CN107513108B - Preparation method and application of antibacterial cellulose ester - Google Patents

Preparation method and application of antibacterial cellulose ester Download PDF

Info

Publication number
CN107513108B
CN107513108B CN201710759287.XA CN201710759287A CN107513108B CN 107513108 B CN107513108 B CN 107513108B CN 201710759287 A CN201710759287 A CN 201710759287A CN 107513108 B CN107513108 B CN 107513108B
Authority
CN
China
Prior art keywords
antibacterial
cellulose
esterified substance
preparation
product
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201710759287.XA
Other languages
Chinese (zh)
Other versions
CN107513108A (en
Inventor
吴德群
汤双双
朱婕
韩华
李发学
王学利
俞建勇
杨占平
曹建华
陈昀
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shenzhen Pu'an Technology Co ltd
Shenzhen Tianfeng Shangyi Culture Communication Co ltd
Original Assignee
Donghua University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Donghua University filed Critical Donghua University
Priority to CN201710759287.XA priority Critical patent/CN107513108B/en
Publication of CN107513108A publication Critical patent/CN107513108A/en
Application granted granted Critical
Publication of CN107513108B publication Critical patent/CN107513108B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/20—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing organic materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
    • A61L15/28—Polysaccharides or their derivatives
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A61L15/46—Deodorants or malodour counteractants, e.g. to inhibit the formation of ammonia or bacteria
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/20—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials
    • A61L2300/216—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials with other specific functional groups, e.g. aldehydes, ketones, phenols, quaternary phosphonium groups
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/404—Biocides, antimicrobial agents, antiseptic agents

Landscapes

  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Animal Behavior & Ethology (AREA)
  • Hematology (AREA)
  • Epidemiology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Biochemistry (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Materials For Medical Uses (AREA)

Abstract

The invention discloses a preparation method of antibacterial cellulose and application of the prepared antibacterial cellulose in preparation of an antibacterial fiber dressing. The preparation method comprises the following steps: purifying the cellulose derivative; adding the purified cellulose derivative and acid anhydride into an acetone solution under the condition of a catalyst, heating and stirring; activating hydroxyl in the esterified substance, precipitating and washing in absolute ethyl alcohol, and performing suction filtration to obtain an esterified substance and a grafted esterified substance; grafting ethylene diamine protected by di-tert-butyl dicarbonate with a broad-spectrum antibacterial agent; and carrying out esterification reaction on the esterified substance and the product to obtain the antibacterial cellulose. The esterification product prepared by the invention has enhanced hygroscopicity, the modified product of the grafted antibacterial agent has good antibacterial effect on negative and positive bacteria, the medical dressing can not only play a role in inhibiting bacteria during bacterial infection and avoid bacteria generation, but also has the advantages of water resistance and moisture permeability, and can form good protection on wound areas.

