CN112300292B - Preparation method of chlorogenic acid modified cellulose antibacterial material based on natural active ingredients - Google Patents

Preparation method of chlorogenic acid modified cellulose antibacterial material based on natural active ingredients Download PDF

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CN112300292B
CN112300292B CN202011317513.7A CN202011317513A CN112300292B CN 112300292 B CN112300292 B CN 112300292B CN 202011317513 A CN202011317513 A CN 202011317513A CN 112300292 B CN112300292 B CN 112300292B
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cellulose
chlorogenic acid
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antibacterial
sodium hydroxide
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张东阳
姚晓慧
胡润泽
陈涛
杨佳昕
赵卫国
沈宇诗
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Jiangsu University of Science and Technology
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Abstract

The invention discloses a preparation method of a chlorogenic acid modified cellulose antibacterial material based on natural active ingredients, which comprises the steps of dissolving cellulose in a mixed aqueous solution of sodium hydroxide and urea to prepare a cellulose solution; adding anhydrous sodium sulfate into the obtained cellulose solution, stirring, and freezing to solidify; soaking the coagulated mixture in water until the material floats on the water surface to obtain a cellulose material; mixing the cellulose material with a sodium hydroxide aqueous solution and epichlorohydrin, and then washing the cellulose material with deionized water until the sodium hydroxide aqueous solution and the epichlorohydrin have no residue; mixing the cellulose material with a sodium carbonate solution and a chlorogenic acid ethanol solution, then taking out the cellulose material, and washing the cellulose material with water until the cellulose material is not decolorized to obtain the chlorogenic acid modified cellulose antibacterial material. According to the invention, the chlorogenic acid and the cellulose are covalently connected by using the epichlorohydrin, so that the antibacterial agent is more stably grafted on the surface of the cellulose, the antibacterial agent is prevented from falling off, and a good antibacterial effect is maintained for a long time.

Description

Preparation method of chlorogenic acid modified cellulose antibacterial material based on natural active ingredients
Technical Field
The invention relates to a preparation method of an antibacterial material, in particular to a preparation method of a chlorogenic acid modified cellulose antibacterial material based on a natural active ingredient.
Background
In recent years, chlorogenic acid has attracted much attention as a natural plant active ingredient for its antibacterial activity. Chlorogenic acid is an esterified product of caffeic acid and quinic acid produced by a phenylpropanoid synthesis pathway in the metabolism of plant growth, and is commonly found in honeysuckle, eucommia ulmoides, coffee bean and mulberry leaf. Chlorogenic acid has effects of regulating blood sugar, lipid metabolism, resisting cancer, lowering blood pressure, etc., and is therefore commonly used as a health product. In addition, chlorogenic acid has good antibacterial effect on bacteria (such as Escherichia coli and Staphylococcus aureus) and fungi (such as Candida albicans). The acquisition way of the chlorogenic acid is green, environment-friendly and very convenient, and the chlorogenic acid can be obtained along with the growth and development of plants without manual excessive intervention in the synthesis process. Therefore, chlorogenic acid has a great potential in the development of natural antibacterial agents.
Cellulose is a polymer with the largest reserve in nature, and the main component of plants is cellulose, so that the cellulose can be easily obtained from nature at low cost and in large quantity, and for example, grass, trees, cotton and the like are common cellulose raw materials. The cellulose is linear polysaccharide formed by connecting beta-D glucopyranose repeating units through beta-1,4 glycosidic bonds, and the structure ensures that the cellulose material has the characteristics of unique chemical characteristics, flexibility, good mechanical strength, biodegradability and the like. Many different functionalized groups exist on the surface of cellulose, such as aldehyde groups, hydroxyl groups at the ends of polysaccharide chains, etc., and these functionalized groups provide reliable sites for the modification of cellulose. Cellulose modification can impart functions that are not originally possessed by cellulose, such as flame retardancy, antibacterial properties, heat resistance, and electrical conductivity.
