CN113712042B - Multifunctional persistent antibacterial composition and preparation method thereof - Google Patents

Multifunctional persistent antibacterial composition and preparation method thereof Download PDF

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CN113712042B
CN113712042B CN202110565800.8A CN202110565800A CN113712042B CN 113712042 B CN113712042 B CN 113712042B CN 202110565800 A CN202110565800 A CN 202110565800A CN 113712042 B CN113712042 B CN 113712042B
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antibacterial
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antibacterial composition
composite material
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CN113712042A (en
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李毕忠
彭红芳
封东廷
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CHANGZHOU CHAMGO NANO MATERIALS CO LTD
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/02—Amines; Quaternary ammonium compounds
    • A01N33/12—Quaternary ammonium compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N65/00—Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N65/00—Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
    • A01N65/08—Magnoliopsida [dicotyledons]
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N65/00—Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
    • A01N65/08—Magnoliopsida [dicotyledons]
    • A01N65/12—Asteraceae or Compositae [Aster or Sunflower family], e.g. daisy, pyrethrum, artichoke, lettuce, sunflower, wormwood or tarragon
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N65/00—Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
    • A01N65/40—Liliopsida [monocotyledons]
    • A01N65/42—Aloeaceae [Aloe family] or Liliaceae [Lily family], e.g. aloe, veratrum, onion, garlic or chives
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

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Abstract

The invention relates to the technical field of antibiosis and antivirus, in particular to a multifunctional persistent antibacterial composition and a preparation method thereof. The multifunctional persistent antibacterial composition comprises the following raw materials in parts by weight: 20-45 parts of antibacterial agent, 1-10 parts of plant extract, 0.01-1 part of coupling agent, 1-5 parts of polysaccharide, 1-6 parts of surfactant and 40-70 parts of water. The antibacterial composition provided by the invention has the following advantages: (1) The antibacterial composition can sterilize in a broad spectrum, can effectively kill viruses, has a remarkable effect on new coronavirus, and has important significance on maintaining safety and sanitation of daily public places; (2) The antibacterial composition has excellent performance, strong instantaneity when acting on microorganisms, can play a role for a long time, and can be stably stored without color change under the change of cold and hot conditions; (3) The antibacterial composition has the advantages of environment-friendly raw materials, no toxicity, no harm, simple and convenient process, wide application in various fields such as textiles, coatings, plastics and the like, and wide application prospect.

Description

Multifunctional persistent antibacterial composition and preparation method thereof
Technical Field
The invention relates to the technical field of antibiosis and antivirus, in particular to a multifunctional persistent antibacterial composition and a preparation method thereof.
Background
Various microorganisms are distributed in daily life, and great potential risks exist for the life health of human bodies. Antimicrobial agents are a class of chemicals that can significantly reduce the level of microorganisms (including bacteria, fungi, yeasts, algae, viruses, etc.) within a particular time scale. The existing antibacterial agents can be classified into inorganic antibacterial agents, organic antibacterial agents and natural antibacterial agents according to different components. The organic antibacterial agent occupies more than 80% of the specific gravity of the market and has the characteristic of immediate effect, but the organic antibacterial agent has larger difference to different strains, is easy to generate drug resistance and is easy to volatilize and decompose, and the limitation problem of applicable conditions is increasingly prominent; the inorganic antibacterial agent has the characteristics of continuous sterilization and broad-spectrum effect, the drug resistance is obviously weaker than that of the organic antibacterial agent, but the inorganic antibacterial agent has longer effective time and is easy to discolor, and the transmittance of a finished product is influenced when the inorganic antibacterial agent is applied to the product; the natural antibacterial agent is a substance with antibacterial activity in the nature, has the characteristics of green and environment-friendly raw materials, high antibacterial efficiency, safety and no toxicity, but has high processing difficulty and insufficient heat resistance, and the prepared antibacterial agent has short service life. In view of the above, the inorganic antibacterial agents, the organic antibacterial agents and the natural antibacterial agents have distinct advantages and disadvantages, and under such a background, the composite antibacterial agents cover different types of antibacterial agents, take advantages of various antibacterial agents into consideration, and greatly widen the application range of the antibacterial agents; however, the technical research on the composite antibacterial agent is not mature at the present stage, and with the improvement of science and technology and the promotion of health consciousness of people, the market demand and the requirement for the antibacterial agent are higher and higher, and the composite antibacterial agent undoubtedly has profound significance.
Chinese patent CN201410387595.0 discloses an organic/inorganic composite antibacterial agent, which combines triclosan and an inorganic silver-containing antibacterial agent by an ion exchange method, so that the composite antibacterial agent can have antibacterial long-acting and quick-acting functions at the same time. Based on the above, the preparation of an antibacterial composition with long-acting antibacterial effect, strong stability, safe and environment-friendly raw materials and convenient process is an urgent problem to be solved in the field.
