Near-equal-diameter organic-inorganic hybrid nanostructure fiber with ultrahigh inorganic phase ratio, functional coating, preparation method and application

Abstract

A preparation method of a near-isometric ultrahigh inorganic phase ratio organic-inorganic hybrid nanostructure fiber and a functional coating comprises the following steps: adding cetyltrimethylammonium bromide and ammonia water into a solvent, stirring, adding tetraorthosilicate and CaCl2, continuously stirring, filtering, washing and centrifuging to obtain powder, drying and grinding to obtain the near-isometric ultrahigh inorganic phase ratio organic-inorganic hybrid nanostructure fiber. Calcining to obtain nano calcium silicate particles; dispersing the nano calcium silicate particles in a solvent, adding alendronate, adjusting the pH value, and then centrifugally drying to obtain drug-loaded nano calcium silicate particles; the preparation method comprises the following steps: adding PCL (Polycaprolactone) into chitosan, then adding drug-loaded nano calcium silicate particles, mixing and dissolving to obtain a spinning solution, and then preparing the near-equal-diameter organic-inorganic hybrid nano-structure fiber with ultrahigh inorganic phase ratio on a substrate by adopting electrostatic spinning to obtain the functional coating of the near-equal-diameter organic-inorganic hybrid nano-structure fiber.

Description

Technical Field

[0001] The present invention belongs to the technical field of nanomaterials, and relates to an organic-inorganic hybrid nanostructured fiber with a nearly equal diameter and a high inorganic phase proportion, a functional coating, a preparation method and an application thereof. Background Art

[0002] Nanofiber materials (such as electrospinning) have been widely used in the fields of environment, energy, catalysis and biomedicine due to their large specific surface area, high porosity, and controllable structure, size and morphology. The organic-inorganic hybrid fibers obtained by mixing inorganic and organic phases have more excellent properties. The proportion of the inorganic phase in the hybrid fiber is very crucial for the properties of the hybrid fiber.

[0003] In the existing research on hybrid fibers, inorganic phases such as inorganic bioactive nanomaterials, carbon nanomaterials or metal oxide nanomaterials are generally used as guest phases to be compounded with the organic host phase to prepare hybrid fibers. The traditional process usually disperses the inorganic phase in the organic phase for coaxial electrospinning, but this technology has the following significant defects: First, with the increase in the addition amount of the inorganic phase, the number of discontinuous connection points between the two phases surges, resulting in the deterioration of the overall connectivity of the material, severely weakening the process formability and mechanical properties, and even causing the fibers to fail to form.

[0004] From a process perspective, in the existing technology, when the addition amount of the inorganic phase exceeds the critical value, it is easy to cause agglomeration and blockage of the electrospinning needle holes, significantly change the viscosity and conductivity of the electrospinning solution, and destroy the stability of the electrospinning electric field, ultimately resulting in the failure of electrospinning. Moreover, the high density and high hardness characteristics of the inorganic phase have significant physical and chemical differences from the organic phase, resulting in poor interfacial compatibility between the two phases. At the same time, a high inorganic proportion will further cause uneven fiber diameters and stress concentration when stressed, seriously affecting the uniformity and mechanical strength of the fibers.

[0005] Currently, although there are methods such as microfluidics-assisted and magnetic field-induced orientation to increase the proportion of the inorganic phase in the hybrid fiber, these methods also have some problems, such as strong dependence on equipment, complex operation processes, limited applicable electrospinning systems, and limited effects in increasing the proportion of the inorganic phase. In summary, for the problems of low inorganic phase proportion and non-formability of fibers with a high inorganic phase proportion widely existing in the existing technology, there is an urgent need for an organic-inorganic hybrid nanostructured fiber with a nearly equal diameter and a high inorganic phase proportion, a functional coating and a preparation method thereof to solve the intractable technical problems. Summary of the Invention

[0006] Aiming at the problems of low inorganic phase proportion and non-formability of fibers with a high inorganic phase proportion existing in the prior art.

