CN114159584A - Preparation method of manganese-doped hollow carbon spheres with light response performance and application of manganese-doped hollow carbon spheres in antibacterial field - Google Patents
Preparation method of manganese-doped hollow carbon spheres with light response performance and application of manganese-doped hollow carbon spheres in antibacterial field Download PDFInfo
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Abstract
The invention discloses a preparation method of a manganese-doped hollow carbon sphere with a light response performance and application of the manganese-doped hollow carbon sphere in the antibacterial field. Synthesis of SiO by the stober method2The core is sequentially added with dopamine and manganese salt, and the dopamine is in SiO2Surface oxidation polymerization is carried out, and then manganese salt is adsorbed with dopamine framework to obtain SiO2A manganese-doped dopamine polymer as a template; calcining to form manganese-doped carbon spheres; etch away the interiorSiO of (2)2And (4) obtaining a manganese-doped hollow carbon sphere, namely the Mn/HNCS nano-particle. The Mn/HNCS synthesized by the method has good appearance, uniform particles and simple preparation process, has activities of similar oxidases and peroxidases, and the interaction of manganese metal and a carbon skeleton, so that the Mn/HNCS has excellent photothermal effect and photoresponse enhanced enzyme activity effect, and has wide application prospects in the fields of drug-resistant bacteria resistance, catalysis, tumor inhibition, virus resistance and the like.
Description
Technical Field
The invention belongs to the field of biomedicine, and particularly relates to a preparation method of a manganese-doped hollow carbon sphere with a light response property and application of the manganese-doped hollow carbon sphere in the field of antibiosis.
Background
Compared with the traditional antibiotic therapy, the nano enzyme is a killer weapon with great potential to resist the infection of multidrug resistant bacteria, and the main characteristic is that the nano enzyme can escape the existing mechanism related to acquired resistance, so that the drug resistance is not easy to generate while the bacteria are inactivated. Reactive Oxygen Species (ROS) generated by nanoenzymes, such as hydroxyl radicals, can oxidize bacterial biomolecules, further destroy the structure of bacterial membranes, and finally kill bacteria. However, the antibacterial efficacy of nanoenzymes is generally influenced by the relatively limited enzyme-like activity and thus cannot be widely used. For example, peroxidase-like nanoenzymes, considered as typical antimicrobial mimics, are also subjected to additional H2O2Limitation of concentration, high concentration of H2O2Not good for wound healing, low concentration of H2O2Failing to achieve a therapeutic effect or causing bacterial defense against oxidative stress, thereby reducing the antibacterial efficacy of hydroxyl radicals. Therefore, it is urgently required to develop a novelNano-enzyme, can be separated from H2O2Can overcome the current research situation that the traditional material has poor antibacterial effect due to insufficient enzyme activity. Currently, photoresponse nano-materials can effectively resist bacteria by utilizing the photothermal effect thereof, but the nano-materials with photo-enhanced enzymatic activity are hardly researched.
In addition, the existing method for preparing manganese-doped carbon sphere nanoenzyme generally comprises the steps of synthesizing a precursor polymer without metal doping, and introducing a manganese source in the processes of grinding, pyrolysis and the like, so that the synthesis process is complicated, the defects of uneven doping, unstable performance and the like exist, and the synthesis process still has many challenges.
Disclosure of Invention
Aiming at the problems, the invention provides the preparation method of the manganese-doped hollow carbon sphere which is simple and convenient to synthesize, stable in performance and good in appearance, and tests prove that the manganese-doped hollow carbon sphere has the synergistic effect of the photo-thermal effect and the photo-enhanced enzyme activity effect under the illumination condition, and can effectively inhibit the growth of multi-drug resistant bacteria. Based on the excellent performance of the material, the nano material can be expected to be widely applied in the fields of biomedicine and biosafety in the future.
The preparation method of the manganese-doped hollow carbon sphere provided by the invention comprises the steps of firstly synthesizing SiO by a stober method2As the inner core, dopamine and manganese salt are added in sequence, and the dopamine can be in SiO state under the alkaline condition2Surface oxidation polymerization to form adhesive dopamine polymer, and then manganese salt is adsorbed to dopamine skeleton to obtain SiO2A manganese-doped dopamine polymer as a template; the obtained SiO2Calcining the manganese-doped dopamine polymer serving as the template to preliminarily form manganese-doped carbon spheres; etching away the inner SiO by a strong alkaline treatment2And (4) obtaining a manganese-doped hollow carbon sphere, namely the Mn/HNCS nano-particle.
Specifically, the preparation method of the manganese-doped hollow carbon sphere provided by the invention comprises the following steps:
1) preparation of manganese-doped dopamine polymer
Uniformly mixing ethanol and ultrapure water under ultrasound, adding ammonia water, stirring for 10-30 min, slowly adding tetraethyl silicate by using a peristaltic pump, completely adding the tetraethyl silicate, reacting for 30-60 min, quickly adding a dopamine hydrochloride solution, reacting for 0.5-12 h, adding soluble manganese salt, continuously reacting for 12-24 h, sequentially centrifugally washing by using deionized water and absolute ethyl alcohol, and drying in vacuum to obtain a manganese-doped dopamine polymer;
2) preparation of manganese-doped carbon spheres
Calcining the polymer prepared in the step 1), and naturally cooling to obtain manganese-doped carbon spheres;
3) preparation of Mn/HNCS
Dispersing the manganese-doped carbon spheres obtained in the step 2) in alkali liquor, and etching under stirring to obtain manganese-doped hollow carbon spheres, namely Mn/HNCS nano-particles.
