Surface functionalized materials and uses thereof

Abstract

The invention provides a surface functional material and application thereof, and particularly relates to a polyethyleneimine functional material, a polyethyleneimine modified material, and a preparation method and application of the polyethyleneimine functional material and the polyethyleneimine modified material. The invention also provides application of the material and the method in preparation of protective articles for resisting bacteria, fungi and viruses. The raw materials and the preparation method disclosed by the invention are simple, economical, environment-friendly and easy for scale enlargement, 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

Surface functionalized materials and their uses Technical Field

[0001] The present disclosure relates to the field of materials, and in particular to a surface functionalized material and uses thereof, and in particular to a polyethyleneimine functionalized material and related modified materials and uses thereof. Background Art

[0002] Pathogenic microorganisms are pathogenic microorganisms that can cause illness in humans, animals, and plants. They include a variety of bacteria, fungi, and viruses and are easily transmitted, for example through airborne, contact, and droplet transmission, posing a significant threat to human health and even causing widespread epidemics. For example, the Spanish flu (H1N1), the first global influenza pandemic of the 20th century, spread almost simultaneously across Europe, Asia, and North America in three peaks of infection between 1918 and 1919, killing approximately 50 million people worldwide in less than 11 months. In recent years, numerous viruses with pandemic potential have emerged, such as SARS-CoV, MERS-CoV, and SARS-CoV-2. To this day, SARS-CoV-2 continues to threaten human life. According to the WHO, as of March 25, approximately 476 million cases of SARS-CoV-2 had been confirmed worldwide, with a cumulative death toll of approximately 6.109 million, causing untold losses to humanity. In addition, there are many bacteria and fungi that pose a threat to health because they are easily spread among the population, such as methicillin-resistant Staphylococcus aureus (MRSA), vancomycin-resistant Enterococci (VRE), dermatophytes, Aspergillus, Candida, etc.

[0003] Blocking the spread of pathogenic microorganisms is a key way to protect public health. However, conventional protective methods (such as medical masks) have limited effects. For example, due to the large filtration pore size, they are ineffective against microorganisms with smaller particle sizes, especially viruses. Protective equipment that can effectively resist viruses (such as European FFP2 or FFP3 and American N95 masks) are generally equipped with small-pore filters, and some also carry an electric charge to play a role in filtering and electrostatic repulsion. However, these masks are expensive, and the pore size is too small, causing the wearer to have difficulty breathing. In addition, masks contaminated with pathogenic microorganisms must undergo special treatment, otherwise they will become a source of infection and cause a large environmental burden.

[0004] The production of most antiviral, antibacterial, and antifungal materials requires complex procedures and expensive chemicals, making them difficult to apply on a large scale. Some commonly used antimicrobial agents (such as silver or other nanoparticle impregnants) cannot be used for medical purposes due to their inherent toxicity, and certain organic solvents used to prepare functionalized materials also impose 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, are not approved by the FDA for use in the production of PPE due to their environmentally unfriendly or harmful properties. On the other hand, economical and environmentally friendly antimicrobial materials often have low inhibitory activity. Common antimicrobial materials have a narrow range of microbial inhibition, for example, they are only effective against specific types of Gram-positive bacteria and cannot effectively inhibit a broad spectrum of microorganisms such as Gram-negative bacteria, fungi, and viruses, especially those with increasing resistance. Other reported antiviral coating technologies have low antiviral activity and are unable to effectively protect against lethal viruses with low viral titers, such as SARS-CoV, H5N1, H5N7, MERS-CoV, and SARS-CoV-2. Furthermore, most antimicrobial technologies are limited to bacteria, viruses, or fungi, and some antimicrobial and antiviral material coatings are only compatible with a limited range of polymers, the properties of which may limit their application.

[0005] Summary of the Invention

[0006] In one aspect of the present disclosure, a polyethyleneimine functionalized material is provided, comprising:

[0007] a support layer composed of one or more porous or non-porous materials; and

[0008] a connecting layer comprising polyethyleneimine, wherein the polyethyleneimine is directly and / or indirectly bonded to the support layer by a method selected from covalent bonding, electrostatic adsorption, hydrogen bonding, or any combination thereof;

[0009] The connecting layer can be bonded to a functional material by a method selected from covalent bonding, electrostatic adsorption, hydrophilic adsorption, hydrophobic adsorption, hydrogen bonding or any combination thereof.

[0010] In another aspect of the present disclosure, a method for preparing the aforementioned polyethyleneimine functionalized material is provided, comprising the following steps:

[0011] After mixing the porous material or non-porous material with the polyethyleneimine aqueous solution, the mixture is shaken at 60-200 rpm at a temperature of 10-100° C. and a pH of 5-11 for 10 minutes to 24 hours. Alternatively, the polyethyleneimine aqueous solution is directly coated or sprayed on the surface of the porous material or non-porous material at a pH of 5-11 and dried at a temperature of 10-100° C. for 10 minutes to 24 hours to obtain the polyethyleneimine-energized material.

[0012] In another aspect of the present disclosure, a method for preparing the aforementioned polyethyleneimine modified material is provided, comprising the following steps:

[0013] The polyethyleneimine functionalized material or the polyethyleneimine functionalized material prepared according to the above method is added to an aqueous solution of a functional material, and the solution is shaken at 60-200 rpm at a temperature of 10-100° C. and a pH of 1.5-8 for 10 minutes to 24 hours; alternatively, the aqueous solution of the functional material is directly coated or sprayed on the polyethyleneimine functionalized material at a pH of 1.5-8 and dried at a temperature of 10-100° C. for 10 minutes to 24 hours to obtain the modified material;

[0014] The functional material can be combined with the connecting layer by covalent bonding, electrostatic adsorption, hydrophilic adsorption, hydrophobic adsorption, hydrogen bonding or any combination thereof.

[0015] In another aspect of the present disclosure, a method for preparing the aforementioned polyethyleneimine modified material is provided, comprising the following steps:

[0016] mixing the functional material with a polyethyleneimine aqueous solution to obtain a polyethyleneimine-functional material aqueous solution;

[0017] The aqueous solution obtained above is reacted with a porous material or a non-porous material at a temperature of 10-100° C. and a pH of 1.5-8 with shaking at 60-200 rpm for 10 minutes to 24 hours, or the aqueous solution obtained above is directly coated or sprayed onto the surface of the porous material or the non-porous material at a pH of 1.5-8 and dried at a temperature of 10-100° C. for 10 minutes to 24 hours to obtain the modified material;

[0018] The functional material can be combined with the connecting layer by covalent bonding, electrostatic adsorption, hydrophilic adsorption, hydrophobic adsorption, hydrogen bonding or any combination thereof.

[0019] In another aspect of the present disclosure, the polyethyleneimine functionalized materials, polyethyleneimine modified materials, preparation methods thereof, or uses of the materials obtained according to the preparation methods described in the aforementioned aspects in the production of medical supplies and antimicrobial supplies are also provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] FIG1 is an X-ray photoelectron spectroscopy (XPS) test result of the polyethyleneimine antimicrobial modified material according to one embodiment of the present invention. DETAILED DESCRIPTION

[0021] In order to make the purpose, technical solutions and advantages of the present disclosure more clearly understood, the present disclosure is further described in detail below in conjunction with the accompanying drawings and specific embodiments. It should be understood that the specific embodiments described herein are only used to explain the present disclosure and do not limit the scope of protection of the present disclosure.

[0022] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this disclosure pertains. The terms used herein in the specification of this disclosure are intended only to describe specific embodiments and are not intended to limit this disclosure. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0023] Poly(ethylenimine) (PEI), also known as polyethylenimine, is a water-soluble polymer. Due to its polar group (amino) structure, polyethyleneimine can bind to different substances through the following actions: (1) physical adhesion to the surface of the substance; (2) its amino groups can react with carboxyl groups to form hydrogen bonds; (3) its amino groups carry a positive charge and electrostatically bind to negatively charged surfaces; and (4) its amino groups can react with carbonyl groups to form covalent bonds. Polyethyleneimine can be used as a linker and antibacterial agent, but its antibacterial properties are limited and its preparation process is relatively complex, which limits its application.

[0024] The inventors of the present application have discovered that the surface coated with PEI can be combined with functional materials through covalent bonding, electrostatic adsorption, hydrophilic adsorption, hydrophobic adsorption, hydrogen bonding, and the like.

[0025] In order to further improve the stability of PEI and the functional layer, the inventors of the present application also discovered that alginate dialdehyde can be used together with PEI to functionalize the material.

[0026] Alginate dialdehyde (ADA) is a sticky polymer that can be firmly attached to the surfaces of various materials through at least one of the following mechanisms: (1) physical adhesion to the surface; (2) covalent bonding with amine or amide groups on the surface through the two aldehyde groups in each monomer; (3) electrostatic bonding to positively charged surfaces through the negative charge carried by the presence of hydroxyl and carboxyl groups; and (4) hydrogen bonding to the surface. Therefore, ADA-coated surfaces can also be attached to substances through covalent bonding, electrostatic adsorption, hydrophilic adsorption, hydrophobic adsorption, hydrogen bonding, and other methods.

[0027] Therefore, in some embodiments of the present disclosure, a polyethyleneimine functionalized material is provided, comprising a support layer composed of a porous material or a non-porous material and a connecting layer comprising polyethyleneimine. In some embodiments of the present disclosure, the connecting layer further comprises alginate dialdehyde. In some embodiments of the present disclosure, the connecting layer is composed of alginate dialdehyde and polyethyleneimine.

[0028] In some embodiments of the present disclosure, a polyethyleneimine-modified material comprising the aforementioned polyethyleneimine functionalized material and a functional layer is also provided, wherein the functional layer can be a functional material. In some embodiments, the functional material is an antimicrobial material.

[0029] In some embodiments of the present disclosure, various preparation methods of the aforementioned polyethyleneimine functionalized materials and polyethyleneimine modified materials are also provided.

[0030] In addition, the present disclosure also provides the use of the above-mentioned materials and preparation methods in the preparation of antimicrobial products. The polyethyleneimine (PEI) in the present disclosure can be obtained by chemical synthesis by various methods or purchased commercially. In some embodiments, the polyethyleneimine in the present disclosure has a molecular weight of about 10,000-125,000 g / mol.

[0031] In some embodiments, polyethyleneimine can be obtained by any existing commercial means.

[0032] The alginate dialdehyde (ADA) disclosed herein can be obtained from seaweed, such as brown algae, or derivatives thereof by various methods. In some embodiments, the alginate dialdehyde disclosed herein has a molecular weight of about 10,000-150,000 g / mol.

[0033] In some embodiments, alginate dialdehyde (ADA) is prepared as follows. An appropriate amount of alginic acid or sodium alginate (1–40% w / v) is dissolved in deionized water or ultrapure (Mill Q) water (200–4000 mL). 50–800 mL of ethanol (90–98% (v / v)) and sodium (meta)periodate (NaIO4, 2–100 g) are added. The solution is stirred or shaken continuously and allowed to react at 15–80°C in the dark for 12–34 hours. Ethylene glycol (20–100 mL) is added, and the reaction is continued at 15–80°C with stirring or shaking for 1–5 hours to reduce excess periodate. To precipitate ADA, 5–20 g of a sodium salt (e.g., sodium chloride) and 800–2000 mL of 70–98% ethanol are added. The solution is stirred for 1–2 hours and allowed to stand for 1–6 hours. After the ADA precipitate is produced, it is filtered and washed three times with 20-60% ethanol. The ADA solution is dialyzed using a dialysis membrane or dialysis tubing (MWCO 1000-3500 Da) or a desalting column and deionized water or ultrapure water to remove the sodium salt and obtain an ADA solution. The obtained ADA can be used directly or stored at -4-25°C for future use. It can also be freeze-dried in a freeze dryer to remove moisture to obtain ADA powder.

