CN114027320B - Graphene antibacterial material and preparation method and application thereof - Google Patents

Graphene antibacterial material and preparation method and application thereof Download PDF

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CN114027320B
CN114027320B CN202111610071.XA CN202111610071A CN114027320B CN 114027320 B CN114027320 B CN 114027320B CN 202111610071 A CN202111610071 A CN 202111610071A CN 114027320 B CN114027320 B CN 114027320B
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graphene
oxygen
antibacterial
annealing
time
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CN114027320A (en
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张亚非
周可心
苗泽萌
杨勇
张习武
江垠
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Shanghai Jinduo Yuchen Water Environment Engineering Co ltd
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    • A—HUMAN NECESSITIES
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    • Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

Abstract

The invention discloses a graphene antibacterial material, and a preparation method and application thereof, wherein the method comprises the following steps: and (3) carrying out annealing treatment on the graphene in an oxygen plasma, ultraviolet irradiation or inert gas atmosphere to form oxygen-deficient active sites on the surface of the graphene, and then carrying out annealing treatment in an oxygen-containing atmosphere to form carbon-oxygen bonds on the surface of the graphene so as to obtain the graphene antibacterial material. The preparation method of the graphene antibacterial material is simple, the operability is good, the stability is high, the oxygen regulation and control are carried out on the surface of graphene, the oxygen on the surface of graphene is enriched, the graphene antibacterial material has high antibacterial property and excellent biocompatibility, and the oxygen carbon bond on the surface of the antibacterial material is utilized to damage the bacterial structure, so that the antibacterial effect is caused on bacteria, and the antibacterial rate can reach 95% at most.

Description

Graphene antibacterial material and preparation method and application thereof
Technical Field
The invention relates to a graphene antibacterial material, in particular to a graphene antibacterial material, and a preparation method and application thereof.
Background
The antibacterial material is a novel functional material with the function of killing or inhibiting microorganisms. At present, the classification of antibacterial materials is mainly divided into the following sources: organic, inorganic and natural, wherein, the organic and natural antibacterial agent has short effective period, poor heat resistance and other defects, wherein the abuse of antibiotics leads to strong drug resistance of bacteria to various antibiotics, and the organic/inorganic metal element antibacterial agent has irritation to skin in the process of contacting with human body and has certain potential safety hazard. Therefore, it is urgent to find an antibacterial material that is stable, efficient and easy to prepare.
Carbon materials are used as materials with good biocompatibility, graphene is attracting attention by virtue of special and excellent properties, and graphene is used as a two-dimensional carbon material and is a two-dimensional crystal with thickness of only a single atomic layer, and the main composition of the graphene is sp 2 The hybridized carbon atoms, macroscopic carbon atoms form a hexagonal shape with each other. In terms of physical properties, the single-layer graphene has a thickness of 0.335 and nm, is the thinnest known non-synthetic material, and the negative electron affinity and the potential for surface functionalization of the surface of the flaky graphene provide a structural place and a performance foundation for antibacterial.
The first report on the antibacterial activity of Graphene (G) was published in 2010, where Huang from the national academy of sciences of china was equal to the first report that G and GO were used as antibacterial materials (graph-based antibacterial paper.[ J ]. Acs Nano, 2010,4 (7): 4317-4323), a Graphene-based antibacterial paper was disclosed, indicating that Graphene oxide has an effect of killing escherichia coli. Graphene, a novel effective antibacterial material, has serious cytotoxicity to bacteria, fungi and plant pathogens, and is less resistant. In addition, graphene is tolerant to mammalian cells as compared to other derived materials such as carbon nanotubes. And as synthetic materials, renewable, readily available and cheaper than metals and metal oxides.
At present, regarding the mechanism of graphene antibiosis, there are mainly the following points:
(1) The graphene is contacted with bacteria to generate electrostatic action to generate strong film stress by virtue of the electric charge on the surface of the graphene;
(2) The abundant groups on the surface of the graphene are favorable for combining with biomolecules, and the graphene can be adsorbed on the surface of a cell membrane layer by the action of electrostatic adsorption to wrap bacteria, so that the permeability of the cell membrane layer is changed, the proliferation of the cell membrane layer is inhibited, and the antibacterial effect is achieved;
(3) The sharp edge structure of the graphene is utilized to be in direct contact with bacteria, so that the cell membrane layer structure is mechanically destroyed (nano blade);
(4) The functional groups (especially oxygen-containing functional groups) rich in the surface of the graphene can damage the constituent components (such as peptidoglycan, phospholipid and the like) of a bacterial cell membrane layer, so that the integrity of the cell membrane layer is damaged, the cytoplasm is lost, and the antibacterial effect is achieved.
