CN113943377B - Cellulose antibacterial material with lysine grafted N-halamine type Schiff base structure and preparation method thereof - Google Patents
Cellulose antibacterial material with lysine grafted N-halamine type Schiff base structure and preparation method thereof Download PDFInfo
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- CN113943377B CN113943377B CN202111239746.4A CN202111239746A CN113943377B CN 113943377 B CN113943377 B CN 113943377B CN 202111239746 A CN202111239746 A CN 202111239746A CN 113943377 B CN113943377 B CN 113943377B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/05—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur
- C08B15/06—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur containing nitrogen, e.g. carbamates
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
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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
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Abstract
The invention provides a cellulose antibacterial material with a lysine grafted N-halamine type Schiff base structure and a preparation method thereof, belonging to the technical field of preparation methods of antibacterial materials. The antibacterial material is prepared by combining lysine and N-halamine through an amide reaction, and simultaneously fixing the lysine grafted N-halamine to cellulose through a Schiff base reaction, so that the cellulose antibacterial material with the amino acid Schiff base sterilization capacity and the N-halamine sterilization capacity is prepared. The invention also provides the cellulose antibacterial material with the lysine grafted N-halamine type Schiff base structure, which is prepared by the preparation method. The cellulose antibacterial material has stronger antibacterial effect and antibacterial activity, the chlorine content of the cellulose antibacterial material reaches 3.62 percent, and 100.00 percent of staphylococcus aureus and escherichia coli can be killed within 5 min.
Description
Technical Field
The invention relates to the technical field of preparation methods of antibacterial materials, and relates to a cellulose antibacterial material with a lysine grafted N-halamine type Schiff base structure and a preparation method thereof.
Background
Cellulose is a natural renewable polymer biomass material widely existing in nature, mainly comes from plant trunks, cotton, jute and other plant cell walls, and is widely applied to the fields of biomedicine, food packaging and the like due to the characteristics of excellent biocompatibility, green degradability, low cost and the like. With the recent advocation of green chemistry and environmental protection requirements, the application field of cellulose materials is further expanded, and people put higher demands on the antibacterial performance of the cellulose materials in order to adapt to the application in various fields.
The halamine antibacterial agent has the characteristics of high sterilization rate, wide antibacterial spectrum, good reproducibility, no drug resistance and the like, so that the halamine antibacterial agent is introduced into the cellulose material in various ways to make the cellulose material obtain antibacterial property. As in chinese patent CN 112813693A: in the preparation method, a halamine antibacterial agent and long-chain hydrophobic alkane are grafted to hydrogen-containing silicone oil PHMS through a hydrosilylation reaction to obtain a halamine antibacterial agent connected with a silane coupling agent, and the antibacterial agent is arranged on a cellulose-based material to obtain an N-halamine sterilization type cellulose fiber. However, the method has long reaction process, complicated preparation and difficult operation. The Schiff base reaction refers to the reaction of a compound containing aldehyde (or ketone) and amino to form an imine bond, has mild and simple reaction conditions, shows excellent biological activity and certain antibacterial activity on a plurality of materials, and enables dialdehyde cellulose to become an important cellulose material intermediate. In many researches, dialdehyde cellulose and amino acid are used as raw materials, and the formed cellulose material with the Schiff base structure has great potential in the aspect of antibiosis, but the single Schiff base structure has low bactericidal activity and cannot kill bacteria in a short time.
Disclosure of Invention
The invention aims to provide a cellulose antibacterial material with a lysine grafted N-halamine type Schiff base structure and a preparation method thereof, the method combines the antibacterial capacity of cellulose and an amino acid Schiff base structure and an N-halamine antibacterial agent through Schiff base reaction, and the cellulose antibacterial material with mild reaction conditions and strong antibacterial effect is obtained.