In the step 1), the feeding volume ratio of ethanol, ultrapure water, ammonia water and tetraethyl silicate is 20-30: 6-10: 0.5-2: 1;
the reaction temperature is 10-40 ℃;
stirring is magnetic stirring; the stirring speed is 250-450 r/min;
the addition rate of the peristaltic pump is 0.16 mL/min;
the soluble manganese salt is at least one of manganese acetylacetonate, manganese chloride and manganese sulfate, and the feeding mass is 10-150 mg;
the feeding volume and concentration of the dopamine hydrochloride are 3-6 mL and 100 mg/mL;
the centrifugal speed is 8000-11000 rpm; centrifuging for 5-15 min;
in the step 2), the calcining temperature is 800-1000 ℃; the temperature rising speed is 2-5 ℃/min; the heat preservation time is 2-3 h;
in the step 3), the alkali liquor can be NaOH solution, and the final molar concentration of NaOH is 3-5M;
stirring is magnetic stirring; the stirring speed is 200-400 rpm;
the etching temperature can be 70-90 ℃, and the time can be 10-20 h;
step 3) after etching, the operation of carrying out centrifugal washing on the obtained product by using deionized water and then carrying out freeze drying can be further carried out, wherein the centrifugal speed can be 11000-14000 rpm; the centrifugation time can be 10-30 min; the freeze drying time can be 24-48 h.
The size range of the obtained Mn/HNCS nano-particles is 50-200 nm.
The manganese-doped hollow carbon spheres (Mn/HNCS nanoparticles) prepared by the method also belong to the protection scope of the invention.
The manganese-doped hollow carbon spheres as antibacterial materials are applied to related fields and also belong to the protection scope of the invention.
The application includes but is not limited to the application of antibacterial drugs, drug carriers or dressings and the like.
The antibacterial drug can be a drug for resisting multi-drug resistant bacterial infection.
The multidrug-resistant bacteria is multidrug-resistant ESKAPE bacteria, including enterococcus faecium (E)Enterococcus faeciumHJP554 strain), Staphylococcus aureus (S. aureus) ((S. aureus)Staphylococcus aureusUSA300-R strain), Klebsiella pneumoniae (Klebsiella pneumoniae)Klebsiella pneumoniaeF726925 Strain), Acinetobacter baumannii: (Acinetobacter baumanniiLAC-4 strain), Pseudomonas aeruginosaPseudomonas aeruginosaF291007 strain), Klebsiella aerogenes (C.aerogenes) (C.EnterobacterKAE3SP strain).
The invention provides a preparation method of a manganese-doped hollow carbon sphere (hereinafter referred to as Mn/HNCS) and researches the application of the manganese-doped hollow carbon sphere in the antibacterial direction. Firstly, SiO is synthesized by the stober method2As a core, and then using synthetic SiO2The regulated alkaline environment promotes the oxidative polymerization of dopamine on the surface, polydopamine has strong adhesion and can be combined with doped manganese metal, thereby preparing SiO2Manganese metal doped dopamine polymer as template. Calcining the mixture in a high-temperature nitrogen environment for a period of time, and then naturally cooling the mixture, wherein in the process, the dopamine polymer is carbonized to form a porous carbon skeleton and is bonded with the doped manganese base to preliminarily form the manganese metal doped carbon spheres. Then, the SiO inside is etched away by strong alkali treatment2The Mn/HNCS nano-particles with stable structure and good appearance are obtained by the template, and the Mn/HNCS nano-particles have good photo-thermal effect and photo-response enhanced enzyme activity effect and can have obvious inhibition effect on multi-drug resistant bacteria.
In the existing synthesis method, the invention has the following advantages: the Mn/HNCS synthesized by the method has good appearance, uniform particles and simple preparation, realizes two processes of synthesizing an internal template and doping metal of an external shell layer by a one-pot method, combines manganese metal and a carbon skeleton, enables the Mn/HNCS to have enzyme activities such as oxidase-like enzyme, peroxidase and the like, and has excellent photo-thermal effect and photo-response enhanced enzyme activity effect due to the interaction of the manganese metal and the carbon skeleton, and has wide application prospects in the fields of catalysis, drug-resistant bacteria resistance, tumor inhibition, virus resistance and the like.
Drawings
Fig. 1 is a transmission electron microscope image of a manganese metal-doped dopamine polymer prepared in example 1 of the present invention.
Fig. 2 is a transmission electron microscope image of manganese metal-doped carbon spheres prepared in example 1 of the present invention.
FIG. 3 is a transmission electron micrograph of Mn/HNCS prepared in example 1 of the present invention.
FIG. 4 is a transmission electron micrograph of Mn/HNCS prepared in example 2 of the present invention.
FIG. 5 is a transmission electron micrograph of Mn/HNCS prepared in example 3.
FIG. 6 is a transmission electron micrograph of Mn/HNCS prepared in example 4.
FIG. 7 is a transmission electron micrograph of Mn/HNCS prepared in example 5.
FIG. 8 is a transmission electron micrograph of Mn/HNCS prepared in example 6.
FIG. 9 is a transmission electron micrograph of Mn/HNCS prepared in example 11.