[0007] By combining chemical sol-gel with the template method, inorganic nanoparticles with a diameter nearly equal to that of the desired fiber are prepared; by surface-modifying the inorganic nanoparticles, a highly binding guest phase is constructed, which can achieve potential physical adsorption and chemical bonding with the polymer host phase while suppressing the host-guest phase separation and ensuring uniform dispersion of the particles; moreover, functional molecules such as drugs can be loaded before or simultaneously with the surface modification, and auxiliary components for binding and filament formation (which can also take into account functions such as biological activity) can be added to the host-phase polymer. Then, through the organic-inorganic blend spinning technology, the mixture of the host and guest phases is controllably extruded, and combined with the electric field stretching effect, an organic-inorganic hybrid nanostructured fiber with a nearly equal diameter and a very high inorganic phase ratio and a functional coating are prepared and formed. This principle is applicable to a variety of inorganic / polymer systems, and by adjusting the types of modifiers, solution formulations, and electric field parameters, composite structures with a nearly equal diameter and a very high inorganic phase ratio can be generally prepared.

[0008] In summary, this method combines organic-inorganic phase interface chemical modification and mixture property regulation with micro-nano fiber preparation technology (such as electrospinning) to prepare a stable and uniform hybrid fiber structure with a very high inorganic phase ratio at the nanoscale, thereby solving the problems and difficulties in the prior art that fibers with a high inorganic phase ratio cannot be formed and thus the inorganic phase ratio is too low.

[0009] The present invention provides a method for preparing an organic-inorganic hybrid nanostructured fiber and a functional coating with a nearly equal diameter and a very high inorganic phase ratio, comprising the following steps:

[0010] S1; Cetyltrimethylammonium bromide and ammonia water are put into a solvent and stirred, tetraethyl orthosilicate and CaCl2 are added, and stirring is continued. After filtration and washing, centrifugation is carried out to obtain a powder, which is dried, ground, and then calcined to obtain calcium silicate nanoparticles;

[0011] S2: The calcium silicate nanoparticles obtained in S1 are dispersed in a solvent, alendronate is added, the pH is adjusted, and then centrifuged and dried to obtain drug-loaded calcium silicate nanoparticles;

[0012] S3: The degradable metal is polished and then cleaned and dried to obtain a substrate; PCL is added to chitosan, and the mass ratio of PCL to chitosan is 1-10:10-1; then the drug-loaded calcium silicate nanoparticles in S2 are added. After mixing and dissolving, a spinning solution is obtained, and an organic-inorganic hybrid nanostructured fiber with a nearly equal diameter and a very high inorganic phase ratio and its functional coating are prepared on the substrate by electrospinning.

[0013] Further, the volume ratio of the ammonia water to the solvent in S1 is 1:10-100.

[0014] Further, the stirring time in S1 is 30 min, the temperature during centrifugation is 25°C, the centrifugation rate is 8500 rpm, the centrifugation time is 10 min, the drying temperature is 60°C, the calcination temperature is 300 - 800°C, and the calcination time is 2 h.

[0015] Further, the solvents in S2 include single or mixed solutions such as water, ethanol, dichloromethane, formic acid, acetic acid, etc.; the pH value is 1 - 12, the centrifugation rate is 8000 rpm, and the centrifugation temperature is 25°C.

[0016] Further, the spinning parameters during the electrospinning process in S3 are a positive voltage of 5 - 20 kV, a negative voltage of 2 kV, a spinning speed of 0.15 mm / h, an acceptance distance of 15 cm, and a spinning time of 3 h.

[0017] An organic - inorganic hybrid nanostructured fiber with a nearly equal - diameter and a high inorganic phase ratio, wherein the fiber is an organic - inorganic composite structure with functionalized inorganic nanoparticles inside, and the functionalized inorganic nanoparticles are nearly equal - diameter to the fiber.

[0018] A functional coating for an organic - inorganic hybrid nanostructured fiber with a nearly equal - diameter and a high inorganic phase ratio, wherein the functional coating is a multi - component, multi - level three - dimensional chimeric structure.