[0034] In the first aspect of the present disclosure, a polyethyleneimine functionalized material is provided, comprising a support layer and a connecting layer; the support layer is composed of one or more porous materials or non-porous materials, the connecting layer comprises polyethyleneimine, and the polyethyleneimine is directly and / or indirectly bonded to the support layer by a method selected from covalent bonding, electrostatic adsorption, hydrogen bonding, or any combination thereof; wherein the connecting layer is capable of bonding to the functional material by a method selected from covalent bonding, electrostatic adsorption, hydrophilic adsorption, hydrophobic adsorption, hydrogen bonding, or any combination thereof.

[0035] In some embodiments, the tie layer may consist solely of polyethyleneimine, which is then directly bonded to the support layer. However, in order to further improve the stability of the PEI and the functional layer, in other embodiments, the tie layer may further comprise alginate dialdehyde. In yet other embodiments, the tie layer may consist of polyethyleneimine and alginate dialdehyde.

[0036] In the embodiment where the connecting layer contains alginate dialdehyde, the alginate dialdehyde is bonded to the support layer and / or the polyethyleneimine by a method selected from covalent bonding, electrostatic adsorption, hydrogen bonding, or any combination thereof.

[0037] In some embodiments, the weight ratio of the connecting layer to the supporting layer is about 1:100 to 1:10. In some embodiments, the weight ratio of the connecting layer to the supporting layer is about 1:50 to 1:20.

[0038] In some embodiments, the mass ratio of alginate dialdehyde to polyethyleneimine in the functionalized material is 100:1 to 10:1. In some embodiments, the mass ratio of alginate dialdehyde to polyethyleneimine in the functionalized material is 50:1 to 20:1.

[0039] In a second aspect of the present disclosure, a polyethyleneimine-modified material is provided, comprising the aforementioned polyethyleneimine-functionalized material and a functional layer, wherein the functional layer is composed of a functional material capable of bonding to the connecting layer via a method selected from covalent bonding, electrostatic adsorption, hydrophilic adsorption, hydrophobic adsorption, hydrogen bonding, or any combination thereof. In some embodiments, the functional material is an antimicrobial material, thereby obtaining a polyethyleneimine-modified functional material or a polyethyleneimine-antimicrobial modified material.

[0040] In some embodiments, the antimicrobial material in the functional layer of the polyethyleneimine modified material accounts for 0.1% to 1% of the total mass of the modified material. In some embodiments, the antimicrobial material in the functional layer accounts for 0.3% to 0.6% of the total mass of the modified material.

[0041] In some embodiments of the present disclosure, the porous material or non-porous material can be made from one or more polymers, composite materials, or any combination thereof. In some embodiments, the porous material or non-porous material can be a polymer, a composite material, a membrane material, a sheet material, a filter material, a non-woven fiber, or any combination thereof. The pore size of the porous material or non-porous material can be any pore size. In some embodiments, the pore size of the porous material can be between 0.001 and 10 μm.

[0042] In some embodiments of the present disclosure, the polymer or composite material can be selected from polypropylene, cellulose, regenerated cellulose, polyvinylidene fluoride (PVDF), polyether sulfone (PES), polystyrene, polytetrafluoroethylene (PTFE), polyethylene, polyimide, polyamide (such as polyhexamethylene adipamide, commonly known as nylon 66) or any combination thereof.

[0043] In some embodiments of the present disclosure, the functional material may be an antimicrobial material, such as an antimicrobial chemical substance, thereby forming an efficient and durable antimicrobial modified material.

[0044] "Antimicrobial" in this application refers to the killing or inhibitory effect on microorganisms. Microorganisms generally refer to a general term for all tiny organisms that are difficult for individuals to observe with the naked eye. Microorganisms include bacteria, viruses, fungi and a few algae, etc., which are divided into space microorganisms, marine microorganisms, etc. according to the different environments in which they exist, and are divided into prokaryotic microorganisms and eukaryotic microorganisms according to the cell structure. In some embodiments of the present disclosure, the microorganisms can be selected from bacteria, fungi, viruses or any combination thereof, but are not limited thereto. In some embodiments, the microorganisms are selected from bacteria, fungi, viruses, etc.

[0045] Bacteria in a broad sense are prokaryotes, which refer to a large class of primitive single-celled organisms whose nuclei are not enclosed by a nuclear membrane and only have exposed DNA called a nuclear region (or nucleoid). They include two major groups: eubacteria and archaea. What people usually refer to are bacteria in a narrow sense. Bacteria in a narrow sense are a type of prokaryotic microorganisms. They are a type of prokaryotic organism with a short and thin shape, a simple structure, and mostly reproduce by binary fission. They are the most widely distributed and most numerous organisms in nature. Some bacteria become pathogens, causing tetanus, typhoid fever, pneumonia, syphilis, cholera, and tuberculosis. In some embodiments, the bacteria can be Gram-positive bacteria and / or Gram-negative bacteria. In some embodiments, the bacteria are selected from Klebsiella pneumoniae, Chlamydia pneumoniae, Streptococcus pneumoniae, Mycobacterium tuberculosis, Streptococcus Group A, Corynebacterium diphtheriae, Haemophilus influenzae, Neisseria meningitidis, Clostridium difficile, Methicillin-Resistant Staphylococcus aureus (MRSA), Vancomycin-Resistant Enterococci (VRE), Acinetobacter baumannii, etc.

[0046] Fungi are a class of eukaryotic organisms. The most common fungi are various mushrooms, and fungi also include molds and yeasts. Fungi that are pathogenic to humans are divided into superficial fungi and deep fungi. The former invade the skin, hair, and nails, are chronic, and are refractory to treatment, but have little impact on the body, while the latter can invade the internal organs of the whole body and can cause death in severe cases. In addition, some fungi parasitize in grain, feed, and food, and can produce toxins that cause toxic fungal diseases. In some embodiments, the fungi are selected from the genus Pneumocystis, Aspergillus (such as Aspergillus Niger), Coccidioides, Blastomyces, Candida, mucormycetes, Sporothrix, dermatophytosis, etc.

[0047] Viruses are non-cellular organisms composed of nucleic acid molecules (DNA or RNA) and a protective protein coat. They parasitize organisms, occupying a niche between living and non-living organisms. Through infection, viruses can replicate within their host's cellular systems, but they cannot grow or replicate independently. Viruses can infect nearly all cellular organisms. Virus particles are approximately one-hundredth the size of bacteria. Viruses cause a wide variety of human diseases, ranging from common illnesses like colds, influenza, and chickenpox to more serious illnesses like smallpox, HIV, SARS, and avian influenza. Some diseases may also be caused by viruses. Viruses are also a contributing factor to cancer. In some embodiments, the virus is selected from respiratory syncytial (sin-SISH-uhl) virus, hepatitis virus, varicella virus, polio virus, smallpox virus, measles virus, mumps virus, Chlamydia trachomatis, influenza virus (such as Myxovirus influenzae), SARS-CoV virus, SARS-CoV-2 virus, H1N1 virus, H5N1 virus, H5N7 virus, MERS-CoV virus, Ebola virus, etc.

[0048] In some embodiments of the present disclosure, the antimicrobial material can be selected from amino acids, quaternary ammonium compounds, chlorhexidine compounds, alexidine compounds, biguanide compounds, or any combination thereof.

[0049] Amino acids are organic compounds containing a basic amino group and an acidic carboxyl group. In some embodiments of the present disclosure, the amino acids can be selected from cysteine, tyrosine, lysine, arginine, and aspartic acid, or any combination thereof. Amino acids with low pKas impart acidic properties to the surface. Amino acids are also zwitterions, thus possessing antimicrobial effects and potentially disrupting viral envelopes in a similar manner.

[0050] Quaternary ammonium compounds are quaternary ammonium cation compounds formed after all four hydrogen ions in the ammonium ion are replaced by hydrocarbon groups. In some embodiments of the present disclosure, the quaternary ammonium compound can 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 embodiments, the quaternary ammonium compound is selected from benzalkonium chloride, hexadecyl trimethyl ammonium chloride (HTMA-Cl), stearyl dimethyl benzyl ammonium chloride (SMBA-Cl), didecyl dimethyl ammonium bromide, dioctyl dimethyl ammonium bromide or any combination thereof. Quaternary ammonium compounds are endowed with a series of physicochemical properties such as emulsification, dispersion, solubilization, foaming, defoaming, sterilization, coagulation, and antiseptic properties due to their unique molecular structure. Among their many unique properties and corresponding practical applications, their excellent antimicrobial properties have particularly attracted people's attention. Quaternary ammonium compounds can be used as antiviral, antibacterial and antifungal agents in solution form. Quaternary ammonium compounds act bactericidal and microbicidal by inactivating energy-generating enzymes, denaturing essential cellular proteins, and destroying cellular material by disrupting intermolecular interactions.

[0051] Chlorhexidine, also known as chlorhexidine, is a cationic surfactant with a broad-spectrum antibacterial and bactericidal effect, making it a preferred disinfectant. Chlorhexidine compounds are a general term for a class of compounds containing a chlorhexidine structure. In some embodiments of the present disclosure, the chlorhexidine compound may be chlorhexidine digluconate and / or chlorhexidine dihydrochloride.

[0052] Alexidine, also known as hexamethylenetetramine, is a nitrogen-containing organic compound with strong broad-spectrum antibacterial and bactericidal properties. It is a highly effective antiseptic and disinfectant against both Gram-positive and Gram-negative bacteria, even in the presence of serum and blood. Alexidine compounds are a general term for compounds containing the Alexidine structure. In some embodiments of the present disclosure, the Alexidine compound is Alexidine dihydrochloride.

[0053] Biguanide, also known as 1-(diaminomethylene)guanidine, is a highly effective antiseptic. Biguanide compounds are a general term for compounds containing a biguanide structure. In some embodiments of the present disclosure, the biguanide compound is phenylbiguanide (1-(3-chlorophenyl)biguanide hydrochloride).

[0054] Chlorhexidine compounds, Alexidine compounds or biguanide compounds are used as antiviral, antibacterial and antifungal agents. For bacteria, according to general understanding, the molecules of these compounds are combined with the cell wall of bacteria, destroying the stability of the cell wall. They will 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). Damaging the semi-permeable material of the cytoplasm can cause the internal components to leak, thereby causing cell death. Similarly, for fungi, the compound damages the integrity of the cell wall and the material, enters the cytoplasm, causing the cell contents to leak and the cell to die. Similarly, for viruses, the compound can kill viruses by destroying the virus structure.