Among a plurality of modified celluloses, an antibacterial cellulose material is one of research hotspots, and the cellulose material has certain antibacterial activity while maintaining the characteristics of high mechanical strength, low price, easy obtaining and the like of the cellulose, and can be applied to fresh-keeping materials, wound dressings and the like. However, the preparation of such materials presents the following problems:
cellulose and an antibacterial agent are generally made into a composite material by a simple mixing method, but the stability of the combination of the antibacterial agent and the cellulose is poor due to the simple mixing, the antibacterial agent is easily lost in the use process of the material, the antibacterial effect is poor, and the service life of the cellulose material is shortened. The invention discloses an antibacterial cellulose fiber as Chinese invention with the application number of 201921739040.2. And coating an anti-corrosion layer, an abrasion-resistant layer and an antibacterial layer outside the fiber, wherein the antibacterial layer is a silver oxide compound and a photocatalytic antibacterial agent. Although the fiber prepared by the method has antibacterial property, the antibacterial layer is arranged on the outermost layer, and the outermost antibacterial layer is easily abraded and even falls off when the fiber is used. The invention further discloses a preparation method of the antibacterial cellulose hydrogel as the Chinese invention with the application number of 201910530345.0, and the method comprises the steps of mixing hydroxyethyl cellulose and methyl cellulose according to a certain proportion, adding the mixture into ciprofloxacin solution, dropwise adding colloidal silica solution with a certain concentration into the solution, heating the solution at 37 ℃ for 8min, and then forming the hydrogel through physical crosslinking. The antibacterial agent ciprofloxacin prepared by the method is loaded in the gel network in a noncritical manner, and when the antibacterial agent ciprofloxacin is used, after ciprofloxacin is slowly released to a wound from the material along with time, the concentration of the antibacterial agent in the material is obviously reduced, the antibacterial effect is weakened, and the wound healing is slowed down.
In many preparation methods of antibacterial cellulose, metal oxides such as silver, titanium and the like are commonly used as antibacterial agents, but the preparation cost of noble metal antibacterial agents such as silver, titanium and the like is high, the process is complex, the environment is easily polluted, and the value of cellulose as an environment-friendly renewable material is greatly reduced. The invention of China with the application number of 202010496600.7 discloses N-doped TiO 2 -Ag 3 PO 4 The cellulose composite antibiotic film and the preparation method, the method prepares the titanium tetrachloride into the N-doped TiO through a series of complex treatments 2 -Ag 3 PO 4 Compounding antibacterial agent, ultrasonic dispersing the antibacterial agent with carboxymethyl cellulose and water, adding gelatin and glycerol to obtain N-doped TiO 2 -Ag 3 PO 4 The cellulose composite antibacterial film; chinese invention with application number 202010524593.7 discloses a pineapple leaf cellulose-based nano TiO-carried 2 The preparation method of the antibacterial preservative film comprises the steps of dissolving the pineapple leaf fibers in ionic liquid and adding the antibacterial agent nano TiO 2 After stirring, the solution is scraped off and then is converted from a gel state to an antibacterial film by phase conversion. Such methods require multiple processing steps, require a great deal of effort and cost to produce the antimicrobial agent, and can result in contamination and even hazardous exposure to toxic or irritating drugs.
In summary, loading the antibacterial agent by non-covalent connection method is easy to cause antibacterial agent loss, weaken antibacterial effect and reduce service life, and the commonly used antibacterial agent made of noble metals such as silver, titanium and the like has high preparation cost, complex process and easy pollution. Therefore, it is important and meaningful to develop a cellulose material capable of grafting green and environmentally friendly renewable antibacterial agents with covalent bonds.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a preparation method of a chlorogenic acid modified cellulose antibacterial material based on natural active ingredients, which has a good antibacterial effect.
The technical scheme is as follows: the invention provides a preparation method of a chlorogenic acid modified cellulose antibacterial material based on natural active ingredients, which comprises the following steps:
dissolving cellulose in a mixed aqueous solution of sodium hydroxide and urea to prepare a cellulose solution;
step two, adding anhydrous sodium sulfate into the cellulose solution obtained in the step one, stirring, and then freezing until solidification;
step three, soaking the solidified mixture obtained in the step two in water until the material floats on the water surface to obtain a cellulose material;
step four, mixing the cellulose material obtained in the step three with a sodium hydroxide aqueous solution and epichlorohydrin, and then washing the cellulose material with deionized water until the sodium hydroxide aqueous solution and the epichlorohydrin do not have residues;
and step five, mixing the cellulose material obtained in the step four with a sodium carbonate solution and a chlorogenic acid ethanol solution, then taking out the cellulose material, and washing the cellulose material with water until the cellulose material is not decolorized to obtain the chlorogenic acid modified cellulose antibacterial material.
