CN111434707A - Antibacterial hydrogel - Google Patents

Antibacterial hydrogel Download PDF

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Publication number
CN111434707A
CN111434707A CN201910026437.5A CN201910026437A CN111434707A CN 111434707 A CN111434707 A CN 111434707A CN 201910026437 A CN201910026437 A CN 201910026437A CN 111434707 A CN111434707 A CN 111434707A
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CN
China
Prior art keywords
hydrogel
plasma
antibacterial
atmospheric pressure
solution
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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.)
Pending
Application number
CN201910026437.5A
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Chinese (zh)
Inventor
刘正鑫
张凯
郑永平
党杰
董飞宏
张珏
方竞
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Peking University
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Peking University
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Priority to CN201910026437.5A priority Critical patent/CN111434707A/en
Publication of CN111434707A publication Critical patent/CN111434707A/en
Pending legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/02Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075Macromolecular gels
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2305/00Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
    • C08J2305/02Dextran; Derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2305/00Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
    • C08J2305/04Alginic acid; Derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2305/00Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
    • C08J2305/12Agar-agar; Derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/02Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/24Homopolymers or copolymers of amides or imides
    • C08J2333/26Homopolymers or copolymers of acrylamide or methacrylamide
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/01Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/015Biocides

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  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Preparation (AREA)

Abstract

The invention relates to a flexible hydrogel material, in particular to a hydrogel material with antibacterial property, which comprises the following components in percentage by weight: the antibacterial hydrogel consists of high-molecular hydrogel and plasma activating liquid. The water solution is activated by low-temperature plasma and is rich in a plurality of long-acting active free radicals, and the solution is called as plasma activation liquid. The plasma activating solution has good microorganism inactivation capacity, and as a novel antibacterial agent, no report of bacterial resistance of the plasma activating solution exists at present. However, since the plasma activating liquid is liquid and has fluidity, it is difficult to continuously act an antibacterial action on a certain portion. The invention realizes the fixation of the plasma activating solution through the polymer hydrogel network by using a simple method, can continuously resist bacteria to a certain part, and is not easy to generate the drug resistance of bacteria because the antibacterial principle is physical antibacterial.