[0055] In some embodiments of the present disclosure, there is provided a polyethyleneimine antibacterial modified material, for example, selected from polypropylene-polyethyleneimine-cysteine, polypropylene-polyethyleneimine-benzalkonium chloride, polypropylene-polyethyleneimine-chlorhexidine, polypropylene-polyethyleneimine-phenylbiguanide, cellulose-polyethyleneimine-cysteine, cellulose-polyethyleneimine-benzalkonium chloride, cellulose-polyethyleneimine-chlorhexidine, cellulose-polyethyleneimine-phenylbiguanide, nylon-polyethyleneimine-cysteine, nylon-polyethyleneimine-benzalkonium chloride, nylon-polyethyleneimine-chlorhexidine, nylon-polyethyleneimine-phenylbiguanide, polypropylene-alginate dialdehyde-polyethyleneimine-cysteine, polypropylene Alginic acid dialdehyde-polyethyleneimine-benzalkonium chloride, polypropylene-alginic acid dialdehyde-polyethyleneimine-chlorhexidine, polypropylene-alginic acid dialdehyde-polyethyleneimine-phenylbiguanide, cellulose-alginic acid dialdehyde-polyethyleneimine-cysteine, cellulose-alginic acid dialdehyde-polyethyleneimine-benzalkonium chloride, cellulose-alginic acid dialdehyde-polyethyleneimine-chlorhexidine, cellulose-alginic acid dialdehyde-polyethyleneimine-phenylbiguanide, nylon-alginic acid dialdehyde-polyethyleneimine-cysteine, nylon-alginic acid dialdehyde-polyethyleneimine-benzalkonium chloride, nylon-alginic acid dialdehyde-polyethyleneimine-chlorhexidine, nylon-alginic acid dialdehyde-polyethyleneimine-phenylbiguanide or any combination thereof.

[0056] In some embodiments of the present disclosure, there is provided a polyethyleneimine antifungal modified material, for example, selected from polypropylene-polyethyleneimine-cysteine, polypropylene-polyethyleneimine-benzalkonium chloride, polypropylene-polyethyleneimine-chlorhexidine, polypropylene-polyethyleneimine-phenylbiguanide, cellulose-polyethyleneimine-cysteine, cellulose-polyethyleneimine-benzalkonium chloride, cellulose-polyethyleneimine-chlorhexidine, cellulose-polyethyleneimine-phenylbiguanide, nylon-polyethyleneimine-cysteine, nylon-polyethyleneimine-benzalkonium chloride, nylon-polyethyleneimine-chlorhexidine, nylon-polyethyleneimine-phenylbiguanide, polypropylene-alginate dialdehyde-polyethyleneimine-cysteine, polypropylene Alginic acid dialdehyde-polyethyleneimine-benzalkonium chloride, polypropylene-alginic acid dialdehyde-polyethyleneimine-chlorhexidine, polypropylene-alginic acid dialdehyde-polyethyleneimine-phenylbiguanide, cellulose-alginic acid dialdehyde-polyethyleneimine-cysteine, cellulose-alginic acid dialdehyde-polyethyleneimine-benzalkonium chloride, cellulose-alginic acid dialdehyde-polyethyleneimine-chlorhexidine, cellulose-alginic acid dialdehyde-polyethyleneimine-phenylbiguanide, nylon-alginic acid dialdehyde-polyethyleneimine-cysteine, nylon-alginic acid dialdehyde-polyethyleneimine-benzalkonium chloride, nylon-alginic acid dialdehyde-polyethyleneimine-chlorhexidine, nylon-alginic acid dialdehyde-polyethyleneimine-phenylbiguanide or any combination thereof.

[0057] In some embodiments of the present disclosure, a polyethyleneimine antiviral modified material is provided, for example, selected from polypropylene-polyethyleneimine-benzalkonium chloride, polypropylene-polyethyleneimine-chlorhexidine, nylon-polyethyleneimine-benzalkonium chloride, nylon-polyethyleneimine-chlorhexidine, polypropylene-alginate dialdehyde-polyethyleneimine-benzalkonium chloride, polypropylene-alginate dialdehyde-polyethyleneimine-chlorhexidine, nylon-alginate dialdehyde-polyethyleneimine-benzalkonium chloride, nylon-alginate dialdehyde-polyethyleneimine-chlorhexidine or any combination thereof.

[0058] In some embodiments of the present disclosure, antibacterial activity testing of the polyethyleneimine antimicrobial modified material of the present disclosure revealed that the modified material exhibited 100% inhibition against both Gram-positive and Gram-negative bacteria and exhibited excellent stability. In some of these embodiments, the polyethyleneimine antimicrobial modified material is a polypropylene-based PEI antimicrobial modified material, a cellulose-based PEI antimicrobial modified material, or a nylon-based PEI antimicrobial modified material. In some embodiments, the polyethyleneimine antimicrobial modified material is selected from polypropylene-polyethyleneimine-cysteine, polypropylene-polyethyleneimine-benzalkonium chloride, polypropylene-polyethyleneimine-chlorhexidine, polypropylene-polyethyleneimine-phenyl biguanide, cellulose-polyethyleneimine-cysteine, cellulose-polyethyleneimine-benzalkonium chloride, cellulose-polyethyleneimine-chlorhexidine, cellulose-polyethyleneimine-phenyl biguanide, nylon-polyethyleneimine-cysteine, nylon-polyethyleneimine-benzalkonium chloride, nylon-polyethyleneimine-chlorhexidine, nylon-polyethyleneimine-phenyl biguanide, polypropylene-alginate dialdehyde-polyethyleneimine-cysteine, polypropylene- Alginate dialdehyde-polyethyleneimine-benzalkonium chloride, polypropylene-alginate dialdehyde-polyethyleneimine-chlorhexidine, polypropylene-alginate dialdehyde-polyethyleneimine-phenyl biguanide, cellulose-alginate dialdehyde-polyethyleneimine-cysteine, cellulose-alginate dialdehyde-polyethyleneimine-benzalkonium chloride, cellulose-alginate dialdehyde-polyethyleneimine-chlorhexidine, cellulose-alginate dialdehyde-polyethyleneimine-phenyl biguanide, nylon-alginate dialdehyde-polyethyleneimine-cysteine, nylon-alginate dialdehyde-polyethyleneimine-benzalkonium chloride, nylon-alginate dialdehyde-polyethyleneimine-chlorhexidine, nylon-alginate dialdehyde-polyethyleneimine-phenyl biguanide or its any combination.In some embodiments, described gram-positive bacteria is micrococcus lysodeikticus (Micrococcus lysodeikticus).In some embodiments, described gram-negative bacteria is escherichia coli (E.coli).

[0059] In some embodiments of the present disclosure, the antifungal activity of the polyethyleneimine antimicrobial modified material of the present disclosure was tested, and it was found that the modified material had a 100% inhibitory effect on fungi and good stability. In some of these embodiments, the polyethyleneimine antimicrobial modified material is a polypropylene-based PEI antimicrobial modified material, a cellulose-based PEI antimicrobial modified material, or a nylon-based PEI antimicrobial modified material. In some embodiments, the polyethyleneimine antimicrobial modified material is selected from polypropylene-polyethyleneimine-cysteine, polypropylene-polyethyleneimine-benzalkonium chloride, polypropylene-polyethyleneimine-chlorhexidine, polypropylene-polyethyleneimine-phenyl biguanide, cellulose-polyethyleneimine-cysteine, cellulose-polyethyleneimine-benzalkonium chloride, cellulose-polyethyleneimine-chlorhexidine, cellulose-polyethyleneimine-phenyl biguanide, nylon-polyethyleneimine-cysteine, nylon-polyethyleneimine-benzalkonium chloride, nylon-polyethyleneimine-chlorhexidine, nylon-polyethyleneimine-phenyl biguanide, polypropylene-alginate dialdehyde-polyethyleneimine-cysteine, polypropylene- Alginate dialdehyde-polyethyleneimine-benzalkonium chloride, polypropylene-alginate dialdehyde-polyethyleneimine-chlorhexidine, polypropylene-alginate dialdehyde-polyethyleneimine-phenylbiguanide, cellulose-alginate dialdehyde-polyethyleneimine-cysteine, cellulose-alginate dialdehyde-polyethyleneimine-benzalkonium chloride, cellulose-alginate dialdehyde-polyethyleneimine-chlorhexidine, cellulose-alginate dialdehyde-polyethyleneimine-phenylbiguanide, nylon-alginate dialdehyde-polyethyleneimine-cysteine, nylon-alginate dialdehyde-polyethyleneimine-benzalkonium chloride, nylon-alginate dialdehyde-polyethyleneimine-chlorhexidine, nylon-alginate dialdehyde-polyethyleneimine-phenylbiguanide or any combination thereof. In some embodiments, the fungus is Saccharomyces cerevisiae.

[0060] In some embodiments of the present disclosure, the polyethyleneimine antimicrobial modified material of the present disclosure was tested for antiviral activity, and it was found that the virus reduction could reach at least 2.5 log or more. In some embodiments, the measured virus reduction was in the range of 2.5 to 6 log. In some embodiments, the virus reduction was in the range of 3.0 to 5.0 log. In some embodiments, the polyethyleneimine antimicrobial modified material is a polypropylene-based polyethyleneimine antimicrobial modified material or a nylon-based polyethyleneimine antimicrobial modified material. In some embodiments, the polyethyleneimine antimicrobial modified material is selected from polypropylene-polyethyleneimine-benzalkonium chloride, polypropylene-polyethyleneimine-chlorhexidine, nylon-polyethyleneimine-benzalkonium chloride, nylon-polyethyleneimine-chlorhexidine, polypropylene-alginate dialdehyde-polyethyleneimine-benzalkonium chloride, polypropylene-alginate dialdehyde-polyethyleneimine-chlorhexidine, nylon-alginate dialdehyde-polyethyleneimine-benzalkonium chloride, nylon-alginate dialdehyde-polyethyleneimine-chlorhexidine, or any combination thereof. In some embodiments, the virus is the novel coronavirus SARS-CoV-2.

[0061] In a third aspect of the present disclosure, a method for preparing the aforementioned polyethyleneimine functionalized material is provided, comprising the following steps: mixing a porous material or a non-porous material with a polyethyleneimine aqueous solution, and then shaking the mixture at 60-200 rpm for 10 minutes to 24 hours at a temperature of 10-100°C and a pH of 5-11.

[0062] In some embodiments, the method further comprises the following steps: before adding the polyethyleneimine aqueous solution or after the porous material or non-porous material reacts with the polyethyleneimine aqueous solution, mixing the porous material or non-porous material with an alginate dialdehyde aqueous solution, and then shaking the mixture at 60-200 rpm for 10 minutes to 24 hours at a temperature of 10-100° C. and a pH of 1.5-8.

[0063] That is, in some embodiments, alginate dialdehyde can be reacted with a porous material or a non-porous material to form an alginate dialdehyde functionalized material, and then polyethyleneimine can be reacted with the alginate dialdehyde functionalized material to form a functionalized material containing both alginate dialdehyde and polyethyleneimine. In some embodiments, polyethyleneimine can be reacted with a porous material or a non-porous material to form a polyethyleneimine functionalized material, and then alginate dialdehyde can be reacted with the polyethyleneimine functionalized material to form a functionalized material containing both alginate dialdehyde and polyethyleneimine. In some embodiments, polyethyleneimine and alginate dialdehyde can also be reacted with a porous material or a non-porous material simultaneously to form a functionalized material containing both alginate dialdehyde and polyethyleneimine.

[0064] In some embodiments, the mass ratio of the sum of the polyethyleneimine contained in the polyethyleneimine aqueous solution and the alginate dialdehyde contained in the alginate dialdehyde aqueous solution to the porous material or non-porous material is 1:100 to 1:10. In some embodiments, the mass ratio is 1:50 to 1:20.

[0065] In some embodiments, the mass ratio of the polyethyleneimine contained in the polyethyleneimine aqueous solution to the alginate dialdehyde contained in the alginate dialdehyde aqueous solution is 100:1 to 10:1.

[0066] In some embodiments, the pH of the polyethyleneimine aqueous solution is 5-11. In some embodiments, the temperature is 10-100° C. In some embodiments, the shaking speed is 60-200 rpm. In some embodiments, the reaction time is 10-24 hours.