Further, the mass percent of the cellulose solution in the step one is 1-3 wt%.
Furthermore, the mass of the anhydrous sodium sulfate added in the second step is 60-100% of the mass of the cellulose solution.
Furthermore, in the fourth step, the concentration of the sodium hydroxide aqueous solution is 1-4 mol/L, the volume ratio of the sodium hydroxide aqueous solution to the epichlorohydrin is 1: 1-3: 1, and the mixed liquid is over the cellulose material.
Further, the mass percent of the sodium carbonate solution in the fifth step is 1-3 wt%, and the balance is water; the mass-volume ratio of the chlorogenic acid to the ethanol is 0.01: 1-0.1: 1; the volume of the sodium carbonate solution is 80-100 ml, and the volume of the chlorogenic acid ethanol solution is 8-10 ml.
The principle of the technical scheme is as follows: in a sodium hydroxide and urea system, hydrogen bonds among cellulose are broken and enough free hydroxyl groups are exposed, after the material is frozen and solidified and is soaked in hot water, the sodium hydroxide and the urea are dissolved in the water and are separated from the cellulose, so that the hydrogen bonds among the cellulose are reformed, and the cellulose is converted into an aerogel form from long-chain fibers. And in the subsequent reaction with epoxy chloropropane, hydrogen in hydroxyl group in the cellulose chain is replaced by epoxy propane part of epoxy chloropropane to generate hydrogen chloride, and the existence of sodium hydroxide solution provides alkaline environment for the reaction system to drive the reaction to proceed forwards. After chlorogenic acid is added, epichlorohydrin used as an arm in the cellulose is combined with the chlorogenic acid, so that the chlorogenic acid is covalently grafted on the surface of the cellulose.
Has the beneficial effects that: the invention has the following advantages:
1. the chlorogenic acid and the cellulose are covalently connected by using the epichlorohydrin, so that the antibacterial agent is more stably grafted on the surface of the cellulose, the antibacterial agent is prevented from falling off, a good antibacterial effect is kept for a long time, and the service life of the material is further prolonged;
2. chlorogenic acid is used as a plant active substance, is synthesized by the growth and metabolism of plants, can be produced in large quantities without artificial excessive intervention, greatly reduces the pollution to the environment, is renewable in source and is a good antibacterial agent;
3. the prepared material has good plasticity and elasticity, can be made into materials with any shape according to requirements, and can be suitable for multiple purposes;
4. the preparation method is simple and convenient to operate, low in cost and has the potential of industrial production.
Drawings
FIG. 1 is a comparison of modified chlorogenic acid of comparative example 1 (left) and example 1 (right) according to the present invention;
FIG. 2 is a graph showing the test results of the elastic ability of the material under the pressure of a weight in example 1 of the present invention;
FIG. 3 is a Fourier infrared spectrum of chlorogenic acid-modified cellulose antibacterial material of example 1 of the present invention;
fig. 4 is a graph of the dynamic contact antibacterial performance of the chlorogenic acid-modified cellulose antibacterial material of example 1 and the chlorogenic acid-unmodified cellulose antibacterial material of comparative example 1 of the present invention, wherein a is the antibacterial performance of comparative example 1 on escherichia coli, b is the antibacterial performance of example 1 on escherichia coli, c is the antibacterial performance of comparative example 1 on staphylococcus aureus, and d is the antibacterial performance of example 1 on staphylococcus aureus.