FIG. 10 shows the results of the photothermal properties test of Mn/HNCS prepared in example 1.
FIG. 11 shows the results of the enzyme activity test of Mn/HNCS photo-enhanced oxidate.
FIG. 12a is a graph showing the effect of Mn/HNCS against Staphylococcus aureus, and FIG. 12b is a graph showing the effect of Mn/HNCS against enterococcus faecium.
FIG. 13a is a graph showing the effect of Mn/HNCS against Pseudomonas aeruginosa, and FIG. 13b is a graph showing the effect of Mn/HNCS against Klebsiella pneumoniae.
FIG. 14a is a graph showing the effect of Mn/HNCS against Klebsiella aerogenes, and FIG. 14b is a graph showing the effect of Mn/HNCS against Acinetobacter baumannii.
Detailed Description
The present invention is described in further detail below with reference to specific embodiments, which are given for the purpose of illustration only and are not intended to limit the scope of the invention. The examples provided below serve as a guide for further modifications by a person skilled in the art and do not constitute a limitation of the invention in any way.
The experimental procedures in the following examples, unless otherwise indicated, are conventional and are carried out according to the techniques or conditions described in the literature in the field or according to the instructions of the products. Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1
Mixing 60 mL of ethanol with 20 mL of ultrapure water, performing ultrasonic dispersion uniformly, placing the mixture on a magnetic stirrer, stirring the mixture at a speed of 350 rpm, adding 2 mL of ammonia water, maintaining the stirring speed of 350 rpm, placing the mixture at 30 ℃, stirring the mixture for 10 min, adding 2.4 mL of tetraethyl silicate by a peristaltic pump at a speed of 0.16 mL/min, after the mixture is completely added, continuing to maintain the stirring speed of 350 rpm, reacting for 45min, rapidly adding 4 mL of dopamine hydrochloride solution with the concentration of 100 mg/mL, reacting for 2h, adding 80 mg of manganese acetylacetonate, continuing to stir and react for 22h, performing centrifugal washing on the product twice by deionized water and absolute ethyl alcohol, placing the product in a vacuum drying oven at 60 ℃ and drying the product for 12h to obtain a solid product (manganese-doped dopamine polymer). And grinding the obtained solid, paving the ground solid in a sample groove, then placing the sample groove in a tubular furnace, raising the temperature to 900 ℃ at the heating rate of 3 ℃/min, carrying out heat preservation and calcination for 2h, and naturally cooling to obtain the manganese-doped carbon spheres. And dispersing the obtained carbonized product into 100 mL of deionized water with the assistance of ultrasonic waves, stirring the product on a magnetic stirrer at the speed of 250 r/min, slowly adding 16 g of NaOH solid, maintaining the stirring speed of 250 rpm, etching the product at 75 ℃ for 12 hours, centrifugally washing the product for three times by using the deionized water, and freeze-drying the product to obtain the Mn/HNCS finished product.
Fig. 1 is a transmission electron micrograph of a prepared manganese-doped dopamine polymer.
Fig. 2 is a transmission electron micrograph of the prepared manganese-doped carbon spheres.
FIG. 3 is a transmission electron micrograph of the prepared Mn/HNCS.
Example 2
Mixing 60 mL of ethanol and 20 mL of ultrapure water, performing ultrasonic dispersion uniformly, placing the mixture on a magnetic stirrer, stirring the mixture at a speed of 350 rpm, adding 2 mL of ammonia water, maintaining the stirring speed of 350 rpm, placing the mixture at 30 ℃, stirring the mixture for 10 min, adding 2.4 mL of tetraethyl silicate by a peristaltic pump at a speed of 0.16 mL/min, after the mixture is completely added, continuing to maintain the stirring speed of 350 rpm, reacting for 45min, rapidly adding 5mL of dopamine hydrochloride solution with the concentration of 100 mg/mL, reacting for 2h, adding 80 mg of manganese acetylacetonate, continuing to stir and react for 22h, performing centrifugal washing twice on the product by deionized water and absolute ethyl alcohol, placing the product in a vacuum drying oven at 60 ℃ and drying the product for 12h to obtain a solid product. And grinding the obtained solid, paving the ground solid in a sample groove, then placing the sample groove in a tubular furnace, raising the temperature to 900 ℃ at the heating rate of 3 ℃/min, carrying out heat preservation and calcination for 2h, and naturally cooling to obtain the manganese-doped carbon spheres. And dispersing the obtained carbonized product into 100 mL of deionized water with the assistance of ultrasonic waves, stirring the product on a magnetic stirrer at the speed of 250 r/min, slowly adding 16 g of NaOH solid, maintaining the stirring speed of 250 rpm, etching the product at 75 ℃ for 12 hours, centrifugally washing the product for three times by using the deionized water, and freeze-drying the product to obtain the Mn/HNCS finished product.
FIG. 4 is a transmission electron micrograph of Mn/HNCS prepared from 5mL of dopamine hydrochloride solution with concentration of 100 mg/mL, and it can be seen that the outer shell layer is locally thicker, and the Mn/HNCS prepared in example 1 has a thinner shell layer (shown in FIG. 3).
Therefore, the shell thickness of Mn/HNCS is influenced by different addition amounts of dopamine hydrochloride.