Description

Preparation method and application of antibacterial cellulose ester
Technical Field
The invention relates to esterification modification and antibacterial performance research of cellulose diacetate, in particular to preparation of electrostatic spinning antibacterial fiber and application of the electrostatic spinning antibacterial fiber in the field of medical dressings.
Background
The acetate fiber has luster and hand feeling similar to silk, is often used as a substitute of silk, and is blended with synthetic fiber to prepare the composite yarn for various high-grade clothes. The acetate fiber is widely used in the fields of medical dressing, cigarette filter tip and the like besides being used in textiles.
The CA fiber has hydrophilic property and good moisture absorption property, so that the fabric is particularly suitable for anti-inflammatory and antibacterial gauze, wound dressing and the like. In a humid environment, various bacteria are easy to breed on the surface of the wound, and the gauze made of the CA material can avoid excessive water so as to improve the sanitation of the wound.
Because of good blood compatibility and biocompatibility, cellulose acetate can be used for preparing hollow fiber separation membranes in the fields of blood filtration, gas and liquid separation and the like. Antibacterial cellulose acetate fibers have appeared abroad, not only maintain the excellent performance of common cellulose acetate fibers, but also have good antibacterial performance, and are widely applied to the fields of hygiene, medical treatment and the like. Cellulose acetate is widely applied to the cigarette industry and the textile industry in recent years, is a degradable bio-friendly regenerated cellulose material, has good development in the aspects of biomedical materials, semipermeable membranes and the like, and has a series of advantages of high selectivity, good blood compatibility, good biocompatibility and the like. The cellulose acetate can also be used for preparing capsules for coating medicaments, thereby achieving the purpose of controllable release of the medicaments. In addition, the non-woven fabric prepared from the acetate staple fibers is widely applied in the field of bandaging of surgical operations, and belongs to advanced medical and health materials because the non-woven fabric is not adhered to wounds. The experiment analysis is carried out aiming at the problems of the cellulose acetate film frequently occurring in the separation of serum protein, the factors influencing the electrophoresis pattern are obtained, in the aspect of the substrate cellulose acetate, the cellulose acetate film is uneven in thickness and hole number, so that the brittleness of the film is different, the separation effect of the whole film is uneven in the protein separation process, the cellulose acetate film is placed in a buffer solution for infiltration before use, the filter paper is not too dry in the process of absorbing the film, otherwise, a sample cannot enter the pores of the separation film, and the good separation effect is not achieved. The cellulose acetate glucose ring is substituted and modified by hydroxyl, phosphate group, sulfonic group and the like, so that the functionality of the cellulose acetate membrane is improved, the leucopenia symptom generated during filtration is reduced, and the compatibility of the cellulose acetate membrane and blood is improved.
The levofloxacin antibacterial agent (Le) has a broad-spectrum antibacterial effect, has no stimulation to skin, is not easy to cause skin allergy, has high stability, and can be used for quickly and effectively inhibiting and sterilizing bacteria.
The electrostatic spinning method can be used for preparing the nano-fibers, the diameter of the nano-fibers can reach several nanometers, the royal jelly and the like take cellulose diacetate as raw materials, and through experimental investigation, the fact that the mixture of acetone as a solvent and acetone/Dimethylacetamide (DMAC) as a solvent (the optimal mass ratio is 2:1) is more ideal is found, and the two electrostatic spinning solvents are used for preparing the electrostatic spinning diacetate nano-fibers. The electrostatic spinning device is simple and easy to assemble and widely applied to processing of various materials, and the electrostatic spinning operation is simple, so that the electrostatic spinning device can produce fibers with various properties, and is gradually and widely applied to the fields of biological medicines, industrial production and the like in recent years.
Disclosure of Invention
The invention aims to provide cellulose diacetate fibers with lasting safe antibacterial performance and a corresponding dressing with antibacterial effect.
In order to solve the above problems, the present invention provides a method for preparing antibacterial cellulose, which is characterized by comprising the following steps:
step 1): purifying the cellulose derivative;
step 2): adding the purified cellulose derivative and acid anhydride into an acetone solution under the condition of a catalyst at the temperature of 50-65 ℃, and heating and stirring for 15-24 hours; the mole number of the acid anhydride is 5-10 times of that of hydroxyl in the cellulose derivative; precipitating and washing the prepared esterified substance in absolute ethyl alcohol for 3-5 times, and performing suction filtration to obtain the esterified substance; vacuum drying the ester at 30-40 ℃ for 8-12 hours; obtaining grafted esterified substance;
taking cellulose diacetate as an example, the chemical formula of grafting is shown in formulas I and II:
Figure GDF0000010897080000021
Figure GDF0000010897080000031
step 3): activating carboxyl in the esterified substance obtained in the step 2) by N-hydroxysuccinimide (NHS) and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC & HCl);