Disclosure of Invention
The invention provides the multifunctional persistent antibacterial composition, solves the problem that the antibacterial efficiency and the stability of an antibacterial agent in the prior art are difficult to be considered at the same time, and realizes the antibacterial composition with long-acting antibacterial effect, strong stability, safe and environment-friendly raw materials and convenient process.
The invention provides a multifunctional persistent antibacterial composition, which comprises the following raw materials in parts by weight: 20-45 parts of antibacterial agent, 1-10 parts of plant extract, 0.01-1 part of coupling agent, 1-5 parts of polysaccharide, 1-6 parts of surfactant and 40-70 parts of water.
In a preferred embodiment, the antibacterial agent comprises at least 2 of inorganic composite materials, high molecular quaternary ammonium salts, biguanide compounds, chitosan derivatives and epoxy derivatives.
In a preferred embodiment, the antibacterial agent is an inorganic composite material, a polymeric quaternary ammonium salt and a chitosan derivative; the inorganic composite material comprises the following components in parts by weight (3-7): 1: (1.4-2).
In a preferred embodiment, the inorganic composite material comprises an antimicrobial component and a carrier; the carrier comprises at least one of zeolite, phosphate, bentonite, mullite, hydroxyapatite, clay mineral and silica gel.
In a preferred embodiment, the antimicrobial component includes at least one of a silver salt, a copper salt, a zinc salt, and a rare earth metal salt.
In a preferred embodiment, the chitosan derivative comprises at least one of carboxymethyl chitosan, sulfonated chitosan, hydroxyethyl chitosan, alkylated chitosan, phosphorylated chitosan, and etherified chitosan.
In a preferred embodiment, the plant extract comprises at least one of wormwood extract, bayberry leaf extract, houttuynia cordata extract, honeysuckle extract, hypericum extract, and aloe extract.
In a preferred embodiment, the polysaccharide has a mass fraction of soluble total sugars of 35-42% and a mass fraction of protein of 1-5%.
In a preferred embodiment, the polymeric quaternary ammonium salt is an aliphatic quaternary ammonium salt polymer.
The second aspect of the invention provides a preparation method of the multifunctional persistent antibacterial composition, which comprises the steps of preparing an inorganic composite material, sequentially adding the inorganic composite material, a chitosan derivative, a high-molecular quaternary ammonium salt, a coupling agent, polysaccharide, a surfactant and a plant extract into water, and uniformly stirring to obtain a finished product.
Has the advantages that:
the antibacterial composition provided by the invention has the following advantages:
(1) The antibacterial composition can sterilize in a broad spectrum, can effectively kill viruses, has a remarkable effect on new coronavirus, and has important significance on maintaining safety and sanitation in daily public places;
(2) The antibacterial composition has excellent performance, strong instantaneity when acting on microorganisms, can play a role for a long time, and can be stably stored without changing color under the change of cold and hot conditions;
(3) The antibacterial composition has the advantages of environment-friendly raw materials, no toxicity or harm, simple and convenient process, wide application in various fields such as textiles, coatings, plastics and the like, and wide application prospect.
Detailed Description
The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
As used herein, the term "prepared from" \8230a "is synonymous with" comprising ". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of 8230comprises" excludes any non-specified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of 8230title" appears in a clause of the subject matter of the claims and not immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
Approximating language, as used herein throughout the specification and claims, is intended to modify a quantity, such that the invention is not limited to the specific quantity, but includes portions that are literally received for modification without substantial change in the basic function to which the invention is related. Accordingly, the use of "about" to modify a numerical value means that the invention is not limited to the precise value. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value. In the present description and claims, range limitations may be combined and/or interchanged, including all sub-ranges contained therein if not otherwise stated.
In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.
"Polymer" means a polymeric compound prepared by polymerizing monomers of the same or different types. The generic term "polymer" embraces the terms "homopolymer", "copolymer", "terpolymer" and "interpolymer". "interpolymer" means a polymer prepared by polymerizing at least two different monomers. The generic term "interpolymer" includes the term "copolymer" (which is generally used to refer to polymers prepared from two different monomers) and the term "terpolymer" (which is generally used to refer to polymers prepared from three different monomers). It also includes polymers made by polymerizing more monomers. "blend" means a polymer formed by two or more polymers being mixed together by physical or chemical means.