The invention firstly provides a preparation method of a cellulose antibacterial material with a lysine grafted N-halamine type Schiff base structure, which comprises the following steps:
the method comprises the following steps: dissolving lysine and aminoethyl-5,5-dimethylhydantoin in water, and then adding carboxyl activating agent carbodiimide hydrochloride (EDC. HCl) and amino protective agent N-hydroxysuccinimide (NHS) to react to obtain lysine grafted N-halamine (Ly-ADMH);
step two: mixing the lysine grafted N-halamine (Ly-ADMH) obtained in the step one with dialdehyde cellulose for reaction to obtain a reaction product;
step three: and chlorinating the reaction product obtained in the step two to obtain the cellulose antibacterial material with the lysine grafted N-halamine type Schiff base structure.
Preferably, in the first step, the molar ratio of lysine to aminoethyl-5,5, -dimethylhydantoin to carbodiimide hydrochloride to N-hydroxysuccinimide is 1.
Preferably, the reaction temperature of the first step is 60-70 ℃, and the reaction time is 16-18h.
Preferably, the molar ratio of the lysine grafted N-halamine (Ly-ADMH) to the dialdehyde cellulose in the second step is 1:1.
Preferably, the reaction temperature of the second step is 30-50 ℃, and the reaction time is 10-12h.
Preferably, the chlorination process of the third step comprises: and (3) chlorinating the reaction product obtained in the step two by using a sodium hypochlorite solution, and washing and drying to obtain the sodium hypochlorite.
Preferably, the sodium hypochlorite solution has pH =7 and a concentration of 10% -15%.
Preferably, the chlorination time is 1-2h.
The invention also provides the cellulose antibacterial material with the lysine grafted N-halamine type Schiff base structure, which is prepared by the preparation method.
The invention has the advantages of
The invention provides a cellulose antibacterial material with a lysine grafted N-halamine type Schiff base structure and a preparation method thereof, wherein the antibacterial material combines amino acid and N-halamine together through an amide reaction, so that a precursor has dual characteristics of the amino acid and the N-halamine; meanwhile, lysine grafted N-halamine is fixed on cellulose through Schiff base reaction, and the cellulose antibacterial material with amino acid Schiff base sterilization capacity and N-halamine sterilization capacity is prepared. The raw materials are renewable, the cost is low, the reaction solvent is water, the condition is mild, the method is green and pollution-free, and the biocompatibility is good. In addition, the invention combines the sterilization mechanism of amino acid Schiff base and N-halamine on cellulose, and the antibacterial action is synergistically exerted, so that the modified cellulose material has stronger antibacterial effect and antibacterial activity, the chlorine content of the modified cellulose material reaches 3.62 percent, 100.00 percent of staphylococcus aureus and escherichia coli can be killed within 5min, and the modified cellulose material is a novel biological material.
Drawings
FIG. 1 is a graph showing the antibacterial effect of the cellulose antibacterial material having a lysine-grafted N-halamine type Schiff base structure on bacteria of example 1.
Detailed Description
The invention firstly provides a preparation method of a cellulose antibacterial material with a lysine grafted N-halamine type Schiff base structure, which comprises the following steps:
the method comprises the following steps: lysine and aminoethyl-5,5, -dimethylhydantoin are dissolved in water, and then a carboxyl activating agent carbodiimide hydrochloride (EDC. HCl) and an amino protecting agent N-hydroxysuccinimide (NHS) are added for reaction, wherein the molar ratio of lysine to aminoethyl-5,5, -dimethylhydantoin to carbodiimide hydrochloride to N-hydroxysuccinimide is preferably 1. The reaction temperature is preferably 60-70 ℃, the reaction time is preferably 16-18h, and lysine grafted N-halamine (Ly-ADMH) is obtained by drying after the reaction is finished; the reaction process is as follows:
step two: mixing the lysine grafted N-halamine (Ly-ADMH) obtained in the step one with dialdehyde cellulose for reaction, wherein the reaction temperature is preferably 30-50 ℃, the reaction time is preferably 10-12h, cooling the product to room temperature after the reaction is finished, filtering under reduced pressure, collecting a solid product, washing the solid product with deionized water for several times, and drying to obtain a reaction product; the molar ratio of the lysine grafted N-halamine (Ly-ADMH) to the dialdehyde cellulose is preferably 1:1. The aldehyde group content of the dialdehyde cellulose is preferably 3.80-4.12mmol/g, and the source of the dialdehyde cellulose is obtained by selectively oxidizing cellulose by using sodium periodate as an oxidizing agent in the prior art.
