CN115569147A - Preparation method and application of platinum monatomic supported MXene nanosheet - Google Patents
Preparation method and application of platinum monatomic supported MXene nanosheet Download PDFInfo
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- CN115569147A CN115569147A CN202211203505.9A CN202211203505A CN115569147A CN 115569147 A CN115569147 A CN 115569147A CN 202211203505 A CN202211203505 A CN 202211203505A CN 115569147 A CN115569147 A CN 115569147A
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- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims abstract description 111
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K33/00—Medicinal preparations containing inorganic active ingredients
- A61K33/24—Heavy metals; Compounds thereof
- A61K33/243—Platinum; Compounds thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
- A61K41/0052—Thermotherapy; Hyperthermia; Magnetic induction; Induction heating therapy
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/02—Inorganic compounds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
- A61P31/04—Antibacterial agents
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
- C01B32/921—Titanium carbide
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Abstract
The invention discloses a preparation method and application of a platinum monatomic supported MXene nanosheet, belongs to the field of monatomic catalyst antibacterial research, and synthesizes the monatomic platinum supported titanium carbide nanosheet through hybridization of platinum monatomic based on titanium carbide MXene, the monatomic catalytic MXene nanosheet with photo-enhanced peroxidase activity can locally catalyze hydrogen peroxide and generate hydroxyl radicals, so that bacteria are effectively killed and a biological membrane is removed, in addition, the high photothermal conversion efficiency is shown under the irradiation of low-concentration (40 mu g/mL) near infrared light, and the temperature rise caused by the photothermal effect of the platinum monatomic supported titanium carbide obviously amplifies the activity of similar peroxidase.
Description
Technical Field
The invention relates to the field of antibacterial bioactivity, in particular to a research on the inhibiting effect of a monatomic catalyst on staphylococcus aureus, and specifically relates to a synthetic method and application of platinum monatomic supported titanium carbide.
Background
Deep bacterial infections, including subcutaneous abscesses, osteomyelitis and septicemia, are common causes of human death worldwide. Although antibiotics have met with some success against bacterial diseases, the continued increase in the number of antibiotic-resistant bacteria, especially multi-resistant bacteria, impairs the efficacy of the antibiotics, resulting in high mortality from infectious diseases. Therefore, the development of high-efficiency, low-toxicity and antibiotic-independent antibacterial drugs and related drugs is imperative. Recently, nano-antibacterial technologies have attracted much attention because inorganic-organic hybrid nano-platforms have the potential to destroy the entire microbial redox system by inducing oxidative stress to eradicate bacterial pathogens. In antibiotic-independent therapy, the generation of reactive oxygen species is critical to the antibacterial activity of the nano-platform. Photodynamic therapy, chemodynamic therapy, and sonodynamic therapy have been recognized as promising alternatives to antibiotic therapy to combat deep bacterial infections. Unfortunately, widespread use is difficult due to low tissue penetration and low efficiency of reactive oxygen species generation by sonosensitizers. The problem of low tissue penetration capacity and catalytic activity can be effectively overcome by the nano enzyme catalysis, and normal tissues are not damaged. Monatomic catalysts are receiving increasing attention due to their efficient catalytic performance. However, the search for and development of new monatomic catalysts remains a challenge.
Compared with the traditional catalyst, the monatomic catalyst has the advantages of excellent catalytic activity, good selectivity, obvious reduction of the amount of catalytic metals and the like. Therefore, monatomic catalysts are considered as emerging candidates for chemical, energy, biological, and environmental fields. Many substrates including metal sulfides, metal oxides, metal nitrides, black phosphorus, and graphene have been used as substrates for metal monatomic catalysts so far. The properties of the monatomic catalyst and its matrix together determine the catalytic performance of the catalyst. Therefore, it is very important to select a suitable substrate to obtain a satisfactory catalytic activity. Most of the reported monatomic catalysts are unstable due to their easy formation of clusters by agglomeration coupling during preparation and participation in the reaction, resulting in low catalytic efficiency. Furthermore, the applications of the monatomic catalyst in biomedical applications, including medical imaging and tumor treatment, which are reported at present, are not reported in the direction of antibacterial drugs.
Wherein MXene is a novel nano two-dimensional sheet layer of metal carbonitride, and has been widely applied to transistors, energy storage equipment, seawater desalination, electrocatalysts, electromagnetic interference shielding, electromagnetic shielding fabrics, electrochemical supercapacitors, lithium ion batteries, potassium ion batteries, zinc ion batteries and conductive films, and part of MXene and composite materials thereof have antibacterial activity to escherichia coli, staphylococcus aureus and bacillus subtilis, so that MXene is also applied to biological medicines at present and is used as an antibacterial material.
However, the single MXene in the prior art is not high in antibacterial performance, and more MXene is used as a carrier of the existing antibacterial drugs to improve the antibacterial performance or modify the MXene to improve the antibacterial activity. As described in patent publication No. CN111184908A, mxene is added into nano niobate, and the nano niobate is loaded on the surface of Mxene in situ, so as to obtain the Mxene composite piezoelectric material with antibacterial property.
