WO2024051552A1 - Surface-functionalized material and use thereof - Google Patents

Surface-functionalized material and use thereof Download PDF

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Publication number
WO2024051552A1
WO2024051552A1 PCT/CN2023/115813 CN2023115813W WO2024051552A1 WO 2024051552 A1 WO2024051552 A1 WO 2024051552A1 CN 2023115813 W CN2023115813 W CN 2023115813W WO 2024051552 A1 WO2024051552 A1 WO 2024051552A1
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polyethyleneimine
virus
dialdehyde
nylon
polypropylene
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PCT/CN2023/115813
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French (fr)
Chinese (zh)
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穆罕默德卡姆拉汉
莫洛尼马克·杰拉德
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牛津大学(苏州)科技有限公司
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Publication of WO2024051552A1 publication Critical patent/WO2024051552A1/en

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A01N25/10—Macromolecular compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36—After-treatment
    • C08J9/40—Impregnation
    • C08J9/42—Impregnation with macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides

Definitions

  • the present disclosure relates to the field of materials, specifically to a surface functionalized material and its use, and in particular to a polyethyleneimine functionalized material and related modified materials and their use.
  • Pathogenic microorganisms refer to pathogenic microorganisms that can cause illness in humans, animals and plants. They include a variety of bacteria, fungi and viruses and are easy to spread, such as through airborne transmission, contact transmission, droplet transmission, etc. It poses a huge threat to human health and even causes widespread epidemic diseases. For example, the "Spanish Flu” (H1N1), the first worldwide influenza pandemic of the 20th century, spread throughout Europe, Asia and North America with three peaks of infection from 1918 to 1919, in no more than 11 months. Approximately 50 million people died worldwide in just one month. In recent years, a variety of viruses with pandemic potential have emerged, such as SARS-CoV, MERS-CoV, and SARS-CoV-2.
  • SARS-CoV-2 continues to threaten normal human life.
  • WHO report the cumulative number of confirmed cases of SARS-CoV-2 in the world is approximately 476 million, and the cumulative number of deaths is approximately 6.109 million.
  • Humanity has caused untold damage.
  • bacteria and fungi that pose a threat to health due to their ease of spread among people, such as methicillin-resistant Staphylococcus aureus (MRSA), vancomycin-resistant enterococci (VRE) ), dermatophytes, Aspergillus, Candida, etc.
  • Interrupting the spread of pathogenic microorganisms is a key way to protect public health.
  • conventional protective methods such as medical masks
  • have limited effectiveness for example, because their large filter pore sizes are ineffective against microorganisms with smaller particle sizes, especially viruses.
  • Protective equipment that can effectively protect against viruses such as European FFP2 or FFP3 and American N95 masks
  • these masks are expensive to make and the holes are too small, causing breathing difficulties for the wearer.
  • masks contaminated by pathogenic microorganisms must undergo special treatment, otherwise they will also become a source of infection and cause a greater environmental burden.
  • Certain antiviral, antibacterial and antifungal chemicals such as calcined and hydrated dolomite, hydroxyapatite whiskers, tungsten oxide, iodide particles (palladium(II), silver(I), copper(I)) and metals Ionic derivatives such as copper(II) oxide or cobalt(II) phthalocyanine are not approved by the FDA for use in the production of PPE due to their non-environmentally friendly or harmful properties.
  • economical and environmentally friendly antimicrobial materials often have low inhibitory activity. Common antimicrobial materials have a narrow range of inhibitory effects on microorganisms.
  • a polyethyleneimine functionalized material including:
  • a support layer consisting of one or more porous or non-porous materials
  • connection layer comprising polyethyleneimine, the polyethyleneimine being directly and/or indirectly bonded to the support layer by means selected from covalent bonding, electrostatic adsorption, hydrogen bonding or any combination thereof;
  • connection layer can be combined with functional materials selected from the group consisting of covalent bonding, electrostatic adsorption, hydrophilic adsorption, hydrophobic adsorption, hydrogen bonding or any combination thereof.
  • a method for preparing the aforementioned polyethyleneimine functionalized material comprising the following steps:
  • the polyethyleneimine aqueous solution After mixing the porous material or non-porous material with the polyethyleneimine aqueous solution, shake the reaction at 60-200rpm at a temperature of 10-100°C and a pH of 5-11 for 10 minutes to 24 hours, or alternatively, the polyethyleneimine aqueous solution is
  • the polyethylene imine-enabled material can be obtained by directly coating or spraying on the surface of the porous material or non-porous material at a pH of 5-11 and drying at a temperature of 10-100°C for 10 minutes to 24 hours.
  • a method for preparing the aforementioned polyethyleneimine modified material comprising the following steps:
  • the functional material can be combined with the connection layer through covalent bonding, electrostatic adsorption, hydrophilic adsorption, hydrophobic adsorption, hydrogen bonding or any combination thereof.
  • a method for preparing the aforementioned polyethyleneimine modified material comprising the following steps:
  • the aqueous solution obtained above is reacted with porous materials or non-porous materials at a temperature of 10-100°C and a pH of 1.5-8 with shaking at 60-200 rpm for 10 minutes to 24 hours, or the aqueous solution obtained above is reacted at a pH of 1.5-8
  • the modified material can be obtained by directly coating or spraying on the surface of porous or non-porous materials and drying at a temperature of 10-100°C for 10 minutes to 24 hours;
  • the functional material can be combined with the connection layer by covalent bonding, electrostatic adsorption, hydrophilic adsorption, hydrophobic adsorption, hydrogen bonding or any combination thereof.
  • polyethyleneimine functionalized materials polyethyleneimine modified materials, preparation methods thereof, or materials obtained according to the preparation methods described in the aforementioned aspects are also provided for use in the production of medical supplies and antimicrobial products. Use in supplies.
  • Figure 1 is an X-ray photoelectron spectroscopy (XPS) detection result of a polyethyleneimine antimicrobial modified material according to one embodiment of the present invention.
  • XPS X-ray photoelectron spectroscopy
  • Polyethyleneimine Poly(ethylenimine), PEI
  • PEI poly(ethylenimine), PEI
  • polyethylenimine is a water-soluble polymer. Because polyethyleneimine has a polar group (amino group) structure, it can be combined with different substances through the following effects: (1) Physical adhesion to the surface of the substance; (2) The amino group it contains can react with the carboxyl group to form Hydrogen bonding; (3) It contains amino groups and is positively charged, electrostatically bonded to the negatively charged surface; (4) The amino groups it contains can react with carbonyl groups to form covalent bonds.
  • Polyethyleneimine can be used as a connecting agent and antibacterial agent, but its limited antibacterial properties and complicated preparation process limit its application.
  • the inventor of the present application discovered that the PEI-coated surface can be combined with functional materials through covalent bonding, electrostatic adsorption, hydrophilic adsorption, hydrophobic adsorption, hydrogen bonding, etc.
  • alginic acid dialdehyde can be used together with PEI to functionalize the material.
  • Alginate Dialdehyde is a sticky polymer that can be firmly attached to the surface of different materials through at least one of the following principles: (1) physical adhesion to the surface; (2) ) Through the two aldehyde groups in each monomer, it forms a covalent bond with the amine or amide group on the surface; (3) Through the negative charge due to the presence of hydroxyl and carboxyl groups, it electrostatically interacts with the positively charged surface Bonding; (4) Forming hydrogen bonds to bond with the surface. Therefore, ADA-coated surfaces can also connect substances through covalent bonding, electrostatic adsorption, hydrophilic adsorption, hydrophobic adsorption, hydrogen bonding, etc.
  • a polyethyleneimine functionalized material which includes a support layer composed of a porous material or a non-porous material and a connecting layer including polyethyleneimine.
  • the tie layer further includes alginic acid dialdehyde.
  • the tie layer consists of alginic dialdehyde and polyethyleneimine.
  • a polyethyleneimine modified material including the aforementioned polyethyleneimine functionalized material and a functional layer is also provided, and the functional layer may be a functional material.
  • the functional material is an antimicrobial material.
  • various preparation methods of the aforementioned polyethyleneimine functionalized materials and polyethyleneimine modified materials are also provided.
  • the present disclosure also provides the use of the above-mentioned materials and preparation methods in preparing antimicrobial articles.
  • the polyethyleneimine (PEI) in the present disclosure can be chemically synthesized by various methods or purchased commercially.
  • the polyethyleneimine of the present disclosure has a molecular weight of about 10,000-125,000 g/mol.
  • the polyethyleneimine can be obtained by any existing commercial means.
  • the alginic acid dialdehyde (ADA) in the present disclosure can be obtained from seaweeds such as brown algae or derivatives thereof by various methods.
  • the alginic acid dialdehyde of the present disclosure has a molecular weight of about 10,000-150,000 g/mol.
  • the preparation method of alginic acid dialdehyde is as follows. Dissolve an appropriate amount of alginic acid or sodium alginate (1-40% w/v) in deionized water or ultrapure (Mill Q) water (200-4000mL), and add 50-800mL ethanol (90-98% (v/ v)) and (meta)sodium periodate (NaIO 4 , 2-100g), the solution is continuously stirred or shaken and protected from light at a temperature of 15-80°C for 12-34 hours. Ethylene glycol (20-100 mL) was added and the reaction was continued with stirring or shaking at 15-80°C for 1-5 hours to reduce excess periodate.
  • ADA ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇
  • a polyethyleneimine functionalized material including a support layer and a connection layer; the support layer is composed of one or more porous materials or non-porous materials, and the connection layer Contains polyethyleneimine, and the polyethyleneimine is directly and/or indirectly bonded to the support layer by means selected from covalent bonding, electrostatic adsorption, hydrogen bonding or any combination thereof; wherein, the The connecting layer can combine the functional materials by means selected from covalent bonding, electrostatic adsorption, hydrophilic adsorption, hydrophobic adsorption, hydrogen bonding, or any combination thereof.
  • the connecting layer may be composed only of polyethyleneimine, and the polyethyleneimine is directly bonded to the support layer.
  • the connection layer may also contain alginic acid dialdehyde.
  • the connecting layer may be composed of polyethyleneimine and alginic acid dialdehyde.
  • the alginic acid dialdehyde is bonded to the support layer and/or the Polyethylenimine bonding.
  • the mass ratio of the connection layer to the support layer is about 1:100 to 1:10. In some embodiments, the mass ratio of the connection layer to the support layer is about 1:50 to 1:20.
  • the mass ratio of alginic dialdehyde to polyethyleneimine in the functionalized material is 100:1 to 10:1. In some embodiments, the mass ratio of alginic dialdehyde to polyethyleneimine in the functionalized material is 50:1 to 20:1.
  • a polyethyleneimine modified material which includes the above-mentioned polyethyleneimine functionalized material and a functional layer.
  • the functional layer is made of a material that can be selected from the group consisting of covalent bonding, electrostatic It is composed of functional materials combined with the connecting layer by adsorption, hydrophilic adsorption, hydrophobic adsorption, hydrogen bonding or any combination thereof.
  • the functional material is an antimicrobial material, thereby obtaining a polyethyleneimine modified functional material or a polyethyleneimine antimicrobial modified material.
  • the percentage of the antimicrobial material in the functional layer of the polyethyleneimine modified material to the total mass of the modified material is 0.1%-1%. In some embodiments, the antimicrobial material of the functional layer accounts for 0.3%-0.6% of the total mass of the modified material.
  • the porous material or non-porous material may be selected from one or more polymers, composite materials, or any combination thereof.
  • the porous material or non-porous material may be a polymer, a composite material, a membrane material, a sheet material, a filter material, a nonwoven fiber, or any combination thereof.
  • the pore size of the porous material or non-porous material may be any pore size. In some embodiments, the pore size of the porous material may be between 0.001-10 ⁇ m.
  • the polymer or composite material may be selected from polypropylene, cellulose, regenerated cellulose, polyvinylidene Fluoride (PVDF), polyether sulfone (PES) , polystyrene, polytetrafluoroethylene (PTFE), polyethylene, polyimide, polyamide (such as polyhexamethylene adipamide, commonly known as nylon 66) or any combination thereof.
  • PVDF polyvinylidene Fluoride
  • PES polyether sulfone
  • PTFE polystyrene
  • polyethylene polyimide
  • polyamide such as polyhexamethylene adipamide, commonly known as nylon 66
  • the functional material may be an antimicrobial material, such as an antimicrobial chemical, thereby forming an efficient and durable antimicrobial modified material.
  • Antimicrobial in this application refers to the killing or inhibiting effect on microorganisms.
  • Microorganisms generally refer to all tiny organisms that are difficult to observe with the naked eye.
  • Microorganisms include bacteria, viruses, fungi and a few algae. They are divided into space microorganisms, marine microorganisms, etc. according to the different environments in which they exist. They are divided into prokaryotic microorganisms and eukaryotic microorganisms according to the classification of cellular structures.
  • the microorganism may be selected from bacteria, fungi, viruses, or any combination thereof, but is not limited thereto.
  • the microorganism is selected from bacteria, fungi, viruses, and the like.
  • Bacteria in a broad sense are prokaryotes, which refer to a large group of cells whose nuclei are not wrapped by a nuclear membrane and only exist in a region called a nucleoid. Primitive single-celled organisms with naked DNA in the region (or nucleoid), including the two major groups of eubacteria and archaea. People usually refer to bacteria in the narrow sense. Bacteria in the narrow sense are a type of prokaryotic microorganisms. They are a type of prokaryotes with short and slender shapes and simple structures that mostly reproduce by binary fission. They are the most widely distributed and individual in nature. The most numerous organisms.
  • the bacteria may be Gram-positive bacteria and/or Gram-negative bacteria.
  • the bacterium is selected from the group consisting of Klebsiella pneumoniae, Chlamydia pneumoniae, Streptococcus pneumoniae, Mycobacterium tuberculosis, Group A chain Streptococcus Group A, Corynebacterium diphtheriae, Haemophilus influenzae, Neisseria meningitidis, Clostridium difficile, methicillin-resistant gold Staphylococcus aureus (Methicillin-Resistant Staphylococcus aureus, MRSA), Vancomycin-Resistant Enterococci (VRE)), Acinetobacter baumannii (Acinetobacter baumannii), etc.
  • Fungi are a type of eukaryote. The most common fungi are various types of mushrooms, but fungi also include molds and yeasts. Fungi that are pathogenic to humans are divided into superficial fungi and deep fungi. The former invades the skin, hair, and nails and is chronic and stubborn to treatment, but has less impact on the body. The latter can invade internal organs throughout the body and can cause death in severe cases. In addition, some fungi are parasitic in grain, feed, and food and can produce toxins and cause toxic fungal diseases.
  • the fungus is selected from the group consisting of Pneumocystis, Aspergillus (such as Aspergillus Niger), Coccidioides, Blastomyces, Candida Candida, mucormycetes, Sporothrix, dermatophytosis, etc.
  • Viruses are non-cellular forms composed of nucleic acid molecules (DNA or RNA) and protein protective shells. They are organic species that live by parasitism between living and non-living bodies. Through the mechanism of infection, the virus can use the host's cell system to replicate itself, but it cannot grow and replicate independently. Viruses can infect almost any living organism with cellular structure. Viral particles are about one percent the size of bacteria.
  • viruses There are many types of human diseases caused by viruses. Common diseases such as colds, influenza, and chickenpox have been identified, as well as serious diseases such as smallpox, AIDS, SARS, and avian influenza. There are also some diseases that may be caused by viruses. Viruses are also a factor in causing cancer.
  • the virus is selected from respiratory syncytial (sin-SISH-uhl) virus, hepatitis virus, varicella virus, polio virus, smallpox virus, measles virus, mumps virus, Chlamydia trachomatis ), influenza virus (such as Myxovirus influenzae), SARS-CoV virus, SARS-CoV-2 virus, H1N1 virus, H5N1 virus, H5N7 virus, MERS-CoV virus, Ebola virus, etc.
  • respiratory syncytial virus such as Myxovirus influenzae
  • SARS-CoV virus SARS-CoV-2 virus
  • H1N1 virus H5N1 virus
  • H5N7 virus H5N7 virus
  • MERS-CoV virus Ebola virus
  • the antimicrobial material may be selected from amino acids, quaternary ammonium compounds, chlorhexidine compounds, alexidine compounds, biguanide compounds, or any combination thereof.
  • Amino acids are organic compounds containing basic amino groups and acidic carboxyl groups.
  • the amino acid may be selected from cysteine, tyrosine, lysine, arginine, and aspartic acid, or any combination thereof.
  • Amino acids with lower pKa impart acidic characteristics to the surface, and the amino acids are also zwitterionic, thus having an antimicrobial effect, possibly by damaging the viral envelope in a similar manner.
  • Quaternary ammonium compounds are quaternary ammonium cationic compounds formed by replacing all four hydrogen ions in ammonium ions with hydrocarbon groups.
  • the quaternary ammonium compound may be selected from the group consisting of alkyl dimethyl benzyl ammonium chloride, alkyl didecyl dimethyl ammonium chloride, dialkyl dimethyl ammonium chloride, and dialkyl quaternary ammonium salt or any combination thereof.
  • the quaternary ammonium compound is selected from benzalkonium chloride, hexadecyltrimethylammonium chloride (HTMA-Cl), stearyldimethylbenzyl ammonium chloride (SMBA-Cl ), didecyldimethylammonium bromide, dioctyldimethylammonium bromide or any combination thereof.
  • Quaternary ammonium compounds are unique Its unique molecular structure gives it a series of physical and chemical properties such as emulsification, dispersion, solubilization, foaming, defoaming, sterilization, coagulation, and antisepsis.
  • Quaternary ammonium compounds can be used as antiviral, antibacterial and antifungal agents in solution form. Quaternary ammonium compounds play bactericidal and microbicidal effects by inactivating energy-producing enzymes, denaturing essential cellular proteins, and destroying cellular materials. The principle is to destroy intermolecular interactions.
  • Chlorhexidine is also known as chlorhexidine, and its chemical name is chlorhexidine. It is a cationic surfactant with a strong broad-spectrum bacteriostatic and bactericidal effect. It is a good bactericidal and disinfectant. Chlorhexidine compounds refer to the general name of a class of compounds containing the chlorhexidine structure. In some embodiments of the present disclosure, the chlorhexidine compound may be chlorhexidine digluconate and/or chlorhexidine dihydrochloride.
  • Alexidine also known as hexagonide, is a nitrogen-containing organic substance that has a strong broad-spectrum bacteriostatic and bactericidal effect. It is a good bactericidal and disinfectant, effective against Gram-positive and Gram-negative bacteria. It has antibacterial effect and is still effective even in the presence of serum, blood, etc.
  • Alexidine compounds refer to the general name of a class of compounds containing the alexidine structure. In some embodiments of the present disclosure, the alexidine compound is alexidine dihydrochloride.
  • Biguanide also known as 1-(diaminomethylene)guanidine, is a good bactericidal and disinfectant. Biguanide compounds are a general term for a class of compounds containing a biguanide structure. In some embodiments of the present disclosure, the biguanide compound is phenylbiguanide (1-(3-chlorophenyl)biguanide hydrochloride).
  • Chlorhexidine compounds, alexidine compounds or biguanide compounds act as antiviral, antibacterial and antifungal agents for bacteria. It is generally understood that the molecules of these compounds bind to the bacterial cell wall and destabilize the cell wall. They act at low At high concentrations, it will affect the integrity of the cell wall, and after the cell wall is damaged, it will enter the cell itself and attack the cytoplasmic material (internal material). Damage to the semipermeable material of the cytoplasm can lead to leakage of internal components, leading to cell death. Similarly, with fungi, the compounds compromise the integrity of the cell wall and cytoplasmic materials, entering the cytoplasm, causing leakage of cell contents and cell death. Likewise, for viruses, the compounds can kill the virus by disrupting its structure.
  • polyethyleneimine antibacterial modified materials are provided, for example, selected from the group consisting of polypropylene-polyethyleneimine-cysteine, polypropylene-polyethyleneimine-benzalkonium chloride, polyethyleneimine Propylene-polyethyleneimine-chlorhexidine, polypropylene-polyethyleneimine-phenylbiguanide, cellulose-polyethyleneimine-cysteine, cellulose-polyethyleneimine-benzalkonium chloride, fiber Element-polyethyleneimine-chlorhexidine, cellulose-polyethyleneimine-phenylbiguanide, nylon-polyethyleneimine-cysteine, nylon-polyethyleneimine-benzalkonium chloride, nylon-polyethyleneimine Ethyleneimine-chlorhexidine, nylon-polyethyleneimine-phenylbiguanide, polypropylene-alginate dialdehyde-polyethyleneimine-cysteine,
  • polyethyleneimine antifungal modified materials are provided, for example, selected from the group consisting of polypropylene-polyethyleneimine-cysteine, polypropylene-polyethyleneimine-benzalkonium chloride, polyethyleneimine Propylene-polyethyleneimine-chlorhexidine, polypropylene-polyethyleneimine-phenylbiguanide, cellulose-polyethyleneimine-cysteine, cellulose-polyethyleneimine-benzalkonium chloride, fiber Element-polyethyleneimine-chlorhexidine, cellulose-polyethyleneimine-phenylbiguanide, nylon-polyethyleneimine-cysteine, nylon-polyethyleneimine-benzalkonium chloride, nylon-polyethyleneimine Ethyleneimine-chlorhexidine, nylon-polyethyleneimine-phenylbiguanide, polypropylene-alginate dialdehyde-polyethyleneimine-cysteine
  • polyethyleneimine antiviral modified materials are provided, for example, selected from the group consisting of polypropylene-polyethyleneimine-benzalkonium chloride, polypropylene-polyethyleneimine-chlorhexidine, nylon- Polyethyleneimine-benzalkonium chloride, nylon-polyethyleneimine-chlorhexidine, polypropylene-alginic acid dialdehyde-polyethyleneimine-benzalkonium chloride, polypropylene-alginic acid dialdehyde-polyethyleneimine Amine-chlorhexidine, nylon-alginate dialdehyde-polyethylenimine-benzalkonium chloride, nylon-alginate dialdehyde-polyethylenimine-chlorhexidine or any combination thereof.
  • the antibacterial activity of the polyethyleneimine antimicrobial modified material of the present disclosure was tested, and it was found that the modified material had a 100% inhibitory effect on both Gram-positive bacteria and Gram-negative bacteria, and Good stability.
  • the polyethyleneimine antimicrobial modified material is a polypropylene-based PEI antimicrobial modified material, a cellulose-based PEI antimicrobial modified material, or a nylon-based PEI antimicrobial modified material.
  • the polyethyleneimine antimicrobial modified material is selected from the group consisting of polypropylene-polyethyleneimine-cysteine, polypropylene-polyethyleneimine-benzalkonium chloride, polypropylene-polyethyleneimine Ethyleneimine-chlorhexidine, polypropylene-polyethyleneimine-phenylbiguanide, cellulose-polyethyleneimine-cysteine, cellulose-polyethyleneimine-benzalkonium chloride, cellulose-polyethyleneimine Ethyleneimine-chlorhexidine, cellulose-polyethyleneimine-phenylbiguanide, nylon-polyethyleneimine-cysteine, nylon-polyethyleneimine-benzalkonium chloride, nylon-polyethyleneimine -Chlorhexidine, nylon-polyethylenimine-phenylbiguanide, polypropylene-alginate dialdehyde-polyethylenimine-cysteine,
  • the antifungal activity of the polyethyleneimine antimicrobial modified material of the present disclosure was tested, and it was found that the modified material had 100% inhibitory effect on fungi and had good stability.
  • the polyethyleneimine antimicrobial modified material is a polypropylene-based PEI antimicrobial modified material, a cellulose-based PEI antimicrobial modified material, or a nylon-based PEI antimicrobial modified material.
  • the polyethyleneimine antimicrobial modified material is selected from the group consisting of polypropylene-polyethyleneimine-cysteine, polypropylene-polyethyleneimine-benzalkonium chloride, polypropylene-polyethyleneimine Ethyleneimine-chlorhexidine, polypropylene-polyethyleneimine-phenylbiguanide, cellulose-polyethyleneimine-cysteine, cellulose-polyethyleneimine-benzalkonium chloride, cellulose-polyethyleneimine Ethyleneimine-chlorhexidine, cellulose-polyethyleneimine-phenylbiguanide, nylon-polyethyleneimine-cysteine, nylon-polyethyleneimine-benzalkonium chloride, nylon-polyethyleneimine -Chlorhexidine, nylon-polyethylenimine-phenylbiguanide, polypropylene-alginate dialdehyde-polyethylenimine-cysteine,
  • the polyethyleneimine antimicrobial modified materials of the present disclosure are tested for antiviral activity. After testing, it was found that the virus reduction amount could reach at least 2.5 log. In some of these examples, the measured viral reduction was in the range of 2.5 to 6 log. In some of these embodiments, the virus reduction ranges from 3.0 to 5.0 log.
  • the polyethyleneimine antimicrobial modified material is a polypropylene-based polyethyleneimine antimicrobial modified material or a nylon-based polyethyleneimine antimicrobial modified material.
  • the polyethyleneimine antimicrobial modified material is selected from polypropylene-polyethyleneimine-benzalkonium chloride, polypropylene-polyethyleneimine-chlorhexidine, nylon-polyethyleneimine Amine-benzalkonium chloride, nylon-polyethyleneimine-chlorhexidine, polypropylene-alginate dialdehyde-polyethyleneimine-benzalkonium chloride, polypropylene-alginate dialdehyde-polyethyleneimine-chlorine Hexidine, nylon-alginate dialdehyde-polyethylenimine-benzalkonium chloride, nylon-alginate dialdehyde-polyethylenimine-chlorhexidine or any combination thereof.
  • the virus is the novel coronavirus SARS-CoV-2.
  • a method for preparing the aforementioned polyethyleneimine functionalized material comprising the following steps: after mixing the porous material or non-porous material and the polyethyleneimine aqueous solution, at 10-100 The reaction is carried out with shaking at 60-200 rpm at a temperature of 5-11°C and a pH of 5-11 for 10 minutes to 24 hours.
  • the method further includes the step of: before adding the polyethyleneimine aqueous solution or after reacting the porous material or non-porous material with the polyethyleneimine aqueous solution, adding the porous material to the polyethyleneimine aqueous solution.
  • the non-porous material is mixed with the alginic acid dialdehyde aqueous solution, and then the reaction is carried out with shaking at 60-200 rpm at a temperature of 10-100°C and a pH of 1.5-8 for 10 minutes to 24 hours.
  • the alginic acid dialdehyde can be reacted with a porous material or a non-porous material first to form an alginic acid dialdehyde functionalized material, and then the polyethyleneimine can be functionalized with the alginic acid dialdehyde. chemical material to form a functionalized material containing both alginic dialdehyde and polyethyleneimine.
  • polyethyleneimine can also be reacted with porous materials or non-porous materials to form polyethyleneimine functionalized materials, and then alginic acid dialdehyde can be reacted with the polyethyleneimine functionalized materials.
  • polyethyleneimine and alginic acid dialdehyde can also be reacted with porous materials or non-porous materials at the same time to form a functionalized material containing both alginic acid dialdehyde and polyethyleneimine.
  • the mass ratio of the sum of polyethyleneimine contained in the polyethyleneimine aqueous solution and alginic acid dialdehyde contained in the alginic acid dialdehyde aqueous solution to the porous material or non-porous material is 1:100 to 1:10. In some embodiments, the mass ratio is 1:50 to 1:20.
  • the mass ratio of the polyethyleneimine contained in the polyethyleneimine aqueous solution to the alginic acid dialdehyde contained in the alginic acid dialdehyde aqueous solution is 100:1 to 10:1.
  • the pH of the polyethyleneimine aqueous solution is 5-11.
  • the temperature is 10-100°C.
  • the shaking speed is 60-200 rpm.
  • the reaction time is 10-24 hours.
  • the pH of the alginic acid dialdehyde aqueous solution is 1.5-8. In some of these embodiments, the temperature is 10-100°C. In some embodiments, the shaking speed is 120-200 rpm. In some embodiments, the reaction time is 10-24 hours.
  • the polyethyleneimine aqueous solution has a concentration of 10-1000 mg/ml and is adjusted to an appropriate pH with acid (such as sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, nitric acid); in some of the embodiments, the The concentration is 50-500 mg/ml; in some embodiments, the concentration is 20-100 mg/ml.
  • acid such as sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, nitric acid
  • the concentration is 50-500 mg/ml; in some embodiments, the concentration is 20-100 mg/ml.
  • the concentration of the alginic acid dialdehyde aqueous solution is 10-1000 mg/ml and is adjusted to an appropriate pH with acid (such as sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, nitric acid); in some embodiments, the The concentration is 50-500 mg/ml; in some embodiments, the concentration is 20-100 mg/ml.
  • acid such as sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, nitric acid
  • the concentration is 50-500 mg/ml; in some embodiments, the concentration is 20-100 mg/ml.
  • the method includes the steps of: adding an aqueous polyethyleneimine solution in The polyethylene imine functionalized material is obtained by directly coating or spraying on the surface of the porous material or non-porous material at a pH of 1.5-8, and drying at a temperature of 10-100°C for 10 minutes to 24 hours.
  • the method further includes the following steps: before or after coating or spraying the polyethyleneimine aqueous solution, directly coating or spraying the alginic acid dialdehyde aqueous solution at a pH of 1.5-8. on the surface of the porous material or non-porous material and dry at a temperature of 10-100°C for 10 minutes to 24 hours.
  • the alginic acid dialdehyde can be coated or sprayed on the surface of the porous material or non-porous material first to form the alginic acid dialdehyde functionalized material, and then the polyethylene oxide can be coated or sprayed on the surface.
  • amine to form functionalized materials containing both alginate dialdehyde and polyethyleneimine.
  • polyethyleneimine can also be coated or sprayed on the surface of porous materials or non-porous materials to form polyethyleneimine functionalized materials, and then alginic acid dialdehyde can be coated or sprayed to form Functionalized materials containing both alginic dialdehyde and polyethyleneimine are formed.
  • polyethyleneimine and alginic acid dialdehyde can also be coated or sprayed on the surface of porous materials or non-porous materials at the same time to form a function that contains both alginic acid dialdehyde and polyethyleneimine. Chemical materials.
  • the mass ratio of the sum of polyethyleneimine contained in the polyethyleneimine aqueous solution and alginic acid dialdehyde contained in the alginic acid dialdehyde aqueous solution to the porous material or non-porous material is 1:100 to 1:10. In some embodiments, the mass ratio is 1:50 to 1:20.
  • the mass ratio of the polyethyleneimine contained in the polyethyleneimine aqueous solution to the alginic acid dialdehyde contained in the alginic acid dialdehyde aqueous solution is 100:1 to 10:1.
  • the temperature is 10-100°C. In some embodiments, the drying time ranges from 10 minutes to 1 hour. In some embodiments, the pH of the polyethyleneimine aqueous solution is 5-11.
