CN117160455A - P-d orbit hybridization enhanced Fenton-like inorganic nano material and preparation method and application thereof - Google Patents
P-d orbit hybridization enhanced Fenton-like inorganic nano material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a p-d orbit hybridization reinforced Fenton-like inorganic nano material, a preparation method and application thereof. The p-d orbital hybridization enhanced Fenton-like inorganic nanomaterial comprises: silicon nanoplates and copper nanoclusters hybridized with the silicon nanoplate orbitals; preferably, the orbital hybridization is p-d orbital hybridization.
Description
Technical Field
The invention relates to a p-d orbit hybridization reinforced Fenton-like inorganic nano material and a preparation method and application thereof, in particular to a copper nanocluster and silicon nano sheet composite material with light response, uniform structure, high stability, excellent ROS production performance and p-d orbit hybridization structure, a preparation method thereof and application thereof in serving as an efficient and low-toxicity nano antibacterial material for catalytic medicine, and belongs to the technical field of inorganic nano materials.
Background
Reactive oxygen species (Reactive oxygen species, ROS) are oxygen-containing molecules, radicals or ions of ultra-high reactivity, derived from O 2 Or other oxygen-containing molecules. These species are involved in most biological processes and play a central role in regulating various physiological functions of organisms. ROS mainly comprise singlet oxygen 1 O 2 ) Superoxide radical (O) 2 ) Hydrogen peroxide (H) 2 O 2 ) And hydroxyl radicals (. OH). Over the past several decades, chemists and biologists have struggled to find these chemicals and their potential redox chemistries to advance the design of ROS-based therapies.
For this reason, many researchers and scientists design and synthesize various functional nano-drugs with ROS-producing effect, deliver nano-drugs with infection/tumor microenvironment response to a lesion site, and realize the treatment of diseases by producing ROS with bacterial/cytotoxicity at the lesion site through a series of chemical processes such as catalysis/Fenton reaction. Among them, the chemical kinetics therapy (Chemodynamic therapy, CDT) is widely studied as a safe and efficient therapeutic strategy,as in 2007 Yan et al found Fe 3 O 4 The nanoparticle has horseradish peroxidase (HRP) -like activity, and can catalyze H 2 O 2 Is a decomposition of (Nat. Nanotechnol.2007,2, 577-583). Zhang et al synthesized nano-sized amorphous iron for the first time to trigger the Fenton reaction at the tumor site, thereby achieving a highly efficient CDT nanoformulation (Angew.chem.int.ed.2016, 55, 2101-2106). In pursuit of higher atom utilization efficiency, researchers have needed to construct a stable Fenton catalyst with more active sites, and Huo et al constructed a new type of single-atom Fe nanocatalyst for specific tumor CDT (ACS Nano 2019,13,2643-2653) by immobilizing Fe atoms in nitrogen doped amorphous carbon. However, the Fenton effect of the iron-based nanomaterial is limited by the reaction environment, such as a molten iron complex [ Fe (H) 2 O) 6 ] 3+ Insoluble at pH above 5 and Fe with organic degradation intermediate 3+ The complex is very stable, and the efficiency is difficult to be improved due to the problems. In addition, based on the inherent quantum size effect and surface effect of the nano material, the atomic coordination is insufficient and the surface energy is high due to the increase of the number of surface atoms, so that the surface atoms have high activity and are in an extremely unstable state and are easily combined with other atoms, and the nano catalytic material prepared by the conventional process has poor stability. Therefore, how to achieve nanoparticle stability and catalytic performance enhancement is a scientific problem that is urgently needed to be solved.
Various copper-based nanomaterials with Fenton-like properties and small environmental impact are designed by some scholars in the prior art to try to solve the problems of the iron-based nano Fenton agent. As proposed by Cremer et al in 2016 Cu 2+ Catalytic increase of oxidation of lipid membranes (J.Am.chem. Soc.2016,138, 1584-1590), and Chen and its team reported in 2019 for H 2 O 2 Synthesis of copper peroxide nanodots from given chemical kinetic treatment (j.am. Chem. Soc.2019,141, 9937-9945). However, there is no report on enhancing the stability and antibacterial performance of nano-sized copper-based Fenton-like CDT catalysts by a p-d orbital hybridization strategy.
Disclosure of Invention
Therefore, the invention provides a p-d orbit hybridization enhanced Fenton-like inorganic nano material, and a preparation method and application thereof.
