CN114190401B - Method for preparing cerium oxide nanoenzyme based on laser liquid phase irradiation and application - Google Patents
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Abstract
The invention belongs to the technical field of nano-enzyme catalysis and antibiosis, and particularly relates to a method for preparing cerium oxide nano-enzyme based on laser liquid phase irradiation and application thereof. The preparation method comprises the following steps: (1) dispersing silver nanoparticles and cerium oxide nanoparticles in a liquid phase solvent to obtain a colloidal suspension; (2) and irradiating the suspension by using laser beams to weld the silver nanoparticles and the cerium oxide nanoparticles into composite nanoparticles, and centrifugally separating, cleaning and drying to obtain the cerium oxide nanoenzyme. The silver-cerium oxide nano composite material is prepared by loading silver nanoparticles on cerium oxide nanoparticles, so that the visible light response capability of the cerium oxide nanoparticles is improved, the silver nanoparticles are introduced as new active centers, the catalytic activity of the cerium oxide nanoparticles is enhanced, the silver-cerium oxide nano composite material is applied to the antibacterial field, the antibacterial rate is up to more than 80%, and the silver-cerium oxide nano composite material has a strong antibacterial effect.
Description
Technical Field
The invention belongs to the technical field of nano-enzyme catalysis and antibiosis, and particularly relates to a method for preparing cerium oxide nano-enzyme based on laser liquid phase irradiation and application thereof.
Background
In biomedicine, nanoenzyme (nanozyme) is a kind of nano material with enzyme-like function, which not only has the inherent optical, electric and magnetic properties of nano material, but also shows excellent catalytic performance. Compared with the traditional biological enzyme, the biological enzyme has the advantages of easy preparation, low cost, good stability, controllable size and the like, and is widely applied to catalytic antibiosis, immunodetection, photothermal therapy, photodynamic therapy, photocatalytic therapy and other therapies of tumor tissues. The nano enzyme for catalyzing the antibiosis, also called nano enzyme bacteriostat, excites a large amount of active oxygen in the surface environment by illumination, the active oxygen has strong oxidation reduction capability, and can act on the cell membrane, protein, genetic material and the like of bacteria to cause the bacteria to be rapidly apoptotic, thereby achieving the aim of antibiosis. At present, commonly used nano enzyme bacteriostats mainly comprise metal oxides, metal-based compounds, carbon-based nano materials, transition metal sulfides, single-atom catalysts, metal-based organic framework materials and the like, and the covered catalytic types comprise oxidase, peroxidase, superoxide dismutase and the like.
Cerium oxide (CeO) 2 ) As one of rare earth metal oxides, attention has recently been paid to the field of catalytic antibacterial such as biomedicine and environmental microbial decontamination, because of their unique cyclic peroxidase functions. In particular, Ce in cerium oxide 4+ And Ce 3+ The reversible conversion of the silicon dioxide is endowed with abundant oxygen vacancies on the surface, and is beneficial to forming good oxidation-reduction capability. However, the current catalytic antibacterial technology is driven by visible light. If ultraviolet light is used for irradiation, the sterilization effect is realized, meanwhile, the biological tissues and the surrounding environment are seriously damaged, and the practical application is not facilitated, so that the visible light photocatalytic antibacterial agent is accepted by the industry and forms the industry standard (the standard number is T/CBMF 70-2019, the release date is 12/4/2019). However, the energy gap of cerium oxide is between 2.9-3.2eV, and during photocatalysis, the cerium oxide is sensitive to ultraviolet light only and has a weak response to visible light. Therefore, the electron-hole pairs formed under the drive of visible light have higher carrier recombination rate, disadvantageouslyIn Ce 4+ And Ce 3+ The reversible transition continues. In order to improve the visible light photocatalytic antibacterial performance of cerium oxide, the surface of the cerium oxide needs to be modified or decorated, and a material with stronger visible light response capability is loaded.
