CN117720768A - Surface-functionalized material and use thereof - Google Patents
Surface-functionalized material and use thereof Download PDFInfo
- Publication number
- CN117720768A CN117720768A CN202211104530.1A CN202211104530A CN117720768A CN 117720768 A CN117720768 A CN 117720768A CN 202211104530 A CN202211104530 A CN 202211104530A CN 117720768 A CN117720768 A CN 117720768A
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- Prior art keywords
- polyethylenimine
- virus
- polyethyleneimine
- nylon
- alginic acid
- Prior art date
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- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
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Classifications
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L1/02—Cellulose; Modified cellulose
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- 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
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- 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
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- 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
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Abstract
The present disclosure provides a surface functionalized material and uses thereof, in particular, a polyethyleneimine functionalized material, a polyethyleneimine modified material, a preparation method thereof and uses thereof. The present disclosure also provides applications of the above materials and methods in the preparation of antibacterial, antifungal and viral protective articles. The raw materials and the preparation method are simple, economical, environment-friendly and easy to expand in scale, have high inhibitory activity on bacteria, fungi and viruses, and have great application potential in the fields of biology, medicine, sanitation and the like.
Description
Technical Field
The disclosure relates to the field of materials, in particular to a surface functionalized material and application thereof, and particularly relates to a polyethyleneimine functionalized material, a related modified material and application thereof.
Background
Pathogenic microorganisms are pathogenic microorganisms capable of causing diseases in humans, animals and plants, and include various bacteria, fungi and viruses, which are easily transmitted, for example, by means of air transmission, contact transmission, droplet transmission, etc., and pose a great threat to human health, even forming a pandemic disease. For example, "spanish influenza" (H1N 1) was the first world influenza pandemic in the 20 th century, spreading through europe, asia and north america almost simultaneously with three peaks of infection in 1918 to 1919, causing about 5000 tens of thousands of deaths worldwide in no more than 11 months. In recent years, there have been many viruses with pandemic potential, such as SARS-CoV, MERS-CoV and SARS-CoV-2. Until now, SARS-CoV-2 is still threatening the normal life of human beings, and according to WHO report, by 3 months and 25 days, the total number of cases of SARS-CoV-2 is about 4.76 hundred million, the total number of cases of death is about 610.9 ten thousand, and the total number of cases of SARS-CoV-2 is lost. In addition, there are also a number of bacteria and fungi that pose a health threat due to their susceptibility to spread among the human population, such as methicillin-resistant staphylococcus aureus (MRSA), vancomycin-resistant enterococci (VRE), dermatophytes, aspergillus, candida, and the like.
Blocking the spread of pathogenic microorganisms is a critical pathway to protect public health. However, conventional protection methods (e.g., medical masks) have limited effectiveness, such as because large filter pore sizes result in ineffective against smaller particle size microorganisms, particularly viruses. Protective articles that are effective against viruses (e.g., european FFP2 or FFP3 and U.S. N95 masks) are typically equipped with small pore filters, some of which also carry an electrical charge to act as a filter and electrostatic repulsion. However, these masks are expensive to manufacture and too small a pore size causes the wearer to breathe poorly. In addition, masks contaminated with pathogenic microorganisms must be specially treated, or they can be a source of infection and create a significant environmental burden.
The manufacture of most antiviral, antibacterial and antifungal materials requires the use of complex procedures and expensive chemicals, which are difficult to use on a large scale. Some common antimicrobial agents (e.g., silver or other nanoparticle impregnants) cannot be used for medical purposes due to their inherent toxicity, and certain organic solvents used to prepare functionalized materials also place a burden on 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 metal ion derivatives, such as copper (II) oxide or cobalt (II) phthalocyanine, have not been approved by the FDA for the production of PPE due to their non-environmental or harmful properties to the human body. On the other hand, the inhibitory activity of economical and environmentally friendly antimicrobial materials tends to be low. Common antimicrobial materials have a narrow range of microbial inhibition, for example, they are effective only against specific types of gram-positive bacteria, but are not effective against a broad spectrum of microorganisms such as gram-negative bacteria, fungi and viruses, especially those with increasingly enhanced resistance. Other reported antiviral coating technologies have low antiviral activity and are not effective against deadly viruses with low viral titers such as SARS-CoV, H5N1, H5N7, MERS-CoV, SARS-CoV-2, etc. Furthermore, most antimicrobial technologies are limited to bacteria, viruses or fungi, and certain antimicrobial and antiviral material coatings are compatible with only a limited variety of polymers, the nature of which may limit their application.
Disclosure of Invention
In one aspect of the present disclosure, there is provided a polyethyleneimine functionalized material comprising:
a support layer composed of one or more porous or non-porous materials; and
a tie layer comprising a polyethyleneimine directly and/or indirectly bonded to the support layer by a means selected from covalent bonding, electrostatic adsorption, hydrogen bonding, or any combination thereof;
wherein the tie layer is capable of binding to the functional material by a means selected from covalent bonding, electrostatic adsorption, hydrophilic adsorption, hydrophobic adsorption, hydrogen bonding, or any combination thereof.
In yet another aspect of the present disclosure, there is provided a method for preparing the aforementioned polyethyleneimine functionalized material, comprising the steps of:
mixing porous material or non-porous material with polyethyleneimine water solution, and shaking at 60-200rpm for reaction for 10 min to 24 h at 10-100 ℃ and pH5-11, or directly coating or spraying polyethyleneimine water solution on the surface of the porous material or non-porous material at pH5-11 and drying at 10-100 ℃ for 10 min to 24 h to obtain the polyethyleneimine functionalized material.
In yet another aspect of the present disclosure, there is provided a method for preparing the aforementioned polyethyleneimine modified material, comprising the steps of:
Adding the polyethyleneimine functionalized material or the polyethyleneimine functionalized material prepared according to the method into an aqueous solution of the functional material, and shaking at 60-200rpm for reaction for 10 minutes to 24 hours at the temperature of 10-100 ℃ and the pH of 1.5-8; or directly coating or spraying the functional material aqueous solution on the polyethyleneimine functional material at the pH of 1.5-8, and drying at the temperature of 10-100 ℃ for 10 minutes to 24 hours to obtain the modified material;
wherein the functional material is capable of binding to the tie layer by a means selected from covalent bonding, electrostatic adsorption, hydrophilic adsorption, hydrophobic adsorption, hydrogen bonding, or any combination thereof.
In yet another aspect of the present disclosure, there is provided a method for preparing the aforementioned polyethyleneimine modified material, comprising the steps of:
mixing a functional material with a polyethyleneimine aqueous solution to obtain a polyethyleneimine-functional material aqueous solution;
the aqueous solution obtained above and the porous material or the non-porous material are subjected to shaking reaction at 60-200rpm for 10 minutes to 24 hours at the temperature of 10-100 ℃ and the pH of 1.5-8, or the aqueous solution obtained above is directly coated or sprayed on the surface of the porous material or the non-porous material at the pH of 1.5-8 and dried at the temperature of 10-100 ℃ for 10 minutes to 24 hours, so that the modified material is obtained;
Wherein the functional material is capable of binding to the tie layer by a means selected from covalent bonding, electrostatic adsorption, hydrophilic adsorption, hydrophobic adsorption, hydrogen bonding, or any combination thereof.
In a further aspect of the present disclosure there is also provided the use of a polyethyleneimine functionalized material, a polyethyleneimine modified material, a method of preparation thereof or a material obtained according to a method of preparation thereof as described in the preceding aspects in the manufacture of medical and antimicrobial articles.
Drawings
FIG. 1 is an X-ray photoelectron spectroscopy (XPS) test result of a polyethyleneimine antimicrobial modified material according to one embodiment of the present invention.
Detailed Description
For the purposes of promoting an understanding of the principles and advantages of the disclosure, reference will now be made to the drawings and specific language will be used to describe the same. It should be understood that the detailed description is presented herein only to illustrate the present disclosure and not to limit the scope of the disclosure.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. The terminology used in the description of the disclosure herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the disclosure. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
Polyethylenimine (Poly (ethylenimine), PEI), also known as polyazacycloalkane, is a water-soluble high molecular polymer. Polyethyleneimine, having a polar group (amino) structure, can be combined with various substances by the following actions: (1) physically adhering to the surface of the substance; (2) the amino group contained therein can react with the carboxyl group to form a hydrogen bond; (3) Which contains amino groups and has positive charges, and is electrostatically combined with the surface having negative charges; (4) The amino group contained therein can react with the carbonyl group to form a covalent bond. Polyethyleneimine can be used as a linking agent and an antibacterial agent, but its antibacterial property is limited and the preparation process is complicated, which limits its application.
The inventors of the present application found that PEI coated surfaces can incorporate functional materials by covalent bonding, electrostatic adsorption, hydrophilic adsorption, hydrophobic adsorption, hydrogen bonding, and the like.
To further increase the stability of the PEI and the functional layer, the inventors of the present application have also found that the material can be functionalized with alginic acid dialdehyde together with PEI.
Alginic acid dialdehyde (Alginate Dialdehyde, ADA) is an adhesive polymer that can be firmly attached to the surface of different materials by at least any one of several principles: (1) physically adhering to the surface; (2) Covalent bonds are formed with amine or amide groups of the surface through two aldehyde groups in each monomer; (3) Electrostatically binding to the positively charged surface by the negative charge carried by the presence of hydroxyl and carboxyl groups; (4) formation of hydrogen bonds to the surface. Thus, the ADA-coated surface may also be attached to the substance by covalent bonding, electrostatic adsorption, hydrophilic adsorption, hydrophobic adsorption, hydrogen bonding, or the like.
Accordingly, in some embodiments of the present disclosure, a polyethyleneimine functionalized material is provided that includes a support layer composed of a porous or non-porous material and a connection layer comprising polyethyleneimine. In some embodiments of the present disclosure, the tie layer further comprises alginic acid dialdehyde. In some embodiments of the present disclosure, the tie layer is comprised of alginic acid dialdehyde and polyethylenimine.
In some embodiments of the present disclosure, there is also provided a polyethyleneimine modified material comprising the aforementioned polyethyleneimine functionalized material and a functional layer, which may be a functional material. In some of these embodiments, the functional material is an antimicrobial material.
In some embodiments of the present disclosure, various methods of preparing the foregoing polyethyleneimine functionalized materials and polyethyleneimine modified materials are also provided.
In addition, the present disclosure also provides the use of the above materials and methods of preparation in the preparation of antimicrobial articles. Polyethyleneimine (PEI) in the present disclosure may be chemically synthesized by various methods or commercially available. In some of these embodiments, the polyethyleneimine in the present disclosure has a molecular weight of about 10000-125000g/mol.
In some of these embodiments, the polyethyleneimine may be obtained by any existing commercial means.
The alginic Acid Dialdehyde (ADA) in the present disclosure may be obtained from seaweed such as brown seaweed or derivatives thereof by various methods. In some of these embodiments, the molecular weight of the alginic acid dialdehydes in the present disclosure is about 10000-150000g/mol.