In one aspect, the invention provides a p-d orbital hybridization enhanced Fenton-like inorganic nanomaterial comprising: silicon nanoplates and copper nanoclusters hybridized with the silicon nanoplate orbitals; preferably, the orbital hybridization is p-d orbital hybridization. The orbital hybridization realizes charge transfer by influencing electron structure distribution, and enriches active sites, thereby promoting Fenton-like reaction. The invention proves that the orbit hybridization exists between the two aspects, firstly, the electron state density of each energy level of SiCu samples is analyzed through theoretical calculation, and the result shows that the energy of Si- (p) band and the energy of Cu- (d) band are well matched, which is favorable for the strong p-d orbit hybridization interaction between Si and Cu; the Cu- (d) band center of the copper nanocluster after being loaded on the silicon nanosheet moves towards the Fermi level direction, so that the influence of the silicon nanosheet on the electronic structure of the copper nanocluster is further verified; in addition, differential charge analysis showed that the number of electrons transferred from the silicon nanoplatelets to the copper nanoclusters was 0.18. Secondly, the peak position change of Cu characteristic peaks before and after hybridization is revealed experimentally by X-ray photoelectron spectroscopy (XPS), which is consistent with the orbital hybridization result in theoretical analysis.
According to the invention, uniform loading of the silicon nano-sheet to the copper nano-cluster is realized through p-d orbit hybridization, the loading not only solves the problems of instability, poor dispersibility, easy aggregation and the like of the independent copper nano-cluster, but also promotes charge transfer of the silicon nano-sheet to the copper nano-cluster through hybridization between the p orbit of Si element in the carrier silicon nano-sheet and the d orbit of Cu element in the copper nano-cluster, and enhances Fenton-like performance of a composite nano system. In addition, the photo-thermal effect of the silicon nano-sheet can be further synergistically enhanced to realize efficient sterilization and anti-infection.
Preferably, the diameter of the silicon nano-sheet is 200-2000 nm, and the thickness is 2-12 nm.
Preferably, the copper nanoclusters are composed of copper nanoparticles; the particle size of the copper nano particles is 2-10nm.
Preferably, the molar ratio of the silicon nano-sheet to the copper nano-cluster is 8:1 to 1:1, preferably 7:1 to 3:2.
preferably, the morphology of the p-d orbit hybridization enhanced Fenton-like inorganic nano material is single-layer or few-layer nano lamellar morphology.
Preferably, the total particle size of the p-d orbital hybridization enhanced Fenton-like inorganic nanomaterial is 0.2-2 μm, for example 0.5-2 μm.
In another aspect, the invention provides a method for preparing a p-d orbital hybridization enhanced Fenton-like inorganic nanomaterial, comprising the steps of: dispersing single-layer or less-layer silicon nano-sheets and copper nano-clusters in a solvent, and stirring to fully combine the single-layer or less-layer silicon nano-sheets and the copper nano-clusters to obtain the p-d orbit hybridization enhanced Fenton-like inorganic nano-material.
Preferably, the molar ratio of the single-layer or less-layer silicon nano-sheets to the copper nano-clusters is 8:1 to 1:1, preferably 7:1 to 3:2 (corresponding mass ratio is 3:1-2:3); the solvent is at least one of water, ethanol, phosphate buffer solution and physiological saline.
Preferably, the stirring speed is 200-800 rpm, and the stirring time is 0.5-2 hours.
In yet another aspect, the invention provides an application of the p-d orbital hybridization enhanced Fenton-like inorganic nanomaterial in preparation of an antibacterial agent. The nanomaterial system of the invention can respond to H of microenvironment 2 O 2 Meanwhile, hydroxyl free radicals are generated through efficient Fenton-like substances, and in addition, a thermal effect is generated at an infection position by synergistic external field light stimulation, so that the killing effect on bacteria is greatly enhanced.
The beneficial effects are that:
according to the invention, a single-layer/few-layer silicon nano sheet and a copper nano cluster are loaded, so that an antibacterial nano material with p-d orbit hybridization enhancement Fenton-like synergistic photo-thermal effect is obtained;
the invention provides a new electron orbit hybridization concept, which combines the high specific surface area of a two-dimensional nanomaterial with Fenton-like catalysis of a copper nanocluster by using p-d orbit hybridization, and illustrates the relation of p-d hybridization on Fenton-like reaction activity from the angle of electron orbit interaction, and experiments prove that the composite nano system can also generate a photo-thermal effect under exogenous laser irradiation, and efficiently resist infection by a large amount of ROS generated by synergic enhanced Fenton-like effect, which is called as electronic orbit hybridization enhanced nano catalysis anti-infection.
