CN113981617B - Nano antibacterial material and its preparation method and use - Google Patents

Nano antibacterial material and its preparation method and use Download PDF

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CN113981617B
CN113981617B CN202111212274.3A CN202111212274A CN113981617B CN 113981617 B CN113981617 B CN 113981617B CN 202111212274 A CN202111212274 A CN 202111212274A CN 113981617 B CN113981617 B CN 113981617B
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molybdenum disulfide
lipoic acid
chitosan oligosaccharide
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nanofiber membrane
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CN113981617A (en
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陈进
徐其兰
张李
蔡铃
柳玉辉
陈�峰
曹玥
姜慧君
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Nanjing Medical University
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    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/50—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyalcohols, polyacetals or polyketals
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
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Abstract

The invention relates to a nano antibacterial material and a preparation method and application thereof. The preparation method comprises the following steps: reacting the molybdenum disulfide nanoflower with alpha-lipoic acid to obtain a molybdenum disulfide-lipoic acid nanocomposite; reacting the molybdenum disulfide-lipoic acid nano composite material with chitosan oligosaccharide under the action of a coupling agent to obtain the molybdenum disulfide-lipoic acid-chitosan oligosaccharide nano composite material; further dispersing the molybdenum disulfide-lipoic acid-chitosan oligosaccharide nano composite material in deionized water, adding polyvinyl alcohol, and drying and crosslinking after electrostatic spinning to obtain the polyvinyl alcohol-molybdenum disulfide-lipoic acid-chitosan oligosaccharide nano fiber membrane. The molybdenum disulfide-lipoic acid-chitosan oligosaccharide nano composite material and the polyvinyl alcohol-molybdenum disulfide-lipoic acid-chitosan oligosaccharide nano fiber film have broad-spectrum antibacterial performance and strong killing capacity on bacteria; can be used for rapid photothermal sterilization of personal hygiene products such as masks.

Description

Nano antibacterial material and its preparation method and use
Technical Field
The invention relates to a preparation method of a nano antibacterial material, the nano antibacterial material prepared by the method and application thereof, belonging to the application field of nano materials and microorganisms and the technical field of antibacterial preparations.
Background
According to the knowledge of the applicant, the existing nano antibacterial materials have the characteristics that the materials generate light and heat under the irradiation of near infrared laser so as to realize the antibacterial effect, and the risk of generating the drug resistance of strains caused by using antibiotics can be avoided by adopting the materials for the antibacterial effect. However, such materials also suffer from the following drawbacks: (1) the synthesis process is complex, and manpower and financial resources are wasted; (2) the photo-thermal performance is not ideal, and energy is wasted when the ideal effect is achieved (such as high-power near-infrared laser irradiation); (3) the powdered or granular antibacterial material is easy to fall off and difficult to continuously sterilize. Therefore, the development of nano antibacterial materials capable of overcoming the above drawbacks is urgently needed.
The invention patents of patent numbers CN201810178541.1 and CN108392675B disclose a preparation method of a near-infrared light response nano antibacterial coating based on molybdenum disulfide and a photosensitizer, and specifically comprise the steps of polishing and decontaminating a titanium sheet, and preparing the molybdenum disulfide nano coating with near-infrared photo-thermal antibacterial property by using a hydrothermal method; the photosensitizer IR780 is added dropwise, so that the photosensitivity of the IR780 and the photothermal property of the molybdenum disulfide generate a synergistic antibacterial effect. The invention patent applications of application numbers CN202010674645.9 and CN111838148A disclose a preparation method of a cobalt-doped zinc oxide/molybdenum disulfide nano composite antibacterial agent, which utilizes the advantages of large specific surface area, strong surface adsorption capacity and the like of a molybdenum disulfide nanosheet to adsorb bacteria to the surface of the molybdenum disulfide nanosheet, and then the cobalt (Co) -doped zinc oxide (ZnO) loaded on the surface of the molybdenum disulfide nanosheet and between layers of the molybdenum disulfide nanosheet cooperatively plays a role in high-efficiency antibacterial action to kill the bacteria, so that the novel nano composite antibacterial agent with good biocompatibility and high antibacterial activity is finally prepared. The technical result of the invention is obviously different from the technical scheme.
