CN1400355A - Preparation method of macromolecular sterilization fibre with grafted antibacterial monomer on its surface - Google Patents
Preparation method of macromolecular sterilization fibre with grafted antibacterial monomer on its surface Download PDFInfo
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- CN1400355A CN1400355A CN 02130694 CN02130694A CN1400355A CN 1400355 A CN1400355 A CN 1400355A CN 02130694 CN02130694 CN 02130694 CN 02130694 A CN02130694 A CN 02130694A CN 1400355 A CN1400355 A CN 1400355A
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Abstract
The preparation method of macromolecular sterilization fibre whose surface is grafted by antibacterial monomer belongs to the field of sewage treatment technology, and includes the following steps: firstly, adding quaternary ammonium salt, halogenated amine and macromolecular fibre in the reactor, then adding reaction solvent, charging nitrogen gas into the reactor and discharging air, adding initiating agent to make reaction, after reaction using lots of solvent to stir and flush, filtering and drying, extracting the grafted collulose fibre by using aqueous solution of acetone, and soaking the grafted cellulose fibre in sodium hypochlorite, taking out fibre and drying at room temp. Said invention macromolecular sterilization fibre is a macromolecular treatment agent, not only can be used for treating water, but also can be used as medical gauze, artificial skin and shell fabric.
Description
Technical field
The present invention relates to a kind of preparation method of macromolecular sterilization fibre of grafted antibacterial monomer on its surface, belong to technical field of sewage.
Background technology
The current bactericide that uses divides from the mechanism of action can be divided into oxidizing bactericide and non-oxidizable bactericide two big classes.Oxidizing bactericide mainly contains Cl
2, NaClO, potassium permanganate, Br
2, O
3, H
2O
2Deng; Non-oxidizable bactericide has (gathering) quaternary ammonium salt, (poly-) quaternary alkylphosphonium salt, silver ion, titanium dioxide, phenols etc.Can be divided into mineral-type, small organic molecule and macromolecule bactericide etc. from the structure of bactericide.But generally there are the problem of excess residual in mineral-type and micromolecule inorganic matter bactericide, can cause the secondary pollution of water.
Compare with traditional low molecule bactericide, that the macromolecule bactericide has is non-volatile, chemically stable good, generally can not infiltrate advantages such as human or animal's skin, toxicity is little, thereby has good application prospects.Because fiber has very big specific area, be filled into easily in the various bactericidal units simultaneously and go, fiber product is one of most important kind of macromolecule sterilization material.Sterilization fibre can or adopt the method for surface graft modification to obtain by bactericide and polyblend spinning.Obviously, latter's economic and reliable more.Its major advantage has: (1) bactericide utilization ratio height.And the bactericide of the fibrous inside that co-blended spinning obtains can not contact with bacterium, and a large amount of bactericide do not have sterilization functions.(2) bactericide is connected with covalent bond with base material, stable performance.The mode of co-blended spinning then exists problems such as bactericide migration, can lose efficacy after use a period of time.(3) surface grafting can be selected different monomers and base material, structure that can be different according to Application Design.
Water is human life's source, and the water quality condition of drinking water and the relation of health are very close, is a very serious health problem owing to drinking the disease that antihygienic water causes, wherein the microorganism in the water is topmost a kind of pollution.Application in water treatment facilities is one of important use of above-mentioned sterilization fibre.
According to the characteristic of graft polymers, grafting polymer bactericide at present commonly used can be divided into two kinds of ion-type and nonionics.The former comprises quaternary ammonium salt, quaternary alkylphosphonium salt and antibacterial metal ions, and the latter mainly is the halo amine.
United States Patent (USP) U.S.5561167 selects ion-exchange fibre (containing cation exchange group and anion exchange groups such as primary amine, secondary amine, tertiary amine and quaternary ammonium salt such as carboxyl or sulfonic group) for use, pass through ion-exchange reactions, make partial cation cation exchange groups (being less than 50%) connect antibacterial metal ions (as silver ion, copper ion, zinc ion etc.), make anti-bacterial fibre.Patent is also used it and activated carbon fiber with, makes water purifier, and has inquired into fiber alignment density (general 0.13g/cm
3) with the relation of water flow velocity.