In some of these embodiments, the method of preparing the alginic Acid Dialdehyde (ADA) is as follows. Dissolving alginic acid or sodium alginate (1-40% w/v) in deionized water or ultrapure (Mill Q) water (200-4000 mL), adding 50-800mL ethanol (90-98% (v/v)) and sodium (meta) periodate (NaIO) 4 2-100 g), and the solution is continuously stirred or shaken and reacted for 12-34 hours at the temperature of 15-80 ℃ in the dark. Ethylene glycol (20-100 mL) was added and the reaction was continued with stirring or shaking at 15-80℃for 1-5 hours to reduce excess periodate. To precipitate ADA, 5-20g of sodium salt (e.g., sodium chloride) and 800-2000mL of 70-98% ethanol are added, the solution is stirred for 1-2 hours, and left to stand for 1-6 hours. After ADA precipitation, it was filtered and washed 3 times with 20-60% ethanol. The ADA solution was dialyzed using a dialysis membrane or tube (MWCO 1000-3500 Da) or a desalting column and deionized water or ultrapure water to remove sodium salts and obtain an ADA solution. The ADA obtained can be used as it is or stored at-4-25deg.C for use, or freeze-dried with a freeze dryer, and the water is removed to obtain ADA powder.
In a first aspect of the present disclosure, there is provided a polyethyleneimine functionalized material comprising a support layer and a connection layer; the support layer is composed of one or more porous or non-porous materials, the tie layer comprises a polyethyleneimine, and the polyethyleneimine is directly and/or indirectly bonded to the support layer by a means selected from covalent bonding, electrostatic adsorption, hydrogen bonding, or any combination thereof; wherein the tie layer is capable of binding to the functional material by a means selected from covalent bonding, electrostatic adsorption, hydrophilic adsorption, hydrophobic adsorption, hydrogen bonding, or any combination thereof.
In some of these embodiments, the tie layer may consist of only polyethylenimine, which is then directly bonded to the support layer. But in order to further increase the stability of the PEI and the functional layer, in other embodiments the tie layer may also comprise alginic acid dialdehyde. In still other embodiments, the tie layer may be comprised of polyethylenimine and alginic acid dialdehyde.
In embodiments in which the tie layer comprises alginic acid dialdehyde, the alginic acid dialdehyde is associated with the support layer and/or the polyethyleneimine by a means selected from covalent bonding, electrostatic adsorption, hydrogen bonding, or any combination thereof.
In some of these embodiments, the mass ratio of the connection layer to the support layer is about 1:100 to about 1:10. In some of these embodiments, the mass ratio of the connection layer to the support layer is about 1:50 to about 1:20.
In some of these embodiments, the mass ratio of alginic acid dialdehyde to polyethyleneimine in the functionalizing material is 100:1 to 10:1. In some of these embodiments, the mass ratio of alginic acid dialdehyde to polyethyleneimine in the functionalizing material is 50:1 to 20:1.
In a second aspect of the present disclosure, there is provided a polyethyleneimine modified material comprising the polyethyleneimine functionalized material described above and a functional layer consisting of a functional material capable of bonding to the connecting layer by a means selected from covalent bonding, electrostatic adsorption, hydrophilic adsorption, hydrophobic adsorption, hydrogen bonding, or any combination thereof. In some of these embodiments, the functional material is an antimicrobial material, thereby resulting in a polyethyleneimine modified functional material or a polyethyleneimine antimicrobial modified material.
In some embodiments, the functional layer of the polyethyleneimine modified material comprises 0.1% -1% of the antimicrobial material by weight of the modified material. In some of these embodiments, the antimicrobial material of the functional layer comprises 0.3% to 0.6% by weight of the total mass of the modified material.
In some embodiments of the present disclosure, the porous or non-porous material may be selected from one or more polymers, composites, or any combination thereof. In some of these embodiments, the porous or non-porous material may be a polymer, a composite, a membrane, a sheet, a filter, a nonwoven fiber, or any combination thereof. The pore size of the porous or nonporous material may be any pore size. In some of these embodiments, the pore size of the porous material may be between 0.001-10 μm.
In some embodiments of the present disclosure, the polymer or composite may be selected from polypropylene, cellulose, regenerated cellulose, polyvinylidene fluoride (Polyvinylidene Fluoride, PVDF), polyethersulfone (Polyether Sulfone, PES), polystyrene, polytetrafluoroethylene (PTFE), polyethylene, polyimide, polyamide (such as polyhexamethylene adipamide, commonly known as nylon 66), or any combination thereof.
In some embodiments of the present disclosure, the functional material may be an antimicrobial material, such as an antimicrobial chemical, to form an efficient and durable antimicrobial modified material.
"antimicrobial" in this application refers to the killing or inhibition of microorganisms. Microorganisms are generally a collective term for all micro-organisms that an individual has difficulty observing with the naked eye. Microorganisms include bacteria, viruses, fungi, few algae, etc., and are classified into space microorganisms, marine microorganisms, etc., according to the different environments present, and prokaryotic microorganisms and eukaryotic microorganisms according to the cell organization. In some embodiments of the present disclosure, the microorganism may be selected from, for example, but not limited to, bacteria, fungi, viruses, or any combination thereof. In some embodiments, the microorganism is selected from bacteria, fungi, viruses, and the like.
The broad sense of bacteria is prokaryotes, which means a large group of cell nucleus coreless membrane-coated, primitive single cell organisms with only naked DNA called pseudonuclear region (or pseudonucleus), including eubacteria (eubacteria) and archaea (archaea). The bacteria are generally called as narrow bacteria, the narrow bacteria are prokaryotic microorganisms, are small and short in shape and simple in structure, and are most organisms which are most widely distributed in nature and have the largest number of individuals. Some bacteria become pathogens, resulting in tetanus, typhoid fever, pneumonia, syphilis, cholera, and tuberculosis. In some of these embodiments, the bacteria may be gram positive and/or gram negative. In some embodiments, the bacteria are selected from klebsiella pneumoniae (Klebsiella pneumoniae), chlamydia pneumoniae (Chlamydia pneumoniae), streptococcus pneumoniae (Streptococcus pneumoniae), mycobacterium tuberculosis (Mycobacterium tuberculosis), streptococcus group a (Streptococcus Group A), corynebacterium diphtheriae (Corynebacterium diphtheriae), haemophilus influenzae (Haemophilus influenzae), neisseria meningitidis (Neisseria meningitidis), clostridium difficile (Clostridium difficile), methicillin-resistant staphylococcus aureus (Methicillin-Resistant Staphylococcus aureus, MRSA), vancomycin-resistant enterococcus (Vancomycin-Resistant Enterococci, VRE), acinetobacter baumannii (Acinetobacter baumannii), and the like.
Fungi (Fungis) is a class of eukaryotes. The most common fungi are the various classes of mushrooms, and in addition fungi include molds and yeasts. Fungi pathogenic to humans are classified into superficial fungi, which invade the skin, hair, nails, which are chronic and refractory to treatment, but less affecting the body, and deep fungi, which invade the viscera of the whole body, which can seriously cause death. In addition, some fungi are parasitic in foods, feeds and foods, and can produce toxins to cause toxic mycosis. In some of these embodiments, the fungus is selected from the group consisting of Pneumocystis (Pneumocystis), aspergillus (Aspergillus, such as Aspergillus nii (Aspergillus Niger)), coccoides (coccoides), blastomyces (blastmyces), candida (Candida), mucor (mucormycetes), sporothrix (sporthrix), dermatophytes (dermotophytis), and the like.
Viruses (viruses) are non-cellular forms composed of nucleic acid molecules (DNA or RNA) and a protective outer shell of proteins, and are organic species that live parasitically between living and non-living organisms. By the mechanism of infection, viruses can self-replicate using the host's cellular system, but cannot grow and replicate independently. Viruses can infect almost all living organisms with cellular structures. The viral particles are approximately one percent of the bacterial size. Human diseases caused by viruses are various, and common diseases such as common cold, influenza, varicella and the like, and serious diseases such as smallpox, AIDS, SARS, avian influenza and the like are determined, and some diseases may take viruses as pathogenic factors. Viruses are also one of the factors that cause cancer. In some of these embodiments, the virus is selected from the group consisting of respiratory syncytial (sin-SISH-uhl) virus, hepatitis virus, varicella virus, poliovirus, smallpox virus, measles virus, mumps virus, chlamydia trachomatis (Chlamydia trachomatis), influenza virus (e.g., myxovirus influenzae), SARS-CoV virus, SARS-CoV-2 virus, H1N1 virus, H5N7 virus, MERS-CoV virus, ebola (Ebola) virus, and the like.
In some embodiments of the present disclosure, the antimicrobial material may be selected from amino acids, quaternary ammonium compounds, chlorhexidine compounds, alexidine compounds, biguanides, or any combination thereof.
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 character to the surface and are also zwitterionic, thus having antimicrobial action, possibly by similar means, to disrupt the viral envelope.
The quaternary ammonium compound is a quaternary ammonium cation compound formed by substituting 4 hydrogen ions in ammonium ions with hydrocarbon groups. In some embodiments of the present disclosure, the quaternary ammonium compound may be selected from alkyl dimethyl benzyl ammonium chloride, alkyl didecyl dimethyl ammonium chloride, dialkyl dimethyl ammonium chloride, and dialkyl quaternary ammonium salts, or any combination thereof. In some of these embodiments, the quaternary ammonium compound is selected from benzalkonium chloride, cetyltrimethylammonium chloride (HTMA-Cl), stearyl dimethylbenzyl ammonium chloride (SMBA-Cl), didecyl dimethyl ammonium bromide, dioctyl dimethyl ammonium bromide, or any combination thereof. Quaternary ammonium compounds, because of their unique molecular structure, impart a number of physicochemical properties to them, such as emulsification, dispersion, solubilization, foaming, defoaming, sterilization, coagulation, corrosion protection, etc., and among their many unique properties and corresponding practical applications, excellent antimicrobial properties have attracted particular attention. Quaternary ammonium compounds can be used as antiviral, antibacterial and antifungal agents in solution. Quaternary ammonium compounds act as bactericides and microbiocides by inactivating energy generating enzymes, denaturing essential cellular proteins, destroying cellular material, and by disrupting intermolecular interactions.
Chlorhexidine, also known as chlorhexidine, has a chemical name of chlorhexidine, is a cationic surfactant, has quite strong broad-spectrum antibacterial and bactericidal effects, and is a better bactericidal disinfectant. Chlorhexidine compounds refer to a generic term for a class of compounds that contain a chlorhexidine structure. In some embodiments of the present disclosure, the chlorhexidine compound can be chlorhexidine digluconate and/or chlorhexidine dihydrochloride.
Alexidine is also called as Jielian Xin Gua, is a nitrogenous organic substance, has quite strong broad-spectrum antibacterial and bactericidal effects, is a better bactericidal disinfectant, has antibacterial effects on gram positive and negative bacteria, and is effective even in the presence of serum, blood and the like. Alexidine compounds refer to the generic name for a class of compounds containing the structure of alexidine. In some embodiments of the disclosure, the alexidine compound is alexidine dihydrochloride.
Biguanide is named 1- (diaminomethylene) guanidine, and is a good bactericidal disinfectant. Biguanide compounds are a generic term for a class of compounds containing biguanide structures. In some embodiments of the present disclosure, the biguanide compound is phenyl biguanide (1- (3-chlorophenyl) biguanide hydrochloride).
Chlorhexidine compounds, alexidine compounds or biguanides act as antiviral, antibacterial and antifungal agents, and for bacteria, according to a general understanding, the molecules of these compounds bind to the cell wall of the bacteria, destroying the stability of the cell wall, they affect the integrity of the cell wall at low concentrations and enter the cell itself after the cell wall is damaged, attacking the cytoplasmic material (inner material). The semipermeable material that damages the cytoplasm causes leakage of the internal components, resulting in cell death. Similarly, for fungi, the compounds compromise the integrity of the cell wall and cytoplasmic material, enter the cytoplasm, leading to leakage of cell contents and cell death. Likewise, for viruses, the compounds may kill the virus by disrupting the viral structure.