step 4): grafting ethylene diamine (Boc-EDA) protected by di-tert-butyl dicarbonate with a broad-spectrum antibacterial agent;
the chemical formula of grafting is shown as formula III:
Figure GDF0000010897080000032
step 5): reacting the esterified substance obtained in the step 3) with the product obtained in the step 4) to obtain antibacterial cellulose;
the chemical equation of the esterification reaction is shown as formula IV:
Figure GDF0000010897080000033
step 6): and precipitating the antibacterial cellulose in a methanol solution, and then drying the antibacterial cellulose in vacuum for 5-8 hours at room temperature.
Preferably, the cellulose derivative in step 1) is cellulose diacetate of the formula [ C6H7O2(OCOCH3)X(OH)3-X]nWherein n is 200-400; when X is 2.28-2.49, the mass content of acetyl is 38-40%.
Preferably, the acid anhydride in step 2) is any one or more of phthalic anhydride, succinic anhydride, acrylic anhydride and maleic anhydride.
Preferably, the catalyst in step 2) is triethylamine.
The invention also provides application of the antibacterial cellulose prepared by the preparation method of the antibacterial cellulose in preparation of an antibacterial fiber dressing.
Preferably, the antibacterial cellulose is prepared into the antibacterial fiber dressing by an electrostatic spinning method.
The prepared esterified product has enhanced hygroscopicity, and the modified product of the grafted antibacterial agent has good antibacterial effect on negative and positive bacteria, and particularly relates to preparation of an electrostatic spinning antibacterial fiber and application thereof in the field of medical dressings. The medical dressing can not only play a role in inhibiting bacteria during bacterial infection and avoid bacteria generation, but also has the advantages of water resistance and moisture permeability, and can well protect a wound surface area. The melting point of the graft is reduced, the decomposition temperature range is not changed greatly, and the thermal stability is good.
The acid anhydride is preferably phthalic anhydride of rigid structure and succinic anhydride of flexible structure.
The cellulose diacetate and the esterified product thereof have higher water content, the hygroscopicity of the grafted product is stronger than that of the raw material CDA, and the average moisture regain is about 9.4 percent. The contact angle of the cellulose diacetate is reduced by 12.9 percent and 22.7 percent relative to the contact angle of the cellulose diacetate, the molecules of the cellulose diacetate have good hydrophilicity no matter CDA or a graft thereof, and the hydrophilicity of the graft is enhanced, thereby being beneficial to the application of the cellulose diacetate in the field of wound dressings.
The graft has broad-spectrum antibacterial property and lasting and stable antibacterial performance, the antibacterial rate to escherichia coli and staphylococcus aureus reaches more than 90%, the antibacterial effect is very good, and the cellulose diacetate has good development prospect in the aspect of application of medical dressings.
The invention adopts an electrostatic spinning method to prepare the fiber dressing grafted with the antibacterial agent, researches the antibacterial property of the fiber dressing, and expands the application of the fiber dressing in the aspects of anti-inflammatory and antibacterial gauze, wound dressing and the like.
Compared with the prior art, the invention has the beneficial effects that:
1. the raw material cellulose diacetate used by the invention is low in price;
2. the moisture absorption performance of the esterification product is enhanced, the moisture absorption of the wound dressing to the moist environment of the wound of a human body is facilitated, and the air permeability of the CDA raw material is good;
3. the esterification product grafted antibacterial product prepared by the invention has excellent antibacterial performance which is more than 90%;
4. the fiber dressing prepared by the esterification product grafted antibacterial product through the electrostatic spinning method has a good antibacterial effect, and the medical dressing not only can play a role in inhibiting bacteria and avoid bacteria generation during bacterial infection, but also has the advantages of water resistance and moisture permeability, and can well protect a wound area.
Drawings
FIG. 1 is a bacteriostatic plot of the esterified grafted antimicrobial product A of the present invention against E.coli and S.aureus; wherein, the CDA-g-PA-g-Le is a product of esterification of cellulose diacetate and phthalic anhydride and grafting with an antibacterial agent;
FIG. 2 is a bacteriostatic plot of the esterified grafted antimicrobial product B of the present invention against E.coli and S.aureus; wherein, the CDA-g-BA-g-Le is a product obtained by esterifying cellulose diacetate with succinic anhydride and grafting with an antibacterial agent;
fig. 3 is a scanning electron microscope representation of electrospun antimicrobial fibers and electrospun CDA fibers of the present invention.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments are described in detail below with reference to the accompanying drawings.
Qualitative antibiosis: in the examples, the antibacterial properties of the CDA-g-PA-g-Le graft were tested by diffusion on agar plates: the method comprises the steps of taking staphylococcus aureus (ATCC 6538) and escherichia coli (ATCC 8099) as test strains, diluting cultured staphylococcus aureus and escherichia coli liquid by 100 times with sterilized deionized water, pouring 1mL of the diluted liquid into a 90mL sterile culture dish, then pouring about 15mL of sterilized agar medium (1.6g of agar medium and 50mL of deionized water) into the sterile culture dish, slightly shaking left and right to uniformly mix the liquid and agar, after the liquid and agar are completely cooled and condensed, slightly placing prepared grafts with the diameter multiplied by the height of 5mm multiplied by 5mm (0.1g) in the center of the culture dish respectively by using tweezers, and uniformly pressing the grafts on the agar medium until a sample and the agar medium are tightly adhered together. And then, inversely placing the culture medium in an SPX-80B-II type biochemical incubator, culturing for 18-24 hours at the constant temperature of 37 ℃, and calculating the size of the inhibition zone according to the following formula:
H＝(D-d)/2 (3-1)
wherein: h is the size of the zone of inhibition in millimeters (mm); d is the average value of the outer diameter of the inhibition zone, and the unit is millimeter (mm); d is the diameter of the sample in millimeters (mm).
Quantitative antibiosis:
the first day: inoculating escherichia coli and staphylococcus aureus into a sterilized agar medium, and culturing in a constant-temperature incubator for 18-24 h.
The next day: dipping the two inoculated strains in the sterilized broth, and culturing the broth in a constant-temperature culture shaker for 18-24 h.
And on the third day: 6 conical flasks containing 70mL of PBS solution, 2 conical flasks containing 45mL of PBS solution, 2 nutrient agar of 50mL, 10 PBS solution of 4.5mL, 4 nutrient broth of 4.5mL, several blue needles and several white needles were sterilized in a vertical pressure steam sterilizer. 0.5mL of cultured Escherichia coli solution is diluted by 100 times in 4.5mL of sterilized broth, 5mL of the bacterium solution diluted by 100 times is added in 45mL of sterilized PBS solution, the mixture is shaken up, and 5mL of the solution is added in 70mL of 3 sterilized PBS solutions and respectively marked as a contact sample, a blank sample and a sample.
The zero-contact sample was taken at 0.5mL in 4.5mL PBS, and the diluted solution was taken at 4.5mL PBS and diluted 4 times. And (3) putting 1mL of the diluted bacterial liquid into a culture dish, pouring 15mL of cultured agar, cooling, and putting the cooled agar into a constant-temperature incubator for culturing for 18-24 hours. And placing the blank sample and the sample in a constant-temperature culture shaker for 18-24 h, respectively taking the uniformly shaken blank sample and sample 0.5mL in 4.5mL PBS solution, and then taking the diluted solution in 4.5mL PBS solution for diluting for 6 times. And (3) putting 1mL of the diluted bacterial liquid into a culture dish, pouring 15mL of cultured agar, cooling, and putting the cooled agar into a constant-temperature incubator for culturing for 18-24 hours. The method for quantitatively resisting staphylococcus aureus by the graft is the same as the above method.
Example 1
A preparation method of antibacterial cellulose ester comprises the following steps:
(1) 1g of Cellulose Diacetate (CDA), 0.36g of equimolar phthalic anhydride and 3.38mL of triethylamine as a catalyst are taken, and the mole number of the catalyst is 10 times of the hydroxyl content of the cellulose diacetate. Firstly, dissolving weighed 1g of cellulose diacetate in a 100mL three-neck round-bottom flask containing 20mL of acetone solution, heating and stirring the mixture on a magnetic stirring instrument at the temperature of 60 ℃ for about 2 hours, raising the temperature to 65 ℃, adding 0.36g of phthalic anhydride and 3.38mL of triethylamine serving as a catalyst after the cellulose diacetate is completely dissolved, and reacting for 24 hours. After the reaction is finished, slowly dropping the reaction solution into 100mL of absolute ethyl alcohol, precipitating and washing for 3 times, carrying out suction filtration to obtain an esterified substance, and carrying out vacuum drying on the obtained esterified substance for 8 hours at the temperature of 40 ℃ to obtain the esterified substance grafted by the cellulose diacetate and the anhydride.
(2) Adding 0.1g N-hydroxysuccinimide (NHS), 0.15g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) and 0.3g of levofloxacin into 10mL of DMF solution, activating overnight under ice bath condition, adding 0.13g of Boc-EDA for reaction for 12h, adding 0.1g of trifluoroacetic acid for removing Boc, adding 0.3mL of triethylamine for adjusting pH after 1h, and stirring for 1h to obtain a product A;
(3) dissolving 0.3g of esterified CDA-g-PA in 10mL of DMF solution, adding 0.1g N-hydroxysuccinimide (NHS) and 0.15g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC), activating overnight under ice bath conditions, adding the product, reacting for 12h, precipitating in methanol solution, and vacuum drying at room temperature for 6h to obtain a final product B.
(4) The conclusion of the quantitative antibacterial experiment of the product B shows that the antibacterial effect of the product B reaches more than 90 percent.
(5) The product B is prepared into the fiber dressing through electrostatic spinning, and the qualitative antibacterial experiment conclusion of the fiber dressing shows that the fiber dressing has a lasting antibacterial effect.
Example 2
A preparation method of antibacterial cellulose ester comprises the following steps:
(1) 1g of purified cellulose diacetate was weighed, 0.25g of succinic anhydride in equimolar amount, and 3.38mL of triethylamine as a catalyst, the number of moles of which was 10 times the hydroxyl content of the cellulose diacetate. Firstly, 1g of weighed cellulose diacetate is dissolved in 100mL of a three-neck round-bottom flask containing 20mL of acetone solution, the mixture is placed on a magnetic stirring instrument and heated and stirred for about 2 hours at the temperature of 60 ℃, the temperature is increased to 65 ℃, after the cellulose diacetate is completely dissolved, 1.98g of succinic anhydride and 3.38mL of triethylamine serving as a catalyst are added, and the reaction is carried out for 24 hours. After the reaction is finished, slowly dropping the reaction solution into 100mL of absolute ethyl alcohol, precipitating and washing for 3 times, carrying out suction filtration to obtain an esterified substance, and carrying out vacuum drying on the obtained esterified substance for 8 hours at the temperature of 40 ℃ to obtain the esterified substance grafted by the cellulose diacetate and the succinic anhydride.