Currently, the construction of noble metal-semiconductor nanocomposites is considered to be an effective strategy to improve the photocatalytic performance of visible light. On one hand, the noble metal has a wider visible light response range; on the other hand, the metal ions released by the noble metals are beneficial to the breakage of the bacterial cell membrane and the inactivation and denaturation of the protein structure. The invention discloses a method for preparing a nano composite material by laser welding in a liquid phase, which is an earlier application CN106041060B, and particularly discloses a nano suspension preparation step, wherein nano granular raw materials are uniformly dispersed in a liquid medium to form a nano suspension; a laser welding step, namely introducing laser with set wavelength and set power into the nano turbid liquid, and continuously setting time to execute laser welding, wherein the nano turbid liquid is continuously stirred in the laser welding process; and a separation step, namely separating a product subjected to the laser welding step, and drying to obtain the composite nano material. The technical scheme adopts the carbon material coating and the liquid phase additive to prepare the nano material by laser liquid phase irradiation heating, does not relate to the improvement of the visible light response capability of the cerium oxide nano particles, does not relate to the application of the cerium oxide nano particles as nano enzyme in the field of visible light photocatalysis antibiosis, and has a space for further research.
In review, the prior art still lacks of the high-activity cerium oxide nanoenzyme applied to visible light photocatalysis antibiosis.
Disclosure of Invention
Aiming at the defects or the improvement requirements of the prior art, the invention provides a method for preparing cerium oxide nanoenzyme based on laser liquid phase irradiation and application thereof, aiming at preparing a nano composite material with high photocatalytic antibacterial activity by taking silver nanoparticles and cerium oxide nanoparticles as precursor materials, taking the cerium oxide nanoparticles as a carrier and the silver nanoparticles as a load and loading the silver nanoparticles on the cerium oxide nanoparticles on the basis of the prior art.
To achieve the above objects, according to one aspect of the present invention, there is provided a method for preparing cerium oxide nanoenzyme based on laser liquid phase irradiation, comprising the steps of:
(1) dispersing silver nanoparticles and cerium oxide nanoparticles in a liquid phase solvent to obtain a colloidal suspension;
(2) and irradiating the suspension by using laser beams to weld the silver nanoparticles and the cerium oxide nanoparticles into composite nanoparticles, and centrifugally separating, cleaning and drying to obtain the cerium oxide nanoenzyme.
Preferably, the mass ratio of the silver nanoparticles to the cerium oxide nanoparticles (1-2): (1-4).
Preferably, the laser beam irradiation of the suspension in the step (2) oscillates the suspension, and the oscillation is magnetic stirring or ultrasonic oscillation.
According to another aspect of the present invention, there is provided an application of the cerium oxide nanoenzyme prepared by the method for preparing the cerium oxide nanoenzyme as an antibacterial material.
Preferably, the method comprises the following steps:
(S1) adding nanoenzyme to the bacterial suspension;
(S2) irradiating the bacterial suspension with light to excite the cerium oxide nanoenzyme to generate active oxygen, and carrying out a photocatalytic antibacterial experiment.
Preferably, the bacterium is staphylococcus aureus or escherichia coli.
Preferably, the wavelength of the light is greater than 420nm, the irradiation time of the light is 1h or more, and the power of the light is 150W or more.
The invention has the following beneficial effects:
(1) the invention adopts the silver-cerium oxide nano composite material as the nano enzyme, has excellent visible light response capability, is applied to the antibacterial field, has the antibacterial rate of more than 80 percent and has strong antibacterial action.
(2) The silver-cerium oxide nano composite material is prepared by adopting a laser liquid phase irradiation heating mode, long-time preliminary chemical process preparation is not needed, toxic chemical reagents are not needed, the preparation method is simple and environment-friendly, the preparation process is controllable, and large-scale production can be realized.
(3) According to the invention, the silver nanoparticles are loaded on the cerium oxide nanoparticles to prepare the silver-cerium oxide nano composite material, so that the visible light response capability of the cerium oxide nanoparticles is improved, the silver nanoparticles are introduced as new active centers, and the catalytic activity of the cerium oxide nanoparticles is enhanced.
(4) The invention adopts silver nano particles as load, and has lower cost compared with similar noble metals such as palladium, gold, platinum and the like. Has very wide application prospect in the catalytic antibacterial fields of biomedicine, environmental microbial purification and the like.
Drawings
FIG. 1 is a TEM image of the cerium oxide nanoenzyme prepared in example 1.
FIG. 2 is an HAADF map and an EDS energy spectrum of the cerium oxide nanoenzyme prepared in example 1, wherein (a) in FIG. 2 is a distribution HAADF map of a hybridization region; fig. 2 (b) is a full element Mapping diagram corresponding to the HAADF diagram; FIG. 2 (c) is a power spectrum diagram of an arbitrarily selected region Area # 1 in (b); FIG. 2 (d) is a Mapping diagram of oxygen element; FIG. 2 (e) is a diagram of cerium Mapping; fig. 2 (f) is a Mapping diagram of silver element.