In some embodiments of the present disclosure, there is provided a polyethyleneimine antibacterial modifying material, for example selected from the group consisting of polypropylene-polyethylenimine-cysteine, polypropylene-polyethylenimine-benzalkonium chloride, polypropylene-polyethylenimine-chlorhexidine, polypropylene-polyethylenimine-phenylbiguanide, cellulose-polyethylenimine-cysteine, cellulose-polyethylenimine-benzalkonium chloride, cellulose-polyethylenimine-phenylbiguanide, nylon-polyethylenimine-cysteine, nylon-polyethylenimine-benzalkonium chloride, nylon-polyethylenimine-chlorhexidine, nylon-polyethylenimine-phenylbiguanide, polypropylene-alginic acid dialdehyde-polyethylenimine-cysteine, polypropylene-alginic acid dialdehyde-polyethylenimine-chlorhexidine, polypropylene-polyethylenimine-phenylbiguanide, cellulose-alginic acid dialdehyde-cysteineine, cellulose-polyethylenimine-phenylbiguanide, cellulose-polyethylenimine-cysteine, cellulose-polyethylenimine-phenylbiguanide, cellulose-polyethyleneimine-phthalimide-phenylbiguanide, cellulose-alginic acid dialdehyde-chlorhexidine, nylon-polyethyleneimine-phenylbiguanide, nylon-alginic acid dialdehyde-phenylbiguanide, polyamide-alginic acid, polyethylenimine-cysteine, and nylon-fluoroethyleneimine-cysteine, nylon-alginic acid dialdehyde-polyethylenimine-chlorhexidine, nylon-alginic acid dialdehyde-polyethylenimine-phenyl biguanide, or any combination thereof.
In some embodiments of the present disclosure, there is provided a polyethyleneimine antifungal modifying material, for example selected from the group consisting of polypropylene-polyethylenimine-cysteine, polypropylene-polyethylenimine-benzalkonium chloride, polypropylene-polyethylenimine-chlorhexidine, polypropylene-polyethylenimine-phenylbiguanide, cellulose-polyethylenimine-cysteine, cellulose-polyethylenimine-benzalkonium chloride, cellulose-polyethylenimine-phenylbiguanide, nylon-polyethylenimine-cysteine, nylon-polyethylenimine-benzalkonium chloride, nylon-polyethylenimine-chlorhexidine, nylon-polyethylenimine-phenylbiguanide, polypropylene-alginic acid dialdehyde-polyethylenimine-cysteine, polypropylene-alginic acid dialdehyde-polyethylenimine-chlorhexidine, polypropylene-polyethylenimine-phenylbiguanide, cellulose-alginic acid dialdehyde-cysteineine, cellulose-polyethylenimine-phenylbiguanide, cellulose-polyethylenimine-cysteine, cellulose-polyethylenimine-phenylbiguanide, cellulose-polyethyleneimine-phthalimide-phenylbiguanide, cellulose-alginic acid dialdehyde-chlorhexidine, nylon-polyethyleneimine-phenylbiguanide, nylon-alginic acid dialdehyde-phenylbiguanide, polyamide-alginic acid, polyethylenimine-cysteine, and nylon-fluoroethyleneimine-cysteine, nylon-alginic acid dialdehyde-polyethylenimine-chlorhexidine, nylon-alginic acid dialdehyde-polyethylenimine-phenyl biguanide, or any combination thereof.
In some embodiments of the present disclosure, a polyethyleneimine antiviral modifying material is provided, such as 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.
In some embodiments of the present disclosure, the anti-bacterial activity of the polyethyleneimine antimicrobial modified materials of the present disclosure was tested, and the modified materials were found to have 100% inhibition to both gram positive and negative bacteria, and good stability. In some of these embodiments, the polyethylenimine antimicrobial modified material is a polypropylene-based PEI antimicrobial modified material or 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-chlorhexidine, polypropylene-polyethyleneimine-phenylbiguanide, cellulose-polyethyleneimine-cysteine, cellulose-polyethyleneimine-benzalkonium chloride, cellulose-polyethyleneimine-chlorhexidine, cellulose-polyethyleneimine-phenylbiguanide, nylon-polyethyleneimine-cysteine, nylon-polyethyleneimine-benzalkonium chloride, nylon-polyethyleneimine-chlorhexidine, nylon-polyethyleneimine-phenylbiguanide, polypropylene-alginic acid dialdehyde-polyethyleneimine-cysteine, polypropylene-alginic acid dialdehyde-polyethyleneimine-benzalkonium chloride, polypropylene-alginic acid dialdehyde-chlorhexidine, polypropylene-alginic acid dialdehyde-polyethyleneimine-phenylbiguanide, cellulose-polyethyleneimine-cysteine, cellulose-polyethyleneimine-dialdehyde-polyethyleneimine-phenylbiguanide, nylon-polyethyleneimine-benzalkonium chloride, nylon-dialdehyde-polyethyleneimine-benzalkonium chloride, nylon-polyethyleneimine-chlorhexidine, nylon-polyethyleneimine-benzalkonium chloride, polypropylene-dialdehyde-alginic acid dialdehyde-polyethyleneimine-benzalkonium chloride, and nylon-polyethyleneimine-benzalkonium chloride, nylon-alginic acid dialdehyde-polyethylenimine-chlorhexidine, nylon-alginic acid dialdehyde-polyethylenimine-phenyl biguanide, or any combination thereof. In some of these embodiments, the gram positive bacterium is micrococcus lywalli (Micrococcus lysodeikticus). In some of these embodiments, the gram negative bacteria is escherichia coli (e.coli).
In some embodiments of the present disclosure, the modified materials of the present disclosure, which are antimicrobial, were tested for antifungal activity and found to have 100% inhibition of fungi, and good stability. In some of these embodiments, the polyethylenimine antimicrobial modified material is a polypropylene-based PEI antimicrobial modified material or 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-chlorhexidine, polypropylene-polyethyleneimine-phenylbiguanide, cellulose-polyethyleneimine-cysteine, cellulose-polyethyleneimine-benzalkonium chloride, cellulose-polyethyleneimine-chlorhexidine, cellulose-polyethyleneimine-phenylbiguanide, nylon-polyethyleneimine-cysteine, nylon-polyethyleneimine-benzalkonium chloride, nylon-polyethyleneimine-chlorhexidine, nylon-polyethyleneimine-phenylbiguanide, polypropylene-alginic acid dialdehyde-polyethyleneimine-cysteine, polypropylene-alginic acid dialdehyde-polyethyleneimine-benzalkonium chloride, polypropylene-alginic acid dialdehyde-chlorhexidine, polypropylene-alginic acid dialdehyde-polyethyleneimine-phenylbiguanide, cellulose-polyethyleneimine-cysteine, cellulose-polyethyleneimine-dialdehyde-polyethyleneimine-phenylbiguanide, nylon-polyethyleneimine-benzalkonium chloride, nylon-dialdehyde-polyethyleneimine-benzalkonium chloride, nylon-polyethyleneimine-chlorhexidine, nylon-polyethyleneimine-benzalkonium chloride, polypropylene-dialdehyde-alginic acid dialdehyde-polyethyleneimine-benzalkonium chloride, and nylon-polyethyleneimine-benzalkonium chloride, nylon-alginic acid dialdehyde-polyethylenimine-chlorhexidine, nylon-alginic acid dialdehyde-polyethylenimine-phenyl biguanide, or any combination thereof. In some of these embodiments, the fungus is saccharomyces cerevisiae.
In some embodiments of the present disclosure, detection of antiviral activity of the polyethyleneimine antimicrobial modified materials of the present disclosure has been found to provide at least a 2.5log reduction in virus relative to a virus control. In some of these embodiments, the measured viral reduction is in the range of 2.5 to 5 log. In some of these embodiments, the viral reduction is in the range of 3.0 to 4.0 log. In some of these embodiments, the polyethylenimine antimicrobial modified material is a polypropylene-based polyethylenimine antimicrobial modified material or a nylon-based polyethylenimine antimicrobial modified material. In some of these embodiments, the polyethylenimine antimicrobial modifying material is selected from the group consisting of polypropylene-polyethylenimine-benzalkonium chloride, polypropylene-polyethylenimine-chlorhexidine, nylon-polyethylenimine-benzalkonium chloride, nylon-polyethylenimine-chlorhexidine, polypropylene-alginic acid dialdehyde-polyethylenimine-benzalkonium chloride, polypropylene-alginic acid dialdehyde-polyethylenimine-chlorhexidine, nylon-alginic acid dialdehyde-polyethylenimine-chlorhexidine, or any combination thereof. In some of these embodiments, the virus is the novel coronavirus SARS-CoV-2.
In a third aspect of the present disclosure, there is provided a process for preparing the aforementioned polyethyleneimine functionalized material, comprising the steps of: after mixing the porous material or the non-porous material with the polyethyleneimine aqueous solution, the mixture is subjected to shaking reaction at 60-200rpm at a temperature of 10-100 ℃ and a pH of 5-11 for 10 minutes to 24 hours.
In some of these embodiments, the method further comprises the steps of: the porous or non-porous material is mixed with an aqueous solution of alginic acid dialdehyde before adding the aqueous solution of polyethylenimine or after reacting the porous or non-porous material with the aqueous solution of polyethylenimine, and then reacted with shaking at 60-200rpm at a temperature of 10-100 ℃ and a pH of 1.5-8 for 10 minutes to 24 hours.
That is, in some of these embodiments, the alginic acid dialdehyde may be reacted with the porous or non-porous material to form an alginic acid dialdehyde functionalized material, and then the polyethyleneimine may be reacted with the alginic acid dialdehyde functionalized material to form a functionalized material comprising both alginic acid dialdehyde and polyethyleneimine. In some of these embodiments, the polyethyleneimine may also be reacted with a porous or non-porous material to form a polyethyleneimine functionalized material, and then the alginic acid dialdehyde reacted with the polyethyleneimine functionalized material to form a functionalized material comprising both alginic acid dialdehyde and polyethyleneimine. And in some of these embodiments, the polyethyleneimine and the alginic acid dialdehyde may also be reacted simultaneously with the porous material or the non-porous material to form a functionalized material comprising both alginic acid dialdehyde and polyethyleneimine.
In some of these embodiments, the mass ratio of the sum of the polyethyleneimine contained in the aqueous polyethyleneimine solution and the alginic acid dialdehyde contained in the aqueous alginic acid dialdehyde solution to the porous material or the nonporous material is 1:100 to 1:10. In some of these embodiments, the mass ratio is 1:50 to 1:20.
In some of these embodiments, the mass ratio of the polyethyleneimine contained in the aqueous polyethyleneimine solution to the alginic acid dialdehyde contained in the aqueous alginic acid dialdehyde solution is 100:1 to 10:1.
In some of these embodiments, the aqueous solution of polyethylenimine has a pH of 5 to 11. In some of these embodiments, the temperature is 10-100 ℃. In some of these embodiments, the shaking speed is 60-200rpm. In some of these embodiments, the reaction time is 10 to 24 hours.
In some of these embodiments, the aqueous solution of alginic acid dialdehyde has a pH of 1.5-8. In some of these embodiments, the temperature is 10-100 ℃. In some of these embodiments, the shaking speed is 120-200rpm. In some of these embodiments, the reaction time is 10 to 24 hours.
