CN114246979A - Piezoelectric-photothermal dual-response MXene/PVDF composite membrane, and preparation method and application thereof - Google Patents
Piezoelectric-photothermal dual-response MXene/PVDF composite membrane, and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of biological materials, and particularly relates to a piezoelectric-photothermal double-response MXene/PVDF composite membrane, and a preparation method and application thereof. The piezoelectric-photothermal double-response MXene/PVDF composite membrane provided by the invention is prepared by taking PVDF and two-dimensional MXene as raw materials and adopting electrostatic spinning, wherein the MXene accounts for 0.2-5% of the mass of the PVDF. The preparation method comprises the following steps: adding PVDF into a solvent, stirring until the PVDF is transparent, adding two-dimensional MXene powder, stirring uniformly, carrying out electrostatic spinning, and drying. The piezoelectric-photothermal double-response MXene/PVDF composite membrane provided by the invention is applied to preparation of materials for treating bone defect. The invention creatively combines the piezoelectric effect and the photothermal effect for repairing bone defects, and simultaneously combines the hydrophobic PVDF coating to prevent MXene from being oxidized so as to obtain the repeatability and stability of photothermal conversion.
Description
Technical Field
The invention belongs to the technical field of biological materials, and particularly relates to a piezoelectric-photothermal double-response MXene/PVDF composite membrane, and a preparation method and application thereof.
Background
Bone defects are important restriction factors for oral implantation treatment, and implanting bone repair substitute materials into the body is one of the current methods for effectively treating bone defects. However, the materials clinically used for bone repair have certain limitations, and most of the bone repair materials scientifically researched can only simply simulate the chemical properties and physical structures of natural bone tissues, and cannot simulate the physical and chemical microenvironments around the natural bone tissues.
The bone has piezoelectricity, and appropriate amount of electric stimulation can increase the concentration of free calcium ions in cell fluid, promote the directional deposition of calcium and phosphorus minerals, regulate the expression of genes related to the bone, improve the activity of alkaline phosphatase and local blood hyporesponsiveness, thereby accelerating the modification of regeneration sites of the bone. Relevant studies prove that polyvinylidene fluoride (PVDF) is the most widely studied piezoelectric polymer at present, and an electric signal generated when deformation occurs can simulate the piezoelectric property of bone and restore and induce a natural electric microenvironment around bone tissues to promote bone healing. But the PVDF is independently adopted as a bone defect repairing material, and the problem of unsatisfactory repairing effect still exists.
Therefore, it is a problem to be solved in the art to provide a material that can mimic the biological activity and biological reactivity of the complex microenvironment surrounding bone tissue.
Disclosure of Invention
One of the purposes of the invention is to provide a piezoelectric-photothermal double-response MXene/PVDF composite membrane which can regulate and control an electrical microenvironment simulating bone tissue repair, has a photothermal effect, and can promote cell growth, adhesion, proliferation and osteogenic differentiation capacity so as to improve bone defect repair efficiency.
The invention also aims to provide a preparation method of the piezoelectric-photothermal double-response MXene/PVDF composite membrane.
The invention also aims to provide application of the piezoelectric-photothermal double-response MXene/PVDF composite film.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the piezoelectric-photothermal double-response MXene/PVDF composite membrane provided by the invention is prepared from PVDF and two-dimensional MXene by electrostatic spinning, wherein the two-dimensional MXene accounts for 0.2-5% of the mass of the PVDF.
In some embodiments of the invention, the composite membrane has a thickness of 60 ± 5 μm.
The two-dimensional MXene has good biocompatibility and osteogenesis activity, and has high-efficiency and controllable photothermal conversion. The invention creatively adopts two-dimensional MXene as a conductive base filler, and compounds the conductive base filler with PVDF by an electrostatic spinning technology to construct a piezoelectric-photothermal double-effect composite membrane, aiming at integrating the material characteristics of PVDF and MXene and realizing double-regulation and repair of bone defects. On one hand, the biological activity and the osteogenic activity of the material can be effectively improved by simulating the electrical characteristics of natural bones and using the bionic bone material with self-charged activity; on the other hand, the surface temperature of the material is increased by utilizing the photo-thermal responsiveness of MXene, osteogenic differentiation is promoted by regulating and controlling a photo-thermal stimulation mode, and meanwhile, the coating of hydrophobic PVDF is combined to prevent oxidation so as to obtain the repeatability and stability of photo-thermal conversion.