Therefore, the invention aims to find a novel modified compound MXene with excellent antibacterial activity and expand the variety of the modified compound MXene as an antibacterial medicament.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a preparation method and a biological activity application of a platinum monatomic supported titanium carbide catalyst.
In order to achieve the aim, the platinum monoatomic load titanium carbide MXene protected by the inventionThe nano-sheet is Ti and the titanium carbide MXene nano-sheet 3 C 2 MXene nanosheets, said Ti 3 C 2 MXene nanosheets are single-layer or few-layer two-dimensional nanosheets, the few-layer is 2-10-layer layered two-dimensional nanosheets, and platinum monatomics are randomly distributed in Ti 3 C 2 MXene nanosheets and occupying titanium vacancies.
The platinum monatomic loaded titanium carbide nanosheet provided by the invention has peroxidase-like activity, can locally catalyze hydrogen peroxide and generate hydroxyl radicals, can show high photothermal conversion efficiency under near-infrared light irradiation, and can be applied to an oxidase-like enzyme preparation.
The invention also provides the platinum monatomic loaded titanium carbide nanosheet which has an antibacterial effect and can be applied to preparation of antibacterial drugs.
In a specific embodiment of the invention, the antibacterial agent is a gram-positive bacteria inhibitor.
In a specific embodiment of the invention, the gram-positive bacteria inhibitor is a staphylococcus aureus lysis inhibitor.
The invention also provides a platinum monatomic loaded titanium carbide nanosheet, which can be applied to preparation of a bacterial biofilm inhibitor.
In a particular embodiment of the invention, the bacterial biofilm inhibitor is a staphylococcus aureus biofilm inhibitor.
The invention also provides a platinum monatomic loaded titanium carbide nanosheet, which can be applied to preparation of a therapeutic agent for subcutaneous bacterial infection abscess.
In a specific embodiment of the present invention, the therapeutic agent for subcutaneous bacterial infection abscess is a therapeutic agent for subcutaneous staphylococcus aureus infection abscess.
In a specific embodiment of the present invention, the gram-positive bacteria inhibitor is a photothermal nanoenzyme gram-positive bacteria inhibitor.
In a specific embodiment of the invention, the staphylococcus aureus biofilm inhibitor is a photothermal nanoenzyme staphylococcus aureus biofilm inhibitor.
In a specific embodiment of the invention, the antibacterial drug is a photothermal antibacterial drug, and the platinum monoatomic supported MXene nanosheet is combined with an NIR photothermal assembly system for preparing the antibacterial drug.
In a specific embodiment of the invention, the antibacterial drug is a nano enzyme antibacterial drug, and the platinum monoatomic ring loads MXene nanosheet and H 2 O 2 Application of the composition in preparing antibacterial drugs.
In a specific embodiment of the invention, the antibacterial drug is a photothermal nanoenzyme antibacterial drug, and the platinum monoatomic supported MXene nanosheet is combined with H 2 O 2 And the application of the NIR photothermal combination system in the preparation of antibacterial drugs.
The invention also provides an antibacterial drug composition which comprises MXene nano-sheets and H, wherein the MXene nano-sheets are loaded by platinum single atoms 2 O 2 The MXene nano-sheet is Ti 3 C 2 MXene nanosheets, said Ti 3 C 2 The MXene nano-sheet is a single-layer or few-layer two-dimensional nano-sheet, the few layers are 2-10 layer-shaped two-dimensional nano-sheets, and platinum single atoms are randomly distributed in Ti 3 C 2 MXene nanosheets and occupying titanium vacancies.
The invention also provides an MXene combined near-infrared photo-thermal synergistic nano antibacterial combined system which comprises MXene nano sheets and H supported by platinum single atoms 2 O 2 And a near-infrared laser, wherein the MXene nano-sheet is Ti 3 C 2 MXene nanosheets, the Ti 3 C 2 The MXene nano-sheet is a single-layer or few-layer two-dimensional nano-sheet, the few layers are 2-10 layer-shaped two-dimensional nano-sheets, and platinum single atoms are randomly distributed in Ti 3 C 2 MXene nanosheets and occupying titanium vacancies.
In various embodiments of the invention, all of the antimicrobial and inhibitor agents are exposed to 808nm laser radiation at an intensity of 0.5 to 1Wcm -2 The effective concentration is 20-40 mug/mL, the time is 3-10 minutes, and the concentration of hydrogen peroxide is 0.1mmol.
In various embodiments of the invention, all antibacterial agents and inhibitorsThe agent is irradiated by laser at 808nm, and the intensity is 1Wcm -2 The conditions were used, the effective concentration was 40. Mu.g/mL, the time was 5 minutes, and the hydrogen peroxide concentration was 0.1mmol.
The invention also provides a preparation method of the platinum monatomic loaded titanium carbide nanosheet, which comprises the following steps:
step one, slowly adding 0.2mM ammonium chloroplatinate solution into a 0.5mg/mL monolayer titanium carbide MXene solution system, and heating for 5 hours at the reflux temperature of 80 ℃;
step two, collecting the precipitate by centrifugation and lyophilizing for 48 hours to obtain a lyophilized precursor;
and step three, placing the freeze-dried precursor in the middle of a tubular furnace, heating to 400 ℃ in a 10% hydrogen/argon atmosphere, keeping for 15 minutes, and then cooling to 25 ℃ to obtain the platinum monatomic loaded titanium carbide nanosheet.
