CN114223675A - Organic-inorganic montmorillonite composite antibacterial material and preparation method thereof - Google Patents

Organic-inorganic montmorillonite composite antibacterial material and preparation method thereof Download PDF

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CN114223675A
CN114223675A CN202210126768.8A CN202210126768A CN114223675A CN 114223675 A CN114223675 A CN 114223675A CN 202210126768 A CN202210126768 A CN 202210126768A CN 114223675 A CN114223675 A CN 114223675A
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montmorillonite
acid
mixing
organic
antibacterial material
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孙志明
郑水林
李盛平
张晓雨
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China University of Mining and Technology Beijing CUMTB
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China University of Mining and Technology Beijing CUMTB
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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
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/33—Heterocyclic compounds
    • A61K31/395—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins
    • A61K31/435—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins having six-membered rings with one nitrogen as the only ring hetero atom
    • A61K31/44—Non condensed pyridines; Hydrogenated derivatives thereof
    • A61K31/4425—Pyridinium derivatives, e.g. pralidoxime, pyridostigmine
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K33/00—Medicinal preparations containing inorganic active ingredients
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    • A61K33/34—Copper; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/02—Inorganic compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • A61P31/04—Antibacterial agents

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Abstract

The invention provides a preparation method of an organic-inorganic montmorillonite composite antibacterial material, which comprises the following steps: mixing the montmorillonite concentrate with water and an acidic solution, and activating to obtain acid-leached montmorillonite; mixing the acid-leached montmorillonite with water to obtain montmorillonite dispersion liquid; and mixing the montmorillonite dispersion liquid with cetyl pyridine and copper chloride, and then carrying out loading to obtain the organic-inorganic montmorillonite composite antibacterial material. According to the invention, acid-leaching montmorillonite is used as a carrier, and the structure and layer charge of montmorillonite are changed through acid-leaching treatment, so that the antibacterial property of the material is effectively improved; the acid-leaching montmorillonite is mixed with water, so that the acid-leaching montmorillonite can be uniformly dispersed in the solution, the subsequent loading of the organic antibacterial agent cetyl pyridine and the inorganic antibacterial agent copper chloride is facilitated, the broad-spectrum performance of the antibacterial material is realized, and the antibacterial material can simultaneously show good resistance to gram-positive bacteria and gram-negative bacteria.

Description

Organic-inorganic montmorillonite composite antibacterial material and preparation method thereof
Technical Field
The invention belongs to the technical field of antibacterial materials, and particularly relates to an organic-inorganic montmorillonite composite antibacterial material and a preparation method thereof.
Background
The antibacterial agent with the functions of sterilization and bacteriostasis is considered as an effective substitute of antibiotics, can generate antibacterial active components, thereby achieving the antibacterial effect, and is not easy to cause the bacteria to generate drug resistance.
At present, montmorillonite is mainly used as a carrier for the antibacterial material, but the existing antibacterial material cannot simultaneously show good resistance to gram-positive bacteria and gram-negative bacteria. Therefore, how to realize the antibacterial material which simultaneously shows good resistance to gram-positive bacteria and gram-negative bacteria becomes a difficult problem to be solved in the field.
Disclosure of Invention
The invention aims to provide an organic-inorganic montmorillonite composite antibacterial material and a preparation method thereof. The organic-inorganic montmorillonite composite antibacterial material prepared by the preparation method provided by the invention can simultaneously show good resistance to gram-positive bacteria and gram-negative bacteria.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of an organic-inorganic montmorillonite composite antibacterial material, which comprises the following steps:
(1) mixing the montmorillonite concentrate with water and an acidic solution, and then activating to obtain acid-leached montmorillonite;
(2) mixing the acid-leached montmorillonite obtained in the step (1) with water to obtain montmorillonite dispersion liquid;
(3) and (3) mixing the montmorillonite dispersion liquid obtained in the step (2) with cetylpyridinium and copper chloride, and then carrying out loading to obtain the organic-inorganic montmorillonite composite antibacterial material.
Preferably, the montmorillonite content in the montmorillonite concentrate in the step (1) is more than 90%.
Preferably, the activation temperature in the step (1) is 90-98 ℃, and the activation time is 4-6 h.
Preferably, the mass ratio of acid-leached montmorillonite to water in the step (2) is 1: (30-100).
Preferably, the mixing of the acid-leached montmorillonite with water in the step (2) is performed under ultrasonic stirring conditions.
Preferably, the stirring speed during the ultrasonic treatment is 400-600 r, and the ultrasonic treatment time is 15-30 min.
Preferably, the copper chloride in the step (3) accounts for 5-20% of the mass of the acid-leached montmorillonite in the montmorillonite dispersion liquid.
Preferably, the mass of the cetyl pyridine in the step (3) is 2-3 times that of the copper chloride.
Preferably, the temperature of the load in the step (3) is 50-80 ℃, and the time of the load is 5-8 h.
The invention also provides the organic-inorganic montmorillonite composite antibacterial material prepared by the preparation method of the technical scheme.