Disclosure of Invention
The main purposes of the invention are: the problems in the prior art are overcome, and the preparation method of the nano antibacterial material is provided, and the obtained nano antibacterial material has broad-spectrum antibacterial performance. Meanwhile, the corresponding nano antibacterial material and the application thereof are also provided.
The technical scheme for solving the technical problems of the invention is as follows:
a preparation method of a nano antibacterial material is characterized by comprising the following steps:
firstly, adopting molybdenum disulfide nanoflowers; uniformly dispersing molybdenum disulfide nanoflowers into absolute ethyl alcohol by ultrasonic, adding alpha-lipoic acid into the absolute ethyl alcohol, and stirring for reaction; after the reaction is finished, centrifuging the reaction solution, removing the supernatant, washing the obtained solid matter, and performing vacuum freeze-drying to obtain the molybdenum disulfide-lipoic acid nano composite material;
secondly, taking the obtained molybdenum disulfide-lipoic acid nano composite material, ultrasonically dispersing the molybdenum disulfide-lipoic acid nano composite material in absolute ethyl alcohol, and adding a coupling agent for activation; then, dropwise adding a solution formed by dissolving chitosan oligosaccharide in deionized water, and stirring for reaction; and after the reaction is finished, centrifuging the reaction solution, removing the supernatant, washing the obtained solid matter, and performing vacuum freeze-drying to obtain the molybdenum disulfide-lipoic acid-chitosan oligosaccharide nanocomposite.
The method firstly adopts molybdenum disulfide (MoS) 2 ) The nanoflower reacts with alpha-Lipoic Acid (LA) to obtain the molybdenum disulfide-lipoic acid nanocomposite (MoS) 2 -LA), and then continuously reacting with Chitosan Oligosaccharide (COS) to obtain the molybdenum disulfide-lipoic acid-chitosan oligosaccharide nanocomposite (MoS) 2 -LA-COS). The method has simple steps and simple and convenient operation, and the obtained molybdenum disulfide-lipoic acid-chitosan oligosaccharide nano composite material has broad-spectrum antibacterial performance.
The further improved technical scheme of the invention is as follows:
preferably, the preparation method further comprises the following steps:
thirdly, dispersing the obtained molybdenum disulfide-lipoic acid-chitosan oligosaccharide nano composite material in deionized water; adding polyvinyl alcohol and stirring; and (3) carrying out ultrasonic treatment on the obtained suspension, carrying out electrostatic spinning to obtain a nanofiber membrane, carrying out vacuum drying on the obtained nanofiber membrane at 40 +/-5 ℃, and then carrying out crosslinking in a vacuum drying oven at 150 +/-5 ℃ to obtain the polyvinyl alcohol-molybdenum disulfide-lipoic acid-chitosan oligosaccharide nanofiber membrane.
By adopting the preferred scheme, the polyvinyl alcohol-molybdenum disulfide-lipoic acid-chitosan oligosaccharide nanofiber membrane (PVA/MoS) can be further obtained 2 LA-COS), the nanofiber membrane has broad-spectrum antibacterial performance, can avoid the application limitation that powder or solid antibacterial materials are easy to fall off, and has strong killing capacity on bacteria.
Preferably, in the first step, the weight of the alpha-lipoic acid is at least 2 times that of the molybdenum disulfide nanoflower; in the second step, the weight of the chitosan oligosaccharide is at least 1.5 times of that of the molybdenum disulfide-lipoic acid nanocomposite.
Preferably, in the third step, the ratio of the molybdenum disulfide-lipoic acid-chitosan oligosaccharide nanocomposite to the deionized water is 8 +/-0.1 mg: 10 ml; the weight ratio of the molybdenum disulfide-lipoic acid-chitosan oligosaccharide nanocomposite to the polyvinyl alcohol is 1: 100 plus or minus 10.
By adopting the preferable scheme, the key material proportion in each step can be further optimized.
Preferably, in the second step, the coupling agent is prepared from a mixture of 3 ± 1: 1 EDC and NHS, for an activation time of at least 15 minutes; in the first step and the second step, the stirring reaction time is at least 12 hours respectively; the centrifugation speeds are respectively at least 5000rpm, and the centrifugation times are respectively at least 5 minutes; washing with absolute ethyl alcohol and deionized water for at least three times; after washing, the supernatant is discarded and is placed in a vacuum freeze dryer for freeze-drying.
