into the reaction solution by using a constant-pressure dropping funnel, and reacting for 3 hours under continuous stirring;
step five, adding acetone with the volume being 3 times that of the reaction liquid in the step four, standing overnight, performing suction filtration, washing with mixed liquid of ethanol and diethyl ether with the volume being 1/5 times that of the filtrate, and performing vacuum constant-temperature drying to obtain a solid;
sixthly, placing the product obtained in the step I into a Soxhlet extractor, performing reflux extraction with absolute ethyl alcohol, and drying the solid in vacuum until the weight is constant to obtain the N-p-phenylmethoxy methyl chitosan quaternary ammonium salt product.
3. The method for preparing N-p-benzyloxy methyl chitosan quaternary ammonium salt according to claim 2, characterized in that: the process conditions of stirring in the step four are: adjusting the reaction temperature to a higher rotation speed by using a constant-temperature stirrer, so that magnetons rotate at a constant speed at the bottom of the three-neck flask;
the suction filtration process conditions in the step fifthly are as follows: drying in a 50-65 deg.C oven for 1-3 hr, vacuum filtering the reaction solution with a water pump at room temperature, washing, and collecting the solid.
4. The method for preparing N-p-benzyloxy methyl chitosan quaternary ammonium salt according to claim 2, characterized in that: the chitosan: anisic aldehyde: the weight ratio of the materials fed into the iodomethane is 1: (1-2): (2-3).
5. The method for preparing N-p-benzyloxy methyl chitosan quaternary ammonium salt according to claim 2, characterized in that: methyl iodide in the fourth step: the weight ratio of sodium iodide is 1: 1.
6. the method for preparing N-p-benzyloxy methyl chitosan quaternary ammonium salt according to claim 2, characterized in that: the mixing volume ratio of the anhydrous ethanol and the anhydrous diethyl ether obtained in the step of the.
7. The method for preparing N-p-benzyloxy methyl chitosan quaternary ammonium salt according to claim 2, characterized in that: the process conditions of the Soxhlet extraction in the sixteenth step are as follows: heating in water bath at 65-75 deg.C, and extracting for 24-30 hr.
8. The method for preparing N-p-benzyloxy methyl chitosan quaternary ammonium salt according to claim 2, characterized in that: the process conditions of the vacuum drying of the sixteenth step and the sixteenth step are as follows: vacuum degree of 8 × 10 at 30-50 deg.C4Pa, drying for 12-24 hours.
9. The use of the N-p-benzyloxy methyl chitosan quaternary ammonium salt of claim 1 as a food preservative additive.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104086670A (en) * | 2014-05-22 | 2014-10-08 | 中国科学院烟台海岸带研究所 | Chitosan quaternary ammonium salt containing triazole, and preparation method and application thereof |
| CN107880153A (en) * | 2017-11-23 | 2018-04-06 | 中国科学院海洋研究所 | 6 Carboxy Chitosan aromatic series quaternary ammonium salt derivatives and its preparation and application |
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| CN107880153A (en) * | 2017-11-23 | 2018-04-06 | 中国科学院海洋研究所 | 6 Carboxy Chitosan aromatic series quaternary ammonium salt derivatives and its preparation and application |
| CN112915252A (en) * | 2021-01-29 | 2021-06-08 | 河南亚都实业有限公司 | Chitosan quaternary ammonium salt derivative wound dressing and preparation method thereof |
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