Description

Antibacterial hydrogel
Technical Field
The invention relates to a flexible hydrogel material, in particular to a hydrogel material with antibacterial property.
Background
In recent years, researchers have found that when low-temperature plasma interacts with aqueous solution, the short-acting active radicals therein are easily converted into long-acting radicals such as hydroxyl radicals, NO, in the aqueous solution. The water solution is activated by low-temperature plasma, and is a solution rich in a plurality of long-acting active free radicals, which is called as a plasma activation solution. The plasma activating solution has higher oxidation-reduction potential, which shows that the plasma activating solution has stronger oxidation capacity and does not need any chemical additive.
Interestingly, the plasma activating solution has good microorganism inactivation capacity, such as inactivation of escherichia coli, staphylococcus aureus and the like. Wherein active oxygen particles and active nitrogen particles in the plasma activating solution play a main role in the process of inactivating microorganisms. The physicochemical properties of the plasma activating solution, such as higher oxidation-reduction potential and lower pH value, play a synergistic role in the process of inactivating microorganisms. More importantly, as a novel antibacterial agent, no report on the bacterial resistance of the plasma activating solution exists at present.
However, since the plasma activating liquid is liquid and has fluidity, it is difficult to continue the action at a certain position. However, continuous antibacterial activity in a certain part is greatly required, for example, a wound area needs continuous antibacterial protection, and the plasma activating solution cannot be used in the application scene like the application scene. Therefore, how to fix the plasma activating liquid becomes a difficult problem for researchers.
Disclosure of Invention
Aiming at the defects of the prior art, the invention discloses an antibacterial hydrogel.
For the hydrogel with antibacterial performance, the invention provides the following technical scheme: the antibacterial hydrogel consists of high-molecular hydrogel and plasma activating liquid.
Preferably, the antibacterial hydrogel is characterized in that: measured by mass percent, the polymer hydrogel accounts for 0.5 to 15 percent, and the plasma activating solution accounts for 85 to 99.5 percent; the polymer hydrogel is one or more of polyacrylamide hydrogel, polyacrylic acid hydrogel, sodium alginate hydrogel, agar hydrogel and glucomannan hydrogel; the plasma activating solution is prepared by reacting atmospheric pressure low temperature plasma with water or water solution using water as solvent, and contains active oxygen radical and active nitrogen radical.
Preferably, the plasma activating liquid is characterized by being prepared by the following steps of introducing working gas into an atmospheric pressure low-temperature plasma generator at the flow rate of 100-1000L/h, starting a high-voltage power supply after the gas flow is stable, exciting the atmospheric pressure low-temperature plasma generator, enabling the atmospheric pressure low-temperature plasma to be in contact with water or an aqueous solution taking water as a solvent for 5-15 minutes to obtain the plasma activating liquid rich in active oxygen free radicals and active nitrogen free radicals, and exciting the atmospheric pressure low-temperature plasma in the water or the aqueous solution taking water as the solvent by using an alternating current power supply, wherein the working gas of the atmospheric pressure low-temperature plasma is selected from one or more of air, nitrogen, oxygen, helium, argon and neon, the working voltage is 3-12kV, and the frequency is 10-50 kHz.
Compared with the prior art, the invention has the following advantages:
1) the antibacterial principle is physical antibacterial, and the drug resistance of bacteria is not easy to generate.
2) Can be continuously applied to a certain part to continuously resist bacteria to the certain part.
Compared with the prior art, the invention has the beneficial effects that:
1) in order to realize the fixation of the plasma activating solution, the plasma activating solution is fixed by adopting a high-molecular polymer hydrogel network to obtain the plasma activating solution hydrogel.
2) In order to realize the antibacterial capability of the hydrogel, the atmospheric pressure low-temperature plasma activating solution is used as an antibacterial active substance, which is rich in various active free radicals and can effectively kill bacteria.
3) The invention does not add antibiotics, and is not easy to generate the drug resistance of bacteria.
4) The invention realizes the preparation of the hydrogel with antibacterial ability by a simple method.
Detailed Description
The present invention will be better understood from the following examples, but any changes or substitutions which can be easily made by those skilled in the art within the technical scope of the present invention will be covered by the protection scope of the claims.
Antimicrobial hydrogel example 1:
the antibacterial hydrogel comprises 10 wt% of polyacrylamide hydrogel and 90 wt% of plasma activating liquid, wherein the plasma activating liquid is prepared by the steps of introducing argon gas into an atmospheric pressure low-temperature plasma generator at the flow speed of 500L/h, starting a high-voltage power supply after airflow is stable, exciting the atmospheric pressure low-temperature plasma generator, and enabling atmospheric pressure low-temperature plasma to be in contact with deionized water for 10min to obtain the plasma activating liquid.
The antibacterial hydrogel in the example can be cut into a cuboid of 100 × 100 × 7mm or directly molded in a cuboid mold of 100 × 100 × 7mm, and can be used as an ultrasonic coupling pad for enhancing ultrasonic imaging.
Antimicrobial hydrogel example 2:
the antibacterial hydrogel comprises 12% of polyacrylic acid hydrogel and 88% of plasma activating solution by weight, wherein the plasma activating solution is prepared by the steps of introducing nitrogen into an atmospheric pressure low-temperature plasma generator at the flow speed of 300L/h, starting a high-voltage power supply after the airflow is stable, exciting the atmospheric pressure low-temperature plasma generator, and enabling the atmospheric pressure low-temperature plasma to be in contact with physiological saline for 15min to obtain the plasma activating solution rich in active nitrogen radicals.
The antibacterial hydrogel in the example can be cut into any shape or formed in a mould with any shape, and can be used as a wound dressing for antibacterial protection of wounds.
Antimicrobial hydrogel example 3:
the antibacterial hydrogel comprises 8 wt% of sodium alginate hydrogel and 92 wt% of plasma activating liquid, wherein the plasma activating liquid is prepared by introducing air into an atmospheric pressure low-temperature plasma generator at the flow speed of 800L/h, starting a high-voltage power supply after the air flow is stable, exciting the atmospheric pressure low-temperature plasma generator, and enabling the atmospheric pressure low-temperature plasma to contact with a lithium chloride aqueous solution for 8min to obtain the plasma activating liquid which is rich in active oxygen radicals and active nitrogen radicals and has good conductivity.
The conductive antibacterial hydrogel in the embodiment can be cut into any shape or formed in a mold with any shape, and can be used as a base material of a flexible electronic skin sensing device.
Antimicrobial hydrogel example 4:
the antibacterial hydrogel comprises 3 weight percent of agar hydrogel and 97 weight percent of plasma activating solution, wherein the plasma activating solution is prepared by the following steps of introducing helium gas into an atmospheric pressure low-temperature plasma generator at the flow speed of 100L/h, starting a high-voltage power supply after the airflow is stable, exciting the atmospheric pressure low-temperature plasma generator, and enabling the atmospheric pressure low-temperature plasma to contact with a cell culture medium for 5min to obtain the plasma activating solution.
The antibacterial hydrogel in the embodiment can be cut into any shape or formed in a mould with any shape, and can be used as a matrix material for growing cells or tissues with antibacterial capacity.
Antimicrobial hydrogel example 5:
the antibacterial hydrogel comprises, by weight, 0.6% of glucomannan hydrogel and 99.4% of plasma activating liquid, wherein the plasma activating liquid is prepared by introducing neon into an atmospheric pressure low-temperature plasma generator at a flow rate of 200L/h, starting a high-voltage power supply after airflow is stabilized, exciting the atmospheric pressure low-temperature plasma generator, and allowing the atmospheric pressure low-temperature plasma to contact with ultrapure water for 15min to obtain the plasma activating liquid.
The antibacterial hydrogel in the embodiment can be cut into any shape or formed in a mould with any shape, and can be used as an antibacterial, safe and nontoxic hydrogel toy.
Antimicrobial hydrogel example 6:
the antibacterial hydrogel comprises 5 wt% of sodium alginate hydrogel and 95 wt% of plasma activating solution, wherein the plasma activating solution is prepared by introducing air into an atmospheric pressure low-temperature plasma generator at a flow rate of 400L/h, starting a high-voltage power supply after the air flow is stable, exciting the atmospheric pressure low-temperature plasma generator, and enabling the atmospheric pressure low-temperature plasma to contact with a deionized water solution for 8min to obtain the plasma activating solution rich in active oxygen radicals and active nitrogen radicals.
The antibacterial hydrogel in the embodiment can be cut into any shape or formed in a mould with any shape to be used as an antibacterial mask.