Detailed Description
Example 1
The preparation method of the chlorogenic acid modified cellulose antibacterial material based on the natural active ingredient comprises the following steps:
step one, dissolving cellulose by using sodium hydroxide, urea and mixed aqueous solution at the temperature of-12 ℃ to prepare cellulose solution with the mass percentage of 3 wt%;
step two, adding anhydrous sodium sulfate with the mass ratio of 80% into the cellulose solution in the step two, fully mixing, and freezing at the temperature of minus 20 ℃ until the mixture is completely solidified;
step three, soaking the mixture obtained in the step two in hot water at the temperature of 80 ℃ until the material floats on the water surface, taking out the material and washing the material with deionized water;
step four, fully reacting the material in the step three with a mixed solution of sodium hydroxide aqueous solution and epoxy chloropropane at 60 ℃ for 2 hours, wherein the concentration of the sodium hydroxide aqueous solution is 3mol/L, the volume ratio of the epoxy chloropropane to the sodium hydroxide aqueous solution is 1: 2, and the mixed solution is required to be over the material;
step five, washing the cellulose material in the step four by using deionized water, mixing the washed cellulose material with 100ml of sodium carbonate solution with the mass percentage of 2wt% and 10ml of chlorogenic acid ethanol solution with the mass-volume ratio of 0.05: 1, and fully reacting for 10 hours at 50 ℃;
and sixthly, taking out the material, and cleaning the material by using deionized water to obtain the chlorogenic acid modified cellulose antibacterial material.
Comparative example 1
By way of comparison, by not performing step five in example 1, a cellulose material that was not modified with chlorogenic acid was obtained. The method specifically comprises the following steps:
(1) Dissolving cellulose in a mixed solution of sodium hydroxide and urea at the temperature of-12 ℃ to prepare a cellulose solution with the mass percent of 3 wt%;
(2) Adding anhydrous sodium sulfate 80% of the cellulose solution, mixing thoroughly, and freezing in a refrigerator at-20 deg.C to completely solidify;
(3) Taking out the solidified material, soaking the solidified material in water at 80 ℃ until the material floats on the water surface, and taking out the material and cleaning the material by deionized water.
From fig. 1, it can be clearly seen that the color of the material before and after modification of chlorogenic acid of the antibacterial agent is obviously changed, the material before modification is pure white, and the material after modification is brown, which proves that chlorogenic acid is successfully modified on the surface of cellulose from the perspective of macroscopic morphology.
As shown in the elasticity measurement of fig. 2, when the weight is lifted after a weight of 200g is placed on the material and is kept still for 3s, the material can be normally bounced, and the material still has good elasticity after chlorogenic acid is modified.
As can be seen from the fourier infrared spectroscopy (FT-IR) of fig. 3, chlorogenic acid shows various characteristic peaks: 3383cm -1 The position is caused by benzene ring-OH stretching vibration; 1687cm -1 In the form of a mixed polymer of ester bond and C = O in carboxyl groupContracting the vibration peak; 1638 1601, 1518, 1443cm -1 The position is caused by the stretching vibration of a benzene ring; 1288 1187cm -1 Is the stretching vibration peak of C-O-C in carboxyl; 603cm -1 The peak of bending vibration of-OH in the carboxyl group is at point (b). The chlorogenic acid modified cellulose is at 1634, 1607, 1509, 1453cm -1 The stretching vibration peak of the benzene ring in the chlorogenic acid is detected at four positions, so that the chlorogenic acid is successfully grafted to the cellulose.
FIG. 4 shows the results of example 1 and comparative example 1 for Escherichia coli (G-) and Staphylococcus aureus (G) + ) Wherein the graphs (a) and (c) are comparative example 1, and the graphs (b) and (d) are example 1. As can be seen from the figure, comparative example 1 has no antibacterial ability because it is not modified by chlorogenic acid as an antibacterial agent, and many colonies are formed on the plate; the cellulose material in example 1 successfully kills the bacteria by using the antibacterial ability of the chlorogenic acid grafted on the surface of the cellulose material, so that no colony is formed on the surface of a plate, and the modified cellulose is proved to have good antibacterial performance.