In order to solve the above problems, the present invention provides a multifunctional persistent antibacterial composition, which comprises the following raw materials by weight: 20-45 parts of antibacterial agent, 1-10 parts of plant extract, 0.01-1 part of coupling agent, 1-5 parts of polysaccharide, 1-6 parts of surfactant and 40-70 parts of water.
In some preferred embodiments, the antimicrobial agent comprises at least 2 of inorganic composite materials, polymeric quaternary ammonium salts, biguanide compounds, chitosan derivatives, and epoxy derivatives.
In some preferred embodiments, the antimicrobial agent is an inorganic composite material, a polymeric quaternary ammonium salt and a chitosan derivative; the inorganic composite material comprises the following components in parts by weight (3-7): 1: (1.4-2).
In some preferred embodiments, the inorganic composite material comprises an antimicrobial component and a carrier; the carrier comprises at least one of zeolite, phosphate, bentonite, mullite, hydroxyapatite, clay mineral and silica gel.
In some preferred embodiments, the antimicrobial component includes at least one of a silver salt, a copper salt, a zinc salt, and a rare earth metal salt.
Further preferably, the carrier is a clay mineral, specifically sepiolite; the antibacterial components are silver salt and rare earth metal salt. The molar mass ratio of the silver salt to the rare earth metal salt is (10-30): 1.
the preparation method of the inorganic composite material is a common technical means in the field and has no special limitation; for example, the solid-to-liquid ratio is 1:10, adding sepiolite into a mixed solution of silver nitrate and cerium nitrate, stirring for 3.5 hours at the neutral condition of 60 ℃, centrifuging, collecting a solid product, washing for 3 times by using distilled water, and drying to obtain the inorganic composite material.
Except inorganic oxides such as titanium dioxide, zinc oxide and the like, most inorganic antibacterial components need to be supported on a porous material to play a sterilization effect. According to the invention, through researches, the sterilization effect of the antibacterial composition is obviously improved when the clay mineral is selected as the antibacterial component carrier; the reason may be that the inorganic composite material formed after the cation exchange between the clay mineral and the antibacterial component can rapidly release metal ions in the using process and chemically react with the hydrosulfury-containing functional group and the nitrogen-containing functional group in the microorganism; further, the inventor finds that when the sepiolite is selected as the antibacterial component carrier, the carrier particles can effectively perform ion exchange with a metal salt solution, and the sepiolite has abundant tubular through channels and 900m in a porous structure 2 The high theoretical surface area is more than g, the characteristics endow enough filling positions for sepiolite cations, metal ions with the capability of killing microbes are replaced into octahedral porous gaps of the sepiolite, the metal ions generate charge attraction with negatively charged cell membranes after contacting with the microbes, the protein structure of the microbes is destroyed, and the metal ions permeate into the inside of microbial cells to enable the microbes to lose activity; meanwhile, the metal ions can absorb oxygen in the environment, generate active free radicals, interfere the normal electronic activity of microorganisms, further disturb the metabolism of cells and achieve the effect of killing bacteria and viruses.
In some preferred embodiments, the chitosan derivative comprises at least one of carboxymethyl chitosan, sulfonated chitosan, hydroxyethyl chitosan, alkylated chitosan, phosphorylated chitosan, and etherified chitosan.
Further preferably, the chitosan derivative is hydroxyethyl chitosan; the preparation method of the hydroxyethyl chitosan comprises the following specific steps: according to the following steps of 1: (5-15) adding chitosan into a sodium hydroxide aqueous solution with the mass concentration of 50%, stirring and mixing uniformly, placing at the temperature of- (20-15) DEG C in a dark place for 6-20h, then adding beta-halohydrin, reacting at the temperature of 75-85 ℃ for 20-28h, adjusting the pH to 6.5-7.5 by using dilute hydrochloric acid, adding acetone to precipitate a product, performing suction filtration, washing and drying to obtain hydroxyethyl chitosan.
In some preferred embodiments, the weight ratio of the β -halohydrin, the aqueous sodium hydroxide solution and the acetone is 1: (1-3.2): (6-8).
Chitosan, as a unique natural alkaline polysaccharide in the nature, has balanced biocompatibility, bioactivity and antibacterial property, and is widely applied to the fields of textiles, medicines and the like. However, chitosan has strong intermolecular force, and the molecular arrangement is compact and ordered, so that it cannot be dissolved in water sufficiently, and its physiological properties are not fully exerted. The molecular chain of the chitosan contains a plurality of functional groups such as hydroxyl, amino and the like, the chemical property is active, and in order to give full play to the excellent performance of the chitosan, the chitosan is modified in various ways to become an effective way for widening the application of the chitosan. According to the invention, a large number of experiments are carried out to discover that the hydroxyethylated chitosan can play the best bacteriostatic effect in the antibacterial composition compared with other modification means. The introduction of R-O-R' in hydroxyethylated chitosan is hypothesized to reduce the internal binding force of chitosan molecules, on one hand, the dissolving capacity of chitosan is greatly improved, and the problem that solid substances are not easy to dissolve out after the antibacterial composition is stored for a long time is solved, on the other hand, the flexibility of a macromolecular chain is improved, the cationization trend of nitrogen-containing groups of chitosan is further promoted, the cationic tendency is further attracted with negative charges on a bacterial cell membrane, the structural charge distribution of the bacterial cell is unbalanced, the normal physiological state of microorganisms is disturbed, and the antibacterial aging of the antibacterial composition is effectively prolonged.