FIG. 3 is an XRD pattern of the cerium oxide nanoenzyme prepared in example 1.
FIG. 4 is a graph showing an antibacterial test using example 1 and comparative examples 1 to 6.
FIG. 5 statistical histogram of colony count of application example 1 and comparative examples 1 to 6.
FIG. 6 is a graph of the photocatalytic antibacterial power of application example 1 and comparative examples 1 to 6.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Examples
Example 1: laser liquid phase irradiation preparation of silver-cerium oxide nano composite material
(1) Preparing a precursor material and a liquid phase solvent: commercial silver nanoparticles are provided by Sigma-Aldrich, cerium oxide nanoparticles are provided by the Shanghai Michelin Biochemical technology, Inc., and an ethanol solvent for precursor material dispersion is provided by the national drug group chemical reagent, Inc.
(2) Preparation of colloidal suspension: transferring 20mL of ethanol solvent by using a pipette gun, placing the transferred solvent into a reagent bottle with the capacity of 25mL, respectively weighing 5mg of silver nanoparticles and 5mg of cerium oxide nanoparticles by using an electronic balance, and dispersing the silver nanoparticles and the cerium oxide nanoparticles in the ethanol solvent to form colloidal suspension.
(3) Ultrasonic oscillation: and placing the colloidal suspension in an ultrasonic pan, and ultrasonically oscillating for 30min to uniformly disperse the colloidal suspension.
(4) Laser irradiation: YAG laser is opened to output a laser beam with the diameter of 8mm and the pulse width of 8ns, the repetition frequency is 10Hz, the laser energy is adjusted to 300mJ, colloid suspension is irradiated for 15min in a non-focusing way, and the suspension is subjected to ultrasonic oscillation while being irradiated by the laser so as to prevent the colloid nano particles from gravity sedimentation.
(5) And (3) product separation: transferring the colloidal suspension subjected to laser irradiation into a centrifuge tube, performing centrifugal separation on the colloidal suspension by using a centrifuge, removing supernatant by using a liquid transfer gun after centrifugation, adding deionized water to wash a product, and drying to obtain the cerium oxide nanoenzyme.
Example 2
The difference between this example and example 1 is that the mass of the silver nanoparticles and the mass of the cerium oxide nanoparticles in step (2) are different, specifically, 2mg of silver nanoparticles and 8mg of cerium oxide nanoparticles are respectively weighed by an electronic balance and dispersed in the ethanol solvent to form a colloidal suspension.
Test examples
FIG. 1 is a TEM image of the cerium oxide nanoenzyme prepared in example 1.
As can be seen from fig. 1, after laser liquid phase irradiation, silver nanoparticles are successfully loaded on the surfaces of bulk cerium oxide nanoparticles.
FIG. 2 is an HAADF map and an EDS energy spectrum of the cerium oxide nanoenzyme prepared in example 1, wherein (a) in FIG. 2 is a distribution HAADF map of a hybridization region; fig. 2 (b) is a full element Mapping diagram corresponding to the HAADF diagram; FIG. 2 (c) is a power spectrum diagram of an arbitrarily selected region Area # 1 in (b); FIG. 2 (d) is a Mapping chart of an oxygen element; FIG. 2 (e) is a diagram of cerium Mapping; fig. 2 (f) is a Mapping diagram of silver element.
Wherein (a) the HAADF graph clearly shows the distribution of the hybridized regions; (b) the EDS energy spectrum shows the area distribution of mixed oxygen (O), silver (Ag), and cerium (Ce) elements corresponding to HAADF areas, thereby distinguishing the positions of silver and cerium oxide components in the TEM image of fig. 2; (c) the energy spectrum is the element distribution condition of an Area # 1 Area randomly selected in the (b), and signals of oxygen (O) element, silver (Ag) element and cerium (Ce) element can be observed (particularly, the signal of copper (Cu) element comes from a copper net bearing a test sample), which indicates that the hybrid silver-cerium oxide nano composite material is successfully prepared. (d) The distribution of oxygen (O), cerium (Ce) and silver (Ag) is independent, and the distribution areas of oxygen (O) and cerium (Ce) are consistent and are derived from cerium oxide; the distribution of silver (Ag) element is similar to both.