  • the temperature is 30-50°C. In some embodiments, the drying time ranges from 10 minutes to 1 hour. In some embodiments, the pH of the alginic acid dialdehyde aqueous solution is 1.5-8.
  • the PEI aqueous solution has a concentration of 10-1000 mg/ml and is adjusted to an appropriate pH with acid (such as sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, nitric acid). In some of these embodiments, the concentration is 50-500 mg/ml. In some of these embodiments, the concentration is 20-100 mg/ml.
  • acid such as sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, nitric acid.
  • the concentration is 50-500 mg/ml. In some of these embodiments, the concentration is 20-100 mg/ml.
  • the ADA aqueous solution has a concentration of 10-1000 mg/ml and is adjusted to an appropriate pH with acid (such as sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, nitric acid). In some of these embodiments, the concentration is 50-500 mg/ml. In some of these embodiments, the concentration is 20-100 mg/ml.
  • acid such as sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, nitric acid.
  • the concentration is 50-500 mg/ml. In some of these embodiments, the concentration is 20-100 mg/ml.
  • a method for preparing the aforementioned polyethyleneimine-modified material comprising the following steps: converting the aforementioned polyethyleneimine-functionalized material or the polyethyleneimine-functionalized material prepared according to the aforementioned method. chemical material, add it to the functional material aqueous solution, and shake at 60-200 rpm for 10 minutes to 24 hours at a temperature of 10-100°C and a pH of 1.5-8 to react to obtain the modified material; wherein, the functional material can It is combined with the connection layer by covalent bonding, electrostatic adsorption, hydrophilic adsorption, hydrophobic adsorption, hydrogen bonding or any combination thereof.
  • the functional material accounts for 0.1%-1% of the total mass of the modified material. In some embodiments, the mass percentage is 0.3%-0.6%.
  • the pH of the functional material aqueous solution is 1.5-8. In some of these embodiments, the temperature is 10-100°C. In some embodiments, the shaking speed is 120-200 rpm. In some embodiments, the reaction time is 8-16 hours.
  • the concentration of the functional material aqueous solution is 10-100 mg/ml and is adjusted to an appropriate pH with acid (such as sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, nitric acid). In some of these embodiments, the concentration is 5-60 mg/ml. In some embodiments, the above concentration is 2-20 mg/ml.
  • acid such as sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, nitric acid.
  • the functional material is an antimicrobial material.
  • the method includes the following steps: directly coating or spraying the functional material aqueous solution on the polyethyleneimine functionalized material, and heating it at a temperature of 10-100°C After drying for 10 minutes to 24 hours, the modified material is obtained; wherein, the functional material can be bonded with the functional material through covalent bonding, electrostatic adsorption, hydrophilic adsorption, hydrophobic adsorption, hydrogen bonding or any combination thereof.
  • the connection layer is combined, and the pH of the functional material aqueous solution is 1.5-8.
  • the functional material accounts for 0.1%-1% of the total mass of the modified material. In some embodiments, the mass percentage is 0.3%-0.6%.
  • the pH of the functional material aqueous solution is 1.5-8. In some of these embodiments, the temperature is 10-100°C. In some embodiments, the drying time is 8-16 hours.
  • the concentration of the functional material aqueous solution is 10-100 mg/ml and is adjusted to an appropriate pH with acid (such as sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, nitric acid). In some of these embodiments, the concentration is 5-60 mg/ml. In some embodiments, the concentration is 2-20 mg/ml.
  • acid such as sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, nitric acid.
  • the functional material is an antimicrobial material.
  • a method for preparing the aforementioned polyethyleneimine modified material comprising the following steps: mixing a functional material and a polyethyleneimine aqueous solution to obtain a polyethyleneimine-functional material aqueous solution ;
  • the aqueous solution obtained above is reacted with porous materials or non-porous materials at a temperature of 10-100°C and a pH of 1.5-8 with shaking at 60-200 rpm for 10 minutes to 24 hours to obtain the modified material; wherein, the The functional material can be combined with the connection layer by covalent bonding, electrostatic adsorption, hydrophilic adsorption, hydrophobic adsorption, hydrogen bonding or any combination thereof.
  • the method further includes the step of mixing the functional material with the alginic acid dialdehyde aqueous solution before, after, or simultaneously with the functional material and the polyethyleneimine aqueous solution.
  • the functional material can be mixed with the polyethyleneimine aqueous solution first, and then mixed with the alginic acid dialdehyde aqueous solution and reacted with porous materials or non-porous materials to obtain polyethyleneimine and alginic acid dialdehyde aqueous solutions. aldehyde modified materials.
  • the functional material can be mixed with the alginic acid dialdehyde aqueous solution first, and then mixed with the polyethyleneimine aqueous solution and reacted with the porous material or non-porous material to obtain a product containing both polyethyleneimine and alginic acid dialdehyde. Modified materials.
  • the functional material can be mixed with the polyethyleneimine aqueous solution and the alginic acid dialdehyde aqueous solution at the same time to form a functional material aqueous solution containing both polyethyleneimine and alginic acid dialdehyde and react with the porous material or non-porous material to obtain A modified material containing both polyethyleneimine and alginic acid dialdehyde.
  • the mass ratio of the functional material, the sum of polyethyleneimine and alginic acid dialdehyde, and the porous material or non-porous material is (1-10):(10-100):1000 .
  • the pH of the polyethyleneimine aqueous solution is 1.5-6. In some of these embodiments, the temperature is 40-60°C. In some embodiments, the shaking speed is 120-200 rpm. In some embodiments, the reaction time is 4-16 hours.
  • the pH of the alginic acid dialdehyde aqueous solution is 3-6. In some of these embodiments, the temperature is 40-70°C. In some embodiments, the shaking speed is 120-200 rpm. In some embodiments, the reaction time is 8-16 hours.
  • the polyethyleneimine aqueous solution has a concentration of 10-1000 mg/ml and is adjusted to an appropriate pH with acid (such as sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, nitric acid). In some of these embodiments, the concentration is 50-500 mg/ml. In some of these embodiments, the concentration is 20-100 mg/ml.
  • acid such as sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, nitric acid.
  • the concentration is 50-500 mg/ml. In some of these embodiments, the concentration is 20-100 mg/ml.
  • the concentration of the alginic acid dialdehyde aqueous solution is 10-1000 mg/ml and is adjusted to an appropriate pH with acid (such as sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, nitric acid). In some of these embodiments, the concentration is 50-500 mg/ml. In some of these embodiments, the concentration is 20-100 mg/ml.
  • acid such as sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, nitric acid.
  • the functional material is an antimicrobial material.
  • the method includes the following steps: mixing the functional material and the polyethyleneimine aqueous solution to obtain a polyethyleneimine-functional material aqueous solution;
  • the modified material can be obtained by directly coating or spraying on the surface of porous or non-porous materials at a pH of 1.5-8 and drying at a temperature of 10-100°C for 10 minutes to 24 hours; wherein, the functional material It can be combined with the connection layer by covalent bonding, electrostatic adsorption, hydrophilic adsorption, hydrophobic adsorption, hydrogen bonding or any combination thereof.
  • the method further includes the step of mixing the functional material with the alginic acid dialdehyde aqueous solution before, after, or simultaneously with the functional material and the polyethyleneimine aqueous solution.
  • the functional material can be mixed with the polyethyleneimine aqueous solution first, and then mixed with the alginic acid dialdehyde aqueous solution and coated or sprayed on the surface of the porous material or non-porous material to obtain a polyethyleneimine-containing polyethyleneimine aqueous solution. and modified materials of alginic acid dialdehyde.
  • the functional material can be mixed with the alginic acid dialdehyde aqueous solution first, and then mixed with the polyethyleneimine aqueous solution and coated or sprayed on the surface of the porous material or non-porous material to obtain a solution containing both polyethyleneimine and seaweed. Acid dialdehyde modified materials.
  • the functional material can be mixed with the polyethyleneimine aqueous solution and the alginic acid dialdehyde aqueous solution at the same time, and then be coated or sprayed on the surface of the porous material or non-porous material to obtain a product containing both polyethyleneimine and alginic acid dialdehyde.
  • Modified materials In some embodiments, the mass ratio of the functional material, the sum of polyethyleneimine and alginic acid dialdehyde, and the porous material or non-porous material is (1-10):(10-100):1000 .
  • the pH of the polyethyleneimine aqueous solution is 5-11. In some embodiments, the pH of the alginic acid dialdehyde aqueous solution is 1.5-8. In some of these embodiments, the temperature is 10-100°C. In some embodiments, the drying time ranges from 10 minutes to 24 hours.
  • the polyethyleneimine aqueous solution has a concentration of 10-1000 mg/ml and is adjusted to an appropriate pH with acid (such as sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, nitric acid). In some of these embodiments, the concentration is 50-500 mg/ml. In some of these embodiments, the concentration is 20-100 mg/ml.
  • acid such as sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, nitric acid.
  • the concentration is 50-500 mg/ml. In some of these embodiments, the concentration is 20-100 mg/ml.
  • the concentration of the alginic acid dialdehyde aqueous solution is 10-1000 mg/ml and is adjusted to an appropriate pH with acid (such as sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, nitric acid). In some of these embodiments, the concentration is 50-500 mg/ml. In some of these embodiments, the concentration is 20-100 mg/ml.
  • acid such as sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, nitric acid.
  • the functional material is an antimicrobial material.
  • the methods described in the third, fourth, and fifth aspects of the present disclosure also include the following steps: after washing the obtained product, store it in a moist state or perform air drying or oven drying.
  • the above products can be washed with detergent and/or water.
  • functionalized materials containing both alginic dialdehyde and polyethyleneimine can be washed with detergent and water while maintaining their activity.
  • the detergent can be selected from any neutral detergent.
  • Neutral detergent refers to a detergent with a pH in the range of 6-8 at a standard use concentration of 25°C.
  • the neutral detergent may be any one or more selected from the following: alkali (eg, sodium carbonate, borax), surfactant (eg, alkyl sulfate, sodium lauryl sulfate, alkyl ethoxylate) sulfate or fatty alcohol ether), functional materials (e.g., pH adjuster, brightening agent, water conditioner, sodium stearate or silicone), catalytic enzymes (e.g., protease, amylase, cellulase, mannase or pectinase) and chelates (e.g., sodium tripolyphosphate, EDTA, HEDTA, PDTA or DTPA).
  • alkali eg, sodium carbonate, borax
  • surfactant eg, alkyl sulfate, sodium lauryl sulfate, alkyl ethoxylate
  • functional materials e.g., pH adjuster, brightening agent, water conditioner, sodium stearate
  • the uses include the production of masks, gowns, gloves, personal protective equipment, bandages, Medical tape, medical caps, medical sheets, medical clothes, air filters, water filters, electronic products, household appliances and auto parts, etc.
  • the disclosed polyethyleneimine functionalized materials and polyethyleneimine modified materials and their preparation methods have various beneficial effects.
  • the raw materials are economical, environmentally friendly, and safe;
  • the support layer (base layer) can use a variety of common base materials with any pore size, polyethyleneimine can be easily purchased commercially or self-synthesized, and antimicrobial materials can be economical and safe.
  • the preparation method is simple, the raw materials are easy to obtain and the cost is low, there is no need to use irritating organic solvents, it is green and environmentally friendly, and it is easy to expand the production scale.
  • the present invention has great application potential in the fields of biology, medicine and health.
  • the polyethyleneimine modified material obtained by using polyethyleneimine alone as the connecting layer has excellent antibacterial, antifungal and antiviral effects.
  • alginic acid dialdehyde is also added.
  • the polyethyleneimine modified material obtained by adding alginic acid dialdehyde also has excellent antibacterial, antifungal and antiviral effects.
  • This embodiment is a preparation example of polyethyleneimine antimicrobial modified material, in which the porous material or non-porous material is polypropylene-based or nylon-based (taking the nylon 66 composite material based on polyhexamethylene adipamide as an example) , cellulose materials as examples, and antimicrobial materials as cysteine, benzalkonium chloride, chlorhexidine, and phenylbiguanide (1-(3-chlorophenyl)biguanide hydrochloride).
  • Polypropylene-based materials were purchased from Tansole China (product number: MFPP047020), cellulose materials were purchased from General Electronics (GE) Whatman (product number: GB/T1914-2007), nylon (polyhexamethylene adipamide, i.e. Nylon 66) was purchased from Merck Millipore (product number: GNWP04700).
  • Method 1 Take 10g of the above-mentioned porous materials or non-porous materials and clean them, then immerse them in a PEI aqueous solution containing 0.1-1g PEI with a pH of 5-11, and react for 30 minutes to an hour with shaking at 60°C and 120rpm to obtain only Functionalized materials for PEI. After the reaction, the obtained PEI functionalized material was washed with distilled water.
  • Method 2 After taking 10g of the porous material or non-porous material respectively and cleaning them, directly apply or spray an aqueous solution of PEI with a pH of 5-11 containing 0.1-1g PEI onto the surface of the material at 60°C, and then After drying at room temperature for 8 hours, a functionalized material containing only PEI is obtained.
  • the products prepared as above are polypropylene-PEI functional materials, cellulose-PEI functional materials and nylon-PEI functional materials.
  • Method 1 Take 10g of the above-mentioned porous materials or non-porous materials and clean them, then immerse them in an ADA aqueous solution containing 0.1-1g ADA with a pH of 3-6, and react at room temperature to 100°C and shaking at 80-120rpm for 30 minutes to 3 ADA functionalized materials can be obtained within hours. After the reaction, the obtained ADA functionalized material was washed with distilled water.
  • Method 2 Take 10g of the porous material or non-porous material respectively and clean them, then directly apply or spray an ADA aqueous solution containing 0.1-1g ADA and a pH of 3-6 onto the surface of the material at room temperature to 100°C. Then dry at 30°C for 8 hours, That is, ADA functionalized materials are obtained.
  • the products prepared above are polypropylene-ADA functionalized materials, cellulose-ADA functionalized materials and nylon-ADA functionalized materials.
  • Method 1 Take 10g of the above ADA functionalized materials, immerse them in a PEI aqueous solution containing 0.01-0.1g PEI with a pH of 5-10, and react at room temperature to 70°C and shaking at 80-120rpm for 30 minutes to 3 hours to obtain ADA- PEI functionalized materials. After the reaction, the obtained ADA-PEI functionalized material was washed sequentially with neutral detergent and distilled water.
  • Method 2 Take 10g of the above-mentioned ADA functionalized materials, and directly apply or spray a PEI aqueous solution containing 0.01-0.1g PEI and a pH of 5-10 onto the surface of the material at room temperature to 70°C. After the reaction, the obtained ADA-PEI functionalized material was washed sequentially with detergent and distilled water. Then dry at room temperature for 8 hours to obtain ADA-PEI functionalized material.
  • the products prepared as above are polypropylene-ADA-PEI functionalized materials, cellulose-ADA-PEI functionalized materials, and nylon-ADA-PEI functionalized materials.
  • Method 1 Take 10g of PEI functionalized material and react with 10-1000mg of the aforementioned antimicrobial material aqueous solution at pH 5-8 for 30 minutes to 3 hours at room temperature and shaking at 120rpm to obtain the PEI microbial modified material;
  • Method 2 directly apply or spray 10-1000mg of the aforementioned antimicrobial material aqueous solution with pH 5-8 onto the surface of 10g PEI functionalized material, and then dry it at room temperature for 8 hours to obtain the PEI microbial modified material;
  • Method 3 Mix 10-100mg antimicrobial material and 0.01-0.1g PEI, mix it with Milli Q ultrapure water, adjust the pH to 3-7, and obtain a PEI antimicrobial material aqueous solution; take 10g porous material or non-porous material and mix it with The obtained PEI antimicrobial material aqueous solution is reacted at room temperature and shaking at 80-120 rpm for 0.5-3 hours to obtain an antimicrobial modified material containing only PEI.
  • the preparation method of ADA-PEI antimicrobial modified materials is similar to the above. Just before mixing the antimicrobial materials and PEI, mix the antimicrobial materials with ADA, then add PEI to mix, and then perform the shaking step;
  • Method 4 Mix 10-100mg of antimicrobial material with 0.01-0.1g of PEI, mix it with Milli Q ultrapure water, and adjust the pH to 3-7 to obtain a PEI antimicrobial material aqueous solution; directly apply the aqueous solution obtained above or Spray onto the surface of 10g of porous or non-porous materials and dry at room temperature for 8 hours to obtain a PEI antimicrobial modified material containing only PEI.
  • the preparation method of ADA-PEI antimicrobial modified materials is similar to the above. You only need to mix the antimicrobial materials with ADA before mixing the antimicrobial materials and PEI, then add the PEI to mix, and then perform the coating or spraying step. Can.
  • polypropylene-PEI-cysteine modified materials polypropylene-PEI-benzalkonium chloride modified materials, polypropylene-PEI-chlorhexidine modified materials, polypropylene-PEI-benzene Biguanide modified material; cellulose-PEI-cysteine modified material, cellulose-PEI-benzalkonium chloride modified material, cellulose-PEI-chlorhexidine modified material, cellulose-PEI-phenyl Biguanide modified materials; nylon-PEI-cysteine modified materials, nylon-PEI-benzalkonium chloride modified materials, nylon-PEI-chlorhexidine modified materials, nylon-PEI-phenyl biguanide modified materials , polypropylene-ADA-PEI-cysteine, polypropylene-ADA-PEI-benzalkonium chloride, polypropylene-ADA-PEI-benzalkonium chloride, polypropylene-ADA-PEI-chlorhexidine, polypropylene-ADA-PEI-phen
  • the PEI modified material product obtained as above can be washed several times and stored for other uses, such as protective clothing and other protective materials.
  • the surface atomic ratio of the PEI antimicrobial modified material prepared in Example 1 was detected by X-ray photoelectron spectroscopy (XPS).
  • XPS X-ray photoelectron spectroscopy
  • method 1.2 in Example 1 was used to prepare a functionalized material containing ADA and PEI.
  • Table 1 Surface atomic ratios of samples obtained according to XPS.
  • This example tests the antibacterial activity of the polypropylene-based, cellulose-based, and nylon-based PEI antimicrobial modified materials prepared in Example 1.
  • This example uses the method one for preparing PEI functionalized materials in Example 1 (method one for functionalized materials containing only PEI and method one for functionalized materials containing ADA and PEI) and method one for preparing PEI antimicrobial modified materials.
  • the prepared PEI antimicrobial modified material is taken as an example, but highly similar results were also obtained using PEI antimicrobial modified materials prepared by other methods in Example 1.
  • LB Lia-Bertani
  • LB Lia-Bertani
  • Bacterial inhibitory activity is calculated according to the following formula:
  • I represents the bacterial inhibitory activity
  • N 0 represents the number of colonies after culture in the control group
  • Ni represents the number of colonies after culture in the treatment group.
  • the antibacterial activity results of polypropylene-based antimicrobial modified materials against Micrococcus lysodeikticus and E.coli are shown in Table 2.
  • the antibacterial activity of the polypropylene material alone is extremely low, and the antibacterial activity of the polypropylene-ADA material is also very low.
  • the newly prepared sample and the 48-hour sample of the polypropylene-ADA material showed 30% and 31% against Gram-positive bacteria respectively. % inhibitory effect, and showed 25% inhibitory effect on Gram-negative bacteria respectively.
  • Both the newly prepared sample and the 48-hour sample of the polypropylene-ADA-PEI material showed 90% inhibitory activity against Gram-positive bacteria.
  • Table 2 Antibacterial activity test results of polypropylene-based antimicrobial modified materials.
  • the antibacterial activity results of cellulose-based antimicrobial modified materials against Micrococcus lysodeikticus and E.coli are shown in Table 3.
  • Cellulosic materials alone have very low antibacterial activity.
  • Freshly prepared samples and 48-hour samples of cellulose-ADA material showed 37% and 36% inhibition against Gram-positive bacteria, respectively, and 20% and 18% inhibition against Gram-negative bacteria, respectively. effect.
  • the newly prepared sample and the 48-hour sample of the cellulose-ADA-PEI material showed 90% inhibitory activity against Gram-positive bacteria and Gram-negative bacteria respectively.
  • cellulose-PEI-cysteine cellulose-PEI-benzalkonium chloride, cellulose-PEI-chlorhexidine, cellulose-PEI-phenylbiguanide, cellulose-ADA-PEI-cysteine , cellulose-ADA-PEI-benzalkonium chloride, cellulose-ADA-PEI-chlorhexidine and cellulose-ADA-PEI-phenylbiguanide, newly prepared samples and 48-hour samples against Gram-positive bacteria and negative bacteria have 100% inhibitory effect. It can be seen that all cellulose-PEI-antimicrobial modified materials and cellulose-ADA-PEI-antimicrobial modified materials of the present disclosure still maintain bacterial inhibition consistent with newly prepared materials after being soaked in water for 48 hours. active.
  • Table 3 Antibacterial activity test results of cellulose-based antimicrobial modified materials.
  • nylon-based antimicrobial modified materials against Micrococcus lysodeikticus and E.coli are shown in Table 4.
  • Nylon material alone has very low antibacterial activity.
  • Newly prepared samples and 48-hour samples of nylon-ADA material showed 27% and 20% inhibitory effects on Gram-positive bacteria and Gram-negative bacteria, respectively.
  • Negative bacteria showed 20% and 18% inhibition respectively.
  • the newly prepared sample and 48-hour sample of nylon-ADA-PEI material showed 90% inhibitory activity against Gram-positive bacteria and Gram-negative bacteria respectively.
  • nylon-PEI-cysteine nylon-PEI-benzalkonium chloride, nylon-PEI-chlorhexidine, nylon-PEI-phenyl biguanide, nylon-ADA-PEI-cysteine, nylon-ADA- Freshly prepared and 48-hour samples of PEI-Benzalkonium Chloride, Nylon-ADA-PEI-Chlorhexidine and Nylon-ADA-PEI-Phenylbiguanide were 100% effective against Gram-positive and Gram-negative bacteria. inhibitory effect.
  • all nylon-PEI-antimicrobial modified materials and nylon-ADA-PEI-antimicrobial modified materials of the present disclosure still maintain bacteria consistent with the newly prepared materials after being soaked in water for 48 hours. inhibitory activity.
  • Table 4 Antibacterial activity test results of nylon-based antimicrobial modified materials.
  • This example tests the antifungal activity of polypropylene-based, cellulose-based, and nylon-based PEI antimicrobial modified materials prepared as in Example 1.
  • This example uses the method one for preparing PEI functionalized materials in Example 1 (method one for functionalized materials containing only PEI and method one for functionalized materials containing ADA and PEI) and method one for preparing PEI antimicrobial modified materials.
  • the prepared PEI antimicrobial modified material is taken as an example, but highly similar results were also obtained using PEI antimicrobial modified materials prepared by other methods in Example 1.
  • polypropylene-PEI-antimicrobial material cellulose-PEI-antimicrobial material, nylon-PEI-antimicrobial material, and polypropylene-ADA-PEI-antimicrobial material are respectively used.
  • material Materials cellulose-ADA-PEI-antimicrobial material and nylon-ADA-PEI-antimicrobial material were used to conduct antifungal activity experiments, and the samples were averaged in triplicate.
  • Saccharomyces cerevisiae was cultured overnight at 30°C with yeast peptone dextrose (YPD) medium, and the fresh fungal culture was diluted into a suspension with a colony count of 10 -4 CFU/ml; 0.1g of antimicrobial modified material was mixed with 10 mL of fungal suspension was mixed and placed in a flask, and cultured on a shaker at 120 rpm and 37°C for 2 hours; another 10 mL of fungal suspension was placed in another flask alone as a control. After the reaction, inoculate 10-100 ⁇ l of the fungal suspension onto the YPD agar plate and culture it at 30°C for 18-36 hours; after 36 hours of culture, count the number of viable colonies by plate counting.
  • YPD yeast peptone dextrose
  • Fungistatic activity is calculated according to the following formula:
  • I represents the fungal inhibitory activity
  • N 0 represents the number of colonies after culture in the control group
  • Ni represents the number of colonies after culture in the treatment group.
  • the antifungal activity results of polypropylene-based antimicrobial modified materials against Saccharomyces cerevisiae are shown in Table 5.
  • the antifungal activity of the polypropylene material itself was only 15%, and the newly prepared samples and 48-hour samples of the polypropylene-ADA material showed 35% and 32% inhibitory effects on Saccharomyces cerevisiae and Saccharomyces cerevisiae, respectively.
  • the newly prepared sample and the 48-hour sample of the polypropylene-ADA-PEI material showed 90% inhibitory activity against Saccharomyces cerevisiae respectively.
  • polypropylene-PEI-cysteine polypropylene-PEI-benzalkonium chloride, polypropylene-PEI-chlorhexidine, polypropylene-PEI-phenyl biguanide, polypropylene-ADA-PEI-cysteine , polypropylene-ADA-PEI-benzalkonium chloride, polypropylene-ADA-PEI-chlorhexidine and polypropylene-ADA-PEI-phenylbiguanide, both newly prepared samples and 48-hour samples have 100% resistance to Saccharomyces cerevisiae % inhibitory effect. It can be seen that all polypropylene-PEI-antimicrobial modified materials and polypropylene-ADA-PEI-antimicrobial modified materials of the present disclosure still maintain fungal inhibition consistent with newly prepared materials after being soaked in water for 48 hours. active.
  • Table 5 Antifungal activity test results of polypropylene-based antimicrobial modified materials.
  • the antifungal activity results of cellulose-based antimicrobial modified materials against Saccharomyces cerevisiae are shown in Table 6.
  • Freshly prepared samples and 48 hour samples of freshly prepared cellulosic material alone showed 23% and 21% inhibitory effects on Saccharomyces cerevisiae, respectively.
  • Newly prepared samples and 48-hour samples of cellulose-ADA material showed 37% and 36% inhibitory effects on Saccharomyces cerevisiae, respectively.
  • the newly prepared sample and the 48-hour sample of the cellulose-ADA-PEI material showed 90% inhibitory activity against Saccharomyces cerevisiae respectively.
  • both newly prepared samples and 48-hour samples have 100% resistance to Saccharomyces cerevisiae % inhibitory effect. It can be seen that all cellulose-PEI-antimicrobial modified materials and cellulose-ADA-PEI-antimicrobial modified materials of the present disclosure still maintain fungal inhibition consistent with newly prepared materials after being soaked in water for 48 hours. active.
  • the antifungal activity results of nylon-based antimicrobial modified materials against Saccharomyces cerevisiae are shown in Table 7.
  • Freshly prepared samples and 48-hour samples of nylon material alone showed 18% and 17% inhibitory effects on Saccharomyces cerevisiae, respectively.
  • Newly prepared samples and 48-hour samples of nylon-ADA material showed 40% and 39% inhibitory effects on Saccharomyces cerevisiae, respectively.
  • the newly prepared sample and the 48-hour sample of nylon-ADA-PEI material showed 90% inhibitory activity against Saccharomyces cerevisiae respectively.
  • nylon-PEI-cysteine nylon-PEI-benzalkonium chloride, nylon-PEI-chlorhexidine, nylon-PEI-phenyl biguanide, nylon-ADA-PEI-cysteine, nylon-ADA- Newly prepared samples and 48-hour samples of PEI-benzalkonium chloride, nylon-ADA-PEI-chlorhexidine and nylon-ADA-PEI-phenylbiguanide have 100% inhibitory effect on Saccharomyces cerevisiae. It can be seen that after being soaked in water for 48 hours, all the nylon-PEI-antimicrobial modified materials and nylon-ADA-PEI-antimicrobial modified materials of the present disclosure still maintain the same fungal inhibitory activity as the newly prepared materials.
  • Table 7 Antifungal activity test results of nylon-based antimicrobial modified materials.
  • This example tests the antiviral activity of the polypropylene-based and nylon-based PEI antimicrobial modified materials prepared as in Example 1.
  • This example uses the method one for preparing PEI functionalized materials in Example 1 (method one for functionalized materials containing only PEI and method one for functionalized materials containing ADA and PEI) and method one for preparing PEI antimicrobial modified materials.
  • the prepared PEI antimicrobial modified material is taken as an example, but highly similar results were also obtained using PEI antimicrobial modified materials prepared by other methods in Example 1.
  • polypropylene-based PEI antimicrobial modified materials and nylon-based PEI antimicrobial modified materials were used to conduct antiviral activity experiments. The samples were averaged in triplicate.
  • the material in a biological safety cabinet, then cut it into a size of about 0.3cm x 0.3cm; mix 200 ⁇ l of virus (SARS-CoV-2) suspension with the material in a 2mL sterile centrifuge tube, and incubate at room temperature for 1 hour; Take another equal amount of virus sample (virus suspension) and place it in another sterile centrifuge tube as a control.
  • virus virus
  • the initial Log TCID50/mL of virus samples is both 6.0log.
  • the virus was eluted with 800 ⁇ l PBS, and 400 ⁇ l elution solution was collected from the MicroSpin S-400HR chromatography column (GE Healthcare) to remove the eluted active ingredients and reduce cytotoxicity; 50% tissue culture infective dose (TCID 50 ) Titrate the control virus eluate and the residual virus eluate of the treatment group respectively; use the Reed-Muench method to calculate the virus titer.
  • TCID 50 tissue culture infective dose
  • the antiviral activity results of polypropylene-based antimicrobial modified materials against the new coronavirus SARS-CoV-2 are shown in Table 8.
  • Polypropylene-PEI-benzalkonium chloride material and polypropylene-ADA-PEI-benzalkonium chloride material reduced the virus titer by 4log and 5log respectively compared to the control, and also reduced the virus titer compared to the polypropylene material. Compared with the polypropylene-PEI material, the virus titer was reduced by 3log and 4log respectively.
  • Polypropylene-PEI-chlorhexidine materials and polypropylene-ADA-PEI-chlorhexidine materials reduced virus titers by 2.5log and 3log respectively compared to the control, and also reduced virus titers by 2.5log and 3log respectively compared to polypropylene materials. , compared to the polypropylene-PEI material, the virus titer was reduced by 1.5log and 2log respectively.
  • polypropylene-PEI material also reduces the virus titer to a certain extent, its principle is to adsorb the virus to the surface of the material so that it will not be eluted, but it does not kill the virus; while polypropylene-PEI-benzachloride Ammonium materials, polypropylene-ADA-PEI-benzalkonium chloride materials, polypropylene-PEI-chlorhexidine materials and polypropylene-ADA-PEI-chlorhexidine materials are directly killed by benzalkonium chloride and chlorhexidine Viruses, achieving almost 100% virus blocking effect.
  • the antiviral activity results of nylon-based antimicrobial modified materials against the new coronavirus SARS-CoV-2 are shown in Table 8.
  • control virus nylon material, nylon-PEI material, nylon-PEI-benzalkonium chloride, nylon-PEI-chlorhexidine, nylon-ADA-PEI-benzalkonium chloride and nylon-ADA-PEI-chlorhexidine
  • the Log TCID50/mL are 6.0, 6.0, 5.0, 1.0, 2.5, 1.0 and 2.0 respectively.