The invention provides a preparation method of an organic-inorganic montmorillonite composite antibacterial material, which comprises the following steps: mixing the montmorillonite concentrate with water and an acidic solution, and activating to obtain acid-leached montmorillonite; mixing the acid-leached montmorillonite with water to obtain montmorillonite dispersion liquid; and mixing the montmorillonite dispersion liquid with cetyl pyridine and copper chloride, and then carrying out loading to obtain the organic-inorganic montmorillonite composite antibacterial material. According to the invention, acid-leaching montmorillonite is used as a carrier, and the structure and layer charge of montmorillonite are changed through acid-leaching treatment, so that the antibacterial property of the material is effectively improved; the acid-leaching montmorillonite is mixed with water, so that the acid-leaching montmorillonite can be uniformly dispersed in the solution, the subsequent loading of the organic antibacterial agent cetyl pyridine and the inorganic antibacterial agent copper chloride is facilitated, the broad-spectrum performance of the antibacterial material is realized, and the antibacterial material can simultaneously show good resistance to gram-positive bacteria and gram-negative bacteria. The results of the examples show that the minimum inhibitory concentration of the organic-inorganic montmorillonite composite antibacterial material prepared by the preparation method is 3.25-24.69 ppm on staphylococcus aureus and 24.69-83.33 ppm on escherichia coli.
Detailed Description
The invention provides a preparation method of an organic-inorganic montmorillonite composite antibacterial material, which comprises the following steps:
(1) mixing the montmorillonite concentrate with water and an acidic solution, and then activating to obtain acid-leached montmorillonite;
(2) mixing the acid-leached montmorillonite obtained in the step (1) with water to obtain montmorillonite dispersion liquid;
(3) and (3) mixing the montmorillonite dispersion liquid obtained in the step (2) with cetylpyridinium and copper chloride, and then carrying out loading to obtain the organic-inorganic montmorillonite composite antibacterial material.
The acid-leaching montmorillonite is obtained by mixing montmorillonite concentrate with water and an acidic solution and then activating. The invention carries out activation treatment on the montmorillonite, so that the montmorillonite generates acidification reaction in an acid solution, and silicon, iron and aluminum at the edges of the structural unit layers are subjected to H+Attack, small partial dissolution occurs, then H+The interlayer cations are replaced, octahedron is gradually destroyed, magnesium, iron and aluminum are dissolved out to different degrees, and most Ca between the layers is replaced2+The layered structure is not influenced, but the number of layer charges is reduced, so that the antibacterial property of the material is effectively improved.
In the present invention, the content of montmorillonite in the montmorillonite concentrate is preferably greater than 90%. The source of the montmorillonite concentrate is not particularly limited in the invention, and the montmorillonite concentrate can be prepared by a preparation method well known in the field. The method limits the purity of the montmorillonite concentrate, can ensure that the structure of the montmorillonite is changed by subsequent acid leaching, but not other impurities, and ensures that the change of the antibacterial performance of the material is completely caused by the change of the structure of the montmorillonite.
In the present invention, the operation of mixing the montmorillonite concentrate with water and an acidic solution preferably comprises the steps of:
1) mixing the montmorillonite concentrate with water to obtain ore pulp;
2) mixing the ore pulp obtained in the step 1) with an acidic solution.
The invention preferably mixes the montmorillonite concentrate with water to obtain the pulp.
The source of the water is not particularly limited in the present invention, and a commercially available product known to those skilled in the art may be used. In the invention, the water is used for dispersing the montmorillonite concentrate, and the montmorillonite can be uniformly dispersed in the water, thereby being beneficial to subsequent acid leaching.
In the present invention, the mass ratio of the montmorillonite concentrate to water is preferably 1: (30-100), more preferably 1: (50-80). The operation of mixing the montmorillonite concentrate with water is not particularly limited in the invention, and the technical scheme for preparing the mixed material, which is well known by the technical personnel in the field, can be adopted.
After obtaining the pulp, the present invention preferably mixes the pulp with an acidic solution.
In the present invention, the acidic solution is preferably a hydrochloric acid solution, a nitric acid solution, or a sulfuric acid solution; the concentration of the acidic solution is preferably 0.1-0.4 mol/L, and more preferably 0.2-0.3 mol/L; the volume ratio of the ore pulp to the acidic solution is preferably (3-6): 1, more preferably 5: 1. the source of the acidic solution is not particularly limited in the present invention, and it may be prepared by a commercially available product or a well-known preparation method well known to those skilled in the art. According to the invention, the acid solution is adopted to activate the montmorillonite concentrate, so that the structure and layer charge of montmorillonite can be changed, and the antibacterial property of the material is effectively improved.
The operation of mixing the ore pulp and the acidic solution is not particularly limited in the invention, and the technical scheme for preparing the mixed material, which is well known to those skilled in the art, can be adopted.
In the invention, the activation temperature is preferably 90-98 ℃, and more preferably 95 ℃; the activation time is preferably 4-6 h, and more preferably 5 h. The invention can further improve the activation degree by controlling the temperature and the time of the activation treatment, thereby further improving the antibacterial property of the material.
After the activation is finished, the invention preferably sequentially filters, washes and dries the product obtained by the activation to obtain the acid-leaching montmorillonite.