In a specific embodiment of the invention, a monolayer titanium carbide MXene solution is prepared by etching a MAX phase of titanium aluminum carbide with lithium fluoride and hydrogen chloride.
In a specific embodiment of the present invention, 50mL of ammonium chloroplatinate (0.2 mM) solution was slowly added to a 200mL monolayer titanium carbide MXene solution system (0.5 mg/mL), and then heated at 80 ℃ under reflux for 5 hours, next, the precipitate was collected by centrifugation and lyophilized for 48 hours to obtain a lyophilized precursor, and finally, the lyophilized precursor was placed in the middle of a tube furnace, heated to 400 ℃ in a 10% hydrogen/argon atmosphere for 15 minutes, and then cooled to 25 ℃ to obtain platinum monatomic supported titanium carbide nanoplatelets.
The invention has the following advantages: the titanium carbide-based nano platform with the titanium carbide loaded by the monoatomic platinum has nano enzyme catalytic activity. The monatomic structure adjusts the light absorption of the platinum monatomic loaded titanium carbide in the near infrared region, thereby improving the photo-thermal conversion efficiency. In addition, the peroxidase-like activity realizes efficient photo-thermal amplification, can be used for anti-infection treatment, and avoids thermal treatment damage to normal tissues. The biological safety and antibacterial properties of the platinum monatomic loaded titanium carbide nano-platform are systematically evaluated in vivo and in vitro, and the work provides application basis for effective treatment of deep bacterial infected wounds.
Drawings
FIG. 1 is a schematic diagram showing the synthesis of monoatomic platinum-supported titanium carbide nanoplates in example 1;
FIG. 2a is a schematic diagram of the synthesis process of single-atom platinum-supported titanium carbide nanosheets in example 2;
2b is the X-ray diffraction (XRD) pattern of the monoatomic platinum-supported titanium carbide nanoplates of example 2;
2c is a Transmission Electron Microscope (TEM) image of a single atom platinum-supported titanium carbide nanoplate of example 2;
2d is a selected-area electron diffraction (SAED) pattern of the monatomic platinum-supported titanium carbide nanosheets of example 2;
2e is an atomic structure diagram of titanium carbide supported on a platinum monoatomic atom simulated in example 2;
2f is an energy dispersive X-ray spectroscopy (EDS) elemental map of a single-atom platinum-supported titanium carbide nanoplate of example 2;
2g is an electron diffraction pattern of the monoatomic platinum-supported titanium carbide nanosheet of example 2;
2h is an enlargement of 2g from example 2;
2i is an enlarged view of 2h in example 2;
2j is the Ti 2p XPS plot of the titanium carbide nanoplates of example 2;
2k is a Ti 2p XPS plot of single atom platinum-supported titanium carbide nanoplates in example 2;
2l is the Pt 2p XPS plot of the monoatomic platinum-supported titanium carbide nanoplates of example 2;
fig. 3a is an absorption spectrum of different concentrations of monatomic platinum-supported titanium carbide nanoplates in example 3;
3b is a statistical graph of the change result of the solution temperature of the monatomic platinum-loaded titanium carbide nanosheet solution with different concentrations irradiated by near-infrared light (10 minutes);
3c is a thermal imaging graph of the change of the temperature of the solution of the monatomic platinum-loaded titanium carbide nanosheets with different concentrations irradiated by near-infrared light;
3d temperature profile of monatomic platinum-loaded titanium carbide nanoplates at 40 μ g/mL under near-infrared radiation (808 nm, 2W/cm 2) for five cycles (laser on 10 minutes in each cycle and off to room temperature);
3e is a photo-thermal conversion efficiency result graph of the titanium carbide nanosheet loaded with the monatomic platinum;
3f is a curve of cooling time and-ln theta;
3g is a TMB/OPD catalysis mode diagram of the monatomic platinum-supported titanium carbide nanosheet in example 3;
3h is the influence of the monatomic platinum-loaded titanium carbide nanosheets with different concentrations on the catalytic activity of TMB; 3i is the influence of different concentrations on the catalytic activity of the titanium carbide nanosheets on TMB;
3j is the influence of the different concentrations of the monatomic platinum-loaded titanium carbide nanosheets on the OPD catalytic activity;
3k is the influence of infrared irradiation on the activity of the monatomic platinum-loaded titanium carbide nanosheets on the POD-like activity;
3l is a monoatomic platinum-supported titanium carbide nanosheet + H 2 O 2 Group-sum titanium carbide nanosheet + H 2 O 2 Electron spin resonance spectra of the set;
FIG. 4a is a graph of the effect of single atom platinum-loaded titanium carbide nanoplatelets and titanium carbide nanoplatelet group plate coating on Staphylococcus aureus in example 4;
4b is the statistical result of the influence of the single-atom platinum-loaded titanium carbide nanosheet group and the titanium carbide nanosheet group flat plate coating on staphylococcus aureus in example 4;
4c is a bacterial live/dead staining analysis chart of the monoatomic platinum-supported titanium carbide nanosheet experimental group and the titanium carbide nanosheet experimental group in example 4;
4d is a graph of the results of the quantitative analysis of bacterial fluorescence of the single-atom platinum-supported titanium carbide nanosheet experimental group and the titanium carbide nanosheet experimental group in example 4;