  • nylon-PEI-benzalkonium chloride material reduced the virus titer by 5, 5 and 4 log respectively.
  • nylon material and nylon-PEI material Compared with the control, nylon material and nylon-PEI material, the nylon-PEI-chlorhexidine material reduced the virus titer by 3.5, 3.5 and 2.5 log respectively.
  • nylon material and nylon-PEI material the nylon-ADA-PEI-benzalkonium chloride material reduced the virus titer by 5, 5 and 4 log respectively.
  • nylon material and nylon-PEI material the nylon-ADA-PEI-chlorhexidine material reduced the virus titer by 4.0, 4.0 and 3.0 log respectively.
  • nylon-PEI material can reduce the virus titer, it adsorbs the virus to the surface of the material without killing the virus; while the nylon-PEI-benzalkonium chloride material, nylon-ADA-PEI-benzalkonium chloride material, and nylon -PEI-chlorhexidine materials and nylon-ADA-PEI-chlorhexidine materials achieve the effect by directly killing viruses through benzalkonium chloride and chlorhexidine.

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Abstract

Provided in the present disclosure are a surface-functionalized material and the use thereof, particularly a polyethyleneimine functionalized material, a polyethyleneimine modified material, preparation methods therefor, and the use thereof. Further provided in the present disclosure is the use of the above materials and methods in the preparation of antibacterial, antifungal and antiviral protection products. The raw materials and preparation methods of the present disclosure are simple, economical and environmentally friendly, are easy to scale up, have high inhibitory activity against bacteria, fungi and viruses, and have great application potential in the fields of biology, medicine, health, etc.

Description

表面功能化材料及其用途Surface functionalized materials and their uses 技术领域Technical field
本公开涉及材料领域，具体涉及一种表面功能化材料及其用途，特别是涉及一种聚乙烯亚胺功能化材料和相关改性材料及其用途。The present disclosure relates to the field of materials, specifically to a surface functionalized material and its use, and in particular to a polyethyleneimine functionalized material and related modified materials and their use.
背景技术Background technique
致病微生物是指能够引起人类、动物和植物生病的具有致病性的微生物，其包括多种细菌、真菌及病毒在内并易于传播，例如通过空气传播、接触传播、飞沫传播等方式，对人体健康造成巨大威胁，甚至形成大范围流行疾病。例如，“西班牙流感”(H1N1)作为20世纪的第一次世界性流感大流行，在1918到1919年，以三个传染高峰几乎同时传遍了欧洲、亚洲和北美洲，在不超过11个月的时间里造成全球约5000万人死亡。而近年来也不断出现多种具有大流行潜力的病毒，例如SARS-CoV、MERS-CoV和SARS-CoV-2等。直至今日，SARS-CoV-2仍在不断威胁着人类的正常生活，据WHO报告，截至3月25日，全球累计确诊SARS-CoV-2的病例约4.76亿，累计死亡病例约610.9万，为人类造成了不计其数的损失。除此之外，还有多种细菌和真菌也因其易于在人群中传播而对健康造成了威胁，例如耐甲氧西林的金黄色葡萄球菌(MRSA)、耐万古霉素的肠球菌(VRE)、皮癣菌、曲霉、念珠菌等。Pathogenic microorganisms refer to pathogenic microorganisms that can cause illness in humans, animals and plants. They include a variety of bacteria, fungi and viruses and are easy to spread, such as through airborne transmission, contact transmission, droplet transmission, etc. It poses a huge threat to human health and even causes widespread epidemic diseases. For example, the "Spanish Flu" (H1N1), the first worldwide influenza pandemic of the 20th century, spread throughout Europe, Asia and North America with three peaks of infection from 1918 to 1919, in no more than 11 months. Approximately 50 million people died worldwide in just one month. In recent years, a variety of viruses with pandemic potential have emerged, such as SARS-CoV, MERS-CoV, and SARS-CoV-2. To this day, SARS-CoV-2 continues to threaten normal human life. According to the WHO report, as of March 25, the cumulative number of confirmed cases of SARS-CoV-2 in the world is approximately 476 million, and the cumulative number of deaths is approximately 6.109 million. Humanity has caused untold damage. In addition, there are a variety of bacteria and fungi that pose a threat to health due to their ease of spread among people, such as methicillin-resistant Staphylococcus aureus (MRSA), vancomycin-resistant enterococci (VRE) ), dermatophytes, Aspergillus, Candida, etc.
阻断致病微生物传播是保护公众健康的关键途径。但是，常规的防护方法(例如医用口罩)作用有限，比如因为大的过滤孔径导致对粒径较小的微生物尤其是病毒无效。可有效抵挡病毒的防护用品(例如欧洲FFP2或FFP3及美国N95口罩)一般都配备有小孔径过滤器，有的还携带电荷，以起到过滤和静电排斥的作用。但是，这些口罩造价昂贵，且孔径太小引起佩戴者呼吸不畅。除此之外，被致病微生物污染的口罩必须经过特殊处理，否则也会成为传染源，并造成较大的环境负担。Interrupting the spread of pathogenic microorganisms is a key way to protect public health. However, conventional protective methods (such as medical masks) have limited effectiveness, for example, because their large filter pore sizes are ineffective against microorganisms with smaller particle sizes, especially viruses. Protective equipment that can effectively protect against viruses (such as European FFP2 or FFP3 and American N95 masks) are generally equipped with small-pore filters, and some also carry electric charges to play a role in filtration and electrostatic repulsion. However, these masks are expensive to make and the holes are too small, causing breathing difficulties for the wearer. In addition, masks contaminated by pathogenic microorganisms must undergo special treatment, otherwise they will also become a source of infection and cause a greater environmental burden.
大多数抗病毒、抗细菌和抗真菌材料的制造都需要使用复杂的程序和昂贵的化学品，难以得到大规模应用。有些常用的抗微生物剂(如银或其他纳米颗粒浸渍剂)因本身毒性不能用于医疗目的，而制备功能化材料使用的某些有机溶剂也对环境造成负担。某些抗病毒、抗菌和抗真菌化学品，例如煅烧和水合白云石、羟基磷灰石晶须、氧化钨、碘化物颗粒(钯(II)、银(I)、铜(I))和金属离子衍生物，例如氧化铜(II)或钴(II)酞菁由于其非环保特性或对人体有害特性而未被FDA批准用于生产PPE。另一方面，经济又环保的抗微生物材料的抑制活性却往往较低。常见的抗微生物材料对微生物的抑制范围较窄，例如只对特定种类的革兰氏阳性菌有效，无法对革兰氏阴性菌、真菌及病毒等广谱微生物，特别是抵抗力不断增强的微生物进行有效抑制。另一些报道的抗病毒涂层技术的抗病毒活性很低，无法有效防护SARS-CoV、H5N1、H5N7、MERS-CoV、SARS-CoV-2等具有低病毒滴度的致命病毒。此外，大多数抗菌技术仅限于细菌、病毒或真菌，且某些抗菌和抗病毒材料涂层仅与有限种类的聚合物相容，而这些聚合物本身的特性可能限制其应用。The manufacture of most antiviral, antibacterial and antifungal materials requires the use of complex procedures and expensive chemicals, making them difficult to apply on a large scale. Some commonly used antimicrobial agents (such as silver or other nanoparticle impregnants) cannot be used for medical purposes due to their inherent toxicity, and some organic solvents used to prepare functionalized materials also pose a burden to the environment. Certain antiviral, antibacterial and antifungal chemicals such as calcined and hydrated dolomite, hydroxyapatite whiskers, tungsten oxide, iodide particles (palladium(II), silver(I), copper(I)) and metals Ionic derivatives such as copper(II) oxide or cobalt(II) phthalocyanine are not approved by the FDA for use in the production of PPE due to their non-environmentally friendly or harmful properties. On the other hand, economical and environmentally friendly antimicrobial materials often have low inhibitory activity. Common antimicrobial materials have a narrow range of inhibitory effects on microorganisms. For example, they are only effective against specific types of Gram-positive bacteria and cannot be used against a broad spectrum of microorganisms such as Gram-negative bacteria, fungi, and viruses, especially microorganisms with increasing resistance. carry out effective suppression. Other reported antiviral coating technologies have very low antiviral activity and cannot effectively protect against deadly viruses with low virus titers such as SARS-CoV, H5N1, H5N7, MERS-CoV, and SARS-CoV-2. Furthermore, most antimicrobial technologies are limited to bacteria, viruses, or fungi, and some antimicrobial and antiviral material coatings are only compatible with a limited variety of polymers, whose own properties may limit their applications.
发明内容Contents of the invention
本公开的一个方面中，提供了一种聚乙烯亚胺功能化材料，包括： In one aspect of the present disclosure, a polyethyleneimine functionalized material is provided, including:
支持层，其由一种或多种多孔材料或无孔材料组成；和a support layer consisting of one or more porous or non-porous materials; and
连接层，其包含聚乙烯亚胺，所述聚乙烯亚胺通过选自共价键合、静电吸附、氢键键合或其任意组合的方式与所述支持层直接和/或间接结合；A connection layer comprising polyethyleneimine, the polyethyleneimine being directly and/or indirectly bonded to the support layer by means selected from covalent bonding, electrostatic adsorption, hydrogen bonding or any combination thereof;
其中，所述连接层能够通过选自共价键合、静电吸附、亲水吸附、疏水吸附、氢键键合或其任意组合的方式结合的功能材料。Wherein, the connection layer can be combined with functional materials selected from the group consisting of covalent bonding, electrostatic adsorption, hydrophilic adsorption, hydrophobic adsorption, hydrogen bonding or any combination thereof.
本公开的又一个方面中，提供了一种用于制备前述聚乙烯亚胺功能化材料的方法，包含以下步骤：In yet another aspect of the present disclosure, a method for preparing the aforementioned polyethyleneimine functionalized material is provided, comprising the following steps:
将多孔材料或无孔材料与聚乙烯亚胺水溶液混合后，在10-100℃温度和pH为5-11下以60-200rpm摇动反应10分钟至24小时，或者，将聚乙烯亚胺水溶液在pH为5-11下直接涂覆或喷涂在所述多孔材料或无孔材料表面上并在10-100℃温度下干燥10分钟至24小时，即得到所述聚乙烯亚胺能化材料。After mixing the porous material or non-porous material with the polyethyleneimine aqueous solution, shake the reaction at 60-200rpm at a temperature of 10-100°C and a pH of 5-11 for 10 minutes to 24 hours, or alternatively, the polyethyleneimine aqueous solution is The polyethylene imine-enabled material can be obtained by directly coating or spraying on the surface of the porous material or non-porous material at a pH of 5-11 and drying at a temperature of 10-100°C for 10 minutes to 24 hours.
本公开的又一个方面中，提供了一种用于制备前述聚乙烯亚胺改性材料的方法，包含以下步骤：In yet another aspect of the present disclosure, a method for preparing the aforementioned polyethyleneimine modified material is provided, comprising the following steps:
将前述聚乙烯亚胺功能化材料或根据前述方法制备的聚乙烯亚胺功能化材料，加入到功能材料水溶液中，在10-100℃温度和pH为1.5-8下以60-200rpm摇动反应10分钟至24小时；或者，将所述功能材料水溶液在pH为1.5-8下直接涂覆或喷涂在所述聚乙烯亚胺功能化材料上并在10-100℃温度下干燥10分钟到24小时，即得到所述改性材料；Add the aforementioned polyethyleneimine functionalized material or the polyethyleneimine functionalized material prepared according to the aforementioned method to the functional material aqueous solution, and shake at 60-200rpm for 10 seconds at a temperature of 10-100°C and a pH of 1.5-8. minutes to 24 hours; alternatively, the functional material aqueous solution is directly coated or sprayed on the polyethyleneimine functionalized material at a pH of 1.5-8 and dried at a temperature of 10-100°C for 10 minutes to 24 hours , that is, the modified material is obtained;
其中，所述功能材料能够通过共价键合、静电吸附、亲水吸附、疏水吸附、氢键键合或其任意组合的方式与所述连接层结合。Wherein, the functional material can be combined with the connection layer through covalent bonding, electrostatic adsorption, hydrophilic adsorption, hydrophobic adsorption, hydrogen bonding or any combination thereof.
本公开的又一个方面中，提供了一种用于制备前述聚乙烯亚胺改性材料的方法，包含以下步骤：In yet another aspect of the present disclosure, a method for preparing the aforementioned polyethyleneimine modified material is provided, comprising the following steps:
将功能材料与聚乙烯亚胺水溶液混合，得到聚乙烯亚胺-功能材料水溶液；Mix the functional material and the polyethyleneimine aqueous solution to obtain a polyethyleneimine-functional material aqueous solution;
将如上所得的水溶液与多孔材料或无孔材料在10-100℃温度和pH为1.5-8下以60-200rpm摇动反应10分钟至24小时，或将如上所得的水溶液在pH为1.5-8下直接涂覆或喷涂到多孔材料或无孔材料的表面并在10-100℃温度下干燥10分钟至24小时，即得所述改性材料；The aqueous solution obtained above is reacted with porous materials or non-porous materials at a temperature of 10-100°C and a pH of 1.5-8 with shaking at 60-200 rpm for 10 minutes to 24 hours, or the aqueous solution obtained above is reacted at a pH of 1.5-8 The modified material can be obtained by directly coating or spraying on the surface of porous or non-porous materials and drying at a temperature of 10-100°C for 10 minutes to 24 hours;
其中，所述功能材料能够共价键合、静电吸附、亲水吸附、疏水吸附、氢键键合或其任意组合的方式与所述连接层结合。Wherein, the functional material can be combined with the connection layer by covalent bonding, electrostatic adsorption, hydrophilic adsorption, hydrophobic adsorption, hydrogen bonding or any combination thereof.
本公开的又一个方面中，还提供前述各方面中所述的聚乙烯亚胺功能化材料、聚乙烯亚胺改性材料、其制备方法或根据其制备方法所得材料在生产医护用品及抗微生物用品中的用途。In yet another aspect of the present disclosure, the polyethyleneimine functionalized materials, polyethyleneimine modified materials, preparation methods thereof, or materials obtained according to the preparation methods described in the aforementioned aspects are also provided for use in the production of medical supplies and antimicrobial products. Use in supplies.
附图说明Description of the drawings
图1是根据本发明其中一个实施例中的聚乙烯亚胺抗微生物改性材料的X射线光电子能谱法(XPS)检测结果。Figure 1 is an X-ray photoelectron spectroscopy (XPS) detection result of a polyethyleneimine antimicrobial modified material according to one embodiment of the present invention.
具体实施方式Detailed ways
为使本公开的目的、技术方案及优点更加清楚明白，以下结合附图及具体实施方式，对本公开进行进一步的详细说明。应当理解的是，此处所描述的具体实施方式仅用以解释本公开，并不限定本公开的保护范围。In order to make the purpose, technical solutions and advantages of the present disclosure more clear, the present disclosure will be further described in detail below in conjunction with the accompanying drawings and specific implementation modes. It should be understood that the specific embodiments described here are only used to explain the present disclosure and do not limit the protection scope of the present disclosure.
除非另有定义，本文所使用的所有的技术和科学术语与属于本公开的技术领域的技术人 员通常理解的含义相同。本文中在本公开的说明书中所使用的术语只是为了描述具体的实施方式的目的，不是旨在于限制本公开。本文所使用的术语“及/或”包括一个或多个相关的所列项目的任意的和所有的组合。Unless otherwise defined, all technical and scientific terms used herein are not interchangeable with those of ordinary skill in the technical field of this disclosure. Members generally understand the same meaning. The terminology used herein in the description of the disclosure is for the purpose of describing specific embodiments only and is not intended to limit the disclosure. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
聚乙烯亚胺(Poly(ethylenimine)，PEI)又称聚氮杂环丙烷，是一种水溶性高分子聚合物。聚乙烯亚胺由于具有极性基团(氨基)结构，能够通过以下作用与不同的物质相结合：(1)物理粘附到所述物质表面；(2)其含有的氨基能与羧基反应生成氢键；(3)其含有氨基而带有正电荷，与带负电荷的表面静电结合；(4)其含有的氨基能与碳酰基反应生成共价健。聚乙烯亚胺可用作连接剂和抗菌剂，但它的抗菌性能有限且制备过程较为复杂，这限制了其应用。Polyethyleneimine (Poly(ethylenimine), PEI), also known as polyethylenimine, is a water-soluble polymer. Because polyethyleneimine has a polar group (amino group) structure, it can be combined with different substances through the following effects: (1) Physical adhesion to the surface of the substance; (2) The amino group it contains can react with the carboxyl group to form Hydrogen bonding; (3) It contains amino groups and is positively charged, electrostatically bonded to the negatively charged surface; (4) The amino groups it contains can react with carbonyl groups to form covalent bonds. Polyethyleneimine can be used as a connecting agent and antibacterial agent, but its limited antibacterial properties and complicated preparation process limit its application.
本申请的发明人发现，经PEI涂覆的表面，可以通过共价键合、静电吸附、亲水吸附、疏水吸附、氢键键合等方式来结合功能材料。The inventor of the present application discovered that the PEI-coated surface can be combined with functional materials through covalent bonding, electrostatic adsorption, hydrophilic adsorption, hydrophobic adsorption, hydrogen bonding, etc.
为了进一步提高PEI和功能层的稳定性，本申请的发明人还发现，可以使用海藻酸二醛与PEI一起对材料进行功能化。In order to further improve the stability of PEI and the functional layer, the inventor of the present application also found that alginic acid dialdehyde can be used together with PEI to functionalize the material.
海藻酸二醛(Alginate Dialdehyde，ADA)是一种粘性聚合物，可以通过至少以下几种原理中的任一种牢固连接到不同材料的表面：(1)物理粘附到所述表面；(2)通过每个单体中的两个醛基，与表面的胺或酰胺基团形成共价键；(3)通过因羟基和羧基的存在而带有的负电荷，与带正电荷的表面静电结合；(4)形成氢键与表面的结合。因此，经ADA涂覆的表面，也可以通过共价键合、静电吸附、亲水吸附、疏水吸附、氢键键合等方式来连接物质。Alginate Dialdehyde (ADA) is a sticky polymer that can be firmly attached to the surface of different materials through at least one of the following principles: (1) physical adhesion to the surface; (2) ) Through the two aldehyde groups in each monomer, it forms a covalent bond with the amine or amide group on the surface; (3) Through the negative charge due to the presence of hydroxyl and carboxyl groups, it electrostatically interacts with the positively charged surface Bonding; (4) Forming hydrogen bonds to bond with the surface. Therefore, ADA-coated surfaces can also connect substances through covalent bonding, electrostatic adsorption, hydrophilic adsorption, hydrophobic adsorption, hydrogen bonding, etc.
因此，本公开的一些实施例中，提供了一种聚乙烯亚胺功能化材料，其包括由多孔材料或无孔材料组成的支持层和包含聚乙烯亚胺的连接层。在本公开的一些实施例中，连接层还包含海藻酸二醛。在本公开的一些实施例中，连接层由海藻酸二醛和聚乙烯亚胺组成。Therefore, in some embodiments of the present disclosure, a polyethyleneimine functionalized material is provided, which includes a support layer composed of a porous material or a non-porous material and a connecting layer including polyethyleneimine. In some embodiments of the present disclosure, the tie layer further includes alginic acid dialdehyde. In some embodiments of the present disclosure, the tie layer consists of alginic dialdehyde and polyethyleneimine.
本公开的一些实施例中，还提供了包含前述聚乙烯亚胺功能化材料和功能层的聚乙烯亚胺改性材料，所述功能层可以是功能材料。在其中一些实施例中，所述功能材料为抗微生物材料。In some embodiments of the present disclosure, a polyethyleneimine modified material including the aforementioned polyethyleneimine functionalized material and a functional layer is also provided, and the functional layer may be a functional material. In some of these embodiments, the functional material is an antimicrobial material.
本公开的一些实施例中，还提供了前述聚乙烯亚胺功能化材料和聚乙烯亚胺改性材料的各种制备方法。In some embodiments of the present disclosure, various preparation methods of the aforementioned polyethyleneimine functionalized materials and polyethyleneimine modified materials are also provided.
此外，本公开还提供了上述材料和制备方法在制备抗微生物用品中的用途。本公开中的聚乙烯亚胺(PEI)可以由各种方法化学合成获得或商业购得。在其中一些实施例中，本公开中的聚乙烯亚胺的分子量约为10000-125000g/mol。In addition, the present disclosure also provides the use of the above-mentioned materials and preparation methods in preparing antimicrobial articles. The polyethyleneimine (PEI) in the present disclosure can be chemically synthesized by various methods or purchased commercially. In some embodiments, the polyethyleneimine of the present disclosure has a molecular weight of about 10,000-125,000 g/mol.
在其中一些实施例中，聚乙烯亚胺可通过任何现有商用方式获得。In some of these embodiments, the polyethyleneimine can be obtained by any existing commercial means.
本公开中的海藻酸二醛(ADA)可以由各种方法从海藻例如褐藻或其衍生物中获得。在其中一些实施例中，本公开中的海藻酸二醛的分子量约为10000-150000g/mol。The alginic acid dialdehyde (ADA) in the present disclosure can be obtained from seaweeds such as brown algae or derivatives thereof by various methods. In some embodiments, the alginic acid dialdehyde of the present disclosure has a molecular weight of about 10,000-150,000 g/mol.
在其中一些实施例中，海藻酸二醛(ADA)的制备方法如下。取适量海藻酸或海藻酸钠(1–40％w/v)溶于去离子水或超纯(Mill Q)水(200-4000mL)中，加入50-800mL乙醇(90-98％(v/v))和(偏)高碘酸钠(NaIO4，2-100g)，将该溶液持续搅拌或摇动并避光于15-80℃温度下反应12-34小时。加入乙二醇(20-100mL)，并将反应继续在15-80℃温度下搅拌或摇动1-5小时以减少过量高碘酸盐。为了沉淀ADA，添加5-20g钠盐(如氯化钠)和800-2000mL 70-98％的乙醇，将溶液搅拌1-2小时，并静置1-6小时。产生ADA沉淀后，将其过滤并用20-60％的乙醇洗涤3次。使用透析膜或透析管(MWCO 1000-3500Da)或脱盐柱和去离子水或超纯水对ADA溶液进行透析，以除去钠盐并得到ADA溶液。所得ADA可以直接 使用或在-4-25℃下储存备用，也可以用冻干机冷冻干燥，除去水分以获得ADA粉末。In some of the embodiments, the preparation method of alginic acid dialdehyde (ADA) is as follows. Dissolve an appropriate amount of alginic acid or sodium alginate (1-40% w/v) in deionized water or ultrapure (Mill Q) water (200-4000mL), and add 50-800mL ethanol (90-98% (v/ v)) and (meta)sodium periodate (NaIO 4 , 2-100g), the solution is continuously stirred or shaken and protected from light at a temperature of 15-80°C for 12-34 hours. Ethylene glycol (20-100 mL) was added and the reaction was continued with stirring or shaking at 15-80°C for 1-5 hours to reduce excess periodate. To precipitate ADA, add 5-20g sodium salt (such as sodium chloride) and 800-2000mL 70-98% ethanol, stir the solution for 1-2 hours, and let stand for 1-6 hours. After ADA precipitate occurs, it is filtered and washed 3 times with 20-60% ethanol. Dialyze the ADA solution using a dialysis membrane or dialysis tube (MWCO 1000-3500Da) or desalting column and deionized water or ultrapure water to remove sodium salt and obtain an ADA solution. The resulting ADA can be directly Use or store at -4-25°C for later use, or freeze-dry with a freeze dryer to remove moisture to obtain ADA powder.
本公开的第一个方面中，提供了一种聚乙烯亚胺功能化材料，包括支持层和连接层；所述支持层由一种或多种多孔材料或无孔材料组成，所述连接层包含聚乙烯亚胺，且所述聚乙烯亚胺通过选自共价键合、静电吸附、氢键键合或其任意组合的方式与所述支持层直接和/或间接结合；其中，所述连接层能够通过选自共价键合、静电吸附、亲水吸附、疏水吸附、氢键键合或其任意组合的方式结合功能材料。In a first aspect of the present disclosure, a polyethyleneimine functionalized material is provided, including a support layer and a connection layer; the support layer is composed of one or more porous materials or non-porous materials, and the connection layer Contains polyethyleneimine, and the polyethyleneimine is directly and/or indirectly bonded to the support layer by means selected from covalent bonding, electrostatic adsorption, hydrogen bonding or any combination thereof; wherein, the The connecting layer can combine the functional materials by means selected from covalent bonding, electrostatic adsorption, hydrophilic adsorption, hydrophobic adsorption, hydrogen bonding, or any combination thereof.
在其中一些实施例中，所述连接层可以仅由聚乙烯亚胺组成，则聚乙烯亚胺与支持层直接结合。但为了进一步提高PEI和功能层的稳定性，在另一些实施例中，所述连接层还可以包含海藻酸二醛。在又一些实施例中，所述连接层可以由聚乙烯亚胺和海藻酸二醛组成。In some embodiments, the connecting layer may be composed only of polyethyleneimine, and the polyethyleneimine is directly bonded to the support layer. However, in order to further improve the stability of the PEI and the functional layer, in other embodiments, the connection layer may also contain alginic acid dialdehyde. In yet other embodiments, the connecting layer may be composed of polyethyleneimine and alginic acid dialdehyde.
在连接层含有海藻酸二醛的实施例中，所述海藻酸二醛通过选自共价键合、静电吸附、氢键键合或其任意组合的方式与所述支持层和/或所述聚乙烯亚胺结合。In the embodiment in which the connecting layer contains alginic acid dialdehyde, the alginic acid dialdehyde is bonded to the support layer and/or the Polyethylenimine bonding.
在其中一些实施例中，所述连接层与所述支持层的质量比例约为1:100至1:10。在其中一些实施例中，所述连接层与所述支持层的质量比例约为1:50至1:20。In some embodiments, the mass ratio of the connection layer to the support layer is about 1:100 to 1:10. In some embodiments, the mass ratio of the connection layer to the support layer is about 1:50 to 1:20.
在其中一些实施例中，所述功能化材料中海藻酸二醛与聚乙烯亚胺的质量比例为100:1至10:1。在其中一些实施例中，所述功能化材料中海藻酸二醛与聚乙烯亚胺的质量比例为50:1至20:1。In some embodiments, the mass ratio of alginic dialdehyde to polyethyleneimine in the functionalized material is 100:1 to 10:1. In some embodiments, the mass ratio of alginic dialdehyde to polyethyleneimine in the functionalized material is 50:1 to 20:1.
本公开的第二个方面中，提供了一种聚乙烯亚胺改性材料，其包括上述聚乙烯亚胺功能化材料和功能层，所述功能层由能够通过选自共价键合、静电吸附、亲水吸附、疏水吸附、氢键键合或其任意组合的方式与所述连接层结合的功能材料组成。在其中一些实施例中，所述功能材料为抗微生物材料，由此得到聚乙烯亚胺改性功能材料或聚乙烯亚胺抗微生物改性材料。In a second aspect of the present disclosure, a polyethyleneimine modified material is provided, which includes the above-mentioned polyethyleneimine functionalized material and a functional layer. The functional layer is made of a material that can be selected from the group consisting of covalent bonding, electrostatic It is composed of functional materials combined with the connecting layer by adsorption, hydrophilic adsorption, hydrophobic adsorption, hydrogen bonding or any combination thereof. In some embodiments, the functional material is an antimicrobial material, thereby obtaining a polyethyleneimine modified functional material or a polyethyleneimine antimicrobial modified material.
其中一些实施例中，所述聚乙烯亚胺改性材料的功能层的抗微生物材料占所述改性材料总质量的百分比为0.1％-1％。在其中一些实施例中，所述功能层的抗微生物材料占所述改性材料总质量的百分比为0.3％-0.6％。In some embodiments, the percentage of the antimicrobial material in the functional layer of the polyethyleneimine modified material to the total mass of the modified material is 0.1%-1%. In some embodiments, the antimicrobial material of the functional layer accounts for 0.3%-0.6% of the total mass of the modified material.
本公开的其中一些实施例中，所述多孔材料或无孔材料可以选自一种或多种聚合物、复合材料或其任意组合制成。在其中一些实施例中，所述多孔材料或无孔材料可以是聚合物、复合材料、膜材、片材、滤材、非织造纤维或其任意组合。所述多孔材料或无孔材料的孔径可以是任意孔径。在其中一些实施例中，所述多孔材料的孔径可以在0.001-10μm之间。In some embodiments of the present disclosure, the porous material or non-porous material may be selected from one or more polymers, composite materials, or any combination thereof. In some embodiments, the porous material or non-porous material may be a polymer, a composite material, a membrane material, a sheet material, a filter material, a nonwoven fiber, or any combination thereof. The pore size of the porous material or non-porous material may be any pore size. In some embodiments, the pore size of the porous material may be between 0.001-10 μm.
本公开的其中一些实施例中，所述聚合物或复合材料可以选自聚丙烯、纤维素、再生纤维素、聚偏二氟乙烯(Polyvinylidene Fluoride，PVDF)、聚醚砜(Polyether Sulfone，PES)、聚苯乙烯、聚四氟乙烯(Polytetrafluoroethylene,PTFE)、聚乙烯、聚酰亚胺、聚酰胺(如聚己二酰己二胺，俗称尼龙66)或其任意组合。In some embodiments of the present disclosure, the polymer or composite material may be selected from polypropylene, cellulose, regenerated cellulose, polyvinylidene Fluoride (PVDF), polyether sulfone (PES) , polystyrene, polytetrafluoroethylene (PTFE), polyethylene, polyimide, polyamide (such as polyhexamethylene adipamide, commonly known as nylon 66) or any combination thereof.
本公开的其中一些实施例中，所述功能材料可以是抗微生物材料，例如抗微生物化学物质，从而形成高效耐用的抗微生物改性材料。In some embodiments of the present disclosure, the functional material may be an antimicrobial material, such as an antimicrobial chemical, thereby forming an efficient and durable antimicrobial modified material.
本申请中的“抗微生物”是指对微生物的杀灭或抑制作用。微生物一般是指个体难以用肉眼观察的一切微小生物之统称。微生物包括细菌、病毒、真菌和少数藻类等，根据存在的不同环境分为空间微生物、海洋微生物等，按照细胞机构分类分为原核微生物和真核微生物。本公开的其中一些实施例中，所述微生物例如可以选自细菌、真菌、病毒或其任意组合，但不限于此。在其中一些实施例中，所述微生物选自细菌、真菌、病毒等。"Antimicrobial" in this application refers to the killing or inhibiting effect on microorganisms. Microorganisms generally refer to all tiny organisms that are difficult to observe with the naked eye. Microorganisms include bacteria, viruses, fungi and a few algae. They are divided into space microorganisms, marine microorganisms, etc. according to the different environments in which they exist. They are divided into prokaryotic microorganisms and eukaryotic microorganisms according to the classification of cellular structures. In some embodiments of the present disclosure, the microorganism may be selected from bacteria, fungi, viruses, or any combination thereof, but is not limited thereto. In some embodiments, the microorganism is selected from bacteria, fungi, viruses, and the like.