The operation of the filtration is not particularly limited in the present invention, and a filtration operation known to those skilled in the art may be employed.
In the present invention, the detergent used for the washing is preferably distilled water. The source of the detergent is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used. The dosage of the detergent is not specially limited, and the detergent is washed until the pH value of the washing liquid is 6-7.
In the invention, the drying temperature is preferably 50-70 ℃. The drying time is not specially limited, and the drying is carried out until the weight is constant.
After acid-leached montmorillonite is obtained, the acid-leached montmorillonite is mixed with water to obtain montmorillonite dispersion liquid.
The source of the water is not particularly limited in the present invention, and a commercially available product known to those skilled in the art may be used. In the present invention, the mass ratio of the acid-leached montmorillonite to water is preferably 1: (30-100), more preferably 1: (50-80).
In the present invention, the mixing of the acid-leached montmorillonite with water is preferably performed under ultrasonic agitation; the stirring speed during ultrasonic treatment is preferably 400-600 r; the time of the ultrasonic treatment is preferably 15-30 min. The invention can further improve the dispersion degree of acid-leaching montmorillonite by controlling the technological parameters of ultrasound, thereby being more beneficial to the load of subsequent antibacterial components.
After the montmorillonite dispersion liquid is obtained, the montmorillonite dispersion liquid is mixed with cetylpyridinium and copper chloride and then loaded to obtain the organic-inorganic montmorillonite composite antibacterial material. According to the invention, acid-leaching montmorillonite is used as a carrier, cetyl pyridine is used as an organic antibacterial component, copper chloride is used as an inorganic antibacterial component, and a composite mode is adopted to realize the broad-spectrum performance of the antibacterial material, so that the antibacterial material can simultaneously show good resistance to gram-positive bacteria and gram-negative bacteria.
In the invention, the copper chloride is preferably 5-20% of the mass of acid-leached montmorillonite in the montmorillonite dispersion liquid, and more preferably 10-15%; the preferable mass of the cetyl pyridine is 2-3 times of that of the copper chloride, and the more preferable mass is 2.5 times of that of the copper chloride. The broad-spectrum antibacterial performance of the organic-inorganic montmorillonite composite antibacterial material can be further improved by controlling the using amounts of the copper chloride and the cetyl pyridine.
In the present invention, the cetylpyridinium is preferably added in the form of a cetylpyridinium aqueous solution; the copper chloride is preferably added as an aqueous solution of copper chloride. The sources of the cetylpyridinium solution and the cupric chloride solution are not particularly limited in the present invention, and the solutions may be prepared by a preparation method known to those skilled in the art. The concentrations of the cetylpyridinium solution and the cupric chloride solution are not specially limited, and the use amount of each raw material can meet the requirement. According to the invention, the cetylpyridinium aqueous solution and the copper chloride aqueous solution are adopted, so that the cetylpyridinium and the copper chloride can be uniformly added into the montmorillonite dispersion liquid, and the phenomenon that the obtained antibacterial material is not uniformly loaded and the broad-spectrum antibacterial performance is influenced due to the fact that the local medicament concentration in a loading system is too high and an over-excitation reaction occurs is avoided.
In the present invention, the mixing of the montmorillonite dispersion with cetylpyridinium chloride and cupric chloride is preferably performed by slowly adding cetylpyridinium chloride and cupric chloride to the montmorillonite dispersion. The invention adopts a slow adding mode to more uniformly add the antibacterial component, so that the load is more uniform.
In the present invention, the slow addition is preferably carried out using a peristaltic pump; the adding speed of the peristaltic pump is preferably 15-30 rpm; the slow addition is preferably carried out under stirring. The stirring operation is not particularly limited in the present invention, and a stirring operation known to those skilled in the art may be employed.
In the invention, the temperature of the load is preferably 50-80 ℃, and more preferably 60-70 ℃; the loading time is preferably 5-8 h, and more preferably 6-7 h. The invention can further improve the load rate by controlling the temperature and time of load, thereby further improving the broad-spectrum antibacterial performance of the organic-inorganic montmorillonite composite antibacterial material.
After loading is finished, the invention preferably sequentially filters, washes and dries the loaded product to obtain the organic-inorganic montmorillonite composite antibacterial material.
The operation of the filtration is not particularly limited in the present invention, and a filtration operation known to those skilled in the art may be employed. The washing operation is not particularly limited in the present invention, and a washing operation known to those skilled in the art may be employed.
In the invention, the drying temperature is preferably 50-70 ℃. The drying time is not specially limited, and the drying is carried out until the weight is constant.
According to the invention, acid-leaching montmorillonite is used as a carrier, and the structure and layer charge of montmorillonite are changed through acid-leaching treatment, so that the antibacterial property of the material is effectively improved; the acid-leaching montmorillonite is mixed with water, so that the acid-leaching montmorillonite can be uniformly dispersed in the solution, the subsequent loading of the organic antibacterial agent cetyl pyridine and the inorganic antibacterial agent copper chloride is facilitated, the broad-spectrum performance of the antibacterial material is realized, and the antibacterial material can simultaneously show good resistance to gram-positive bacteria and gram-negative bacteria.