Example 3
Mixing 60 mL of ethanol with 20 mL of ultrapure water, performing ultrasonic dispersion uniformly, placing the mixture on a magnetic stirrer, stirring the mixture at a speed of 350 rpm, adding 2.5 mL of ammonia water, maintaining the stirring speed of 350 rpm, placing the mixture at 30 ℃, stirring the mixture for 10 min, adding 2.4 mL of tetraethyl silicate by using a peristaltic pump at a speed of 0.16 mL/min, after the mixture is completely added, continuously maintaining the stirring speed of 350 rpm, reacting for 45min, rapidly adding 4 mL of dopamine hydrochloride solution with the concentration of 100 mg/mL, reacting for 2h, adding 80 mg of manganese acetylacetonate, continuously stirring and reacting for 22h, performing centrifugal washing twice on the product by deionized water and absolute ethyl alcohol, placing the product in a vacuum drying oven at 60 ℃, and drying for 12h to obtain a solid product. And grinding the obtained solid, paving the ground solid in a sample groove, then placing the sample groove in a tubular furnace, raising the temperature to 900 ℃ at the heating rate of 3 ℃/min, carrying out heat preservation and calcination for 2h, and naturally cooling to obtain the manganese-doped carbon spheres. And dispersing the obtained carbonized product into 100 mL of deionized water with the assistance of ultrasonic waves, stirring the product on a magnetic stirrer at the speed of 250 r/min, slowly adding 16 g of NaOH solid, maintaining the stirring speed of 250 rpm, etching the product at 75 ℃ for 12 hours, centrifugally washing the product for three times by using the deionized water, and freeze-drying the product to obtain the Mn/HNCS finished product.
FIG. 5 shows the particle size of about 150 nm obtained by using 2.5 mL of aqueous ammonia under the same conditions, and the particle size of Mn/HNCS obtained in example 1 was about 100 nm.
It can be seen that the difference in the volume of the added ammonia water affects the particle size of the finally formed Mn/HNCS.
Example 4
Mixing 60 mL of ethanol with 20 mL of ultrapure water, performing ultrasonic dispersion uniformly, placing the mixture on a magnetic stirrer, stirring the mixture at a speed of 350 rpm, adding 2.5 mL of ammonia water, maintaining the stirring speed of 350 rpm, placing the mixture at 30 ℃, stirring the mixture for 10 min, adding 2.4 mL of tetraethyl silicate by using a peristaltic pump at a speed of 0.16 mL/min, after the mixture is completely added, continuously maintaining the stirring speed of 350 rpm, reacting for 45min, rapidly adding 4 mL of dopamine hydrochloride solution with the concentration of 100 mg/mL, reacting for 1h, adding 80 mg of manganese acetylacetonate, continuously stirring and reacting for 22h, performing centrifugal washing twice on the product by deionized water and absolute ethyl alcohol, placing the product in a vacuum drying oven at 60 ℃, and drying for 12h to obtain a solid product. And grinding the obtained solid, paving the ground solid in a sample groove, then placing the sample groove in a tubular furnace, raising the temperature to 900 ℃ at the heating rate of 3 ℃/min, carrying out heat preservation and calcination for 2h, and naturally cooling to obtain the manganese-doped carbon spheres. And dispersing the obtained carbonized product into 100 mL of deionized water with the assistance of ultrasonic waves, stirring the product on a magnetic stirrer at the speed of 250 r/min, slowly adding 16 g of NaOH solid, maintaining the stirring speed of 250 rpm, etching the product at 75 ℃ for 12 hours, centrifugally washing the product for three times by using the deionized water, and freeze-drying the product to obtain the Mn/HNCS finished product.
Fig. 6 shows that the reaction time is 1 hour after the dopamine hydrochloride solution is reacted, and it can be seen that some manganese-based doped carbon spheres even do not maintain a complete spherical structure, and the distribution of the whole shell layer of the carbon spheres is not uniform, and fig. 5 shows that the dopamine hydrochloride is reacted for 2 hours under the same conditions in example 3, and a complete shell layer is formed.
Therefore, the reaction time is shortened after the dopamine hydrochloride solution is added, the stability of the core-shell structure of the Mn/HNCS is reduced, and the shell layer may be incomplete.
Example 5
Mixing 60 mL of ethanol with 20 mL of ultrapure water, performing ultrasonic dispersion uniformly, placing the mixture on a magnetic stirrer, stirring the mixture at a speed of 400 rpm, adding 2.5 mL of ammonia water, maintaining the stirring speed of 400 rpm, placing the mixture at 30 ℃, stirring the mixture for 10 min, adding 2.4 mL of tetraethyl silicate by using a peristaltic pump at a speed of 0.16 mL/min, after the mixture is completely added, continuously maintaining the stirring speed of 400 rpm, reacting for 45min, rapidly adding 4 mL of dopamine hydrochloride solution with the concentration of 100 mg/mL, reacting for 2h, adding 80 mg of manganese acetylacetonate, continuously stirring and reacting for 22h, performing centrifugal washing twice on the product by deionized water and absolute ethyl alcohol, placing the product in a vacuum drying oven at 60 ℃, and drying for 12h to obtain a solid product. And grinding the obtained solid, paving the ground solid in a sample groove, then placing the sample groove in a tubular furnace, raising the temperature to 900 ℃ at the heating rate of 3 ℃/min, carrying out heat preservation and calcination for 2h, and naturally cooling to obtain the manganese-doped carbon spheres. And dispersing the obtained carbonized product into 100 mL of deionized water with the assistance of ultrasonic waves, stirring the product on a magnetic stirrer at the speed of 250 r/min, slowly adding 16 g of NaOH solid, maintaining the stirring speed of 250 rpm, etching the product at 75 ℃ for 12 hours, centrifugally washing the product for three times by using the deionized water, and freeze-drying the product to obtain the Mn/HNCS finished product.