The preparation method of the piezoelectric-photothermal double-response MXene/PVDF composite membrane provided by the invention comprises the following steps:
step 1, preparing a PVDF solution: adding PVDF into a solvent, and stirring until the solution is transparent to obtain a PVDF solution;
and 3, taking the MXene/PVDF solution, carrying out electrostatic spinning and drying to obtain the MXene/PVDF composite membrane.
In some embodiments of the present invention, the solvent used in step 1 is a mixed solution of N, N dimethylformamide and acetone.
In one embodiment of the invention, the volume ratio of N, N dimethylformamide to acetone is 3: 2.
In some embodiments of the present invention, in step 1, the mass-to-volume ratio of PVDF to solvent is 15 to 20: 100, mass unit is g, volume unit is ml.
In some embodiments of the invention, in step 2, the mass of the two-dimensional MXene powder accounts for 0.2-5 wt% of the total mass of the two-dimensional MXene powder and the PVDF.
In some embodiments of the invention, the conditions for electrospinning in step 3 are: the voltage is-1.5/11.5 KV, or/and the receiving distance of the needle head and the aluminum foil roller is 15cm, or/and the flow rate of the spinning solution is 0.08 mm/min.
In some embodiments of the invention, the conditions for electrospinning in step 3 are: the voltage is-1.5/11.5 KV, or/and the receiving distance of the needle head and the aluminum foil roller is 15cm, or/and the flow rate of the spinning solution is 0.08 mm/min.
In an embodiment of the invention, in the step 2, after the two-dimensional MXene powder is added, the two-dimensional MXene powder is magnetically stirred, then subjected to low-temperature ultrasonic oscillation and then stirred.
Preferably, the magnetic stirring is performed for 2 hours, followed by 30 minutes of sonication at 4 ℃ and then for 2 hours.
The piezoelectric-photothermal double-response MXene/PVDF composite membrane provided by the invention is applied to preparation of materials for treating bone defect.
Compared with the prior art, the invention has the following beneficial effects:
the invention has scientific design and simple method. The invention creatively combines the piezoelectric effect and the photothermal effect for repairing bone defects. On one hand, the piezoelectric-photothermal dual-response polymer modified by conductive filler MXene is constructed by an electrostatic spinning technology, an ideal microstructure is constructed, the piezoelectric performance of the PVDF composite material is regulated and controlled, and an electrical microenvironment for bone tissue repair is simulated; on the other hand, the photothermal effect of MXene is utilized to endow the composite membrane with enhanced functionality on the basis of ensuring good cell growth, so that cells on the surface of the material generate cell response under proper photothermal stimulation, and the adhesion, proliferation and osteogenic differentiation capabilities of the cells are further improved, thereby improving the bone defect repair efficiency. The invention realizes the regulation and control of the cell growth microenvironment by changing the physical characteristics (surface potential and surface temperature) of the material surface so as to deeply analyze how the material regulates and controls the cell growth behavior, which is indispensable for designing and utilizing the material to guide the cell fate and promote the tissue repair and regeneration.
The PVDF membrane after high-pressure spinning is self-charged and simulates electrical stimulation, the influence of MXene on the piezoelectric performance of the composite membrane is explored, and the interaction of different surface charge properties on the interface of cells and charged biological materials is evaluated to obtain the optimal electrical performance for promoting bone differentiation.