Aiming at the problems of application limitation of a single antibacterial component, non-ideal montmorillonite loading effect, poor antibacterial performance and the like, the organic antibacterial component and the inorganic antibacterial component are cooperatively loaded on acid-leaching montmorillonite to prepare the Cu with the broad-spectrum antibacterial function2+Pyridine/acid-dipped montmorillonite organic-inorganic montmorillonite composite antibacterial material; the acid-leached montmorillonite is more beneficial to the action of an antibacterial agent and minerals after acid leaching treatment, thereby effectively improving the antibacterial effect of the material.
The invention also provides the organic-inorganic montmorillonite composite antibacterial material prepared by the preparation method of the technical scheme. The antibacterial mechanism of the inorganic antibacterial component in the organic-inorganic montmorillonite composite antibacterial material provided by the invention is as follows: when a trace amount of metal ions contact with bacteria, the metal ions are coulomb attracted and firmly combined with the bacteria with negative charges on the surface, namely, the so-called micro-power effect, so that the metal ions penetrate through cell membranes, enter the interior of the bacteria and react with sulfydryl on proteins in the bacteria, the reaction can inactivate the proteins, reduce the activity of synthetase in the bacteria and possibly interfere the synthesis of bacterial DNA, and the microorganisms lose metabolism and multiplication capacity to die; meanwhile, the combination of metal ions and proteins can also damage an electron transmission system, a respiratory system and a substance transmission system of bacteria, so that the antibacterial effect on gram-negative bacteria is more remarkable; the antibacterial mechanism of the organic antibacterial agent is as follows: can be combined with the surface of bacteria to destroy the wall membrane structure of the bacteria and cause the cell content of the bacteria to flow out and die, and can also react with the mercapto group and other groups on the surface of the bacterial cells to destroy the synthesis system of protein and cell membranes and inhibit the proliferation of the bacteria, so that the antibacterial effect on gram-positive bacteria is more obvious.
The organic-inorganic montmorillonite composite antibacterial material provided by the invention improves the broad-spectrum antibacterial property of the antibacterial material through the synergistic effect of the organic antibacterial component and the inorganic antibacterial component, widens the application range, and can be applied to the environment of gram-positive bacteria and/or gram-negative bacteria.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The preparation method of the organic-inorganic montmorillonite composite antibacterial material comprises the following steps:
(1) mixing 5g of montmorillonite concentrate (the content of montmorillonite is more than 90%) with 250mL of distilled water to obtain ore pulp; wherein the mass ratio of the montmorillonite concentrate to the distilled water is 1: 50;
(2) mixing the ore pulp obtained in the step (1) with 0.1mol/L hydrochloric acid solution, activating at 95 ℃ for 5 hours, filtering, washing with distilled water until the pH value of a washing solution is 7, and drying at 60 ℃ to obtain acid-leached montmorillonite; wherein, the volume ratio of the ore pulp to the hydrochloric acid solution is 5: 1;
(3) mixing 2g of acid-dipped montmorillonite obtained in the step (2) with 100mL of distilled water under the condition of ultrasonic stirring to obtain montmorillonite dispersion liquid; wherein the mass ratio of the acid-leached montmorillonite to the distilled water is 1: 50, stirring speed during ultrasonic treatment is 500r, and ultrasonic treatment time is 25 min;
(4) pre-dissolving 0.2g of copper chloride in water to obtain a copper chloride solution, pre-dissolving 0.5g of cetylpyridinium in water to obtain a cetylpyridinium solution, slowly adding the copper chloride solution and the cetylpyridinium solution into the montmorillonite dispersion liquid obtained in the step (3) at the same time, carrying out loading, filtering, washing and drying at 60 ℃ to obtain the organic-inorganic montmorillonite composite antibacterial material; wherein the copper chloride accounts for 10% of the mass of acid-leached montmorillonite in the montmorillonite dispersion liquid, and the cetyl pyridine accounts for 2.5 times of the mass of the copper chloride; slowly adding by using a peristaltic pump; the rate of addition of the peristaltic pump was 20 rpm; slowly adding the mixture under stirring; the temperature of the load was 70 ℃ and the time was 6 h.
Example 2
The preparation method of the organic-inorganic montmorillonite composite antibacterial material comprises the following steps:
(1) mixing 5g of montmorillonite concentrate (the content of montmorillonite is more than 90%) with 250mL of distilled water to obtain ore pulp; wherein the mass ratio of the montmorillonite concentrate to the distilled water is 1: 50;
(2) mixing the ore pulp obtained in the step (1) with 0.2mol/L hydrochloric acid solution, activating at 95 ℃ for 5 hours, filtering, washing with distilled water until the pH value of a washing solution is 7, and drying at 60 ℃ to obtain acid-leached montmorillonite; wherein, the volume ratio of the ore pulp to the hydrochloric acid solution is 5: 1;
(3) mixing 2g of acid-dipped montmorillonite obtained in the step (2) with 100mL of distilled water under the condition of ultrasonic stirring to obtain montmorillonite dispersion liquid; wherein the mass ratio of the acid-leached montmorillonite to the distilled water is 1: 50, stirring speed during ultrasonic treatment is 500r, and ultrasonic treatment time is 25 min;
(4) pre-dissolving 0.2g of copper chloride in water to obtain a copper chloride solution, pre-dissolving 0.5g of cetylpyridinium in water to obtain a cetylpyridinium solution, slowly adding the copper chloride solution and the cetylpyridinium solution into the montmorillonite dispersion liquid obtained in the step (3) at the same time, carrying out loading, filtering, washing and drying at 60 ℃ to obtain the organic-inorganic montmorillonite composite antibacterial material; wherein the copper chloride accounts for 10% of the mass of acid-leached montmorillonite in the montmorillonite dispersion liquid, and the cetyl pyridine accounts for 2.5 times of the mass of the copper chloride; slowly adding by using a peristaltic pump; the rate of addition of the peristaltic pump was 20 rpm; slowly adding the mixture under stirring; the temperature of the load was 70 ℃ and the time was 6 h.