Preferably, in the first step, the molybdenum disulfide nanoflowers are in LiCl-KCl- (NH) 4 ) 6 Mo 7 O 24 Prepared electrolytically in a KSCN melt system at a temperature of 673K and a constant current of 0.5A.
By adopting the preferred scheme, the specific technical characteristics of the first step and the second step can be further optimized. Note: EDC is N-ethyl-N' - (3-dimethylaminopropyl) carbodiimide hydrochloride and NHS is N-hydroxysuccinimide.
Preferably, in the third step, the stirring temperature is ambient temperature and the stirring time is at least 12 hours; the ultrasound time is at least 10 minutes; firstly, transferring the suspension after ultrasonic treatment into an injector, and then carrying out electrostatic spinning; the time of electrospinning is at least 10 hours; attaching the nanofiber membrane obtained by electrostatic spinning to a receiving base fabric, stripping the nanofiber membrane from the base fabric after vacuum drying, and then placing the nanofiber membrane in a vacuum drying oven for crosslinking; the vacuum drying time is at least 12 hours and the crosslinking time is at least 24 hours.
More preferably, the syringe is a sterile syringe, the syringe having a needle size of 20-G; the specific parameters of electrostatic spinning are as follows: positive voltage: 20.0 kV; negative voltage: -3 kV; tip to receiver distance: 15 cm; suspension flow rate: 1.00 mL/h; the base cloth is made of aluminum foil paper.
By adopting the preferable scheme, the specific technical characteristics of the third step can be further optimized.
The invention also proposes:
the molybdenum disulfide-lipoic acid-chitosan oligosaccharide nanocomposite prepared by the preparation method or the polyvinyl alcohol-molybdenum disulfide-lipoic acid-chitosan oligosaccharide nanofiber membrane prepared by the preparation method.
The application of the molybdenum disulfide-lipoic acid-chitosan oligosaccharide nano composite material or the polyvinyl alcohol-molybdenum disulfide-lipoic acid-chitosan oligosaccharide nano fiber film in preparing the antibacterial agent.
Compared with the prior art, the preparation method has the advantages that the steps are simple, the operation is simple and convenient, the obtained molybdenum disulfide-lipoic acid-chitosan oligosaccharide nano composite material has broad-spectrum antibacterial performance, the obtained polyvinyl alcohol-molybdenum disulfide-lipoic acid-chitosan oligosaccharide nano fiber film not only has broad-spectrum antibacterial performance, but also can avoid the application limitation that powder or solid antibacterial materials are easy to fall off, and has strong killing capacity on bacteria; can be used for rapid photothermal sterilization of personal hygiene products such as masks.
Drawings
FIG. 1 is a schematic diagram of the reaction principle of example 1 of the present invention.
FIG. 2 is a Scanning Electron Micrograph (SEM) (a), EDS spectroscopy and elemental distribution (b, c) of example 2 of the present invention.
FIG. 3 shows a Fourier Infrared Spectroscopy (a) and an XPS full Spectroscopy (b) in example 2 of the present invention.
FIG. 4 shows photothermal temperature curves and photothermal images (A) and results of tests on an antibacterial coated plate (B) in example 3 of the present invention.
FIG. 5 is a scanning electron micrograph (a, b, c), a diameter distribution (d, e, f) and an element distribution (g) of example 4 of the present invention. Wherein, the materials of the pictures a and d are PVA, and the materials of the pictures b and e are PVA/MoS 2 -LA-COS0.5, graph c, graph f and graph g are PVA/MoS 2 -LA-COS1。
FIG. 6 shows photothermal temperature curves and photothermal images (a) and results of tests on an antibacterial coated plate (b) in example 5 of the present invention.
Detailed Description
The invention is described in further detail below with reference to embodiments and with reference to the drawings. The invention is not limited to the examples given.
Example 1
This example is to prepare a molybdenum disulfide-lipoic acid-chitosan oligosaccharide nanocomposite and a polyvinyl alcohol-molybdenum disulfide-lipoic acid-chitosan oligosaccharide nanofiber membrane.
The basic preparation process of this example comprises:
firstly, adopting molybdenum disulfide nanoflowers; uniformly dispersing molybdenum disulfide nanoflowers into absolute ethyl alcohol by ultrasonic, adding alpha-lipoic acid into the absolute ethyl alcohol, and stirring for reaction; and after the reaction is finished, centrifuging the reaction solution, removing the supernatant, washing the obtained solid matter, and performing vacuum freeze-drying to obtain the molybdenum disulfide-lipoic acid nano composite material.