In some of these embodiments, the aqueous polyethyleneimine solution is at a concentration of 10-1000mg/ml and is adjusted to an appropriate pH with an acid (e.g., sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, nitric acid); in some of these embodiments, the concentration is 50-500mg/ml; in some of these embodiments, the concentration is 20-100mg/ml.
In some of these embodiments, the aqueous alginic acid dialdehyde solution is 10-1000mg/ml in concentration and is adjusted to the appropriate pH with an acid (e.g., sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, nitric acid); in some of these embodiments, the concentration is 50-500mg/ml; in some of these embodiments, the concentration is 20-100mg/ml.
In a third aspect of the disclosure, alternatively, the method comprises the steps of: directly coating or spraying the polyethyleneimine water solution on the surface of the porous material or the nonporous material at the pH of 1.5-8, and drying at the temperature of 10-100 ℃ for 10 minutes to 24 hours to obtain the polyethyleneimine functionalized material.
In some of these embodiments, the method further comprises the steps of: before or after coating or spraying the aqueous polyethyleneimine solution, an aqueous solution of alginic acid dialdehyde is directly coated or sprayed on the surface of the porous or non-porous material at a pH of 1.5 to 8 and dried at a temperature of 10 to 100 ℃ for 10 minutes to 24 hours.
That is, in some of these embodiments, the alginic acid dialdehyde may be coated or sprayed onto the surface of the porous or non-porous material to form an alginic acid dialdehyde functionalized material, and then the polyethyleneimine may be coated or sprayed to form a functionalized material comprising both alginic acid dialdehyde and polyethyleneimine. In some of these embodiments, the polyethyleneimine may also be coated or sprayed onto the surface of the porous or non-porous material to form a polyethyleneimine functionalized material, and then the alginic acid dialdehyde may be coated or sprayed to form a functionalized material comprising both alginic acid dialdehyde and polyethyleneimine. And in some of these embodiments, the polyethyleneimine and the alginic acid dialdehyde may also be coated or sprayed simultaneously on the surface of the porous or nonporous material to form a functionalized material comprising both alginic acid dialdehyde and polyethyleneimine.
In some of these embodiments, the mass ratio of the sum of the polyethyleneimine contained in the aqueous polyethyleneimine solution and the alginic acid dialdehyde contained in the aqueous alginic acid dialdehyde solution to the porous material or the nonporous material is 1:100 to 1:10. In some of these embodiments, the mass ratio is 1:50 to 1:20.
In some of these embodiments, the mass ratio of the polyethyleneimine contained in the aqueous polyethyleneimine solution to the alginic acid dialdehyde contained in the aqueous alginic acid dialdehyde solution is 100:1 to 10:1.
In some of these embodiments, the temperature is 10-100 ℃. In some of these embodiments, the drying time is from 10 minutes to 1 hour. In some of these embodiments, the aqueous solution of polyethylenimine has a pH of 5 to 11.
In some of these embodiments, the temperature is 30-50 ℃. In some of these embodiments, the drying time is from 10 minutes to 1 hour. In some of these embodiments, the aqueous solution of alginic acid dialdehyde has a pH of 1.5-8.
In some of these embodiments, the PEI aqueous solution is at a concentration of 10-1000mg/ml and is adjusted to an appropriate pH with an acid (e.g., sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, nitric acid). In some of these embodiments, the concentration is 50-500mg/ml. In some of these embodiments, the concentration is 20-100mg/ml.
In some of these embodiments, the ADA aqueous solution is at a concentration of 10-1000mg/ml and is adjusted to an appropriate pH with an acid (e.g., sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, nitric acid). In some of these embodiments, the concentration is 50-500mg/ml. In some of these embodiments, the concentration is 20-100mg/ml.
In a fourth aspect of the present disclosure, there is provided a process for preparing the aforementioned polyethyleneimine modified material, comprising the steps of: adding the polyethyleneimine functionalized material or the polyethyleneimine functionalized material prepared according to the method into a functional material aqueous solution, and shaking at 60-200rpm for reaction for 10 minutes to 24 hours at the temperature of 10-100 ℃ and the pH of 1.5-8 to obtain the modified material; wherein the functional material is capable of binding to the tie layer by a means selected from covalent bonding, electrostatic adsorption, hydrophilic adsorption, hydrophobic adsorption, hydrogen bonding, or any combination thereof.
In some of these embodiments, the functional material comprises 0.1% to 1% by weight of the total mass of the modified material. In some embodiments, the mass percent is 0.3% -0.6%.
In some of these embodiments, the aqueous solution of the functional material has a pH of 1.5 to 8. In some of these embodiments, the temperature is 10-100 ℃. In some of these embodiments, the shaking speed is 120-200rpm. In some of these embodiments, the reaction time is 8-16 hours.
In some of these embodiments, the aqueous functional material solution is at a concentration of 10-100mg/ml and is adjusted to an appropriate pH with an acid (e.g., sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, nitric acid). In some of these embodiments, the concentration is 5-60mg/ml. In some of these embodiments, the concentration is 2-20mg/ml.
In one embodiment, the functional material is an antimicrobial material.
In a fourth aspect of the disclosure, alternatively, the method comprises the steps of: directly coating or spraying the functional material aqueous solution on the polyethyleneimine functionalized material, and drying at the temperature of 10-100 ℃ for 10 minutes to 24 hours to obtain the modified material; wherein the functional material is capable of being bonded to the tie layer by a means selected from covalent bonding, electrostatic adsorption, hydrophilic adsorption, hydrophobic adsorption, hydrogen bonding, or any combination thereof, and the aqueous solution of the functional material has a pH of 1.5 to 8.
In some of these embodiments, the functional material comprises 0.1% to 1% by weight of the total mass of the modified material. In some embodiments, the mass percent is 0.3% -0.6%.
In some of these embodiments, the aqueous solution of the functional material has a pH of 1.5 to 8. In some of these embodiments, the temperature is 10-100 ℃. In some of these embodiments, the drying time is 8-16 hours.
In some of these embodiments, the aqueous functional material solution is at a concentration of 10-100mg/ml and is adjusted to an appropriate pH with an acid (e.g., sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, nitric acid). In some of these embodiments, the concentration is 5-60mg/ml. In some of these embodiments, the concentration is 2-20mg/ml.
In one embodiment, the functional material is an antimicrobial material.
In a fifth aspect of the present disclosure, there is provided a process for preparing the aforementioned polyethyleneimine modified material, comprising the steps of: mixing a functional material with a polyethyleneimine aqueous solution to obtain a polyethyleneimine-functional material aqueous solution; the aqueous solution obtained in the above way and porous materials or non-porous materials are subjected to shaking reaction for 10 minutes to 24 hours at the temperature of 10 to 100 ℃ and the pH of 1.5 to 8 at 60 to 200rpm, so as to obtain the modified materials; wherein the functional material is capable of binding to the tie layer by a means selected from covalent bonding, electrostatic adsorption, hydrophilic adsorption, hydrophobic adsorption, hydrogen bonding, or any combination thereof.
In some of these embodiments, the method further comprises the steps of: the functional material is mixed with the aqueous solution of alginic acid dialdehyde before, after or simultaneously with the mixing of the functional material with the aqueous solution of polyethylenimine.
That is, the modified material containing both polyethyleneimine and alginic acid dialdehyde can be obtained by mixing the functional material with an aqueous solution of polyethyleneimine, then mixing it with an aqueous solution of alginic acid dialdehyde, and reacting with a porous material or a nonporous material. Alternatively, the functional material may be mixed with an aqueous solution of alginic acid dialdehyde first, then mixed with an aqueous solution of polyethylenimine and reacted with a porous or non-porous material to obtain a modified material containing both polyethylenimine and alginic acid dialdehyde. Or, the functional material can be mixed with the polyethyleneimine aqueous solution and the alginic acid dialdehyde aqueous solution simultaneously to form a functional material aqueous solution containing polyethyleneimine and alginic acid dialdehyde simultaneously, and the functional material aqueous solution is reacted with the porous material or the nonporous material to obtain the modified material containing polyethyleneimine and alginic acid dialdehyde simultaneously.
In some of these embodiments, the mass ratio of the functional material, the sum of polyethyleneimine and alginic acid dialdehyde, to the porous or non-porous material is (1-10): (10-100): 1000.
In some of these embodiments, the aqueous solution of polyethylenimine has a pH of 1.5 to 6. In some of these embodiments, the temperature is 40-60 ℃. In some of these embodiments, the shaking speed is 120-200rpm. In some of these embodiments, the reaction time is from 4 to 16 hours.
In some of these embodiments, the aqueous solution of alginic acid dialdehyde has a pH of 3-6. In some of these embodiments, the temperature is 40-70 ℃. In some of these embodiments, the shaking speed is 120-200rpm. In some of these embodiments, the reaction time is 8-16 hours.
In some of these embodiments, the aqueous polyethyleneimine solution is at a concentration of 10-1000mg/ml and is adjusted to an appropriate pH with an acid (e.g., sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, nitric acid). In some of these embodiments, the concentration is 50-500mg/ml.
In some of these embodiments, the concentration is 20-100mg/ml.
In some of these embodiments, the aqueous solution of alginic acid dialdehyde has a concentration of 10-1000mg/ml and is adjusted to an appropriate pH with an acid (e.g., sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, nitric acid). In some of these embodiments, the concentration is 50-500mg/ml. In some of these embodiments, the concentration is 20-100mg/ml.
In one embodiment, the functional material is an antimicrobial material.
In the method according to the fifth aspect of the present disclosure, alternatively, the method includes the steps of: mixing a functional material with a polyethyleneimine aqueous solution to obtain a polyethyleneimine-functional material aqueous solution; directly coating or spraying the aqueous solution obtained in the above to the surface of a porous material or a non-porous material at a pH of 1.5-8, and drying at a temperature of 10-100 ℃ for 10 minutes to 24 hours to obtain the modified material; wherein the functional material is capable of binding to the tie layer by a means selected from covalent bonding, electrostatic adsorption, hydrophilic adsorption, hydrophobic adsorption, hydrogen bonding, or any combination thereof.
In some of these embodiments, the method further comprises the steps of: the functional material is mixed with the aqueous solution of alginic acid dialdehyde before, after or simultaneously with the mixing of the functional material with the aqueous solution of polyethylenimine.
That is, the modified material containing both polyethyleneimine and alginic acid dialdehyde can be obtained by mixing the functional material with an aqueous polyethyleneimine solution, then mixing it with an aqueous alginic acid dialdehyde solution, and coating or spraying the mixture on the surface of the porous material or the nonporous material. Alternatively, the functional material may be mixed with an aqueous solution of alginic acid dialdehyde first, then mixed with an aqueous solution of polyethyleneimine and coated or sprayed onto the surface of the porous material or the nonporous material to obtain a modified material containing both polyethyleneimine and alginic acid dialdehyde. Or, the functional material may be mixed with the aqueous solution of polyethylenimine and the aqueous solution of alginic acid dialdehyde simultaneously, and then coated or sprayed onto the surface of the porous material or the nonporous material to obtain a modified material containing polyethylenimine and alginic acid dialdehyde simultaneously. In some of these embodiments, the mass ratio of the functional material, the sum of polyethyleneimine and alginic acid dialdehyde, to the porous or non-porous material is (1-10): (10-100): 1000.