(2) Adding 0.1g N-hydroxysuccinimide (NHS), 0.15g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) and 0.3g of levofloxacin into 10mL of DMF solution, activating overnight under ice bath condition, adding 0.13g of Boc-EDA for reaction for 12h, adding 0.1g of trifluoroacetic acid for removing Boc, adding 0.3mL of triethylamine for adjusting pH after 1h, and stirring for 1h to obtain a product A;
(3) dissolving 0.3g of esterified substance CDA-g-BA in 10mL of DMF solution, adding 0.1g N-hydroxysuccinimide (NHS) and 0.15g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC), activating overnight under ice bath conditions, adding the product A, reacting for 12h, precipitating in methanol solution, and vacuum drying at room temperature for 6h to obtain the final product 3.
(4) The conclusion of the quantitative antibacterial experiment of the product 3 shows that the antibacterial effect reaches more than 90 percent.
(5) The product 3 is prepared into the fiber dressing through electrostatic spinning, and the qualitative antibacterial experiment conclusion of the fiber dressing shows that the fiber dressing has a lasting antibacterial effect.
Example 3
A preparation method of antibacterial cellulose ester comprises the following steps:
(1) 1g of Cellulose Diacetate (CDA), 1.34g of an equimolar amount of Stearic Anhydride (SA), and 3.38mL of triethylamine as a catalyst were added. Dissolving cellulose diacetate in 20mL of acetone solution, placing the solution on a magnetic stirrer, heating and stirring the solution at the temperature of 60 ℃, raising the temperature to 65 ℃, adding 1.34g of stearic anhydride and 3.38mL of triethylamine serving as a catalyst after the cellulose diacetate is completely dissolved, and reacting the solution for 10 hours.
(2) Adding 0.1g N-hydroxysuccinimide (NHS), 0.15g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) and 0.3g of levofloxacin into 10mL of DMF solution, activating overnight under ice bath condition, adding 0.13g of Boc-EDA for reaction for 12h, adding 0.1g of trifluoroacetic acid to remove Boc, adding 0.3mL of triethylamine dropwise after 1h to adjust the pH, and stirring for 1 h;
(3) dissolving 0.3g of esterified product CDA-g-SA in 10mL of DMF solution, adding 0.1g N-hydroxysuccinimide (NHS) and 0.15g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC), activating overnight under ice bath conditions, adding the product, reacting for 12h, precipitating in methanol solution, and vacuum drying at room temperature for 6h to obtain the final product.
(4) And (3) carrying out qualitative antibacterial experiments on the final product, and finding that the final product has an obvious and stable inhibition zone within one week.
(5) The product is then prepared into the fiber dressing through electrostatic spinning, and the qualitative antibacterial experiment conclusion of the fiber dressing shows that the fiber dressing has a lasting antibacterial effect.
Example 4
(1) Quantitative antibacterial experiments are carried out on the final product prepared in the example 3, and the antibacterial effect is found to be more than 85%.
(2) The product is then electrostatically spun to prepare the fiber dressing, and the qualitative antibacterial experiment results show that the fiber dressing has a lasting antibacterial effect and has an obvious and stable antibacterial ring size within one continuous week.
Example 5
A preparation method of antibacterial cellulose ester comprises the following steps:
(1) 1g of Cellulose Diacetate (CDA) and 0.66g of an equimolar amount of Octanoic Anhydride (OA) were taken. Dissolving cellulose diacetate in 20mL of acetone solution, placing the solution on a magnetic stirrer, heating and stirring the solution at the temperature of 60 ℃, raising the temperature to 65 ℃, adding 1.34g of caprylic anhydride and 3.38mL of triethylamine serving as a catalyst after the cellulose diacetate is completely dissolved, and reacting for 8 hours.
(2) Adding 0.1g of N-hydroxysuccinimide (NHS), 0.15g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) and 0.3g of levofloxacin into 10mL of DMF solution, activating overnight under ice bath condition, adding 0.13g of Boc-EDA for reaction for 12h, adding 0.1g of trifluoroacetic acid to remove Boc, adding 0.3mL of triethylamine dropwise after 1h to adjust the pH, and stirring for 1 h;
(3) dissolving 0.3g of esterified CDA-g-OA in 10mL of DMF solution, adding 0.1g N-hydroxysuccinimide (NHS) and 0.15g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC), activating overnight under ice bath conditions, adding the product, reacting for 12h, precipitating in methanol solution, and vacuum drying at room temperature for 6h to obtain the final product.
(4) And (3) carrying out qualitative antibacterial experiments on the final product, and finding that the final product has an obvious and stable inhibition zone within one week.
(5) The product is then prepared into the fiber dressing through electrostatic spinning, and the qualitative antibacterial experiment conclusion of the fiber dressing shows that the fiber dressing has a lasting antibacterial effect.
Example 6
(1) Quantitative antibacterial experiments are carried out on the final product prepared in the example 5, and the antibacterial effect is found to be more than 80%.
(2) The product is then electrostatically spun to prepare the fiber dressing, and the qualitative antibacterial experiment results show that the fiber dressing has a lasting antibacterial effect and has an obvious and stable antibacterial ring size within one continuous week.