It is stable bactericide that United States Patent (USP) U.S.5902818 has discussed N-halamine monomer, homopolymers, copolymer, only emit a spot of free chlorine and other impurity, also have low price, sterilization wide spectrum, environment is had no adverse effects, insensitive to pH value, advantages such as sterilizing time weak point.Also be initator simultaneously with the ammonium ceric nitrate, N-halamine is monomer-grafted on resins such as polyacrylonitrile, polystyrene, polyvinyl acetate, polyvinyl alcohol, polyvinyl chloride and cellulose.
It is generally acknowledged that the mechanism of cationic germicide is the surface that CATION is adsorbed on bacterium.Halogenated amine is then emitted free halogen atom, and halogen atom is with the amino combination of the protein of bacteria cell wall, thereby destroys the higher structure of protein, causes the cell wall rupture of bacterium and death.But, find that in a large amount of tests antibacterial metal ions will be subjected to the influence of water temperature, PH as silver salt disinfectant, silver resin, also will be subjected to organic influence in the water; Quaternary ammonium salt, quaternary phosphine salt graft materials are bad to the anti-active fruit of bacterium; Halo amine graft materials hydrophily is very poor, and effect is difficult to give full play in water treatment.
Summary of the invention
The objective of the invention is to propose a kind of preparation method of macromolecular sterilization fibre of grafted antibacterial monomer on its surface,, expand its purposes to improve the hydrophily and the bactericidal effect of sterilization fibre.
The preparation method of the macromolecular sterilization fibre of the grafted antibacterial monomer on its surface that the present invention proposes may further comprise the steps:
(1) in reactor, adds quaternary ammonium salt, halogenated amine and macromolecular fibre.Quaternary ammonium salt can be the rare acyl-oxygen ethyl-benzyl of methyl-prop-alkyl dimethyl ammonium chloride, third rare acyl-oxygen ethyl-benzyl-alkyl dimethyl ammonium chloride, the rare acyl-oxygen ethyl-benzyl of methyl-prop-diethyl ammonium chloride, third rare acyl-oxygen ethyl-benzyl-diethyl ammonium chloride, the rare acyl-oxygen ethyl-trimethyl ammonium chloride of methyl-prop, third rare acyl-oxygen ethyl-trimethyl ammonium chloride, the rare acyl-oxygen ethyl-benzyl of dipropyl-ammonio methacrylate; Halogenated amine can be 4-acryloyl-oxy ylmethyl-4-ethyl-1, and 3-is azoles alkane-2-ketone, 4-methacryloxy methyl-4-ethyl-1 oh, and 3-is azoles alkane-2-ketone, 1-allyl-glycolylurea oh.Macromolecular fibre can be cellulose fibre, chitin fiber.Add reaction dissolvent then.Solvent can be water, rare nitric acid, dilute sulfuric acid, watery hydrochloric acid.The molar concentration of quaternary ammonium salt in solvent is 0.6～1.4mol/L, and the molar concentration of halogenated amine in solvent is 0.1～0.4mol/L, and the weight ratio of macromolecular fibre and solvent is 1: 10～25.
(2) inflated with nitrogen drains air in reactor, adds initator, and initiator concentration is 0.01～0.03mol/L, stirs and fills nitrogen, and initator can be ammonium ceric nitrate, Cericammoniumsulfate; Reaction temperature is 20 ℃～60 ℃; Reaction time is 0.5～2 hour.
(3) reaction finishes, with a large amount of stirring solvent flushings.Suction filtration, drying, the aqueous solution with acetone carried out extracting about 6～24 hours to the good cellulose fibre of grafting then, then 40 ℃～70 ℃ dryings.The percent grafting scope of method mensuration is between 40% to 150% by weight.
(4) cellulose fibre of grafting is immersed among 3%～15% liquor natrii hypochloritis 0.5～1 hour, takes out fiber, drying at room temperature.