FIG. 3 is an XRD pattern of the cerium oxide nanoenzyme prepared in example 1.
As can be seen from FIG. 3, for the silver nanoparticles, diffraction peaks corresponding to 2-fold diffraction angles of 38.1 °, 44.3 °, 64.4 °, 77.4 ° and 81.5 ° were observed, and compared with the standard JCPDS data card (PDF: 00-004-0783), it was confirmed that they respectively correspond to (111), (200), (220), (311) and (222) lattice planes of silver; for the cerium oxide nanoparticles, diffraction peaks corresponding to 2-fold diffraction angles of 28.6 °, 33.1 °, 47.6 °, 56.4 °, 59.2 °, 69.5 °, 76.8 °, 79.2 ° and 88.6 ° were observed, confirming that they correspond to (111), (200), (220), (311), (222), (400), (331), (420) and (422) lattice planes of silver, respectively, in comparison with the standard JCPDS data card (PDF: 03-065-; the diffraction peaks of the prepared silver-cerium oxide nano composite material cover the diffraction peaks of the silver nanoparticles and the cerium oxide nanoparticles, which shows that the components of the silver and the cerium oxide are contained in the silver-cerium oxide nano composite material, and further shows that the silver-cerium oxide nano composite material, namely the cerium oxide nanoenzyme, is successfully prepared.
Application examples
The cerium oxide nano enzyme is applied to the antibacterial field, and comprises the following steps:
(S1) adding nanoenzyme to the bacterial suspension;
(S2) irradiating the bacterial suspension with light to excite the cerium oxide nanoenzyme to generate active oxygen, and carrying out a photocatalytic antibacterial experiment.
As a preferred example, the bacterium is Staphylococcus aureus or Escherichia coli.
In a preferred embodiment, the wavelength of the light is greater than 420nm, the irradiation time of the light is 1h or more, and the power of the light is 150W or more.
Application example 1 the cerium oxide nanoenzyme prepared in example 1 is applied to staphylococcus aureus antibacterial, including the following steps:
(1) preparing an LB culture medium: weighing 10mg of nutrient agar by using an electronic balance, placing the nutrient agar into a conical flask, adding 200mL of deionized water, performing ultrasonic dissolution, and adjusting the pH value of the nutrient agar to be between 7.2 and 7.4 by using sodium hydroxide to obtain a solid culture medium; sterilizing at 120 deg.C under 0.1MPa, pouring into flat plate, making into LB plate, and placing in refrigerator. Weighing 0.6g of yeast extract powder, 1.2g of sodium chloride and 1.2g of tryptone by using an electronic balance, placing the yeast extract powder, the sodium chloride and the tryptone in a conical flask, adding 120mL of deionized water, performing ultrasonic dissolution, adjusting the pH value to be between 7.2 and 7.4 by using sodium hydroxide to obtain a liquid culture medium, sterilizing under the same conditions, and placing the liquid culture medium in a refrigerator for later use. All the glass instruments are sterilized in an autoclave for standby.
(2) Preparing a bacterial suspension: taking 0-generation staphylococcus aureus freeze-dried powder as a strain (S.aureus, reference number: CMCC (B)26003), sterilizing an inoculating loop, selecting the staphylococcus aureus freeze-dried powder, drawing three lines on a solid culture medium, culturing for 12-24 h in a constant-temperature biochemical incubator at 37 ℃, selecting a single colony in the three lines by using the inoculating loop burned by an alcohol burner, adding into 10mL of liquid culture medium, and placing in a constant-temperature oscillator at 37 ℃ for oscillating for 12h to obtain a bacterial suspension with an OD value of 2.488.
(3) And (3) diluting the bacterial suspension: placing 5mL of the bacterial suspension in a centrifuge tube, placing in a centrifuge for centrifugation at 6000r/min for 15min, taking out supernatant with a pipette, washing the bacterial suspension with sodium acetate buffer solution with pH of 4.5 for 2 times, wherein the concentration of the bacterial suspension is 10 9 CFU/mL, gradually diluting the bacterial suspension with sodium acetate buffer solution to obtain final bacterial suspension with concentration of 10 5 CFU/mL。
(4) Adding enzyme, illuminating and plating: weighing 0.01mg of nano enzyme bacteriostatic agent into a centrifuge tube by using an electronic balance, and respectively adding 1mL of 10-concentration nano enzyme into the centrifuge tube containing the nano enzyme 5 CFU/mL bacterial suspension, fully shaking to make it mixed uniformly. LED visible light lamp using 150W (wavelength range:. lambda.)>420nm) for 1 hour, then taking 20 mu L of mixed liquor to evenly coat on a solid culture medium of an LB plate, placing the solid culture medium in a constant-temperature biochemical incubator at 37 ℃ for overnight culture for 12 hours, observing the growth condition of colonies, calculating the number of the colonies on the LB plate, and comparing with a blank group under the same condition. In order to facilitate comparison of antibacterial effects, antibacterial experiments without visible light irradiation under the same conditions are carried out together.