Generally, the antibacterial rate of GO and its derivatives is higher than that of G and its derivatives, however, the GO preparation process is complicated and high in cost, and has higher toxic effects on the environment and human body than G, and has more effects of inducing the genetic toxicity of bacteria and activating cells and biological signal paths, while G only shows reduced cell viability and no other side effects.
Regarding in vivo persistence or toxicity persistence of G, kun Lu utilization from university of Nanjing 14 After one year of C-labeled G intravenous mice, it was found that only a few layers of G accumulated the liver, while larger size G was degraded by Kupffer cells 14 CO 2 （Kupffer Cells Degrade 14 C-Labeled Few-Layer Graphene to 14 CO 2 in Liver through Erythrophagocytosis[J].ACS Nano, 2020, 15(1)）。
Moreover, it has been reported in the literature that after the graphene-based carbon nanomaterial is degraded in a biological or non-biological manner, the original structure is destroyed, and thus the environmental behavior of the graphene-based carbon nanomaterial is fundamentally changed, and the toxic effect (the environmental degradation of the carbon nanomaterial and the degradation mechanism thereof [ J ]. Chinese science: chemistry, 2019,49 (02): 285-298) is affected, and the biotoxicity of the degraded graphene is reduced, so that the graphene-based carbon nanomaterial is environment-friendly. Therefore, selecting graphene as the main body of the antibacterial is an excellent choice.
At present, most of graphene-based antibacterial materials are composite materials, such as graphene-nano silver composite, yang Dengren, and graphene/silver nanoparticle composite materials are prepared through one-step electrochemical deposition: preparing stable dispersion liquid of graphene oxide and silver salt, and preparing a graphene/silver nanoparticle composite material by a one-step cyclic voltammetry electrodeposition method (one-step preparation and application research of graphene and graphene/silver composite material [ D ]. Hunan university, 2013); the preparation method comprises the steps of preparing Graphite Oxide (GO) by adopting an improved Hummers method, adding a certain amount of polyethyleneimine and silver nitrate (PEI-Ag+) coordination compound, preparing a graphene/silver nanocomposite material by adopting a self-assembly method and reducing sodium borohydride (preparation of the graphene/silver nanocomposite material and antibacterial property research [ J ]. Rare metal materials and engineering, 2015, 44 (01): 169-173), taking graphene as a carrier by adopting a chemical method, wherein the graphene is used as a carrier, and the initial antibacterial effect of the material is better by releasing nano silver ions, but the contact antibacterial effective time of the graphene is shorter due to the limited silver ions loaded by the graphene, so that the problem of poor antibacterial stability and long antibacterial effective time exists, and the preparation cost of the graphene/silver nanocomposite material is higher, the economic ratio is lower, and the wide application and popularization of graphene antibacterial are not facilitated. While graphene oxide is excellent in antibacterial performance, but is low in biocompatibility.
Disclosure of Invention
The invention aims to provide a graphene antibacterial material, a preparation method and application thereof, and solves the problems of complex preparation process and poor antibacterial stability of the graphene antibacterial material in the prior art.
In order to achieve the above object, the present invention provides a preparation method of a graphene antibacterial material, the method comprising: and (3) carrying out annealing treatment on the graphene in an oxygen plasma, ultraviolet irradiation or inert gas atmosphere to form oxygen-deficient active sites on the surface of the graphene, and then carrying out annealing treatment in an oxygen-containing atmosphere to form carbon-oxygen bonds on the surface of the graphene so as to obtain the graphene antibacterial material. Wherein the wavelength of the ultraviolet irradiation is 200-275 nm; the annealing treatment under inert gas atmosphere and the annealing treatment under oxygen-containing atmosphere have the preannealing time of t 1 The annealing time is T, the annealing temperature is T, and the time for recovering to room temperature is T 2 And the annealing temperature and time satisfy the formulas shown in formulas (1) and (2), respectively;
T*t=C （1）
t 1 =t 2 =T/K （2）
in the formula (1), C is a time constant, and the value is 100-3000 ℃ h;
in the formula (2), K is a time constant and has a value of 2-70 ℃/min.