The preparation method of the macromolecular sterilization fibre of the grafted antibacterial monomer on its surface that the present invention proposes, the high-molecular anti-bacteria fibrous material that is synthesized contains quaternary ammonium salt and halogenated amine two class functional groups.Two class monomers have different sterilization mechanisms.Quaternary ammonium salt is because the effect of positive charge, the bacterium of adsoption band negative electrical charge rapidly, but killing bacteria then can't realization in the short time; But killing bacteria in the glycolylurea class monomer short time, but because hydrophily is poor, poor with the effect of water body.By the synergy of two class monomeric units, graft copolymer can have the fast and fast advantage of sterilization of absorption simultaneously.By the proportioning of quaternary ammonium salt monomer and glycolylurea class monomer, can reach best bactericidal effect.High-molecular anti-bacteria fiber through surface grafting preparation is a kind of portable above, does not need specific operation condition, cheap polymeric treating agent.Processing target mainly concentrates on the removal to pathogenetic bacteria.This anti-bacterial fibre also can be used as hospital gauze except being used for the water treatment, artificial skin and take lining.
Infrared spectrum, nuclear magnetic resoance spectrum and elementary analysis by to all kinds of quaternary ammonium salt processes of method for preparing prove to have obtained pure monomer.Macromolecular fibre behind the surface grafting by infrared spectrum analysis, TGA analysis and the analysis etc. of weighing, is proved that monomer is by the surface of glycerol polymerization to fiber.Simultaneously, the halogenated amine monomer is activated.
Escherichia coli E.coli and staphylococcus aureus are cultivated through 18hr, with the mixed of sterilized water with 1: 4.Above-mentioned bacterium liquid 100ml and a certain amount of anti-bacterial fibre are mixed in shaking bottle, under 37 ℃, 150rpm, cultivate, regularly take out certain amount of mixed solution, survey viable count with dull and stereotyped progression dilution method.The order of magnitude of number of bacteria decline 3～8 in the bacterium liquid.
To mix the anti-bacterial fibre of certain hour in bacterium liquid directly observes under environmental scanning electron microscope.Can observe bacterium metamorphosis under the anti-bacterial fibre effect, thalline splits broken.
The specific embodiment
Embodiment 1
(1) 4-acryloyl-oxy ylmethyl-4-ethyl-1 of the rare acyl-oxygen ethyl-benzyl of adding 1g cellulose fiber peacekeeping 0.02mol methyl-prop-alkyl dimethyl ammonium chloride and 0.0025mol in reactor, 3-is azoles alkane-2-ketone oh, and the rare nitric acid 25ml that adds 0.05M is a solvent.
(2) fill nitrogen in reactor and drain air, add the 0.000376mol ammonium ceric nitrate, stir, fill nitrogen, reaction temperature is 30 ℃, 0.5 hour reaction time.
(3) after reaction finishes, wash with stirring solvent.Suction filtration, drying, the aqueous solution with acetone carried out extracting about 6 hours to the good cellulose fibre of grafting then, and is dry down at 40 ℃ then.The percent grafting 76% measured of method by weight
(4) cellulose fibre of grafting is immersed among 10% liquor natrii hypochloritis 0.5 hour, takes out fiber, drying at room temperature.
Embodiment 2
(1) add the rare acyl-oxygen ethyl-trimethyl ammonium chloride of 1g cellulose fiber peacekeeping 0.02mol methyl-prop in reactor, adding 25ml water is solvent.
(2) fill nitrogen in reactor and drain air, add the 0.000376mol ammonium ceric nitrate, stir, fill nitrogen, reaction temperature is 60 ℃, 0.5 hour reaction time.
(3) after reaction finishes, wash with stirring solvent.Suction filtration, drying, the aqueous solution with acetone carried out extracting about 6 hours to the good cellulose fibre of grafting then, and is dry down at 40 ℃ then.The percent grafting 45% measured of method by weight.
(4) 4-acryloyl-oxy ylmethyl-4-ethyl-1 of above-mentioned fiber of adding and 0.004mol in reactor, 3-is azoles alkane-2-ketone oh, and the rare nitric acid 20ml that adds 0.05M is a solvent.
(5) fill nitrogen in reactor and drain air, add the 0.000376mol ammonium ceric nitrate, stir, fill nitrogen, reaction temperature is 30 ℃, 0.5 hour reaction time.
(6) after reaction finishes, wash with stirring solvent.Suction filtration, drying, the aqueous solution with acetone carried out extracting about 6 hours to the good cellulose fibre of grafting then, and is dry down at 40 ℃ then.The percent grafting 62% measured of method by weight.
(7) cellulose fibre of grafting is immersed among 3% liquor natrii hypochloritis 0.5 hour, takes out fiber, drying at room temperature.