Drawings
FIG. 1 is a flow chart of preparing a nano-antimicrobial agent with enhanced Fenton-like effect according to an embodiment of the present invention;
FIG. 2 is a double spherical aberration correcting transmission electron microscope (AC-TEM) image of calcium silicide in the example;
FIG. 3 is a Transmission Electron Microscope (TEM) image and Atomic Force Microscope (AFM) image of a silicon nanoplate before and after loading copper nanoclusters, where D is before loading and E is a TEM image after loading copper nanoclusters;
fig. 4 is an energy spectrum of a silicon nano-sheet (abbreviated as SiCu) after loading copper nanoclusters in the example. Wherein F is a surface scanning image of element distribution; g is a corresponding energy spectrum element peak bitmap;
FIG. 5 is an X-ray photoelectron Spectroscopy (XPS) of a SiCu complex after copper nanoclusters alone (abbreviated as Cu) and silicon nanoplatelets are bonded;
FIG. 6 is a simulation calculation of the p-d orbital hybridization interactions and Fenton-like processes for SiCu samples. Wherein H is the projected state density (PDOS) of SiCu; i is the density of states (DOS) of surface Cu atoms; j is H 2 O 2 Free energy of dissociation at Cu and si@cu surfaces. K is H on the surface of Si@Cu 2 O 2 Dissociating the optimized atomic structure of the intermediate; l is a differential charge map of two different viewing angles, wherein the isosurface value is set toThe charge accumulation and depletion regions are shown in orange and green, respectively.
FIG. 7 is a graph of Cu and SiCu catalytic H for individual copper nanoclusters 2 O 2 Electron spin resonance (EPR) test results for generating hydroxyl radicals;
FIG. 8 is a test result of the growth state of bacterial colonies after different treatments. Wherein the control group 1, the experimental group 1-2 and the experimental group 1-3 are respectively PBS, an independent silicon nano-sheet, an independent copper nano-cluster and a copper nano-cluster hybridized with the silicon nano-sheet orbit;
FIG. 9 is a thermal imaging of PBS and copper nanoclusters SiCu after orbital hybridization with silicon nanoplatelets after treatment with a near infrared two-zone laser at 1064 nm;
FIG. 10 is a graph of quantitative temperature versus time for a thermogram;
FIG. 11 shows the antimicrobial effect of different materials after laser treatment with 1064nm (NIR-II). Wherein, the control group 2, the experimental group 2-1, the experimental group 2-2 and the experimental group 2-3 are respectively PBS plus NIR-II, independent silicon nano-sheets plus NIR-II, independent copper nano-clusters plus NIR-II and copper nano-clusters plus NIR-II after orbital hybridization with the silicon nano-sheets;
FIG. 12 is a Scanning Electron Microscope (SEM) image of a Staphylococcus aureus biofilm on a titanium plate of an implant after treatment with 1064nm (NIR-II) laser, where H-K is PBS plus NIR-II, silicon nanoplate alone plus NIR-II, copper nanocluster alone plus NIR-II, and copper nanocluster plus NIR-II after orbital hybridization with silicon nanoplate, respectively;
FIG. 13 shows the results of growth status test of treated bacterial colonies and quantitative data thereof, with silicon nanoplatelets and copper nanoclusters having different loading molar ratios. The molar ratio of the silicon nano-sheet to the copper nano-cluster is as follows: (1) 1:1. (2) 3:2. (3) 5:1. (4) 7: 1. (5) 8:1, a step of; and the antibacterial effect evaluation is carried out on the nano materials with the five different loading ratios respectively.
Detailed Description
The invention is further illustrated by the following embodiments, which are to be understood as merely illustrative of the invention and not limiting thereof.
In the present disclosure, the p-d orbital hybridization enhanced Fenton-like synergistic photo-thermal inorganic nanomaterial comprises a single-layer or a few-layer silicon nanosheets serving as a carrier and copper nanoclusters loaded on the surface of the carrier through p-d orbital hybridization. According to the invention, after the silicon nano-sheet is used for carrying out orbital hybridization load on the copper nano-cluster material, the composite nano-particle has excellent Fenton-like catalytic property, and in addition, the composite nano-particle has the effect of photo-thermal treatment under the irradiation of near infrared light. Compared with the pure use of the copper nanoclusters, the composite nanomaterial system shows more excellent Fenton-like effect and antibacterial effect. The inventor also discovers that the Fenton-like chemical kinetics treatment effect is enhanced, and meanwhile, the heat effect can be generated in response to the light stimulus, so that the killing efficiency of staphylococcus aureus is improved, and a good antibacterial and anti-infection effect is realized.
In an alternative embodiment, the nanomaterial as a support may be a two-dimensional nanoplatelet lamellar material system well known in the art, but it should be noted that the support itself must have suitable electronegativity and orbital electron distribution characteristics to satisfy electron charge transfer with the nanoclusters supported thereon. For example, the carrier nanomaterial may be a two-dimensional silicon nanoplatelet.
In an alternative embodiment, the copper nanoclusters may be uniformly supported on the surface of the two-dimensional silicon nanoplatelets, and the composite nanosystem has higher dispersibility and utilization rate than the single nanoclusters themselves are easily aggregated to reduce the catalytic efficiency. Preferably, the attached nanoclusters may be copper nanoclusters, which may have a particle size of 3 to 10nm, and the d-band center of Cu at the surface thereof may be-2.31 eV. Other functions that the carrier has may be the photo-thermal effect.