In the oxygen plasma treatment process, the surface of the graphene is bombarded to cause defects, and meanwhile, the oxygen plasma treatment can cause the desorption of combined oxygen with different valence states and types on the surface to form CO,CO 2 Active sites are also provided for subsequent annealing treatment, and a reaction basis is provided for forming graphene with only oxygen-carbon bond bonding on the surface. The ultraviolet irradiation treatment of the invention adopts short wave sterilization ultraviolet rays, the wave band is UVC wave band, the wavelength range is 200-275 nm, when the ultraviolet rays of the wave band are irradiated, oxygen in the irradiation range can be formed into ozone, the formed ozone is stable, when the graphene is treated by the ultraviolet rays, the combined oxygen on the surface is desorbed to form ozone, meanwhile, the oxygen deficiency provides active sites for the subsequent annealing treatment, and a reaction basis is provided for forming the graphene with only oxygen-carbon bonds on the surface.
The annealing treatment provided by the invention is characterized in that the pre-annealing is a heating process, the environmental temperature is provided for the graphene, the reaction basis of the subsequent annealing treatment is provided, the recovery stage is a process of cooling to room temperature, and the final stage of the annealing treatment is provided. With respect to the preanneal time t 1 And recovery time t 2 The pre-annealing and recovery processes are not too short or too long to ensure the stability of the graphene structure, and the too short process is easy to cause the overlarge contact temperature difference between the surface and the inside of the graphene, so that the structure is unstable; too long the effectiveness is low and does not contribute to the actual antimicrobial effect. The time constant K is mainly dependent on the annealing temperature. The graphene has different adsorption and desorption types and contents of surface groups at different temperatures, namely, oxygen-containing groups are formed and desorbed at specific temperatures; meanwhile, annealing treatment is carried out at a certain temperature, a reaction state and a saturation state exist, and different reaction graphenes with time constants C are annealed completely at different temperatures and are corresponding parameters of the saturation state.
Therefore, the method can provide a reaction basis for the subsequent oxygen-containing gas annealing treatment by taking oxygen plasma treatment, ultraviolet irradiation treatment and non-oxygen-containing gas annealing treatment as oxygen desorption means, so as to improve the oxygen content of the surface of the graphene and form the graphene antibacterial material with the oxygen-carbon bond combined surface.
Preferably, the carbon oxygen bond is an o=c bond and/or an o—c bond.
Preferably, the oxygen plasma treatment conditions are: the plasma gas source is O 2 Processing ofThe temperature is 100-300 ℃, and the treatment time is 10-120 min; the conditions of the ultraviolet irradiation treatment are as follows: the wavelength is 200-275 nm, and the irradiation time is 10-100 min.
Preferably, the inert gas is selected from any one or more than two of argon, nitrogen and helium; the oxygen-containing atmosphere is selected from air or oxygen. Air and oxygen are used as oxygen-containing gases, and the oxygen is used as an oxygen source in the annealing treatment to provide reactants for forming oxygen with surface oxygen carbon bonds combined with graphene, and the oxygen-containing gases are of an oxygen adsorption type. Argon, nitrogen and helium are used as non-oxygen-containing gases, and in the annealing treatment, the combined oxygen on the surface of the graphene can be desorbed to form CO and CO 2 Is of the oxygen desorption type.
Preferably, the graphene is selected from graphene prepared by a mechanical exfoliation method, a crystal epitaxy method or a CVD method, reduced graphene oxide obtained by reducing graphene oxide prepared by a Hummer method, or reduced graphene oxide film prepared by a vacuum-assisted filtration method (see Large-area ultrathin films of reduced graphene oxide as a transparent and flexible electronic material [ J ]. Nature nanotechnology, 2008, 3, 270-274), or graphene film prepared by a coating method, LB method (see Highly conducting graphene sheets and Langmuir-Blodgett films [ J ]. Nature nanotechnology, 2008, 3 (9): 538-542), or planar self-assembly method.
Preferably, the graphene antibacterial material is sonicated with a dispersant and/or thickener.