FIG. 7 shows that the Mn-doped carbon spheres prepared at 400 rpm have significant size difference, and FIG. 5 shows that the Mn-doped carbon spheres prepared at 350 rpm in the same conditions as in example 3 have more uniform size.
Therefore, the different stirring speeds can influence the uniformity of Mn/HNCS.
Example 6
Mixing 60 mL of ethanol and 20 mL of ultrapure water, performing ultrasonic dispersion uniformly, placing the mixture on a magnetic stirrer, stirring the mixture at a speed of 350 rpm, adding 2.5 mL of ammonia water, maintaining the stirring speed of 350 rpm, placing the mixture at 30 ℃, stirring the mixture for 10 min, adding 2.4 mL of tetraethyl silicate by using a peristaltic pump at a speed of 0.16 mL/min, after the mixture is completely added, continuously maintaining the stirring speed of 350 rpm, reacting the mixture for 20min, rapidly adding 4 mL of dopamine hydrochloride solution with the concentration of 100 mg/mL, reacting the mixture for 2h, then adding 80 mg of manganese acetylacetonate, continuously stirring the mixture for reacting the mixture for 22h, performing centrifugal washing on the product twice by deionized water and absolute ethyl alcohol sequentially, and placing the product in a vacuum drying oven at 60 ℃ for drying the product for 12h to obtain a solid product. And grinding the obtained solid, paving the ground solid in a sample groove, then placing the sample groove in a tubular furnace, raising the temperature to 900 ℃ at the heating rate of 3 ℃/min, carrying out heat preservation and calcination for 2h, and naturally cooling to obtain the manganese-doped carbon spheres. And dispersing the obtained carbonized product into 100 mL of deionized water with the assistance of ultrasonic waves, stirring the product on a magnetic stirrer at the speed of 250 r/min, slowly adding 16 g of NaOH solid, maintaining the stirring speed of 250 rpm, etching the product at 75 ℃ for 12 hours, centrifugally washing the product for three times by using the deionized water, and freeze-drying the product to obtain the Mn/HNCS finished product.
FIG. 8 shows that the manganese-doped carbon spheres prepared by the reaction for 20min have different sizes, and FIG. 5 shows that the manganese-doped carbon spheres prepared by the reaction for 45min under the same conditions in example 3 have more uniform sizes.
The difference in reaction time after the addition of tetraethyl silicate affects the degree of particle size uniformity of the finally formed Mn/HNCS.
Example 7
Mixing 60 mL of ethanol with 20 mL of ultrapure water, performing ultrasonic dispersion uniformly, placing the mixture on a magnetic stirrer, stirring the mixture at a speed of 350 rpm, adding 2.5 mL of ammonia water, maintaining the stirring speed of 350 rpm, placing the mixture at 30 ℃, stirring the mixture for 10 min, adding 2.4 mL of tetraethyl silicate by using a peristaltic pump at a speed of 0.16 mL/min, after the mixture is completely added, continuously maintaining the stirring speed of 350 rpm, reacting for 45min, rapidly adding 4 mL of dopamine hydrochloride solution with the concentration of 100 mg/mL, reacting for 2h, adding 60 mg of manganese acetylacetonate, continuously stirring and reacting for 22h, performing centrifugal washing twice on the product by deionized water and absolute ethyl alcohol, placing the product in a vacuum drying oven at 60 ℃, and drying for 12h to obtain a solid product. And grinding the obtained solid, paving the ground solid in a sample groove, then placing the sample groove in a tubular furnace, raising the temperature to 900 ℃ at the heating rate of 3 ℃/min, carrying out heat preservation and calcination for 2h, and naturally cooling to obtain the manganese-doped carbon spheres. And dispersing the obtained carbonized product into 100 mL of deionized water with the assistance of ultrasonic waves, stirring the product on a magnetic stirrer at the speed of 250 r/min, slowly adding 16 g of NaOH solid, maintaining the stirring speed of 250 rpm, etching the product at 75 ℃ for 12 hours, centrifugally washing the product for three times by using the deionized water, and freeze-drying the product to obtain the Mn/HNCS finished product.