In an alternative embodiment, in the p-d orbital hybridization enhanced Fenton-like synergistic photothermal antibacterial nanomaterial, the molar ratio between the carrier two-dimensional silicon nanoplatelets and the loaded copper nanoclusters may be 7:1 to 3:2, the optimal molar ratio is 5:1, the remaining ratios such as 6:1,3:1,5:2 may be used. At these molar ratios, the copper nanoclusters can be well and uniformly dispersed on the surface of the silicon nanoplatelets, thereby achieving an enhanced Fenton-like effect.
In a preferred embodiment, the p-d orbital hybridization enhances the Fenton-like synergistic photo-thermal effect of the antibacterial nanomaterial loaded with Fenton-like nanoclusters. The hybrid nano particles are in a single-layer or few-layer nano lamellar morphology, and the particle size is 0.2-2 mu m. The nanoclusters may be selected as desired, preferably materials having a Fenton-like effect, more preferably copper nanoclusters. The p-d orbit hybridization enhanced Fenton-like synergistic photo-thermal antibacterial nano material can realize high-efficiency Fenton-like effect on organism infected tissues, so that a large amount of active oxygen species are generated, and the killing effect on infected bacteria is greatly enhanced; in addition, the heat effect can be generated under the action of near infrared two-region laser, so that the anti-infection is further realized in a synergistic way, and the drug resistance and toxic and side effects brought by antibiotic drugs are avoided.
The preparation method provided by the invention is simple, convenient and feasible, high in yield, high in efficiency, free of pollution and low in cost, the obtained p-d orbit hybridization enhanced Fenton-like synergistic photo-thermal antibacterial nano material is regular in morphology, controllable in particle size, good in stability, has micro-environment responsiveness, is beneficial to efficiently catalyzing and generating hydroxyl free radicals with bacterial toxicity, can generate photo-thermal effect under near infrared laser radiation, has excellent relieving and treating effects due to the enhanced Fenton-like synergistic photo-thermal effect, and is one of antibacterial treatment schemes with great application prospects, and the nano-drug system for treating microbial infection is expected to be prepared. The following illustrates the preparation method of the p-d orbit hybridization enhanced Fenton-like synergistic photo-thermal inorganic nano material.
FIG. 1 is a flow chart of preparing a p-d orbital hybridization enhanced Fenton-like synergistic photo-thermal antibacterial nanomaterial according to an embodiment of the present invention. As shown in fig. 1, a two-dimensional silicon nanomaterial may be first prepared.
The preparation method of the two-dimensional silicon nano material is not limited, and for example, the two-dimensional silicon nano sheet can be prepared by utilizing wet chemical method intercalation etching or by ultrasonic liquid phase stripping technology. The intercalation etching solution used may be a polar aprotic solvent in an organic solvent, preferably acetonitrile; the etchant used may be elemental iodine. The preparation method comprises the steps of taking silicon-based powder as a precursor, taking an organic solvent as a reaction solution system, taking iodine as an etchant, slowly reacting by stirring in a glove box to synthesize a nano-sheet material only containing silicon elements, and dispersing by an ultrasonic crusher to obtain single-layer/few-layer silicon nano-sheets. The silicon-based powder is a metal compound of silicon, preferably calcium silicide; the organic solvent is a polar aprotic solvent, preferably acetonitrile. The molar ratio of silicon-based powder, acetonitrile and iodine is 1:300:1 to 1:700:1, preferably 1:500:1, wherein the acetonitrile density is 0.786g/mL.
In one embodiment, the calcium silicide powder and the iodine simple substance are dissolved in acetonitrile solution in a glove box, mixed and stirred uniformly, and stirred vigorously and mechanically for 10-20 days at room temperature, and then ultrasonic is carried out, so that the two-dimensional silicon nano-sheet with uniform thickness can be obtained. The molar ratio of the calcium silicide to the iodine simple substance can be 1:1. the mole ratio of elemental iodine to acetonitrile may be 1:500.
copper nanoclusters with Fenton-like properties are prepared. The preparation method of the cluster can be to prepare the copper nanocluster with Fenton-like effect by reacting Glutathione (GSH) and a copper source in an ice-water bath. Specifically, pre-chilled Glutathione (GSH) and a copper source are reacted in an ice-water bath. According to the coating method, the copper-containing sphere-like nanocluster can be obtained, and can expose a large number of active sites, so that the copper-containing sphere-like nanocluster has high copper atom utilization rate and becomes a good functional medicament. Among them, the copper source may be a corresponding salt such as copper nitrate, copper chloride, copper sulfate, etc., and among them, copper nitrate is preferable from the viewpoints of material stability and convenience in acquisition. The ratio of GSH to copper source may be selected according to the amount of copper nanoclusters desired, e.g. the molar ratio of the two may be 6:1 to 3:1, for example 4: 1. 9: 2. 5:1. the solution is water and the reaction temperature may be 4 ℃.