Secondly, taking the obtained molybdenum disulfide-lipoic acid nano composite material, dispersing the molybdenum disulfide-lipoic acid nano composite material in absolute ethyl alcohol by ultrasonic waves, and adding a coupling agent for activation; then, dropwise adding a solution formed by dissolving chitosan oligosaccharide in deionized water, and stirring for reaction; and after the reaction is finished, centrifuging the reaction liquid, removing the supernatant, washing the obtained solid matter, and performing vacuum freeze-drying to obtain the molybdenum disulfide-lipoic acid-chitosan oligosaccharide nano composite material.
Thirdly, dispersing the obtained molybdenum disulfide-lipoic acid-chitosan oligosaccharide nano composite material in deionized water; adding polyvinyl alcohol and stirring; and (3) carrying out ultrasonic treatment on the obtained suspension, carrying out electrostatic spinning to obtain a nanofiber membrane, carrying out vacuum drying on the obtained nanofiber membrane at 40 +/-5 ℃, and then carrying out crosslinking in a vacuum drying oven at 150 +/-5 ℃ to obtain the polyvinyl alcohol-molybdenum disulfide-lipoic acid-chitosan oligosaccharide nanofiber membrane.
Specifically, in the first step, the weight of the alpha-lipoic acid is at least 2 times of that of the molybdenum disulfide nanoflower; in the second step, the weight of the chitosan oligosaccharide is at least 1.5 times of that of the molybdenum disulfide-lipoic acid nanocomposite.
In the third step, the ratio of the molybdenum disulfide-lipoic acid-chitosan oligosaccharide nano composite material to the deionized water is 8 +/-0.1 mg: 10 ml; the weight ratio of the molybdenum disulfide-lipoic acid-chitosan oligosaccharide nanocomposite to the polyvinyl alcohol is 1: 100 +/-10.
In the second step, the coupling agent is prepared by mixing the following components in a mass ratio of 3 +/-1: 1 EDC and NHS, for an activation time of at least 15 minutes; in the first step and the second step, the stirring reaction time is at least 12 hours respectively; the centrifugation speeds are respectively at least 5000rpm, and the centrifugation times are respectively at least 5 minutes; washing with absolute ethyl alcohol and deionized water for at least three times; after washing, the supernatant is discarded and is placed in a vacuum freeze dryer for freeze-drying.
In addition, in the first step, the molybdenum disulfide nanoflower is prepared in LiCl-KCl- (NH) 4 ) 6 Mo 7 O 24 Prepared electrolytically in a KSCN melt system at a temperature of 673K and a constant current of 0.5A.
In the third step, the stirring temperature is ambient temperature, and the stirring time is at least 12 hours; the ultrasound time is at least 10 minutes; firstly, transferring the suspension after ultrasonic treatment into an injector, and then carrying out electrostatic spinning; the time of electrospinning is at least 10 hours; attaching the nanofiber membrane obtained by electrostatic spinning to a receiving base fabric, stripping the nanofiber membrane from the base fabric after vacuum drying, and then placing the nanofiber membrane in a vacuum drying oven for crosslinking; the vacuum drying time is at least 12 hours and the crosslinking time is at least 24 hours.
The syringe is a sterile syringe, and the type of a needle head of the syringe is 20-G; the specific parameters of electrostatic spinning are as follows: positive voltage: 20.0 kV; negative voltage: -3 kV; tip to receiver distance: 15 cm; suspension flow rate: 1.00 mL/h; the base cloth is aluminum foil paper.
The following are exemplary specific preparation procedures:
(1) in LiCl-KCl- (NH) 4 ) 6 Mo 7 O 24 Electrolyzing at 673K and 0.5A in a-KSCN melt system to obtain petal-shaped nano MoS 2 (i.e., MoS) 2 Nanoflower).
(2) Weighing 50 mg MoS 2 The nanoflower is uniformly dispersed in absolute ethyl alcohol by ultrasonic, and then 100 mg of alpha-Lipoic Acid (LA) is weighed and added into the mixture containing MoS 2 Stirring in absolute ethanol of nanoflower overnight. The resulting suspension was centrifuged at 5000rpm for 5 minutes, the supernatant was removed, and the solutions were each washed with anhydrous waterWashing with ethanol and deionized water for three times, discarding supernatant, and lyophilizing the obtained sample in a vacuum lyophilizer to obtain MoS 2 -LA. In the material, alpha-Lipoic Acid (LA) is connected and modified MoS through disulfide bonds 2 And (4) nano flowers.