[0067] In some embodiments, the pH of the alginic acid dialdehyde aqueous solution is 1.5-8. In some embodiments, the temperature is 10-100° C. In some embodiments, the shaking speed is 120-200 rpm. In some embodiments, the reaction time is 10-24 hours.

[0068] In some embodiments, the concentration of the polyethyleneimine aqueous solution is 10-1000 mg / 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 embodiments, the concentration is 50-500 mg / ml; in some embodiments, the concentration is 20-100 mg / ml.

[0069] In some embodiments, the concentration of the alginate dialdehyde aqueous solution is 10-1000 mg / 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 embodiments, the concentration is 50-500 mg / ml; in some embodiments, the concentration is 20-100 mg / ml.

[0070] In the third aspect of the present disclosure, alternatively, the method comprises the following steps: directly coating or spraying an aqueous solution of polyethyleneimine at a pH of 1.5-8 on the surface of the porous material or non-porous material, and drying at a temperature of 10-100°C for 10 minutes to 24 hours to obtain the polyethyleneimine functionalized material.

[0071] In some embodiments, the method further comprises the following steps: before or after coating or spraying the polyethyleneimine aqueous solution, directly coating or spraying an alginate dialdehyde aqueous solution at a pH of 1.5-8 on the surface of the porous material or non-porous material and drying at a temperature of 10-100° C. for 10 minutes to 24 hours.

[0072] That is to say, in some embodiments, alginate dialdehyde can be first coated or sprayed on the surface of a porous material or a non-porous material to form an alginate dialdehyde functionalized material, and then coated or sprayed with polyethyleneimine to form a functionalized material comprising both alginate dialdehyde and polyethyleneimine. In some embodiments, polyethyleneimine can also be first coated or sprayed on the surface of a porous material or a non-porous material to form a polyethyleneimine functionalized material, and then coated or sprayed with alginate dialdehyde to form a functionalized material comprising both alginate dialdehyde and polyethyleneimine. In some embodiments, polyethyleneimine and alginate dialdehyde can also be coated or sprayed on the surface of a porous material or a non-porous material at the same time to form a functionalized material comprising both alginate dialdehyde and polyethyleneimine.

[0073] In some embodiments, the mass ratio of the sum of the polyethyleneimine contained in the polyethyleneimine aqueous solution and the alginate dialdehyde contained in the alginate dialdehyde aqueous solution to the porous material or non-porous material is 1:100 to 1:10. In some embodiments, the mass ratio is 1:50 to 1:20.

[0074] In some embodiments, the mass ratio of the polyethyleneimine contained in the polyethyleneimine aqueous solution to the alginate dialdehyde contained in the alginate dialdehyde aqueous solution is 100:1 to 10:1.

[0075] In some embodiments, the temperature is 10-100° C. In some embodiments, the drying time is 10 minutes to 1 hour. In some embodiments, the pH of the polyethyleneimine aqueous solution is 5-11.

[0076] In some embodiments, the temperature is 30-50° C. In some embodiments, the drying time is 10 minutes to 1 hour. In some embodiments, the pH of the alginic acid dialdehyde aqueous solution is 1.5-8.

[0077] In some embodiments, the PEI aqueous solution has a concentration of 10-1000 mg / 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 embodiments, the concentration is 50-500 mg / ml. In some embodiments, the concentration is 20-100 mg / ml.

[0078] In some embodiments, the ADA aqueous solution has a concentration of 10-1000 mg / 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 embodiments, the concentration is 50-500 mg / ml. In some embodiments, the concentration is 20-100 mg / ml.

[0079] In a fourth aspect of the present disclosure, a method for preparing the aforementioned polyethyleneimine modified material is provided, comprising the following steps: adding the aforementioned polyethyleneimine functionalized material or the polyethyleneimine functionalized material prepared according to the aforementioned method to an aqueous solution of a functional material, and shaking the solution at 60-200 rpm for 10 minutes to 24 hours at a temperature of 10-100°C and a pH of 1.5-8 to obtain the modified material; wherein the functional material can be combined with the connecting layer by covalent bonding, electrostatic adsorption, hydrophilic adsorption, hydrophobic adsorption, hydrogen bonding, or any combination thereof.

[0080] In some embodiments, the functional material accounts for 0.1% to 1% of the total mass of the modified material. In some embodiments, the mass percentage is 0.3% to 0.6%.

[0081] In some embodiments, the pH of the functional material aqueous solution is 1.5-8. In some embodiments, the temperature is 10-100° C. In some embodiments, the shaking speed is 120-200 rpm. In some embodiments, the reaction time is 8-16 hours.

[0082] In some embodiments, the functional material aqueous solution has a concentration of 10-100 mg / 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 embodiments, the concentration is 5-60 mg / ml. In some embodiments, the concentration is 2-20 mg / ml.

[0083] In one embodiment, the functional material is an antimicrobial material.

[0084] In the fourth aspect of the present disclosure, alternatively, the method comprises the following steps: directly coating or spraying the aqueous solution of the functional material on the polyethyleneimine functionalized material, and drying at a temperature of 10-100°C for 10 minutes to 24 hours to obtain the modified material; wherein the functional material can be combined with the connecting layer by covalent bonding, electrostatic adsorption, hydrophilic adsorption, hydrophobic adsorption, hydrogen bonding or any combination thereof, and the pH of the aqueous solution of the functional material is 1.5-8.

[0085] In some embodiments, the functional material accounts for 0.1% to 1% of the total mass of the modified material. In some embodiments, the mass percentage is 0.3% to 0.6%.

[0086] In some embodiments, the pH of the functional material aqueous solution is 1.5-8. In some embodiments, the temperature is 10-100° C. In some embodiments, the drying time is 8-16 hours.

[0087] In some embodiments, the functional material aqueous solution has a concentration of 10-100 mg / 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 embodiments, the concentration is 5-60 mg / ml. In some embodiments, the concentration is 2-20 mg / ml.

[0088] In one embodiment, the functional material is an antimicrobial material.

[0089] In a fifth aspect of the present disclosure, a method for preparing the aforementioned polyethyleneimine modified material is provided, comprising the following steps: mixing a functional material with a polyethyleneimine aqueous solution to obtain a polyethyleneimine-functional material aqueous solution; shaking the aqueous solution obtained as above with a porous material or a non-porous material at a temperature of 10-100°C and a pH of 1.5-8 at 60-200 rpm for 10 minutes to 24 hours to obtain the modified material; wherein the functional material can be combined with the connecting layer by covalent bonding, electrostatic adsorption, hydrophilic adsorption, hydrophobic adsorption, hydrogen bonding or any combination thereof.

[0090] In some embodiments, the method further comprises the step of mixing the functional material with an aqueous solution of alginate dialdehyde before, after, or simultaneously with mixing the functional material with the aqueous solution of polyethyleneimine.

[0091] That is to say, the functional material can be first mixed with the polyethyleneimine aqueous solution, and then mixed with the alginic acid dialdehyde aqueous solution and reacted with a porous material or a non-porous material to obtain a modified material containing polyethyleneimine and alginic acid dialdehyde simultaneously. Alternatively, the functional material can be first mixed with the alginic acid dialdehyde aqueous solution, and then mixed with the polyethyleneimine aqueous solution and reacted with a porous material or a non-porous material to obtain a modified material containing polyethyleneimine and alginic acid dialdehyde simultaneously. Alternatively, the functional material can be simultaneously mixed with the polyethyleneimine aqueous solution and the alginic acid dialdehyde aqueous solution to form a functional material aqueous solution containing polyethyleneimine and alginic acid dialdehyde simultaneously and reacted with a porous material or a non-porous material to obtain a modified material containing polyethyleneimine and alginic acid dialdehyde simultaneously.

[0092] In some embodiments, the mass ratio of the functional material, the sum of polyethyleneimine and alginate dialdehyde to the porous material or the non-porous material is (1-10):(10-100):1000.

[0093] In some embodiments, the pH of the polyethyleneimine aqueous solution is 1.5-6. In some embodiments, the temperature is 40-60° C. In some embodiments, the shaking speed is 120-200 rpm. In some embodiments, the reaction time is 4-16 hours.

[0094] In some embodiments, the pH of the alginic acid dialdehyde aqueous solution is 3-6. In some embodiments, the temperature is 40-70° C. In some embodiments, the shaking speed is 120-200 rpm. In some embodiments, the reaction time is 8-16 hours.

[0095] In some embodiments, the concentration of the polyethyleneimine aqueous solution is 10-1000 mg / 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 embodiments, the concentration is 50-500 mg / ml. In some embodiments, the concentration is 20-100 mg / ml.

[0096] In some embodiments, the concentration of the alginic acid dialdehyde aqueous solution is 10-1000 mg / ml and is adjusted to an appropriate pH with an acid (e.g., sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, nitric acid). In some embodiments, the concentration is 50-500 mg / ml. In some embodiments, the concentration is 20-100 mg / ml.

[0097] In one embodiment, the functional material is an antimicrobial material.

[0098] In the method described in the fifth aspect of the present disclosure, alternatively, the method comprises the following steps: 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 as above onto 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°C for 10 minutes to 24 hours to obtain the modified material; wherein the functional material can be combined with the connecting layer by covalent bonding, electrostatic adsorption, hydrophilic adsorption, hydrophobic adsorption, hydrogen bonding or any combination thereof.

[0099] In some embodiments, the method further comprises the step of mixing the functional material with an aqueous solution of alginate dialdehyde before, after, or simultaneously with mixing the functional material with the aqueous solution of polyethyleneimine.

[0100] That is to say, functional material can be first mixed with polyethyleneimine aqueous solution, and then mixed with alginate dialdehyde aqueous solution and coated or sprayed onto the surface of porous material or non-porous material, to obtain the modifying material containing polyethyleneimine and alginate dialdehyde simultaneously. Alternatively, functional material can be first mixed with alginate dialdehyde aqueous solution, and then mixed with alginate dialdehyde aqueous solution and coated or sprayed onto the surface of porous material or non-porous material, to obtain the modifying material containing polyethyleneimine and alginate dialdehyde simultaneously. Alternatively, functional material can be simultaneously mixed with polyethyleneimine aqueous solution and alginate dialdehyde aqueous solution, and then coated or sprayed onto the surface of porous material or non-porous material, to obtain the modifying material containing polyethyleneimine and alginate dialdehyde simultaneously. In some embodiments, the summation of the functional material, polyethyleneimine and alginate dialdehyde, and the mass ratio of the porous material or non-porous material are (1-10): (10-100): 1000.

[0101] In some embodiments, the pH of the polyethyleneimine aqueous solution is 5-11. In some embodiments, the pH of the alginate dialdehyde aqueous solution is 1.5-8. In some embodiments, the temperature is 10-100° C. In some embodiments, the drying time is 10 minutes to 24 hours.

[0102] In some embodiments, the concentration of the polyethyleneimine aqueous solution is 10-1000 mg / 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 embodiments, the concentration is 50-500 mg / ml. In some embodiments, the concentration is 20-100 mg / ml.

[0103] In some embodiments, the concentration of the alginic acid dialdehyde aqueous solution is 10-1000 mg / ml and is adjusted to an appropriate pH with an acid (e.g., sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, nitric acid). In some embodiments, the concentration is 50-500 mg / ml. In some embodiments, the concentration is 20-100 mg / ml.

[0104] In one embodiment, the functional material is an antimicrobial material.

[0105] In some embodiments, the methods described in the third, fourth, and fifth aspects of the present disclosure further include the following steps: washing the obtained product, and then storing it wet or air-drying or oven-drying it.