The copper nanoclusters are uniformly loaded on the surface of the silicon nanosheets, and the prepared copper nanoclusters and the silicon nanosheets are stirred vigorously at normal temperature as a loading method, so that the method is simple and convenient. Antibacterial nanomaterial with p-d orbit hybridization enhancement Fenton-like synergistic photo-thermal effect and capable of responding to H after being infected in area 2 O 2 A higher Fenton-like catalytic effect is achieved to release a large amount of active oxygen species. The silicon nano-sheet is of a lamellar structure, and the diameter of the lamellar structure is 0.2-2 mu m. The copper nanocluster size is 2-10nm.
In the invention, the p-d orbit hybridization enhanced Fenton-like synergistic photo-thermal inorganic nano material system can also effectively respond to an infected microenvironment to generate ROS, and preferably, the microenvironment is high-expression H 2 O 2 More preferably, the ROS are hydroxyl radicals with strong cytotoxicity. For example, the nanomaterial system may also be applied to staphylococcus aureusA biofilm of bacteria. The removal of the stubborn biofilm formed by bacteria can be better realized through the synergistic effect of the enhanced Fenton-like effect and the photo-thermal effect.
The invention provides a simple and easy and environment-friendly method for synthesizing a novel nanomaterial system with controllable lamellar particle size, stable physicochemical property, unique external field response treatment mode and guaranteed safety. The preparation method disclosed herein has simple and feasible synthesis process and controllable and accurate reaction conditions. The p-d orbit hybridization enhancement Fenton-like synergistic photo-thermal antibacterial nano material disclosed herein can remarkably enhance the capability of generating hydroxyl free radicals and the photo-thermal effect to synergistically accelerate bacterial death; and can greatly enhance the treatment effect of bacterial infection while reducing the biotoxicity brought by clinical medicines such as antibiotics and the like. The track hybridization functional nano material has good application prospect in the aspect of selectively releasing antibacterial drugs and resisting refractory infection.
The present invention will be further illustrated by the following examples. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations upon the scope of the invention, since numerous insubstantial modifications and variations will now occur to those skilled in the art in light of the foregoing disclosure. The specific process parameters and the like described below are also merely examples of suitable ranges, i.e., one skilled in the art can make a suitable selection from the description herein and are not intended to be limited to the specific values described below.
Example 1
(1) Preparing a two-dimensional silicon nano-sheet with a lamellar structure: dissolving 2.4g of calcium silicide powder and 6.35g of elemental iodine in 750mL of acetonitrile solution in a glove box, uniformly mixing, stirring for 15 days at room temperature, then carrying out ultrasonic treatment on the obtained multilayer silicon nano material in an ultrasonic crusher for 2 hours to obtain single-layer silicon nano sheets, and centrifugally flushing and drying the product for later use;
(2) Preparing copper nanoclusters with Fenton-like effect: 230.5mg of GSH is dissolved in 2000. Mu.L of ultra pure water, and after the dissolution is completed by continuous stirring, the solution is put into 4Precooling for 30min at the temperature of the refrigerator. Subsequently, the pre-chilled GSH solution was transferred to an ice water bath and 20mg of CuSO was added 4 After magnetic stirring for 60s, the ice-water bath was stopped. After the reaction was returned to room temperature, 500 μ L N, N-dimethylformamide was added thereto, and the product was collected by centrifugation and repeatedly centrifuged with ultrapure water for 2 times to remove impurities;
(3) Construction of p-d orbit hybridization nano antibacterial drugs: the prepared 4.5mg copper nanoclusters (0.0703 mmol) and 10mg (0.357 mmol) two-dimensional silicon nanoplatelets are dispersed in 2mL of aqueous solution, and are fully combined after being vigorously stirred for 1h, and the p-d orbital hybridization enhanced Fenton-like synergistic photo-thermal antibacterial nanomaterial (the molar ratio of the silicon nanoplatelets to the copper nanoclusters is 5:1) is obtained through centrifugal collection at the rotating speed of 13000rpm, and the preparation flow is shown in figure 1.
Fig. 2 is an AC-TEM image of the calcium silicide powder in this example 1, where a is a monoatomic image, B is a graph of atomic ratio of calcium and silicon as a function of distance (left to right in the horizontal direction) and C is the corresponding selected-area electron diffraction. Intuitively, the silicon and calcium atoms in calcium silicide are shown in the formula 2:1 and good crystallinity of calcium silicide, which lays a foundation for stripping Ca from calcium silicide powder to obtain a nano lamellar structure of Si element.