Preferably, the dispersing agent is selected from any one or more than two of SDBS, pyrene butyric acid, brij700, PVP, CTAB, triton-X, tween-80, PSS and PDDA; the thickener is selected from one or more of carboxymethyl cellulose, propylene glycol alginate, methyl cellulose, sodium starch phosphate, sodium carboxymethyl cellulose, sodium alginate, chitosan and sodium polyacrylate. When graphene is in an aqueous solvent, the dispersion is extremely uneven and is easy to sink due to the hydrophobicity of the structure, and the graphene is unfavorable for being fully contacted with bacteria or in an antibacterial test, so that the antibacterial performance of the graphene antibacterial material cannot be exerted, and therefore the dispersibility of the graphene is improved by a dispersing agent.
The invention also aims to provide the graphene antibacterial material obtained by the preparation method.
The invention further aims to provide an application of the graphene antibacterial material in antibacterial aspect.
The graphene antibacterial material and the preparation method and application thereof solve the problems of complex preparation process and poor antibacterial stability of the graphene antibacterial material in the prior art, and have the following advantages:
according to the preparation method of the graphene antibacterial material, the active sites with oxygen deficiency are formed on the surface of the graphene antibacterial material through oxygen plasma, ultraviolet irradiation or annealing treatment under an inert gas atmosphere, then carbon-oxygen bonds are formed on the surface of the graphene through annealing treatment under an oxygen-containing atmosphere, oxygen on the surface of the graphene is enriched, the preparation method is simple, the operability is good, the prepared graphene antibacterial material is high in stability, the surface structure of the prepared graphene antibacterial material is unchanged after being stored for 7 months, the graphene antibacterial material has high antibacterial property and excellent biocompatibility, the surface oxygen-carbon bonds of the antibacterial material are utilized to damage the bacterial structure, so that the inhibition effect is caused on bacteria, and the antibacterial rate on staphylococcus aureus (gram positive bacteria) can reach 95%.
Drawings
Fig. 1 is a preparation flow chart of the graphene antibacterial material of the present invention.
Fig. 2 is an infrared spectrum of the high-efficiency graphene material and untreated graphene of examples 1-4 of the present invention.
Fig. 3 is an X-ray photoelectron spectrum of the high efficiency graphene material of example 4 of the present invention.
FIG. 4 is a plate colony plot of the high efficiency graphene material of example 4 of the present invention.
FIG. 5 shows the results of the antibacterial effective duration of experimental example 1 of the present invention.
FIG. 6 shows the biocompatibility results of experimental example 2 of the present invention.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
A method for preparing a graphene antibacterial material, see fig. 1, the method comprising:
(S1) washing 50 mg graphene (graphene purchased from Shanghai Litsea nano technology Co., ltd.) with deionized water, filtering, drying at 80deg.C for 15 h to remove impurities and pollutants;
(S2) subjecting the graphene material treated in the step (S1) to oxygen plasma, wherein the conditions of the oxygen plasma treatment are as follows: the plasma gas source is O 2 The treatment temperature is 150 ℃ and the treatment time is 30 min;
(S3) annealing the graphene material treated in the step (S2) in an oxygen-containing atmosphere, wherein the treatment conditions are as follows: the annealing is carried out in an air atmosphere, the annealing time is 5 h, the annealing temperature is 200 ℃, the pre-annealing time is 30 min, and the recovery time is 30 min;
and (S4) carrying out ultrasonic treatment on the graphene material treated in the step (S3), wherein the ultrasonic time is 0.5 and h, and thus the graphene antibacterial material is obtained.
Example 2
A method for preparing a graphene antibacterial material, the method comprising:
(S1) washing 50 mg graphene (graphene purchased from Shanghai Litsea nano technology Co., ltd.) with deionized water, filtering, drying at 80deg.C for 15 h to remove impurities and pollutants;
(S2) carrying out ultraviolet irradiation treatment on the graphene material treated in the step (S1), wherein the condition is that the irradiation time is 60 min and the ultraviolet wave band range is 200-275 nm;
(S3) annealing the graphene material treated in the step (S2) in an oxygen-containing atmosphere, wherein the treatment conditions are as follows: the annealing is carried out in an air atmosphere, the annealing time is 5 h, the annealing temperature is 200 ℃, the pre-annealing time is 30 min, and the recovery time is 30 min;
and (S4) carrying out ultrasonic treatment on the graphene material treated in the step (S3) and a dispersing agent PVP (polyvinylpyrrolidone), wherein the ultrasonic time is 0.5 and h, and obtaining the graphene antibacterial material.