[0106] In some embodiments, the above product can be washed with detergent and / or water. In some embodiments, the functionalized material comprising both alginate dialdehyde and polyethyleneimine can be washed with detergent and water while maintaining its activity. In some embodiments, the detergent can be selected from any neutral detergent. As used herein, "neutral detergent" refers to a detergent having a pH range of 6-8 at a standard use concentration of 25°C. For example, the neutral detergent can be selected from any one or more of the following: an alkali (e.g., sodium carbonate, borax), a surfactant (e.g., alkyl sulfate, sodium lauryl sulfate, alkyl ethoxy sulfate or fatty alcohol ether), a functional material (e.g., a pH regulator, a brightener, a water regulator, sodium stearate or silicone), a catalytic enzyme (e.g., a protease, an amylase, a cellulase, a mannoses or pectinase) and a chelate (e.g., sodium tripolyphosphate, EDTA, HEDTA, PDTA or DTPA).

[0107] In a sixth aspect of the present disclosure, there is provided use of the polyethyleneimine functionalized material, polyethyleneimine modified material, or preparation method thereof described in the aforementioned aspects in the production of medical supplies and antimicrobial supplies.

[0108] In some embodiments, the uses include the production of masks, isolation gowns, gloves, personal protective equipment, bandages, medical tapes, medical caps, medical sheets, medical clothing, air filters, water filters, electronic products, household appliances and automotive accessories, etc.

[0109] The polyethyleneimine functionalized materials and polyethyleneimine modified materials disclosed herein and their preparation methods have multiple beneficial effects. For example, the raw materials are economical, environmentally friendly, and safe; the support layer (base layer) can be made of a variety of common base materials with any pore size, polyethyleneimine can be easily purchased commercially or synthesized, and the antimicrobial materials can be made of economical and safe amino acids, quaternary ammonium salts, chlorhexidine, biguanide compounds, etc. For another example, the preparation method is simple, the raw materials are easily available and low-cost, and no irritating organic solvents are required. It is environmentally friendly and easy to scale up production. In addition, it has high inhibitory activity against bacteria (including Gram-positive and Gram-negative bacteria), fungi, and viruses, reducing the risk of secondary infection. Therefore, the present invention has great application potential in the fields of biology, medicine, and health. Among them, the polyethyleneimine modified material obtained by using polyethyleneimine alone as a connecting layer has excellent antibacterial, antifungal, and antiviral effects. However, in order to further improve its stability, alginate dialdehyde is also added, and the polyethyleneimine modified material obtained by adding alginate dialdehyde also has excellent antibacterial, antifungal, and antiviral effects.

[0110] Unless otherwise specified, the chemicals in the following examples are commercially available and will not be described again.

[0111] Example 1: Preparation of polyethyleneimine (PEI) antimicrobial modified material

[0112] This embodiment is a preparation example of a polyethyleneimine antimicrobial modified material, wherein the porous or non-porous material is polypropylene-based, nylon-based (taking nylon 66 composite material based on polyhexamethylene adipamide as an example), and cellulose material as an example, and the antimicrobial material is cysteine, benzalkonium chloride, chlorhexidine, and phenylbiguanide (1-(3-chlorophenyl)biguanide hydrochloride) as an example. The polypropylene-based material is purchased from Tansole China (product number: MFPP047020), the cellulose material is purchased from General Electronics (GE) Whatman (product number: GB / T1914-2007), and the nylon (polyhexamethylene adipamide, i.e., nylon 66) is purchased from Merck Millipore (product number: GNWP04700).

[0113] 1. Preparation of PEI functionalized materials:

[0114] 1.1 Preparation of functionalized materials containing only PEI:

[0115] The functionalized material containing only PEI was prepared by one of the following methods:

[0116] Method 1: Take 10g of each of the aforementioned porous or non-porous materials, clean them, and immerse them in a PEI aqueous solution containing 0.1-1g of PEI at a pH of 5-11. The reaction is carried out at 60°C with shaking at 120 rpm for 30 minutes to 1 hour to obtain a functionalized material containing only PEI. After the reaction, the resulting PEI-functionalized material is washed with distilled water.

[0117] Method 2: Take 10g of the porous material or non-porous material and clean it, then directly apply or spray an aqueous solution of PEI containing 0.1-1g PEI at a pH of 5-11 onto the surface of the material at 60°C, and then dry it at room temperature for 8 hours to obtain a functionalized material containing only PEI.

[0118] The products prepared as above are polypropylene-PEI functionalized materials, cellulose-PEI functionalized materials and nylon-PEI functionalized materials.

[0119] 1.2 Preparation of functionalized materials containing ADA and PEI:

[0120] 1.2.1 Prepare ADA functionalized materials by one of the following methods:

[0121] Method 1: Take 10g of each of the aforementioned porous or non-porous materials, clean them, and immerse them in an ADA aqueous solution containing 0.1-1g of ADA at a pH of 3-6. The ADA-functionalized material is prepared by reacting the material at room temperature to 100°C with shaking at 80-120 rpm for 30 minutes to 3 hours. After the reaction, the ADA-functionalized material is washed with distilled water.

[0122] Method 2: Take 10g of the porous material or non-porous material and clean it, then directly coat or spray an ADA aqueous solution containing 0.1-1g ADA at a pH of 3-6 onto the surface of the material at room temperature to 100°C, and then dry it at 30°C for 8 hours to obtain an ADA functionalized material.

[0123] The products prepared as above are polypropylene-ADA functionalized materials, cellulose-ADA functionalized materials and nylon-ADA functionalized materials.

[0124] 1.2.2 Prepare a functionalized material comprising ADA and PEI (ADA-PEI functionalized material) by one of the following methods:

[0125] Method 1: Take 10g of each of the above ADA-functionalized materials and immerse them in a PEI aqueous solution containing 0.01-0.1g of PEI at a pH of 5-10. The mixture is allowed to react at room temperature to 70°C with shaking at 80-120 rpm for 30 minutes to 3 hours to obtain an ADA-PEI-functionalized material. After the reaction, wash the resulting ADA-PEI-functionalized material with a neutral detergent and then distilled water.

[0126] Method 2: Take 10g of each of the aforementioned ADA-functionalized materials and directly coat or spray a PEI aqueous solution containing 0.01-0.1g PEI at a pH of 5-10 onto the surface of the material at room temperature to 70°C. After the reaction, wash the resulting ADA-PEI-functionalized material with detergent and then distilled water. Then, dry the material at room temperature for 8 hours to obtain the ADA-PEI-functionalized material.

[0127] The products obtained as above are polypropylene-ADA-PEI functionalized material, cellulose-ADA-PEI functionalized material and nylon-ADA-PEI functionalized material.

[0128] 2. Preparation of PEI antimicrobial modified materials:

[0129] The PEI antimicrobial modified material was prepared by one of the following methods:

[0130] Method 1: 10 g of PEI functionalized material and 10-1000 mg of the aforementioned antimicrobial material aqueous solution with a pH of 5-8 were reacted at room temperature and shaken at 120 rpm for 30 minutes to 3 hours to obtain a PEI microbial modified material;

[0131] Method 2: 10-1000 mg of the aforementioned antimicrobial material aqueous solution with a pH of 5-8 is directly coated or sprayed onto the surface of 10 g of PEI functionalized material, and then dried at room temperature for 8 hours to obtain the PEI microbial modified material;

[0132] Method 3: Mix 10-100mg of antimicrobial material with 0.01-0.1g of PEI, then mix with Milli Q ultrapure water and adjust the pH to 3-7 to obtain an aqueous solution of PEI antimicrobial material. 10g of porous or non-porous material is reacted with the obtained aqueous solution of PEI antimicrobial material at room temperature and shaken at 80-120rpm for 0.5-3 hours to obtain an antimicrobial modified material containing only PEI. The preparation method of ADA-PEI antimicrobial modified material is similar to the above, except that the antimicrobial material is mixed with ADA before mixing with PEI, and then PEI is added and mixed, followed by a shaking step.

[0133] Method 4: 10-100 mg of the antimicrobial material is mixed with 0.01-0.1 g of PEI, then mixed with Milli Q ultrapure water and adjusted to a pH of 3-7 to obtain an aqueous solution of the PEI antimicrobial material. This aqueous solution is directly coated or sprayed onto the surface of 10 g of a porous or non-porous material and allowed to dry at room temperature for 8 hours to obtain a PEI antimicrobial modified material containing only PEI. The preparation method for the ADA-PEI antimicrobial modified material is similar to the above, except that the antimicrobial material and ADA are mixed before mixing the antimicrobial material and PEI, followed by the addition of PEI and mixing, and then the coating or spraying step.

[0134] The products obtained as above are polypropylene-PEI-cysteine ​​modified materials, polypropylene-PEI-benzalkonium chloride modified materials, polypropylene-PEI-chlorhexidine modified materials, polypropylene-PEI-phenylbiguanide modified materials; cellulose-PEI-cysteine ​​modified materials, cellulose-PEI-benzalkonium chloride modified materials, cellulose-PEI-chlorhexidine modified materials, cellulose-PEI-phenylbiguanide modified materials; nylon-PEI-cysteine ​​modified materials, nylon-PEI-benzalkonium chloride modified materials, nylon-PEI-chlorhexidine modified materials, nylon-PEI-phenylbiguanide modified materials. Materials, 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.

[0135] The PEI modified material product obtained above can be washed several times and stored for other uses, such as protective clothing and other protective materials.

[0136] Example 2: XPS Characterization of PEI Antimicrobial Modified Materials

[0137] The surface atomic ratio of the PEI antimicrobial modified material prepared in Example 1 was detected by X-ray photoelectron spectroscopy (XPS). This example takes the PEI antimicrobial modified material (nylon-ADA-PEI-benzalkonium chloride) prepared by method 1 for preparing a functionalized material comprising ADA and PEI in 1.2 of Example 1 and method 1 for preparing a PEI antimicrobial modified material as an example.

[0138] Table 1: Surface atomic ratios of the samples obtained from XPS.

[0139] As shown in Figure 1 and Table 1, ADA coating of nylon increased the oxygen content of nylon-ADA compared to nylon due to the oxygen-rich content of ADA. The addition of PEI increased the nitrogen content from 10.88% to 20.36% after PEI coating on nylon-ADA-PEI. Furthermore, the benzalkonium chloride coating on nylon-ADA-PEI-benzalkonium chloride increased the carbon ratio, while also detecting the presence of chlorine atoms. Thus, XPS confirmed the successful functionalization of the PEI antimicrobial modified material.

[0140] Example 3: Determination of antibacterial activity of PEI antimicrobial modified materials

[0141] This example tests the antibacterial activity of polypropylene-based, cellulose-based, and nylon-based PEI antimicrobial modified materials prepared in Example 1. This example uses the PEI antimicrobial modified materials prepared by Method 1 (Method 1 for preparing PEI functionalized materials only and Method 1 for preparing ADA and PEI) and Method 1 for preparing PEI antimicrobial modified materials in Example 1 as examples, but highly similar results were obtained using PEI antimicrobial modified materials prepared by other methods in Example 1.

[0142] I. Experimental Methods

[0143] Taking Gram-positive bacteria Micrococcus lysodeikticus and Gram-negative bacteria Escherichia coli (E. coli) as examples, antibacterial activity experiments were carried out using polypropylene-PEI-antimicrobial material, cellulose-PEI-antimicrobial material, 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 performed in triplicate and the average value was taken.