广义的细菌即为原核生物，是指一大类细胞核无核膜包裹、只存在称作拟核区(nuclear  region)(或拟核)的裸露DNA的原始单细胞生物，包括真细菌(eubacteria)和古生菌(archaea)两大类群。人们通常所说的即为狭义的细菌，狭义的细菌为原核微生物的一类，是一类形状细短，结构简单，多以二分裂方式进行繁殖的原核生物，是在自然界分布最广、个体数量最多的有机体。一些细菌成为病原体，导致了破伤风、伤寒、肺炎、梅毒、霍乱和肺结核。在其中一些实施例中，所述细菌可以是革兰氏阳性菌和/或革兰氏阴性菌。在其中一些实施例中，所述细菌选自肺炎克雷伯氏菌(Klebsiella pneumoniae)、肺炎衣原体(Chlamydia pneumoniae)、肺炎链球菌(Streptococcus pneumoniae)、结核分枝杆菌(Mycobacterium tuberculosis)、A群链球菌(Streptococcus Group A)、白喉棒杆菌(Corynebacterium diphtheriae)、流感嗜血杆菌(Haemophilus influenzae)、脑膜炎奈瑟菌(Neisseria meningitidis)、难辨梭状芽孢杆菌(Clostridium difficile)、耐甲氧西林金黄色葡萄球菌(Methicillin-Resistant Staphylococcus aureus，MRSA))、耐万古霉素肠球菌(Vancomycin-Resistant Enterococci，VRE))、鲍曼不动杆菌(Acinetobacter baumannii)等。Bacteria in a broad sense are prokaryotes, which refer to a large group of cells whose nuclei are not wrapped by a nuclear membrane and only exist in a region called a nucleoid. Primitive single-celled organisms with naked DNA in the region (or nucleoid), including the two major groups of eubacteria and archaea. People usually refer to bacteria in the narrow sense. Bacteria in the narrow sense are a type of prokaryotic microorganisms. They are a type of prokaryotes with short and slender shapes and simple structures that mostly reproduce by binary fission. They are the most widely distributed and individual in nature. The most numerous organisms. Some bacteria became pathogens, causing tetanus, typhoid, pneumonia, syphilis, cholera, and tuberculosis. In some of these embodiments, the bacteria may be Gram-positive bacteria and/or Gram-negative bacteria. In some embodiments, the bacterium is selected from the group consisting of Klebsiella pneumoniae, Chlamydia pneumoniae, Streptococcus pneumoniae, Mycobacterium tuberculosis, Group A chain Streptococcus Group A, Corynebacterium diphtheriae, Haemophilus influenzae, Neisseria meningitidis, Clostridium difficile, methicillin-resistant gold Staphylococcus aureus (Methicillin-Resistant Staphylococcus aureus, MRSA), Vancomycin-Resistant Enterococci (VRE)), Acinetobacter baumannii (Acinetobacter baumannii), etc.
真菌(Fungis)是一类真核生物。最常见的真菌是各类蕈类，另外真菌也包括霉菌和酵母。对人类致病的真菌分浅部真菌和深部真菌，前者侵犯皮肤、毛发、指甲，为慢性，对治疗有顽固性，但影响身体较小，后者可侵犯全身内脏，严重的可引起死亡。此外有些真菌寄生于粮食、饲料、食品中，能产生毒素引起中毒性真菌病。在其中一些实施例中，所述真菌选自肺囊虫属(Pneumocystis)、曲霉属(Aspergillus，如尼日尔曲霉(Aspergillus Niger))、球霉菌属(Coccidioides)、芽酵母属(Blastomyces)、念珠菌属(Candida)、毛霉菌(mucormycetes)、孢子丝菌属(Sporothrix)、皮癣菌(dermatophytosis)等。Fungi are a type of eukaryote. The most common fungi are various types of mushrooms, but fungi also include molds and yeasts. Fungi that are pathogenic to humans are divided into superficial fungi and deep fungi. The former invades the skin, hair, and nails and is chronic and stubborn to treatment, but has less impact on the body. The latter can invade internal organs throughout the body and can cause death in severe cases. In addition, some fungi are parasitic in grain, feed, and food and can produce toxins and cause toxic fungal diseases. In some embodiments, the fungus is selected from the group consisting of Pneumocystis, Aspergillus (such as Aspergillus Niger), Coccidioides, Blastomyces, Candida Candida, mucormycetes, Sporothrix, dermatophytosis, etc.
病毒(Virus)是由核酸分子(DNA或RNA)与蛋白质保护性外壳构成的非细胞形态，靠寄生生活介于生命体及非生命体之间的有机物种。借由感染的机制，病毒可以利用宿主的细胞系统进行自我复制，但无法独立生长和复制。病毒可以感染几乎所有具有细胞结构的生命体。病毒颗粒大约是细菌大小的百分之一。由病毒引起的人类疾病种类繁多，已经确定的如，伤风、流感、水痘等一般性疾病，以及天花、艾滋病、SARS和禽流感等严重疾病，还有一些疾病可能是以病毒为致病因子。病毒还是引发癌症的因素之一。在其中一些实施例中，所述病毒选自呼吸道合胞(sin-SISH-uhl)病毒、肝炎病毒、水痘病毒、脊髓灰质炎病毒、天花病毒、麻疹病毒、腮腺炎病毒、沙眼衣原体(Chlamydia trachomatis)、流感病毒(如Myxovirus influenzae)、SARS-CoV病毒、SARS-CoV-2病毒、H1N1病毒、H5N1病毒、H5N7病毒、MERS-CoV病毒、埃博拉(Ebola)病毒等。Viruses are non-cellular forms composed of nucleic acid molecules (DNA or RNA) and protein protective shells. They are organic species that live by parasitism between living and non-living bodies. Through the mechanism of infection, the virus can use the host's cell system to replicate itself, but it cannot grow and replicate independently. Viruses can infect almost any living organism with cellular structure. Viral particles are about one percent the size of bacteria. There are many types of human diseases caused by viruses. Common diseases such as colds, influenza, and chickenpox have been identified, as well as serious diseases such as smallpox, AIDS, SARS, and avian influenza. There are also some diseases that may be caused by viruses. Viruses are also a factor in causing cancer. In some embodiments, the virus is selected from respiratory syncytial (sin-SISH-uhl) virus, hepatitis virus, varicella virus, polio virus, smallpox virus, measles virus, mumps virus, Chlamydia trachomatis ), influenza virus (such as Myxovirus influenzae), SARS-CoV virus, SARS-CoV-2 virus, H1N1 virus, H5N1 virus, H5N7 virus, MERS-CoV virus, Ebola virus, etc.
本公开的其中一些实施例中，所述抗微生物材料可以选自氨基酸、季铵化合物、氯己定化合物、阿来西定化合物、双胍类化合物或其任意组合。In some embodiments of the present disclosure, the antimicrobial material may be selected from amino acids, quaternary ammonium compounds, chlorhexidine compounds, alexidine compounds, biguanide compounds, or any combination thereof.
氨基酸是含有碱性氨基和酸性羧基的有机化合物。本公开的其中一些实施例中，所述氨基酸可以选自半胱氨酸、酪氨酸、赖氨酸、精氨酸和天冬氨酸或其任意组合。pKa较低的氨基酸赋予所述表面酸性特征，且氨基酸也是两性离子，从而具有抗微生物作用，也可能是通过类似方式破坏病毒包膜。Amino acids are organic compounds containing basic amino groups and acidic carboxyl groups. In some embodiments of the present disclosure, the amino acid may be selected from cysteine, tyrosine, lysine, arginine, and aspartic acid, or any combination thereof. Amino acids with lower pKa impart acidic characteristics to the surface, and the amino acids are also zwitterionic, thus having an antimicrobial effect, possibly by damaging the viral envelope in a similar manner.
季铵化合物是铵离子中的4个氢离子都被烃基取代后形成的季铵阳离子化合物。本公开的其中一些实施例中，所述季铵化合物可以选自烷基二甲基苄基氯化铵、烷基二癸基二甲基氯化铵、二烷基二甲基氯化铵和二烷基季铵盐或其任意组合。在其中一些实施例中，所述季铵化合物选自苯扎氯铵、十六烷基三甲基氯化铵(HTMA-Cl)、硬脂基二甲基苄基氯化铵(SMBA-Cl)、二癸基二甲基溴化铵、二辛基二甲基溴化铵或其任意组合。季铵化合物因其独 特的分子结构而赋予其乳化、分散、增溶、发泡、消泡、杀菌、凝聚、防腐等一些列物理化学性质，在其诸多独特性能及相应的实际应用中，优异的抗微生物性质尤其吸引了人们的注意。季铵化合物可以溶液形式用作抗病毒、抗细菌和抗真菌剂。季铵化合物通过使产生能量的酶失活、使必要细胞蛋白变性、破坏细胞材料来起到杀菌作用和杀微生物作用，其原理在于破坏分子间相互作用。Quaternary ammonium compounds are quaternary ammonium cationic compounds formed by replacing all four hydrogen ions in ammonium ions with hydrocarbon groups. In some embodiments of the present disclosure, the quaternary ammonium compound may be selected from the group consisting of alkyl dimethyl benzyl ammonium chloride, alkyl didecyl dimethyl ammonium chloride, dialkyl dimethyl ammonium chloride, and dialkyl quaternary ammonium salt or any combination thereof. In some embodiments, the quaternary ammonium compound is selected from benzalkonium chloride, hexadecyltrimethylammonium chloride (HTMA-Cl), stearyldimethylbenzyl ammonium chloride (SMBA-Cl ), didecyldimethylammonium bromide, dioctyldimethylammonium bromide or any combination thereof. Quaternary ammonium compounds are unique Its unique molecular structure gives it a series of physical and chemical properties such as emulsification, dispersion, solubilization, foaming, defoaming, sterilization, coagulation, and antisepsis. Among its many unique properties and corresponding practical applications, its excellent antimicrobial properties are especially attracted people's attention. Quaternary ammonium compounds can be used as antiviral, antibacterial and antifungal agents in solution form. Quaternary ammonium compounds play bactericidal and microbicidal effects by inactivating energy-producing enzymes, denaturing essential cellular proteins, and destroying cellular materials. The principle is to destroy intermolecular interactions.
氯己定又名洗必泰，化学名为双氯苯双胍己烷，其是阳离子表面活性剂，具有相当强的广谱抑菌、杀菌作用，是一种较好的杀菌消毒药。氯己定化合物是指含有氯己定结构的一类化合物的总称。本公开的其中一些实施例中，所述氯己定化合物可以是氯己定二葡糖酸盐和/或氯己定二盐酸盐。Chlorhexidine is also known as chlorhexidine, and its chemical name is chlorhexidine. It is a cationic surfactant with a strong broad-spectrum bacteriostatic and bactericidal effect. It is a good bactericidal and disinfectant. Chlorhexidine compounds refer to the general name of a class of compounds containing the chlorhexidine structure. In some embodiments of the present disclosure, the chlorhexidine compound may be chlorhexidine digluconate and/or chlorhexidine dihydrochloride.
阿来西定又称为己联双辛胍，其为含氮类有机物，具有相当强的广谱抑菌、杀菌作用，是一种较好的杀菌消毒药，对革兰氏阳性和阴性菌具有抗菌作用，即使在有血清、血液等存在时仍有效。阿来西定化合物是指含有阿来西定结构的一类化合物的总称。本公开的其中一些实施例中，所述阿来西定化合物是阿来西定二盐酸盐。Alexidine, also known as hexagonide, is a nitrogen-containing organic substance that has a strong broad-spectrum bacteriostatic and bactericidal effect. It is a good bactericidal and disinfectant, effective against Gram-positive and Gram-negative bacteria. It has antibacterial effect and is still effective even in the presence of serum, blood, etc. Alexidine compounds refer to the general name of a class of compounds containing the alexidine structure. In some embodiments of the present disclosure, the alexidine compound is alexidine dihydrochloride.
双胍别名为1-(二氨基亚甲基)胍，是一种较好的杀菌消毒药。双胍类化合物是含有双胍结构的一类化合物的总称。本公开的其中一些实施例中，所述双胍类化合物是苯基双胍(1-(3-氯苯基)双胍盐酸盐)。Biguanide, also known as 1-(diaminomethylene)guanidine, is a good bactericidal and disinfectant. Biguanide compounds are a general term for a class of compounds containing a biguanide structure. In some embodiments of the present disclosure, the biguanide compound is phenylbiguanide (1-(3-chlorophenyl)biguanide hydrochloride).
氯己定化合物、阿来西定化合物或双胍类化合物作为抗病毒、抗细菌和抗真菌剂，对于细菌，根据一般理解，这些化合物的分子与细菌的细胞壁结合，破坏细胞壁的稳定性它们在低浓度下就会影响细胞壁的完整性，并在细胞壁损坏后进入细胞本身，攻击细胞质材料(内材料)。损坏细胞质的半透材料会导致内部成分泄漏，从而导致细胞死亡。类似地，对于真菌，所述化合物损害细胞壁和质材料的完整性，进入细胞质，导致细胞内含物泄漏和细胞死亡。同样地，对于病毒，所述化合物可以通过破坏病毒结构来杀死病毒。Chlorhexidine compounds, alexidine compounds or biguanide compounds act as antiviral, antibacterial and antifungal agents for bacteria. It is generally understood that the molecules of these compounds bind to the bacterial cell wall and destabilize the cell wall. They act at low At high concentrations, it will affect the integrity of the cell wall, and after the cell wall is damaged, it will enter the cell itself and attack the cytoplasmic material (internal material). Damage to the semipermeable material of the cytoplasm can lead to leakage of internal components, leading to cell death. Similarly, with fungi, the compounds compromise the integrity of the cell wall and cytoplasmic materials, entering the cytoplasm, causing leakage of cell contents and cell death. Likewise, for viruses, the compounds can kill the virus by disrupting its structure.
本公开的其中一些实施例中，提供聚乙烯亚胺抗细菌改性材料，例如选自聚丙烯-聚乙烯亚胺-半胱氨酸、聚丙烯-聚乙烯亚胺-苯扎氯铵、聚丙烯-聚乙烯亚胺-氯己定、聚丙烯-聚乙烯亚胺-苯基双胍、纤维素-聚乙烯亚胺-半胱氨酸、纤维素-聚乙烯亚胺-苯扎氯铵、纤维素-聚乙烯亚胺-氯己定、纤维素-聚乙烯亚胺-苯基双胍、尼龙-聚乙烯亚胺-半胱氨酸、尼龙-聚乙烯亚胺-苯扎氯铵、尼龙-聚乙烯亚胺-氯己定、尼龙-聚乙烯亚胺-苯基双胍、聚丙烯-海藻酸二醛-聚乙烯亚胺-半胱氨酸、聚丙烯-海藻酸二醛-聚乙烯亚胺-苯扎氯铵、聚丙烯-海藻酸二醛-聚乙烯亚胺-氯己定、聚丙烯-海藻酸二醛-聚乙烯亚胺-苯基双胍、纤维素-海藻酸二醛-聚乙烯亚胺-半胱氨酸、纤维素-海藻酸二醛-聚乙烯亚胺-苯扎氯铵、纤维素-海藻酸二醛-聚乙烯亚胺-氯己定、纤维素-海藻酸二醛-聚乙烯亚胺-苯基双胍、尼龙-海藻酸二醛-聚乙烯亚胺-半胱氨酸、尼龙-海藻酸二醛-聚乙烯亚胺-苯扎氯铵、尼龙-海藻酸二醛-聚乙烯亚胺-氯己定、尼龙-海藻酸二醛-聚乙烯亚胺-苯基双胍或其任意组合。In some embodiments of the present disclosure, polyethyleneimine antibacterial modified materials are provided, for example, selected from the group consisting of polypropylene-polyethyleneimine-cysteine, polypropylene-polyethyleneimine-benzalkonium chloride, polyethyleneimine Propylene-polyethyleneimine-chlorhexidine, polypropylene-polyethyleneimine-phenylbiguanide, cellulose-polyethyleneimine-cysteine, cellulose-polyethyleneimine-benzalkonium chloride, fiber Element-polyethyleneimine-chlorhexidine, cellulose-polyethyleneimine-phenylbiguanide, nylon-polyethyleneimine-cysteine, nylon-polyethyleneimine-benzalkonium chloride, nylon-polyethyleneimine Ethyleneimine-chlorhexidine, nylon-polyethyleneimine-phenylbiguanide, polypropylene-alginate dialdehyde-polyethyleneimine-cysteine, polypropylene-alginate dialdehyde-polyethyleneimine- Benzalkonium chloride, polypropylene-alginic acid dialdehyde-polyethyleneimine-chlorhexidine, polypropylene-alginic acid dialdehyde-polyethyleneimine-phenyl biguanide, cellulose-alginic acid dialdehyde-polyethyleneimine Amine-cysteine, cellulose-alginate dialdehyde-polyethylenimine-benzalkonium chloride, cellulose-alginate dialdehyde-polyethylenimine-chlorhexidine, cellulose-alginate dialdehyde- Polyethyleneimine-phenylbiguanide, nylon-alginate dialdehyde-polyethyleneimine-cysteine, nylon-alginate dialdehyde-polyethyleneimine-benzalkonium chloride, nylon-alginate dialdehyde- Polyethylenimine-chlorhexidine, nylon-alginate dialdehyde-polyethylenimine-phenylbiguanide or any combination thereof.
本公开的其中一些实施例中，提供聚乙烯亚胺抗真菌改性材料，例如选自聚丙烯-聚乙烯亚胺-半胱氨酸、聚丙烯-聚乙烯亚胺-苯扎氯铵、聚丙烯-聚乙烯亚胺-氯己定、聚丙烯-聚乙烯亚胺-苯基双胍、纤维素-聚乙烯亚胺-半胱氨酸、纤维素-聚乙烯亚胺-苯扎氯铵、纤维素-聚乙烯亚胺-氯己定、纤维素-聚乙烯亚胺-苯基双胍、尼龙-聚乙烯亚胺-半胱氨酸、尼龙-聚乙烯亚胺-苯扎氯铵、尼龙-聚乙烯亚胺-氯己定、尼龙-聚乙烯亚胺-苯基双胍、聚丙烯-海藻酸二醛-聚乙烯亚胺-半胱氨酸、聚丙烯-海藻酸二醛-聚乙烯亚胺-苯扎氯铵、聚丙烯-海藻酸二醛-聚乙烯亚胺-氯己定、聚丙烯-海藻酸二醛-聚乙烯亚胺-苯基双胍、纤维素-海藻酸二醛-聚乙烯亚胺-半 胱氨酸、纤维素-海藻酸二醛-聚乙烯亚胺-苯扎氯铵、纤维素-海藻酸二醛-聚乙烯亚胺-氯己定、纤维素-海藻酸二醛-聚乙烯亚胺-苯基双胍、尼龙-海藻酸二醛-聚乙烯亚胺-半胱氨酸、尼龙-海藻酸二醛-聚乙烯亚胺-苯扎氯铵、尼龙-海藻酸二醛-聚乙烯亚胺-氯己定、尼龙-海藻酸二醛-聚乙烯亚胺-苯基双胍或其任意组合。In some embodiments of the present disclosure, polyethyleneimine antifungal modified materials are provided, for example, selected from the group consisting of polypropylene-polyethyleneimine-cysteine, polypropylene-polyethyleneimine-benzalkonium chloride, polyethyleneimine Propylene-polyethyleneimine-chlorhexidine, polypropylene-polyethyleneimine-phenylbiguanide, cellulose-polyethyleneimine-cysteine, cellulose-polyethyleneimine-benzalkonium chloride, fiber Element-polyethyleneimine-chlorhexidine, cellulose-polyethyleneimine-phenylbiguanide, nylon-polyethyleneimine-cysteine, nylon-polyethyleneimine-benzalkonium chloride, nylon-polyethyleneimine Ethyleneimine-chlorhexidine, nylon-polyethyleneimine-phenylbiguanide, polypropylene-alginate dialdehyde-polyethyleneimine-cysteine, polypropylene-alginate dialdehyde-polyethyleneimine- Benzalkonium chloride, polypropylene-alginic acid dialdehyde-polyethyleneimine-chlorhexidine, polypropylene-alginic acid dialdehyde-polyethyleneimine-phenyl biguanide, cellulose-alginic acid dialdehyde-polyethyleneimine Amine-half Cystine, cellulose-alginate dialdehyde-polyethyleneimine-benzalkonium chloride, cellulose-alginate dialdehyde-polyethyleneimine-chlorhexidine, cellulose-alginate dialdehyde-polyethyleneimine Amine-phenyl biguanide, nylon-alginic acid dialdehyde-polyethyleneimine-cysteine, nylon-alginic acid dialdehyde-polyethylenimine-benzalkonium chloride, nylon-alginic acid dialdehyde-polyethyleneimine Amine-chlorhexidine, nylon-alginate dialdehyde-polyethylenimine-phenylbiguanide or any combination thereof.
本公开的其中一些实施例中，提供聚乙烯亚胺抗病毒改性材料，例如选自聚丙烯-聚乙烯亚胺-苯扎氯铵、聚丙烯-聚乙烯亚胺-氯己定、尼龙-聚乙烯亚胺-苯扎氯铵、尼龙-聚乙烯亚胺-氯己定、聚丙烯-海藻酸二醛-聚乙烯亚胺-苯扎氯铵、聚丙烯-海藻酸二醛-聚乙烯亚胺-氯己定、尼龙-海藻酸二醛-聚乙烯亚胺-苯扎氯铵、尼龙-海藻酸二醛-聚乙烯亚胺-氯己定或其任意组合。In some embodiments of the present disclosure, polyethyleneimine antiviral modified materials are provided, for example, selected from the group consisting of polypropylene-polyethyleneimine-benzalkonium chloride, polypropylene-polyethyleneimine-chlorhexidine, nylon- Polyethyleneimine-benzalkonium chloride, nylon-polyethyleneimine-chlorhexidine, polypropylene-alginic acid dialdehyde-polyethyleneimine-benzalkonium chloride, polypropylene-alginic acid dialdehyde-polyethyleneimine Amine-chlorhexidine, nylon-alginate dialdehyde-polyethylenimine-benzalkonium chloride, nylon-alginate dialdehyde-polyethylenimine-chlorhexidine or any combination thereof.
在本公开的一些实施例中，对本公开的聚乙烯亚胺抗微生物改性材料进行抗细菌活性检测，发现该改性材料对革兰氏阳性菌和阴性菌都有100％的抑制作用，并且稳定性良好。在其中一些实施例中，所述聚乙烯亚胺抗微生物改性材料为聚丙烯基PEI抗微生物改性材料或纤维素基PEI抗微生物改性材料或尼龙基PEI抗微生物改性材料。在其中一些实施例中，所述聚乙烯亚胺抗微生物改性材料选自聚丙烯-聚乙烯亚胺-半胱氨酸、聚丙烯-聚乙烯亚胺-苯扎氯铵、聚丙烯-聚乙烯亚胺-氯己定、聚丙烯-聚乙烯亚胺-苯基双胍、纤维素-聚乙烯亚胺-半胱氨酸、纤维素-聚乙烯亚胺-苯扎氯铵、纤维素-聚乙烯亚胺-氯己定、纤维素-聚乙烯亚胺-苯基双胍、尼龙-聚乙烯亚胺-半胱氨酸、尼龙-聚乙烯亚胺-苯扎氯铵、尼龙-聚乙烯亚胺-氯己定、尼龙-聚乙烯亚胺-苯基双胍、聚丙烯-海藻酸二醛-聚乙烯亚胺-半胱氨酸、聚丙烯-海藻酸二醛-聚乙烯亚胺-苯扎氯铵、聚丙烯-海藻酸二醛-聚乙烯亚胺-氯己定、聚丙烯-海藻酸二醛-聚乙烯亚胺-苯基双胍、纤维素-海藻酸二醛-聚乙烯亚胺-半胱氨酸、纤维素-海藻酸二醛-聚乙烯亚胺-苯扎氯铵、纤维素-海藻酸二醛-聚乙烯亚胺-氯己定、纤维素-海藻酸二醛-聚乙烯亚胺-苯基双胍、尼龙-海藻酸二醛-聚乙烯亚胺-半胱氨酸、尼龙-海藻酸二醛-聚乙烯亚胺-苯扎氯铵、尼龙-海藻酸二醛-聚乙烯亚胺-氯己定、尼龙-海藻酸二醛-聚乙烯亚胺-苯基双胍或其任意组合。在其中一些实施例中，所述革兰氏阳性菌为溶壁微球菌(Micrococcus lysodeikticus)。在其中一些实施例中，所述革兰氏阴性菌为大肠杆菌(E.coli)。In some embodiments of the present disclosure, the antibacterial activity of the polyethyleneimine antimicrobial modified material of the present disclosure was tested, and it was found that the modified material had a 100% inhibitory effect on both Gram-positive bacteria and Gram-negative bacteria, and Good stability. In some embodiments, the polyethyleneimine antimicrobial modified material is a polypropylene-based PEI antimicrobial modified material, a cellulose-based PEI antimicrobial modified material, or a nylon-based PEI antimicrobial modified material. In some embodiments, the polyethyleneimine antimicrobial modified material is selected from the group consisting of polypropylene-polyethyleneimine-cysteine, polypropylene-polyethyleneimine-benzalkonium chloride, polypropylene-polyethyleneimine Ethyleneimine-chlorhexidine, polypropylene-polyethyleneimine-phenylbiguanide, cellulose-polyethyleneimine-cysteine, cellulose-polyethyleneimine-benzalkonium chloride, cellulose-polyethyleneimine Ethyleneimine-chlorhexidine, cellulose-polyethyleneimine-phenylbiguanide, nylon-polyethyleneimine-cysteine, nylon-polyethyleneimine-benzalkonium chloride, nylon-polyethyleneimine -Chlorhexidine, nylon-polyethylenimine-phenylbiguanide, polypropylene-alginate dialdehyde-polyethylenimine-cysteine, polypropylene-alginate dialdehyde-polyethylenimine-benzachloride Ammonium, polypropylene-alginic acid dialdehyde-polyethyleneimine-chlorhexidine, polypropylene-alginic acid dialdehyde-polyethyleneimine-phenyl biguanide, cellulose-alginic acid dialdehyde-polyethyleneimine-semi- Cystine, cellulose-alginate dialdehyde-polyethyleneimine-benzalkonium chloride, cellulose-alginate dialdehyde-polyethyleneimine-chlorhexidine, cellulose-alginate dialdehyde-polyethyleneimine Amine-phenyl biguanide, nylon-alginic acid dialdehyde-polyethyleneimine-cysteine, nylon-alginic acid dialdehyde-polyethylenimine-benzalkonium chloride, nylon-alginic acid dialdehyde-polyethyleneimine Amine-chlorhexidine, nylon-alginate dialdehyde-polyethylenimine-phenylbiguanide or any combination thereof. In some embodiments, the Gram-positive bacterium is Micrococcus lysodeikticus. In some embodiments, the Gram-negative bacterium is E. coli.
在本公开的一些实施例中，对本公开的聚乙烯亚胺抗微生物改性材料进行抗真菌活性检测，发现该改性材料对真菌都有100％的抑制作用，并且稳定性良好。在其中一些实施例中，所述聚乙烯亚胺抗微生物改性材料为聚丙烯基PEI抗微生物改性材料或纤维素基PEI抗微生物改性材料或尼龙基PEI抗微生物改性材料。在其中一些实施例中，所述聚乙烯亚胺抗微生物改性材料选自聚丙烯-聚乙烯亚胺-半胱氨酸、聚丙烯-聚乙烯亚胺-苯扎氯铵、聚丙烯-聚乙烯亚胺-氯己定、聚丙烯-聚乙烯亚胺-苯基双胍、纤维素-聚乙烯亚胺-半胱氨酸、纤维素-聚乙烯亚胺-苯扎氯铵、纤维素-聚乙烯亚胺-氯己定、纤维素-聚乙烯亚胺-苯基双胍、尼龙-聚乙烯亚胺-半胱氨酸、尼龙-聚乙烯亚胺-苯扎氯铵、尼龙-聚乙烯亚胺-氯己定、尼龙-聚乙烯亚胺-苯基双胍、聚丙烯-海藻酸二醛-聚乙烯亚胺-半胱氨酸、聚丙烯-海藻酸二醛-聚乙烯亚胺-苯扎氯铵、聚丙烯-海藻酸二醛-聚乙烯亚胺-氯己定、聚丙烯-海藻酸二醛-聚乙烯亚胺-苯基双胍、纤维素-海藻酸二醛-聚乙烯亚胺-半胱氨酸、纤维素-海藻酸二醛-聚乙烯亚胺-苯扎氯铵、纤维素-海藻酸二醛-聚乙烯亚胺-氯己定、纤维素-海藻酸二醛-聚乙烯亚胺-苯基双胍、尼龙-海藻酸二醛-聚乙烯亚胺-半胱氨酸、尼龙-海藻酸二醛-聚乙烯亚胺-苯扎氯铵、尼龙-海藻酸二醛-聚乙烯亚胺-氯己定、尼龙-海藻酸二醛-聚乙烯亚胺-苯基双胍或其任意组合。在其中一些实施例中，所述真菌是酿酒酵母。In some embodiments of the present disclosure, the antifungal activity of the polyethyleneimine antimicrobial modified material of the present disclosure was tested, and it was found that the modified material had 100% inhibitory effect on fungi and had good stability. In some embodiments, the polyethyleneimine antimicrobial modified material is a polypropylene-based PEI antimicrobial modified material, a cellulose-based PEI antimicrobial modified material, or a nylon-based PEI antimicrobial modified material. In some embodiments, the polyethyleneimine antimicrobial modified material is selected from the group consisting of polypropylene-polyethyleneimine-cysteine, polypropylene-polyethyleneimine-benzalkonium chloride, polypropylene-polyethyleneimine Ethyleneimine-chlorhexidine, polypropylene-polyethyleneimine-phenylbiguanide, cellulose-polyethyleneimine-cysteine, cellulose-polyethyleneimine-benzalkonium chloride, cellulose-polyethyleneimine Ethyleneimine-chlorhexidine, cellulose-polyethyleneimine-phenylbiguanide, nylon-polyethyleneimine-cysteine, nylon-polyethyleneimine-benzalkonium chloride, nylon-polyethyleneimine -Chlorhexidine, nylon-polyethylenimine-phenylbiguanide, polypropylene-alginate dialdehyde-polyethylenimine-cysteine, polypropylene-alginate dialdehyde-polyethylenimine-benzachloride Ammonium, polypropylene-alginic acid dialdehyde-polyethyleneimine-chlorhexidine, polypropylene-alginic acid dialdehyde-polyethyleneimine-phenyl biguanide, cellulose-alginic acid dialdehyde-polyethyleneimine-semi- Cystine, cellulose-alginate dialdehyde-polyethyleneimine-benzalkonium chloride, cellulose-alginate dialdehyde-polyethyleneimine-chlorhexidine, cellulose-alginate dialdehyde-polyethyleneimine Amine-phenyl biguanide, nylon-alginic acid dialdehyde-polyethyleneimine-cysteine, nylon-alginic acid dialdehyde-polyethylenimine-benzalkonium chloride, nylon-alginic acid dialdehyde-polyethyleneimine Amine-chlorhexidine, nylon-alginate dialdehyde-polyethylenimine-phenylbiguanide or any combination thereof. In some of these embodiments, the fungus is Saccharomyces cerevisiae.