Example 8
Mixing 60 mL of ethanol and 20 mL of ultrapure water, performing ultrasonic dispersion uniformly, placing the mixture on a magnetic stirrer, stirring the mixture at a speed of 350 rpm, adding 2 mL of ammonia water, maintaining the stirring speed of 350 rpm, placing the mixture at 30 ℃, stirring the mixture for 10 min, adding 2.4 mL of tetraethyl silicate by a peristaltic pump at a speed of 0.16 mL/min, after the mixture is completely added, continuing to maintain the stirring speed of 350 rpm, reacting for 45min, rapidly adding 4 mL of dopamine hydrochloride solution with the concentration of 100 mg/mL, reacting for 2h, adding 30 mg of manganese acetylacetonate, continuing to stir and react for 22h, performing centrifugal washing on the product twice by deionized water and absolute ethyl alcohol sequentially, and placing the product in a vacuum drying oven at 60 ℃ for drying for 12h to obtain a solid product. And grinding the obtained solid, paving the ground solid in a sample groove, then placing the sample groove in a tubular furnace, raising the temperature to 900 ℃ at the heating rate of 3 ℃/min, carrying out heat preservation and calcination for 2h, and naturally cooling to obtain the manganese-doped carbon spheres. And dispersing the obtained carbonized product into 100 mL of deionized water with the assistance of ultrasonic waves, stirring the product on a magnetic stirrer at the speed of 250 r/min, slowly adding 16 g of NaOH solid, maintaining the stirring speed of 250 rpm, etching the product at 75 ℃ for 12 hours, centrifugally washing the product for three times by using the deionized water, and freeze-drying the product to obtain the Mn/HNCS finished product.
Example 9
Mixing 60 mL of ethanol and 20 mL of ultrapure water, performing ultrasonic dispersion uniformly, placing the mixture on a magnetic stirrer, stirring the mixture at a speed of 350 rpm, adding 2 mL of ammonia water, maintaining the stirring speed of 350 rpm, placing the mixture at 30 ℃, stirring the mixture for 10 min, adding 2.4 mL of tetraethyl silicate by a peristaltic pump at a speed of 0.16 mL/min, after the mixture is completely added, continuing to maintain the stirring speed of 350 rpm, reacting for 45min, rapidly adding 4 mL of dopamine hydrochloride solution with the concentration of 100 mg/mL, reacting for 2h, adding 30 mg of manganese chloride, continuing to stir and react for 22h, performing centrifugal washing on the product twice by deionized water and absolute ethyl alcohol, placing the product in a vacuum drying oven at 60 ℃ and drying the product for 12h to obtain a solid product. And grinding the obtained solid, paving the ground solid in a sample groove, then placing the sample groove in a tubular furnace, raising the temperature to 900 ℃ at the heating rate of 3 ℃/min, carrying out heat preservation and calcination for 2h, and naturally cooling to obtain the manganese-doped carbon spheres. And dispersing the obtained carbonized product into 100 mL of deionized water with the assistance of ultrasonic waves, stirring the product on a magnetic stirrer at the speed of 250 r/min, slowly adding 16 g of NaOH solid, then etching the product at 75 ℃ at the stirring speed of 250 rpm for 12h, centrifugally washing the product for three times by using the deionized water, and freeze-drying the product to obtain the Mn/HNCS finished product.
Example 10
Mixing 60 mL of ethanol and 20 mL of ultrapure water, performing ultrasonic dispersion uniformly, placing the mixture on a magnetic stirrer, stirring the mixture at a speed of 350 rpm, adding 2 mL of ammonia water, maintaining the stirring speed of 350 rpm, placing the mixture at 30 ℃, stirring the mixture for 10 min, adding 2.4 mL of tetraethyl silicate by using a peristaltic pump at a speed of 0.16 mL/min, after the mixture is completely added, continuing to maintain the stirring speed of 350 rpm, reacting for 45min, rapidly adding 4 mL of dopamine hydrochloride solution with the concentration of 100 mg/mL, reacting for 2h, adding 30 mg of manganese sulfate, continuing to stir and react for 22h, centrifugally washing the product twice by using deionized water and absolute ethyl alcohol, placing the product in a vacuum drying oven at 60 ℃ and drying the product for 12h sequentially, and obtaining a solid product. And grinding the obtained solid, paving the ground solid in a sample groove, then placing the sample groove in a tubular furnace, raising the temperature to 900 ℃ at the heating rate of 3 ℃/min, carrying out heat preservation and calcination for 2h, and naturally cooling to obtain the manganese-doped carbon spheres. And dispersing the obtained carbonized product into 100 mL of deionized water with the assistance of ultrasonic waves, stirring the product on a magnetic stirrer at the speed of 250 r/min, slowly adding 16 g of NaOH solid, then etching the product at 75 ℃ at the stirring speed of 250 rpm for 12h, centrifugally washing the product for three times by using the deionized water, and freeze-drying the product to obtain the Mn/HNCS finished product.
Examples 1, 7 and 8 show that the manganese doping amount of the finally synthesized manganese-based doped carbon spheres is influenced by the change of manganese salt feeding, and examples 8, 9 and 10 show that the manganese doping amount of the finally synthesized manganese-based doped carbon spheres is also influenced by the change of the manganese salt type, and the manganese doping amount is shown in table 1.