[0019] An application of a functional coating formed by an organic - inorganic hybrid nanostructured fiber with a nearly equal - diameter and a high inorganic phase ratio, characterized in that the functional coating can be used for a surface functionalized modification layer.

[0020] Beneficial effects

[0021] Through an organic - inorganic hybrid nanostructured fiber with a nearly equal - diameter and a high inorganic phase ratio and a functional coating provided by the present invention, wherein the composite structure of spherical inorganic nanoparticles and the fiber with nearly equal - diameter enables the proportion of inorganic nanoparticles to be greatly increased compared with 10% - 20% in the prior art. Through the nearly equal - diameter hybridization on the nanoscale by the present invention, the inorganic phase ratio can reach 30% - 50%. Furthermore, it solves the problems of low inorganic phase ratio and the inability to form fibers with a high inorganic phase ratio in the prior art.

[0022] Through a preparation method of an organic - inorganic hybrid nanostructured fiber with a nearly equal - diameter and a high inorganic phase ratio and a functional coating provided by the present invention, the equidistant distribution of spherical nanoparticles loaded with drugs and the fiber during the preparation process can increase the proportion of inorganic components in the fiber, solve the technical problem of difficult electrospinning due to too high inorganic components, and can fully exert the functional role of the inorganic phase in the hybrid fiber.

[0023] Through the application of an organic-inorganic hybrid nanostructured fiber and a functional coating with a nearly equal diameter and a high inorganic phase ratio provided by the present invention, through the design of loading drugs with calcium silicate inorganic nanoparticles and then loading them into the fibers, the drug release behavior can be better controlled, the drug release period can be longer, and the initial drug burst release can be avoided. This cannot be achieved by single components and two combinations, and the drug loading amount of calcium silicate inorganic nanoparticles can be adjusted and designed according to requirements to meet the drug amount requirements; at the same time, calcium silicate inorganic nanoparticles can load different types of drugs, have a certain range of practicability, and can be used in different scenarios. The functional coating provided by the present invention can be used as a surface functional modification layer, which can endow degradable bone implant materials (such as zinc and alloys, magnesium and alloys) with the ability of long-term and stable drug controlled release. Cooperating with the multi-dimensional multi-component and ultra-high inorganic bioactive phase ratio of the coating itself, it can regulate the bone regeneration microenvironment, realize anti-inflammatory, antibacterial and "vascularization-osteogenesis" coupled bone regeneration repair, and realize the dynamically adaptive bone healing function. Similarly, the unique nanofibers with a high inorganic phase ratio can be extended to applications in tissue engineering scaffolds, long-term and stable drug-targeted tumor treatment, intelligent responsive tissue repair dressings and other fields Description of the Drawings

[0024] In order to more clearly illustrate the technical solutions of the exemplary embodiments of the present invention, the drawings required for use in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present invention, and therefore should not be regarded as limiting the scope. For those of ordinary skill in the art, without creative efforts, other related drawings can also be obtained based on these drawings. In the drawings:

[0025] Figure 1 SEM and FTIR diagrams of the synthesized calcium silicate nanoparticles (CS) and drug-loaded nanoparticles (AL@CS) in Example 1 of the present invention;

[0026] Figure 2 TEM of the drug-loaded nanoparticle composite organic fiber (PCS&AL@CS) of the present invention, SEM diagrams of the surface and cross-section of the composite nanofiber three-dimensional coating;

[0027] Figure 3 Potentiodynamic polarization diagrams of Zn, Zn modified with the composite nanofiber three-dimensional coating, and PCS&AL@CS of the present invention;

[0028] Figure 4 Diagrams of the corrosion conditions of Zn, Zn modified with the composite nanofiber three-dimensional coating, and PCS&AL@CS samples of the present invention after soaking for 21 days;

[0029] Figure 5In vitro CaP deposition, ARS staining and ALP activity diagrams of the Zn and composite nanofiber three-dimensional coating modified Zn, PCS&AL@CS samples of the present invention;

[0030] Figure 6 Colony diagrams of the Zn and composite nanofiber three-dimensional coating modified Zn, PCS&AL@CS samples of the present invention. Detailed implementation manners

[0031] Next, in combination with Examples 1 to 4 of the present invention and the attached Figures 1 to 6 , the technical solutions in the embodiments of the present invention will be clearly and completely described. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts shall fall within the protection scope of the present invention.