Comparative example 1
Blank, namely no nano enzyme bacteriostatic agent.
Comparative example 2
Raw silver, i.e. 0.01mg of silver nanoparticles.
Comparative example 3
Laser silver, i.e., 0.01mg of silver nanoparticles after laser liquid phase irradiation.
Comparative example 4
Original cerium oxide, i.e., 0.01mg of cerium oxide nanoparticles.
Comparative example 5
Laser cerium oxide, i.e. 0.01mg of cerium oxide nanoparticles after laser liquid phase irradiation
Comparative example 6
The original silver-cerium oxide, i.e., 0.005mg silver nanoparticle and 0.005mg cerium oxide nanoparticle mixture.
The conditions of laser liquid phase irradiation of comparative examples 1 to 6 of the present invention were all the same.
The application example 1 and the comparative examples 1 to 6 were subjected to the antibacterial effect test.
FIG. 4 is a graph showing an antibacterial test using example 1 and comparative examples 1 to 6.
FIG. 5 statistical histogram of colony count using example 1 and comparative examples 1-6.
FIG. 6 is a graph of the photocatalytic antibacterial power of application example 1 and comparative examples 1 to 6. The photocatalytic antibacterial rate refers to the percentage of the ratio of the difference between the number of colonies of the nano enzyme bacteriostatic agent under the non-illumination condition and the number of colonies under the illumination condition to the number of colonies under the non-illumination condition.
As can be seen from FIGS. 4 and 5, the silver cerium oxide nanocomposite prepared by heating through laser liquid phase irradiation under the illumination condition exhibited the least number of colonies as the nanoenzyme bacteriostatic agent, about 0.39X 10 7 CFU/mL. As can be seen from FIG. 6, the photocatalytic antibacterial rate of the silver cerium oxide nanocomposite prepared by laser liquid phase irradiation and heating is as high as 82.4%, which is 2.54 times and 2.71 times of that of the silver nanoparticles and cerium oxide nanoparticles under the same conditions, respectively, indicating that the nanoenzyme has excellent antibacterial performance and potential application in the field of catalytic antibacterial.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (4)
1. A method for preparing cerium oxide nanoenzyme based on laser liquid phase irradiation is characterized by comprising the following steps:
(1) dispersing silver nanoparticles and cerium oxide nanoparticles in a liquid phase solvent to obtain a colloidal suspension; the mass ratio of the silver nanoparticles to the cerium oxide nanoparticles is (1-2): (1-4);
(2) irradiating the suspension by using laser beams to weld silver nanoparticles and cerium oxide nanoparticles into composite nanoparticles, and centrifugally separating, cleaning and drying to obtain the cerium oxide nanoenzyme;
the laser beam irradiation is: a532 nm laser beam with a diameter of 8mm, a laser pulse width of 8ns, a repetition frequency of 10Hz and laser energy of 300mJ is adopted to irradiate the colloidal suspension for 15min in a non-focusing manner.
2. The method for preparing cerium oxide nanoenzyme according to claim 1, wherein the suspension is oscillated by irradiating the suspension with laser beam in step (2), and the oscillation is magnetic stirring or ultrasonic oscillation.
3. Use of the cerium oxide nanoenzyme prepared by the method for preparing cerium oxide nanoenzyme according to claim 1 or 2 for preparing an antibacterial material; the cerium oxide nanoenzyme is excited by light irradiation to generate active oxygen, and the active oxygen can destroy the biological structure of bacteria to realize antibiosis; the wavelength of the light is more than 420nm, the irradiation time of the light is more than 1h, and the power of the light is more than 150W.
4. Use according to claim 3, wherein the bacteria are Staphylococcus aureus or Escherichia coli.
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