4e is a morphological experiment of the single-atom platinum-supported titanium carbide nanosheet experimental group and the titanium carbide nanosheet experimental group on staphylococcus aureus by flat plate coating in example 4;
4f is an experiment for removing a staphylococcus aureus biofilm by using the monoatomic platinum-loaded titanium carbide nanosheet in example 4;
4g is a quantitative result statistical chart of the staphylococcus aureus biomembrane after single-atom platinum-loaded titanium carbide nanosheets and other experimental groups in example 4;
4h is a Confocal Laser Scanning Microscope (CLSM) imaging picture of the staphylococcus aureus biomembrane after the monoatomic platinum-loaded titanium carbide nanosheet and other experimental groups are treated in example 4;
FIG. 5a is a flow chart of the establishment of a subcutaneous abscess model for mice in example 5;
5b is a picture of subcutaneous abscess of the mouse treated by the monoatomic platinum-loaded titanium carbide nanosheet and other experimental groups in example 5;
5c is a schematic diagram of an area processing image for collecting subcutaneous abscess of a mouse by using the monoatomic platinum-loaded titanium carbide nanosheet in example 5;
5d, a statistical result chart of infection areas related to subcutaneous abscesses of the mice;
5e, collecting skin tissues at subcutaneous abscess of the mouse and counting colonies;
5f, collecting skin tissues at subcutaneous abscess of the mouse and carrying out colony counting statistical result chart;
5g collecting H & E staining patterns of tissues after 10 days of different treatment groups of skin tissues at subcutaneous abscesses of the mice;
5h is an enlarged view of FIG. 5 g;
5i collecting Masson staining patterns of tissues after 10 days of different treatment groups of skin tissues at subcutaneous abscesses of the mice;
5j, collecting gram staining tissue images of tissues 10 days after different treatment groups of skin tissues at subcutaneous abscesses of the mice;
fig. 6 is a two-dimensional code of the color memory map of fig. 1-5.
Detailed Description
The present invention will be further described in detail with reference to examples and effect examples, but the scope of the present invention is not limited thereto.
Example 1 Synthesis route of monatomic platinum-supported titanium carbide nanoplates
The platinum monatomic supported titanium carbide was prepared by a rapid thermal shock method under hydrogen. Firstly, titanium carbide (Pt-Ti) is loaded on a single atom of synthetic platinum 3 C 2 ) Previously, monolayer Ti was prepared according to the prior art 3 C 2 Nanosheets. Etching of Ti by lithium fluoride/hydrogen chloride 3 AlC 2 MAX phase, end groups (F, OH and O) attached to the surface of the titanium carbide. The preparation method of the titanium carbide MXene solution can adopt the specific preparation steps existing in the prior art. Ammonium chloroplatinate (50 mL, 0.2 mM) solution was then added slowly to a 200mL monolayer titanium carbide MXene solution system (0.5 mg/mL) and then heated at 80 ℃ under reflux for 5 hours. Next, the precipitate was collected by centrifugation and lyophilized for 48 hours to obtain a lyophilized precursor. And finally, placing the freeze-dried precursor in the middle of a tube furnace, heating to 400 ℃ in a 10% hydrogen/argon atmosphere, keeping for 15 minutes, and then cooling to 25 ℃ to obtain the platinum monatomic supported titanium carbide nanosheet.
Example 2 characterization of monoatomic platinum-loaded titanium carbide nanoplates
The catalyst of platinum monoatomic load titanium carbide is prepared from N 2 H 8 PtCl 6 And a single layer of titanium carbide in an argon/hydrogen atmosphere, and is formed by high-temperature treatment and annealing, and the synthesis mode is shown in figure 1 and figure 2 a. Platinum monoatomic atoms are randomly distributed on the titanium carbide nano-sheet and occupy titanium vacancy. The X-ray diffraction (XRD) patterns of pristine titanium aluminum carbide and platinum monatomic supported titanium carbide are shown in fig. 2 b. After etching and subsequent ultrasonic treatment of the MAX phase, the main XRD peak of the platinum monatomic supported titanium carbide catalyst is different from that of the original MAX phase; ti 3 AlC 2 The (104) peak at 39 ℃ disappeared, the (002) and (004) peaks shifted to lower 2 theta values, indicating that the aluminum layer was removed and converted to platinum monatomic supported titanium carbide. The (002) reflecting surface of the platinum monatomic supported titanium carbide was retained, indicating that the morphology remained unchanged after rapid thermal shock. In addition, the characteristic peaks have significantly higher 2 θ values, which are attributable to H in the molecular layer after calcination of titanium carbide 2 Volatilization of O and some OH groups results in a reduction of the interlayer. No characteristic platinum peak was observed in the XRD pattern, excluding the formation of platinum particles. The platinum monatomic supported titanium carbide surface remained smooth and its ultrathin character was also observed by TEM (fig. 2 c). The SAED patterns shown in fig. 2d all showed good crystallinity and similar crystal structure. Based on the above results, the atomic structural diagram of platinum monatomic supported titanium carbide was simulated (fig. 2 e). As shown in FIG. 