在本公开的一些实施例中，对本公开的聚乙烯亚胺抗微生物改性材料进行抗病毒活性检 测，发现病毒减少量可达至少2.5log以上。在其中一些实施例中，测得的病毒减少量在2.5至6log的范围中。在其中一些实施例中，病毒减少量在3.0至5.0log的范围内。在其中一些实施例中，所述聚乙烯亚胺抗微生物改性材料为聚丙烯基聚乙烯亚胺抗微生物改性材料或尼龙基聚乙烯亚胺抗微生物改性材料。在其中一些实施例中，所述聚乙烯亚胺抗微生物改性材料选自聚丙烯-聚乙烯亚胺-苯扎氯铵、聚丙烯-聚乙烯亚胺-氯己定、尼龙-聚乙烯亚胺-苯扎氯铵、尼龙-聚乙烯亚胺-氯己定、聚丙烯-海藻酸二醛-聚乙烯亚胺-苯扎氯铵、聚丙烯-海藻酸二醛-聚乙烯亚胺-氯己定、尼龙-海藻酸二醛-聚乙烯亚胺-苯扎氯铵、尼龙-海藻酸二醛-聚乙烯亚胺-氯己定或其任意组合。在其中一些实施例中，所述病毒为新型冠状病毒SARS-CoV-2。In some embodiments of the present disclosure, the polyethyleneimine antimicrobial modified materials of the present disclosure are tested for antiviral activity. After testing, it was found that the virus reduction amount could reach at least 2.5 log. In some of these examples, the measured viral reduction was in the range of 2.5 to 6 log. In some of these embodiments, the virus reduction ranges from 3.0 to 5.0 log. In some embodiments, the polyethyleneimine antimicrobial modified material is a polypropylene-based polyethyleneimine antimicrobial modified material or a nylon-based polyethyleneimine antimicrobial modified material. In some embodiments, the polyethyleneimine antimicrobial modified material is selected from polypropylene-polyethyleneimine-benzalkonium chloride, polypropylene-polyethyleneimine-chlorhexidine, nylon-polyethyleneimine Amine-benzalkonium chloride, nylon-polyethyleneimine-chlorhexidine, polypropylene-alginate dialdehyde-polyethyleneimine-benzalkonium chloride, polypropylene-alginate dialdehyde-polyethyleneimine-chlorine Hexidine, nylon-alginate dialdehyde-polyethylenimine-benzalkonium chloride, nylon-alginate dialdehyde-polyethylenimine-chlorhexidine or any combination thereof. In some embodiments, the virus is the novel coronavirus SARS-CoV-2.
本公开的第三个方面中，提供一种用于制备前述聚乙烯亚胺功能化材料的方法，包含以下步骤：将多孔材料或无孔材料与聚乙烯亚胺水溶液混合后，在10-100℃温度和pH为5-11下以60-200rpm摇动反应10分钟至24小时。In a third aspect of the present disclosure, a method for preparing the aforementioned polyethyleneimine functionalized material is provided, comprising the following steps: after mixing the porous material or non-porous material and the polyethyleneimine aqueous solution, at 10-100 The reaction is carried out with shaking at 60-200 rpm at a temperature of 5-11°C and a pH of 5-11 for 10 minutes to 24 hours.
在其中一些实施例中，该方法还包括以下步骤：在添加所述聚乙烯亚胺水溶液之前或在所述多孔材料或无孔材料与所述聚乙烯亚胺水溶液反应之后，将所述多孔材料或无孔材料与海藻酸二醛水溶液混合，然后在10-100℃温度和pH为1.5-8下以60-200rpm摇动反应10分钟至24小时。In some embodiments, the method further includes the step of: before adding the polyethyleneimine aqueous solution or after reacting the porous material or non-porous material with the polyethyleneimine aqueous solution, adding the porous material to the polyethyleneimine aqueous solution. Or the non-porous material is mixed with the alginic acid dialdehyde aqueous solution, and then the reaction is carried out with shaking at 60-200 rpm at a temperature of 10-100°C and a pH of 1.5-8 for 10 minutes to 24 hours.
也就是说，在其中一些实施例中，可以先使海藻酸二醛与多孔材料或无孔材料反应，形成海藻酸二醛功能化材料，然后再使聚乙烯亚胺与该海藻酸二醛功能化材料反应，以形成同时包含海藻酸二醛和聚乙烯亚胺的功能化材料。在其中一些实施例中，也可以先使聚乙烯亚胺与多孔材料或无孔材料反应，形成聚乙烯亚胺功能化材料，然后再使海藻酸二醛与该聚乙烯亚胺功能化材料反应，以形成同时包含海藻酸二醛和聚乙烯亚胺的功能化材料。并且在其中一些实施例中，也可以使聚乙烯亚胺和海藻酸二醛同时与多孔材料或无孔材料反应，以形成同时包含海藻酸二醛和聚乙烯亚胺的功能化材料。That is to say, in some embodiments, the alginic acid dialdehyde can be reacted with a porous material or a non-porous material first to form an alginic acid dialdehyde functionalized material, and then the polyethyleneimine can be functionalized with the alginic acid dialdehyde. chemical material to form a functionalized material containing both alginic dialdehyde and polyethyleneimine. In some embodiments, polyethyleneimine can also be reacted with porous materials or non-porous materials to form polyethyleneimine functionalized materials, and then alginic acid dialdehyde can be reacted with the polyethyleneimine functionalized materials. , to form functionalized materials containing both alginic dialdehyde and polyethyleneimine. And in some embodiments, polyethyleneimine and alginic acid dialdehyde can also be reacted with porous materials or non-porous materials at the same time to form a functionalized material containing both alginic acid dialdehyde and polyethyleneimine.
在其中一些实施例中，所述聚乙烯亚胺水溶液所含的聚乙烯亚胺与所述海藻酸二醛水溶液所含的海藻酸二醛的总和与所述多孔材料或无孔材料的质量比例为1:100至1:10。在其中一些实施例中，所述质量比例为1:50至1:20。In some embodiments, the mass ratio of the sum of polyethyleneimine contained in the polyethyleneimine aqueous solution and alginic acid dialdehyde contained in the alginic acid dialdehyde aqueous solution to the porous material or non-porous material is 1:100 to 1:10. In some embodiments, the mass ratio is 1:50 to 1:20.
在其中一些实施例中，所述聚乙烯亚胺水溶液所含的聚乙烯亚胺与所述海藻酸二醛水溶液所含的海藻酸二醛的质量比例为100:1至10:1。In some embodiments, the mass ratio of the polyethyleneimine contained in the polyethyleneimine aqueous solution to the alginic acid dialdehyde contained in the alginic acid dialdehyde aqueous solution is 100:1 to 10:1.
在其中一些实施例中，所述聚乙烯亚胺水溶液的pH为5-11。在其中一些实施例中，所述温度为10-100℃。在其中一些实施例中，所述摇动速度为60-200rpm。在其中一些实施例中，所述反应时间为10-24小时。In some embodiments, the pH of the polyethyleneimine aqueous solution is 5-11. In some of these embodiments, the temperature is 10-100°C. In some embodiments, the shaking speed is 60-200 rpm. In some embodiments, the reaction time is 10-24 hours.
在其中一些实施例中，所述海藻酸二醛水溶液的pH为1.5-8。在其中一些实施例中，所述温度为10-100℃。在其中一些实施例中，所述摇动速度为120-200rpm。在其中一些实施例中，所述反应时间为10-24小时。In some embodiments, the pH of the alginic acid dialdehyde aqueous solution is 1.5-8. In some of these embodiments, the temperature is 10-100°C. In some embodiments, the shaking speed is 120-200 rpm. In some embodiments, the reaction time is 10-24 hours.
在其中一些实施例中，所述聚乙烯亚胺水溶液浓度为10-1000mg/ml且以酸(例如硫酸、盐酸、乙酸、磷酸、硝酸)调节到适当pH；在其中一些实施例中，所述浓度为50-500mg/ml；在其中一些实施例中，所述浓度为20-100mg/ml。In some of the embodiments, the polyethyleneimine aqueous solution has a concentration of 10-1000 mg/ml and is adjusted to an appropriate pH with acid (such as sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, nitric acid); in some of the embodiments, the The concentration is 50-500 mg/ml; in some embodiments, the concentration is 20-100 mg/ml.
在其中一些实施例中，所述海藻酸二醛水溶液浓度为10-1000mg/ml且以酸(例如硫酸、盐酸、乙酸、磷酸、硝酸)调节到适当pH；在其中一些实施例中，所述浓度为50-500mg/ml；在其中一些实施例中，所述浓度为20-100mg/ml。In some embodiments, the concentration of the alginic acid dialdehyde aqueous solution is 10-1000 mg/ml and is adjusted to an appropriate pH with acid (such as sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, nitric acid); in some embodiments, the The concentration is 50-500 mg/ml; in some embodiments, the concentration is 20-100 mg/ml.
本公开的第三个方面中，替代性地，所述的方法包含以下步骤：将聚乙烯亚胺水溶液在 pH为1.5-8下直接涂覆或喷涂在所述多孔材料或无孔材料表面上，并在10-100℃温度下干燥10分钟到24小时，即得到所述聚乙烯亚胺功能化材料。In a third aspect of the present disclosure, alternatively, the method includes the steps of: adding an aqueous polyethyleneimine solution in The polyethylene imine functionalized material is obtained by directly coating or spraying on the surface of the porous material or non-porous material at a pH of 1.5-8, and drying at a temperature of 10-100°C for 10 minutes to 24 hours.
在其中一些实施例中，该方法还包括以下步骤：在涂覆或喷涂所述聚乙烯亚胺水溶液之前或之后，将海藻酸二醛水溶液在pH为1.5-8下直接涂覆或喷涂在所述多孔材料或无孔材料表面上并在10-100℃温度下干燥10分钟至24小时。In some embodiments, the method further includes the following steps: before or after coating or spraying the polyethyleneimine aqueous solution, directly coating or spraying the alginic acid dialdehyde aqueous solution at a pH of 1.5-8. on the surface of the porous material or non-porous material and dry at a temperature of 10-100°C for 10 minutes to 24 hours.
也就是说，在其中一些实施例中，可以先将海藻酸二醛涂覆或喷涂在多孔材料或无孔材料表面上，形成海藻酸二醛功能化材料，然后再涂覆或喷涂聚乙烯亚胺，以形成同时包含海藻酸二醛和聚乙烯亚胺的功能化材料。在其中一些实施例中，也可以先将聚乙烯亚胺涂覆或喷涂在多孔材料或无孔材料表面上，形成聚乙烯亚胺功能化材料，然后再涂覆或喷涂海藻酸二醛，以形成同时包含海藻酸二醛和聚乙烯亚胺的功能化材料。并且在其中一些实施例中，也可以同时将聚乙烯亚胺和海藻酸二醛涂覆或喷涂在多孔材料或无孔材料表面上，以形成同时包含海藻酸二醛和聚乙烯亚胺的功能化材料。That is to say, in some embodiments, the alginic acid dialdehyde can be coated or sprayed on the surface of the porous material or non-porous material first to form the alginic acid dialdehyde functionalized material, and then the polyethylene oxide can be coated or sprayed on the surface. amine to form functionalized materials containing both alginate dialdehyde and polyethyleneimine. In some of the embodiments, polyethyleneimine can also be coated or sprayed on the surface of porous materials or non-porous materials to form polyethyleneimine functionalized materials, and then alginic acid dialdehyde can be coated or sprayed to form Functionalized materials containing both alginic dialdehyde and polyethyleneimine are formed. And in some embodiments, polyethyleneimine and alginic acid dialdehyde can also be coated or sprayed on the surface of porous materials or non-porous materials at the same time to form a function that contains both alginic acid dialdehyde and polyethyleneimine. Chemical materials.
在其中一些实施例中，所述聚乙烯亚胺水溶液所含的聚乙烯亚胺与所述海藻酸二醛水溶液所含的海藻酸二醛的总和与所述多孔材料或无孔材料的质量比例为1:100至1:10。在其中一些实施例中，所述质量比例为1:50至1:20。In some embodiments, the mass ratio of the sum of polyethyleneimine contained in the polyethyleneimine aqueous solution and alginic acid dialdehyde contained in the alginic acid dialdehyde aqueous solution to the porous material or non-porous material is 1:100 to 1:10. In some embodiments, the mass ratio is 1:50 to 1:20.
在其中一些实施例中，所述聚乙烯亚胺水溶液所含的聚乙烯亚胺与所述海藻酸二醛水溶液所含的海藻酸二醛的质量比例为100:1至10:1。In some embodiments, the mass ratio of the polyethyleneimine contained in the polyethyleneimine aqueous solution to the alginic acid dialdehyde contained in the alginic acid dialdehyde aqueous solution is 100:1 to 10:1.
在其中一些实施例中，所述温度为10-100℃。在其中一些实施例中，所述干燥时间为10分钟到1小时。在其中一些实施例中，所述聚乙烯亚胺水溶液的pH为5-11。In some of these embodiments, the temperature is 10-100°C. In some embodiments, the drying time ranges from 10 minutes to 1 hour. In some embodiments, the pH of the polyethyleneimine aqueous solution is 5-11.
在其中一些实施例中，所述温度为30-50℃。在其中一些实施例中，所述干燥时间为10分钟到1小时。在其中一些实施例中，所述海藻酸二醛水溶液的pH为1.5-8。In some of these embodiments, the temperature is 30-50°C. In some embodiments, the drying time ranges from 10 minutes to 1 hour. In some embodiments, the pH of the alginic acid dialdehyde aqueous solution is 1.5-8.
在其中一些实施例中，所述PEI水溶液浓度为10-1000mg/ml且以酸(例如硫酸、盐酸、乙酸、磷酸、硝酸)调节到适当pH。在其中一些实施例中，所述浓度为50-500mg/ml。在其中一些实施例中，所述浓度为20-100mg/ml。In some embodiments, the PEI aqueous solution has a concentration of 10-1000 mg/ml and is adjusted to an appropriate pH with acid (such as sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, nitric acid). In some of these embodiments, the concentration is 50-500 mg/ml. In some of these embodiments, the concentration is 20-100 mg/ml.
在其中一些实施例中，所述ADA水溶液浓度为10-1000mg/ml且以酸(例如硫酸、盐酸、乙酸、磷酸、硝酸)调节到适当pH。在其中一些实施例中，所述浓度为50-500mg/ml。在其中一些实施例中，所述浓度为20-100mg/ml。In some embodiments, the ADA aqueous solution has a concentration of 10-1000 mg/ml and is adjusted to an appropriate pH with acid (such as sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, nitric acid). In some of these embodiments, the concentration is 50-500 mg/ml. In some of these embodiments, the concentration is 20-100 mg/ml.
本公开的第四个方面中，提供一种用于制备前述聚乙烯亚胺改性材料的方法，包含以下步骤：将前述聚乙烯亚胺功能化材料或根据前述方法制备的聚乙烯亚胺功能化材料，加入到功能材料水溶液中，在10-100℃温度和pH为1.5-8下以60-200rpm摇动反应10分钟至24小时，即得到所述改性材料；其中，所述功能材料能够通过共价键合、静电吸附、亲水吸附、疏水吸附、氢键键合或其任意组合的方式与所述连接层结合。In a fourth aspect of the present disclosure, a method for preparing the aforementioned polyethyleneimine-modified material is provided, comprising the following steps: converting the aforementioned polyethyleneimine-functionalized material or the polyethyleneimine-functionalized material prepared according to the aforementioned method. chemical material, add it to the functional material aqueous solution, and shake at 60-200 rpm for 10 minutes to 24 hours at a temperature of 10-100°C and a pH of 1.5-8 to react to obtain the modified material; wherein, the functional material can It is combined with the connection layer by covalent bonding, electrostatic adsorption, hydrophilic adsorption, hydrophobic adsorption, hydrogen bonding or any combination thereof.
在其中一些实施例中，所述功能材料占所述改性材料总质量的百分比为0.1％-1％。在其中一些实施例中，所述质量百分比为0.3％-0.6％。In some embodiments, the functional material accounts for 0.1%-1% of the total mass of the modified material. In some embodiments, the mass percentage is 0.3%-0.6%.
在其中一些实施例中，所述功能材料水溶液的pH为1.5-8。在其中一些实施例中，所述温度为10-100℃。在其中一些实施例中，所述摇动速度为120-200rpm。在其中一些实施例中，所述反应时间为8-16小时。In some embodiments, the pH of the functional material aqueous solution is 1.5-8. In some of these embodiments, the temperature is 10-100°C. In some embodiments, the shaking speed is 120-200 rpm. In some embodiments, the reaction time is 8-16 hours.
在其中一些实施例中，所述功能材料水溶液的浓度为10-100mg/ml并以酸(例如硫酸、盐酸、乙酸、磷酸、硝酸)调节到适当pH。在其中一些实施例中，所述浓度为5-60mg/ml。在其中一些实施例中，上述浓度为2-20mg/ml。 In some embodiments, the concentration of the functional material aqueous solution is 10-100 mg/ml and is adjusted to an appropriate pH with acid (such as sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, nitric acid). In some of these embodiments, the concentration is 5-60 mg/ml. In some embodiments, the above concentration is 2-20 mg/ml.
在其中一个实施例中，所述功能材料为抗微生物材料。In one embodiment, the functional material is an antimicrobial material.
本公开的第四个方面中，替代性地，所述方法包含以下步骤：将所述功能材料水溶液直接涂覆或喷涂在所述聚乙烯亚胺功能化材料上，并在10-100℃温度下干燥10分钟到24小时，即得到所述改性材料；其中，所述功能材料能够通过共价键合、静电吸附、亲水吸附、疏水吸附、氢键键合或其任意组合的方式与所述连接层结合，所述功能材料水溶液的pH为1.5-8。In a fourth aspect of the present disclosure, alternatively, the method includes the following steps: directly coating or spraying the functional material aqueous solution on the polyethyleneimine functionalized material, and heating it at a temperature of 10-100°C After drying for 10 minutes to 24 hours, the modified material is obtained; wherein, the functional material can be bonded with the functional material through covalent bonding, electrostatic adsorption, hydrophilic adsorption, hydrophobic adsorption, hydrogen bonding or any combination thereof. The connection layer is combined, and the pH of the functional material aqueous solution is 1.5-8.
在其中一些实施例中，所述功能材料占所述改性材料总质量的百分比为0.1％-1％。在其中一些实施例中，所述质量百分比为0.3％-0.6％。In some embodiments, the functional material accounts for 0.1%-1% of the total mass of the modified material. In some embodiments, the mass percentage is 0.3%-0.6%.
在其中一些实施例中，所述功能材料水溶液的pH为1.5-8。在其中一些实施例中，所述温度为10-100℃。在其中一些实施例中，所述干燥时间为8-16小时。In some embodiments, the pH of the functional material aqueous solution is 1.5-8. In some of these embodiments, the temperature is 10-100°C. In some embodiments, the drying time is 8-16 hours.
在其中一些实施例中，所述功能材料水溶液的浓度为10-100mg/ml并以酸(例如硫酸、盐酸、乙酸、磷酸、硝酸)调节到适当pH。在其中一些实施例中，所述浓度为5-60mg/ml。在其中一些实施例中，所述浓度为2-20mg/ml。In some embodiments, the concentration of the functional material aqueous solution is 10-100 mg/ml and is adjusted to an appropriate pH with acid (such as sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, nitric acid). In some of these embodiments, the concentration is 5-60 mg/ml. In some embodiments, the concentration is 2-20 mg/ml.
在其中一个实施例中，所述功能材料为抗微生物材料。In one embodiment, the functional material is an antimicrobial material.
本公开的第五个方面中，提供一种用于制备前述聚乙烯亚胺改性材料的方法，包含以下步骤：将功能材料与聚乙烯亚胺水溶液混合，得到聚乙烯亚胺-功能材料水溶液；将如上所得的水溶液与多孔材料或无孔材料在10-100℃温度和pH为1.5-8下以60-200rpm摇动反应10分钟至24小时，即得所述改性材料；其中，所述功能材料能够共价键合、静电吸附、亲水吸附、疏水吸附、氢键键合或其任意组合的方式与所述连接层结合。In a fifth aspect of the present disclosure, a method for preparing the aforementioned polyethyleneimine modified material is provided, comprising the following steps: mixing a functional material and a polyethyleneimine aqueous solution to obtain a polyethyleneimine-functional material aqueous solution ; The aqueous solution obtained above is reacted with porous materials or non-porous materials at a temperature of 10-100°C and a pH of 1.5-8 with shaking at 60-200 rpm for 10 minutes to 24 hours to obtain the modified material; wherein, the The functional material can be combined with the connection layer by covalent bonding, electrostatic adsorption, hydrophilic adsorption, hydrophobic adsorption, hydrogen bonding or any combination thereof.
在其中一些实施例中，该方法还包括以下步骤：在将功能材料与聚乙烯亚胺水溶液混合之前、之后或同时，将功能材料与海藻酸二醛水溶液混合。In some embodiments, the method further includes the step of mixing the functional material with the alginic acid dialdehyde aqueous solution before, after, or simultaneously with the functional material and the polyethyleneimine aqueous solution.
也就是说，可以先将功能材料与聚乙烯亚胺水溶液混合，然后再将其与海藻酸二醛水溶液混合并与多孔材料或无孔材料进行反应，得到同时含有聚乙烯亚胺和海藻酸二醛的改性材料。或者，可以先将功能材料与海藻酸二醛水溶液混合，然后再将其与聚乙烯亚胺水溶液混合并与多孔材料或无孔材料进行反应，得到同时含有聚乙烯亚胺和海藻酸二醛的改性材料。再或者，可以同时将功能材料与聚乙烯亚胺水溶液和海藻酸二醛水溶液混合，形成同时含有聚乙烯亚胺和海藻酸二醛的功能材料水溶液并与多孔材料或无孔材料进行反应，得到同时含有聚乙烯亚胺和海藻酸二醛的改性材料。That is to say, the functional material can be mixed with the polyethyleneimine aqueous solution first, and then mixed with the alginic acid dialdehyde aqueous solution and reacted with porous materials or non-porous materials to obtain polyethyleneimine and alginic acid dialdehyde aqueous solutions. aldehyde modified materials. Alternatively, the functional material can be mixed with the alginic acid dialdehyde aqueous solution first, and then mixed with the polyethyleneimine aqueous solution and reacted with the porous material or non-porous material to obtain a product containing both polyethyleneimine and alginic acid dialdehyde. Modified materials. Or, the functional material can be mixed with the polyethyleneimine aqueous solution and the alginic acid dialdehyde aqueous solution at the same time to form a functional material aqueous solution containing both polyethyleneimine and alginic acid dialdehyde and react with the porous material or non-porous material to obtain A modified material containing both polyethyleneimine and alginic acid dialdehyde.
在其中一些实施例中，所述功能材料、聚乙烯亚胺与海藻酸二醛的总和、与所述多孔材料或无孔材料的质量比例为(1-10):(10-100):1000。In some embodiments, the mass ratio of the functional material, the sum of polyethyleneimine and alginic acid dialdehyde, and the porous material or non-porous material is (1-10):(10-100):1000 .
在其中一些实施例中，所述聚乙烯亚胺水溶液的pH为1.5-6。在其中一些实施例中，所述温度为40-60℃。在其中一些实施例中，所述摇动速度为120-200rpm。在其中一些实施例中，所述反应时间为4-16小时。In some embodiments, the pH of the polyethyleneimine aqueous solution is 1.5-6. In some of these embodiments, the temperature is 40-60°C. In some embodiments, the shaking speed is 120-200 rpm. In some embodiments, the reaction time is 4-16 hours.
在其中一些实施例中，所述海藻酸二醛水溶液的pH为3-6。在其中一些实施例中，所述温度为40-70℃。在其中一些实施例中，所述摇动速度为120-200rpm。在其中一些实施例中，所述反应时间为8-16小时。In some embodiments, the pH of the alginic acid dialdehyde aqueous solution is 3-6. In some of these embodiments, the temperature is 40-70°C. In some embodiments, the shaking speed is 120-200 rpm. In some embodiments, the reaction time is 8-16 hours.
在其中一些实施例中，所述聚乙烯亚胺水溶液的浓度为10-1000mg/ml并以酸(例如硫酸、盐酸、乙酸、磷酸、硝酸)调节到适当pH。在其中一些实施例中，所述浓度为50-500mg/ml。在其中一些实施例中，所述浓度为20-100mg/ml。In some embodiments, the polyethyleneimine aqueous solution has a concentration of 10-1000 mg/ml and is adjusted to an appropriate pH with acid (such as sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, nitric acid). In some of these embodiments, the concentration is 50-500 mg/ml. In some of these embodiments, the concentration is 20-100 mg/ml.
在其中一些实施例中，所述海藻酸二醛水溶液的浓度为10-1000mg/ml并以酸(例如硫酸、盐酸、乙酸、磷酸、硝酸)调节到适当pH。在其中一些实施例中，所述浓度为50-500mg/ml。 在其中一些实施例中，所述浓度为20-100mg/ml。In some embodiments, the concentration of the alginic acid dialdehyde aqueous solution is 10-1000 mg/ml and is adjusted to an appropriate pH with acid (such as sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, nitric acid). In some of these embodiments, the concentration is 50-500 mg/ml. In some of these embodiments, the concentration is 20-100 mg/ml.
在其中一个实施例中，所述功能材料为抗微生物材料。In one embodiment, the functional material is an antimicrobial material.
本公开的第五个方面所述的方法中，可替代地，所述方法包含以下步骤：将功能材料与聚乙烯亚胺水溶液混合，得到聚乙烯亚胺-功能材料水溶液；将如上所得的水溶液在pH为1.5-8下直接涂覆或喷涂到多孔材料或无孔材料的表面并在10-100℃温度下干燥10分钟至24小时，即得所述改性材料；其中，所述功能材料能够共价键合、静电吸附、亲水吸附、疏水吸附、氢键键合或其任意组合的方式与所述连接层结合。In the method according to the fifth aspect of the present disclosure, alternatively, the method includes the following steps: mixing the functional material and the polyethyleneimine aqueous solution to obtain a polyethyleneimine-functional material aqueous solution; The modified material can be obtained by directly coating or spraying on the surface of porous or non-porous materials at a pH of 1.5-8 and drying at a temperature of 10-100°C for 10 minutes to 24 hours; wherein, the functional material It can be combined with the connection layer by covalent bonding, electrostatic adsorption, hydrophilic adsorption, hydrophobic adsorption, hydrogen bonding or any combination thereof.
在其中一些实施例中，该方法还包括以下步骤：在将功能材料与聚乙烯亚胺水溶液混合之前、之后或同时，将功能材料与海藻酸二醛水溶液混合。In some embodiments, the method further includes the step of mixing the functional material with the alginic acid dialdehyde aqueous solution before, after, or simultaneously with the functional material and the polyethyleneimine aqueous solution.
也就是说，可以先将功能材料与聚乙烯亚胺水溶液混合，然后再将其与海藻酸二醛水溶液混合并涂覆或喷涂到多孔材料或无孔材料的表面，得到同时含有聚乙烯亚胺和海藻酸二醛的改性材料。或者，可以先将功能材料与海藻酸二醛水溶液混合，然后再将其与聚乙烯亚胺水溶液混合并涂覆或喷涂到多孔材料或无孔材料的表面，得到同时含有聚乙烯亚胺和海藻酸二醛的改性材料。再或者，可以同时将功能材料与聚乙烯亚胺水溶液和海藻酸二醛水溶液混合，然后涂覆或喷涂到多孔材料或无孔材料的表面，得到同时含有聚乙烯亚胺和海藻酸二醛的改性材料。在其中一些实施例中，所述功能材料、聚乙烯亚胺与海藻酸二醛的总和、与所述多孔材料或无孔材料的质量比例为(1-10):(10-100):1000。That is to say, the functional material can be mixed with the polyethyleneimine aqueous solution first, and then mixed with the alginic acid dialdehyde aqueous solution and coated or sprayed on the surface of the porous material or non-porous material to obtain a polyethyleneimine-containing polyethyleneimine aqueous solution. and modified materials of alginic acid dialdehyde. Alternatively, the functional material can be mixed with the alginic acid dialdehyde aqueous solution first, and then mixed with the polyethyleneimine aqueous solution and coated or sprayed on the surface of the porous material or non-porous material to obtain a solution containing both polyethyleneimine and seaweed. Acid dialdehyde modified materials. Or, the functional material can be mixed with the polyethyleneimine aqueous solution and the alginic acid dialdehyde aqueous solution at the same time, and then be coated or sprayed on the surface of the porous material or non-porous material to obtain a product containing both polyethyleneimine and alginic acid dialdehyde. Modified materials. In some embodiments, the mass ratio of the functional material, the sum of polyethyleneimine and alginic acid dialdehyde, and the porous material or non-porous material is (1-10):(10-100):1000 .
在其中一些实施例中，所述聚乙烯亚胺水溶液的pH为5-11。在其中一些实施例中，所述海藻酸二醛水溶液的pH为1.5-8。在其中一些实施例中，所述温度为10-100℃。在其中一些实施例中，所述干燥时间为10分钟至24小时。In some embodiments, the pH of the polyethyleneimine aqueous solution is 5-11. In some embodiments, the pH of the alginic acid dialdehyde aqueous solution is 1.5-8. In some of these embodiments, the temperature is 10-100°C. In some embodiments, the drying time ranges from 10 minutes to 24 hours.
在其中一些实施例中，所述聚乙烯亚胺水溶液的浓度为10-1000mg/ml并以酸(例如硫酸、盐酸、乙酸、磷酸、硝酸)调节到适当pH。在其中一些实施例中，所述浓度为50-500mg/ml。在其中一些实施例中，所述浓度为20-100mg/ml。In some embodiments, the polyethyleneimine aqueous solution has a concentration of 10-1000 mg/ml and is adjusted to an appropriate pH with acid (such as sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, nitric acid). In some of these embodiments, the concentration is 50-500 mg/ml. In some of these embodiments, the concentration is 20-100 mg/ml.