Step three: and chlorinating the reaction product obtained in the step two to obtain the cellulose antibacterial material with the lysine grafted N-halamine type Schiff base structure. Preferably, the chlorination process comprises: and (3) chlorinating the reaction product obtained in the step two with a sodium hypochlorite solution, and washing and drying to obtain the catalyst. The pH =7 of the sodium hypochlorite solution, the concentration is 10% -15%, and the chlorination time is preferably 1-2h.
The invention also provides the cellulose antibacterial material with the lysine grafted N-halamine type Schiff base structure, which is prepared by the preparation method.
The following detailed description of the embodiments of the present invention is provided in conjunction with the accompanying drawings, which are intended to be illustrative, not limiting, and not limiting.
Example 1
(1) 7.4g of lysine and 8.6g of aminoethyl-5,5-dimethylhydantoin were weighed into a flask containing 150ml of water, and then 9.6g of EDC & HCl and 5.8g of NHS as catalysts were weighed into the flask and reacted at 60 ℃ for 16 hours to obtain lysine grafted N-halamine (Ly-ADMH).
(2) Weighing 5g of 3.96mmol/g dialdehyde cellulose and 6.0g lysine grafted N-halamine, placing the mixture in a 200ml flask, adding 150ml water, reacting at the temperature of 40 ℃ for 12h, filtering, washing with deionized water for 5 times, and drying the obtained product for later use.
(3) And (3) putting the product obtained in the step (2) into a sodium hypochlorite solution with the pH =7 and the concentration of 10% for chlorination for 2h to obtain the lysine grafted N-halamine type cellulose antibacterial material. The chlorine content in the antibacterial material was 3.62%.
Example 2
(1) 12.8g of lysine and 17.2g of aminoethyl-5,5, -dimethylhydantoin were weighed into a flask containing 200ml of water, and then catalysts of 19.2g of EDC & HCl and 11.5g of NHS were weighed into the flask and reacted at 65 ℃ for 18 hours to obtain lysine grafted N-halamine (Ly-ADMH).
(2) 4.05mmol/g of dialdehyde cellulose 4g and lysine grafted N-halamine 4.9g are weighed and placed in a 200ml flask, then 150ml of water is added, the reaction is carried out for 12h at the temperature of 40 ℃, deionized water is used for washing 5 times after filtration, and the obtained product is dried for later use.
(3) And (3) putting the product obtained in the step (2) into a sodium hypochlorite solution with the pH =7 and the concentration of 10% for chlorination for 2h to obtain the lysine grafted N-halamine type cellulose antibacterial material. The chlorine content in the antibacterial material was 3.12%.
Example 3
(1) 10.3g of lysine and 12.1g of aminoethyl-5,5, -dimethylhydantoin were weighed into a flask containing 200ml of water, and then catalysts 13.4g of EDC & HCl and 8.1g of NHS were weighed into the flask and reacted at 70 ℃ for 16h to obtain lysine grafted N-halamine (Ly-ADMH).
(2) Weighing 5g of 3.96mmol/g dialdehyde cellulose and 6.0g lysine grafted N-halamine, placing the mixture in a 200ml flask, adding 150ml water, reacting at the temperature of 40 ℃ for 11h, filtering, washing with deionized water for 5 times, and drying the obtained product for later use.
(3) And (3) putting the product obtained in the step (2) into a sodium hypochlorite solution with the pH =7 and the concentration of 15% for chlorination for 2h to obtain the lysine grafted N-halamine type cellulose antibacterial material. The chlorine content in the antibacterial material is 2.64%.
Example 4
(1) 10.3g lysine and 13.7g aminoethyl-5,5, -dimethylhydantoin were weighed into a flask containing 200ml water, then catalysts 15.3g EDC & HCl and 9.2g NHS were weighed into the flask and reacted at 60 ℃ for 17h to give lysine grafted N-halamine (Ly-ADMH).