Example 3
The preparation method of the organic-inorganic montmorillonite composite antibacterial material comprises the following steps:
(1) mixing 5g of montmorillonite concentrate (the content of montmorillonite is more than 90%) with 250mL of distilled water to obtain ore pulp; wherein the mass ratio of the montmorillonite concentrate to the distilled water is 1: 50;
(2) mixing the ore pulp obtained in the step (1) with 0.3mol/L hydrochloric acid solution, activating at 95 ℃ for 5 hours, filtering, washing with distilled water until the pH value of a washing solution is 7, and drying at 60 ℃ to obtain acid-leached montmorillonite; wherein, the volume ratio of the ore pulp to the hydrochloric acid solution is 5: 1; calculating the number of layer charges of the acid-leaching montmorillonite to be 0.21 by adopting a structure deduction algorithm;
(3) mixing 2g of acid-dipped montmorillonite obtained in the step (2) with 100mL of distilled water under the condition of ultrasonic stirring to obtain montmorillonite dispersion liquid; wherein the mass ratio of the acid-leached montmorillonite to the distilled water is 1: 50, stirring speed during ultrasonic treatment is 500r, and ultrasonic treatment time is 25 min;
(4) pre-dissolving 0.2g of copper chloride in water to obtain a copper chloride solution, pre-dissolving 0.5g of cetylpyridinium in water to obtain a cetylpyridinium solution, slowly adding the copper chloride solution and the cetylpyridinium solution into the montmorillonite dispersion liquid obtained in the step (3) at the same time, carrying out loading, filtering, washing and drying at 60 ℃ to obtain the organic-inorganic montmorillonite composite antibacterial material; wherein the copper chloride accounts for 10% of the mass of acid-leached montmorillonite in the montmorillonite dispersion liquid, and the cetyl pyridine accounts for 2.5 times of the mass of the copper chloride; slowly adding by using a peristaltic pump; the rate of addition of the peristaltic pump was 20 rpm; slowly adding the mixture under stirring; the temperature of the load was 70 ℃ and the time was 6 h.
Comparative example 1
The preparation method of the organic-inorganic montmorillonite composite antibacterial material comprises the following steps:
(1) 2g of montmorillonite concentrate (montmorillonite content is more than 90%) (i.e. montmorillonite which has not been subjected to acid leaching) was mixed with 100mL of distilled water under ultrasonic stirring to obtain a montmorillonite dispersion; wherein the mass ratio of the montmorillonite concentrate to the distilled water is 1: 50, stirring speed during ultrasonic treatment is 500r, and ultrasonic treatment time is 25 min;
(2) pre-dissolving 0.2g of copper chloride in water to obtain a copper chloride solution, pre-dissolving 0.5g of cetylpyridinium in water to obtain a cetylpyridinium solution, slowly adding the copper chloride solution and the cetylpyridinium solution into the montmorillonite dispersion liquid obtained in the step (1) at the same time, carrying out loading, filtering, washing and drying at 60 ℃ to obtain the organic-inorganic montmorillonite composite antibacterial material; wherein the copper chloride accounts for 10% of the mass of acid-leached montmorillonite in the montmorillonite dispersion liquid, and the cetyl pyridine accounts for 2.5 times of the mass of the copper chloride; slowly adding by using a peristaltic pump; the rate of addition of the peristaltic pump was 20 rpm; slowly adding the mixture under stirring; the temperature of the load was 70 ℃ and the time was 6 h.