The invention further discovers that when the inorganic composite material is prepared from the high-molecular quaternary ammonium salt and the chitosan derivative in a weight ratio of (3-7): 1: (1.4-2), the compatibility among the antibacterial agent components is improved, the metal salt antibacterial component is attached to the inside of an inorganic carrier, the hydroxyethyl chitosan wraps the inorganic composite material and is intertwined with the high molecular quaternary ammonium salt (especially) in an inserting manner, the density of functional groups of the composition is increased, the binding capacity with a bacterial cell structure is improved, the large molecular functional groups adsorb thalli, and the small molecular functional groups permeate the insides of the thalli, so that the effective action area of the antibacterial composition when the antibacterial composition is contacted with microorganisms is ensured under the combined action, the slow effect of the inorganic antibacterial agent is improved, and the temperature resistance of the antibacterial composition is also improved.
In some preferred embodiments, the plant extract comprises at least one of wormwood extract, bayberry leaf extract, houttuynia cordata extract, honeysuckle extract, hypericum extract, and aloe extract.
Further preferably, the plant extract includes an artemisia argyi extract, a myrica rubra leaf extract and an aloe vera extract.
More preferably, the method for extracting the wormwood extract comprises the steps of weighing 5g of wormwood powder, adding the wormwood powder into 60-80mL of ethanol solution with the volume concentration of 60-70%, carrying out ultrasonic extraction for 2 times, wherein the extraction time is 0.5-2h each time, and carrying out suction filtration and concentration to obtain the wormwood extract.
The plant extracts are prepared from natural plants in the nature by mechanical extraction or biological processing to obtain active plant essences, and with the progress and development of biological extraction technology, various plant extracts have been found to have the effect of killing microorganisms, but are limited by the variety of the types and components of the plant extracts, the specific sterilization mechanism of the plant extracts is not yet determined, and the selection of the plant extracts in different systems (including the types of the raw materials and the extraction method) is still in preliminary investigation. According to the invention, the antibacterial effect of the antibacterial composition can be further improved by selecting the combined action of the wormwood extract, the bayberry leaf extract and the aloe extract in a composite antibacterial system consisting of an inorganic composite material, hydroxyethylated chitosan and a high-molecular quaternary ammonium salt, and the active groups such as anthraquinone, flavonoid and the like in the specific plant extract can destroy the bacterial cell structure and influence the permeability of the cell membrane structure; meanwhile, the extract inhibits the metabolism of essential life elements in microbial cells, and the protein synthesis pathway of the microbes is blocked. The invention further discovers that when the weight ratio of the wormwood extract, the waxberry leaf extract and the aloe extract is (1.5-3): 1: and (2-5), the temperature resistance of the antibacterial composition is obviously improved, and the antibacterial composition can still keep a stable state under the conditions of high temperature and low temperature.
In some preferred embodiments, the polysaccharide has a mass fraction of soluble total sugars of 35-42% and a mass fraction of protein of 1-5%.
In some preferred embodiments, the polymeric quaternary ammonium salt is an aliphatic quaternary ammonium salt polymer.
As an example of an aliphatic quaternary ammonium salt polymer, but not limited to, quaternary ammonium salt-37 is included.
The invention provides a preparation method of a multifunctional persistent antibacterial composition, which comprises the steps of preparing an inorganic composite material, sequentially adding the inorganic composite material, a chitosan derivative, a high-molecular quaternary ammonium salt, a coupling agent, polysaccharide, a surfactant and a plant extract into water, and uniformly stirring to obtain a finished product.
Examples
In order to better understand the above technical solutions, the following detailed descriptions will be provided with reference to specific embodiments. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention. In addition, the raw materials are commercially available and the extraction method of the extract is a conventional extraction method unless otherwise stated.
Example 1.
The embodiment provides a multifunctional persistent antibacterial composition, which comprises the following raw materials in parts by weight: 25 parts of antibacterial agent, 3 parts of plant extract, 0.5 part of coupling agent, 1.5 parts of polysaccharide, 2 parts of surfactant and 60 parts of water.