TABLE 1
Example 11
Mixing 60 mL of ethanol and 20 mL of ultrapure water, performing ultrasonic dispersion uniformly, placing the mixture on a magnetic stirrer, stirring the mixture at a speed of 350 rpm, adding 2 mL of ammonia water, maintaining the stirring speed of 350 rpm, placing the mixture at 30 ℃, stirring the mixture for 10 min, adding 2.4 mL of tetraethyl silicate by a peristaltic pump at a speed of 0.16 mL/min, after the mixture is completely added, continuing to maintain the stirring speed of 350 rpm, reacting for 45min, rapidly adding 4 mL of dopamine hydrochloride solution with the concentration of 100 mg/mL, reacting for 2h, adding 80 mg of manganese acetylacetonate, continuing to stir and react for 12h, performing centrifugal washing on the product twice by deionized water and absolute ethyl alcohol sequentially, and placing the product in a vacuum drying oven at 60 ℃ for drying for 12h to obtain a solid product. And grinding the obtained solid, paving the ground solid in a sample groove, then placing the sample groove in a tubular furnace, raising the temperature to 900 ℃ at the heating rate of 3 ℃/min, carrying out heat preservation and calcination for 2h, and naturally cooling to obtain the manganese-doped carbon spheres. And dispersing the obtained carbonized product into 100 mL of deionized water with the assistance of ultrasonic waves, stirring the product on a magnetic stirrer at the speed of 250 r/min, slowly adding 16 g of NaOH solid, maintaining the stirring speed of 250 rpm, etching the product at 75 ℃ for 12 hours, centrifugally washing the product for three times by using the deionized water, and freeze-drying the product to obtain the Mn/HNCS finished product.
Fig. 9 shows that the manganese acetylacetonate is added and stirred for 12 hours to prepare the manganese doped carbon sphere, the shell layer of the prepared manganese doped carbon sphere is incomplete and damaged, and fig. 3 shows that the manganese acetylacetonate is added and stirred for 22 hours under the same conditions as in example 1 to prepare the manganese doped carbon sphere, and the shell layer is more complete.
Therefore, the stability of the final shell layer is influenced by the difference of stirring time after adding the manganese acetylacetonate, and the shell layer may be incomplete due to too short stirring time.
Example 12
The morphology of the manganese-doped carbon spheres is determined by a Japanese Electron JEM-1011 field emission Transmission Electron Microscope (TEM). The specific morphology of the nano-particle Mn/HNCS and the intermediate product thereof is shown in the attached figures 1, 2 and 3.
Example 13
Measurement of photothermal Properties
Various concentrations (0, 25, 50, 100, 200. mu.g mL) were recorded with a PT-3S heat detector-1) In an aqueous solution (1.5 mL) of Mn/HNCS (prepared in example 1) under near-infrared (NIR) laser irradiation (808 nm, 1.5W cm)−2) The photo-thermal performance.
FIG. 10 shows the results of the photothermal properties test of Mn/HNCS prepared in example 1.
As can be seen from fig. 10: the Mn/HNCS has excellent photo-thermal performance.
Example 14
Photo-enhanced oxidase activity assay
Detection of O Using 5, 5-dimethyl-1-pyrroline-N-oxide (DMPO)2 ·-. 20 μ L of DMPO was mixed with 100 μ L of Mn/HNCSs (100 μ g mL)−1) (prepared in example 1) were mixed. The mixed solution was transferred to a quartz capillary for detection. 100. mu.g mL−1 Similar methods were also used for HNCSs (carbon spheres prepared under the same conditions without manganese metal doping). For all near infrared illumination groups, a 808nm laser (1.5W cm) was used before detection−21 min) the mixture was irradiated.
FIG. 11 shows the results of the Mn/HNCS photo-enhanced oxidase activity test.
As can be seen from fig. 11: Mn/HNCS can produce O2 ·-And under laser irradiation, O is generated2 ·-Increased activity of photo-enhanced enzyme.
Example 15
Measurement of antibacterial inhibitory Effect
Clinically isolated and preserved multi-drug resistant ESKAPE bacteria (enterococcus faecium HJP554, Staphylococcus aureus USA300-R, Klebsiella pneumoniae F726925, Acinetobacter baumannii LAC-4, Pseudomonas aeruginosa F291007 and Klebsiella aerogenes KAE3 SP) are taken as experimental bacteria, and the inhibition result of Mn/HNCS on 6 multi-drug resistant bacteria is detected through incubation with the material. Light control conditions 808nm and 1.5W cm−2Irradiation time 5 min.
The operation is as follows:
the bacterial culture method comprises the following steps: respectively sucking 20 mu L of frozen stock solution of clinically separated multidrug-resistant ESKAPE bacteria (enterococcus faecium HJP554, Staphylococcus aureus USA300-R, Klebsiella pneumoniae F726925, Acinetobacter baumannii LAC-4, Pseudomonas aeruginosa F291007 and Klebsiella aerogenes KAE3 SP), inoculating into 1 mL of BHI liquid culture medium, placing in a shaker at 37 ℃, culturing overnight at 200 rpm, and taking the third generation bacteria for evaluating the antibacterial effect of Mn/HNCS. The Mn/HNCS nano material prepared in the method example 1 is weighed, 2 mg of the material is weighed and added into an EP tube, the EP tube is irradiated by ultraviolet for 30 min for sterilization, 2 mL of sterile deionized water is added, the sterile deionized water is sealed and placed into an ultrasonic instrument for ultrasonic treatment for 15 min for dispersion, and the concentration of the material is 1 mg/mL (mother solution). Then adding 100 mu L of material into a 1 mL system, wherein the working concentration of the material is 100 mu g mL−1The system bacteria concentration is 106 CFU mL-1。
The method for measuring the antibacterial performance comprises the following steps: 1 mg/mL mother liquor of 100 muL Mn/HNCS nano material (prepared in example 1) and 100 muL bacteria liquid (10) are respectively prepared7 CFUmL-1) And 800 mu LPBS solution are mixed in a 1.5mL centrifuge tube and incubated for 2 h. After the incubation was completed, the sample was subjected to laser treatment for 5min (808 nm, 1.5W/cm)2). Diluting the treated bacterial liquid by 10 times (preparing 3 1.5mL Ep tubes, adding 900 muL PBS and then 100 muL sample liquid, and diluting by the method)6 CFU mL-1Then diluted three times respectively, the bacterial quantity is 10 respectively5、104、103CFU mL-1) From 10 after dilution4CFU mL-1And respectively sucking 100 mu L of solution to coat the plates. The plates were incubated in a 37 ℃ incubator for 24h, photographed and counted. As shown in FIG. 12aMn/HNCS anti-Staphylococcus aureus effect diagram, FIG. 12b Mn/HNCS anti-enterococcus faecium effect diagram, FIG. 13a Mn/HNCS anti-Pseudomonas aeruginosa effect diagram, FIG. 13b Mn/HNCS anti-Klebsiella pneumoniae effect diagram, FIG. 14a Mn/HNCS anti-Klebsiella aerogenes effect diagram, and FIG. 14b Mn/HNCS anti-Acinetobacter baumannii effect diagram, the Mn/HNCS nanomaterial prepared in example 1 has an inhibitory effect on multidrug-resistant ESCAPE bacteria, and the inhibitory rate is up to 99% or more. Similar results were obtained by conducting antibacterial tests on the materials prepared in the other examples.