Comparative example 2
The preparation method of the inorganic montmorillonite composite antibacterial material comprises the following steps:
(1) mixing 5g of montmorillonite concentrate (the content of montmorillonite is more than 90%) with 250mL of distilled water to obtain ore pulp; wherein the mass ratio of the montmorillonite concentrate to the distilled water is 1: 50;
(2) mixing the ore pulp obtained in the step (1) with 0.1mol/L hydrochloric acid solution, activating at 95 ℃ for 5 hours, filtering, washing with distilled water until the pH value of a washing solution is 7, and drying at 60 ℃ to obtain acid-leached montmorillonite; wherein, the volume ratio of the ore pulp to the hydrochloric acid solution is 5: 1;
(3) mixing 2g of acid-dipped montmorillonite obtained in the step (2) with 100mL of distilled water under the condition of ultrasonic stirring to obtain montmorillonite dispersion liquid; wherein the mass ratio of the acid-leached montmorillonite to the distilled water is 1: 50, stirring speed during ultrasonic treatment is 500r, and ultrasonic treatment time is 25 min;
(4) dissolving 0.7g of copper chloride in water in advance to obtain a copper chloride solution, slowly adding the copper chloride solution into the montmorillonite dispersion liquid obtained in the step (3) for loading, filtering, washing and drying at 60 ℃ to obtain the antibacterial material only loading copper ions; wherein the copper chloride accounts for 10% of the mass of acid-leached montmorillonite in the montmorillonite dispersion liquid; slowly adding by using a peristaltic pump; the rate of addition of the peristaltic pump was 20 rpm; slowly adding the mixture under stirring; the temperature of the load was 70 ℃ and the time was 6 h.
Comparative example 3
The preparation method of the organic montmorillonite composite antibacterial material comprises the following steps:
(1) mixing 5g of montmorillonite concentrate (the content of montmorillonite is more than 90%) with 250mL of distilled water to obtain ore pulp; wherein the mass ratio of the montmorillonite concentrate to the distilled water is 1: 50;
(2) mixing the ore pulp obtained in the step (1) with 0.1mol/L hydrochloric acid solution, activating at 95 ℃ for 5 hours, filtering, washing with distilled water until the pH value of a washing solution is 7, and drying at 60 ℃ to obtain acid-leached montmorillonite; wherein, the volume ratio of the ore pulp to the hydrochloric acid solution is 5: 1;
(3) mixing 2g of acid-dipped montmorillonite obtained in the step (2) with 100mL of distilled water under the condition of ultrasonic stirring to obtain montmorillonite dispersion liquid; wherein the mass ratio of the acid-leached montmorillonite to the distilled water is 1: 50, stirring speed during ultrasonic treatment is 500r, and ultrasonic treatment time is 25 min;
(4) dissolving 0.7g of cetylpyridinium in water in advance to obtain a cetylpyridinium solution, slowly adding the cetylpyridinium solution into the montmorillonite dispersion liquid obtained in the step (3), carrying out loading, filtering, washing and drying at 60 ℃ to obtain the antibacterial material only carrying the pyridinium; wherein the cetyl pyridine accounts for 25 percent of the mass of acid-leached montmorillonite in the montmorillonite dispersion liquid; slowly adding by using a peristaltic pump; the rate of addition of the peristaltic pump was 20 rpm; slowly adding the mixture under stirring; the temperature of the load was 70 ℃ and the time was 6 h.
Comparative example 4
The preparation method of the inorganic montmorillonite composite antibacterial material comprises the following steps:
(1) mixing 5g of montmorillonite concentrate (the content of montmorillonite is more than 90%) with 250mL of distilled water to obtain ore pulp; wherein the mass ratio of the montmorillonite concentrate to the distilled water is 1: 50;
(2) mixing the ore pulp obtained in the step (1) with 0.2mol/L hydrochloric acid solution, activating at 95 ℃ for 5 hours, filtering, washing with distilled water until the pH value of a washing solution is 7, and drying at 60 ℃ to obtain acid-leached montmorillonite; wherein, the volume ratio of the ore pulp to the hydrochloric acid solution is 5: 1;
(3) mixing 2g of acid-dipped montmorillonite obtained in the step (2) with 100mL of distilled water under the condition of ultrasonic stirring to obtain montmorillonite dispersion liquid; wherein the mass ratio of the acid-leached montmorillonite to the distilled water is 1: 50, stirring speed during ultrasonic treatment is 500r, and ultrasonic treatment time is 25 min;
(4) dissolving 0.7g of copper chloride in water in advance to obtain a copper chloride solution, slowly adding the copper chloride solution into the montmorillonite dispersion liquid obtained in the step (3) for loading, filtering, washing and drying at 60 ℃ to obtain the antibacterial material only loading copper ions; wherein the copper chloride accounts for 10% of the mass of acid-leached montmorillonite in the montmorillonite dispersion liquid; slowly adding by using a peristaltic pump; the rate of addition of the peristaltic pump was 20 rpm; slowly adding the mixture under stirring; the temperature of the load was 70 ℃ and the time was 6 h.