Claims (3)

1. An antimicrobial hydrogel, comprising: consists of high molecular hydrogel and plasma activating liquid.
2. The antimicrobial hydrogel of claim 1, wherein: measured by mass percent, the polymer hydrogel accounts for 0.5 to 15 percent, and the plasma activating solution accounts for 85 to 99.5 percent; the polymer hydrogel is one or more of polyacrylamide hydrogel, polyacrylic acid hydrogel, sodium alginate hydrogel, agar hydrogel and glucomannan hydrogel; the plasma activating solution is prepared by reacting atmospheric pressure low temperature plasma with water or water solution using water as solvent, and contains active oxygen radical and active nitrogen radical.
3. The plasma activating solution as claimed in claim 1, wherein the plasma activating solution is prepared by introducing a working gas into an atmospheric pressure low temperature plasma generator at a flow rate of 100-1000L/h, starting a high voltage power supply after the gas flow is stabilized, exciting the atmospheric pressure low temperature plasma generator, allowing the atmospheric pressure low temperature plasma to contact water or an aqueous solution using water as a solvent for 5-15 minutes to obtain a plasma activating solution rich in active oxygen radicals and active nitrogen radicals, and exciting the atmospheric pressure low temperature plasma in water or an aqueous solution using water as a solvent by using an alternating current power supply, wherein the working gas of the atmospheric pressure low temperature plasma is selected from one or more of air, nitrogen, oxygen, helium, argon and neon, the working voltage is 3-12kV, and the frequency is 10-50 kHz.
CN201910026437.5A 2019-01-11 2019-01-11 Antibacterial hydrogel Pending CN111434707A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112022797A (en) * 2020-07-24 2020-12-04 西安交通大学 Preparation method of temperature-sensitive plasma active biogel and active biogel
CN115413749A (en) * 2022-08-09 2022-12-02 大连民族大学 Atmospheric pressure cold plasma preparation method and application of efficient bacteriostatic active oil-water emulsion

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040082716A1 (en) * 2001-03-08 2004-04-29 Marie-Pierre Faure Hydrogel attached to backing and method for making same
CN103340756A (en) * 2013-07-10 2013-10-09 北京大学 Preparation method of tooth whitening gel based on barometric low-temperature plasma
CN107320094A (en) * 2016-04-28 2017-11-07 北京大学 It is a kind of for gel of skin treatment and preparation method thereof
CN107999742A (en) * 2017-11-23 2018-05-08 华南理工大学 A kind of preparation method of nano silver wire micro-patterning
CN108703973A (en) * 2017-04-10 2018-10-26 北京大学 A kind of external-use gel preparation method for treating periodontitis

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040082716A1 (en) * 2001-03-08 2004-04-29 Marie-Pierre Faure Hydrogel attached to backing and method for making same
CN103340756A (en) * 2013-07-10 2013-10-09 北京大学 Preparation method of tooth whitening gel based on barometric low-temperature plasma
CN107320094A (en) * 2016-04-28 2017-11-07 北京大学 It is a kind of for gel of skin treatment and preparation method thereof
CN108703973A (en) * 2017-04-10 2018-10-26 北京大学 A kind of external-use gel preparation method for treating periodontitis
CN107999742A (en) * 2017-11-23 2018-05-08 华南理工大学 A kind of preparation method of nano silver wire micro-patterning

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112022797A (en) * 2020-07-24 2020-12-04 西安交通大学 Preparation method of temperature-sensitive plasma active biogel and active biogel
CN112022797B (en) * 2020-07-24 2022-05-03 西安交通大学 Preparation method of temperature-sensitive plasma active biogel and active biogel
CN115413749A (en) * 2022-08-09 2022-12-02 大连民族大学 Atmospheric pressure cold plasma preparation method and application of efficient bacteriostatic active oil-water emulsion
CN115413749B (en) * 2022-08-09 2024-01-05 大连民族大学 Preparation method and application of atmospheric pressure cold plasma of efficient antibacterial active oil-water emulsion

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Application publication date: 20200721