The present invention has been described in detail above. It will be apparent to those skilled in the art that the invention can be practiced in a wide range of equivalent parameters, concentrations, and conditions without departing from the spirit and scope of the invention and without undue experimentation. While the invention has been described with reference to specific embodiments, it will be appreciated that the invention can be further modified. In general, this application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains.
Claims (10)
1. A preparation method of a manganese-doped hollow carbon sphere with light response performance is characterized by comprising the following steps: firstly, SiO is synthesized by the stober method2As a core, dopamine and manganese salt are added in sequence, wherein the dopamine is in SiO2Surface oxidation polymerization is carried out, and then manganese salt is adsorbed with dopamine framework to obtain SiO2A manganese-doped dopamine polymer as a template; the obtained SiO2Calcining the manganese-doped dopamine polymer serving as the template to form manganese-doped carbon spheres; etching away the inner SiO by a strong alkaline treatment2And (4) obtaining a manganese-doped hollow carbon sphere, namely the Mn/HNCS nano-particle.
2. The method of claim 1, wherein: the preparation method comprises the following steps:
1) preparation of manganese-doped dopamine polymer
Uniformly mixing ethanol and ultrapure water under ultrasonic waves, adding ammonia water, stirring, and adding tetraethyl silicate; after complete reaction, quickly adding a dopamine hydrochloride solution, after the reaction is finished, adding a soluble manganese salt, continuing the reaction, sequentially centrifugally washing by deionized water and absolute ethyl alcohol, and drying in vacuum to obtain a manganese-doped dopamine polymer;
2) preparation of manganese-doped carbon spheres
Calcining the polymer prepared in the step 1), and naturally cooling to obtain manganese-doped carbon spheres;
3) preparation of Mn/HNCS
Dispersing the manganese-doped carbon spheres obtained in the step 2) in alkali liquor, and etching under stirring to obtain manganese-doped hollow carbon spheres, namely Mn/HNCS nano-particles.
3. The method of claim 2, wherein: in the step 1), the feeding volume ratio of ethanol, ultrapure water, ammonia water and tetraethyl silicate is 20-30: 6-10: 0.5-2: 1;
the reaction temperature is 10-40 ℃;
adding ammonia water and stirring for 10-30 min; and adding tetraethyl silicate, reacting for 30-60 min, adding a dopamine hydrochloride solution, reacting for 0.5-12 h, adding a manganese salt, and continuing to react for 12-24 h.
4. A method according to claim 2 or 3, characterized in that: slowly adding tetraethyl silicate by a peristaltic pump in the step 1);
the addition rate of the peristaltic pump is 0.16 mL/min;
the soluble manganese salt is at least one of manganese acetylacetonate, manganese chloride and manganese sulfate, and the feeding mass is 10-150 mg;
the feeding volume and concentration of the dopamine hydrochloride are 3-6 mL and 100 mg/mL;
the centrifugal speed is 8000-11000 rpm; the centrifugation time is 5-15 min.
5. The method of claim 2, wherein: in the step 2), the calcining temperature is 800-1000 ℃; the temperature rising speed is 2-5 ℃/min; the heat preservation time is 2-3 h.
6. The method of claim 2, wherein: in the step 3), the alkali liquor is NaOH solution, and the final molar concentration of NaOH is 3-5M;
stirring is magnetic stirring; the stirring speed is 200-400 rpm;
the etching temperature is 70-90 ℃, and the time is 10-20 h.
7. The method of claim 2, wherein: the size range of the obtained Mn/HNCS nano-particles is 50-200 nm.
8. Manganese-doped hollow carbon spheres prepared according to the method of any one of claims 1 to 7.
9. The manganese-doped hollow carbon spheres prepared by the method of any one of claims 1 to 7 are applied to the antibacterial related field as antibacterial materials.
10. Use according to claim 9, characterized in that: the antibacterial material is applied to the relevant antibacterial field and can be used as an antibacterial drug, a drug carrier or an auxiliary material;
the antibacterial drug is used as a drug for resisting multidrug resistant bacteria infection.
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