[0144] Micrococcus lysodeikticus and Escherichia coli were cultured with stirring at 37°C overnight in LB (Luria-Bertani) medium. The fresh bacterial culture was diluted to a colony count of 10 -4 CFU / mL bacterial suspension; 0.1g of antimicrobial modified material was mixed with 10mL of bacterial suspension in a flask and incubated at 37°C for 2 hours on a shaker at 120 rpm. Another 10mL of bacterial suspension, without modified material, was placed in another flask as a control. After the reaction, 10-100μl of the bacterial suspension was inoculated onto LB agar plates and incubated at 37°C for 18-36 hours. After 18 hours of incubation, the number of viable colonies was counted using the plate count method.

[0145] The bacterial inhibition activity was calculated according to the following formula:

[0146] Where I represents the bacterial inhibition activity, N0 represents the number of colonies after culture in the control group, and N i It indicates the number of colonies after culture in the treatment group.

[0147] In addition, to examine the stability of the antibacterial coating, all antimicrobial modified materials were immersed in ultrapure water (Milli Q) after autoclaving for 48 h, and the antibacterial activity was compared with that of the freshly prepared modified materials.

[0148] II. Experimental Results

[0149] 1. Polypropylene-based antimicrobial modified materials:

[0150] Table 2 shows the antibacterial activity of polypropylene-based antimicrobial modified materials against Micrococcus lysodeikticus and Escherichia coli. The antibacterial activity of polypropylene alone was extremely low, as was the activity of the polypropylene-ADA material. Freshly prepared and 48-hour samples of the polypropylene-ADA material exhibited 30% and 31% inhibition against Gram-positive bacteria, respectively, and 25% inhibition against Gram-negative bacteria. Both freshly prepared and 48-hour samples of the polypropylene-ADA-PEI material exhibited 90% inhibition against Gram-positive bacteria. The newly prepared samples and 48-hour samples of polypropylene-PEI-cysteine, polypropylene-PEI-benzalkonium chloride, polypropylene-PEI-chlorhexidine, polypropylene-ADA-PEI-cysteine, polypropylene-PEI-phenylbiguanide, polypropylene-ADA-PEI-benzalkonium chloride, polypropylene-ADA-PEI-chlorhexidine, and polypropylene-ADA-PEI-phenylbiguanide all showed 100% inhibition against both Gram-positive and Gram-negative bacteria. It can be seen that all polypropylene-PEI-antimicrobial modified materials and polypropylene-ADA-PEI-antimicrobial modified materials disclosed herein still maintained the same bacterial inhibition activity as the newly prepared materials after being soaked in water for 48 hours.

[0151] Table 2: Antibacterial activity test results of polypropylene-based antimicrobial modified materials.

[0152] 2. Cellulose-based antimicrobial modified materials:

[0153] The antibacterial activity results of the cellulose-based antimicrobial modified materials against Micrococcus lysodeikticus and Escherichia coli are shown in Table 3. The antibacterial activity of the cellulose material alone was extremely low. Freshly prepared and 48-hour samples of the cellulose-ADA material showed 37% and 36% inhibition against Gram-positive bacteria, respectively, and 20% and 18% inhibition against Gram-negative bacteria, respectively. Freshly prepared and 48-hour samples of the cellulose-ADA-PEI material showed 90% inhibition against Gram-positive and Gram-negative bacteria, respectively. The freshly prepared samples and 48-hour samples of cellulose-PEI-cysteine, cellulose-PEI-benzalkonium chloride, cellulose-PEI-chlorhexidine, cellulose-PEI-phenylbiguanide, cellulose-ADA-PEI-cysteine, cellulose-ADA-PEI-benzalkonium chloride, cellulose-ADA-PEI-chlorhexidine, and cellulose-ADA-PEI-phenylbiguanide all showed 100% inhibition against both Gram-positive and Gram-negative bacteria. It can be seen that all of the cellulose-PEI-antimicrobial modified materials and cellulose-ADA-PEI-antimicrobial modified materials disclosed herein still maintained the same bacterial inhibition activity as the freshly prepared materials after being soaked in water for 48 hours.

[0154] Table 3: Antibacterial activity test results of cellulose-based antimicrobial modified materials.

[0155] 3. Nylon-based antimicrobial modified materials

[0156] Table 4 shows the antibacterial activity of the nylon-based antimicrobial modified materials against Micrococcus lysodeikticus and Escherichia coli. Nylon alone showed very low antibacterial activity. Freshly prepared and 48-hour samples of the nylon-ADA material exhibited 27% and 20% inhibition against Gram-positive and Gram-negative bacteria, respectively, and 20% and 18% inhibition against Gram-negative bacteria, respectively. Freshly prepared and 48-hour samples of the nylon-ADA-PEI material exhibited 90% inhibition against Gram-positive and Gram-negative bacteria, respectively. The newly prepared samples and 48-hour samples of nylon-PEI-cysteine, nylon-PEI-benzalkonium chloride, nylon-PEI-chlorhexidine, nylon-PEI-phenylbiguanide, nylon-ADA-PEI-cysteine, nylon-ADA-PEI-benzalkonium chloride, nylon-ADA-PEI-chlorhexidine, and nylon-ADA-PEI-phenylbiguanide all showed 100% inhibition against both Gram-positive and Gram-negative bacteria. Furthermore, it can be seen that all of the nylon-PEI-antimicrobial modified materials and nylon-ADA-PEI-antimicrobial modified materials disclosed herein still maintained the same bacterial inhibition activity as the newly prepared materials after being immersed in water for 48 hours.

[0157] Table 4: Antibacterial activity test results of nylon-based antimicrobial modified materials.

[0158] Example 4: Determination of antifungal activity of PEI antimicrobial modified materials

[0159] This example tests the antifungal activity of polypropylene-based, cellulose-based, and nylon-based PEI antimicrobial modified materials prepared in Example 1. This example uses the PEI antimicrobial modified materials prepared by Method 1 (Method 1 for preparing PEI functionalized materials only and Method 1 for preparing ADA and PEI functionalized materials) and Method 1 for preparing PEI antimicrobial modified materials in Example 1 as examples, but highly similar results were obtained using PEI antimicrobial modified materials prepared by other methods in Example 1.

[0160] I. Experimental Methods

[0161] Taking Saccharomyces cerevisiae as an example of fungi, antifungal activity experiments were carried out using polypropylene-PEI-antimicrobial material, cellulose-PEI-antimicrobial material, nylon-PEI-antimicrobial material, polypropylene-ADA-PEI-antimicrobial material, cellulose-ADA-PEI-antimicrobial material and nylon-ADA-PEI-antimicrobial material, and the average value of triplicate samples was taken.

[0162] Saccharomyces cerevisiae was cultured overnight with stirring at 30°C using yeast peptone dextrose (YPD) medium. Fresh fungal culture was 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 in a flask and incubated at 37°C at 120rpm for 2 hours. Another 10mL of the fungal suspension was placed in another flask as a control. After the reaction, 10-100μl of the fungal suspension was inoculated onto a YPD agar plate and incubated at 30°C for 18-36 hours. After 36 hours of incubation, the number of viable colonies was calculated using the plate count method.

[0163] The fungal inhibitory activity was calculated according to the following formula:

[0164] Where I represents the fungal inhibitory activity, N0 represents the number of colonies after culture in the control group, and N i It indicates the number of colonies after culture in the treatment group.

[0165] In addition, to examine the stability of the antifungal coating, all antimicrobial modified materials were also immersed in ultrapure water (Milli Q) after autoclaving for 48 h and the antifungal activity was compared with that of freshly prepared materials.

[0166] II. Experimental Results

[0167] 1. Polypropylene-based antimicrobial modified materials:

[0168] Table 5 shows the antifungal activity of polypropylene-based antimicrobial modified materials against Saccharomyces cerevisiae. The antifungal activity of polypropylene alone was only 15%. Freshly prepared and 48-hour samples of polypropylene-ADA material exhibited 35% and 32% inhibitory activity against Saccharomyces cerevisiae, respectively. Freshly prepared and 48-hour samples of polypropylene-ADA-PEI material exhibited 90% inhibitory activity against Saccharomyces cerevisiae, respectively. Freshly prepared and 48-hour samples of polypropylene-PEI-cysteine, polypropylene-PEI-benzalkonium chloride, polypropylene-PEI-chlorhexidine, polypropylene-PEI-phenylbiguanide, polypropylene-ADA-PEI-cysteine, polypropylene-ADA-PEI-benzalkonium chloride, polypropylene-ADA-PEI-chlorhexidine, and polypropylene-ADA-PEI-phenylbiguanide all exhibited 100% inhibitory activity against Saccharomyces cerevisiae. As can be seen, all of the polypropylene-PEI antimicrobial modified materials and polypropylene-ADA-PEI antimicrobial modified materials disclosed herein maintained the same fungal inhibitory activity as freshly prepared materials after immersion in water for 48 hours.

[0169] Table 5: Antifungal activity test results of polypropylene-based antimicrobial modified materials.

[0170] 2. Cellulose-based antimicrobial modified materials

[0171] Table 6 shows the antifungal activity of the cellulose-based antimicrobial modified materials against Saccharomyces cerevisiae. Freshly prepared and 48-hour samples of the freshly prepared cellulose material alone exhibited 23% and 21% inhibition against Saccharomyces cerevisiae, respectively. Freshly prepared and 48-hour samples of the cellulose-ADA material exhibited 37% and 36% inhibition against Saccharomyces cerevisiae, respectively. Freshly prepared and 48-hour samples of the cellulose-ADA-PEI material each exhibited 90% inhibition against Saccharomyces cerevisiae. Furthermore, freshly prepared and 48-hour samples of the cellulose-PEI-cysteine, cellulose-PEI-benzalkonium chloride, cellulose-PEI-chlorhexidine, cellulose-PEI-phenylbiguanide, cellulose-ADA-PEI-cysteine, cellulose-ADA-PEI-benzalkonium chloride, cellulose-ADA-PEI-chlorhexidine, and cellulose-ADA-PEI-phenylbiguanide all exhibited 100% inhibition against Saccharomyces cerevisiae. It can be seen that all the cellulose-PEI-antimicrobial modified materials and cellulose-ADA-PEI-antimicrobial modified materials disclosed in the present invention still maintained the same fungal inhibition activity as the newly prepared materials after being soaked in water for 48 hours.

[0172] Table 6: Antifungal activity test results of cellulose-based antimicrobial modified materials.

[0173] 3. Nylon-based antimicrobial modified materials

[0174] Table 7 shows the antifungal activity of the nylon-based antimicrobial modified materials against Saccharomyces cerevisiae. Freshly prepared and 48-hour samples of the nylon material alone exhibited 18% and 17% inhibition against Saccharomyces cerevisiae, respectively. Freshly prepared and 48-hour samples of the nylon-ADA material exhibited 40% and 39% inhibition against Saccharomyces cerevisiae, respectively. Freshly prepared and 48-hour samples of the nylon-ADA-PEI material exhibited 90% inhibition against Saccharomyces cerevisiae. Furthermore, freshly prepared and 48-hour samples of nylon-PEI-cysteine, nylon-PEI-benzalkonium chloride, nylon-PEI-chlorhexidine, nylon-PEI-phenylbiguanide, nylon-ADA-PEI-cysteine, nylon-ADA-PEI-benzalkonium chloride, nylon-ADA-PEI-chlorhexidine, and nylon-ADA-PEI-phenylbiguanide all exhibited 100% inhibition against Saccharomyces cerevisiae. It can be seen that all the nylon-PEI-antimicrobial modified materials and nylon-ADA-PEI-antimicrobial modified materials disclosed herein still maintain the same fungal inhibition activity as the newly prepared materials after being soaked in water for 48 hours.