Comparative example 5
The preparation method of the organic montmorillonite composite antibacterial material comprises the following steps:
(1) mixing 5g of montmorillonite concentrate (the content of montmorillonite is more than 90%) with 250mL of distilled water to obtain ore pulp; wherein the mass ratio of the montmorillonite concentrate to the distilled water is 1: 50;
(2) mixing the ore pulp obtained in the step (1) with 0.2mol/L hydrochloric acid solution, activating at 95 ℃ for 5 hours, filtering, washing with distilled water until the pH value of a washing solution is 7, and drying at 60 ℃ to obtain acid-leached montmorillonite; wherein, the volume ratio of the ore pulp to the hydrochloric acid solution is 5: 1;
(3) mixing 2g of acid-dipped montmorillonite obtained in the step (2) with 100mL of distilled water under the condition of ultrasonic stirring to obtain montmorillonite dispersion liquid; wherein the mass ratio of the acid-leached montmorillonite to the distilled water is 1: 50, stirring speed during ultrasonic treatment is 500r, and ultrasonic treatment time is 25 min;
(4) dissolving 0.7g of cetylpyridinium in water in advance to obtain a cetylpyridinium solution, slowly adding the cetylpyridinium solution into the montmorillonite dispersion liquid obtained in the step (3), carrying out loading, filtering, washing and drying at 60 ℃ to obtain the antibacterial material only carrying the pyridinium; wherein the cetyl pyridine accounts for 25 percent of the mass of acid-leached montmorillonite in the montmorillonite dispersion liquid; slowly adding by using a peristaltic pump; the rate of addition of the peristaltic pump was 20 rpm; slowly adding the mixture under stirring; the temperature of the load was 70 ℃ and the time was 6 h.
Comparative example 6
The preparation method of the inorganic montmorillonite composite antibacterial material comprises the following steps:
(1) mixing 5g of montmorillonite concentrate (the content of montmorillonite is more than 90%) with 250mL of distilled water to obtain ore pulp; wherein the mass ratio of the montmorillonite concentrate to the distilled water is 1: 50;
(2) mixing the ore pulp obtained in the step (1) with 0.3mol/L hydrochloric acid solution, activating at 95 ℃ for 5 hours, filtering, washing with distilled water until the pH value of a washing solution is 7, and drying at 60 ℃ to obtain acid-leached montmorillonite; wherein, the volume ratio of the ore pulp to the hydrochloric acid solution is 5: 1;
(3) mixing 2g of acid-dipped montmorillonite obtained in the step (2) with 100mL of distilled water under the condition of ultrasonic stirring to obtain montmorillonite dispersion liquid; wherein the mass ratio of the acid-leached montmorillonite to the distilled water is 1: 50, stirring speed during ultrasonic treatment is 500r, and ultrasonic treatment time is 25 min;
(4) dissolving 0.7g of copper chloride in water in advance to obtain a copper chloride solution, slowly adding the copper chloride solution into the montmorillonite dispersion liquid obtained in the step (3) for loading, filtering, washing and drying at 60 ℃ to obtain the antibacterial material only loading copper ions; wherein the copper chloride accounts for 10% of the mass of acid-leached montmorillonite in the montmorillonite dispersion liquid; slowly adding by using a peristaltic pump; the rate of addition of the peristaltic pump was 20 rpm; slowly adding the mixture under stirring; the temperature of the load was 70 ℃ and the time was 6 h.
Comparative example 7
The preparation method of the organic montmorillonite composite antibacterial material comprises the following steps:
(1) mixing 5g of montmorillonite concentrate (the content of montmorillonite is more than 90%) with 250mL of distilled water to obtain ore pulp; wherein the mass ratio of the montmorillonite concentrate to the distilled water is 1: 50;
(2) mixing the ore pulp obtained in the step (1) with 0.3mol/L hydrochloric acid solution, activating at 95 ℃ for 5 hours, filtering, washing with distilled water until the pH value of a washing solution is 7, and drying at 60 ℃ to obtain acid-leached montmorillonite; wherein, the volume ratio of the ore pulp to the hydrochloric acid solution is 5: 1;
(3) mixing 2g of acid-dipped montmorillonite obtained in the step (2) with 100mL of distilled water under the condition of ultrasonic stirring to obtain montmorillonite dispersion liquid; wherein the mass ratio of the acid-leached montmorillonite to the distilled water is 1: 50, stirring speed during ultrasonic treatment is 500r, and ultrasonic treatment time is 25 min;
(4) dissolving 0.7g of cetylpyridinium in water in advance to obtain a cetylpyridinium solution, slowly adding the cetylpyridinium solution into the montmorillonite dispersion liquid obtained in the step (3), carrying out loading, filtering, washing and drying at 60 ℃ to obtain the antibacterial material only carrying the pyridinium; wherein the cetyl pyridine accounts for 25 percent of the mass of acid-leached montmorillonite in the montmorillonite dispersion liquid; slowly adding by using a peristaltic pump; the rate of addition of the peristaltic pump was 20 rpm; slowly adding the mixture under stirring; the temperature of the load was 70 ℃ and the time was 6 h.
The composite antibacterial materials prepared in the examples 1 to 3 and the comparative examples 1 to 7 are tested for the minimum inhibitory concentration, and the test method comprises the following steps: respectively culturing Escherichia coli (negative bacteria) and Staphylococcus aureus (positive bacteria) overnight, and preparing into bacterial suspension with OD600 about 0.04 (determination condition: 200 μ L liquid in 96-well plate); preparing the composite antibacterial material into 250ppm suspension in a conical flask, sealing with a sealing film, and performing ultrasonic treatment until no obvious particles exist; adding 100 mu L of physiological saline into a 96-well plate, uniformly sampling 200 mu L of the suspension into a first hole of the 96-well plate, uniformly mixing, taking out 200 mu L of the suspension into a second hole, continuously operating for 8 times, uniformly mixing the last hole, taking out 200 mu L of liquid, and discarding; adding 50 mu L of physiological saline and 50 mu L of bacterial liquid into a 96-well plate again, sealing by using a sealing plate membrane, and putting into an oscillator for contact reaction for 1 h; adding 180 mu L of culture solution into a new 96-well plate, transferring 20 mu L of each well of the 96-well plate after contact reaction to the corresponding well, and then sealing by using a sealing plate film to prevent liquid from evaporating; placing the 96-well plate in an enzyme-labeling instrument, carrying out constant-temperature oscillation culture at 37 ℃, and measuring the air-spaced absorbance every 15min to finally obtain the lowest bacteriostatic concentration of the composite antibacterial material; the larger the minimum inhibitory concentration value is, the poorer the antibacterial performance is, and the results are shown in tables 1-4.