Example 2
A preparation method of a chlorogenic acid modified cellulose antibacterial material based on natural active ingredients comprises the following steps:
step one, dissolving cellulose by using sodium hydroxide, urea and mixed aqueous solution at the temperature of-12 ℃ to prepare cellulose solution with the mass percentage of 3 wt%;
step two, adding anhydrous sodium sulfate with the mass ratio of 80% into the cellulose solution in the step two, fully mixing, and freezing at the temperature of minus 20 ℃ until the mixture is completely solidified;
step three, soaking the mixture obtained in the step two in hot water at the temperature of 80 ℃ until the material floats on the water surface, taking out deionized water and cleaning;
step four, fully reacting the material in the step three with a mixed solution of sodium hydroxide aqueous solution and epichlorohydrin for 2 hours at 60 ℃, wherein the concentration of the sodium hydroxide aqueous solution is 3mol/L, the volume ratio of the epichlorohydrin to the sodium hydroxide aqueous solution is 1: 2, and the mixed solution is required to be over the material;
step five, washing the cellulose material in the step four by using deionized water, mixing the washed cellulose material with 100ml of sodium carbonate solution with the mass percentage of 2wt% and 10ml of chlorogenic acid ethanol solution with the mass-volume ratio of 0.01:1, and fully reacting for 10 hours at 50 ℃;
and sixthly, taking out the material, and cleaning the material by using deionized water to obtain the chlorogenic acid modified cellulose antibacterial material.
Example 3
A preparation method of a chlorogenic acid modified cellulose antibacterial material based on natural active ingredients comprises the following steps:
step one, dissolving cellulose by using sodium hydroxide, urea and mixed aqueous solution at the temperature of-12 ℃ to prepare cellulose solution with the mass percentage of 3 wt%;
step two, adding anhydrous sodium sulfate with the mass ratio of 80% into the cellulose solution in the step two, fully mixing, and freezing at the temperature of minus 20 ℃ until the mixture is completely solidified;
step three, soaking the mixture obtained in the step two in hot water at the temperature of 80 ℃ until the material floats on the water surface, taking out deionized water and cleaning;
step four, cleaning the material in the step three, and then fully reacting the material with a mixed solution of sodium hydroxide water solution and epoxy chloropropane for 2 hours at the temperature of 60 ℃, wherein the concentration of the sodium hydroxide water solution is 3mol/L, the volume ratio of the epoxy chloropropane to the sodium hydroxide water solution is 1: 2, and the mixed solution is required to be over the material;
step five, washing the cellulose material in the step four by using deionized water, mixing the washed cellulose material with 100ml of sodium carbonate solution with the mass percentage of 2wt% and 10ml of chlorogenic acid ethanol solution with the mass volume ratio of 0.03: 1, and fully reacting for 10 hours at 50 ℃;
and sixthly, taking out the material, and cleaning the material by using deionized water to obtain the chlorogenic acid modified cellulose antibacterial material.
Example 4
The preparation method of the chlorogenic acid modified cellulose antibacterial material based on the natural active ingredient comprises the following steps:
step one, dissolving cellulose by using sodium hydroxide, urea and mixed aqueous solution at the temperature of-12 ℃ to prepare cellulose solution with the mass percent of 1 wt%;
step two, adding anhydrous sodium sulfate with the mass ratio of 60% into the cellulose solution in the step two, fully mixing, and freezing at the temperature of minus 20 ℃ until the mixture is completely solidified;
step three, soaking the mixture obtained in the step two in hot water at the temperature of 80 ℃ until the material floats on the water surface, taking out deionized water and cleaning;
step four, fully reacting the material in the step three with a mixed solution of sodium hydroxide aqueous solution and epichlorohydrin for 2 hours at 60 ℃, wherein the concentration of the sodium hydroxide aqueous solution is 1mol/L, the volume ratio of the epichlorohydrin to the sodium hydroxide aqueous solution is 1:1, and the mixed solution is required to be over the material;
step five, washing the cellulose material in the step four by using deionized water, mixing the washed cellulose material with 80ml of sodium carbonate solution with the mass percent of 1wt% and 8ml of chlorogenic acid ethanol solution with the mass-volume ratio of 0.01:1, and fully reacting for 10 hours at 50 ℃;
and sixthly, taking out the material, and cleaning the material by using deionized water to obtain the chlorogenic acid modified cellulose antibacterial material.