Claims (3)

1. The preparation method of the antibacterial cellulose is characterized by comprising the following steps:
step 1): purifying the cellulose derivative; the cellulose derivative is cellulose diacetate with a molecular formula of [ C6H7O2(OCOCH3)X(OH)3-X]nWherein n is 200-400; when X is 2.28-2.49, the mass content of acetyl is 38-40%;
step 2): adding the purified cellulose derivative and acid anhydride into an acetone solution under the condition of a catalyst at the temperature of 50-65 ℃, and heating and stirring for 15-24 hours; the mole number of the acid anhydride is 5-10 times of that of hydroxyl in the cellulose derivative; precipitating and washing the prepared esterified substance in absolute ethyl alcohol for 3-5 times, and performing suction filtration to obtain the esterified substance; vacuum drying the ester at 30-40 ℃ for 8-12 hours; obtaining grafted esterified substance;
step 3): activating carboxyl in the esterified substance obtained in the step 2) by N-hydroxysuccinimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride;
step 4): grafting ethylene diamine protected by di-tert-butyl dicarbonate with a broad-spectrum antibacterial agent;
step 5): reacting the esterified substance obtained in the step 3) with the product obtained in the step 4) to obtain antibacterial cellulose;
step 6): and precipitating the antibacterial cellulose in a methanol solution, and then drying the antibacterial cellulose in vacuum for 5-8 hours at room temperature.
2. The method for preparing antibacterial cellulose according to claim 1, wherein the acid anhydride in step 2) is any one or more of phthalic anhydride, succinic anhydride, acrylic anhydride and maleic anhydride.
3. The method for preparing antibacterial cellulose according to claim 1, wherein the catalyst in step 2) is triethylamine.
CN201710759287.XA 2017-08-29 2017-08-29 Preparation method and application of antibacterial cellulose ester Active CN107513108B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710759287.XA CN107513108B (en) 2017-08-29 2017-08-29 Preparation method and application of antibacterial cellulose ester