In some of these embodiments, the aqueous solution of polyethylenimine has a pH of 5 to 11. In some of these embodiments, the aqueous solution of alginic acid dialdehyde has a pH of 1.5-8. In some of these embodiments, the temperature is 10-100 ℃. In some of these embodiments, the drying time is from 10 minutes to 24 hours.
In some of these embodiments, the aqueous polyethyleneimine solution is at a concentration of 10-1000mg/ml and is adjusted to an appropriate pH with an acid (e.g., sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, nitric acid). In some of these embodiments, the concentration is 50-500mg/ml. In some of these embodiments, the concentration is 20-100mg/ml.
In some of these embodiments, the aqueous solution of alginic acid dialdehyde has a concentration of 10-1000mg/ml and is adjusted to an appropriate pH with an acid (e.g., sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, nitric acid). In some of these embodiments, the concentration is 50-500mg/ml. In some of these embodiments, the concentration is 20-100mg/ml.
In one embodiment, the functional material is an antimicrobial material.
In some embodiments, the method described in the third, fourth, and fifth aspects of the present disclosure further comprises the steps of: after washing the resulting product, it is stored wet or air-dried or oven-dried.
In some of these embodiments, the above-described products may be washed with a detergent and/or water. In some of these embodiments, the functionalized material comprising both alginic acid dialdehyde and polyethyleneimine may be washed with a detergent and water while retaining its activity. In some of these embodiments, the detergent may be selected from any neutral detergent. As used herein, "neutral detergent" refers to a detergent having a pH in the range of from 6 to 8 at standard use concentrations of 25 ℃. For example, the neutral detergent may be any one or more selected from the group consisting of: bases (e.g., sodium carbonate, borax), surfactants (e.g., alkyl sulfate, sodium lauryl sulfate, alkyl ethoxy sulfate, or fatty alcohol ether), functional materials (e.g., pH adjuster, gloss enhancer, water adjuster, 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).
In a sixth aspect of the present disclosure there is provided the use of a polyethyleneimine functionalized material, a polyethyleneimine modified material or a method of preparation thereof as described in the preceding aspects in the manufacture of medical and antimicrobial articles.
In some of these embodiments, the use includes the production of masks, barrier gowns, gloves, personal protective articles, bandages, medical tapes, medical caps, medical sheets, medical garments, air filters, water filters, electronics, household appliances, and automotive parts, among others.
The polyethyleneimine functionalized material and the polyethyleneimine modified material and the preparation method thereof have various beneficial effects. For example, raw materials are economical, environment-friendly and safe; the support layer (substrate layer) may be made of various common substrate materials with arbitrary pore diameters, polyethyleneimine is conveniently commercially available or self-synthesized, and the antimicrobial material may be made of economical and safe amino acids, quaternary ammonium salts, chlorhexidine, biguanides, and the like. For another example, the preparation method is simple, the raw materials are easy to obtain, the cost is low, no irritating organic solvent is needed, and the preparation method is environment-friendly and easy to expand the production scale. In addition, it has high inhibitory activity against bacteria (including gram positive and negative bacteria), fungi and viruses, reducing the risk of secondary infections. Therefore, the invention has great application potential in the fields of biology, medicine, sanitation and the like. Wherein, the polyethyleneimine modified material obtained by taking the polyethyleneimine alone as a connecting layer has excellent antibacterial, antifungal and antiviral effects. However, in order to further improve the stability, alginic acid dialdehyde is also added, and the polyethyleneimine modified material obtained by adding alginic acid dialdehyde also has excellent antibacterial, antifungal and antiviral effects.
The chemicals in the following examples, unless otherwise specified, were all from commercial sources and will not be described again.
Example 1: preparation of Polyethylenimine (PEI) antimicrobial modified materials
This example is an example of the preparation of a polyethyleneimine antimicrobial modified material, wherein the porous or non-porous material is exemplified by polypropylene-based, nylon-based (exemplified by a nylon 66 composite based on polyhexamethylene adipamide), and cellulosic materials, and the antimicrobial material is exemplified by cysteine, benzalkonium chloride, chlorhexidine, phenyl biguanide (1- (3-chlorophenyl) biguanide hydrochloride). Polypropylene based materials were purchased from Tansole China (product number: MFPP 047020), cellulose materials were purchased from General Electronics (GE) Whatman (product number: GB/T1914-2007), and nylon (polyhexamethylene adipamide, nylon 66) were purchased from Merck Millipore (product number: GNWP 04700).
1. Preparing PEI functionalized material:
1.1 preparation of a functionalized material containing only PEI:
the PEI-only functionalized material was prepared in one of the following ways:
the method comprises the following steps: respectively taking 10g of the porous material or the non-porous material, cleaning, immersing into a PEI aqueous solution containing 0.1-1g of PEI with the pH of 5-11, and reacting for 30 minutes to 3 hours under shaking at 60 ℃ and 120rpm to obtain the functionalized material only containing PEI. After the reaction, the obtained PEI functionalized material was washed with distilled water.
The second method is as follows: and respectively taking 10g of the porous material or the non-porous material, cleaning, directly coating or spraying a PEI aqueous solution containing 0.1-1g of PEI with the pH of 5-11 on the surface of the material at 60 ℃, and then drying at room temperature for 8 hours to obtain the functionalized material only containing PEI.
The products prepared above are polypropylene-PEI functionalized material, cellulose-PEI functionalized material and nylon-PEI functionalized material.
1.2 preparation of functionalized materials comprising ADA and PEI:
1.2.1 ADA functionalized materials were prepared in one of the following ways:
the method comprises the following steps: respectively taking 10g of the porous material or the nonporous material, cleaning, immersing into an ADA aqueous solution containing 0.1-1g of ADA with the pH of 3-6, and reacting for 30 minutes to 3 hours at the temperature of between room temperature and 100 ℃ under shaking of 80-120rpm to obtain the ADA functionalized material. After the reaction, the resulting ADA functionalized material was washed with distilled water.
The second method is as follows: and respectively taking 10g of the porous material or the nonporous material, cleaning, directly coating or spraying an ADA aqueous solution containing 0.1-1g of ADA and having the pH of 3-6 on the surface of the material at the temperature of between room temperature and 100 ℃, and then drying at the temperature of 30 ℃ for 8 hours to obtain the ADA functionalized material.
The products prepared above were polypropylene-ADA functionalized material, cellulose-ADA functionalized material and nylon-ADA functionalized material.
1.2.2.2 preparation of functionalized materials comprising ADA and PEI (ADA-PEI functionalized materials) in one of the following ways:
the method comprises the following steps: respectively taking 10g of the ADA functionalized material, immersing the ADA functionalized material into a PEI aqueous solution containing 0.01-0.1g of PEI with the pH of 5-10, and reacting for 30 minutes to 3 hours at the temperature of between room temperature and 70 ℃ under shaking at the speed of 80-120rpm to obtain the ADA-PEI functionalized material. After the reaction, the resulting ADA-PEI functionalized material was washed sequentially with a neutral detergent and distilled water.
The second method is as follows: 10g of the ADA functionalized material is respectively taken, and a PEI aqueous solution containing 0.01-0.1g of PEI and having the pH of 5-10 is directly coated or sprayed on the surface of the material at the room temperature to 70 ℃. After the reaction, the resulting ADA-PEI functionalized material was washed with a detergent and distilled water in this order. And then drying for 8 hours at room temperature to obtain the ADA-PEI functionalized material.
The products prepared above were polypropylene-ADA-PEI functionalized material, cellulose-ADA-PEI functionalized material and nylon-ADA-PEI functionalized material.
2. Preparation of PEI antimicrobial modified material:
the PEI antimicrobial modified material is prepared in one of the following ways:
the method comprises the following steps: respectively taking 10g of PEI functionalized material and 10-1000mg of the antimicrobial material aqueous solution with pH of 5-8, and carrying out a reaction for 30 minutes to 3 hours at room temperature under shaking at 120rpm to obtain a PEI microorganism modified material;
The second method is as follows: directly coating or spraying 10-1000mg of the aqueous solution of the antimicrobial material with the pH value of 5-8 on the surface of 10g of PEI functional material, and then drying for 8 hours at room temperature to obtain the PEI microbial modified material;
and a third method: mixing 10-100mg of antimicrobial material and 0.01-0.1g of PEI, mixing with Milli Q ultrapure water, and regulating pH to 3-7 to obtain an aqueous solution of PEI antimicrobial material; taking 10g of porous material or non-porous material and the obtained PEI antimicrobial material aqueous solution to react for 0.5-3 hours at room temperature under shaking of 80-120rpm, thus obtaining the antimicrobial modified material only containing PEI. The preparation method of the ADA-PEI antimicrobial modified material is similar to the above, and the antimicrobial material and the ADA are mixed before the antimicrobial material and the PEI are mixed, and then the PEI is added for mixing, and then the shaking step is carried out;
the method four: mixing 10-100mg of antimicrobial material with 0.01-0.1g of PEI, mixing with Milli Q ultrapure water, and regulating pH to 3-7 to obtain an aqueous solution of PEI antimicrobial material; the aqueous solution obtained in the above is directly coated or sprayed on the surface of 10g of porous material or non-porous material and dried for 8 hours at room temperature, thus obtaining the PEI antimicrobial modified material only containing PEI. The preparation of the ADA-PEI antimicrobial modified material is similar to that described above, except that the antimicrobial material is mixed with ADA before mixing with PEI, then PEI is added to mix, and then a coating or spraying step is performed.
The products prepared in the above way are polypropylene-PEI-cysteine modified material, polypropylene-PEI-benzalkonium chloride modified material, polypropylene-PEI-chlorhexidine modified material and polypropylene-PEI-phenyl biguanide modified material; cellulose-PEI-cysteine modified material, cellulose-PEI-benzalkonium chloride modified material, cellulose-PEI-chlorhexidine modified material, cellulose-PEI-phenyl biguanide modified material; nylon-PEI-cysteine modified material, nylon-PEI-benzalkonium chloride modified material, nylon-PEI-chlorhexidine modified material, nylon-PEI-phenyl biguanide modified material, polypropylene-ADA-PEI-cysteine, polypropylene-ADA-PEI-benzalkonium chloride, polypropylene-ADA-PEI-chlorhexidine, polypropylene-ADA-PEI-phenyl biguanide, cellulose-ADA-PEI-cysteine, cellulose-ADA-PEI-benzalkonium chloride, cellulose-ADA-PEI-chlorhexidine, cellulose-ADA-PEI-phenyl biguanide, nylon-ADA-PEI-cysteine, nylon-ADA-PEI-benzalkonium chloride, nylon-ADA-PEI-chlorhexidine, nylon-ADA-PEI-phenyl biguanide.
The PEI modified material product obtained in the above way can be stored after being washed for a plurality of times for other purposes, for example, being used as other protective materials such as protective clothing and the like.
Example 2: XPS characterization of PEI antimicrobial modified materials
The surface atomic ratio of the PEI antimicrobial modified material prepared in example 1 was measured by X-ray photoelectron spectroscopy (XPS), and this example exemplifies the PEI antimicrobial modified material (nylon-ADA-PEI-benzalkonium chloride) prepared by method one of preparing a functionalized material containing ADA and PEI and method one of preparing a PEI antimicrobial modified material in example 1, 1.2.
Table 1: surface atomic ratio of the sample obtained according to XPS.