Example 5
The preparation method of the chlorogenic acid modified cellulose antibacterial material based on the natural active ingredient comprises the following steps:
step one, dissolving cellulose by using sodium hydroxide, urea and mixed aqueous solution at the temperature of-12 ℃ to prepare cellulose solution with the mass percentage of 3 wt%;
step two, adding anhydrous sodium sulfate with the mass ratio of 100% into the cellulose solution in the step two, fully mixing, and freezing at the temperature of minus 20 ℃ until the mixture is completely solidified;
step three, soaking the mixture obtained in the step two in hot water at the temperature of 80 ℃ until the material floats on the water surface, taking out deionized water and cleaning;
step four, fully reacting the material in the step three with a mixed solution of sodium hydroxide aqueous solution and epichlorohydrin for 2 hours at 60 ℃, wherein the concentration of the sodium hydroxide aqueous solution is 4mol/L, the volume ratio of the epichlorohydrin to the sodium hydroxide aqueous solution is 3:1, and the mixed solution is required to be over the material;
step five, washing the cellulose material in the step four by using deionized water, mixing the washed cellulose material with 100ml of sodium carbonate solution with the mass percentage of 3wt% and 10ml of chlorogenic acid ethanol solution with the mass-volume ratio of 0.1:1, and fully reacting for 10 hours at 50 ℃;
and sixthly, taking out the material, and cleaning the material by using deionized water to obtain the chlorogenic acid modified cellulose antibacterial material.

Claims (4)

1. A preparation method of a chlorogenic acid modified cellulose antibacterial material based on natural active ingredients is characterized by comprising the following steps: the method comprises the following steps:
dissolving cellulose in a mixed aqueous solution of sodium hydroxide and urea to prepare a cellulose solution;
step two, adding anhydrous sodium sulfate into the cellulose solution obtained in the step one, stirring, and then freezing until solidification;
step three, soaking the solidified mixture obtained in the step two in water until the material floats on the water surface to obtain a cellulose material;
step four, mixing the cellulose material obtained in the step three with a sodium hydroxide aqueous solution and epichlorohydrin, and then washing the cellulose material with deionized water until the sodium hydroxide aqueous solution and the epichlorohydrin have no residue;
step five, taking out the cellulose material obtained in the step four, sodium carbonate solution and chlorogenic acid ethanol solution, and then washing the cellulose material with water until the cellulose material is not decolorized to obtain a chlorogenic acid modified cellulose antibacterial material;
the mass percent of the cellulose solution in the first step is 1-3wt%.
2. The method for preparing a chlorogenic acid modified cellulose antibacterial material based on natural active ingredients as claimed in claim 1, wherein: and in the second step, the mass of the added anhydrous sodium sulfate is 60 to 100 percent of the mass of the cellulose solution.
3. The method for preparing a chlorogenic acid modified cellulose antibacterial material based on natural active ingredients as claimed in claim 1, wherein: in the fourth step, the concentration of the sodium hydroxide aqueous solution is 1 to 4mol/L, the volume ratio of the sodium hydroxide aqueous solution to the epichlorohydrin is 1 to 1, and the mixed liquid is submerged in the cellulose material.
4. The method for preparing a chlorogenic acid modified cellulose antibacterial material based on natural active ingredients as claimed in claim 1, wherein: the mass percent of the sodium carbonate solution in the fifth step is 1 to 3wt percent, and the balance is water; the mass volume ratio of the chlorogenic acid to the ethanol is 0.01 to 0.1; the volume of the sodium carbonate solution is 80-100 ml, and the volume of the chlorogenic acid ethanol solution is 8-10 ml.
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CN107325212A (en) * 2017-08-03 2017-11-07 中北大学 A kind of high-performance Rosmarinic acid molecular surface engram particulate and preparation method thereof
CN108727516A (en) * 2018-09-19 2018-11-02 中国科学院烟台海岸带研究所 A kind of chitosan chlorogenic acid salt and its preparation method and application
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CN108727516A (en) * 2018-09-19 2018-11-02 中国科学院烟台海岸带研究所 A kind of chitosan chlorogenic acid salt and its preparation method and application
CN110144054A (en) * 2019-05-30 2019-08-20 李明霞 A kind of preparation method of ventilated bacterium-suppressing protection of trees film

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