[0175] Table 7: Antifungal activity test results of nylon-based antimicrobial modified materials.

[0176] Example 5: Determination of antiviral activity of PEI antimicrobial modified materials

[0177] This example tests the antiviral activity of polypropylene-based and nylon-based PEI antimicrobial modified materials prepared in Example 1. This example uses the PEI antimicrobial modified materials prepared by Method 1 (Method 1 for preparing PEI functionalized materials only and Method 1 for preparing ADA and PEI functionalized materials) and Method 1 for preparing PEI antimicrobial modified materials in Example 1 as examples, but highly similar results were obtained using PEI antimicrobial modified materials prepared by other methods in Example 1.

[0178] I. Experimental Methods

[0179] Taking the new coronavirus (SARS-CoV-2) as an example of the virus, antiviral activity experiments were carried out using polypropylene-based PEI antimicrobial modified materials and nylon-based PEI antimicrobial modified materials, respectively. The samples were performed in triplicate and the average value was taken.

[0180] The material was dried in a biosafety cabinet and then cut into approximately 0.3 cm x 0.3 cm pieces. 200 μl of a virus (SARS-CoV-2) suspension was mixed with the material in a 2 mL sterile centrifuge tube and incubated at room temperature for 1 hour. An equal amount of virus sample (virus suspension) was placed in another sterile centrifuge tube as a control. The initial log TCID50 / mL of the virus sample was 6.0 log 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 μl of PBS, and 400 μl of the eluate was collected from a MicroSpin S-400HR column (GE Healthcare) to remove the eluted active components and reduce cytotoxicity. The control virus eluate and residual virus eluate from the treated group were titrated with 50% tissue culture infectious dose (TCID50). Viral titers were calculated using the Reed-Muench method.

[0181] II. Experimental Results

[0182] 1. Polypropylene-based antimicrobial modified materials:

[0183] The antiviral activity results of polypropylene-based antimicrobial modified materials against the novel coronavirus SARS-CoV-2 are shown in Table 8. The Log TCID50 / mL values ​​for the control virus sample and virus samples treated with polypropylene, polypropylene-PEI, polypropylene-PEI-benzalkonium chloride, polypropylene-PEI-chlorhexidine, polypropylene-ADA-PEI-benzalkonium chloride, and polypropylene-ADA-PEI-chlorhexidine were 6.0, 6.0, 5.0, 2.0, 3.5, 1.0, and 3.0 log, respectively. The polypropylene-PEI-benzalkonium chloride and polypropylene-ADA-PEI-benzalkonium chloride materials reduced viral titers by 4 and 5 logs, respectively, relative to the control, 4 and 5 logs, respectively, relative to the polypropylene material, and 3 and 4 logs, respectively, relative to the polypropylene-PEI material. Polypropylene-PEI-chlorhexidine material and polypropylene-ADA-PEI-chlorhexidine material reduced the viral titer by 2.5 log and 3 log, respectively, relative to the control, and also by 2.5 log and 3 log, respectively, relative to the polypropylene material, and reduced the viral titer by 1.5 log and 2 log, respectively, relative to the polypropylene-PEI material.

[0184] Although polypropylene-PEI material also reduces the virus titer to a certain extent, its principle is to adsorb the virus to the surface of the material so that it is not eluted, but it does not kill the virus; while polypropylene-PEI-benzalkonium chloride material, polypropylene-ADA-PEI-benzalkonium chloride material, polypropylene-PEI-chlorhexidine material and polypropylene-ADA-PEI-chlorhexidine material directly kill the virus through benzalkonium chloride and chlorhexidine, achieving almost 100% virus blocking effect.

[0185] Table 8. Antiviral activity test results of polypropylene-based antimicrobial modified materials (SARS-CoV-2).

[0186] 2. Nylon-based antimicrobial modified materials:

[0187] Table 8 shows the antiviral activity of nylon-based antimicrobial modified materials against the novel coronavirus SARS-CoV-2. The Log TCID50 / mL values ​​for the control virus, nylon material, nylon-PEI material, nylon-PEI-benzalkonium chloride, nylon-PEI-chlorhexidine, nylon-ADA-PEI-benzalkonium chloride, and nylon-ADA-PEI-chlorhexidine were 6.0, 6.0, 5.0, 1.0, 2.5, 1.0, and 2.0, respectively. The nylon-PEI-benzalkonium chloride material reduced viral titers by 5, 5, and 4 logs relative to the control, nylon material, and nylon-PEI material, respectively. The nylon-PEI-chlorhexidine material reduced viral titers by 3.5, 3.5, and 2.5 logs relative to the control, nylon material, and nylon-PEI material, respectively. The nylon-ADA-PEI-benzalkonium chloride material reduced viral titers by 5, 5, and 4 logs relative to the control, nylon material, and nylon-PEI material, respectively. The nylon-ADA-PEI-chlorhexidine material reduced the viral titer by 4.0, 4.0, and 3.0 log relative to the control, nylon material, and nylon-PEI material, respectively.

[0188] Although nylon-PEI material can reduce viral titer, it adsorbs the virus to the surface of the material without killing the virus; while nylon-PEI-benzalkonium chloride material, nylon-ADA-PEI-benzalkonium chloride material, nylon-PEI-chlorhexidine material and nylon-ADA-PEI-chlorhexidine material achieve the effect by directly killing the virus through benzalkonium chloride and chlorhexidine.

[0189] Table 8. Antiviral activity test results of nylon-based antimicrobial modified materials (SARS-CoV-2).

[0190] The above-described embodiments merely represent several implementation methods of the present disclosure. While the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that a person of ordinary skill in the art could make various modifications and improvements without departing from the spirit of the present disclosure, all of which fall within the scope of protection of the present disclosure. Therefore, the scope of protection of the present patent shall be determined by the appended claims.

Claims

1. Polyethyleneimine functionalized materials, including: a support layer composed of one or more porous or non-porous materials; and a connecting layer comprising polyethyleneimine, wherein the polyethyleneimine is directly and / or indirectly bonded to the support layer by a method selected from covalent bonding, electrostatic adsorption, hydrogen bonding, or any combination thereof; The connecting layer can be combined with the functional material by a method selected from covalent bonding, electrostatic adsorption, hydrophilic adsorption, hydrophobic adsorption, hydrogen bonding or any combination thereof.

2. The functionalized material according to claim 1, characterized in that The connecting layer further comprises alginate dialdehyde, which is bonded to the supporting layer and / or the polyethyleneimine by a method selected from covalent bonding, electrostatic adsorption, hydrogen bonding or any combination thereof.

3. The functionalized material according to claim 1, characterized in that The one or more porous materials or non-porous materials are made of one or more polymers or composite materials or any combination thereof.

4. The functionalized material according to claim 3, characterized in that The polymer or composite material is selected from polypropylene, cellulose, regenerated cellulose, polyvinylidene fluoride, polyethersulfone, polystyrene, polytetrafluoroethylene, polyethylene, polyimide, polyamide or any combination thereof.

5. The functionalized material according to any one of claims 1 to 4, characterized in that The mass ratio of the connecting layer to the supporting layer is 1:100 to 1:

10.

6. The functionalized material according to claim 5, characterized in that The mass ratio of the connecting layer to the supporting layer is 1:50 to 1:

20.

7. The functionalized material according to claim 2, characterized in that The mass ratio of alginate 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 alginate dialdehyde to polyethyleneimine in the functionalized material is 50:1 to 20:

1.

9. The functionalized material according to any one of claims 1 to 4, characterized in that The functional material is an antimicrobial material, and the microorganism is selected from bacteria, fungi, viruses or any combination thereof, wherein: the bacteria are selected from Chlamydia pneumoniae, Streptococcus pneumoniae, Mycobacterium tuberculosis, Group A Streptococcus, Corynebacterium diphtheriae, Haemophilus influenzae, Neisseria meningitidis, Clostridium difficile, methicillin-resistant Staphylococcus aureus, vancomycin-resistant Enterococcus, Acinetobacter baumannii or any combination thereof; the fungi are selected from Pneumocystis, Aspergillus, Coccidioides, Saccharomyces, Candida, Mucor The virus is selected from respiratory syncytial virus, hepatitis virus, varicella virus, polio virus, smallpox virus, measles virus, mumps virus, Chlamydia trachomatis, influenza virus, SARS-CoV virus, SARS-CoV-2 virus, H1N1 virus, H5N1 virus, H5N7 virus, MERS-CoV virus, Staphylococcus aureus, Klebsiella pneumoniae, Aspergillus niger, Ebola virus or any combination thereof.

10. The functionalized material according to claim 9, characterized in that The antimicrobial material is selected from amino acids, quaternary ammonium compounds, chlorhexidine compounds, alexidine compounds, biguanide compounds or any combination thereof, and wherein the amino acids are selected from cysteine, tyrosine, lysine, arginine and aspartic acid or any combination thereof; the quaternary ammonium compound is selected from alkyldimethylbenzyl ammonium chloride, alkyldidecyldimethylammonium chloride, dialkyldimethylammonium chloride and dialkyl quaternary ammonium salt 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. Polyethyleneimine modified materials, including: The polyethyleneimine functionalized material according to any one of claims 1 to 10; and The functional layer is composed of a functional material that can be combined with the connecting layer by a method selected from covalent bonding, electrostatic adsorption, hydrophilic adsorption, hydrophobic adsorption, hydrogen bonding or any combination thereof.

12. The modified material according to claim 11, characterized in that The functional material is an antimicrobial material, and the polyethyleneimine modified material is a polyethyleneimine antimicrobial modified material.

13. The modified material according to claim 12, characterized in that The antimicrobial material is selected from amino acids, quaternary ammonium compounds, chlorhexidine compounds, alexidine compounds, biguanide compounds or any combination thereof.

14. The modified material according to claim 13, characterized in that The amino acids are selected from cysteine, tyrosine, lysine, arginine and aspartic acid or any combination thereof.

15. The modified material according to claim 13, characterized in that The quaternary ammonium compound is selected from alkyldimethylbenzyl ammonium chloride, alkyldidecyldimethylammonium chloride, dialkyldimethylammonium chloride and dialkyl quaternary ammonium salt or any combination thereof.

16. The modified material according to claim 13, characterized in that The chlorhexidine compound is chlorhexidine digluconate and / or chlorhexidine dihydrochloride; the alexidine compound is alexidine dihydrochloride; and the biguanide compound is 1-(3-chlorophenyl)biguanide hydrochloride.

17. The modified material according to claim 12, characterized in that The antimicrobial activity of the antimicrobial material and the polyethyleneimine antimicrobial modified material is directed against bacteria, fungi, viruses or any combination thereof, and wherein the bacteria are selected from Chlamydia pneumoniae, Streptococcus pneumoniae, Mycobacterium tuberculosis, Group A Streptococcus, Corynebacterium diphtheriae, Haemophilus influenzae, Neisseria meningitidis, Clostridium difficile, methicillin-resistant Staphylococcus aureus, vancomycin-resistant Enterococcus, Acinetobacter baumannii or any combination thereof; the fungi are selected from Pneumocystis, Aspergillus, Coccidium, Saccharomyces, Candida, Candida, Mucor, Sporothrix, Dermatophytes or any combination thereof; the virus is selected from respiratory syncytial virus, hepatitis virus, varicella virus, polio virus, smallpox virus, measles virus, mumps virus, Chlamydia trachomatis, influenza virus, SARS-CoV virus, SARS-CoV-2 virus, H1N1 virus, H5N1 virus, H5N7 virus, MERS-CoV virus, Staphylococcus aureus, Klebsiella pneumoniae, Aspergillus niger, Ebola virus or any combination thereof.