The antibacterial agent is an inorganic composite material, a high-molecular quaternary ammonium salt and a chitosan derivative; the inorganic composite material comprises the following components in percentage by weight: 1:1.6.
the inorganic composite material comprises an antibacterial component and a carrier; the carrier is clay mineral, in particular sepiolite; the antibacterial components are silver nitrate and cerium nitrate.
The chitosan derivative is hydroxyethyl chitosan; the preparation method of the hydroxyethyl chitosan comprises the following specific steps: according to the following steps of 1: adding chitosan into a sodium hydroxide aqueous solution with the mass concentration of 50% according to the solid-liquid ratio of 10, stirring and mixing uniformly, placing at-18 ℃ for 12h in a dark place, then adding 2-chloroethanol, reacting at 80 ℃ for 24h, adjusting the pH to 7 by using dilute hydrochloric acid, adding acetone to precipitate a product, performing suction filtration, washing and drying to obtain the hydroxyethyl chitosan.
The weight ratio of the 2-chloroethanol to the sodium hydroxide aqueous solution to the acetone is 1:1.5:7.
the plant extract is folium Artemisiae Argyi extract, folium Myricae Rubrae extract and Aloe extract. The latin science of wormwood is named Artemisia argyi levl.et Van, the latin science of waxberry is myricarura (lour.) s.etzucc, and the latin science of Aloe is Aloe vera (haw.) Berg; the weight ratio of the wormwood extract, the waxberry leaf extract and the aloe extract is 2:1:4.
the method for extracting the wormwood extract comprises the steps of weighing 5g of wormwood powder, adding the wormwood powder into 70mL of 65% ethanol solution, carrying out ultrasonic extraction for 2 times, wherein the extraction time is 1h each time, and carrying out suction filtration and concentration to obtain the wormwood extract.
The Myrica rubra leaf extract was purchased from Woltlese Biotech, inc. of Lanzhou, and the Aloe extract was purchased from Sienkangwei bioengineering, inc.
The polysaccharide is algal polysaccharide, and the algal polysaccharide is prepared by removing moisture of an algal sample, performing reflux extraction by using an ethanol water solution with the volume fraction of 85%, then adding water, performing reflux extraction at 95 ℃ for 2.5 hours, centrifuging, taking supernatant, putting the supernatant into a rotary evaporator for concentration, and then heating to remove a solvent to obtain the algal polysaccharide. The weight ratio of the ethanol water solution to the water of the seaweed sample is 1:5:40; the seaweed sample is thallus laminariae, purchased from Qiyu flagship shop for nourishing and health promotion.
The mass fraction of soluble total sugar in the polysaccharide is 38%, and the mass fraction of protein is 3.7%.
The high molecular quaternary ammonium salt is aliphatic quaternary ammonium salt polymer, specifically quaternary ammonium salt-37, CAS number 26161-33-1.
The coupling agent is aminopropyltriethoxysilane, and the CAS number is 919-30-2.
The surfactant is Tween 20, and the CAS number is 9005-64-5.
The preparation method of the multifunctional persistent antibacterial composition comprises the following steps of,
s1, preparing an inorganic composite material: according to the solid-liquid ratio of 1:10, adding sepiolite into a mixed solution of silver nitrate and cerium nitrate, stirring for 3.5 hours at the neutral condition of 60 ℃, centrifuging, collecting a solid product, washing for 3 times by using distilled water, and drying to obtain the inorganic composite material. The concentration of the silver nitrate is 0.2mol/L, and the concentration of the cerium nitrate is 0.01mol/L.
S2, sequentially adding the inorganic composite material, hydroxyethyl chitosan, high-molecular quaternary ammonium salt, a coupling agent, polysaccharide, a surfactant and the plant extract into water, and uniformly stirring to obtain a finished product.
Example 2.
The embodiment provides a multifunctional persistent antibacterial composition, which comprises the following raw materials in parts by weight: 40 parts of antibacterial agent, 6 parts of plant extract, 1 part of coupling agent, 2 parts of polysaccharide, 3 parts of surfactant and 70 parts of water.
The antibacterial agent is an inorganic composite material, a high-molecular quaternary ammonium salt and a chitosan derivative; the inorganic composite material comprises the following components in percentage by weight: 1:1.6.
the inorganic composite material comprises an antibacterial component and a carrier; the carrier is clay mineral, in particular sepiolite; the antibacterial components are silver nitrate and cerium nitrate.