(3) Weighing 30 mg of the MoS 2 -LA product, dispersing in absolute ethyl alcohol by ultrasonic, adding the mixture in a mass ratio of 3: 1 EDC: NHS coupling agent was activated for 15 min. Excess Chitosan Oligosaccharide (COS) was dissolved in a small amount of deionized water, and the above suspension was added dropwise and stirred overnight. Centrifuging the obtained suspension for 5 minutes at 5000rpm, removing supernatant, washing with anhydrous ethanol and deionized water for three times, respectively, discarding supernatant, and lyophilizing in vacuum lyophilizer to obtain MoS 2 -LA-COS. In the material, Chitosan Oligosaccharide (COS) is connected with MoS through amido bond 2 -LA。
(4) Weigh 8 mg of the above MoS 2 Dispersing the LA-COS product in 10ml of deionized water, adding 0.8G of polyvinyl alcohol (PVA) into the deionized water, stirring the mixture at the ambient temperature overnight, carrying out ultrasonic treatment on the obtained suspension for 10 minutes, and transferring the suspension into a 10ml disposable sterile syringe with the needle head model of 20-G; electrostatic spinning parameters: positive voltage: 20.0 kV; negative voltage: -3 kV; tip to receiver distance: 15 cm; suspension flow rate: 1.00 mL/h. Performing electrostatic spinning for 10h to obtain a nanofiber membrane, drying in a vacuum drying oven at 40 ℃ overnight, stripping from the aluminum foil paper of the receiving base fabric, and then crosslinking in a vacuum drying oven at 150 ℃ for 24 hours to obtain PVA/MoS 2 -LA-COS nanofibrous membrane.
Example 2
In this example, the molybdenum disulfide-lipoic acid-chitosan oligosaccharide nanocomposite (MoS) prepared in example 1 was used 2 LA-COS) were tested in multiple ways. The following is the MoS prepared as exemplified in example 1 2 -results of LA-COS assay.
FIG. 2 shows MoS 2 Scanning Electron Microscopy (SEM) and EDS spectroscopy analysis and elemental distribution plots of LA-COS. As can be seen from the figure, MoS 2 The surface of LA-COS is rough and has a certain thickness, but still retains MoS 2 Petal-shaped appearance. EDS energy spectrum analysis and element distribution diagram show that MoS 2 -LA-COS mainly comprises Mo, S, C, N and other elements, and the existence of COS in MoS is proved 2 A surface.
FIG. 3 shows MoS 2 LA-COS and control groups (MoS) 2 、LA、COS、MoS 2 -LA) fourier ir spectrum and XPS survey. In Fourier Infrared Spectroscopy, MoS 2 The new C ═ O characteristic peak appears at 1720 wavenumbers of LA-COS, which indicates that LA is successfully modified to MoS 2 A surface; MoS 2 LA-COS and COS at a similar wavenumber at 750-. XPS survey shows characteristic peaks for C (284.0eV), N (398.0eV), O (532.0eV), Mo (229.0eV), S (163.0eV), and also demonstrates MoS 2 Successful preparation of-LA-COS nanocomposites.
In addition, other MoS prepared from example 1 2 The results of LA-COS are the same or substantially the same as above, and the conclusions drawn from the results are the same as above.
Example 3
In this example, the molybdenum disulfide-lipoic acid-chitosan oligosaccharide nanocomposite (MoS) prepared in example 1 was used 2 LA-COS) was subjected to photothermal antimicrobial test, and molybdenum disulfide nanoflower used in example 1 was used as a comparison.
The following is the MoS prepared as exemplified in example 1 2 LA-COS, and the petaloid NanoS adopted for this example 2 Detection was performed as a comparison.