2fIt is shown that elemental mapping of platinum monoatomic titanium carbide-loaded high angle annular dark field scanning TEM (HAADF-STEM) energy dispersive X-ray spectroscopy (EDS) shows Ti, C, O and Pt distributions in isolation without accumulation. All the characterizations show that Pt-Ti is synthesized by a rapid thermal shock method 3 C 2 Is feasible. As shown in fig. 2g, bright spots (marked with yellow circles) corresponding to heavy platinum atoms were uniformly distributed on the titanium carbide support. The clear lattice fringes were measured with lattice spacings of 0.342 and 0.332nm, corresponding to Ti respectively 3 C 2 The (100) and (110) lattice planes of (1). The image also shows that the small optical platinum atomic points (represented by red circles) are uniformly distributed within the regular titanium carbide lattice stripes, as shown in fig. 2 h. The figure in fig. 2i shows the atomic column scheme superimposed on the experimental image for comparison, where one platinum atom is much brighter than the other atoms. These images show that all the small points of platinum lie on the lattice plane walls of the titanium pillars, rather than within the spacing of the Ti pillars. Ti at 454.8 (460.4) and 458.8 (464.3) eV, as shown in FIGS. 2j and 2k 2 p3/2(Ti 2 p 1/2) region can be attributed to Ti-C and Ti, respectively 2+ -O (or Ti) 3+ -O) bond. As shown in FIG. 2l, the platinum 4f region is located at 71.0 and 74.4eV, indicating that the platinum monoatomic support is in the positive valence state for the platinum monoatomic support in titanium carbide. Especially at 400 ℃ Pt 2+ Rapid reduction of ions to Pt 0 Titanium vacancies are occupied in a locally positively charged environment. The charge transfer between the platinum and titanium ambient causes them to assume a positive valence state. The above results demonstrate the success of the anchoring of platinum monoatomic atoms on titanium carbide nanoplates by a rapid thermal shock technique.
Example 3 photothermal and nanoenzyme Performance of Single atom platinum-loaded titanium carbide nanoplates
The absorption of different concentrations of titanium carbide and platinum monoatomic support of titanium carbide was investigated by ultraviolet-visible-near infrared (UV-Vis-NIR) spectroscopy. Platinum monatomic supported titanium carbide showed significant absorption in the near infrared region compared to titanium carbide (fig. 3 a). In particular, a significant absorption signal is generated at 808nm, which is important for photothermal therapy (PTT) at 808nm wavelength. Different concentrations of synthetic platinum monatomic supported titanium carbide were exposed to 808nm laser light (1.0W-cm) -2 10 minutes). Platinum monoatomic atomThe temperature of the titanium carbide-loaded system gradually increased with time, reaching the maximum temperature at 5 min. When the concentration is 40 mug. Multidot.mL -1 The temperature rose by 60.1 ℃ within 5 minutes (fig. 3 b). We also recorded thermal images of temperature changes (FIG. 3 c) and further explored at 0.5 and 1.0W-cm -2 The near infrared photothermal property. Surprisingly, the platinum monatomic structure mediates the local surface plasmon resonance effect of the platinum monatomic loaded titanium carbide, so that the ultrathin platinum monatomic loaded titanium carbide nano-platform shows strong absorption and high conversion efficiency for near-infrared radiation (808 nm). The aqueous dispersion maintained good photothermal effect after five heating/cooling cycles (fig. 3 d), and the photothermal conversion efficiency (η) calculated by heating and cooling for the platinum monatomic supported titanium carbide nanoplatform was 76.4% (fig. 2e and 2 f), indicating that it can effectively kill bacteria by hyperthermia.
On the basis of successfully manufacturing the platinum monatomic loaded titanium carbide, the invention explores various functions thereof. The platinum monoatomic atom endows the platinum monoatomic atom loaded titanium carbide nano platform with high-efficiency catalytic activity and can catalyze H 2 O 2 Generates hydroxyl radical (. OH) having catalase-like activity. The activity was verified using 3,3,5,5-Tetramethylbenzidine (TMB) and o-phenylenediamine (OPD). After OH oxidation, TMB (colorless) was oxidized to oxTMB (blue) showing absorbance at 652 nm. Likewise, OH can oxidize colorless OPD to yellow oxypD, showing a characteristic absorbance at 425nm (FIG. 3 g). For platinum monoatomic supported titanium carbide at H 2 O 2 (0.1 mM), the absorption of TMB at 625nm gradually increased with increasing concentration, indicating that nanoenzyme activity is concentration-dependent. The color change of the TMB can be seen in the figures of fig. 3h and 3 i. In contrast, ti 3 C 2 The catalase-like activity (POD-like activity) of the MXene nanoplatelets did not change significantly with increasing concentration, indicating that no nanoenzyme activity was present. Also, OPD was used to assess nanoenzyme activity at different concentrations of platinum monatomic supported titanium carbide. As shown in FIG. 3j, the absorbance of OPD at 425nm gradually increased with increasing concentration of platinum monatomic supported titanium carbide. The change in OPD color can be seen in the inset of FIG. 3j, indicating thatHigh concentration of Pt-Ti 3 C 2 MXene nanosheets produce a large amount of OH through their nanoenzyme activity. In contrast, ti increases with concentration 3 C 2 MXene nanoplatelets produce little OH.