Example 3
A method for preparing a graphene antibacterial material, the method comprising:
(S1) washing 50 mg graphene (graphene purchased from Shanghai Litsea nano technology Co., ltd.) with deionized water, filtering, drying at 80deg.C for 15 h to remove impurities and pollutants;
(S2) annealing the graphene material treated in the step (S1) in an inert gas atmosphere, wherein the treatment conditions are as follows: the annealing is carried out in nitrogen atmosphere, the annealing time is 5 h, the annealing temperature is 100 ℃, the pre-annealing time is 30 min, and the recovery time is 30 min;
(S3) annealing the graphene material treated in the step (S2) in an oxygen-containing atmosphere, wherein the treatment conditions are as follows: the annealing is carried out in an air atmosphere, the annealing time is 5 h, the annealing temperature is 200 ℃, the pre-annealing time is 30 min, and the recovery time is 30 min;
and (S4) carrying out ultrasonic treatment on the graphene material treated in the step (S3) and chitosan (thickener), wherein the ultrasonic time is 0.5 and h, and obtaining the graphene antibacterial material.
Example 4
A method for preparing a graphene antibacterial material, the method comprising:
(S1) washing 50 mg graphene (graphene purchased from Shanghai Litsea nano technology Co., ltd.) with deionized water, filtering, drying at 80deg.C for 15 h to remove impurities and pollutants;
(S2) annealing the graphene material treated in the step (S1) in an inert gas atmosphere, wherein the treatment conditions are as follows: the annealing is carried out in nitrogen atmosphere, the annealing time is 5 h, the annealing temperature is 200 ℃, the pre-annealing time is 30 min, and the recovery time is 30 min;
(S3) annealing the graphene material treated in the step (S1) in an oxygen-containing atmosphere, wherein the treatment conditions are as follows: the annealing is carried out in an air atmosphere, the annealing time is 5 h, the annealing temperature is 200 ℃, the pre-annealing time is 30 min, and the recovery time is 30 min;
and (S3) carrying out ultrasonic treatment on the graphene material treated in the step (S2) together with dispersing agent PVP and chitosan (thickening agent), wherein the ultrasonic time is 0.5 and h, and obtaining the graphene antibacterial material.
Characterization of the Material Structure of the examples
1. Infrared spectrum
The results of infrared spectroscopic examination of the high-efficiency antibacterial graphene materials prepared in the above examples 1 to 4 (hereinafter referred to as examples 1 to 4) and graphene (untreated group) without any treatment are shown in fig. 2.
As can be seen from fig. 2, at 3435 cm -1 A strong broad peak is shown as the-OH group. Here-OH is the OH stretching vibration peak (poly association) of the intermolecular hydrogen bond and the absorption vibration peak of the-OH group of the adsorbed water. At the same time 1730 cm -1 Where c=o groups, the peak intensities were increased in sequence from sample 1 to sample 4, whereas the untreated graphene had a very flat peak, indicating a very good c=o bond content. 1180-1250 and 1250 cm -1 The peaks in the range are C-O-C groups where the peak intensities are sequentially increased from sample 1 to sample 4, where the peak intensities of untreated graphene are lower relative to sample 3 and sample 4.
2. X-ray photoelectron spectroscopy
In order to further characterize the graphene antibacterial material with surface oxygen carbon bond regulation prepared by the invention, an X-ray photoelectron spectroscopy test is performed on sample 4 to obtain a C1 s high-resolution spectrogram, and the surface groups of the annealed graphene are characterized as shown in fig. 3.
As can be seen from fig. 3, the surface C element binding group is c=c (sp 2 ) C=O and C-O bonds, which are equivalent to the test result of FTIR, prove that the graphene antibacterial material with surface oxygen-carbon bond combination is effectively prepared。
Experimental example 1 antibacterial experiment
1. Antibacterial effect
The high-efficiency graphene materials prepared in the above examples 1 to 4 (for short, examples 1 to 4) were respectively subjected to a plate colony counting method antibacterial test, and the standard antibacterial test procedure was specifically as follows:
according to the national standard for antibacterial experiments (GB/T21510-2008), bacterial mother liquor in the non-attenuated phase is obtained as staphylococcus aureus (S.aureus), and is placed in a Luria-Bertani (LB) culture medium of 5 mL for activation to obtain bacterial seed liquor.