As shown in fig. 1 and table 1, after coating nylon with ADA, the oxygen atom content in ADA was rich, so that nylon-ADA was increased compared to nylon oxygen atom content. After the PEI coating was added, the PEI coating on the nylon-ADA-PEI increased the nitrogen atoms from 10.88% to 20.36%. Further, the benzalkonium chloride coating on nylon-ADA-PEI-benzalkonium chloride increased the carbon atom ratio while the presence of chlorine atoms was also detected. Thus XPS confirmed the successful functionalization of the PEI antimicrobial modified material.
Example 3: determination of antibacterial Activity of PEI antimicrobial modified Material
This example tests the antimicrobial activity of the polypropylene-based, cellulose-based, nylon-based PEI antimicrobial modified materials prepared in example 1. This example exemplifies the PEI antimicrobial modified material prepared by the method one of example 1 (method one of the functionalized material containing only PEI and method one of the functionalized material containing ADA and PEI) and the method one of the antimicrobial modified material prepared by the method one of example 1, but highly similar results were obtained with the other methods of example 1.
I. The experimental method comprises the following steps:
taking gram-positive bacteria Micrococcus wall (Micrococcus lysodeikticus) and gram-negative bacteria Escherichia coli (E.coli) as examples, an antibacterial activity test was performed by using polypropylene-PEI-antimicrobial material, cellulose-PEI-antimicrobial material and nylon-PEI-antimicrobial material, polypropylene-ADA-PEI-antimicrobial material, cellulose-ADA-PEI-antimicrobial material and nylon-ADA-PEI-antimicrobial material, respectively, and the samples were averaged in triplicate.
Micrococcus lywallicum and E.coli were cultured overnight with LB (Luria-Bertani) medium under stirring at 37℃and the fresh bacterial culture was diluted to a colony count of 10 -4 CFU/ml bacterial suspension; 0.1g of the antimicrobial modified material was mixed with 10mL of the bacterial suspension and placed in a flask and incubated at 120rpm shaker and 37℃for 2 hours. Another 10mL of bacteria was takenThe suspension was placed alone in another flask without modifying material as a control. After the reaction, 10-100. Mu.l of the bacterial suspension was inoculated on LB agar plates and cultured at 37℃for 18-36 hours; after 18 hours of incubation, the number of viable colonies was counted by plate counting.
The bacterial inhibition activity was calculated according to the following formula:
wherein I represents a bacterial inhibitory activity, N 0 Represents the colony count after the culture of the control group, N i The number of colonies after the treatment group culture was represented.
In addition, in order to examine the stability of the antibacterial coating, all the antimicrobial modified materials were also compared with the above-mentioned modified materials newly prepared after immersing them in ultrapure water (Milli Q) after the autoclave treatment for 48 hours.
II. Experimental results
1. Polypropylene-based antimicrobial modified material:
the antibacterial activity results of the polypropylene-based antimicrobial modified materials against micrococcus lyticus (Micrococcus lysodeikticus) and escherichia coli (e.coli) are shown in table 2. The antibacterial activity of the polypropylene material alone is extremely low, the antibacterial activity of the polypropylene-ADA material is also extremely low, and the newly prepared sample and the 48-hour sample of the polypropylene-ADA material respectively show 30% and 31% of inhibition effect on gram-positive bacteria and 25% of inhibition effect on gram-negative bacteria. Both the freshly prepared samples of the polypropylene-ADA-PEI material and the 48 hour samples showed 90% inhibitory activity against gram positive bacteria. And the newly prepared samples of polypropylene-PEI-cysteine, polypropylene-PEI-benzalkonium chloride, polypropylene-PEI-chlorhexidine, polypropylene-ADA-PEI-cysteine, polypropylene-PEI-phenyl biguanide, polypropylene-ADA-PEI-benzalkonium chloride, polypropylene-ADA-PEI-chlorhexidine and polypropylene-ADA-PEI-phenyl biguanide and the 48-hour samples have 100% inhibition effect on gram positive bacteria and negative bacteria. It can be seen that all of the polypropylene-PEI-antimicrobial modified materials and polypropylene-ADA-PEI-antimicrobial modified materials of the present disclosure retain bacterial inhibition activity consistent with the freshly prepared materials after being immersed in water for 48 hours.
Table 2: antibacterial activity test results of the polypropylene-based antimicrobial modified material.
2. Cellulose-based antimicrobial modified material:
the antibacterial activity results of the cellulose-based antimicrobial modified materials against micrococcus lyticus (Micrococcus lysodeikticus) and escherichia coli (e.coli) are shown in table 3. The antibacterial activity of the cellulose material alone is extremely low. The freshly prepared samples and 48 hour samples of the cellulose-ADA material showed 37% and 36% inhibition, respectively, against gram positive bacteria and 20% and 18% inhibition, respectively, against gram negative bacteria. The freshly prepared sample and 48 hour sample of the cellulose-ADA-PEI material showed 90% inhibitory activity against gram positive and negative bacteria, respectively. And the newly prepared samples of cellulose-PEI-cysteine, cellulose-PEI-benzalkonium chloride, cellulose-PEI-chlorhexidine, cellulose-PEI-phenyl biguanide, cellulose-ADA-PEI-cysteine, cellulose-ADA-PEI-benzalkonium chloride, cellulose-ADA-PEI-chlorhexidine and cellulose-ADA-PEI-phenyl biguanide and 48-hour samples have 100% inhibition effect on gram positive bacteria and negative bacteria. It can be seen that all of the cellulose-PEI-antimicrobial modified materials and cellulose-ADA-PEI-antimicrobial modified materials of the present disclosure retain bacterial inhibition activity consistent with the freshly prepared materials after being immersed in water for 48 hours.
Table 3: results of antibacterial activity test of cellulose-based antimicrobial modified materials.
3. Nylon-based antimicrobial modified material
The results of the antibacterial activity of the nylon-based antimicrobial modified material against micrococcus lyticus (Micrococcus lysodeikticus) and escherichia coli (e.coli) are shown in table 4. Nylon materials alone have very low antibacterial activity. The freshly prepared samples and 48 hour samples of nylon-ADA material showed 27% and 20% inhibition of gram positive and negative bacteria, respectively, and 20% and 18% inhibition of gram negative bacteria, respectively. The freshly prepared sample and 48 hour sample of nylon-ADA-PEI material showed 90% inhibitory activity against gram positive and negative bacteria, respectively. And the newly prepared nylon-PEI-cysteine, nylon-PEI-benzalkonium chloride, nylon-PEI-chlorhexidine, nylon-PEI-phenyl biguanide, nylon-ADA-PEI-cysteine, nylon-ADA-PEI-benzalkonium chloride, nylon-ADA-PEI-chlorhexidine and nylon-ADA-PEI-phenyl biguanide have 100% inhibition effect on gram positive bacteria and negative bacteria in 48-hour samples. In addition, it can be seen that all of the nylon-PEI-antimicrobial modified materials and nylon-ADA-PEI-antimicrobial modified materials of the present disclosure maintained bacterial inhibition activity consistent with the freshly prepared materials after being immersed in water for 48 hours.
Table 4: results of antibacterial activity test of nylon-based antimicrobial modified materials.
Example 4: determination of antifungal Activity of PEI antimicrobial modified Material
This example tests the antifungal activity of polypropylene-based, cellulose-based, nylon-based PEI antimicrobial modified materials prepared as in example 1. This example exemplifies the PEI antimicrobial modified material prepared by the method one of example 1 (method one of the functionalized material containing only PEI and method one of the functionalized material containing ADA and PEI) and the method one of the antimicrobial modified material prepared by the method one of example 1, but highly similar results were obtained with the other methods of example 1.
I. The experimental method comprises the following steps:
an antifungal activity experiment was performed using Saccharomyces cerevisiae (Saccharomyces cerevisiae) as an example of fungi, and a polypropylene-PEI-antimicrobial material, a cellulose-PEI-antimicrobial material, a nylon-PEI-antimicrobial material, a polypropylene-ADA-PEI-antimicrobial material, a cellulose-ADA-PEI-antimicrobial material, and a nylon-ADA-PEI-antimicrobial material were used, respectively, and the samples were averaged in triplicate.
Saccharomyces cerevisiae was cultured overnight with Yeast Peptone Dextrose (YPD) medium with stirring at 30℃and fresh fungal cultures were diluted to a colony count of 10 -4 CFU/ml suspension; 0.1g of the antimicrobial modified material was mixed with 10mL of the fungal suspension and placed in a flask and incubated at 120rpm and 37℃for 2 hours; another 10mL of fungal suspension was placed alone in another flask as a control. After the reaction, 10-100. Mu.l of the fungal suspension was inoculated onto YPD agar plates and incubated at 30℃for 18-36 hours; after 36 hours of incubation, the number of viable colonies was counted by plate counting.
The fungal inhibitory activity was calculated according to the following formula:
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wherein I represents a fungal inhibitory activity, N 0 Represents the colony count after the culture of the control group, N i The number of colonies after the treatment group culture was represented.
In addition, in order to examine the stability of the antifungal coating, all the antimicrobial modified materials were also compared with the freshly prepared materials for antifungal activity after being immersed in ultrapure water (Milli Q) after autoclaving for 48 hours.
II. Experimental results
1. Polypropylene-based antimicrobial modified material:
the results of the antifungal activity of the polypropylene-based antimicrobial modified material against Saccharomyces cerevisiae are shown in Table 5. The antifungal activity of the polypropylene material alone was only 15%, and the freshly prepared samples and 48 hour samples of the polypropylene-ADA material showed 35% and 32% inhibition of saccharomyces cerevisiae and, respectively. The freshly prepared sample and 48 hour sample of the polypropylene-ADA-PEI material showed 90% inhibitory activity against Saccharomyces cerevisiae, respectively. And the newly prepared samples of 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-phenyl biguanide and the 48-hour samples have 100 percent inhibition effect on saccharomyces cerevisiae. It can be seen that all of the polypropylene-PEI-antimicrobial modified materials and polypropylene-ADA-PEI-antimicrobial modified materials of the present disclosure retain fungal inhibitory activity consistent with the freshly prepared materials after being immersed in water for 48 hours.
Table 5: results of test of antifungal Activity of the Polypropylene-based antimicrobial modified materials.
2. Cellulose-based antimicrobial modified material
The results of the antifungal activity of the cellulose-based antimicrobial modified material against Saccharomyces cerevisiae are shown in Table 6. Freshly prepared samples of freshly prepared cellulosic material alone and 48 hour samples showed 23% and 21% inhibition, respectively, on s.cerevisiae. Freshly prepared samples and 48 hour samples of cellulose-ADA material showed 37% and 36% inhibition, respectively, on saccharomyces cerevisiae. The freshly prepared sample and 48 hour sample of the cellulose-ADA-PEI material showed 90% inhibitory activity against saccharomyces cerevisiae, respectively. And the newly prepared samples of cellulose-PEI-cysteine, cellulose-PEI-benzalkonium chloride, cellulose-PEI-chlorhexidine, cellulose-PEI-phenyl biguanide, cellulose-ADA-PEI-cysteine, cellulose-ADA-PEI-benzalkonium chloride, cellulose-ADA-PEI-chlorhexidine and cellulose-ADA-PEI-phenyl biguanide and the 48-hour samples have 100 percent inhibition effect on saccharomyces cerevisiae. It can be seen that all of the cellulose-PEI-antimicrobial modified materials and cellulose-ADA-PEI-antimicrobial modified materials of the present disclosure retain fungal inhibitory activity consistent with the freshly prepared materials after being immersed in water for 48 hours.
Table 6: results of the test for antifungal activity of the cellulose-based antimicrobial modified material.