Embodiment 3
(1) 4-acryloyl-oxy ylmethyl-4-ethyl-1 of adding 1g cellulose fiber peacekeeping 0.004mol in reactor, 3-is azoles alkane-2-ketone oh, and the watery hydrochloric acid 10ml that adds 0.05M is a solvent.
(2) fill nitrogen in reactor and drain air, add the 0.000376mol ammonium ceric nitrate, stir, fill nitrogen, reaction temperature is 20 ℃, 0.5 hour reaction time.
(3) after reaction finishes, wash with stirring solvent.Suction filtration, drying, the aqueous solution with acetone carried out extracting about 6 hours to the good cellulose fibre of grafting then, and is dry down at 40 ℃ then.The percent grafting 18% measured of method by weight.
(4) add above-mentioned fiber and 0.02mol third rare acyl-oxygen ethyl-trimethyl ammonium chloride in reactor, the dilute sulfuric acid 25ml that adds 0.05M is a solvent.
(5) fill nitrogen in reactor and drain air, add the 0.000376mol Cericammoniumsulfate, stir, fill nitrogen, reaction temperature is 30 ℃, 0.5 hour reaction time.
(6) after reaction finishes, wash with stirring solvent.Suction filtration, drying, the aqueous solution with acetone carried out extracting about 6 hours to the good cellulose fibre of grafting then, and is dry down at 40 ℃ then.The percent grafting 78% measured of method by weight.
(7) cellulose fibre of grafting is immersed among 6% liquor natrii hypochloritis 0.5 hour, takes out fiber, drying at room temperature.
Embodiment 4
(1) 4-acryloyl-oxy ylmethyl-4-ethyl-1 of adding 1g cellulose fiber peacekeeping 0.015mol third rare acyl-oxygen ethyl-benzyl-alkyl dimethyl ammonium chloride and 0.007mol in reactor, 3-is azoles alkane-2-ketone oh, and the rare nitric acid 25ml that adds 0.05M is a solvent.
(2) fill nitrogen in reactor and drain air, add the 0.000376mol ammonium ceric nitrate, stir, fill nitrogen, reaction temperature is 50 ℃, 1 hour reaction time.
(3) after reaction finishes, wash with stirring solvent.Suction filtration, drying, the aqueous solution with acetone carried out extracting about 6 hours to the good cellulose fibre of grafting then, and is dry down at 50 ℃ then.The percent grafting 68% measured of method by weight
(4) cellulose fibre of grafting is immersed among 15% liquor natrii hypochloritis 0.5 hour, takes out fiber, drying at room temperature.
Embodiment 5
(1) 4-acryloyl-oxy ylmethyl-4-ethyl-1 of the rare acyl-oxygen ethyl-benzyl of adding 1g cellulose fiber peacekeeping 0.025mol methyl-prop-diethyl ammonium chloride and 0.004mol in reactor, 3-is azoles alkane-2-ketone oh, and the rare nitric acid 25ml that adds 0.05M is a solvent.
(2) fill nitrogen in reactor and drain air, add the 0.000752mol ammonium ceric nitrate, stir, fill nitrogen, reaction temperature is 40 ℃, 1.5 hours reaction time.
(3) after reaction finishes, wash with stirring solvent.Suction filtration, drying, the aqueous solution with acetone carried out extracting about 12 hours to the good cellulose fibre of grafting then, and is dry down at 60 ℃ then.The percent grafting 74% measured of method by weight
(4) cellulose fibre of grafting is immersed among 10% liquor natrii hypochloritis 0.5 hour, takes out fiber, drying at room temperature.
Embodiment 6
(1) 4-acryloyl-oxy ylmethyl-4-ethyl-1 of adding 1g cellulose fiber peacekeeping 0.035mol third rare acyl-oxygen ethyl-benzyl-diethyl ammonium chloride and 0.004mol in reactor, 3-is azoles alkane-2-ketone oh, and the rare nitric acid 25ml that adds 0.05M is a solvent.
(2) fill nitrogen in reactor and drain air, add the 0.000501mol ammonium ceric nitrate, stir, fill nitrogen, reaction temperature is 30 ℃, 2 hours reaction time.
(3) after reaction finishes, wash with stirring solvent.Suction filtration, drying, the aqueous solution with acetone carried out extracting about 18 hours to the good cellulose fibre of grafting then, and is dry down at 70 ℃ then.The percent grafting 83% measured of method by weight
(4) cellulose fibre of grafting is immersed among 10% liquor natrii hypochloritis 45 minutes, takes out fiber, drying at room temperature.