Subjecting petal-shaped nano MoS 2 、MoS 2 And respectively dispersing the-LA-COS nano composite materials in deionized water, and testing the photo-thermal effect of the system under near infrared light of 808 nm. As shown in graph A of FIG. 4, the power density was constant at 808nm near-infrared laser irradiation (0.8 w/cm) 2 ，1.3w/cm 2 ，1.8w/cm 2 )，MoS 2 The photothermal effect of LA-COS nanocomposites increases with increasing concentration (25. mu.g/mL, 50. mu.g/mL, 100. mu.g/mL); in maintaining MoS 2 Photothermal effect with power density (0.8 w/cm) at concentration of-LA-COS nanocomposite (25 μ g/mL) 2 ，1.3w/cm 2 ，1.8w/cm 2 ) And increased and enhanced. After 10 minutes of 808nm near-infrared laser irradiation, MoS 2 And MoS 2 -LA-COS solution (concentration 25. mu.g/mL, power density 1.3w/cm 2 ) The temperature rise was 12 deg.C and 27 deg.C, respectively, while the temperature rise of pure water was only 3.2 deg.C. The difference in temperature rise between the two may result from oxidation of molybdenum disulfide by LA grafting to produce pentavalent molybdenum with a stronger photothermal effect. Real-time photothermographic display of MoS 2 -LA-COS nanocomposites compared to petaloid MoS 2 Has stronger photothermal effect, which is mainly derived from MoS 2 -the presence of LA in the LA-COS nanocomposite, in terms of: MoS 2 -LA nanocomposites compared to MoS 2 The temperature rises greatly, and MoS 2 -LA-COS nanocomposite and MoS 2 The temperature change of the-LA nanocomposite material is small.
Flower petal-shaped MoS 2 And MoS 2 The power density of the-LA-COS nano composite material after being respectively incubated with escherichia coli and staphylococcus aureus is 1.3w/cm 2 The 808nm near infrared laser is irradiated for 10 minutes and is uniformly coated on an agar solid culture medium, the experimental result is shown as a B picture in figure 4, and when near infrared laser (NIR) irradiation is not carried out, the two materials have almost no antibacterial action on two bacteria; control and MoS after near Infrared laser (NIR) irradiation 2 Bacterial colonies on agar plates of the (25. mu.g/mL) group did not differ significantly from those without NIR, whereas MoS 2 The kill rate for both bacteria for the-LA-COS + NIR group is evident from the agar plates, with few new colonies appearing. Due to MoS 2 The LA-COS surface is positively charged, can reach the surface of bacteria through electrostatic interaction, and can generate local thermotherapy under the irradiation of near infrared light to inactivate enzyme and metabolize disorder in the bacteria so as to achieve the effect of killing the bacteria.
The above results show that MoS 2 The LA-COS nano composite material has an enhanced antibacterial effect under the irradiation of near-infrared laser, and can enhance the photo-thermal performance and the antibacterial effect of the molybdenum disulfide nano material; has the function of killing various bacteria, and achieves broad-spectrum, high-efficiency and continuous sterilization. Because antibiotics are not involved in the antibacterial process, the generation of drug resistance of the strain can be prevented while the antibacterial process is carried out.
In addition, itIt was the MoS obtained in example 1 2 The results of LA-COS are the same or substantially the same as above, and the conclusions drawn from the results are the same as above.
Example 4
In this example, the polyvinyl alcohol-molybdenum disulfide-lipoic acid-chitosan oligosaccharide nanofiber membrane (PVA/MoS) prepared in example 1 was used 2 LA-COS) were tested in multiple ways.
The following is a PVA/MoS prepared as an example in example 1 2 -results of the assay performed on LA-COS.
The comparative material is a PVA nanofiber membrane, and the preparation process is as follows: weighing 0.8G of polyvinyl alcohol (PVA) and adding into 10ml of deionized water, stirring overnight at ambient temperature, carrying out ultrasonic treatment on the obtained suspension for 10 minutes, transferring into a 10ml disposable sterile syringe, wherein the model of a needle is 20-G; electrostatic spinning parameters: positive voltage: 20.0 kV; negative voltage: -3 kV; tip to receiver distance: 15 cm; suspension flow rate: 1.00 mL/h. And (3) carrying out electrostatic spinning for 10h to obtain a nanofiber membrane, drying the nanofiber membrane in a vacuum drying oven at 40 ℃ overnight, stripping the nanofiber membrane from the receiving base cloth aluminum foil paper, and then crosslinking the nanofiber membrane in a vacuum drying oven at 150 ℃ for 24 hours to obtain the PVA nanofiber membrane.