18. The modified material according to claim 12, characterized in that The polyethyleneimine antimicrobial modified material is selected from polypropylene-polyethyleneimine-cysteine, polypropylene-polyethyleneimine-benzalkonium chloride, polypropylene-polyethyleneimine-chlorhexidine, polypropylene-polyethyleneimine-phenylbiguanide, cellulose-polyethyleneimine-cysteine, cellulose-polyethyleneimine-benzalkonium chloride, cellulose-polyethyleneimine-chlorhexidine, cellulose-polyethyleneimine-phenylbiguanide, nylon-polyethyleneimine-cysteine, nylon-polyethyleneimine-benzalkonium chloride, nylon-polyethyleneimine-chlorhexidine, nylon-polyethyleneimine-phenylbiguanide, polypropylene-alginate dialdehyde-polyethyleneimine-cysteine, polypropylene-alginate dialdehyde-polyethyleneimine -benzalkonium chloride, polypropylene-alginic acid dialdehyde-polyethyleneimine-chlorhexidine, polypropylene-alginic acid dialdehyde-polyethyleneimine-phenylbiguanide, cellulose-alginic acid dialdehyde-polyethyleneimine-cysteine, cellulose-alginic acid dialdehyde-polyethyleneimine-benzalkonium chloride, cellulose-alginic acid dialdehyde-polyethyleneimine-chlorhexidine, cellulose-alginic acid dialdehyde-polyethyleneimine-phenylbiguanide, nylon-alginic acid dialdehyde-polyethyleneimine-cysteine, nylon-alginic acid dialdehyde-polyethyleneimine-benzalkonium chloride, nylon-alginic acid dialdehyde-polyethyleneimine-chlorhexidine, nylon-alginic acid dialdehyde-polyethyleneimine-phenylbiguanide or any combination thereof of polyethyleneimine antibacterial modified materials.

19. The modified material according to claim 12, characterized in that The polyethyleneimine antimicrobial modified material is selected from polypropylene-polyethyleneimine-cysteine, polypropylene-polyethyleneimine-benzalkonium chloride, polypropylene-polyethyleneimine-chlorhexidine, polypropylene-polyethyleneimine-phenylbiguanide, cellulose-polyethyleneimine-cysteine, cellulose-polyethyleneimine-benzalkonium chloride, cellulose-polyethyleneimine-chlorhexidine, cellulose-polyethyleneimine-phenylbiguanide, nylon-polyethyleneimine-cysteine, nylon-polyethyleneimine-benzalkonium chloride, nylon-polyethyleneimine-chlorhexidine, nylon-polyethyleneimine-phenylbiguanide, polypropylene-alginate dialdehyde-polyethyleneimine-cysteine, polypropylene-alginate dialdehyde-polyethyleneimine -benzalkonium chloride, polypropylene-alginate dialdehyde-polyethyleneimine-chlorhexidine, polypropylene-alginate dialdehyde-polyethyleneimine-phenylbiguanide, cellulose-alginate dialdehyde-polyethyleneimine-cysteine, cellulose-alginate dialdehyde-polyethyleneimine-benzalkonium chloride, cellulose-alginate dialdehyde-polyethyleneimine-chlorhexidine, cellulose-alginate dialdehyde-polyethyleneimine-phenylbiguanide, nylon-alginate dialdehyde-polyethyleneimine-cysteine, nylon-alginate dialdehyde-polyethyleneimine-benzalkonium chloride, nylon-alginate dialdehyde-polyethyleneimine-chlorhexidine, nylon-alginate dialdehyde-polyethyleneimine-phenylbiguanide or any combination thereof of polyethyleneimine antifungal modified materials.

20. The modified material according to claim 12, characterized in that The polyethyleneimine antimicrobial modified material is a polyethyleneimine antiviral modified material selected from polypropylene-polyethyleneimine-benzalkonium chloride, polypropylene-polyethyleneimine-chlorhexidine, nylon-polyethyleneimine-benzalkonium chloride, nylon-polyethyleneimine-chlorhexidine, polypropylene-alginate dialdehyde-polyethyleneimine-benzalkonium chloride, polypropylene-alginate dialdehyde-polyethyleneimine-chlorhexidine, nylon-alginate dialdehyde-polyethyleneimine-benzalkonium chloride, nylon-alginate dialdehyde-polyethyleneimine-chlorhexidine or any combination thereof.

21. The modified material according to any one of claims 11 to 20, characterized in that: The percentage of the functional material of the functional layer to the total mass of the modified material is 0.1%-1%.

22. The modified material according to claim 21, characterized in that The functional material of the functional layer accounts for 0.3% to 0.6% of the total mass of the modified material.

23. A method for preparing a polyethyleneimine functionalized material according to any one of claims 1 to 10, comprising the following steps: After the porous material or non-porous material is mixed with the polyethyleneimine aqueous solution, the mixture is shaken at 60-200 rpm at a temperature of 10-100°C and a pH of 5-11 for 10 minutes to 24 hours. or, The polyethyleneimine functionalized material is obtained by directly coating or spraying a polyethyleneimine aqueous solution at a pH of 5-11 on the surface of the porous material or the non-porous material and drying the solution at a temperature of 10-100° C. for 10 minutes to 24 hours.

24. The method according to claim 23, wherein The method further comprises the following steps: before adding the polyethyleneimine aqueous solution or after the porous material or non-porous material reacts with the polyethyleneimine aqueous solution, mixing the porous material or non-porous material with an alginate dialdehyde aqueous solution, and then shaking the mixture at 60-200 rpm for 10 minutes to 24 hours at a temperature of 10-100° C. and a pH of 1.5-8, or, Before or after coating or spraying the polyethyleneimine aqueous solution, an alginate dialdehyde aqueous solution at a pH of 1.5-8 is directly coated or sprayed on the surface of the porous or non-porous material and dried at a temperature of 10-100° C. for 10 minutes to 24 hours.

25. The method according to claim 24, characterized in that The mass ratio of the sum of the polyethyleneimine contained in the polyethyleneimine aqueous solution and the alginate dialdehyde contained in the alginate dialdehyde aqueous solution to the porous material or the non-porous material is 1:100 to 1:

10.

26. The method according to claim 25, characterized in that The mass ratio of the polyethyleneimine contained in the polyethyleneimine aqueous solution to the alginate dialdehyde contained in the alginate dialdehyde aqueous solution is 100:1 to 10:

1.

27. A method for preparing a polyethyleneimine modified material according to any one of claims 11 to 22, comprising the following steps: Adding the polyethyleneimine functionalized material according to any one of claims 1 to 10 or prepared by the method according to any one of claims 23 to 26 to the functional material aqueous solution, shaking at 60 to 200 rpm at a temperature of 10 to 100° C. and a pH of 1.5 to 8 to react for 10 minutes to 24 hours; or, Directly coating or spraying the functional material aqueous solution at a pH of 1.5-8 on the polyethyleneimine functional material and drying at a temperature of 10-100° C. for 10 minutes to 24 hours, That is, the modified material is obtained; in, The functional material can be combined with the connecting layer by covalent bonding, electrostatic adsorption, hydrophilic adsorption, hydrophobic adsorption, hydrogen bonding or any combination thereof.

28. The method according to claim 27, characterized in that The percentage of the functional material to the total mass of the modified material is 0.1%-1%.

29. A method for preparing a polyethyleneimine modified material according to any one of claims 11 to 22, comprising the following steps: mixing the functional material with a polyethyleneimine aqueous solution to obtain a polyethyleneimine-functional material aqueous solution; The aqueous solution obtained above is reacted with a porous material or a non-porous material at a temperature of 10-100° C. and a pH of 1.5-8 with shaking at 60-200 rpm for 10 minutes to 24 hours, or the aqueous solution obtained above is directly coated or sprayed onto the surface of the porous material or the non-porous material at a pH of 1.5-8 and dried at a temperature of 10-100° C. for 10 minutes to 24 hours to obtain the modified material; in, The functional material can be combined with the connecting layer by covalent bonding, electrostatic adsorption, hydrophilic adsorption, hydrophobic adsorption, hydrogen bonding or any combination thereof.

30. The method according to claim 29, wherein The method further comprises the following step: before, after or simultaneously with mixing the functional material with the polyethyleneimine aqueous solution, mixing the functional material with the alginate dialdehyde aqueous solution.

31. The method according to claim 30, wherein The mass ratio of the sum of the functional material, polyethyleneimine and alginate dialdehyde to the porous material or the non-porous material is (1-10):(10-100):1000.

32. The method according to any one of claims 23 to 31, characterized in that The method further comprises the following steps: washing the obtained product, and then storing it in a wet state or performing air drying or oven drying.

33. The method according to any one of claims 23 to 31, characterized in that The porous material or non-porous material is one or more polymers, composite materials or any combination thereof, and the polymer or composite material is selected from polypropylene, cellulose, regenerated cellulose, polyvinylidene fluoride, polyethersulfone, polystyrene, polytetrafluoroethylene, polyethylene, polyimide, polyamide or any combination thereof.

34. The method according to any one of claims 23 to 31, wherein: The functional material is an antimicrobial material, and the microorganism is selected from bacteria, fungi, viruses or any combination thereof, and the bacteria is selected from Chlamydia pneumoniae, Streptococcus pneumoniae, Mycobacterium tuberculosis, Group A Streptococcus, Corynebacterium diphtheriae, Haemophilus influenzae, Neisseria meningitidis, Clostridium difficile, methicillin-resistant Staphylococcus aureus, vancomycin-resistant Enterococcus, Acinetobacter baumannii or any combination thereof; the fungus is selected from Pneumocystis, Aspergillus, Coccidioides, Saccharomyces, Candida, Mucor The virus is selected from respiratory syncytial virus, hepatitis virus, varicella virus, polio virus, smallpox virus, measles virus, mumps virus, Chlamydia trachomatis, influenza virus, SARS-CoV virus, SARS-CoV-2 virus, H1N1 virus, H5N1 virus, H5N7 virus, MERS-CoV virus, Staphylococcus aureus, Klebsiella pneumoniae, Aspergillus niger, Ebola virus or any combination thereof.

35. The method according to any one of claims 23 to 31, wherein The functional material is an antimicrobial material, and the antimicrobial material is selected from amino acids, quaternary ammonium compounds, chlorhexidine compounds, alexidine compounds, biguanide compounds or any combination thereof, and the amino acids are selected from cysteine, tyrosine, lysine, arginine and aspartic acid or any combination thereof; the quaternary ammonium compound is selected from alkyldimethylbenzyl ammonium chloride, alkyldidecyldimethylammonium chloride, dialkyldimethylammonium chloride and dialkyl quaternary ammonium salt or any combination thereof; the chlorhexidine compound is chlorhexidine digluconate and / or chlorhexidine dihydrochloride; the alexidine compound is alexidine dihydrochloride; and the biguanide compound is 1-(3-chlorophenyl)biguanide hydrochloride.

36. Use of the polyethyleneimine functionalized material according to any one of claims 1 to 10, the polyethyleneimine modified material according to any one of claims 11 to 22, the preparation method according to any one of claims 23 to 35, or the material produced by the preparation method according to any one of claims 23 to 36 in the production of medical supplies and other antimicrobial products.

37. The use according to claim 36, characterized in that The uses mentioned include the production of masks, isolation gowns, gloves, personal protective equipment, bandages, medical tapes, medical caps, medical sheets, medical clothing, air filters, water filters, electronic products, household appliances and automotive accessories.

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