Embodiment 7
(1) in reactor, adds the rare acyl-oxygen ethyl-benzyl of 1g cellulose fiber peacekeeping 0.02mol methyl-prop-alkyl dimethyl ammonium chloride, 0.002mol 4-acryloyl-oxy ylmethyl-4-ethyl-1 of the rare acyl-oxygen ethyl-benzyl of dipropyl-ammonio methacrylate and 0.004mol, 3-is azoles alkane-2-ketone oh, and the rare nitric acid 25ml that adds 0.05M is a solvent.
(2) fill nitrogen in reactor and drain air, add the 0.000251mol ammonium ceric nitrate, stir, fill nitrogen, reaction temperature is 30 ℃, 0.5 hour reaction time.
(3) after reaction finishes, wash with stirring solvent.Suction filtration, drying, the aqueous solution with acetone carried out extracting about 24 hours to the good cellulose fibre of grafting then, and is dry down at 70 ℃ then.The percent grafting 95% measured of method by weight
(4) cellulose fibre of grafting is immersed among 10% liquor natrii hypochloritis 1 hour, takes out fiber, drying at room temperature.
Claims (6)
1, a kind of preparation method of macromolecular sterilization fibre of grafted antibacterial monomer on its surface is characterized in that this method may further comprise the steps:
(1) in reactor, adds quaternary ammonium salt, halogenated amine and macromolecular fibre add reaction dissolvent again, and making the molar concentration of quaternary ammonium salt in solvent is 0.6～1.4mol/L, the molar concentration of halogenated amine in solvent is 0.1～0.4mol/L, and the weight ratio of macromolecular fibre and solvent is 1: 10～25;
(2) inflated with nitrogen drains air in reactor, adds initator, and initiator concentration is 0.01～0.03mol/L, stirs and fills nitrogen, and reaction temperature is 20 ℃～60 ℃, and the reaction time is 0.5～2 hour;
(3) wash above-mentioned reactant with above-mentioned stirring solvent, suction filtration, drying, the aqueous solution with acetone carried out extracting 6～24 hours to the good cellulose fibre of grafting then, 40 ℃～70 ℃ dryings;
(4) cellulose fibre of above-mentioned grafting is immersed among 3%～15% liquor natrii hypochloritis 0.5～1 hour, takes out fiber, drying at room temperature.
2, the method for claim 1 is characterized in that wherein quaternary ammonium salt is any in the rare acyl-oxygen ethyl-benzyl of methyl-prop-alkyl dimethyl ammonium chloride, third rare acyl-oxygen ethyl-benzyl-alkyl dimethyl ammonium chloride, the rare acyl-oxygen ethyl-benzyl of methyl-prop-diethyl ammonium chloride, third rare acyl-oxygen ethyl-benzyl-diethyl ammonium chloride, the rare acyl-oxygen ethyl-trimethyl ammonium chloride of methyl-prop, third rare acyl-oxygen ethyl-trimethyl ammonium chloride or the rare acyl-oxygen ethyl-benzyl of the dipropyl-ammonio methacrylate.
3, the method for claim 1, it is characterized in that halogenated amine wherein is 4-acryloyl-oxy ylmethyl-4-ethyl-1,3-is azoles alkane-2-ketone, 4-methacryloxy methyl-4-ethyl-1 oh, and 3-is any in azoles alkane-2-ketone or the 1-allyl-glycolylurea oh.
4, the method for claim 1 is characterized in that macromolecular fibre wherein is cellulose fibre or chitin fiber.
5, the method for claim 1 is characterized in that solvent wherein is water, rare nitric acid, any in dilute sulfuric acid or the watery hydrochloric acid.