FIG. 3 is a Transmission Electron Microscope (TEM) image and Atomic Force Microscope (AFM) image of an individual silicon nanoplate and a copper nanoclusted loaded silicon nanoplate (SiCu for short), wherein D is the front of loading, the surface of the silicon nanoplate exhibits a flat structure, has a regular shape, and has typical two-dimensional nanomaterial characteristics; e is an image loaded with copper nanoclusters, and shows black bright spots uniformly distributed on the surface, because the atomic number of Cu is larger than that of Si, and the contrast is higher in TEM; furthermore, AFM images and statistical heights further illustrate the uniform loading of copper nanoclusters.
FIG. 4 is a graph of the energy spectrum of the p-d orbital hybridization enhanced Fenton-like synergistic photo-thermal antibacterial nanomaterial SiCu in the examples. Wherein F is the surface scanning image of the element distribution and shows Si, O and Cu elements contained in SiCu; and G is a corresponding energy spectrum element peak bitmap, and the occurrence of Cu element characteristic peaks in G also indicates successful loading of the copper nanoclusters.
Fig. 5 is an X-ray photoelectron spectrum (XPS) of copper nanoclusters alone (Cu for short) and SiCu. XPS demonstrates the elemental composition of Cu and SiCu, and the chemical state of Cu therein. C. The binding energy of N, O, si and Cu are recorded in FIG. 5, the right side is copper element at 2P 3/2 Is notable for SiCu NSs at Cu 2p 3/2 The binding energy of the peak shows a negative shift of 0.1eV with respect to Cu. Cu 2p 3/2 This negative shift in binding energy represents electron charge transfer from Si to Cu, which can be attributed to the electronegativity of Cu (1.9 eV) being higher than Si (1.8 eV).
FIG. 6 is a simulation calculation of the p-d orbital hybridization interactions and Fenton-like processes for SiCu samples. Where H is the projected state density (PDOS) of SiCu, showing a good match of the energy of the Si- (p) band with the energy of the Cu- (d) band, indicating a strong p-d orbital hybridization interaction between Si and Cu. I is the calculated local DOS of the surface Cu atoms, where the corresponding d-band center (ε d ) Marked with a dashed line, the fermi level is set to zero; the d-band center of Cu on the surface of the copper nanocluster is-2.31 eV; and the DOS of Si@Cu combined with the silylene has a remarkable left shift trend (namely, toward the fermi level). Thus, the d-band center of the surface Cu atom became aligned to be-2.20 eV, which is consistent with the test result of XPS. The Cu has stronger adsorption capacity to the reaction intermediate after being loaded on the silicon nano-sheet, and is favorable for Fenton-like reaction. J is H 2 O 2 Free energy of dissociation at Cu and si@cu surfaces. K is H on the surface of Si@Cu 2 O 2 Dissociating the optimized atomic structure of the intermediate. By simulating copper nanoclusters and H on SiCu structure 2 O 2 The results show H 2 O 2 The energy absorbed on SiCu (-0.98 eV) was much lower than on Cu (-0.34 eV), indicating H 2 O 2 Molecules are more easily activated on SiCu surfaces. Subsequently, the energy to form 2 x oh on SiCu was calculated to be-3.69 eV, while the energy of the individual copper nanoclusters was calculated to be-2.97 eV. The L graph can find that significant charge interaction exists at the interface of the silicon nano-sheet and the copper nano-cluster, which means that strong bonding action and charge transfer process exist between the two materials, which is beneficial to the promotion of the materialsCatalytic properties of (a); the barer charge analysis showed that the silicon nanoplatelets transferred 0.18 electrons to the copper nanoclusters. Taken together, these results indicate that p-d hybridization interactions between Si and Cu are mediated by redistributing the electronic structure and promoting H 2 O 2 The Fenton-like effect of SiCu is enhanced by the adsorption of SiCu.
FIG. 7 is a Cu and SiCu catalytic H 2 O 2 Electron spin resonance (EPR) test results of generating hydroxyl radicals can prove that SiCu hybridized with copper nanoclusters through silicon nanoplates has more excellent hydroxyl radical generating capability than copper nanoclusters alone.