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710759287.XA CN107513108B (en) 2017-08-29 2017-08-29 Preparation method and application of antibacterial cellulose ester

Publications (2)

Publication Number Publication Date
CN107513108A CN107513108A (en) 2017-12-26
CN107513108B true CN107513108B (en) 2021-06-01

Family

ID=60724536

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710759287.XA Active CN107513108B (en) 2017-08-29 2017-08-29 Preparation method and application of antibacterial cellulose ester

Country Status (1)

Country Link
CN (1) CN107513108B (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109629026A (en) * 2018-12-10 2019-04-16 东华大学 A kind of cellulose melt spun fibre and preparation method thereof with durable antibiotic performance
CN110747579A (en) * 2019-11-02 2020-02-04 东华大学 Double-layer one-way moisture-conducting antibacterial micro-nano acetate fiber membrane and preparation method and application thereof
CN110981974B (en) * 2019-11-29 2021-09-24 安徽三宝棉纺针织投资有限公司 Antibacterial cellulose modification system and method
CN112064193A (en) * 2020-08-28 2020-12-11 华东理工大学 Preparation method of cellulose diacetate based three-dimensional scaffold with antibacterial and biocompatibility functions
CN112724267A (en) * 2020-12-23 2021-04-30 广东省微生物研究所（广东省微生物分析检测中心） Preparation method and application of carboxymethyl cellulose antibacterial peptide
CN115368694B (en) * 2022-09-30 2023-10-13 河北百展科技发展有限公司 Biomass-based reinforced polyvinyl alcohol composite material and preparation method thereof
CN117050198A (en) * 2023-08-07 2023-11-14 张琦 High-stability cellulose acetate and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102219812A (en) * 2011-04-14 2011-10-19 中国药科大学 Tumor targeting deoxyglucose composite drug and preparation method thereof
CN103360330A (en) * 2013-08-07 2013-10-23 刘怀振 Synthetic method for homopiperazine
CN104098777A (en) * 2014-07-10 2014-10-15 苏州大学 Tri-block polymer and preparation method thereof
CN105803556A (en) * 2016-03-31 2016-07-27 东华大学 Cellulose diacetate grafted copolymer capable of achieving melt spinning and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102219812A (en) * 2011-04-14 2011-10-19 中国药科大学 Tumor targeting deoxyglucose composite drug and preparation method thereof
CN103360330A (en) * 2013-08-07 2013-10-23 刘怀振 Synthetic method for homopiperazine
CN104098777A (en) * 2014-07-10 2014-10-15 苏州大学 Tri-block polymer and preparation method thereof
CN105803556A (en) * 2016-03-31 2016-07-27 东华大学 Cellulose diacetate grafted copolymer capable of achieving melt spinning and preparation method thereof