6, the method for claim 1 is characterized in that initator wherein is ammonium ceric nitrate or Cericammoniumsulfate.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100344823C (en) * | 2005-05-18 | 2007-10-24 | 东华大学 | Textile grafted by quaternary ammonium group and grafting method thereof |
| CN104892842A (en) * | 2015-05-15 | 2015-09-09 | 深圳先进技术研究院 | Antimicrobial bacterial cellulose, preparation method and application thereof |
| CN105461814A (en) * | 2015-12-14 | 2016-04-06 | 上海交通大学医学院附属仁济医院 | Cellulose acetate derivative and preparation method and application thereof |
| CN106835699A (en) * | 2017-02-07 | 2017-06-13 | 广东泰宝医疗器械技术研究院有限公司 | A kind of antibacterial hemostatic gauze and preparation method thereof |
| CN108411626A (en) * | 2018-03-06 | 2018-08-17 | 玉林师范学院 | A kind of preparation method and application of quaternary ammonium salt-N- halogen amine type antiseptic nano-fiber |
| CN109082889A (en) * | 2018-07-27 | 2018-12-25 | 望江汇通纺织有限公司 | A kind of antibacterial nonwoven cloth material |
| CN109248334A (en) * | 2018-08-31 | 2019-01-22 | 湖南博隽生物医药有限公司 | A kind of surgical sewing thread antibacterial agent and preparation method thereof |
| CN111519432A (en) * | 2020-05-12 | 2020-08-11 | 北京福田戴姆勒汽车有限公司 | Non-woven fabric material and preparation method and application thereof |
| CN111549529A (en) * | 2020-05-12 | 2020-08-18 | 北京福田戴姆勒汽车有限公司 | Non-woven fabric material and preparation method and application thereof |
| CN111591989A (en) * | 2020-05-12 | 2020-08-28 | 北京福田戴姆勒汽车有限公司 | Activated carbon material and preparation method and application thereof |
| CN113087759A (en) * | 2021-06-09 | 2021-07-09 | 南京杰肽生物科技有限公司 | Synthetic method of antibacterial polypeptide derivative |
-
2002
- 2002-09-20 CN CNB02130694XA patent/CN1164827C/en not_active Expired - Fee Related
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100344823C (en) * | 2005-05-18 | 2007-10-24 | 东华大学 | Textile grafted by quaternary ammonium group and grafting method thereof |
| CN104892842A (en) * | 2015-05-15 | 2015-09-09 | 深圳先进技术研究院 | Antimicrobial bacterial cellulose, preparation method and application thereof |
| CN105461814A (en) * | 2015-12-14 | 2016-04-06 | 上海交通大学医学院附属仁济医院 | Cellulose acetate derivative and preparation method and application thereof |
| CN105461814B (en) * | 2015-12-14 | 2018-03-27 | 上海交通大学医学院附属仁济医院 | A kind of cellulose acetate derivative and its production and use |
| CN106835699A (en) * | 2017-02-07 | 2017-06-13 | 广东泰宝医疗器械技术研究院有限公司 | A kind of antibacterial hemostatic gauze and preparation method thereof |
| CN108411626B (en) * | 2018-03-06 | 2020-08-25 | 玉林师范学院 | Preparation method and application of quaternary ammonium salt-N-halamine type nano antibacterial fiber |
| CN108411626A (en) * | 2018-03-06 | 2018-08-17 | 玉林师范学院 | A kind of preparation method and application of quaternary ammonium salt-N- halogen amine type antiseptic nano-fiber |
| CN109082889A (en) * | 2018-07-27 | 2018-12-25 | 望江汇通纺织有限公司 | A kind of antibacterial nonwoven cloth material |
| CN109248334A (en) * | 2018-08-31 | 2019-01-22 | 湖南博隽生物医药有限公司 | A kind of surgical sewing thread antibacterial agent and preparation method thereof |
| CN111519432A (en) * | 2020-05-12 | 2020-08-11 | 北京福田戴姆勒汽车有限公司 | Non-woven fabric material and preparation method and application thereof |
| CN111549529A (en) * | 2020-05-12 | 2020-08-18 | 北京福田戴姆勒汽车有限公司 | Non-woven fabric material and preparation method and application thereof |
| CN111591989A (en) * | 2020-05-12 | 2020-08-28 | 北京福田戴姆勒汽车有限公司 | Activated carbon material and preparation method and application thereof |
| CN111549529B (en) * | 2020-05-12 | 2022-08-23 | 北京福田戴姆勒汽车有限公司 | Non-woven fabric material and preparation method and application thereof |
| CN113087759A (en) * | 2021-06-09 | 2021-07-09 | 南京杰肽生物科技有限公司 | Synthetic method of antibacterial polypeptide derivative |
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