3. Nylon-based antimicrobial modified material
The results of the antifungal activity of the nylon-based antimicrobial modified material against Saccharomyces cerevisiae are shown in Table 7. Freshly prepared samples of nylon material alone and 48 hour samples showed 18% and 17% inhibition, respectively, on s.cerevisiae. Freshly prepared samples and 48 hour samples of nylon-ADA material showed 40% and 39% inhibition, respectively, on saccharomyces cerevisiae. The freshly prepared sample and 48 hour sample of nylon-ADA-PEI material showed 90% inhibitory activity against saccharomyces cerevisiae, respectively. And the newly prepared samples of nylon-PEI-cysteine, nylon-PEI-benzalkonium chloride, nylon-PEI-chlorhexidine, nylon-PEI-phenyl biguanide, nylon-ADA-PEI-cysteine, nylon-ADA-PEI-benzalkonium chloride, nylon-ADA-PEI-chlorhexidine and nylon-ADA-PEI-phenyl biguanide and the 48-hour samples have 100% inhibition effect on saccharomyces cerevisiae. It can be seen that all of the nylon-PEI-antimicrobial modified materials and nylon-ADA-PEI-antimicrobial modified materials of the present disclosure retain fungal inhibition activity consistent with the freshly prepared materials after being immersed in water for 48 hours.
Table 7: results of the antifungal activity test of the nylon-based antimicrobial modified material.
Example 5: determination of antiviral Activity of PEI antimicrobial modified Material
This example tests the antiviral activity of a polypropylene-based, nylon-based PEI antimicrobial modified material prepared as in example 1. This example exemplifies the PEI antimicrobial modified material prepared by the method one of example 1 (method one of the functionalized material containing only PEI and method one of the functionalized material containing ADA and PEI) and the method one of the antimicrobial modified material prepared by the method one of example 1, but highly similar results were obtained with the other methods of example 1.
I. The experimental method comprises the following steps:
taking a novel coronavirus (SARS-CoV-2) as a virus example, respectively adopting a polypropylene PEI antimicrobial modified material and a nylon PEI antimicrobial modified material to carry out an antiviral activity experiment, and taking an average value of the samples in triplicate.
Drying the material in a biosafety cabinet and then cutting to a size of about 0.3cm x 0.3 cm; 200 μl of virus (SARS-CoV-2) suspension was mixed with the material in a 2mL sterile centrifuge tube and incubated for 1h at room temperature; an additional aliquot of the virus sample (virus suspension) was placed in another sterile centrifuge tube as a control. The initial Log TCID50/mL for the virus samples was 6.0Log for both the polypropylene-based PEI antimicrobial modified material and the nylon-based PEI antimicrobial modified material. After the reaction, the virus was eluted with 800. Mu.l of PBS and 400. Mu.l of the eluted solution was collected from a Microspin S-400HR column (GE Healthcare) to remove the eluted active ingredients and reduce cytotoxicity; titrating the control virus eluate and the residual virus eluate of the treatment group with 50% tissue culture infection dose (TCID 50), respectively; the virus titer was calculated using the Reed-Muench method.
II. Experimental results
1. Polypropylene-based antimicrobial modified material:
the results of antiviral activity of the polypropylene-based antimicrobial modified material against the novel coronavirus SARS-CoV-2 are shown in Table 8. Wherein Log TCID50/mL of the control virus sample and the virus sample treated with the polypropylene material, the polypropylene-PEI-benzalkonium chloride material, the polypropylene-PEI-chlorhexidine material, the polypropylene-ADA-PEI-benzalkonium chloride material, the polypropylene-ADA-PEI-chlorhexidine material are 6.0, 5.0,2.0, 3.5, 1.0, and 3.0Log, respectively. The polypropylene-PEI-benzalkonium chloride material and the polypropylene-ADA-PEI-benzalkonium chloride material reduced viral titers by 4.0log and 5.0log, respectively, relative to the control, and also reduced viral titers by 4.0log and 5.0log, respectively, relative to the polypropylene material, and reduced viral titers by 3.0log and 4.0log, respectively, relative to the polypropylene-PEI material. The polypropylene-PEI-chlorhexidine material and the polypropylene-ADA-PEI-chlorhexidine material reduced viral titers by 2.5log and 3.0log, respectively, relative to the control, and also reduced viral titers by 2.5log and 3.0log, respectively, relative to the polypropylene material, and reduced viral titers by 1.5log and 2.0log, respectively, relative to the polypropylene-PEI material.
Although the polypropylene-PEI material also reduces the virus titer to a certain extent, the principle is that viruses are adsorbed on the surface of the material so as not to be eluted, but the viruses are not killed; and the polypropylene-PEI-benzalkonium chloride material, the polypropylene-ADA-PEI-benzalkonium chloride material, the polypropylene-PEI-chlorhexidine material and the polypropylene-ADA-PEI-chlorhexidine material directly kill viruses through benzalkonium chloride and chlorhexidine, so that the effect of resisting viruses is almost 100%.
Table 8. Antiviral Activity test results of the polypropylene-based antimicrobial modified material (SARS-CoV-2).
2. Nylon-based antimicrobial modified material:
the results of the antiviral activity of the nylon-based antimicrobial modified material against the novel coronavirus SARS-CoV-2 are shown in Table 8. Wherein, log TCID50/mL of the control virus, nylon material, nylon-PEI-benzalkonium chloride, nylon-PEI-chlorhexidine, nylon-ADA-PEI-benzalkonium chloride, and nylon-ADA-PEI-chlorhexidine are 6.0, 5.0, 1.0, 2.5, 1.0, and 2.0, respectively. nylon-PEI-benzalkonium chloride material reduced viral titers by 5.0, 5.0 and 4.0 logs, respectively, relative to control, nylon material and nylon-PEI material. nylon-PEI-chlorhexidine material reduced viral titers by 3.5, 3.5 and 2.5 logs, respectively, relative to control, nylon material and nylon-PEI material. nylon-ADA-PEI-benzalkonium chloride material reduced viral titers by 5.0, 5.0 and 4.0 logs, respectively, relative to control, nylon material and nylon-PEI material. nylon-ADA-PEI-chlorhexidine material reduced viral titers by 4.0, 4.0 and 3.0 logs, respectively, relative to control, nylon material and nylon-PEI material.
While nylon-PEI materials can reduce virus titer, they adsorb viruses to the material surface without killing the viruses; and nylon-PEI-benzalkonium chloride material, nylon-ADA-PEI-benzalkonium chloride material, nylon-PEI-chlorhexidine material and nylon-ADA-PEI-chlorhexidine material can directly kill viruses through benzalkonium chloride and chlorhexidine to achieve the effect.
Table 8. Antiviral Activity test results of Nylon-based antimicrobial modified materials (SARS-CoV-2).
The foregoing examples represent only a few embodiments of the present disclosure, which are described in more detail and are not to be construed as limiting the scope of the invention. It should be noted that variations and modifications can be made by those skilled in the art without departing from the spirit of the disclosure, which are within the scope of the disclosure. Accordingly, the scope of protection of the present disclosure should be determined by the following claims.
Claims (37)
1. A polyethyleneimine functionalized material comprising:
a support layer composed of one or more porous or non-porous materials; and
a tie layer comprising a polyethyleneimine directly and/or indirectly bonded to the support layer by a means selected from covalent bonding, electrostatic adsorption, hydrogen bonding, or any combination thereof;
wherein the tie layer is capable of binding to the functional material by a means selected from covalent bonding, electrostatic adsorption, hydrophilic adsorption, hydrophobic adsorption, hydrogen bonding, or any combination thereof.
2. The functionalized material of claim 1, wherein the tie layer further comprises an alginic acid dialdehyde bound to the support layer and/or the polyethylenimine by a means selected from covalent bonding, electrostatic adsorption, hydrogen bonding, or any combination thereof.
3. The functionalized material of claim 1, wherein the one or more porous or non-porous materials are made of one or more polymers or composites or any combination thereof.
4. A functionalized material according to claim 3, characterized in that the polymer or composite is selected from polypropylene, cellulose, regenerated cellulose, polyvinylidene fluoride, polyethersulfone, polystyrene, polytetrafluoroethylene, polyethylene, polyimide, polyamide or any combination thereof.
5. The functionalizing material according to any one of claims 1-4, wherein the mass ratio of the tie layer to the support layer is 1:100 to 1:10.
6. The functionalizing material of claim 5 wherein the mass ratio of said tie layer to said support layer is from 1:50 to 1:20.
7. The functionalized material according to claim 2, characterized in that the mass ratio of alginic acid dialdehyde to polyethyleneimine in the functionalized material is 100:1 to 10:1.
8. The functionalized material according to claim 2, characterized in that the mass ratio of alginic acid dialdehyde to polyethyleneimine in the functionalized material is 50:1 to 20:1.
9. The functional material of any one of claims 1-4, wherein the functional material is an antimicrobial material and the microorganism is selected from the group consisting of a bacterium, a fungus, a virus, or any combination thereof, wherein the bacterium is selected from the group consisting of: chlamydia pneumoniae, streptococcus pneumoniae, mycobacterium tuberculosis, streptococcus group A, corynebacterium diphtheriae, haemophilus influenzae, neisseria meningitidis, clostridium difficile, 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, blastomyces, candida, mucor, sporotrichosis, dermatophytes, or any combination thereof; and the virus is selected from the group consisting of respiratory syncytial virus, hepatitis virus, varicella virus, polio virus, smallpox virus, measles virus, mumps virus, chlamydia trachomatis, influenza virus, SARS-CoV-2 virus, H1N1 virus, H5N7 virus, MERS-CoV virus, staphylococcus aureus, klebsiella pneumoniae, aspergillus nieri, ebola virus, or any combination thereof.
10. The functionalizing material of claim 9, wherein said antimicrobial material is selected from the group consisting of amino acids, quaternary ammonium compounds, chlorhexidine compounds, alexidine compounds, biguanides, or any combination thereof, and wherein said amino acids are selected from the group consisting of cysteine, tyrosine, lysine, arginine, and aspartic acid, or any combination thereof; the quaternary ammonium compound is selected from the group consisting of alkyl dimethyl benzyl ammonium chloride, alkyl didecyl dimethyl ammonium chloride, dialkyl dimethyl ammonium chloride, and dialkyl quaternary ammonium salts, or any combination thereof; the chlorhexidine compound is chlorhexidine digluconate and/or chlorhexidine dihydrochloride; the alexidine compound is alexidine dihydrochloride; the biguanide compound is 1- (3-chlorophenyl) biguanide hydrochloride.
11. A polyethyleneimine modified material comprising:
the polyethylenimine functionalized material of any one of claims 1-10; and
a functional layer composed of a functional material capable of binding to the connection layer by a means selected from covalent bonding, electrostatic adsorption, hydrophilic adsorption, hydrophobic adsorption, hydrogen bonding, or any combination thereof.
12. The modified material of claim 11, wherein the functional material is an antimicrobial material and the polyethyleneimine modified material is a polyethyleneimine antimicrobial modified material.
13. The modified material of claim 12, wherein the antimicrobial material is selected from the group consisting of amino acids, quaternary ammonium compounds, chlorhexidine compounds, alexidine compounds, biguanides compounds, or any combination thereof.
14. The modified material of claim 13, wherein the amino acid is selected from the group consisting of cysteine, tyrosine, lysine, arginine, and aspartic acid, or any combination thereof.