To better explore the photothermal modulation of nanoenzyme activity, nanoenzyme activity was studied in the presence and absence of near-infrared radiation. As shown in FIG. 3k, near-infrared irradiation significantly amplified the catalase-like activity of titanium carbide supported on platinum monatomic, and reached the maximum OH production in a short time, indicating effective photothermal modulation of POD-like activity.
Generation of platinum monoatomic supported titanium carbide nanoplatform OH was further confirmed by electron spin resonance spectroscopy, in which 5, 5-dimethyl-1-pyrroline-N-oxide was used as a scavenger of OH. As shown in FIG. 3l, at H 2 O 2 In the presence, the platinum monoatomic-supported titanium carbide showed a characteristic signal (1 3 C 2 The nanocomposite has good catalase-like activity.
Example 4 Single atom platinum-loaded titanium carbide nanoplates inhibit the formation of gram-positive bacteria and Staphylococcus aureus biofilms
In view of the excellent photothermal effect and catalase-like activity of platinum monatomic supported titanium carbide nanoplates, the potential antibacterial activity was evaluated using gram-positive bacteria (staphylococcus aureus). Plate colony count for studying different concentrations of Ti co-cultured with bacteria 3 C 2 MXene nanosheet and platinum monoatomic supported Ti 3 C 2 Intrinsic antibacterial activity of MXene nanoplatelets. Staphylococcus aureus was selected as the bacterium to study Ti 3 C 2 MXene nanosheet and platinum monatomic supported Ti 3 C 2 And the sterilization performance of the MXene nanosheet under the photo-thermal condition. Platinum monoatomic supported Ti 3 C 2 MXene nanosheets exhibit good photothermal time dependence and H 2 O 2 Concentration-dependent antibacterial activity. In contrast, ti 3 C 2 MXene nanosheets do not exhibit photothermal antimicrobial activity. These results indicate that the platinum monoatomic support for Ti 3 C 2 MXene nanosheet has excellent propertiesDifferent photo-thermal and nano-enzyme antibacterial potential. Based on plate colony counts (FIG. 4 a), ti 3 C 2 MXene nanosheets did not affect bacterial growth under different conditions. In contrast, platinum monoatomic support of Ti 3 C 2 MXene nano-sheet under near infrared irradiation (808nm, 1.0Wcm) -2 3 min) and H 2 O 2 (0.1 mM) significantly inhibited bacterial growth in the presence of NIR + H 2 O 2 The complete bactericidal effect condition was observed. Colony count statistics in FIG. 4b show that platinum monoatomic supports Ti 3 C 2 The sterilization effect of MXene nano-sheets is obviously different from that of a control (p)<0.001). Subsequently, bacterial live/dead staining analysis and bacterial fluorescence quantitative analysis confirmed that near-infrared irradiation amplified the platinum monoatomic loading of Ti 3 C 2 Catalase-like activity of MXene nanoplatelets, achieving high efficiency sterilization (fig. 4c and 4 d). Platinum monoatomic support Ti 3 C 2 MXene nanosheets in NIR + H 2 O 2 The bactericidal mechanism in the bactericidal system is further demonstrated by the change in the morphology of staphylococcus aureus, which can be seen in the SEM image (fig. 4 e). In the NIR radiation or H 2 O 2 Loading Ti by platinum monoatomic atom in the presence of 3 C 2 After MXene nanosheet treatment, the cell wall of staphylococcus aureus is folded and ruptured, and the cell wall of bacteria is completely ruptured. Under all conditions, with Ti 3 C 2 None of these effects were observed in bacterial cells treated with MXene nanoplatelets. The above results show that Ti is supported by a single atom of platinum 3 C 2 The catalase-like activity of the MXene nanosheets generates OH, cell walls are broken, photo-thermal damage of bacterial cell walls is accelerated, and an excellent sterilization effect is achieved. Most bacterial infections are due to the presence of bacterial biofilms, which help bacteria avoid exposure to antibiotics or antibacterial agents. Biofilms comprise bacterial extracellular matrix polymers that protect bacteria from host immune cells and resist penetration by antibiotics or antibacterial drugs. Therefore, inhibition and destruction of bacterial biofilms to combat infections is of paramount importance. The staphylococcus aureus biofilms were analyzed by crystal violet staining and the relative biofilm clearance after each treatment was evaluated. As shown in FIGS. 4f and 4g, there were many in the control groupA whole biofilm structure, and Ti is loaded on a platinum monoatomic atom 3 C 2 MXene nanosheets in NIR + H 2 O 2 After treatment, the bacterial biofilm is basically eliminated. Effective biofilm removal was revealed by quantitative analysis of bacterial biofilms. In addition, confocal Laser Scanning Microscopy (CLSM) imaging confirmed that its treatment disrupted the bacterial biofilm (yellow arrows in fig. 4 h) and rapidly killed bacterial cells within the biofilm (red fluorescence in fig. 4 h). The above results indicate that the platinum monoatomic atom imparts the platinum monoatomic atom with Ti supported 3 C 2 MXene nano-sheet has multiple antibacterial modes. Platinum monoatomic supported Ti 3 C 2 Local hyperthermia produced by MXene nanoplatelets under NIR irradiation kills bacteria and the platinum monoatomic atom produces catalase-like activity to disrupt the bacterial cell wall. Finally, the high temperature under near infrared irradiation further amplifies the catalase-like activity to enhance the antibacterial and anti-biofilm efficacy.