PVA/MoS as shown in FIG. 5, panels a to f 2 Scanning electron microscopy of-LA-COS nanofiber membranes showed PVA/MoS 2 the-LA-COS nanofiber membrane has a relatively uniform fiber structure, in which PVA/MoS 2 Fiber diameter of-LA-COS 0.5 169.4. + -. 23.0nm, PVA/MoS 2 Fiber diameter of LA-COS1 was 165.7. + -. 16.4nm (note: PVA/MoS) 2 -LA-COS0.5、PVA/MoS 2 The numbers 0.5, 1 in LA-COS1 denote MoS 2 -LA-COS nanocomposites vs PVA/MoS 2 The mass percentage of the LA-COS nanofiber membrane was 0.5%, 1%), and MoS was observed 2 the-LA-COS nanocomposites were successfully incorporated on PVA nanofiber substrates. EDS energy spectrum analysis and element distribution diagram (g diagram of figure 5) show that C, N, Mo and S elements are uniformly distributed on the nano-fiber, and the results show that PVA/MoS 2 Successful preparation of LA-COS nanofiber membranes.
Example 5
In this example, the PVA-molybdenum disulfide-lipoic acid-chitosan oligosaccharide nanofiber membrane (PVA/MoS) prepared in example 1 was used 2 -LA-COS) for photothermal antimicrobial detection.
The following is the PVA/MoS prepared as exemplified in example 1 2 -results of the assay performed on LA-COS.
The comparative material was a PVA nanofiber membrane and the procedure for its preparation was the same as in example 4.
Shearing PVA nanofiber membrane and PVA/MoS 2 the-LA-COS nanofiber membrane is placed in a 24-pore plate filled with physiological saline, and the near infrared laser with the power density of 1.3w/cm at 808nm 2 The temperature change and photothermal image are shown in graph a of FIG. 6, MoS, with 10 minutes of irradiation 2 PVA/MoS with highest-LA-COS content 2 The LA-COS1 nanofiber membrane rose by 36.5 ℃ compared to the PVA nanofiber membrane alone by only 4.8 ℃, indicating that the PVA/MoS 2 The heating effect of the-LA-COS nanofiber membrane is completely derived from MoS 2 -LA-COS。
PVA nanofiber membrane and PVA/MoS with different contents 2 the-LA-COS nanofiber membrane is placed in a 24-pore plate containing escherichia coli and staphylococcus aureus, and the power density is 1.3w/cm 2 808nm near infrared laser irradiation for 10 minutes, sucking 100 microliters of bacterial liquid and uniformly coating on the agar solid medium, the experimental result is shown in the b diagram of figure 6, the PVA nanofiber membrane without near infrared laser irradiation has almost no antibacterial effect, and the PVA/MoS 2 The LA-COS nanofiber membrane shows a certain antibacterial capacity, and a dose response relation exists; PVA/MoS after 10 minutes of irradiation with near-infrared laser 2 The antibacterial effect of the-LA-COS nanofiber membrane is obviously enhanced, wherein the PVA/MoS 2 The LA-COS1 nanofiber membrane can even completely kill bacteria. The above results show that PVA/MoS 2 the-LA-COS nanofiber membrane has enhanced antibacterial effect.
From the above examples, it can be seen that the molybdenum disulfide-lipoic acid-chitosan oligosaccharide nanocomposite and the polyvinyl alcohol-molybdenum disulfide-lipoic acid-chitosan oligosaccharide nanofiber membrane have broad-spectrum antibacterial performance, and can be applied to rapid photo-thermal sterilization of personal hygiene products such as masks.
In addition to the above embodiments, the present invention may have other embodiments. All technical solutions formed by adopting equivalent substitutions or equivalent transformations fall within the protection scope of the claims of the present invention.

Claims (12)

1. A preparation method of a nano antibacterial material is characterized by comprising the following steps:
firstly, adopting molybdenum disulfide nanoflowers; uniformly dispersing molybdenum disulfide nanoflowers into absolute ethyl alcohol by ultrasonic, adding alpha-lipoic acid into the absolute ethyl alcohol, and stirring for reaction; after the reaction is finished, centrifuging the reaction solution, removing the supernatant, washing the obtained solid matter, and performing vacuum freeze-drying to obtain the molybdenum disulfide-lipoic acid nano composite material;
secondly, taking the obtained molybdenum disulfide-lipoic acid nano composite material, ultrasonically dispersing the molybdenum disulfide-lipoic acid nano composite material in absolute ethyl alcohol, and adding a coupling agent for activation; then, dropwise adding a solution formed by dissolving chitosan oligosaccharide in deionized water, and stirring for reaction; and after the reaction is finished, centrifuging the reaction solution, removing the supernatant, washing the obtained solid matter, and performing vacuum freeze-drying to obtain the molybdenum disulfide-lipoic acid-chitosan oligosaccharide nanocomposite.