Drawings
FIG. 1 is a scanning electron micrograph of MXene/PVDF from example 1;
FIG. 2 is a plot of the Fourier infrared spectra of PVDF from test example 1 and MXene/PVDF of various ratios;
FIG. 3 is a graph showing the temperature rise of the surface of a wet film under laser irradiation;
FIG. 4 is a graph showing the temperature rise of the surface of a dried film under laser irradiation;
FIG. 5 is a schematic view of the preparation process of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
The embodiment discloses a preparation method of an MXene/PVDF composite membrane, which has a preparation flow shown in the attached figure 4 and specifically comprises the following steps:
step 1, dissolving PVDF powder in a mixed solution of N, N Dimethylformamide (DMF) and acetone (volume ratio of 3:2) to form a mixed solution with a mass volume fraction of 20: 100 parts of PVDF spinning solution, and magnetically stirring for 6 hours until the solution is transparent to obtain the PVDF solution. Wherein, when the mass unit is g, the volume unit is ml.
And 2, adding MXene powder into the PVDF solution, magnetically stirring for 2 hours, ultrasonically oscillating for 30 minutes at 4 ℃, and stirring for 2 hours to form a uniformly mixed MXene/PVDF solution, wherein the mass of the two-dimensional MXene powder accounts for 0.2 wt% of the total mass of the two-dimensional MXene powder and the PVDF.
And 3, taking 10ml of MXene/PVDF solution by using an injector, spinning for 10 hours by using a needle with the pinhole diameter of 0.6mm, the voltage of-1.5/11.5 KV, the receiving distance of the needle from an aluminum foil roller of 15cm and the flow rate of spinning solution of 0.08mm/min to obtain a 0.2 wt% MXene/PVDF spinning film with the thickness of 60 +/-5 microns, and drying in a vacuum drying box at 37 ℃ for overnight.
The scanning electron microscope picture of the MXene/PVDF composite membrane prepared in the embodiment is shown in the attached figure 1, the fibers are uniform and have no fracture, and no obvious string of beads is seen.
Example 2
In this example, different volume ratios of N, N-dimethylformamide to acetone were examined. An MXene/PVDF composite membrane was prepared by the method of example 1 except that the volume ratio of N, N dimethylformamide to acetone in step 1 was different, and the remaining conditions were the same. The MXene/PVDF composite membrane prepared is observed under an electron microscope, and the results are shown in the following table:
TABLE 1
| Numbering | DMF: acetone (v: v) | Fiber morphology |
| 1 | 1:4 | The fiber is uniform and has no fracture and obvious string beads. |
| 2 | 1:1 | The fiber is uniform and has no fracture and obvious string beads. |
| 3 (example 1) | 3:2 | The fiber is uniform and has no fracture, and no obvious string beads are seen. |
| 4 | 4:1 | Uniform fibre, no fracture and beadingMore are. |
As can be seen from the above table, when the volume ratio of N, N dimethylformamide to acetone was 1:4, 4:1, or 1:1, fibers having no breaks were obtained uniformly, but the fibers had many beads.
Example 3
In this example, the mass-to-volume ratio of PVDF powder to a mixed solution of N, N-dimethylformamide and acetone was examined. An MXene/PVDF composite membrane was prepared according to the method of example 1, except that the amount of PVDF powder used in step 1 was different, and the remaining conditions were the same. The MXene/PVDF composite membrane prepared is observed under an electron microscope, and the results are shown in the following table:
TABLE 2
As can be seen from Table 2, the mass-to-volume ratio of the PVDF powder to the mixed solution of N, N-dimethylformamide and acetone is 15-20: at 100, a better fiber can be obtained.
Example 4
Compared with example 1, the amount of MXene powder used in this example is different, and the mass of the two-dimensional MXene powder in this example accounts for 1 wt% of the total mass of the powder and PVDF, and the rest conditions are the same.
Example 5
The amount of MXene powder used was different from that used in example 1, and the mass of the two-dimensional MXene powder of this example was 5 wt% of the total mass of the powder and PVDF, and the rest of the conditions were the same.
Comparative example 1
Compared with example 1, MXene powder is not added, and PVDF solution is directly used for spinning, and the rest conditions are the same.
Test example 1
This test example tests were conducted on the MXene/PVDF composite membranes obtained in examples 1 and 4 to 5 and the PVDF membrane obtained in comparative example 1. Wherein the Fourier infrared spectrum of each film is shown in FIG. 2. As shown in the attached figure 2, as the proportion of MXene increases, the C-H, C-F stretching vibration peak gradually increases to indicate that the MXene is successfully compounded, and meanwhile, the alpha phase gradually converts into the beta phase to indicate that the piezoelectricity is enhanced. The surface charge is increased, which is beneficial to promoting osteogenesis.