Example 5 Single atom platinum-loaded titanium carbide nanoplates inhibit bacterial growth and promote wound repair in mice
To further verify the monoatomic support of Ti by platinum 3 C 2 The sterilizing performance of the MXene nanosheet is evaluated by constructing a mouse subcutaneous abscess model (deep tissue infection model) to evaluate the curative effect on deep bacterial infection. BALB/c mice (female, 6 weeks old) were used to create a model of subcutaneous abscess in mice, the process of which is shown in FIG. 5 a. The specific process is as follows: the mice were de-furled from their backs and injected subcutaneously on both sides of the spine with 50. Mu.L of Staphylococcus aureus (1X 10) 9 CFUmL -1 ). Abscess formation after 24h, treatment was by topical administration. The mice were randomly divided into 5 groups, PBS group, ti 3 C 2 +H 2 O 2 + NIR group, pt-Ti 3 C 22 + NIR group, pt-Ti 3 C 2 +H 2 O 2 Group, pt-Ti 3 C 2 +H 2 O 2 + NIR group (n = 5), pt-Ti 3 C 2 MXene and H 2 O 2 The concentration was 40. Mu.g/mL -1 And 0.1mM, 200. Mu.L of LPt-Ti was injected into the mice, respectively 3 C 2 MXene and H 2 O 2 . NIR-II laser administration to NIR-II miceIrradiation (1W. Cm) -2 10 min). Photographs of the mouse abscess were taken at 0, 1, 3,5, 7, and 10 days, respectively, and the healing of the abscess was recorded. And mice were sacrificed after 10 days, skin tissues were collected for colony counting.
In the platinum monoatomic titanium carbide-loaded treatment group, the temperature of the abscess region of the mouse was increased from about 34 ℃ to 54 ℃, indicating that Pt-Ti 3 C 2 And the film shows good photothermal conversion efficiency in deep tissue infection. Mice were randomly divided into 5 groups based on the photothermal properties and catalase-like activity of platinum monatomic supported titanium carbide. The degree of healing of each group of subcutaneous infected tissues was monitored 10 days after treatment. As shown in FIG. 5b, with PBS and Ti 3 C 2 +NIR+H 2 O 2 Group comparison, in Pt-Ti 3 C 2 +H 2 O 2 、Pt-Ti 3 C 2 + NIR and Pt-Ti 3 C 2 +NIR+H 2 O 2 Better healing was observed in the group. Especially in Pt-Ti 3 C 2 +NIR+H 2 O 2 In the group, abscess size gradually decreased over time, and the infected tissue completely healed by day 10. PBS and Ti 3 C 2 + NIR healing of infected tissue not significantly different + H 2 O 2 And (4) grouping. Pt-Ti 3 C 2 +NIR+H 2 O 2 The abscess area of the group decreased significantly from day 3 and recovered completely on day 10, indicating that platinum monatomic loaded titanium carbide nanoplates effectively promoted healing of the infected tissue by photothermal amplification of catalase-like activity (fig. 5c and 5 d). In addition, the bactericidal effect of the different treatments was evaluated by spreading the bacterial suspension extracted from deep abscesses (day 10) on a solid tryptic soy broth plate. As shown in FIGS. 5e and 5f, in NIR + H, titanium carbide is loaded from a single atom of platinum 2 O 2 A small amount of bacteria was observed in the suspension extracted from the group mice, consistent with the in vitro bactericidal performance results. In order to gain insight into the healing process of infected tissue, a series of histological analyses were performed. H of tissue after 10 days according to different treatments&E staining (FIG. 5 g) in PBS and Ti 3 C 2 +NIR+H 2 O 2 Obvious scab areas were still visible in the groupsPt-Ti 3 C 2 +H 2 O 2 A small area of scabbing was observed and complete healing of the infected tissue was seen, confirming the antibacterial and anti-inflammatory effects of platinum monatomic loaded titanium carbide under NIR irradiation. The position of the arrows in fig. 5h represents the status of each indicator light: intact epidermis (black arrow), non-intact epidermis (red arrow), inflammatory cells (yellow arrow), nascent capillaries (cyan arrow) and hair follicles (orange arrow). Subsequently, collagen fibril formation in the different groups was compared by Masson staining (fig. 5 i). In the presence of Pt-Ti 3 C 2 +NIR+H 2 O 2 Significantly more collagen fibril deposition was observed in the groups than PBS and Ti 3 C 2 +NIR+H 2 O 2 And (4) grouping. The formation of collagen fibrils is indicated by the green arrows in fig. 5 i. Furthermore, from the gram stained tissue image in FIG. 5j, in PBS, ti 3 C 2 +NIR+H 2 O 2 And Pt-Ti 3 C 2 A large number of Staphylococcus aureus bacteria were found in the + NIR group of bacteria infected tissues (blue arrows) compared to Pt-Ti 3 C 2 +H 2 O 2 And Pt-Ti 3 C 2 +NIR+H 2 O 2 Only a few S.aureus bacteria were observed in the infected tissues of the group, indicating that the platinum monoatomic support Ti 3 C 2 The MXene nano-sheet has excellent bactericidal effect.