Four groups of sample materials are placed in 10 mL of LB liquid medium, graphene solutions of samples 1 to 4 with mass concentrations of 1 mg/mL are prepared, and a blank LB liquid medium without any antibacterial material is additionally arranged as a blank control group.
Subsequently, 10. Mu.L of bacterial seed solution was added to the five experimental groups and incubated in a constant temperature shaking table at 37℃for 4 h. And (3) carrying out dilution operation on the solutions of the five groups of experimental groups by utilizing an LB culture medium according to a gradient dilution method, respectively taking 30 mu L of mixed solution to coat on an agar plate after the solutions are diluted to proper multiples (100 times) so as to finish the transfer culture operation of bacteria, and then placing the five groups of coated agar plates in a 37 ℃ environment. After 15-h, the number of colonies on the agar plate was observed to complete the plate count method, and the material was evaluated for antibacterial property.
As shown in FIG. 4, the bacterial colony patterns are counted and calculated, and the antibacterial rates of the obtained bacterial colony patterns can reach 72.5%, 73%, 89.3% and 95% respectively, and the antibacterial rates of sample 1-4 are different due to different treatment processes and parameters and have no correlation with the selection of dispersing agents and thickening agents. The results are consistent with the material characterization results of the samples 1-4, and the sample 4 with the highest C=O and C-O-C bond content shows better antibacterial effect. From the results of the antibacterial test and the surface structure, it can be seen that the c=o and C-O bonds on the surface of the graphene antibacterial material of examples 1 to 4 play a key synergistic effect, and have excellent antibacterial effect on staphylococcus aureus.
2. Duration of antibacterial effectiveness
Antibacterial effective duration test experiments were performed on samples 1-4. 5X 50 mL LB medium was placed in five centrifuge tubes, and 20X mg samples 1-4 were added to the test and no material was added as blank. Then carrying out ultrasonic treatment on the five groups of samples for 20 min; then 50 mu L of staphylococcus aureus in the growing period is added in sequence, and finally the staphylococcus aureus is placed in a shaking table at 37 ℃ for culture. Every 2 h at 0 h,2 h,4 h,6 h,8 h,10 h,12 h time nodes, each set of 1 ml solutions was taken and OD values were monitored at 600 nm using uv-vis spectrophotometry to see bacterial growth exposed to different samples.
For bacteria, which have a specific absorption peak at 600 nm, a relatively large OD value indicates a higher concentration of bacteria, but cannot correspond to a specific number of bacteria, and thus is generally presented as a qualitative analysis by using the change in OD value when observing a change in the number of bacteria (change in growth curve). Thus, the results of the antibacterial effect against Staphylococcus aureus in different examples are shown in FIG. 5.
As can be seen from fig. 5, the antimicrobial rates remained substantially the same across each group over time. Of these, sample 4 exhibited the best antibacterial effect, samples 1-3 were affected by the initial (0-2 h) antibacterial effect, and the antibacterial effect as a whole was slightly inferior to sample 4. The bacterial growth characteristics influence (the growth speed and the number of the bacteria grow rapidly), the growth space and the nutrients of the blank control group in the culture medium in the later period gradually decrease, the growth slows down, and the number of bacteria in an actual scene is less than that obtained by experiments, so that the effective antibacterial duration can be higher and the antibacterial rate can be higher due to the limitation of detection means, the accurate antibacterial rate of the samples 1-4 is determined by the plate colony counting method, and the effective antibacterial duration of the samples 1-4 can reach 12 h in the comprehensive view.
Experimental example 2 biocompatibility
Biocompatibility experiments were performed on samples 1-4. 1mg of each sample 1-4 is added into a centrifuge tube, 1 mL pig sperm biological cells are respectively added and mixed for contact culture 4 h to serve as an experimental group, pig sperm cells without added materials are additionally used as a blank control group, the blank control group is finally placed in a 17 ℃ environment for culture, 10 mL mixed solutions are respectively taken at time nodes of 1 h and 3 h of culture, sperm activity values are obtained by using a computer-aided sperm mass analysis (computer auxiliary spermatozoa analysis, CASA) system instrument, cell activity after contact culture is tested to characterize biocompatibility, and the higher sperm cell activity represents better biocompatibility, and the result is shown in figure 6.