在其中一些实施例中，所述海藻酸二醛水溶液的浓度为10-1000mg/ml并以酸(例如硫酸、盐酸、乙酸、磷酸、硝酸)调节到适当pH。在其中一些实施例中，所述浓度为50-500mg/ml。在其中一些实施例中，所述浓度为20-100mg/ml。In some embodiments, the concentration of the alginic acid dialdehyde aqueous solution is 10-1000 mg/ml and is adjusted to an appropriate pH with acid (such as sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, nitric acid). In some of these embodiments, the concentration is 50-500 mg/ml. In some of these embodiments, the concentration is 20-100 mg/ml.
在其中一个实施例中，所述功能材料为抗微生物材料。In one embodiment, the functional material is an antimicrobial material.
在其中一些实施例中，本公开的第三、第四、第五个方面中所述的方法，还包括如下步骤：将所得产物洗涤后，湿润储藏或者进行空气干燥或烘箱干燥。In some embodiments, the methods described in the third, fourth, and fifth aspects of the present disclosure also include the following steps: after washing the obtained product, store it in a moist state or perform air drying or oven drying.
在其中一些实施例中，上述产物可以用洗涤剂和/或水洗涤。在其中一些实施例中，同时包含海藻酸二醛和聚乙烯亚胺的功能化材料可以用洗涤剂和水洗涤而保持其活性。在其中一些实施例中，洗涤剂可以选自任何中性洗涤剂。如本文所用的“中性洗涤剂”是指在25℃标准使用浓度时，具有pH＝6-8的范围的洗涤剂。例如，中性洗涤剂可以是选自以下中的任何一种或多种：碱(例如，碳酸钠、硼砂)、表面活性剂(例如，烷基硫酸盐、月桂基硫酸钠、烷基乙氧基硫酸盐或脂肪醇醚)、功能材料(例如，pH调节剂、增光剂、水调节剂、硬脂酸钠或有机硅)、催化酶(例如，蛋白酶、淀粉酶、纤维素酶、甘露酶或果胶酶)和螯合物(例如，三聚磷酸钠、EDTA、HEDTA、PDTA或DTPA)。In some embodiments, the above products can be washed with detergent and/or water. In some of these embodiments, functionalized materials containing both alginic dialdehyde and polyethyleneimine can be washed with detergent and water while maintaining their activity. In some of these embodiments, the detergent can be selected from any neutral detergent. "Neutral detergent" as used herein refers to a detergent with a pH in the range of 6-8 at a standard use concentration of 25°C. For example, the neutral detergent may be any one or more selected from the following: alkali (eg, sodium carbonate, borax), surfactant (eg, alkyl sulfate, sodium lauryl sulfate, alkyl ethoxylate) sulfate or fatty alcohol ether), functional materials (e.g., pH adjuster, brightening agent, water conditioner, sodium stearate or silicone), catalytic enzymes (e.g., protease, amylase, cellulase, mannase or pectinase) and chelates (e.g., sodium tripolyphosphate, EDTA, HEDTA, PDTA or DTPA).
本公开的第六个方面中，提供前述各方面中所述的聚乙烯亚胺功能化材料、聚乙烯亚胺改性材料或其制备方法在生产医护用品及抗微生物用品中的用途。In the sixth aspect of the present disclosure, there is provided the use of the polyethyleneimine functionalized materials, polyethyleneimine modified materials or their preparation methods described in the previous aspects in the production of medical care products and antimicrobial products.
在其中一些实施例中，所述用途包括生产口罩、隔离衣、手套、个人防护用品、绷带、 医用胶带、医用帽、医用床单、医用衣服、空气过滤器、水过滤器、电子产品、家用电器及汽车配件等。In some embodiments, the uses include the production of masks, gowns, gloves, personal protective equipment, bandages, Medical tape, medical caps, medical sheets, medical clothes, air filters, water filters, electronic products, household appliances and auto parts, etc.
本公开的聚乙烯亚胺功能化材料和聚乙烯亚胺改性材料及其制备方法具有多种有益效果。例如，原料经济、环保、安全；支持层(基底层)可以采用多种常见的、任意孔径的基底材料，聚乙烯亚胺可方便地商购或自合成，抗微生物材料可采用经济、安全的氨基酸、季铵盐、氯己定、双胍类化合物等。又如，制备方法简单，原料易获得且成本低，无需使用刺激性有机溶剂，绿色环保且容易生产规模扩大化。此外，其对细菌(包括革兰氏阳性菌和阴性菌)、真菌及病毒的抑制活性高，降低二次感染风险。因此，本发明在生物、医药和卫生等领域具有极大应用潜力。其中，单独的聚乙烯亚胺作为连接层得到的聚乙烯亚胺改性材料得到了优异的抗细菌、抗真菌及抗病毒效果。但为了进一步提高其稳定性，还添加了海藻酸二醛，添加了海藻酸二醛得到的聚乙烯亚胺改性材料同样得到了优异的抗细菌、抗真菌及抗病毒效果。The disclosed polyethyleneimine functionalized materials and polyethyleneimine modified materials and their preparation methods have various beneficial effects. For example, the raw materials are economical, environmentally friendly, and safe; the support layer (base layer) can use a variety of common base materials with any pore size, polyethyleneimine can be easily purchased commercially or self-synthesized, and antimicrobial materials can be economical and safe. Amino acids, quaternary ammonium salts, chlorhexidine, biguanide compounds, etc. For another example, the preparation method is simple, the raw materials are easy to obtain and the cost is low, there is no need to use irritating organic solvents, it is green and environmentally friendly, and it is easy to expand the production scale. In addition, it has high inhibitory activity against bacteria (including Gram-positive bacteria and negative bacteria), fungi and viruses, reducing the risk of secondary infection. Therefore, the present invention has great application potential in the fields of biology, medicine and health. Among them, the polyethyleneimine modified material obtained by using polyethyleneimine alone as the connecting layer has excellent antibacterial, antifungal and antiviral effects. However, in order to further improve its stability, alginic acid dialdehyde is also added. The polyethyleneimine modified material obtained by adding alginic acid dialdehyde also has excellent antibacterial, antifungal and antiviral effects.
以下实施例中的化学品，如无特别说明，均来自商购，不再累述。Unless otherwise specified, the chemicals in the following examples are all commercially available and will not be described again.
实施例1：聚乙烯亚胺(PEI)抗微生物改性材料的制备Example 1: Preparation of polyethyleneimine (PEI) antimicrobial modified materials
本实施例是聚乙烯亚胺抗微生物改性材料的制备实施例，其中多孔材料或无孔材料以聚丙烯基、尼龙基(以基于聚己二酰己二胺的尼龙66复合材料为例)、纤维素材料为例，抗微生物材料以半胱氨酸、苯扎氯铵、氯己定、苯基双胍(1-(3-氯苯基)双胍盐酸盐)为例。聚丙烯基材料购自Tansole China公司(产品号:MFPP047020)，纤维素材料购自General Electronics(GE)Whatman公司(产品号:GB/T1914-2007)，尼龙(聚己二酰己二胺，即尼龙66)购自Merck Millipore公司(产品号:GNWP04700)。This embodiment is a preparation example of polyethyleneimine antimicrobial modified material, in which the porous material or non-porous material is polypropylene-based or nylon-based (taking the nylon 66 composite material based on polyhexamethylene adipamide as an example) , cellulose materials as examples, and antimicrobial materials as cysteine, benzalkonium chloride, chlorhexidine, and phenylbiguanide (1-(3-chlorophenyl)biguanide hydrochloride). Polypropylene-based materials were purchased from Tansole China (product number: MFPP047020), cellulose materials were purchased from General Electronics (GE) Whatman (product number: GB/T1914-2007), nylon (polyhexamethylene adipamide, i.e. Nylon 66) was purchased from Merck Millipore (product number: GNWP04700).
1.制备PEI功能化材料：1. Preparation of PEI functionalized materials:
1.1制备仅含PEI的功能化材料：1.1 Preparation of functionalized materials containing only PEI:
以如下方法之一制备仅含PEI的功能化材料：Prepare functionalized materials containing only PEI by one of the following methods:
方法一：分别取10g上述多孔材料或无孔材料并清洁后，浸入pH为5-11的含0.1-1g PEI的PEI水溶液中，在60℃和120rpm摇动下反应30分钟至小时即得仅含PEI的功能化材料。反应后，用蒸馏水洗涤所得的PEI功能化材料。Method 1: Take 10g of the above-mentioned porous materials or non-porous materials and clean them, then immerse them in a PEI aqueous solution containing 0.1-1g PEI with a pH of 5-11, and react for 30 minutes to an hour with shaking at 60°C and 120rpm to obtain only Functionalized materials for PEI. After the reaction, the obtained PEI functionalized material was washed with distilled water.
方法二：分别取10g所述多孔材料或无孔材料并清洁后，将pH为5-11的含0.1-1g PEI的PEI的水溶液在60℃下直接涂覆或喷涂到所述材料表面，然后在室温下干燥8小时，即得仅含PEI的功能化材料。Method 2: After taking 10g of the porous material or non-porous material respectively and cleaning them, directly apply or spray an aqueous solution of PEI with a pH of 5-11 containing 0.1-1g PEI onto the surface of the material at 60°C, and then After drying at room temperature for 8 hours, a functionalized material containing only PEI is obtained.
如上制得的产物为聚丙烯-PEI功能化材料、纤维素-PEI功能化材料和尼龙-PEI功能化材料。The products prepared as above are polypropylene-PEI functional materials, cellulose-PEI functional materials and nylon-PEI functional materials.
1.2制备包含ADA和PEI的功能化材料：1.2 Preparation of functionalized materials containing ADA and PEI:
1.2.1以如下方法之一制备ADA功能化材料：1.2.1 Prepare ADA functionalized materials by one of the following methods:
方法一：分别取10g上述多孔材料或无孔材料并清洁后，浸入pH为3-6的含0.1-1g ADA的ADA水溶液中，在室温至100℃和80-120rpm摇动下反应30分钟至3小时即得ADA功能化材料。反应后，用蒸馏水洗涤所得的ADA功能化材料。Method 1: Take 10g of the above-mentioned porous materials or non-porous materials and clean them, then immerse them in an ADA aqueous solution containing 0.1-1g ADA with a pH of 3-6, and react at room temperature to 100°C and shaking at 80-120rpm for 30 minutes to 3 ADA functionalized materials can be obtained within hours. After the reaction, the obtained ADA functionalized material was washed with distilled water.
方法二：分别取10g所述多孔材料或无孔材料并清洁后，将含0.1-1g ADA、pH为3-6的ADA水溶液在室温至100℃下直接涂覆或喷涂到所述材料表面，然后在30℃下干燥8小时， 即得ADA功能化材料。Method 2: Take 10g of the porous material or non-porous material respectively and clean them, then directly apply or spray an ADA aqueous solution containing 0.1-1g ADA and a pH of 3-6 onto the surface of the material at room temperature to 100°C. Then dry at 30℃ for 8 hours, That is, ADA functionalized materials are obtained.
如上制得的产物为聚丙烯-ADA功能化材料、纤维素-ADA功能化材料和尼龙-ADA功能化材料。The products prepared above are polypropylene-ADA functionalized materials, cellulose-ADA functionalized materials and nylon-ADA functionalized materials.
1.2.2以如下方法之一制备包含ADA和PEI的功能化材料(ADA-PEI功能化材料)：1.2.2 Prepare functionalized materials containing ADA and PEI (ADA-PEI functionalized materials) by one of the following methods:
方法一：分别取10g上述ADA功能化材料，浸入pH为5-10的含0.01-0.1gPEI的PEI水溶液中，在室温至70℃和80-120rpm摇动下反应30分钟至3小时即得ADA-PEI功能化材料。反应后，用中性洗涤剂和蒸馏水依次洗涤所得的ADA-PEI功能化材料。Method 1: Take 10g of the above ADA functionalized materials, immerse them in a PEI aqueous solution containing 0.01-0.1g PEI with a pH of 5-10, and react at room temperature to 70°C and shaking at 80-120rpm for 30 minutes to 3 hours to obtain ADA- PEI functionalized materials. After the reaction, the obtained ADA-PEI functionalized material was washed sequentially with neutral detergent and distilled water.
方法二：分别取10g上述ADA功能化材料，将含0.01-0.1g PEI、pH为5-10的PEI水溶液在室温至70℃下直接涂覆或喷涂到所述材料表面。反应后，用洗涤剂和蒸馏水依次洗涤所得的ADA-PEI功能化材料。然后在室温下干燥8小时，即得ADA-PEI功能化材料。Method 2: Take 10g of the above-mentioned ADA functionalized materials, and directly apply or spray a PEI aqueous solution containing 0.01-0.1g PEI and a pH of 5-10 onto the surface of the material at room temperature to 70°C. After the reaction, the obtained ADA-PEI functionalized material was washed sequentially with detergent and distilled water. Then dry at room temperature for 8 hours to obtain ADA-PEI functionalized material.
如上制得的产物为聚丙烯-ADA-PEI功能化材料、纤维素-ADA-PEI功能化材料和尼龙-ADA-PEI功能化材料。The products prepared as above are polypropylene-ADA-PEI functionalized materials, cellulose-ADA-PEI functionalized materials, and nylon-ADA-PEI functionalized materials.
2.制备PEI抗微生物改性材料：2. Preparation of PEI antimicrobial modified materials:
以如下方法之一制备PEI抗微生物改性材料：Prepare PEI antimicrobial modified materials by one of the following methods:
方法一：分别取10g PEI功能化材料与10-1000mg、pH 5-8的前述抗微生物材料水溶液在室温和120rpm摇动下反应30分钟至3小时，即得PEI微生物改性材料；Method 1: Take 10g of PEI functionalized material and react with 10-1000mg of the aforementioned antimicrobial material aqueous solution at pH 5-8 for 30 minutes to 3 hours at room temperature and shaking at 120rpm to obtain the PEI microbial modified material;
方法二：将10-1000mg、pH 5-8的前述抗微生物材料水溶液直接涂覆或喷涂到10g PEI功能化材料表面，然后室温下干燥8小时，即得PEI微生物改性材料；Method 2: directly apply or spray 10-1000mg of the aforementioned antimicrobial material aqueous solution with pH 5-8 onto the surface of 10g PEI functionalized material, and then dry it at room temperature for 8 hours to obtain the PEI microbial modified material;
方法三：取10-100mg抗微生物材料和0.01-0.1g PEI混合后，与Milli Q超纯水混合，pH调节为3-7，得到PEI抗微生物材料水溶液；取10g多孔材料或无孔材料与所得PEI抗微生物材料水溶液在室温和80-120rpm摇动下反应0.5-3小时，即得仅含PEI的抗微生物改性材料。ADA-PEI抗微生物改性材料的制备方法与上述类似，只需在将抗微生物材料和PEI混合之前，将抗微生物材料与ADA混合，然后再加入PEI混合，之后再进行摇动步骤；Method 3: Mix 10-100mg antimicrobial material and 0.01-0.1g PEI, mix it with Milli Q ultrapure water, adjust the pH to 3-7, and obtain a PEI antimicrobial material aqueous solution; take 10g porous material or non-porous material and mix it with The obtained PEI antimicrobial material aqueous solution is reacted at room temperature and shaking at 80-120 rpm for 0.5-3 hours to obtain an antimicrobial modified material containing only PEI. The preparation method of ADA-PEI antimicrobial modified materials is similar to the above. Just before mixing the antimicrobial materials and PEI, mix the antimicrobial materials with ADA, then add PEI to mix, and then perform the shaking step;
方法四：取10-100mg抗微生物材料与0.01-0.1g PEI混合后，与Milli Q超纯水混合，pH调节为3-7，得到PEI抗微生物材料水溶液；将如上所得的水溶液直接涂覆或喷涂到10g多孔材料或无孔材料的表面并在室温下干燥8小时，即得仅含PEI的PEI抗微生物改性材料。ADA-PEI抗微生物改性材料的制备方法与上述类似，只需在将抗微生物材料和PEI混合之前，将抗微生物材料与ADA混合，然后再加入PEI混合，之后再进行涂覆或喷涂步骤即可。Method 4: Mix 10-100mg of antimicrobial material with 0.01-0.1g of PEI, mix it with Milli Q ultrapure water, and adjust the pH to 3-7 to obtain a PEI antimicrobial material aqueous solution; directly apply the aqueous solution obtained above or Spray onto the surface of 10g of porous or non-porous materials and dry at room temperature for 8 hours to obtain a PEI antimicrobial modified material containing only PEI. The preparation method of ADA-PEI antimicrobial modified materials is similar to the above. You only need to mix the antimicrobial materials with ADA before mixing the antimicrobial materials and PEI, then add the PEI to mix, and then perform the coating or spraying step. Can.
如上制得的产物为聚丙烯-PEI-半胱氨酸改性材料、聚丙烯-PEI-苯扎氯铵改性材料、聚丙烯-PEI-氯己定改性材料、聚丙烯-PEI-苯基双胍改性材料；纤维素-PEI-半胱氨酸改性材料、纤维素-PEI-苯扎氯铵改性材料、纤维素-PEI-氯己定改性材料、纤维素PEI-苯基双胍改性材料；尼龙-PEI-半胱氨酸改性材料、尼龙-PEI-苯扎氯铵改性材料、尼龙-PEI-氯己定改性材料、尼龙-PEI-苯基双胍改性材料、聚丙烯-ADA-PEI-半胱氨酸、聚丙烯-ADA-PEI-苯扎氯铵、聚丙烯-ADA-PEI-氯己定、聚丙烯-ADA-PEI-苯基双胍、纤维素-ADA-PEI-半胱氨酸、纤维素-ADA-PEI-苯扎氯铵、纤维素-ADA-PEI-氯己定、纤维素-ADA-PEI-苯基双胍、尼龙-ADA-PEI-半胱氨酸、尼龙-ADA-PEI-苯扎氯铵、尼龙-ADA-PEI-氯己定、尼龙-ADA-PEI-苯基双胍。The products prepared as above are polypropylene-PEI-cysteine modified materials, polypropylene-PEI-benzalkonium chloride modified materials, polypropylene-PEI-chlorhexidine modified materials, polypropylene-PEI-benzene Biguanide modified material; cellulose-PEI-cysteine modified material, cellulose-PEI-benzalkonium chloride modified material, cellulose-PEI-chlorhexidine modified material, cellulose-PEI-phenyl Biguanide modified materials; nylon-PEI-cysteine modified materials, nylon-PEI-benzalkonium chloride modified materials, nylon-PEI-chlorhexidine modified materials, nylon-PEI-phenyl biguanide modified materials , polypropylene-ADA-PEI-cysteine, polypropylene-ADA-PEI-benzalkonium chloride, polypropylene-ADA-PEI-chlorhexidine, polypropylene-ADA-PEI-phenylbiguanide, cellulose- ADA-PEI-cysteine, cellulose-ADA-PEI-benzalkonium chloride, cellulose-ADA-PEI-chlorhexidine, cellulose-ADA-PEI-phenyl biguanide, nylon-ADA-PEI-semi Cystine, Nylon-ADA-PEI-Benzalkonium Chloride, Nylon-ADA-PEI-Chlorhexidine, Nylon-ADA-PEI-Phenylbiguanide.
将如上获得PEI改性材料产物洗涤数次可进行保存，以备其他用途，例如用作防护服等其他防护材料等。The PEI modified material product obtained as above can be washed several times and stored for other uses, such as protective clothing and other protective materials.
实施例2：PEI抗微生物改性材料的XPS表征 Example 2: XPS characterization of PEI antimicrobial modified materials
通过X射线光电子能谱法(XPS)检测实施例1中制备的PEI抗微生物改性材料的表面原子比率，本实施例以实施例1中的1.2制备包含ADA和PEI的功能化材料的方法一和制备PEI抗微生物改性材料方法一所制得的PEI抗微生物改性材料(尼龙-ADA-PEI-苯扎氯铵)为例。The surface atomic ratio of the PEI antimicrobial modified material prepared in Example 1 was detected by X-ray photoelectron spectroscopy (XPS). In this example, method 1.2 in Example 1 was used to prepare a functionalized material containing ADA and PEI. Take the PEI antimicrobial modified material (nylon-ADA-PEI-benzalkonium chloride) prepared by method 1 of preparing the PEI antimicrobial modified material as an example.
表1：根据XPS获得的样品的表面原子比率。
Table 1: Surface atomic ratios of samples obtained according to XPS.
如图1和表1所示，用ADA涂覆尼龙后，由于ADA中的氧原子含量丰富，因此尼龙-ADA相比尼龙氧原子含量有所增加。添加了PEI涂层后，尼龙-ADA-PEI上的PEI涂层将氮原子从10.88％增加到20.36％。进一步地，尼龙-ADA-PEI-苯扎氯铵上的苯扎氯铵涂层增加了碳原子比率，同时也检测到了氯原子的存在。由此，XPS证实了PEI抗微生物改性材料的成功功能化。As shown in Figure 1 and Table 1, after coating nylon with ADA, the oxygen atom content of nylon-ADA increases compared to nylon due to the rich content of oxygen atoms in ADA. With the addition of the PEI coating, the PEI coating on nylon-ADA-PEI increases nitrogen atoms from 10.88% to 20.36%. Further, the benzalkonium chloride coating on nylon-ADA-PEI-benzalkonium chloride increased the carbon atom ratio, and the presence of chlorine atoms was also detected. Thus, XPS confirmed the successful functionalization of PEI antimicrobial modified materials.
实施例3：PEI抗微生物改性材料的抗细菌活性测定Example 3: Determination of antibacterial activity of PEI antimicrobial modified materials
本实施例测试了实施例1中制备的聚丙烯基、纤维素基、尼龙基PEI抗微生物改性材料的抗细菌活性。本实施例以实施例1中的制备PEI功能化材料方法一(仅含PEI的功能化材料的方法一和包含ADA和PEI的功能化材料的方法一)和制备PEI抗微生物改性材料方法一所制得的PEI抗微生物改性材料为例，但以实施例1中其他方法制备的PEI抗微生物改性材料也获得了高度相似的结果。This example tests the antibacterial activity of the polypropylene-based, cellulose-based, and nylon-based PEI antimicrobial modified materials prepared in Example 1. This example uses the method one for preparing PEI functionalized materials in Example 1 (method one for functionalized materials containing only PEI and method one for functionalized materials containing ADA and PEI) and method one for preparing PEI antimicrobial modified materials. The prepared PEI antimicrobial modified material is taken as an example, but highly similar results were also obtained using PEI antimicrobial modified materials prepared by other methods in Example 1.
I.实验方法：I. Experimental methods:
以革兰氏阳性菌溶壁微球菌(Micrococcus lysodeikticus)和革兰氏阴性菌大肠杆菌(E.coli)为例，分别采用聚丙烯-PEI-抗微生物材料、纤维素-PEI-抗微生物材料和尼龙-PEI-抗微生物材料、聚丙烯-ADA-PEI-抗微生物材料、纤维素-ADA-PEI-抗微生物材料和尼龙-ADA-PEI-抗微生物材料进行抗细菌活性实验，试样一式三份取平均值。Taking Gram-positive bacteria Micrococcus lysodeikticus (Micrococcus lysodeikticus) and Gram-negative bacteria Escherichia coli (E.coli) as examples, polypropylene-PEI-antimicrobial materials, cellulose-PEI-antimicrobial materials and Antibacterial activity experiments were carried out on nylon-PEI-antimicrobial material, polypropylene-ADA-PEI-antimicrobial material, cellulose-ADA-PEI-antimicrobial material and nylon-ADA-PEI-antimicrobial material, and the samples were prepared in triplicate. take the average.
用LB(Luria-Bertani)培养基将溶壁微球菌和大肠杆菌37℃下搅拌培养过夜，将新鲜细菌培养物稀释成菌落数为10-4CFU/ml细菌悬浮液；将0.1g抗微生物改性材料与10mL细菌悬浮液混合置于烧瓶中，在120rpm摇床和37℃下培养2小时。另取10mL细菌悬浮液不加改性材料单独置于另一烧瓶中作为对照。反应后，取10-100μl细菌悬浮液接种到LB琼脂板上，并在37℃下培养18-36小时；培养18小时后，通过平板计数法计算活菌落数。Use LB (Luria-Bertani) medium to culture Micrococcus wall-dissolving bacteria and Escherichia coli with stirring at 37°C overnight. Dilute the fresh bacterial culture into a bacterial suspension with a colony count of 10 -4 CFU/ml; add 0.1g of antimicrobial Mix the bacterial suspension with 10 mL of bacterial suspension in a flask, and incubate on a 120 rpm shaker and 37°C for 2 hours. Another 10 mL of bacterial suspension without modified materials was placed in another flask as a control. After the reaction, inoculate 10-100 μl of bacterial suspension onto an LB agar plate and incubate at 37°C for 18-36 hours; after 18 hours of incubation, count the number of viable colonies by plate counting.
细菌抑制活性按照如下公式进行计算：
Bacterial inhibitory activity is calculated according to the following formula:
其中I表示细菌抑制活性，N0表示对照组培养后的菌落数，Ni表示处理组培养后的菌落数。Among them, I represents the bacterial inhibitory activity, N 0 represents the number of colonies after culture in the control group, and Ni represents the number of colonies after culture in the treatment group.
此外，为了检查抗细菌涂层的稳定性，还将所有抗微生物改性材料在热压处理后的超纯 水(Milli Q)中浸泡48小时后，与新制备的上述改性材料比较抗细菌活性。In addition, to check the stability of the antibacterial coating, all antimicrobial modified materials were subjected to ultrapure After soaking in water (Milli Q) for 48 hours, the antibacterial activity was compared with the newly prepared modified material.
II.实验结果II.Experimental results
1.聚丙烯基抗微生物改性材料：1. Polypropylene-based antimicrobial modified materials:
聚丙烯基抗微生物改性材料对溶壁微球菌(Micrococcus lysodeikticus)和大肠杆菌(E.coli)的抗细菌活性结果如表2所示。单独聚丙烯材料本身抗菌活性极低，聚丙烯-ADA材料的抗菌活性也很低，聚丙烯-ADA材料的新制备试样和48小时试样对革兰氏阳性菌分别显示出30％和31％的抑制作用，且对革兰氏阴性菌分别显示出25％的抑制作用。聚丙烯-ADA-PEI材料的新制备试样和48小时试样对革兰氏阳性菌都显示出90％的抑制活性。而聚丙烯-PEI-半胱氨酸、聚丙烯-PEI-苯扎氯铵、聚丙烯-PEI-氯己定、聚丙烯-ADA-PEI-半胱氨酸、聚丙烯-PEI-苯基双胍、聚丙烯-ADA-PEI-苯扎氯铵、聚丙烯-ADA-PEI-氯己定和聚丙烯-ADA-PEI-苯基双胍的新制备试样和48小时试样对革兰氏阳性菌和阴性菌都有100％的抑制作用。可以看出，本公开的所有聚丙烯-PEI-抗微生物改性材料和聚丙烯-ADA-PEI-抗微生物改性材料在水中浸泡48小时后，都仍保持了与新制备材料一致的细菌抑制活性。The antibacterial activity results of polypropylene-based antimicrobial modified materials against Micrococcus lysodeikticus and E.coli are shown in Table 2. The antibacterial activity of the polypropylene material alone is extremely low, and the antibacterial activity of the polypropylene-ADA material is also very low. The newly prepared sample and the 48-hour sample of the polypropylene-ADA material showed 30% and 31% against Gram-positive bacteria respectively. % inhibitory effect, and showed 25% inhibitory effect on Gram-negative bacteria respectively. Both the newly prepared sample and the 48-hour sample of the polypropylene-ADA-PEI material showed 90% inhibitory activity against Gram-positive bacteria. And polypropylene-PEI-cysteine, polypropylene-PEI-benzalkonium chloride, polypropylene-PEI-chlorhexidine, polypropylene-ADA-PEI-cysteine, polypropylene-PEI-phenyl biguanide , newly prepared samples and 48-hour samples of polypropylene-ADA-PEI-benzalkonium chloride, polypropylene-ADA-PEI-chlorhexidine and polypropylene-ADA-PEI-phenylbiguanide against Gram-positive bacteria and negative bacteria have 100% inhibitory effect. It can be seen that all polypropylene-PEI-antimicrobial modified materials and polypropylene-ADA-PEI-antimicrobial modified materials of the present disclosure still maintain bacterial inhibition consistent with newly prepared materials after being soaked in water for 48 hours. active.
表2：聚丙烯基抗微生物改性材料的抗细菌活性测试结果。
Table 2: Antibacterial activity test results of polypropylene-based antimicrobial modified materials.
2.纤维素基抗微生物改性材料： 2. Cellulose-based antimicrobial modified materials:
纤维素基抗微生物改性材料对溶壁微球菌(Micrococcus lysodeikticus)和大肠杆菌(E.coli)的抗细菌活性结果如表3所示。单独纤维素材料抗细菌活性极低。纤维素-ADA材料的新制备试样和48小时试样对革兰氏阳性菌分别显示出37％和36％的抑制作用，且对革兰氏阴性菌分别显示出20％和18％的抑制作用。纤维素-ADA-PEI材料的新制备试样和48小时试样对革兰氏阳性菌和阴性菌分别显示出90％的抑制活性。而纤维素-PEI-半胱氨酸、纤维素-PEI-苯扎氯铵、纤维素-PEI-氯己定、纤维素-PEI-苯基双胍、纤维素-ADA-PEI-半胱氨酸、纤维素-ADA-PEI-苯扎氯铵、纤维素-ADA-PEI-氯己定和纤维素-ADA-PEI-苯基双胍的新制备试样和48小时试样对革兰氏阳性菌和阴性菌都有100％的抑制作用。可以看出，本公开的所有纤维素-PEI-抗微生物改性材料和纤维素-ADA-PEI-抗微生物改性材料在水中浸泡48小时后，都仍保持了与新制备材料一致的细菌抑制活性。The antibacterial activity results of cellulose-based antimicrobial modified materials against Micrococcus lysodeikticus and E.coli are shown in Table 3. Cellulosic materials alone have very low antibacterial activity. Freshly prepared samples and 48-hour samples of cellulose-ADA material showed 37% and 36% inhibition against Gram-positive bacteria, respectively, and 20% and 18% inhibition against Gram-negative bacteria, respectively. effect. The newly prepared sample and the 48-hour sample of the cellulose-ADA-PEI material showed 90% inhibitory activity against Gram-positive bacteria and Gram-negative bacteria respectively. And cellulose-PEI-cysteine, cellulose-PEI-benzalkonium chloride, cellulose-PEI-chlorhexidine, cellulose-PEI-phenylbiguanide, cellulose-ADA-PEI-cysteine , cellulose-ADA-PEI-benzalkonium chloride, cellulose-ADA-PEI-chlorhexidine and cellulose-ADA-PEI-phenylbiguanide, newly prepared samples and 48-hour samples against Gram-positive bacteria and negative bacteria have 100% inhibitory effect. It can be seen that all cellulose-PEI-antimicrobial modified materials and cellulose-ADA-PEI-antimicrobial modified materials of the present disclosure still maintain bacterial inhibition consistent with newly prepared materials after being soaked in water for 48 hours. active.