Table 1 results of the minimum inhibitory concentration test on aureodextran of the composite antibacterial material prepared in examples 1 to 3 and comparative example 1
Figure BDA0003500750820000121
Table 2 results of testing the minimum inhibitory concentration of the composite antibacterial material prepared in examples 1 to 3 and comparative example 1 against escherichia coli
Figure BDA0003500750820000131
As can be seen from tables 1 and 2, the antibacterial performance of the composite antibacterial material can be improved by performing acid leaching treatment on montmorillonite, and the organic-inorganic montmorillonite composite antibacterial material provided by the invention has broad-spectrum antibacterial performance, and under the condition that other conditions are not changed, when the concentration of a hydrochloric acid solution during acid leaching is 0.3mol/L, the broad-spectrum antibacterial performance of the composite antibacterial material is the best.
Table 3 test results of minimum inhibitory concentration of the composite antibacterial material prepared in comparative examples 2-7 on aureodextran
Figure BDA0003500750820000132
Table 4 test results of minimum inhibitory concentration of composite antibacterial material prepared in comparative examples 2-7 on escherichia coli
Figure BDA0003500750820000133
Comparing comparative examples 2 and 3 with example 1, comparative examples 4 and 5 with example 2, and comparative examples 6 and 7 with example 3, it can be seen that the use of the same amount of the organic antibiotic component or the inorganic antibiotic component does not achieve an excellent antibiotic effect, nor has a broad-spectrum antibiotic property, and the use of the same total amount of the organic antibiotic component and the inorganic antibiotic component can achieve a synergistic effect, thereby further improving the broad-spectrum antibiotic property of the material.
As can be seen from the comparative examples and the examples, the organic-inorganic montmorillonite composite antibacterial material prepared by the preparation method provided by the invention can simultaneously show good resistance to gram-positive bacteria and gram-negative bacteria.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A preparation method of an organic-inorganic montmorillonite composite antibacterial material comprises the following steps:
(1) mixing the montmorillonite concentrate with water and an acidic solution, and then activating to obtain acid-leached montmorillonite;
(2) mixing the acid-leached montmorillonite obtained in the step (1) with water to obtain montmorillonite dispersion liquid;
(3) and (3) mixing the montmorillonite dispersion liquid obtained in the step (2) with cetylpyridinium and copper chloride, and then carrying out loading to obtain the organic-inorganic montmorillonite composite antibacterial material.
2. The method according to claim 1, wherein the content of montmorillonite in the montmorillonite concentrate in the step (1) is more than 90%.
3. The preparation method according to claim 1, wherein the temperature for activation in the step (1) is 90-98 ℃, and the time for activation is 4-6 h.
4. The production method according to claim 1, wherein the mass ratio of acid-leached montmorillonite to water in step (2) is 1: (30-100).
5. The production method according to claim 1, wherein the mixing of the acid-leached montmorillonite with water in the step (2) is performed under ultrasonic agitation.
6. The preparation method according to claim 5, wherein the stirring speed during the ultrasonic treatment is 400 to 600r, and the ultrasonic treatment time is 15 to 30 min.
7. The production method according to claim 1, wherein the copper chloride in the step (3) accounts for 5 to 20% by mass of the acid-leached montmorillonite in the montmorillonite dispersion liquid.
8. The method according to claim 1, wherein the amount of cetylpyridinium in the step (3) is 2 to 3 times the amount of cupric chloride.
9. The preparation method according to claim 1, wherein the temperature of the load in the step (3) is 50-80 ℃ and the time of the load is 5-8 h.
10. The organic-inorganic montmorillonite composite antibacterial material prepared by the preparation method of any one of claims 1 to 9.
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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100015245A1 (en) * 2008-04-24 2010-01-21 Joe Harrison Combination of Copper Cations with Peroxides or Quaternary Ammonium Compounds for the Treatment of Biofilms

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100015245A1 (en) * 2008-04-24 2010-01-21 Joe Harrison Combination of Copper Cations with Peroxides or Quaternary Ammonium Compounds for the Treatment of Biofilms

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Title
余志伟; 王筱明; 王霞: "蒙脱石抗菌材料研究", 《矿物岩石》 *
谢桂香; 唐治炜; 林标声; 温德才: "季铵盐-铜-蒙脱土复合材料的制备及抗菌性能", 《龙岩学院学报》 *

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