As can be seen from FIG. 6, the activities of examples 1-4 were substantially leveled with the blank, and decreased within a reasonable range. Among them, the biocompatibility of sample 1 is preferable because the oxygen desorption on the surface of sample 1 after oxygen plasma treatment also reduces the influence on the cell wall of sperm cells and other components, while the oxygen enrichment on the surface of sample 4 can affect the structure of sperm cells to some extent, but the activity is reduced by only 7% after culturing 3 h, and the pig sperm cells are very fragile as cells which are extremely easily affected by the environment. Therefore, the compatibility experiment well shows that the graphene antibacterial material prepared by the sample has high antibacterial property and excellent biocompatibility.
Experimental example 3 stability test
After the graphene antibacterial material prepared in the embodiment 4 is stored for 7 months, fourier infrared spectrum test is carried out, and compared with the infrared spectrum immediately after preparation, the graphene antibacterial material has unchanged surface structures, is consistent, and has high stability.
While the present invention has been described in detail through the foregoing description of the preferred embodiment, it should be understood that the foregoing description is not to be considered as limiting the invention. Many modifications and substitutions of the present invention will become apparent to those of ordinary skill in the art upon reading the foregoing. Accordingly, the scope of the invention should be limited only by the attached claims.

Claims (8)

1. The preparation method of the graphene antibacterial material is characterized by comprising the following steps of:
annealing graphene in oxygen plasma, ultraviolet irradiation or inert gas atmosphere to form oxygen-deficient active sites on the surface of the graphene, and annealing in oxygen-containing atmosphere to form carbon-oxygen bonds on the surface of the graphene to obtain a graphene antibacterial material;
wherein the wavelength of the ultraviolet irradiation is 200-275 nm;
the annealing treatment under inert gas atmosphere and the annealing treatment under oxygen-containing atmosphere have the preannealing time of t 1 The annealing time is T, the annealing temperature is T, and the time for recovering to room temperature is T 2 And the annealing temperature and time satisfy the formulas shown in formulas (1) and (2), respectively;
T*t=C （1）
t 1 =t 2 =T/K （2）
in the formula (1), C is a time constant, and the value is 100-3000 ℃ h;
in the formula (2), K is a time constant and has a value of 2-70 ℃/min.
2. The method of claim 1, wherein the carbon-oxygen bond is an o=c bond and/or an O-C bond.
3. The method according to claim 1, wherein the oxygen plasma treatment conditions are: the plasma gas source is O 2 The treatment temperature is 100-300 ℃, and the treatment time is 10-120 min;
the conditions of the ultraviolet irradiation treatment are as follows: the wavelength is 200-275 nm, and the irradiation time is 10-100 min.
4. The production method according to claim 1, wherein the inert gas is selected from any one or two or more of argon, nitrogen and helium; the oxygen-containing atmosphere is selected from air or oxygen.
5. The preparation method according to claim 1, wherein the graphene is selected from graphene prepared by a mechanical exfoliation method, a crystal epitaxy method or a CVD method, reduced graphene oxide obtained by reducing graphene oxide prepared by a Hummer method, reduced graphene oxide film prepared by a vacuum assisted filtration method, or graphene film prepared by a coating method, an LB method or a planar self-assembly method.
6. The method of any one of claims 1-5, wherein the graphene antimicrobial material is sonicated with a dispersant and/or thickener.
7. The method according to claim 6, wherein the dispersant is one or more selected from the group consisting of SDBS, pyrene butyric acid, brij700, PVP, CTAB, triton-X, tween-80, PSS and PDDA; the thickener is selected from one or more of carboxymethyl cellulose, propylene glycol alginate, methyl cellulose, sodium starch phosphate, sodium carboxymethyl cellulose, sodium alginate, chitosan and sodium polyacrylate.
8. Use of the graphene antibacterial material obtained by the preparation method according to any one of claims 1 to 7 in antibacterial aspect.
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