Also Published As

Publication number Publication date
CN107513108A (en) 2017-12-26

Similar Documents

Publication Publication Date Title
CN107513108B (en) Preparation method and application of antibacterial cellulose ester
Yang et al. Green electrospun Manuka honey/silk fibroin fibrous matrices as potential wound dressing
Unnithan et al. Electrospun zwitterionic nanofibers with in situ decelerated epithelialization property for non-adherent and easy removable wound dressing application
Napavichayanun et al. Interaction and effectiveness of antimicrobials along with healing-promoting agents in a novel biocellulose wound dressing
Mou et al. 2, 3-Dialdehyde nanofibrillated cellulose as a potential material for the treatment of MRSA infection
Selvaraj et al. Electrospinning of casein nanofibers with silver nanoparticles for potential biomedical applications
RU2468129C2 (en) Biopolymeric fibre, composition of forming solution for its obtaining, method of forming solution preparation, linen of biomedical purpose, biological bandage and method of wound treatment
Mary et al. Centrifugal spun ultrafine fibrous web as a potential drug delivery vehicle
Nagarajan et al. Novel biocompatible electrospun gelatin fiber mats with antibiotic drug delivery properties
CN105908363B (en) A kind of electrostatic spraying laminated film and preparation method and application
Guo et al. Synthesis of polyacrylonitrile/polytetrahydropyrimidine (PAN/PTHP) nanofibers with enhanced antibacterial and anti-viral activities for personal protective equipment
Zhou et al. Quaternized chitin/tannic acid bilayers layer-by-layer deposited poly (lactic acid)/polyurethane nanofibrous mats decorated with photoresponsive complex and silver nanoparticles for antibacterial activity
Amalorpava Mary et al. Centrifugal spun ultrafine fibrous web as a potential drug delivery vehicle.
CN109350762B (en) Medical dressing applied to chronic wound surface and preparation method thereof
CN110292652A (en) Mercaptophenyl boronic acid activates gold nano grain, preparation method and application
CN108716115B (en) Antibacterial fiber, preparation method and application thereof
CN109505031A (en) Stereocomplex crystalline substance polylactic acid nano fiber, biocidal property Stereocomplex crystalline substance polylactic acid nano fiber and the preparation method and application thereof
Kumar et al. Microgravity biosynthesized penicillin loaded electrospun polyurethane–dextran nanofibrous mats for biomedical applications
Rajora et al. Evaluating neem gum-polyvinyl alcohol (NGP-PVA) blend nanofiber mat as a novel platform for wound healing in murine model
CN111744049A (en) Preparation method of wound repair material with cell growth regulation function
Cestari et al. Silk fibroin nanofibers containing chondroitin sulfate and silver sulfadiazine for wound healing treatment
CN109646706A (en) Method for preparing anti-scar overlay film using method of electrostatic spinning and products thereof and application
Li et al. Sandwich structure Aloin-PVP/Aloin-PVP-PLA/PLA as a wound dressing to accelerate wound healing
Xu et al. Synthesis of poly-tetrahydropyrimidine antibacterial polymers and research of their basic properties
CN109778350B (en) Preparation method and application of alginate fiber containing chlorhexidine antibacterial drugs

Legal Events

Date Code Title Description
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20211013

Address after: 518063 3009a, block 1-A, 101 / F, building 9, zone 2, Shenzhen Bay science and technology ecological park, 3609 Baishi Road, community, high tech Zone, Yuehai street, Nanshan District, Shenzhen, Guangdong

Patentee after: Shenzhen Pu'an Technology Co.,Ltd.

Address before: 518116 Room 102, No. 4, Huangwu 11th lane, Tongle community, Longgang street, Longgang District, Shenzhen City, Guangdong Province

Patentee before: Shenzhen Tianfeng Shangyi Culture Communication Co.,Ltd.

Effective date of registration: 20211013

Address after: 518116 Room 102, No. 4, Huangwu 11th lane, Tongle community, Longgang street, Longgang District, Shenzhen City, Guangdong Province

Patentee after: Shenzhen Tianfeng Shangyi Culture Communication Co.,Ltd.

Address before: 200050 No. 1882, Changning District, Shanghai, West Yan'an Road

Patentee before: DONGHUA University