The above results further confirm that the platinum monoatomic support of Ti 3 C 2 The MXene nanosheet has an effective sterilization effect through photo-thermal amplification of nano-enzyme-like activity.
Finally, it must be said here that: the above embodiments are only used for further detailed description of the technical solutions of the present invention, and should not be understood as limiting the scope of the present invention, and the insubstantial modifications and adaptations made by those skilled in the art according to the above descriptions of the present invention are within the scope of the present invention.
Claims (10)
1. The application of the platinum monatomic supported MXene nanosheet in preparation of the mimic-oxidase preparation is characterized in that: the MXene nano-sheet is Ti 3 C 2 MXene nano-scaleA sheet of Ti 3 C 2 The MXene nano-sheet is a single-layer or few-layer two-dimensional nano-sheet, the few layers are 2-10 layer-shaped two-dimensional nano-sheets, and platinum single atoms are randomly distributed in Ti 3 C 2 MXene nanosheets and occupying titanium vacancies.
2. An application of a platinum monatomic loaded MXene nanosheet in preparation of antibacterial drugs is characterized in that: the MXene nano-sheet is Ti 3 C 2 MXene nanosheets, said Ti 3 C 2 The MXene nano-sheet is a single-layer or few-layer two-dimensional nano-sheet, the few layers are 2-10 layer-shaped two-dimensional nano-sheets, and platinum single atoms are randomly distributed in Ti 3 C 2 MXene nanosheets and occupying titanium vacancies.
3. The application of the platinum monatomic supported MXene nanosheet of claim 2, wherein: the application of the platinum monatomic supported MXene nanosheet combined with NIR photothermal assembly in preparation of antibacterial drugs.
4. The application of the platinum monatomic supported MXene nanosheet of claim 2, wherein: the platinum monoatomic supported MXene nanosheet and H 2 O 2 Application of the composition in preparing antibacterial drugs.
5. Use of MXene according to claim 2, characterized in that: the platinum monoatomic supported MXene nanosheet is combined with H 2 O 2 And the application of the NIR photothermal combination system in the preparation of antibacterial drugs.
6. An MXene application according to any one of claims 2-5, characterized in that: the antibacterial drug is a drug for resisting staphylococcus aureus.
7. An antibacterial pharmaceutical composition, characterized in that: the composition comprises MXene nano-sheets and H supported by platinum single atoms 2 O 2 The MXene nano-sheet is Ti 3 C 2 MXene nanosheets, said Ti 3 C 2 The MXene nano-sheet is a single-layer or few-layer two-dimensional nano-sheet, the few layers are 2-10 layer-shaped two-dimensional nano-sheets, and platinum single atoms are randomly distributed in Ti 3 C 2 MXene nanosheets and occupying titanium vacancies.
8. An MXene combined near-infrared photo-thermal synergistic nano-antibacterial combined system is characterized by comprising MXene nano-sheets and H loaded by platinum single atoms 2 O 2 And a near-infrared laser, wherein the MXene nano-sheet is Ti 3 C 2 MXene nanosheets, the Ti 3 C 2 The MXene nano-sheet is a single-layer or few-layer two-dimensional nano-sheet, the few layers are 2-10 layer-shaped two-dimensional nano-sheets, and platinum single atoms are randomly distributed in Ti 3 C 2 MXene nanosheets and occupying titanium vacancies.
9. The MXene combined near-infrared photothermal synergistic nano antibacterial combined system according to claim 8, wherein the concentration of the solution of the platinum monatomic supported MXene nanosheets is 20-40 μ g-mL -1 Said H is 2 O 2 The concentration of (A) is 0.1mmol, and the near-infrared power density of the near-infrared laser is 0.5-1W cm -2 And irradiating for 3-10 min.
10. A preparation method of a platinum monatomic loaded titanium carbide nanosheet is characterized by comprising the following steps:
step one, slowly adding 0.2mM ammonium chloroplatinate solution into a 0.5mg/mL monolayer titanium carbide MXene solution system, and heating for 5 hours at the reflux temperature of 80 ℃;
step two, collecting the precipitate by centrifugation and lyophilizing for 48 hours to obtain a lyophilized precursor;
and step three, placing the freeze-dried precursor in the middle of a tubular furnace, heating to 400 ℃ in a 10% hydrogen/argon atmosphere, keeping for 15 minutes, and then cooling to 25 ℃ to obtain the platinum monatomic loaded titanium carbide nanosheet.
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| CN117504750A (en) * | 2024-01-04 | 2024-02-06 | 中国科学院合肥物质科学研究院 | Low Pt-loaded MXene-carbon nanotube aerogel film, and preparation method and application thereof |
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