The chitosan derivative is hydroxyethyl chitosan; the preparation method of the hydroxyethyl chitosan comprises the following specific steps: according to the following steps of 1: adding chitosan into a sodium hydroxide aqueous solution with the mass concentration of 50% according to the solid-liquid ratio of 10, stirring and mixing uniformly, placing at-18 ℃ for 12h in a dark place, then adding 2-chloroethanol, reacting at 80 ℃ for 24h, adjusting the pH to 7 by using dilute hydrochloric acid, adding acetone to precipitate a product, performing suction filtration, washing and drying to obtain the hydroxyethyl chitosan.
The weight ratio of the 2-chloroethanol to the sodium hydroxide aqueous solution to the acetone is 1:1.5:7.
the plant extract is folium Artemisiae Argyi extract, folium Myricae Rubrae extract and Aloe extract. The latin name of Artemisia argyi levl.et Van, the latin name of myrica rubra (lour.) s.etzucc, the latin name of Aloe vera (haw.) Berg; the weight ratio of the wormwood extract, the waxberry leaf extract and the aloe extract is 2:1:4.
the method for extracting the wormwood extract comprises the steps of weighing 5g of wormwood powder, adding the wormwood powder into 70mL of 65% ethanol solution, carrying out ultrasonic extraction for 2 times, wherein the extraction time is 1h each time, and carrying out suction filtration and concentration to obtain the wormwood extract.
The Myrica rubra leaf extract was purchased from Woltlese Biotech, inc. of Lanzhou, and the Aloe extract was purchased from Sienkangwei bioengineering, inc.
The polysaccharide is algal polysaccharide, and the algal polysaccharide is prepared by removing moisture of an algal sample, performing reflux extraction by using an ethanol water solution with the volume fraction of 85%, then adding water, performing reflux extraction at 95 ℃ for 2.5 hours, centrifuging, taking supernatant, putting the supernatant into a rotary evaporator for concentration, and then heating to remove a solvent to obtain the algal polysaccharide. The weight ratio of the ethanol water solution to the water of the seaweed sample is 1:5:40; the seaweed sample is thallus laminariae, purchased from Qiyu flagship shop for nourishing and health promotion.
The mass fraction of soluble total sugar in the polysaccharide is 38%, and the mass fraction of protein is 3.7%.
The high molecular quaternary ammonium salt is aliphatic quaternary ammonium salt polymer, specifically quaternary ammonium salt-37, CAS number 26161-33-1.
The coupling agent is aminopropyltriethoxysilane, and the CAS number is 919-30-2.
The surfactant is Tween 20, and the CAS number is 9005-64-5.
The preparation method of the multifunctional persistent antibacterial composition comprises the following steps of,
s1, preparing an inorganic composite material: according to the solid-liquid ratio of 1:10, adding sepiolite into a mixed solution of silver nitrate and cerium nitrate, stirring for 3.5 hours at the neutral condition of 60 ℃, centrifuging, collecting a solid product, washing for 3 times by using distilled water, and drying to obtain the inorganic composite material. The concentration of the silver nitrate is 0.2mol/L, and the concentration of the cerium nitrate is 0.01mol/L.
S2, adding the inorganic composite material, hydroxyethyl chitosan, high-molecular quaternary ammonium salt, a coupling agent, polysaccharide, a surfactant and the plant extract into water in sequence, and stirring uniformly to obtain a finished product.
Example 3.
The embodiment provides a multifunctional persistent antibacterial composition, which comprises the following raw materials in parts by weight: 25 parts of antibacterial agent, 3 parts of plant extract, 0.5 part of coupling agent, 1.5 parts of polysaccharide, 2 parts of surfactant and 60 parts of water.
The antibacterial agent is an inorganic composite material, a high-molecular quaternary ammonium salt and a chitosan derivative; the inorganic composite material comprises the following components in percentage by weight: 1:2.
the inorganic composite material comprises an antibacterial component and a carrier; the carrier is clay mineral, in particular sepiolite; the antibacterial components are silver nitrate and cerium nitrate.
The chitosan derivative is hydroxyethyl chitosan; the preparation method of the hydroxyethyl chitosan comprises the following specific steps: according to the following steps of 1: adding chitosan into a sodium hydroxide aqueous solution with the mass concentration of 50% according to the solid-liquid ratio of 10, stirring and mixing uniformly, placing at-18 ℃ for 12h in a dark place, then adding 2-chloroethanol, reacting at 80 ℃ for 24h, adjusting the pH to 7 by using dilute hydrochloric acid, adding acetone to precipitate a product, performing suction filtration, washing and drying to obtain the hydroxyethyl chitosan.