表3：纤维素基抗微生物改性材料的抗细菌活性测试结果。
Table 3: Antibacterial activity test results of cellulose-based antimicrobial modified materials.
3.尼龙基抗微生物改性材料3. Nylon-based antimicrobial modified materials
尼龙基抗微生物改性材料对溶壁微球菌(Micrococcus lysodeikticus)和大肠杆菌(E.coli)的抗细菌活性结果如表4所示。单独尼龙材料抗细菌活性极低。尼龙-ADA材料的新制备试样和48小时试样对革兰氏阳性菌和阴性菌分别显示出27％和20％的抑制作用，且对革兰氏 阴性菌分别显示出20％和18％的抑制作用。尼龙-ADA-PEI材料的新制备试样和48小时试样对革兰氏阳性菌和阴性菌分别显示出90％的抑制活性。而尼龙-PEI-半胱氨酸、尼龙-PEI-苯扎氯铵、尼龙-PEI-氯己定、尼龙-PEI-苯基双胍、尼龙-ADA-PEI-半胱氨酸、尼龙-ADA-PEI-苯扎氯铵、尼龙-ADA-PEI-氯己定和尼龙-ADA-PEI-苯基双胍的新制备试样和48小时试样对革兰氏阳性菌和阴性菌都有100％的抑制作用。此外，还可以看出，本公开的所有尼龙-PEI-抗微生物改性材料和尼龙-ADA-PEI-抗微生物改性材料在水中浸泡48小时后，都仍保持了与新制备材料一致的细菌抑制活性。The antibacterial activity results of nylon-based antimicrobial modified materials against Micrococcus lysodeikticus and E.coli are shown in Table 4. Nylon material alone has very low antibacterial activity. Newly prepared samples and 48-hour samples of nylon-ADA material showed 27% and 20% inhibitory effects on Gram-positive bacteria and Gram-negative bacteria, respectively. Negative bacteria showed 20% and 18% inhibition respectively. The newly prepared sample and 48-hour sample of nylon-ADA-PEI material showed 90% inhibitory activity against Gram-positive bacteria and Gram-negative bacteria respectively. And nylon-PEI-cysteine, nylon-PEI-benzalkonium chloride, nylon-PEI-chlorhexidine, nylon-PEI-phenyl biguanide, nylon-ADA-PEI-cysteine, nylon-ADA- Freshly prepared and 48-hour samples of PEI-Benzalkonium Chloride, Nylon-ADA-PEI-Chlorhexidine and Nylon-ADA-PEI-Phenylbiguanide were 100% effective against Gram-positive and Gram-negative bacteria. inhibitory effect. In addition, it can also be seen that all nylon-PEI-antimicrobial modified materials and nylon-ADA-PEI-antimicrobial modified materials of the present disclosure still maintain bacteria consistent with the newly prepared materials after being soaked in water for 48 hours. inhibitory activity.
表4：尼龙基抗微生物改性材料的抗细菌活性测试结果。
Table 4: Antibacterial activity test results of nylon-based antimicrobial modified materials.
实施例4：PEI抗微生物改性材料的抗真菌活性测定Example 4: Determination of antifungal activity of PEI antimicrobial modified materials
本实施例测试了如实施例1所制备的聚丙烯基、纤维素基、尼龙基PEI抗微生物改性材料的抗真菌活性。本实施例以实施例1中的制备PEI功能化材料方法一(仅含PEI的功能化材料的方法一和包含ADA和PEI的功能化材料的方法一)和制备PEI抗微生物改性材料方法一所制得的PEI抗微生物改性材料为例，但以实施例1中其他方法制备的PEI抗微生物改性材料也获得了高度相似的结果。This example tests the antifungal activity of polypropylene-based, cellulose-based, and nylon-based PEI antimicrobial modified materials prepared as in Example 1. This example uses the method one for preparing PEI functionalized materials in Example 1 (method one for functionalized materials containing only PEI and method one for functionalized materials containing ADA and PEI) and method one for preparing PEI antimicrobial modified materials. The prepared PEI antimicrobial modified material is taken as an example, but highly similar results were also obtained using PEI antimicrobial modified materials prepared by other methods in Example 1.
I.实验方法：I. Experimental methods:
以酿酒酵母(Saccharomyces cerevisiae)作为真菌类的示例，分别采用聚丙烯-PEI-抗微生物材料、纤维素-PEI-抗微生物材料、尼龙-PEI-抗微生物材料、聚丙烯-ADA-PEI-抗微生物材 料、纤维素-ADA-PEI-抗微生物材料和尼龙-ADA-PEI-抗微生物材料进行抗真菌活性实验，试样一式三份取平均值。Taking Saccharomyces cerevisiae as an example of fungi, polypropylene-PEI-antimicrobial material, cellulose-PEI-antimicrobial material, nylon-PEI-antimicrobial material, and polypropylene-ADA-PEI-antimicrobial material are respectively used. material Materials, cellulose-ADA-PEI-antimicrobial material and nylon-ADA-PEI-antimicrobial material were used to conduct antifungal activity experiments, and the samples were averaged in triplicate.
用酵母蛋白胨右旋糖(YPD)培养基将酿酒酵母在30℃下搅拌培养过夜，将新鲜真菌培养物稀释成菌落数为10-4CFU/ml悬浮液；将0.1g抗微生物改性材料与10mL真菌悬浮液混合置于烧瓶中在摇床120rpm和37℃下培养2小时；另取10mL真菌悬浮液单独置于另一烧瓶中作为对照。反应后，取10-100μl真菌悬浮液接种到YPD琼脂板上，并在30℃下培养18-36小时；培养36小时后，通过平板计数法计算活菌落数。Saccharomyces cerevisiae was cultured overnight at 30°C with yeast peptone dextrose (YPD) medium, and the fresh fungal culture was diluted into a suspension with a colony count of 10 -4 CFU/ml; 0.1g of antimicrobial modified material was mixed with 10 mL of fungal suspension was mixed and placed in a flask, and cultured on a shaker at 120 rpm and 37°C for 2 hours; another 10 mL of fungal suspension was placed in another flask alone as a control. After the reaction, inoculate 10-100 μl of the fungal suspension onto the YPD agar plate and culture it at 30°C for 18-36 hours; after 36 hours of culture, count the number of viable colonies by plate counting.
真菌抑制活性按照如下公式进行计算：
Fungistatic activity is calculated according to the following formula:
其中I表示真菌抑制活性，N0表示对照组培养后的菌落数，Ni表示处理组培养后的菌落数。Among them, I represents the fungal inhibitory activity, N 0 represents the number of colonies after culture in the control group, and Ni represents the number of colonies after culture in the treatment group.
此外，为了检查抗真菌涂层的稳定性，还将所有抗微生物改性材料在热压处理后的超纯水(Milli Q)中浸泡48小时后，与新制备材料比较抗真菌活性。In addition, in order to check the stability of the antifungal coating, all antimicrobial modified materials were soaked in hot-pressed ultrapure water (Milli Q) for 48 hours, and the antifungal activity was compared with newly prepared materials.
II.实验结果II.Experimental results
1.聚丙烯基抗微生物改性材料：1. Polypropylene-based antimicrobial modified materials:
聚丙烯基抗微生物改性材料对酿酒酵母的抗真菌活性结果如表5所示。单独聚丙烯材料本身的抗真菌活性仅为15％，聚丙烯-ADA材料的新制备试样和48小时试样对酿酒酵母和分别显示出35％和32％的抑制作用。聚丙烯-ADA-PEI材料的新制备试样和48小时试样对酿酒酵母分别显示出90％的抑制活性。而聚丙烯-PEI-半胱氨酸、聚丙烯-PEI-苯扎氯铵、聚丙烯-PEI-氯己定、聚丙烯-PEI-苯基双胍、聚丙烯-ADA-PEI-半胱氨酸、聚丙烯-ADA-PEI-苯扎氯铵、聚丙烯-ADA-PEI-氯己定和聚丙烯-ADA-PEI-苯基双胍的新制备试样和48小时试样对酿酒酵母都有100％的抑制作用。可以看出，本公开的所有聚丙烯-PEI-抗微生物改性材料和聚丙烯-ADA-PEI-抗微生物改性材料在水中浸泡48小时后，都仍保持了与新制备材料一致的真菌抑制活性。The antifungal activity results of polypropylene-based antimicrobial modified materials against Saccharomyces cerevisiae are shown in Table 5. The antifungal activity of the polypropylene material itself was only 15%, and the newly prepared samples and 48-hour samples of the polypropylene-ADA material showed 35% and 32% inhibitory effects on Saccharomyces cerevisiae and Saccharomyces cerevisiae, respectively. The newly prepared sample and the 48-hour sample of the polypropylene-ADA-PEI material showed 90% inhibitory activity against Saccharomyces cerevisiae respectively. And polypropylene-PEI-cysteine, polypropylene-PEI-benzalkonium chloride, polypropylene-PEI-chlorhexidine, polypropylene-PEI-phenyl biguanide, polypropylene-ADA-PEI-cysteine , polypropylene-ADA-PEI-benzalkonium chloride, polypropylene-ADA-PEI-chlorhexidine and polypropylene-ADA-PEI-phenylbiguanide, both newly prepared samples and 48-hour samples have 100% resistance to Saccharomyces cerevisiae % inhibitory effect. It can be seen that all polypropylene-PEI-antimicrobial modified materials and polypropylene-ADA-PEI-antimicrobial modified materials of the present disclosure still maintain fungal inhibition consistent with newly prepared materials after being soaked in water for 48 hours. active.
表5：聚丙烯基抗微生物改性材料的抗真菌活性测试结果。

Table 5: Antifungal activity test results of polypropylene-based antimicrobial modified materials.

2.纤维素基抗微生物改性材料2. Cellulose-based antimicrobial modified materials
纤维素基抗微生物改性材料对酿酒酵母的抗真菌活性结果如表6所示。单独的新制备纤维素材料的的新制备试样和48小时试样对酿酒酵母分别显示出23％和21％的抑制作用。纤维素-ADA材料的新制备试样和48小时试样对酿酒酵母分别显示出37％和36％的抑制作用。纤维素-ADA-PEI材料的新制备试样和48小时试样对酿酒酵母分别显示出90％的抑制活性。而纤维素-PEI-半胱氨酸、纤维素-PEI-苯扎氯铵、纤维素-PEI-氯己定、纤维素-PEI-苯基双胍、纤维素-ADA-PEI-半胱氨酸、纤维素-ADA-PEI-苯扎氯铵、纤维素-ADA-PEI-氯己定和纤维素-ADA-PEI-苯基双胍的新制备试样和48小时试样对酿酒酵母都有100％的抑制作用。可以看出，本公开的所有纤维素-PEI-抗微生物改性材料和纤维素-ADA-PEI-抗微生物改性材料在水中浸泡48小时后，都仍保持了与新制备材料一致的真菌抑制活性。The antifungal activity results of cellulose-based antimicrobial modified materials against Saccharomyces cerevisiae are shown in Table 6. Freshly prepared samples and 48 hour samples of freshly prepared cellulosic material alone showed 23% and 21% inhibitory effects on Saccharomyces cerevisiae, respectively. Newly prepared samples and 48-hour samples of cellulose-ADA material showed 37% and 36% inhibitory effects on Saccharomyces cerevisiae, respectively. The newly prepared sample and the 48-hour sample of the cellulose-ADA-PEI material showed 90% inhibitory activity against Saccharomyces cerevisiae respectively. And cellulose-PEI-cysteine, cellulose-PEI-benzalkonium chloride, cellulose-PEI-chlorhexidine, cellulose-PEI-phenylbiguanide, cellulose-ADA-PEI-cysteine , cellulose-ADA-PEI-benzalkonium chloride, cellulose-ADA-PEI-chlorhexidine and cellulose-ADA-PEI-phenylbiguanide, both newly prepared samples and 48-hour samples have 100% resistance to Saccharomyces cerevisiae % inhibitory effect. It can be seen that all cellulose-PEI-antimicrobial modified materials and cellulose-ADA-PEI-antimicrobial modified materials of the present disclosure still maintain fungal inhibition consistent with newly prepared materials after being soaked in water for 48 hours. active.
表6：纤维素基抗微生物改性材料的抗真菌活性测试结果。
Table 6: Antifungal activity test results of cellulose-based antimicrobial modified materials.
3.尼龙基抗微生物改性材料 3. Nylon-based antimicrobial modified materials
尼龙基抗微生物改性材料对酿酒酵母的抗真菌活性结果如表7所示。单独尼龙材料的新制备试样和48小时试样对酿酒酵母分别显示出18％和17％的抑制作用。尼龙-ADA材料的新制备试样和48小时试样对酿酒酵母分别显示出40％和39％的抑制作用。尼龙-ADA-PEI材料的新制备试样和48小时试样对酿酒酵母分别显示出90％的抑制活性。而尼龙-PEI-半胱氨酸、尼龙-PEI-苯扎氯铵、尼龙-PEI-氯己定、尼龙-PEI-苯基双胍、尼龙-ADA-PEI-半胱氨酸、尼龙-ADA-PEI-苯扎氯铵、尼龙-ADA-PEI-氯己定和尼龙-ADA-PEI-苯基双胍的新制备试样和48小时试样对酿酒酵母都有100％的抑制作用。可以看出，本公开的所有尼龙-PEI-抗微生物改性材料和尼龙-ADA-PEI-抗微生物改性材料在水中浸泡48小时后，都仍保持了与新制备材料一致的真菌抑制活性。The antifungal activity results of nylon-based antimicrobial modified materials against Saccharomyces cerevisiae are shown in Table 7. Freshly prepared samples and 48-hour samples of nylon material alone showed 18% and 17% inhibitory effects on Saccharomyces cerevisiae, respectively. Newly prepared samples and 48-hour samples of nylon-ADA material showed 40% and 39% inhibitory effects on Saccharomyces cerevisiae, respectively. The newly prepared sample and the 48-hour sample of nylon-ADA-PEI material showed 90% inhibitory activity against Saccharomyces cerevisiae respectively. And nylon-PEI-cysteine, nylon-PEI-benzalkonium chloride, nylon-PEI-chlorhexidine, nylon-PEI-phenyl biguanide, nylon-ADA-PEI-cysteine, nylon-ADA- Newly prepared samples and 48-hour samples of PEI-benzalkonium chloride, nylon-ADA-PEI-chlorhexidine and nylon-ADA-PEI-phenylbiguanide have 100% inhibitory effect on Saccharomyces cerevisiae. It can be seen that after being soaked in water for 48 hours, all the nylon-PEI-antimicrobial modified materials and nylon-ADA-PEI-antimicrobial modified materials of the present disclosure still maintain the same fungal inhibitory activity as the newly prepared materials.
表7：尼龙基抗微生物改性材料的抗真菌活性测试结果。
Table 7: Antifungal activity test results of nylon-based antimicrobial modified materials.
实施例5：PEI抗微生物改性材料的抗病毒活性测定Example 5: Determination of antiviral activity of PEI antimicrobial modified materials
本实施例测试了如实施例1所制备的聚丙烯基、尼龙基PEI抗微生物改性材料的抗病毒活性。本实施例以实施例1中的制备PEI功能化材料方法一(仅含PEI的功能化材料的方法一和包含ADA和PEI的功能化材料的方法一)和制备PEI抗微生物改性材料方法一所制得的PEI抗微生物改性材料为例，但以实施例1中其他方法制备的PEI抗微生物改性材料也获得了高度相似的结果。This example tests the antiviral activity of the polypropylene-based and nylon-based PEI antimicrobial modified materials prepared as in Example 1. This example uses the method one for preparing PEI functionalized materials in Example 1 (method one for functionalized materials containing only PEI and method one for functionalized materials containing ADA and PEI) and method one for preparing PEI antimicrobial modified materials. The prepared PEI antimicrobial modified material is taken as an example, but highly similar results were also obtained using PEI antimicrobial modified materials prepared by other methods in Example 1.
I.实验方法： I. Experimental methods:
以新型冠状病毒(SARS-CoV-2)为病毒示例，分别采用聚丙烯基PEI抗微生物改性材料和尼龙基PEI抗微生物改性材料进行抗病毒活性实验，试样一式三份取平均值。Taking the new coronavirus (SARS-CoV-2) as an example of a virus, polypropylene-based PEI antimicrobial modified materials and nylon-based PEI antimicrobial modified materials were used to conduct antiviral activity experiments. The samples were averaged in triplicate.
将材料在生物安全柜中干燥，然后切成约0.3cm x 0.3cm的大小；取200μl病毒(SARS-CoV-2)悬浮液与材料在2mL无菌离心管中混合，在室温下培养1h；另取等量病毒样品(病毒悬浮液)置于另一无菌离心管中作为对照。对于聚丙烯基PEI抗微生物改性材料和尼龙基PEI抗微生物改性材料，病毒样品的初始Log TCID50/mL均为6.0log。反应后，用800μl PBS洗脱病毒，从MicroSpin S-400HR色谱柱(GE Healthcare)上收集400μl洗脱溶液，以除去洗脱的活性成分并降低细胞毒性；用50％组织培养感染剂量(TCID 50)分别滴定对照病毒洗脱液和处理组的残留病毒洗脱液；用Reed-Muench法计算病毒滴度。Dry the material in a biological safety cabinet, then cut it into a size of about 0.3cm x 0.3cm; mix 200 μl of virus (SARS-CoV-2) suspension with the material in a 2mL sterile centrifuge tube, and incubate at room temperature for 1 hour; Take another equal amount of virus sample (virus suspension) and place it in another sterile centrifuge tube as a control. For polypropylene-based PEI antimicrobial modified materials and nylon-based PEI antimicrobial modified materials, the initial Log TCID50/mL of virus samples is both 6.0log. After the reaction, the virus was eluted with 800 μl PBS, and 400 μl elution solution was collected from the MicroSpin S-400HR chromatography column (GE Healthcare) to remove the eluted active ingredients and reduce cytotoxicity; 50% tissue culture infective dose (TCID 50 ) Titrate the control virus eluate and the residual virus eluate of the treatment group respectively; use the Reed-Muench method to calculate the virus titer.
II.实验结果II.Experimental results
1.聚丙烯基抗微生物改性材料：1. Polypropylene-based antimicrobial modified materials:
聚丙烯基抗微生物改性材料对新型冠状病毒SARS-CoV-2的抗病毒活性结果如表8所示。其中，对照病毒样品和经聚丙烯材料、聚丙烯-PEI材料、聚丙烯-PEI-苯扎氯铵材料、聚丙烯-PEI-氯己定材料、聚丙烯-ADA-PEI-苯扎氯铵材料、聚丙烯-ADA-PEI-氯己定材料处理的病毒样品的Log TCID50/mL分别为6.0、6.0、5.0，2.0、3.5、1.0和3.0log。聚丙烯-PEI-苯扎氯铵材料和聚丙烯-ADA-PEI-苯扎氯铵材料相对于对照使病毒滴度分别降低了4log和5log，而相对于聚丙烯材料也使病毒滴度分别降低了4log和5log，相对于聚丙烯-PEI材料使病毒滴度分别降低了3log和4log。聚丙烯-PEI-氯己定材料和聚丙烯-ADA-PEI-氯己定材料相对于对照将病毒滴度分别降低了2.5log和3log，且相对于聚丙烯材料也分别降低了2.5log和3log，相对于聚丙烯-PEI材料使病毒滴度分别降低了1.5log和2log。The antiviral activity results of polypropylene-based antimicrobial modified materials against the new coronavirus SARS-CoV-2 are shown in Table 8. Among them, control virus samples and polypropylene materials, polypropylene-PEI materials, polypropylene-PEI-benzalkonium chloride materials, polypropylene-PEI-chlorhexidine materials, polypropylene-ADA-PEI-benzalkonium chloride materials , the Log TCID50/mL of virus samples treated with polypropylene-ADA-PEI-chlorhexidine materials were 6.0, 6.0, 5.0, 2.0, 3.5, 1.0 and 3.0log respectively. Polypropylene-PEI-benzalkonium chloride material and polypropylene-ADA-PEI-benzalkonium chloride material reduced the virus titer by 4log and 5log respectively compared to the control, and also reduced the virus titer compared to the polypropylene material. Compared with the polypropylene-PEI material, the virus titer was reduced by 3log and 4log respectively. Polypropylene-PEI-chlorhexidine materials and polypropylene-ADA-PEI-chlorhexidine materials reduced virus titers by 2.5log and 3log respectively compared to the control, and also reduced virus titers by 2.5log and 3log respectively compared to polypropylene materials. , compared to the polypropylene-PEI material, the virus titer was reduced by 1.5log and 2log respectively.
虽然聚丙烯-PEI材料也一定程度上降低了病毒滴度，但其原理是将病毒吸附到材料表面，使其不被洗脱，但并不杀死病毒；而聚丙烯-PEI-苯扎氯铵材料、聚丙烯-ADA-PEI-苯扎氯铵材料、聚丙烯-PEI-氯己定材料和聚丙烯-ADA-PEI-氯己定材料则通过苯扎氯铵和氯已定直接杀灭病毒，达到几乎100％的阻挡病毒效果。Although the polypropylene-PEI material also reduces the virus titer to a certain extent, its principle is to adsorb the virus to the surface of the material so that it will not be eluted, but it does not kill the virus; while polypropylene-PEI-benzachloride Ammonium materials, polypropylene-ADA-PEI-benzalkonium chloride materials, polypropylene-PEI-chlorhexidine materials and polypropylene-ADA-PEI-chlorhexidine materials are directly killed by benzalkonium chloride and chlorhexidine Viruses, achieving almost 100% virus blocking effect.
表8.聚丙烯基抗微生物改性材料的抗病毒活性测试结果(SARS-CoV-2)。
Table 8. Antiviral activity test results of polypropylene-based antimicrobial modified materials (SARS-CoV-2).
2.尼龙基抗微生物改性材料：2. Nylon-based antimicrobial modified materials:
尼龙基抗微生物改性材料对新型冠状病毒SARS-CoV-2的抗病毒活性结果如表8所示。 其中，对照病毒、尼龙材料、尼龙-PEI材料、尼龙-PEI-苯扎氯铵、尼龙-PEI-氯己定、尼龙-ADA-PEI-苯扎氯铵和尼龙-ADA-PEI-氯己定的Log TCID50/mL分别为6.0、6.0、5.0、1.0、2.5、1.0和2.0。尼龙-PEI-苯扎氯铵材料相对于对照、尼龙材料和尼龙-PEI材料使病毒滴度分别降低了5、5和4log。尼龙-PEI-氯已定材料相对于对照、尼龙材料和尼龙-PEI材料使病毒滴度分别降低了3.5、3.5和2.5log。尼龙-ADA-PEI-苯扎氯铵材料相对于对照、尼龙材料和尼龙-PEI材料使病毒滴度分别降低了5、5和4log。尼龙-ADA-PEI-氯已定材料相对于对照、尼龙材料和尼龙-PEI材料使病毒滴度分别降低了4.0、4.0和3.0log。The antiviral activity results of nylon-based antimicrobial modified materials against the new coronavirus SARS-CoV-2 are shown in Table 8. Among them, control virus, nylon material, nylon-PEI material, nylon-PEI-benzalkonium chloride, nylon-PEI-chlorhexidine, nylon-ADA-PEI-benzalkonium chloride and nylon-ADA-PEI-chlorhexidine The Log TCID50/mL are 6.0, 6.0, 5.0, 1.0, 2.5, 1.0 and 2.0 respectively. Compared with the control, nylon material and nylon-PEI material, the nylon-PEI-benzalkonium chloride material reduced the virus titer by 5, 5 and 4 log respectively. Compared with the control, nylon material and nylon-PEI material, the nylon-PEI-chlorhexidine material reduced the virus titer by 3.5, 3.5 and 2.5 log respectively. Compared with the control, nylon material and nylon-PEI material, the nylon-ADA-PEI-benzalkonium chloride material reduced the virus titer by 5, 5 and 4 log respectively. Compared with the control, nylon material and nylon-PEI material, the nylon-ADA-PEI-chlorhexidine material reduced the virus titer by 4.0, 4.0 and 3.0 log respectively.
虽然尼龙-PEI材料能够降低病毒滴度，但其将病毒吸附到材料表面而并不杀死病毒；而尼龙-PEI-苯扎氯铵材料、尼龙-ADA-PEI-苯扎氯铵材料、尼龙-PEI-氯己定材料和尼龙-ADA-PEI-氯己定材料则通过苯扎氯铵和氯已定直接杀灭病毒来达到效果。Although the nylon-PEI material can reduce the virus titer, it adsorbs the virus to the surface of the material without killing the virus; while the nylon-PEI-benzalkonium chloride material, nylon-ADA-PEI-benzalkonium chloride material, and nylon -PEI-chlorhexidine materials and nylon-ADA-PEI-chlorhexidine materials achieve the effect by directly killing viruses through benzalkonium chloride and chlorhexidine.
表8.尼龙基抗微生物改性材料的抗病毒活性测试结果(SARS-CoV-2)。
Table 8. Antiviral activity test results of nylon-based antimicrobial modified materials (SARS-CoV-2).
以上所述实施例仅表达了本公开的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本公开构思的前提下，还可以做出若干变形和改进，这些都属于本公开的保护范围。因此，本公开专利的保护范围应以所附权利要求为准。 The above-described embodiments only express several implementation modes of the present disclosure, and their descriptions are relatively specific and detailed, but they should not be construed as limiting the scope of the invention. It should be noted that, for those of ordinary skill in the art, several modifications and improvements can be made without departing from the concept of the present disclosure, and these all fall within the protection scope of the present disclosure. Therefore, the protection scope of the patent disclosed should be determined by the appended claims.

Claims (37)

  1. 聚乙烯亚胺功能化材料，包括：Polyethyleneimine functionalized materials, including:
    支持层，其由一种或多种多孔材料或无孔材料组成；和a support layer consisting of one or more porous or non-porous materials; and
    连接层，其包含聚乙烯亚胺，所述聚乙烯亚胺通过选自共价键合、静电吸附、氢键键合或其任意组合的方式与所述支持层直接和/或间接结合；A connection layer comprising polyethyleneimine, the polyethyleneimine being directly and/or indirectly bonded to the support layer by means selected from covalent bonding, electrostatic adsorption, hydrogen bonding or any combination thereof;
    其中，所述连接层能够通过选自共价键合、静电吸附、亲水吸附、疏水吸附、氢键键合或其任意组合的方式结合功能材料。Wherein, the connection layer can be combined with the functional material through a method selected from covalent bonding, electrostatic adsorption, hydrophilic adsorption, hydrophobic adsorption, hydrogen bonding or any combination thereof.
  2. 根据权利要求1所述的功能化材料，其特征在于，所述连接层还包含海藻酸二醛，所述海藻酸二醛通过选自共价键合、静电吸附、氢键键合或其任意组合的方式与所述支持层和/或所述聚乙烯亚胺结合。The functionalized material according to claim 1, characterized in that the connection layer further comprises alginic acid dialdehyde, and the alginic acid dialdehyde is bonded through covalent bonding, electrostatic adsorption, hydrogen bonding or any of them. Combined with the support layer and/or the polyethyleneimine in a combined manner.
  3. 根据权利要求1所述的功能化材料，其特征在于，所述一种或多种多孔材料或无孔材料由一种或多种聚合物或复合材料或其任意组合制成。The functionalized material according to claim 1, characterized in that the one or more porous materials or non-porous materials are made of one or more polymers or composite materials or any combination thereof.
  4. 根据权利要求3所述的功能化材料，其特征在于，所述聚合物或复合材料选自聚丙烯、纤维素、再生纤维素、聚偏二氟乙烯、聚醚砜、聚苯乙烯、聚四氟乙烯、聚乙烯、聚酰亚胺、聚酰胺或其任意组合。The functionalized material according to claim 3, characterized in that the polymer or composite material is selected from polypropylene, cellulose, regenerated cellulose, polyvinylidene fluoride, polyethersulfone, polystyrene, polytetraethylene Vinyl fluoride, polyethylene, polyimide, polyamide or any combination thereof.
  5. 根据权利要求1-4中任一项所述的功能化材料，其特征在于，所述连接层与所述支持层的质量比例为1:100至1:10。The functionalized material according to any one of claims 1 to 4, characterized in that the mass ratio of the connection layer to the support layer is 1:100 to 1:10.
  6. 根据权利要求5所述的功能化材料，其特征在于，所述连接层与所述支持层的质量比例为1:50至1:20。The functional material according to claim 5, characterized in that the mass ratio of the connection layer to the support layer is 1:50 to 1:20.
  7. 根据权利要求2所述的功能化材料，其特征在于，所述功能化材料中海藻酸二醛与聚乙烯亚胺的质量比例为100:1至10:1。The functionalized material according to claim 2, characterized in that the mass ratio of alginic dialdehyde and polyethyleneimine in the functionalized material is 100:1 to 10:1.
  8. 权利要求2所述的功能化材料，其特征在于，所述功能化材料中海藻酸二醛与聚乙烯亚胺的质量比例为50:1至20:1。The functionalized material according to claim 2, characterized in that the mass ratio of alginic acid dialdehyde and polyethyleneimine in the functionalized material is 50:1 to 20:1.
  9. 根据权利要求1-4中任一项所述的功能化材料，其特征在于，所述功能材料为抗微生物材料，且所述微生物选自细菌、真菌、病毒或其任意组合，其中：所述细菌选自肺炎衣原体、肺炎链球菌、结核分枝杆菌、A群链球菌、白喉棒杆菌、流感嗜血杆菌、脑膜炎奈瑟菌、难辨梭状芽孢杆菌、耐甲氧西林金黄色葡萄球菌、耐万古霉素肠球菌、鲍曼不动杆菌或其任意组合；所述真菌选自肺囊虫属、曲霉属、球霉菌属、芽酵母属、念珠菌属、毛霉菌属、孢子丝菌属、皮癣菌属或其任意组合；所述病毒选自呼吸道合胞病毒、肝炎病毒、水痘病毒、脊髓灰质炎病毒、天花病毒、麻疹病毒、腮腺炎病毒、沙眼衣原体、流感病毒、SARS-CoV病毒、SARS-CoV-2病毒、H1N1病毒、H5N1病毒、H5N7病毒、MERS-CoV病毒、金黄色葡萄球菌、肺炎克雷伯菌、尼日尔曲霉、埃博拉病毒或其任意组合。The functionalized material according to any one of claims 1 to 4, characterized in that the functional material is an antimicrobial material, and the microorganism is selected from bacteria, fungi, viruses or any combination thereof, wherein: the The bacteria are selected from the group consisting of Chlamydia pneumoniae, Streptococcus pneumoniae, Mycobacterium tuberculosis, Group A Streptococcus, Corynebacterium diphtheriae, Haemophilus influenzae, Neisseria meningitidis, Clostridium difficile, and methicillin-resistant Staphylococcus aureus. , vancomycin-resistant enterococci, Acinetobacter baumannii or any combination thereof; the fungus is selected from the group consisting of Pneumocystis, Aspergillus, Coccidioides, Budding Saccharomyces, Candida, Mucor, Sporothrix genus, dermatophytes, or any combination thereof; the virus is selected from respiratory syncytial virus, hepatitis virus, varicella virus, polio virus, smallpox virus, measles virus, mumps virus, Chlamydia trachomatis, influenza virus, SARS- CoV virus, SARS-CoV-2 virus, H1N1 virus, H5N1 virus, H5N7 virus, MERS-CoV virus, Staphylococcus aureus, Klebsiella pneumoniae, Aspergillus niger, Ebola virus, or any combination thereof.