15. The modified material of claim 13, wherein the quaternary ammonium compound is selected from the group consisting of alkyl dimethyl benzyl ammonium chloride, alkyl didecyl dimethyl ammonium chloride, dialkyl dimethyl ammonium chloride, and dialkyl quaternary ammonium salts, or any combination thereof.
16. The modified material of claim 13, wherein the chlorhexidine compound is chlorhexidine digluconate and/or chlorhexidine dihydrochloride; the alexidine compound is alexidine dihydrochloride; the biguanide compound is 1- (3-chlorophenyl) biguanide hydrochloride.
17. The modified material of claim 12, wherein the antimicrobial activity of the antimicrobial material and the polyethyleneimine antimicrobial modified material is against a bacterium, a fungus, a virus, or any combination thereof, and wherein the bacterium is selected from the group consisting of chlamydia pneumoniae, streptococcus pneumoniae, mycobacterium tuberculosis, streptococcus group a, corynebacterium diphtheriae, haemophilus influenzae, neisseria meningitidis, clostridium difficile, 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, blastomyces, candida, mucor, sporotrichosis, dermatophytes, or any combination thereof; the virus is selected from the group consisting of respiratory syncytial virus, hepatitis virus, varicella virus, polio virus, smallpox virus, measles virus, mumps virus, chlamydia trachomatis, influenza virus, SARS-CoV-2 virus, H1N1 virus, H5N7 virus, MERS-CoV virus, staphylococcus aureus, klebsiella pneumoniae, aspergillus nieri, ebola virus, or any combination thereof.
18. The modified material of claim 12, wherein the polyethylenimine antimicrobial modified material is selected from the group consisting of polypropylene-polyethylenimine-cysteine, polypropylene-polyethylenimine-benzalkonium chloride, polypropylene-polyethylenimine-chlorhexidine, polypropylene-polyethylenimine-phenylbiguanide, cellulose-polyethylenimine-cysteine, cellulose-polyethylenimine-benzalkonium chloride, cellulose-polyethylenimine-chlorhexidine, cellulose-polyethylenimine-phenylbiguanide, nylon-polyethylenimine-cysteine, nylon-polyethylenimine-benzalkonium chloride, nylon-polyethylenimine-chlorhexidine, nylon-polyethylenimine-phenylbiguanide, polypropylene-alginic acid dialdehyde-polyethylenimine-cysteine, polypropylene-alginic acid dialdehyde-polyethylenimine-phenylbiguanide, cellulose-polyethylenimine-cysteine dialdehyde, cellulose-polyethylenimine-phenylbiguanide, nylon-alginic acid dialdehyde-polyethylenimine-benzalkonium chloride, nylon-glyoxaline-kappylenimine-phthalide, and nylon-kappylenimine-phthalide, nylon-alginic acid dialdehyde-polyethylenimine-chlorhexidine, nylon-alginic acid dialdehyde-polyethylenimine-phenyl biguanide or any combination thereof.
19. The modified material of claim 12, wherein the polyethylenimine antimicrobial modified material is selected from the group consisting of polypropylene-polyethylenimine-cysteine, polypropylene-polyethylenimine-benzalkonium chloride, polypropylene-polyethylenimine-chlorhexidine, polypropylene-polyethylenimine-phenylbiguanide, cellulose-polyethylenimine-cysteine, cellulose-polyethylenimine-benzalkonium chloride, cellulose-polyethylenimine-chlorhexidine, cellulose-polyethylenimine-phenylbiguanide, nylon-polyethylenimine-cysteine, nylon-polyethylenimine-benzalkonium chloride, nylon-polyethylenimine-chlorhexidine, nylon-polyethylenimine-phenylbiguanide, polypropylene-alginic acid dialdehyde-polyethylenimine-cysteine, polypropylene-alginic acid dialdehyde-polyethylenimine-phenylbiguanide, cellulose-polyethylenimine-cysteine dialdehyde, cellulose-polyethylenimine-phenylbiguanide, nylon-alginic acid dialdehyde-polyethylenimine-benzalkonium chloride, nylon-glyoxaline-kappylenimine-phthalide, and nylon-kappylenimine-phthalide, nylon-alginic acid dialdehyde-polyethylenimine-chlorhexidine, nylon-alginic acid dialdehyde-polyethylenimine-phenyl biguanide or any combination thereof.
20. The modified material of claim 12, wherein the polyethylenimine antimicrobial modified material is a polyethylenimine antiviral modified material selected from the group consisting of polypropylene-polyethylenimine-benzalkonium chloride, polypropylene-polyethylenimine-chlorhexidine, nylon-polyethylenimine-benzalkonium chloride, nylon-polyethylenimine-chlorhexidine, polypropylene-alginic acid dialdehyde-polyethylenimine-benzalkonium chloride, polypropylene-alginic acid dialdehyde-polyethylenimine-chlorhexidine, nylon-alginic acid dialdehyde-polyethylenimine-benzalkonium chloride, nylon-alginic acid dialdehyde-polyethylenimine-chlorhexidine, or any combination thereof.
21. The modified material of any of claims 11-20, wherein the functional material of the functional layer comprises 0.1% -1% of the total mass of the modified material.
22. The modified material of claim 21, wherein the functional material of the functional layer comprises 0.3% to 0.6% by weight of the total mass of the modified material.
23. A process for preparing a polyethyleneimine functionalized material according to any one of claims 1 to 10, comprising the steps of:
mixing porous material or nonporous material with polyethylenimine water solution, shaking at 60-200rpm at 10-100deg.C and pH 5-11 for 10 min to 24 hr,
Or,
directly coating or spraying the polyethyleneimine water solution on the surface of the porous material or the nonporous material at the pH of 5-11, and drying at the temperature of 10-100 ℃ for 10 minutes to 24 hours to obtain the polyethyleneimine functionalized material.
24. The method of claim 23, further comprising the step of: mixing the porous or non-porous material with an aqueous solution of alginic acid dialdehyde before adding the aqueous solution of polyethylenimine or after reacting the porous or non-porous material with the aqueous solution of polyethylenimine, then shaking-reacting at 60-200rpm at a temperature of 10-100 ℃ and a pH of 1.5-8 for 10 minutes to 24 hours,
or,
before or after coating or spraying the aqueous polyethyleneimine solution, an aqueous solution of alginic acid dialdehyde is directly coated or sprayed on the surface of the porous or non-porous material at a pH of 1.5 to 8 and dried at a temperature of 10 to 100 ℃ for 10 minutes to 24 hours.
25. The method according to claim 24, wherein a mass ratio of a 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 the nonporous material is 1:100 to 1:10.
26. The method according to claim 25, wherein the mass ratio of the polyethylenimine contained in the polyethylenimine aqueous solution to the alginic acid dialdehyde contained in the alginic acid dialdehyde aqueous solution is 100:1 to 10:1.
27. A process for preparing a polyethyleneimine modified material according to any one of claims 11 to 22, comprising the steps of:
adding the polyethylenimine functionalized material according to any one of claims 1-10 or prepared according to the method of any one of claims 23-26 to an aqueous solution of the functional material, shaking at a temperature of 10-100 ℃ and pH of 1.5-8 for reaction at 60-200rpm for 10 minutes to 24 hours;
or,
directly coating or spraying the functional material aqueous solution on the polyethyleneimine functional material at a pH of 1.5-8 and drying at a temperature of 10-100 ℃ for 10 minutes to 24 hours,
obtaining the modified material;
wherein the functional material is capable of binding to the tie layer by a means selected from covalent bonding, electrostatic adsorption, hydrophilic adsorption, hydrophobic adsorption, hydrogen bonding, or any combination thereof.
28. The method of claim 27, wherein the functional material comprises 0.1% to 1% of the total mass of the modified material.
29. A process for preparing a polyethyleneimine modified material according to any one of claims 11 to 22, comprising the steps of:
mixing a functional material with a polyethyleneimine aqueous solution to obtain a polyethyleneimine-functional material aqueous solution;
the aqueous solution obtained above and the porous material or the non-porous material are subjected to shaking reaction at 60-200rpm for 10 minutes to 24 hours at the temperature of 10-100 ℃ and the pH of 1.5-8, or the aqueous solution obtained above is directly coated or sprayed on the surface of the porous material or the non-porous material at the pH of 1.5-8 and dried at the temperature of 10-100 ℃ for 10 minutes to 24 hours, so that the modified material is obtained;
wherein the functional material is capable of binding to the tie layer by a means selected from covalent bonding, electrostatic adsorption, hydrophilic adsorption, hydrophobic adsorption, hydrogen bonding, or any combination thereof.
30. The method of claim 29, further comprising the step of: the functional material is mixed with the aqueous solution of alginic acid dialdehyde before, after or simultaneously with the mixing of the functional material with the aqueous solution of polyethylenimine.
31. The method according to claim 30, wherein the mass ratio of the functional material, the sum of polyethylenimine and alginic acid dialdehyde to the porous or non-porous material is (1-10): (10-100): 1000.
32. The method according to any one of claims 23-31, further comprising the step of: after washing the resulting product, it is stored wet or air-dried or oven-dried.
33. The method of any one of claims 23-31, wherein the porous or non-porous material is one or more polymers, composites, or any combination thereof, and the polymers or composites are selected from polypropylene, cellulose, regenerated cellulose, polyvinylidene fluoride, polyethersulfone, polystyrene, polytetrafluoroethylene, polyethylene, polyimide, polyamide, or any combination thereof.
34. The method of any one of claims 23-31, wherein the functional material is an antimicrobial material and the microorganism is selected from the group consisting of a bacterium, a fungus, a virus, or any combination thereof, and the bacterium is selected from the group consisting of chlamydia pneumoniae, streptococcus pneumoniae, mycobacterium tuberculosis, streptococcus group a, corynebacterium diphtheriae, haemophilus influenzae, neisseria meningitidis, clostridium difficile, 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, blastomyces, candida, mucor, sporotrichosis, dermatophytes, or any combination thereof; the virus is selected from the group consisting of respiratory syncytial virus, hepatitis virus, varicella virus, polio virus, smallpox virus, measles virus, mumps virus, chlamydia trachomatis, influenza virus, SARS-CoV-2 virus, H1N1 virus, H5N7 virus, MERS-CoV virus, staphylococcus aureus, klebsiella pneumoniae, aspergillus nieri, ebola virus, or any combination thereof.
35. The method of any one of claims 23-31, wherein the functional material is an antimicrobial material and the antimicrobial material is selected from an amino acid, a quaternary ammonium compound, a chlorhexidine compound, an alexidine compound, a biguanide compound, 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 the group consisting of alkyl dimethyl benzyl ammonium chloride, alkyl didecyl dimethyl ammonium chloride, dialkyl dimethyl ammonium chloride, and dialkyl quaternary ammonium salts, or any combination thereof; the chlorhexidine compound is chlorhexidine digluconate and/or chlorhexidine dihydrochloride; the alexidine compound is alexidine dihydrochloride; the biguanide compound is 1- (3-chlorophenyl) biguanide hydrochloride.
36. Use of the polyethylenimine functionalized material according to any one of claims 1 to 10, the polyethylenimine modified material according to any one of claims 11 to 22, the method of preparation according to any one of claims 23 to 35 or the material prepared according to the method of preparation according to any one of claims 23 to 36 in the production of medical and other antimicrobial articles.
37. The use according to claim 36, wherein the use comprises the production of masks, barrier gowns, gloves, personal protection products, bandages, medical tapes, medical caps, medical sheets, medical garments, air filters, water filters, electronic products, household appliances and automotive parts.
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