(2) Weighing 7g of 3.85mmol/g dialdehyde cellulose and 8.2g lysine grafted N-halamine, placing the mixture in a 200ml flask, adding 150ml water, reacting at the temperature of 50 ℃ for 10h, filtering, washing with deionized water for 5 times, and drying the obtained product for later use.
(3) And (3) putting the product obtained in the step (2) into a sodium hypochlorite solution with the pH =7 and the concentration of 10% for chlorination for 1.5h to obtain the lysine grafted N-halamine type cellulose antibacterial material. The chlorine content in the antibacterial material was 3.20%.
Example 5
(1) 7.4g lysine and 8.6g aminoethyl-5,5, -dimethylhydantoin were weighed into a flask containing 200ml water, then catalysts 9.6g EDC & HCl and 5.8g NHS were weighed into the flask and reacted at 65 ℃ for 18h to give lysine grafted N-halamine (Ly-ADMH).
(2) Weighing 8g of 4.06mmol/g dialdehyde cellulose and 9.8g lysine grafted N-halamine, placing in a 200ml flask, adding 150ml water, reacting at 30 ℃ for 12h, filtering, washing with deionized water for 5 times, and drying the obtained product for later use.
(3) And (3) putting the product obtained in the step (2) into a sodium hypochlorite solution with the pH =7 and the concentration of 10% for chlorination for 2h to obtain the lysine grafted N-halamine type cellulose antibacterial material. The chlorine content in the antibacterial material is 2.76%.
Example 6
(1) 7.7g lysine and 10.3g aminoethyl-5,5, -dimethylhydantoin were weighed into a flask containing 200ml water, and then catalysts 11.5g EDC & HCl and 6.9g NHS were weighed into the flask and reacted at 60 ℃ for 16h to obtain lysine grafted N-halamine (Ly-ADMH).
(2) Weighing 5g of 3.92mmol/g dialdehyde cellulose and 5.7g lysine grafted N-halamine, placing the mixture in a 200ml flask, adding 150ml water, reacting at 35 ℃ for 12h, filtering, washing with deionized water for 5 times, and drying the obtained product for later use.
(3) And (3) putting the product obtained in the step (2) into a sodium hypochlorite solution with the pH =7 and the concentration of 15% for chlorination for 1h to obtain the lysine grafted N-halamine type cellulose antibacterial material. The chlorine content in the antibacterial material was 3.14%.
Example 7
(1) 12.8g of lysine and 17.1g of aminoethyl-5,5, -dimethylhydantoin were weighed into a flask containing 200ml of water, and then 19.1g of EDC. HCl and 11.5g of NHS as catalysts were weighed into the flask and reacted at 60 ℃ for 17 hours to obtain lysine grafted N-halamine (Ly-ADMH).
(2) Weighing 5g of 3.89mmol/g dialdehyde cellulose and 5.9g lysine grafted N-halamine, placing the mixture in a 200ml flask, adding 150ml water, reacting at the temperature of 50 ℃ for 11h, filtering, washing with deionized water for 5 times, and drying the obtained product for later use.
(3) And (3) putting the product obtained in the step (2) into a sodium hypochlorite solution with the concentration of 12% and the pH =7 for chlorination for 2h to obtain the lysine grafted N-halamine type cellulose antibacterial material. The chlorine content in the antibacterial material was 3.54%.
Example 8 plate count test of cellulose antibacterial Material having lysine-grafted N-Haloamine type Schiff base Structure
Test samples were prepared as described in example 1, and antibiotic tests were carried out using Staphylococcus aureus and Escherichia coli using cellulose as a control. After subculturing the bacteria, the viable bacteria concentration of 10 was prepared by gradient dilution in phosphate buffer solution 6 -10 7 CFU/ml bacterial suspension, after which 100. Mu.l of bacterial suspension was added to 900. Mu.l of phosphate buffer containing 0.01g of the test sample, and after 5min,10min,30min at 37 ℃ contact, the test sample was crushed out with 0.5ml,0.05N of sterile sodium thiosulfate solution which had no effect on any of the bacteria in the control test, and both the test sample and the control sample were continuously diluted with phosphate buffer solution, and then 100. Mu.l was placed in sterile medium, and after 12 hours of incubation at 37 ℃, the bactericidal effect was observed. The test results are shown in Table 1.