The weight ratio of the 2-chloroethanol to the sodium hydroxide aqueous solution to the acetone is 1:1.5:7.
the plant extract is folium Artemisiae Argyi extract, folium Myricae Rubrae extract and Aloe extract. The latin name of Artemisia argyi levl.et Van, the latin name of myrica rubra (lour.) s.etzucc, the latin name of Aloe vera (haw.) Berg; the weight ratio of the wormwood extract, the waxberry leaf extract and the aloe extract is 2:1:4.
the method for extracting the wormwood extract comprises the steps of weighing 5g of wormwood powder, adding the wormwood powder into 70mL of 65% ethanol solution, carrying out ultrasonic extraction for 2 times, wherein the extraction time is 1h each time, and carrying out suction filtration and concentration to obtain the wormwood extract.
The Myrica rubra leaf extract was purchased from Woltlese Biotech, inc. of Lanzhou, and the Aloe extract was purchased from Sienkangwei bioengineering, inc.
The polysaccharide is algal polysaccharide, and the algal polysaccharide is prepared by removing moisture of an algal sample, performing reflux extraction by using an ethanol aqueous solution with the volume fraction of 85%, then adding water, performing reflux extraction at 95 ℃ for 2.5 hours, centrifuging, taking supernatant, putting the supernatant into a rotary evaporator for concentration, and then heating to remove a solvent to obtain the algal polysaccharide. The weight ratio of the ethanol water solution to the water of the seaweed sample is 1:5:40; the seaweed sample is thallus laminariae, purchased from Qiyu flagship shop for nourishing and health promotion.
The mass fraction of soluble total sugar in the polysaccharide is 38%, and the mass fraction of protein is 3.7%.
The high molecular quaternary ammonium salt is aliphatic quaternary ammonium salt polymer, specifically quaternary ammonium salt-37, CAS number 26161-33-1.
The coupling agent is aminopropyltriethoxysilane, and the CAS number is 919-30-2.
The surfactant is Tween 20, and the CAS number is 9005-64-5.
The preparation method of the multifunctional persistent antibacterial composition comprises the following steps of,
s1, preparing an inorganic composite material: according to the solid-liquid ratio of 1:10, adding sepiolite into a mixed solution of silver nitrate and cerium nitrate, stirring for 3.5 hours at the neutral condition of 60 ℃, centrifuging, collecting a solid product, washing for 3 times by using distilled water, and drying to obtain the inorganic composite material. The concentration of the silver nitrate is 0.2mol/L, and the concentration of the cerium nitrate is 0.01mol/L.
S2, adding the inorganic composite material, hydroxyethyl chitosan, high-molecular quaternary ammonium salt, a coupling agent, polysaccharide, a surfactant and the plant extract into water in sequence, and stirring uniformly to obtain a finished product.
Example 4.
The embodiment provides a multifunctional persistent antibacterial composition, and the specific implementation manner is the same as that of embodiment 1; the difference is that the addition amount of the antibacterial agent is 5 parts.
Example 5.
The embodiment provides a multifunctional persistent antibacterial composition, and the specific implementation manner is the same as that of embodiment 1; the difference lies in that the weight ratio of the high molecular quaternary ammonium salt and the chitosan derivative of the inorganic composite material is 2:1:5.
example 6.
The embodiment provides a multifunctional persistent antibacterial composition, and the specific implementation manner is the same as that of embodiment 1; the difference is that the chitosan is hydroxypropyl chitosan and is purchased from Siemens Mei He Biotechnology Co., ltd.
Example 7.
The embodiment provides a multifunctional persistent antibacterial composition, and the specific implementation manner is the same as that of embodiment 1; the difference is that no high molecular quaternary ammonium salt is added.
Example 8.
The embodiment provides a multifunctional persistent antibacterial composition, and the specific implementation manner is the same as that of embodiment 1; the difference is that the plant extract is honeysuckle extract, purchased from Langeria; lonicera japonica Thunb is the Latin chemical name of Lonicera japonica.
Example 9.
The embodiment provides a multifunctional persistent antibacterial composition, and the specific implementation mode is the same as that of the embodiment 1; the difference is that the weight ratio of the wormwood extract, the waxberry leaf extract and the aloe extract is 1:2:3.
example 10.
The embodiment provides a multifunctional persistent antibacterial composition, and the specific implementation manner is the same as that of embodiment 1; the difference is that the step S2 is to add hydroxyethyl chitosan, high molecular quaternary ammonium salt, coupling agent, polysaccharide, surfactant, plant extract and inorganic composite material into water in sequence and stir evenly to obtain the finished product.