Antibacterial experiment: gram-positive staphylococcus aureus was grown overnight on sheep blood agar plates (5-7% by volume of sheep blood) at 37 ℃. Individual colonies of the strain were picked and cultured overnight at 37 ℃ in 4mL tryptone soy broth. Serial dilution of the suspension of staphylococcus aureus 10-fold, 1X 10 concentration in trypticase soy broth 6 CFUs mL -1 Is a bacterial liquid of (a) a strain. Staphylococcus aureus was diluted to a concentration of 1X 10 with PBS 7 CFU mL -1 . Antibacterial activity experiments were performed by the expansion plate colony counting method. Wherein the control group 1, the experimental group 1-2 and the experimental group 1-3 are respectively that PBS, independent silicon nano-sheets, cu and SiCu are added into the mixture with the concentration of 1 multiplied by 10 6 CFU mL -1 Culturing for 12-48h in the bacterial liquid of the experiment group 1-1, wherein the adding concentration of the single silicon nano sheet material is 50mg mL -1 Experimental group 1-2 copper nanoclusters were added at a concentration of 10mg mL -1 . The experimental group 1-3 is that the single silicon nanomaterial in the experimental group 1-1 is replaced by an antibacterial nanomaterial SiCu with p-d orbit hybridization enhancement Fenton-like synergistic photo-thermal, and the addition amount of the nano-drug is completely consistent with the content of the nanomaterial in the experimental group 1-1. The control PBS served as a blank, and was different from the other three experimental groups in that only an equal volume of PBS solution was added.
Fig. 8 is a growth state test result of bacterial colonies after different treatments in this example, and the copper nanoclusters hybridized with the silicon nanoplatelet orbitals exhibited better antibacterial effect compared to the copper nanoclusters alone, which is consistent with the theory of the previous hybridization enhancement Fenton-like. The antibacterial test result shows that the p-d orbit hybridization enhanced Fenton-like synergistic photo-thermal antibacterial nanomaterial can effectively kill bacterial colonies through the Fenton-like effect enhanced by p-d hybridization without external field treatment.
Fig. 9 is a thermal imaging of PBS and copper nanocluster SiCu hybridized with silicon nanoplate orbitals after treatment with a near infrared two-region laser at 1064 nm. Under the irradiation of the external laser, siCu shows good heating effect (the corresponding temperature rising curve is shown in FIG. 10).
FIG. 10 is a graph of quantitative temperature versus time for a thermogram showing the change at 50mg mL -1 The temperature can be raised to more than 48 ℃ within 5 minutes under the concentration of (2), and the synergistic sterilization can be realized.
FIG. 11 is a graph showing the antimicrobial effect of different materials after laser treatment at 1064nm (NIR-II) and quantitative data thereof. Wherein, the control group 2, the experimental group 2-1, the experimental group 2-2 and the experimental group 2-3 are PBS plus NIR-II, independent silicon nano-sheets plus NIR-II, cu plus NIR-II and SiCu plus NIR-II respectively; the concentration of the nanomaterial is the same as above. The antibacterial result shows that the antibacterial effect of SiCu is more remarkable under the assistance of near infrared two-region laser, and the antibacterial performance of the nano material is further improved by cooperating with photo-thermal on the basis of p-d orbit hybridization enhancement Fenton-like.
FIG. 12 is a Scanning Electron Microscope (SEM) image of a Staphylococcus aureus biofilm on an implant (titanium plate) after treatment with 1064nm (NIR-II) laser, where H-K is PBS plus NIR-II, silicon nanoplatelets alone plus NIR-II, cu plus NIR-II, siCu plus NIR-II, respectively; the concentration of the nanomaterial is the same as above. SEM results clearly show that a large amount of bacteria exist in the control group H, and the PBS has weak heating effect under the action of NIR-II, so that sterilization is difficult to realize; in the group I of the silicon nano-sheet and the NIR-II, bacteria are killed due to the temperature rise caused by the photo-thermal effect of the silicon nano-sheet, so that the silicon nano-sheet has a certain curative effect; meanwhile, in the J group of the independent copper nanocluster and the NIR-II, certain bacterial killing is brought on the basis of the Fenton-like effect of the copper nanocluster; in the K group of the copper nanoclusters hybridized with the silicon nanosheets and the NIR-II, the composite nanosystem not only comprises the reinforced Fenton-like effect after hybridization, but also exerts the thermal effect of the silicon nanosheets through light irradiation, and realizes efficient antibacterial through photo-thermal and reinforced chemical kinetics.
Fig. 13 is antibacterial experimental data for silicon nanoplatelets and copper nanoclusters at different loading molar ratios. Experimental results show that under the condition that the loading addition amounts of the copper nanoclusters are consistent, the copper nanocluster loading group with high molar ratio cannot be effectively loaded on the silicon nanosheets due to the fact that mutual agglomeration easily occurs among the nanoclusters, so that the active sites are few and the catalytic efficiency is low. Along with the reduction of the loading proportion of the copper nanoclusters, proper space distance is reserved among the copper nanoclusters, so that the copper nanoclusters are favorably loaded on the silicon nanosheets and form an orbital hybridization enhanced Fenton-like effect. However, as the molar ratio of the loaded copper nanoclusters is further reduced, the copper nanoclusters are difficult to be effectively loaded by the silicon nanoplatelets due to the too thin concentration, so that the catalytic effect of the copper nanoclusters is gradually reduced.