Test example 2
The test example employed 808nm laser irradiation (power 0.55W/cm)2) The MXene/PVDF composite films obtained in examples 1, 4 to 5, the PVDF film obtained in comparative example 1, and glass were examined for their photothermal properties.
The temperature rise profiles of the wet film (the film placed in a 24-well plate and 1ml of aqueous solution added) and the dried film surface are shown in FIGS. 3 and 4. It can be seen that the surface temperature of pure PVDF hardly changes under laser irradiation, and glass does not have obvious temperature change after laser irradiation. The surface temperature of the composite membrane modified by MXene is continuously increased until the surface temperature is stable, and the temperature of the composite membrane is increased more obviously along with the increase of the MXene content and has concentration dependence. The thermal stimulation is beneficial to promote osteogenesis. The experimental result indicates that the MXene modified composite membrane has stable and controllable photo-thermal performance, can meet the conditions required by bone formation, and is expected to be applied to the field of biomedicine as a photo-thermal controllable biological material.
Finally, it should be noted that: the above embodiments are only preferred embodiments of the present invention to illustrate the technical solutions of the present invention, but not to limit the technical solutions, and certainly not to limit the patent scope of the present invention; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention; that is, the technical problems to be solved by the present invention, which are not substantially changed or supplemented by the spirit and the concept of the main body of the present invention, are still consistent with the present invention and shall be included in the scope of the present invention; in addition, the technical scheme of the invention is directly or indirectly applied to other related technical fields, and the technical scheme is included in the patent protection scope of the invention.
Claims (9)
1. The piezoelectric-photothermal double-response MXene/PVDF composite membrane is characterized in that PVDF and two-dimensional MXene are used as raw materials and are prepared by electrostatic spinning, wherein the content of the two-dimensional MXene in the composite membrane is 0.2-5 wt.%.
2. The piezoelectric-photothermal dual response MXene/PVDF composite film according to claim 1, wherein the thickness of the composite film is 60 ± 5 μm.
3. The preparation method of the piezoelectric-photothermal double response MXene/PVDF composite membrane as claimed in claim 1 or 2, characterized by comprising the following steps:
step 1, preparing a PVDF solution: adding PVDF into a solvent, and stirring until the solution is transparent to obtain a PVDF solution;
step 2, preparing MXene/PVDF solution: adding two-dimensional MXene powder into the PVDF solution, and uniformly stirring to obtain MXene/PVDF solution;
and 3, taking the MXene/PVDF solution, carrying out electrostatic spinning and drying to obtain the MXene/PVDF composite membrane.
4. The method according to claim 3, wherein the solvent used in step 1 is a mixed solution of N, N-dimethylformamide and acetone, and the volume ratio of N, N-dimethylformamide to acetone is 3: 2.
5. The preparation method according to claim 3 or 4, wherein in the step 1, the mass-to-volume ratio of the PVDF to the solvent is 15-20: 100, mass unit is g, volume unit is ml.
6. The preparation method according to claim 5, wherein in the step 2, the mass of the two-dimensional MXene powder accounts for 0.2-5 wt% of the total mass of the two-dimensional MXene powder and the PVDF.
7. The method according to claim 6, wherein the conditions for the electrospinning in the step 3 are: the voltage is-1.5/11.5 KV, or/and the receiving distance of the needle head and the aluminum foil roller is 15cm, or/and the flow rate of the spinning solution is 0.08 mm/min.
8. The method according to claim 7, wherein the conditions for electrospinning in step 3 are as follows: the voltage is-1.5/11.5 KV, or/and the receiving distance of the needle head and the aluminum foil roller is 15cm, or/and the flow rate of the spinning solution is 0.08 mm/min.
9. Use of the piezoelectric-photothermal double response MXene/PVDF composite membrane according to claim 1 or 2 in preparation of a material for treating bone defect.
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