Performance test method
Antibacterial immediate effect:
the antibacterial compositions of examples 1 to 10 were tested for antibacterial ability with reference to GB/T38502-2020; the experimental strain is staphylococcus aureus, and the initial strain concentration is 3 multiplied by 10 8 CFU/mL; the antibacterial composition sample is 1mL, and is placed in a constant temperature incubator (36.5 deg.C) to act on the experimental strain, and viable bacteria concentration in the incubator is measured every 1min and converted into logarithm value N x According to the killing logarithm value KL = N 0 -N x The time taken for the kill log to reach 5 or more (including 5) was recorded.
The lasting effect is as follows:
the antibacterial compositions of examples 1 to 10 were left to stand at room temperature for 6 months, and then the kill log values before and after the placement of the antibacterial compositions (before placement: KL) were measured with reference to GB/T38502-2020 and the above-mentioned antibacterial ability test method 0 And after placing: KL 1 ) (ii) a Calculation of Δ = | KL 0 -KL 1 |/KL 0 X 100%. A lower Δ indicates a more potent antimicrobial composition.
Antiviral ability:
the antiviral capacity of the antibacterial compositions of examples 1 to 10 was determined with reference to ISO 18184-2014, the test virus was Vero E6 cells, the operating conditions were 37 ℃, 5% CO 2 The action time is 7 days, and the Vero E6 cell concentration C after 7 days is recorded 1 And initial Vero E6 cell concentration C 0 Calculating viral cell death rate = (C) 0 -C 1 )/C 0 X is 100%; defining that the death rate of the virus cell is more than or equal to 99.9 percent, the antiviral capacity is excellent, the death rate of the virus cell is 99 to 99.9 percent, the antiviral capacity is good, and the death rate of the virus cell is<99% is poor antiviral ability.
Stability:
each of the antimicrobial compositions of examples 1-10 was divided into 10 samples in parallel, and the samples were sequentially placed at 40 ℃,10 ℃ and-5 ℃ for 3 hours each, and circulated 5 times, and then the number of samples showing precipitation and discoloration in each set of parallel samples was counted.
Performance test data
TABLE 1 Performance test results
Immediate effect/min Persistence Δ/%) Antiviral ability Stability of
Example 1 1 0.4 Superior food 0
Example 2 1 0.8 Superior food 0
Example 3 1 0.6 Superior food 0
Example 4 6 8.3 Good wine 1
Example 5 3 5.8 Good wine 2
Example 6 4 6.5 Good wine 2
Example 7 5 7.2 Good wine 2
Example 8 7 6.9 Difference (D) 3
Example 9 4 4.7 Good wine 2
Example 10 7 8.8 Difference (D) 4
Finally, it is pointed out that the foregoing examples are illustrative only, serving to explain some of the characteristics of the process according to the invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.

Claims (3)

1. The multifunctional sustained-effect antibacterial composition is characterized by comprising the following raw materials in parts by weight: 20-45 parts of an antibacterial agent, 1-10 parts of a plant extract, 0.01-1 part of a coupling agent, 1-5 parts of polysaccharide, 1-6 parts of a surfactant and 40-70 parts of water; the antibacterial agent is an inorganic composite material, a high-molecular quaternary ammonium salt and a chitosan derivative; the inorganic composite material comprises the following components in parts by weight (3-7): 1: (1.4-2); the plant extract is folium Artemisiae Argyi extract, folium Myricae Rubrae extract and Aloe extract; the weight ratio of the wormwood extract, the waxberry leaf extract and the aloe extract is (1.5-3): 1: (2-5); the high-molecular quaternary ammonium salt is an aliphatic quaternary ammonium salt polymer; the preparation method of the multifunctional persistent antibacterial composition comprises the steps of preparing an inorganic composite material, sequentially adding the inorganic composite material, a chitosan derivative, a high-molecular quaternary ammonium salt, a coupling agent, polysaccharide, a surfactant and a plant extract into water, and uniformly stirring to obtain a finished product; the inorganic composite material comprises an antibacterial component and a carrier; the carrier comprises at least one of zeolite, phosphate, bentonite, mullite, hydroxyapatite, clay mineral and silica gel; the antibacterial component comprises at least one of silver salt, copper salt, zinc salt and rare earth metal salt; the chitosan derivative is hydroxyethyl chitosan.
2. The multifunctional sustained-effect antibacterial composition according to claim 1, wherein the polysaccharide comprises 35-42% by mass of soluble total sugars and 1-5% by mass of protein.
3. The multifunctional sustained-effect antibacterial composition according to any one of claims 1 to 2, which is prepared by preparing an inorganic composite material, sequentially adding the inorganic composite material, the chitosan derivative, the polymeric quaternary ammonium salt, the coupling agent, the polysaccharide, the surfactant and the plant extract into water, and uniformly stirring to obtain a finished product.
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