Example 2
The preparation process of the p-d orbital hybridization nano inorganic material in the present example 2 is described in example 1, and the difference is that: in the step (3), 3.2mg of copper nanoclusters (0.0513 mmol) and 10mg (0.357 mmol) of two-dimensional silicon nanoplatelets obtained by preparation are dispersed in 2mL of aqueous solution, and are fully combined after being vigorously stirred for 1h, and the p-d orbit hybridization enhancement Fenton-like synergistic photo-thermal antibacterial nanomaterial is obtained by centrifugal collection at the rotating speed of 13000rpm (the mol ratio of the silicon nanoplatelets to the copper nanoclusters is 7:1).
Example 3
The preparation process of the p-d orbital hybridization nano inorganic material in the present example 3 is described in example 1, and the difference is only that: in the step (3), 15mg of copper nanoclusters (0.238 mmol) and 10mg (0.357 mmol) of the prepared two-dimensional silicon nanoplatelets are dispersed in 2mL of aqueous solution, and are fully combined after being vigorously stirred for 1h, and the p-d orbital hybridization enhanced Fenton-like synergistic photo-thermal antibacterial nanomaterial is obtained by centrifugal collection at the rotating speed of 13000rpm (the molar ratio of the silicon nanoplatelets to the copper nanoclusters is 3:2).
Example 4
The preparation process of the p-d orbital hybridization nano inorganic material in this example 4 is described in example 1, and the only difference is that: in the step (3), the prepared 22.7mg copper nanoclusters (0.357 mmol) and 10mg (0.357 mmol) two-dimensional silicon nanoplatelets are dispersed in 2mL of aqueous solution, and are fully combined after being vigorously stirred for 1h, and the p-d orbit hybridization enhanced Fenton-like synergistic photo-thermal antibacterial nanomaterial is obtained by centrifugal collection at the rotating speed of 13000rpm (the mol ratio of the silicon nanoplatelets to the copper nanoclusters is 1:1).
Example 5
The preparation process of the p-d orbital hybridization nano inorganic material in the present example 5 is described in example 1, and the difference is that: in the step (3), 2.8mg of copper nanoclusters (0.0446 mmol) and 10mg (0.357 mmol) of two-dimensional silicon nanoplatelets prepared are dispersed in 2mL of aqueous solution, and are fully combined after being vigorously stirred for 1h, and the p-d orbital hybridization enhanced Fenton-like synergistic photo-thermal antibacterial nanomaterial is obtained by centrifugal collection at the rotating speed of 13000rpm (the molar ratio of the silicon nanoplatelets to the copper nanoclusters is 8:1).
Claims (9)
1. A p-d orbital hybridization enhanced Fenton-like inorganic nanomaterial comprising: silicon nanoplates and copper nanoclusters hybridized with the silicon nanoplate orbitals; preferably, the orbital hybridization is p-d orbital hybridization.
2. The p-d orbital hybridization enhanced Fenton-like inorganic nanomaterial of claim 1, wherein the silicon nanoplatelets have a diameter of 200-2000 nm and a thickness of 2-12 nm.
3. The p-d orbital hybridization enhanced Fenton-like inorganic nanomaterial according to claim 1 or 2, wherein the copper nanoclusters are composed of copper nanoparticles; the particle size of the copper nano particles is 2-10nm.
4. The p-d orbital hybridization enhanced Fenton-like inorganic nanomaterial according to any of claims 1-3, wherein the molar ratio of silicon nanoplatelets to copper nanoclusters is 8:1 to 1:1, preferably 7:1 to 3:2.
5. the p-d orbital hybridization enhanced Fenton-like inorganic nanomaterial according to any of claims 1-4, wherein the morphology of the p-d orbital hybridization enhanced Fenton-like inorganic nanomaterial is a monolayer or less nano-platelet lamellar morphology;
the total particle size of the p-d orbit hybridization enhanced Fenton-like inorganic nano material is 0.2-2 mu m.
6. A method for preparing the p-d orbital hybridization enhanced Fenton-like inorganic nanomaterial according to any of claims 1 to 5, comprising: dispersing single-layer or less-layer silicon nano-sheets and copper nano-clusters in a solvent, and stirring to fully combine the single-layer or less-layer silicon nano-sheets and the copper nano-clusters to obtain the p-d orbit hybridization enhanced Fenton-like inorganic nano-material.
7. The method of claim 6, wherein the single or few layer silicon nanoplatelets and copper nanoclusters are in a molar ratio of 8:1 to 1:1, preferably 7:1 to 3:2; the solvent is at least one of water, ethanol, phosphate buffer solution and physiological saline.
8. The method according to claim 6 or 7, wherein the stirring speed is 200 to 800 rpm and the stirring time is 0.5 to 2 hours.
9. Use of the p-d orbital hybridization enhanced Fenton-like inorganic nanomaterial according to any of claims 1-5 in the preparation of an antibacterial agent.
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