2. The method for preparing nano antibacterial material according to claim 1, wherein the method further comprises the following steps:
thirdly, dispersing the obtained molybdenum disulfide-lipoic acid-chitosan oligosaccharide nano composite material in deionized water; adding polyvinyl alcohol and stirring; and (3) carrying out ultrasonic treatment on the obtained suspension, carrying out electrostatic spinning to obtain a nanofiber membrane, carrying out vacuum drying on the obtained nanofiber membrane at 40 +/-5 ℃, and then carrying out crosslinking in a vacuum drying oven at 150 +/-5 ℃ to obtain the polyvinyl alcohol-molybdenum disulfide-lipoic acid-chitosan oligosaccharide nanofiber membrane.
3. The method for preparing nano antibacterial material according to claim 1 or 2,
in the first step, the weight of alpha-lipoic acid is at least 2 times of that of the molybdenum disulfide nanoflower; in the second step, the weight of the chitosan oligosaccharide is at least 1.5 times of that of the molybdenum disulfide-lipoic acid nanocomposite.
4. The method for preparing nano antibacterial material according to claim 2, wherein in the third step, the ratio of the molybdenum disulfide-lipoic acid-chitosan oligosaccharide nano composite material to the deionized water is 8 ± 0.1 mg: 10 ml; the weight ratio of the molybdenum disulfide-lipoic acid-chitosan oligosaccharide nanocomposite to the polyvinyl alcohol is 1: 100 +/-10.
5. The method for preparing nano antibacterial material according to claim 3, wherein in the second step, the coupling agent is prepared by mixing the components in a mass ratio of 3 ± 1: 1 EDC and NHS, for an activation time of at least 15 minutes; in the first step and the second step, the stirring reaction time is at least 12 hours respectively; the centrifugation speeds are respectively at least 5000rpm, and the centrifugation times are respectively at least 5 minutes; washing with absolute ethyl alcohol and deionized water for at least three times; after washing, the supernatant is discarded and is freeze-dried in a vacuum freeze-dryer.
6. The method for preparing nano antibacterial material according to claim 3, wherein in the first step, the molybdenum disulfide nanoflower is prepared in LiCl-KCl- (NH) 4 ) 6 Mo 7 O 24 Prepared electrolytically in a KSCN melt system at a temperature of 673K and a constant current of 0.5A.
7. The method for preparing nano antibacterial material according to claim 4, wherein in the third step, the stirring temperature is ambient temperature and the stirring time is at least 12 hours; the ultrasound time is at least 10 minutes; firstly, transferring the suspension after ultrasonic treatment into an injector, and then carrying out electrostatic spinning; the time of electrospinning is at least 10 hours; attaching the nanofiber membrane obtained by electrostatic spinning to a receiving base fabric, stripping the nanofiber membrane from the base fabric after vacuum drying, and then placing the nanofiber membrane in a vacuum drying oven for crosslinking; the vacuum drying time is at least 12 hours and the crosslinking time is at least 24 hours.
8. The method for preparing nano antibacterial material according to claim 7, wherein the syringe is a sterile syringe, and the needle type of the syringe is 20-G; the specific parameters of electrostatic spinning are as follows: positive voltage: 20.0 kV; negative voltage: -3 kV; tip to receiver distance: 15 cm; suspension flow rate: 1.00 mL/h; the base cloth is made of aluminum foil paper.
9. Molybdenum disulfide-lipoic acid-chitosan oligosaccharide nanocomposite prepared by the preparation method of any one of claims 1 to 8.
10. Use of the molybdenum disulfide-lipoic acid-chitosan oligosaccharide nanocomposite of claim 9 for the preparation of an antibacterial agent.
11. The polyvinyl alcohol-molybdenum disulfide-lipoic acid-chitosan oligosaccharide nanofiber membrane prepared by the preparation method of claim 2 or 4 or 7 or 8.
12. Use of the polyvinyl alcohol-molybdenum disulfide-lipoic acid-chitosan oligosaccharide nanofibrous membrane of claim 11 for the preparation of an antibacterial agent.
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