TABLE 1 results of plate counting of cellulose and cellulose antibacterial materials
The inoculation concentrations of Staphylococcus aureus and Escherichia coli were 1.47X 10, respectively 6 CFU/ml and 2.81X 10 6 CFU/ml; as can be seen from the analysis of Table 1, the cellulose antibacterial material of the present invention can kill 100% of Staphylococcus aureus and Escherichia coli within 5min, compared to cellulose.
Example 9 agar diffusion test of cellulose antibacterial Material having lysine-grafted N-Haloamine type Schiff base Structure
The test samples were prepared as described in example 1, with cellulose as a control. Uniformly smearing 100 μ L of viable bacteria with concentration of 10 6 -10 7 CFU/ml of Staphylococcus aureus and Escherichia coli suspension on solid medium. The fibrous specimen was prepared into a disc having a diameter of 12mm and gently placed in a petri dish. After incubation at 37 ℃ for 12h, the zone of inhibition was observed and the results are shown in FIG. 1.
FIG. 1A represents cellulose versus Staphylococcus aureus, FIG. 1B represents antibacterial material of the present invention versus Staphylococcus aureus, FIG. 1C represents cellulose versus Escherichia coli, and FIG. 1D represents antibacterial material of the present invention versus Escherichia coli with DAC aldehyde group content of 3.96mmol/g. As can be seen from the analysis of figure 1, the cellulose antibacterial material of the invention shows excellent antibacterial activity, has strong release bactericidal performance, and has the bacteriostatic radius of 18.5mm and 14.8mm for staphylococcus aureus and escherichia coli.
Claims (7)
1. A preparation method of a cellulose antibacterial material with a lysine grafted N-halamine type Schiff base structure is characterized by comprising the following steps:
the method comprises the following steps: dissolving lysine and aminoethyl-5,5-dimethylhydantoin in water, and then adding a carboxyl activating agent carbodiimide hydrochloride and an amino protective agent N-hydroxysuccinimide to react to obtain lysine grafted N-halamine Ly-ADMH; in the first step, the molar ratio of lysine to aminoethyl-5,5 to dimethylhydantoin to carbodiimide hydrochloride to N-hydroxysuccinimide is 1;
step two: mixing the lysine grafted N-halamine Ly-ADMH obtained in the step one with dialdehyde cellulose for reaction to obtain a reaction product; the reaction temperature of the second step is 30-50 ℃, and the reaction time is 10-12h;
step three: and (4) chlorinating the reaction product obtained in the step two to obtain the cellulose antibacterial material with the lysine grafted N-halamine type Schiff base structure.
2. The method for preparing the cellulose antibacterial material with the lysine grafted N-halamine type Schiff base structure as claimed in claim 1, wherein the reaction temperature in the first step is 60-70 ℃ and the reaction time is 16-18h.
3. The method for preparing the cellulose antibacterial material with the lysine grafted N-halamine type Schiff base structure as claimed in claim 1, wherein the molar ratio of the lysine grafted N-halamine Ly-ADMH to the dialdehyde cellulose in the second step is 1:1.
4. The method for preparing the cellulose antibacterial material with the lysine grafted N-halamine type Schiff base structure according to claim 1, wherein the chlorination process of the third step comprises: and (3) chlorinating the reaction product obtained in the step two with a sodium hypochlorite solution, and washing and drying to obtain the catalyst.
5. The method for preparing the cellulose antibacterial material with the lysine grafted N-halamine type Schiff base structure according to claim 4, wherein the sodium hypochlorite solution has a pH =7 and a concentration of 10% -15%.
6. The method for preparing the cellulose antibacterial material with the lysine grafted N-halamine type Schiff base structure according to claim 1, wherein the chlorination time is 1-2h.
7. A cellulose antibacterial material having a lysine-grafted N-halamine-type Schiff base structure obtained by the production method according to any one of claims 1 to 6.
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