  10. 根据权利要求9所述的功能化材料，其特征在于，所述抗微生物材料选自氨基酸、季铵化合物、氯己定化合物、阿来西定化合物、双胍类化合物或其任意组合，且其中所述氨基酸选自半胱氨酸、酪氨酸、赖氨酸、精氨酸和天冬氨酸或其任意组合；所述季铵化合物选自烷基二甲基苄基氯化铵、烷基二癸基二甲基氯化铵、二烷基二甲基氯化铵和二烷基季铵盐或其任意组合；所述氯己定化合物是氯己定二葡糖酸盐和/或氯己定二盐酸盐；所述阿来西定化合物是阿来西定二盐酸盐；所述双胍类化合物是1-(3-氯苯基)双胍盐酸盐。The functionalized material according to claim 9, wherein the antimicrobial material is selected from amino acids, quaternary ammonium compounds, chlorhexidine compounds, alexidine compounds, biguanide compounds or any combination thereof, and wherein the The amino acid is selected from cysteine, tyrosine, lysine, arginine and aspartic acid or any combination thereof; the quaternary ammonium compound is selected from alkyl dimethyl benzyl ammonium chloride, alkyl didecyldimethylammonium chloride, dialkyldimethylammonium chloride and dialkyl quaternary ammonium salt or any combination thereof; the chlorhexidine compound is chlorhexidine digluconate and/or chlorhexidine digluconate alexidine dihydrochloride; the alexidine compound is alexidine dihydrochloride; the biguanide compound is 1-(3-chlorophenyl)biguanide hydrochloride.
  11. 聚乙烯亚胺改性材料，包括： Polyethyleneimine modified materials, including:
    根据权利要求1-10中任一项所述的聚乙烯亚胺功能化材料；和The polyethyleneimine functionalized material according to any one of claims 1-10; and
    功能层，其由能够通过选自共价键合、静电吸附、亲水吸附、疏水吸附、氢键键合或其任意组合的方式与所述连接层结合的功能材料组成。The functional layer is composed of a functional material that can be combined with the connection layer by a method selected from covalent bonding, electrostatic adsorption, hydrophilic adsorption, hydrophobic adsorption, hydrogen bonding or any combination thereof.
  12. 根据权利要求11所述的改性材料，其特征在于，所述功能材料为抗微生物材料，所述聚乙烯亚胺改性材料为聚乙烯亚胺抗微生物改性材料。The modified material according to claim 11, wherein the functional material is an antimicrobial material, and the polyethyleneimine modified material is a polyethyleneimine antimicrobial modified material.
  13. 根据权利要求12所述的改性材料，其特征在于，所述抗微生物材料选自氨基酸、季铵化合物、氯己定化合物、阿来西定化合物、双胍类化合物或其任意组合。The modified material according to claim 12, characterized in that the antimicrobial material is selected from amino acids, quaternary ammonium compounds, chlorhexidine compounds, alexidine compounds, biguanide compounds or any combination thereof.
  14. 根据权利要求13所述的改性材料，其特征在于，所述氨基酸选自半胱氨酸、酪氨酸、赖氨酸、精氨酸和天冬氨酸或其任意组合。The modified material according to claim 13, characterized in that the amino acid is selected from cysteine, tyrosine, lysine, arginine and aspartic acid or any combination thereof.
  15. 根据权利要求13所述的改性材料，其特征在于，所述季铵化合物选自烷基二甲基苄基氯化铵、烷基二癸基二甲基氯化铵、二烷基二甲基氯化铵和二烷基季铵盐或其任意组合。The modified material according to claim 13, wherein the quaternary ammonium compound is selected from the group consisting of alkyl dimethyl benzyl ammonium chloride, alkyl didecyl dimethyl ammonium chloride, and dialkyl dimethyl ammonium chloride. ammonium chloride and dialkyl quaternary ammonium salt or any combination thereof.
  16. 根据权利要求13所述的改性材料，其特征在于，所述氯己定化合物是氯己定二葡糖酸盐和/或氯己定二盐酸盐；所述阿来西定化合物是阿来西定二盐酸盐；所述双胍类化合物是1-(3-氯苯基)双胍盐酸盐。The modified material according to claim 13, characterized in that the chlorhexidine compound is chlorhexidine digluconate and/or chlorhexidine dihydrochloride; the alexidine compound is alexidine Lexidine dihydrochloride; the biguanide compound is 1-(3-chlorophenyl)biguanide hydrochloride.
  17. 根据权利要求12所述的改性材料，其特征在于，所述抗微生物材料和所述聚乙烯亚胺抗微生物改性材料的抗微生物活性是针对细菌、真菌、病毒或其任意组合，且其中所述细菌选自肺炎衣原体、肺炎链球菌、结核分枝杆菌、A群链球菌、白喉棒杆菌、流感嗜血杆菌、脑膜炎奈瑟菌、难辨梭状芽孢杆菌、耐甲氧西林金黄色葡萄球菌、耐万古霉素肠球菌、鲍曼不动杆菌或其任意组合；所述真菌选自肺囊虫属、曲霉属、球霉菌属、芽酵母属、念珠菌属、毛霉菌属、孢子丝菌属、皮癣菌属或其任意组合；所述病毒选自呼吸道合胞病毒、肝炎病毒、水痘病毒、脊髓灰质炎病毒、天花病毒、麻疹病毒、腮腺炎病毒、沙眼衣原体、流感病毒、SARS-CoV病毒、SARS-CoV-2病毒、H1N1病毒、H5N1病毒、H5N7病毒、MERS-CoV病毒、金黄色葡萄球菌、肺炎克雷伯菌、尼日尔曲霉、埃博拉病毒或其任意组合。The modified material according to claim 12, wherein the antimicrobial activity of the antimicrobial material and the polyethyleneimine antimicrobial modified material is against bacteria, fungi, viruses or any combination thereof, and wherein The bacteria are selected from the group consisting of Chlamydia pneumoniae, Streptococcus pneumoniae, Mycobacterium tuberculosis, Group A Streptococcus, Corynebacterium diphtheriae, Haemophilus influenzae, Neisseria meningitidis, Clostridium difficile, MRSA Staphylococci, vancomycin-resistant enterococci, Acinetobacter baumannii or any combination thereof; the fungus is selected from the group consisting of Pneumocystis, Aspergillus, Coccidioides, Budding Saccharomyces, Candida, Mucor, Spore Rhizoma, Dermatophytes or any combination thereof; the virus is selected from respiratory syncytial virus, hepatitis virus, chickenpox virus, polio virus, smallpox virus, measles virus, mumps virus, Chlamydia trachomatis, influenza virus, SARS-CoV virus, SARS-CoV-2 virus, H1N1 virus, H5N1 virus, H5N7 virus, MERS-CoV virus, Staphylococcus aureus, Klebsiella pneumoniae, Aspergillus niger, Ebola virus, or any combination thereof.
  18. 根据权利要求12所述的改性材料，其特征在于，所述聚乙烯亚胺抗微生物改性材料为选自的聚丙烯-聚乙烯亚胺-半胱氨酸、聚丙烯-聚乙烯亚胺-苯扎氯铵、聚丙烯-聚乙烯亚胺-氯己定、聚丙烯-聚乙烯亚胺-苯基双胍、纤维素-聚乙烯亚胺-半胱氨酸、纤维素-聚乙烯亚胺-苯扎氯铵、纤维素-聚乙烯亚胺-氯己定、纤维素-聚乙烯亚胺-苯基双胍、尼龙-聚乙烯亚胺-半胱氨酸、尼龙-聚乙烯亚胺-苯扎氯铵、尼龙-聚乙烯亚胺-氯己定、尼龙-聚乙烯亚胺-苯基双胍、聚丙烯-海藻酸二醛-聚乙烯亚胺-半胱氨酸、聚丙烯-海藻酸二醛-聚乙烯亚胺-苯扎氯铵、聚丙烯-海藻酸二醛-聚乙烯亚胺-氯己定、聚丙烯-海藻酸二醛-聚乙烯亚胺-苯基双胍、纤维素-海藻酸二醛-聚乙烯亚胺-半胱氨酸、纤维素-海藻酸二醛-聚乙烯亚胺-苯扎氯铵、纤维素-海藻酸二醛-聚乙烯亚胺-氯己定、纤维素-海藻酸二醛-聚乙烯亚胺-苯基双胍、尼龙-海藻酸二醛-聚乙烯亚胺-半胱氨酸、尼龙-海藻酸二醛-聚乙烯亚胺-苯扎氯铵、尼龙-海藻酸二醛-聚乙烯亚胺-氯己定、尼龙-海藻酸二醛-聚乙烯亚胺-苯基双胍或其任意组合的聚乙烯亚胺抗细菌改性材料。The modified material according to claim 12, characterized in that the polyethyleneimine antimicrobial modified material is selected from polypropylene-polyethyleneimine-cysteine, polypropylene-polyethyleneimine -Benzalkonium chloride, polypropylene-polyethyleneimine-chlorhexidine, polypropylene-polyethyleneimine-phenylbiguanide, cellulose-polyethyleneimine-cysteine, cellulose-polyethyleneimine -Benzalkonium chloride, cellulose-polyethyleneimine-chlorhexidine, cellulose-polyethyleneimine-phenylbiguanide, nylon-polyethyleneimine-cysteine, nylon-polyethyleneimine-benzene Zalkonium chloride, nylon-polyethylenimine-chlorhexidine, nylon-polyethylenimine-phenylbiguanide, polypropylene-alginate dialdehyde-polyethylenimine-cysteine, polypropylene-alginate dialdehyde Aldehyde-polyethylenimine-benzalkonium chloride, polypropylene-alginate dialdehyde-polyethylenimine-chlorhexidine, polypropylene-alginate dialdehyde-polyethyleneimine-phenyl biguanide, cellulose-seaweed Acid dialdehyde-polyethyleneimine-cysteine, cellulose-alginate dialdehyde-polyethyleneimine-benzalkonium chloride, cellulose-alginate dialdehyde-polyethyleneimine-chlorhexidine, fiber Element-alginic acid dialdehyde-polyethyleneimine-phenyl biguanide, nylon-alginic acid dialdehyde-polyethyleneimine-cysteine, nylon-alginic acid dialdehyde-polyethyleneimine-benzalkonium chloride, Polyethyleneimine antibacterial modified materials of nylon-alginate dialdehyde-polyethyleneimine-chlorhexidine, nylon-alginate dialdehyde-polyethyleneimine-phenylbiguanide or any combination thereof.
  19. 根据权利要求12所述的改性材料，其特征在于，所述聚乙烯亚胺抗微生物改性材料为选自的聚丙烯-聚乙烯亚胺-半胱氨酸、聚丙烯-聚乙烯亚胺-苯扎氯铵、聚丙烯-聚乙烯亚胺-氯己定、聚丙烯-聚乙烯亚胺-苯基双胍、纤维素-聚乙烯亚胺-半胱氨酸、纤维素-聚乙烯亚胺-苯扎氯铵、纤维素-聚乙烯亚胺-氯己定、纤维素-聚乙烯亚胺-苯基双胍、尼龙-聚乙烯亚胺-半胱氨酸、尼龙-聚乙烯亚胺-苯扎氯铵、尼龙-聚乙烯亚胺-氯己定、尼龙-聚乙烯亚胺-苯基双胍、聚丙烯-海藻酸二醛-聚乙烯亚胺-半胱氨酸、聚丙烯-海藻酸二醛-聚乙烯亚胺-苯扎氯铵、聚丙 烯-海藻酸二醛-聚乙烯亚胺-氯己定、聚丙烯-海藻酸二醛-聚乙烯亚胺-苯基双胍、纤维素-海藻酸二醛-聚乙烯亚胺-半胱氨酸、纤维素-海藻酸二醛-聚乙烯亚胺-苯扎氯铵、纤维素-海藻酸二醛-聚乙烯亚胺-氯己定、纤维素-海藻酸二醛-聚乙烯亚胺-苯基双胍、尼龙-海藻酸二醛-聚乙烯亚胺-半胱氨酸、尼龙-海藻酸二醛-聚乙烯亚胺-苯扎氯铵、尼龙-海藻酸二醛-聚乙烯亚胺-氯己定、尼龙-海藻酸二醛-聚乙烯亚胺-苯基双胍或其任意组合的聚乙烯亚胺抗真菌改性材料。The modified material according to claim 12, characterized in that the polyethyleneimine antimicrobial modified material is selected from polypropylene-polyethyleneimine-cysteine, polypropylene-polyethyleneimine -Benzalkonium chloride, polypropylene-polyethyleneimine-chlorhexidine, polypropylene-polyethyleneimine-phenylbiguanide, cellulose-polyethyleneimine-cysteine, cellulose-polyethyleneimine -Benzalkonium chloride, cellulose-polyethyleneimine-chlorhexidine, cellulose-polyethyleneimine-phenylbiguanide, nylon-polyethyleneimine-cysteine, nylon-polyethyleneimine-benzene Zalkonium chloride, nylon-polyethylenimine-chlorhexidine, nylon-polyethylenimine-phenylbiguanide, polypropylene-alginate dialdehyde-polyethylenimine-cysteine, polypropylene-alginate dialdehyde Aldehyde-Polyethylenimine-Benzalkonium Chloride, Polypropylene Ethylene-alginic acid dialdehyde-polyethyleneimine-chlorhexidine, polypropylene-alginic acid dialdehyde-polyethyleneimine-phenyl biguanide, cellulose-alginic acid dialdehyde-polyethyleneimine-cysteine , cellulose-alginic acid dialdehyde-polyethyleneimine-benzalkonium chloride, cellulose-alginic acid dialdehyde-polyethyleneimine-chlorhexidine, cellulose-alginic acid dialdehyde-polyethyleneimine-benzene Biguanide, nylon-alginate dialdehyde-polyethyleneimine-cysteine, nylon-alginate dialdehyde-polyethylenimine-benzalkonium chloride, nylon-alginate dialdehyde-polyethyleneimine-chlorine Polyethyleneimine antifungal modified materials such as hexadine, nylon-alginate dialdehyde-polyethyleneimine-phenyl biguanide or any combination thereof.
  20. 根据权利要求12所述的改性材料，其特征在于，所述聚乙烯亚胺抗微生物改性材料为选自聚丙烯-聚乙烯亚胺-苯扎氯铵、聚丙烯-聚乙烯亚胺-氯己定、尼龙-聚乙烯亚胺-苯扎氯铵、尼龙-聚乙烯亚胺-氯己定、聚丙烯-海藻酸二醛-聚乙烯亚胺-苯扎氯铵、聚丙烯-海藻酸二醛-聚乙烯亚胺-氯己定、尼龙-海藻酸二醛-聚乙烯亚胺-苯扎氯铵、尼龙-海藻酸二醛-聚乙烯亚胺-氯己定或其任意组合的聚乙烯亚胺抗病毒改性材料。The modified material according to claim 12, characterized in that the polyethyleneimine antimicrobial modified material is selected from the group consisting of polypropylene-polyethyleneimine-benzalkonium chloride, polypropylene-polyethyleneimine- Chlorhexidine, nylon-polyethyleneimine-benzalkonium chloride, nylon-polyethyleneimine-chlorhexidine, polypropylene-alginic acid dialdehyde-polyethyleneimine-benzalkonium chloride, polypropylene-alginic acid Dialdehyde-polyethyleneimine-chlorhexidine, nylon-alginic acid dialdehyde-polyethyleneimine-benzalkonium chloride, nylon-alginic acid dialdehyde-polyethyleneimine-chlorhexidine or any combination thereof. Ethyleneimine antiviral modified material.
  21. 根据权利要求11-20中任一项所述的改性材料，其特征在于，所述功能层的功能材料占所述改性材料总质量的百分比为0.1％-1％。The modified material according to any one of claims 11 to 20, characterized in that the functional material of the functional layer accounts for 0.1%-1% of the total mass of the modified material.
  22. 根据权利要求21所述的改性材料，其特征在于，所述功能层的功能材料占所述改性材料总质量的百分比为0.3％-0.6％。The modified material according to claim 21, characterized in that the functional material of the functional layer accounts for 0.3%-0.6% of the total mass of the modified material.
  23. 用于制备根据权利要求1-10中任一项所述的聚乙烯亚胺功能化材料的方法，包含以下步骤：A method for preparing the polyethyleneimine functionalized material according to any one of claims 1-10, comprising the following steps:
    将多孔材料或无孔材料与聚乙烯亚胺水溶液混合后，在10-100℃温度和pH为5-11下以60-200rpm摇动反应10分钟至24小时，After mixing the porous material or non-porous material with the polyethyleneimine aqueous solution, shake the reaction at 60-200rpm at a temperature of 10-100°C and a pH of 5-11 for 10 minutes to 24 hours.
    或者，or,
    将聚乙烯亚胺水溶液在pH为5-11下直接涂覆或喷涂在所述多孔材料或无孔材料表面上并在10-100℃温度下干燥10分钟至24小时，即得到所述聚乙烯亚胺功能化材料。The polyethylene imine aqueous solution is directly coated or sprayed on the surface of the porous material or non-porous material at a pH of 5-11 and dried at a temperature of 10-100°C for 10 minutes to 24 hours to obtain the polyethylene Imine functionalized materials.
  24. 根据权利要求23所述的方法，其特征在于，还包括如下步骤：在添加所述聚乙烯亚胺水溶液之前或在所述多孔材料或无孔材料与所述聚乙烯亚胺水溶液反应之后，将所述多孔材料或无孔材料与海藻酸二醛水溶液混合，然后在10-100℃温度和pH为1.5-8下以60-200rpm摇动反应10分钟至24小时，The method according to claim 23, further comprising the step of: before adding the polyethyleneimine aqueous solution or after the porous material or non-porous material reacts with the polyethyleneimine aqueous solution, The porous material or non-porous material is mixed with the alginic acid dialdehyde aqueous solution, and then shaken at 60-200 rpm for 10 minutes to 24 hours at a temperature of 10-100°C and a pH of 1.5-8.
    或者，or,
    在涂覆或喷涂所述聚乙烯亚胺水溶液之前或之后，将海藻酸二醛水溶液在pH为1.5-8下直接涂覆或喷涂在所述多孔材料或无孔材料表面上并在10-100℃温度下干燥10分钟至24小时。Before or after coating or spraying the polyethyleneimine aqueous solution, the alginic acid dialdehyde aqueous solution is directly coated or sprayed on the surface of the porous material or non-porous material at a pH of 1.5-8 and at 10-100 Dry at ℃ temperature for 10 minutes to 24 hours.
  25. 根据权利要求24所述的方法，其特征在于，所述聚乙烯亚胺水溶液所含的聚乙烯亚胺与所述海藻酸二醛水溶液所含的海藻酸二醛的总和与所述多孔材料或无孔材料的质量比例为1:100至1:10。The method according to claim 24, characterized in that the sum of the polyethyleneimine contained in the polyethyleneimine aqueous solution and the alginic acid dialdehyde contained in the alginic acid dialdehyde aqueous solution is equal to the porous material or The mass ratio of non-porous materials is 1:100 to 1:10.
  26. 根据权利要求25所述的方法，其特征在于，所述聚乙烯亚胺水溶液所含的聚乙烯亚胺与所述海藻酸二醛水溶液所含的海藻酸二醛的质量比例为100:1至10:1。The method according to claim 25, characterized in that the mass ratio of the polyethyleneimine contained in the polyethyleneimine aqueous solution to the alginic acid dialdehyde contained in the alginic acid dialdehyde aqueous solution is 100:1 to 10:1.
  27. 用于制备根据权利要求11-22中任一项所述的聚乙烯亚胺改性材料的方法，包含以下步骤：A method for preparing the polyethyleneimine modified material according to any one of claims 11-22, comprising the following steps:
    将根据权利要求1-10中任一项所述的或根据权利要求23-26中任一项所述方法制备的聚乙烯亚胺功能化材料，加入到功能材料水溶液中，在10-100℃温度和pH为1.5-8下以60-200rpm摇动反应10分钟至24小时；The polyethyleneimine functionalized material according to any one of claims 1 to 10 or prepared according to the method according to any one of claims 23 to 26 is added to the functional material aqueous solution and heated at 10-100°C. The temperature and pH are 1.5-8, shaking at 60-200rpm for 10 minutes to 24 hours;
    或者， or,
    将所述功能材料水溶液在pH为1.5-8下直接涂覆或喷涂在所述聚乙烯亚胺功能化材料上并在10-100℃温度下干燥10分钟到24小时，The functional material aqueous solution is directly coated or sprayed on the polyethyleneimine functionalized material at a pH of 1.5-8 and dried at a temperature of 10-100°C for 10 minutes to 24 hours,
    即得到所述改性材料；That is, the modified material is obtained;
    其中，所述功能材料能够通过共价键合、静电吸附、亲水吸附、疏水吸附、氢键键合或其任意组合的方式与所述连接层结合。Wherein, the functional material can be combined with the connection layer through covalent bonding, electrostatic adsorption, hydrophilic adsorption, hydrophobic adsorption, hydrogen bonding or any combination thereof.
  28. 根据权利要求27所述的方法，其特征在于，所述功能材料占所述改性材料总质量的百分比为0.1％-1％。The method according to claim 27, wherein the functional material accounts for 0.1%-1% of the total mass of the modified material.
  29. 用于制备根据权利要求11-22中任一项所述的聚乙烯亚胺改性材料的方法，包含以下步骤：A method for preparing the polyethyleneimine modified material according to any one of claims 11-22, comprising the following steps:
    将功能材料与聚乙烯亚胺水溶液混合，得到聚乙烯亚胺-功能材料水溶液；Mix the functional material and the polyethyleneimine aqueous solution to obtain a polyethyleneimine-functional material aqueous solution;
    将如上所得的水溶液与多孔材料或无孔材料在10-100℃温度和pH为1.5-8下以60-200rpm摇动反应10分钟至24小时，或将如上所得的水溶液在pH为1.5-8下直接涂覆或喷涂到多孔材料或无孔材料的表面并在10-100℃温度下干燥10分钟至24小时，即得所述改性材料；The aqueous solution obtained above is reacted with porous materials or non-porous materials at a temperature of 10-100°C and a pH of 1.5-8 with shaking at 60-200 rpm for 10 minutes to 24 hours, or the aqueous solution obtained above is reacted at a pH of 1.5-8 The modified material can be obtained by directly coating or spraying on the surface of porous or non-porous materials and drying at a temperature of 10-100°C for 10 minutes to 24 hours;
    其中，所述功能材料能够共价键合、静电吸附、亲水吸附、疏水吸附、氢键键合或其任意组合的方式与所述连接层结合。Wherein, the functional material can be combined with the connection layer by covalent bonding, electrostatic adsorption, hydrophilic adsorption, hydrophobic adsorption, hydrogen bonding or any combination thereof.
  30. 根据权利要求29所述的方法，其特征在于，还包括如下步骤：在将功能材料与聚乙烯亚胺水溶液混合之前、之后或同时，将功能材料与海藻酸二醛水溶液混合。The method according to claim 29, further comprising the step of: mixing the functional material with the alginic acid dialdehyde aqueous solution before, after or at the same time as mixing the functional material with the polyethyleneimine aqueous solution.
  31. 根据权利要求30所述的方法，其特征在于，所述功能材料、聚乙烯亚胺与海藻酸二醛的总和、与所述多孔材料或无孔材料的质量比例为(1-10):(10-100):1000。The method according to claim 30, characterized in that the mass ratio of the functional material, the sum of polyethyleneimine and alginic acid dialdehyde, and the porous material or non-porous material is (1-10): ( 10-100):1000.
  32. 根据权利要求23-31中任一项所述的方法，其特征在于，还包括如下步骤：将所得产物洗涤后，湿润储藏或者进行空气干燥或烘箱干燥。The method according to any one of claims 23 to 31, characterized in that it also includes the following steps: after washing the obtained product, store it in a moist state or perform air drying or oven drying.
  33. 根据权利要求23-31中任一项所述的方法，其特征在于，所述多孔材料或无孔材料为一种或多种聚合物、复合材料或其任意组合，且所述聚合物或复合材料选自聚丙烯、纤维素、再生纤维素、聚偏二氟乙烯、聚醚砜、聚苯乙烯、聚四氟乙烯、聚乙烯、聚酰亚胺、聚酰胺或其任意组合。The method according to any one of claims 23-31, characterized in that the porous material or non-porous material is one or more polymers, composite materials or any combination thereof, and the polymer or composite material The material is selected from polypropylene, cellulose, regenerated cellulose, polyvinylidene fluoride, polyethersulfone, polystyrene, polytetrafluoroethylene, polyethylene, polyimide, polyamide or any combination thereof.
  34. 根据权利要求23-31中任一项所述的方法，其特征在于，所述功能材料为抗微生物材料，且所述微生物选自细菌、真菌、病毒或其任意组合，且所述细菌选自肺炎衣原体、肺炎链球菌、结核分枝杆菌、A群链球菌、白喉棒杆菌、流感嗜血杆菌、脑膜炎奈瑟菌、难辨梭状芽孢杆菌、耐甲氧西林金黄色葡萄球菌、耐万古霉素肠球菌、鲍曼不动杆菌或其任意组合；所述真菌选自肺囊虫属、曲霉属、球霉菌属、芽酵母属、念珠菌属、毛霉菌属、孢子丝菌属、皮癣菌属或其任意组合；所述病毒选自呼吸道合胞病毒、肝炎病毒、水痘病毒、脊髓灰质炎病毒、天花病毒、麻疹病毒、腮腺炎病毒、沙眼衣原体、流感病毒、SARS-CoV病毒、SARS-CoV-2病毒、H1N1病毒、H5N1病毒、H5N7病毒、MERS-CoV病毒、金黄色葡萄球菌、肺炎克雷伯菌、尼日尔曲霉、埃博拉病毒或其任意组合。The method according to any one of claims 23 to 31, wherein the functional material is an antimicrobial material, and the microorganism is selected from bacteria, fungi, viruses or any combination thereof, and the bacteria is selected from Chlamydia pneumoniae, Streptococcus pneumoniae, Mycobacterium tuberculosis, Group A Streptococcus, Corynebacterium diphtheriae, Haemophilus influenzae, Neisseria meningitidis, Clostridium difficile, methicillin-resistant Staphylococcus aureus, V. enterococci, Acinetobacter baumannii or any combination thereof; the fungus is selected from the group consisting of Pneumocystis, Aspergillus, Coccidioides, Budding Saccharomyces, Candida, Mucor, Sporothrix, Dermatospermum, Trichophyton or any combination thereof; the virus is selected from respiratory syncytial virus, hepatitis virus, varicella virus, polio virus, smallpox virus, measles virus, mumps virus, Chlamydia trachomatis, influenza virus, SARS-CoV virus, SARS-CoV-2 virus, H1N1 virus, H5N1 virus, H5N7 virus, MERS-CoV virus, Staphylococcus aureus, Klebsiella pneumoniae, Aspergillus niger, Ebola virus, or any combination thereof.
  35. 根据权利要求23-31中任一项所述的方法，其特征在于，所述功能材料为抗微生物材料，且所述抗微生物材料选自氨基酸、季铵化合物、氯己定化合物、阿来西定化合物、双胍类化合物或其任意组合，且其中所述氨基酸选自半胱氨酸、酪氨酸、赖氨酸、精氨酸和天冬氨酸或其任意组合；所述季铵化合物选自烷基二甲基苄基氯化铵、烷基二癸基二甲基氯化铵、二烷基二甲基氯化铵和二烷基季铵盐或其任意组合；所述氯己定化合物是氯己定二葡糖酸盐和/或氯己定二盐酸盐；所述阿来西定化合物是阿来西定二盐酸盐；所述双胍类化合物是1-(3- 氯苯基)双胍盐酸盐。The method according to any one of claims 23 to 31, characterized in that the functional material is an antimicrobial material, and the antimicrobial material is selected from the group consisting of amino acids, quaternary ammonium compounds, chlorhexidine compounds, alexidine compounds, Certain compounds, biguanide compounds or any combination thereof, and wherein the amino acid is selected from cysteine, tyrosine, lysine, arginine and aspartic acid or any combination thereof; the quaternary ammonium compound is selected from From alkyl dimethyl benzyl ammonium chloride, alkyl didecyl dimethyl ammonium chloride, dialkyl dimethyl ammonium chloride and dialkyl quaternary ammonium salt or any combination thereof; the chlorhexidine The compound is chlorhexidine digluconate and/or chlorhexidine dihydrochloride; the alexidine compound is alexidine dihydrochloride; the biguanide compound is 1-(3- Chlorphenyl) biguanide hydrochloride.
  36. 根据权利要求1-10中任一项所述的聚乙烯亚胺功能化材料、权利要求11-22任一项所述的聚乙烯亚胺改性材料、根据权利要求23-35中任一项所述的制备方法或根据权利要求23-36中任一项所述的制备方法制得的材料在生产医护用品及其他抗微生物用品中的用途。The polyethyleneimine functionalized material according to any one of claims 1 to 10, the polyethyleneimine modified material according to any one of claims 11 to 22, the polyethyleneimine functionalized material according to any one of claims 11 to 22, or the polyethyleneimine functionalized material according to any one of claims 23 to 35 The use of the material prepared by the preparation method or the preparation method according to any one of claims 23-36 in the production of medical supplies and other antimicrobial supplies.
  37. 根据权利要求36所述的用途，其特征在于，所述用途包括生产口罩、隔离衣、手套、个人防护用品、绷带、医用胶带、医用帽、医用床单、医用衣服、空气过滤器、水过滤器、电子产品、家用电器及汽车配件。 The use according to claim 36, characterized in that the use includes the production of masks, isolation gowns, gloves, personal protective equipment, bandages, medical tapes, medical caps, medical sheets, medical clothes, air filters, water filters , electronic products, household appliances and auto parts.
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