[0032] The creativity and practical progress of the present invention are reflected in the creative ideas and the progress of the substantial fiber structure. First, hydrophobic polycaprolactone (PCL) is selected, and chitosan (CS) is added to adjust the properties of the PCL solution (conductivity, viscosity) so that the PCL / CS mixed spinning solution can spin out nano-scale matrix fibers, and at the same time, the antibacterial performance, hydrophilicity, etc. can also be improved. Secondly, nano-scale spherical (spherical is beneficial for regular and uniform distribution) calcium silicate inorganic particles are independently synthesized, and alendronate drugs are loaded on the calcium silicate nano-particles (this is only a demonstration drug, and it can be loaded by adjusting the pH so that the drug and the calcium silicate particles have different electric charges). Then, the drug-loaded nano-particles are blended in the PCL / CS spinning solution in the simplest way. In the preparation of the spinning solution, the proportions of PCL and CS, concentration, solvent system, etc. should be adjusted to ensure that the viscosity of the spinning solution can spin the fibers and at the same time can play a forced dispersion role on the nano-particles. Finally, by selecting appropriate electrospinning parameters, a structure of functionalized inorganic nano-particles and nano-fiber isodiametric organic-inorganic composites is obtained. This structure can make the inorganic particles mix more evenly in the fibers and avoid agglomeration. At the same time, due to the proportion of the blended inorganic phase at the nano-scale can reach 30% - 50%.

[0033] Example 1

[0034] S1: First, add 3.3g of hexadecyltrimethylammonium bromide (CTAB) with a concentration of 0.001g / ml and 6mL of ammonia water into 300mL of deionized water, stir for 30min, then add 15mL of tetraethylorthosilicate (TEOS) and 15.60gCaCl2, and continue stirring for 3 hours; filter and wash with deionized water and ethanol three times each. Then, centrifuge for 10 minutes at 25°C and 8500rpm. The collected powder is dried at 60°C and ground with a grinding mortar, and finally calcined in a tubular furnace at 550°C for 2 hours to obtain nano calcium silicate particles;

[0035] S2: Disperse the nano calcium silicate particles obtained in S1 in a single or mixed solution of water, ethanol, dichloromethane, formic acid, acetic acid, etc., add 300umol / L of alendronic acid, adjust the pH value to 1, shake well and centrifuge at a centrifugal speed of 8000rpm and a centrifugal temperature of 25°C; after centrifugation, take out and dry for use, to obtain drug-loaded nano calcium silicate particles;

[0036] S3: Grind the metal zinc with sandpaper, then wash it three times with deionized water, ethanol and acetone. Dry the washed sample in a vacuum dryer to obtain a substrate, then add 1g of PCL to 10g of chitosan, and then add 1% drug-loaded nano-calcium silicate particles, mix and dissolve them thoroughly to obtain a configured electrospinning solution, and then adjust the positive voltage of electrospinning to 20kV, the negative voltage to 2kV, the speed to 0.15mm / h, and the spinning time to 3h. After the electrospinning is completed, vacuum drying is performed to obtain organic-inorganic hybrid nanostructured fibers and functional coatings with a near-equal diameter and ultra-high inorganic phase ratio.

[0037] Combination Figure 1 , Figure 1 (a) SEM images of calcium silicate nanoparticles (CS) and drug-loaded nanoparticles (AL@CS); Figure 1 (b) FTIR images of calcium silicate nanoparticles (CS) and drug-loaded nanoparticles (AL@CS); Figure 1 It can be seen that calcium silicate nanoparticles have been successfully synthesized and alendronic acid has been successfully loaded.

[0038] Combination Figure 2 , Figure 2 (a) TEM image of drug-loaded nanoparticle composite organic fiber (PCS&AL@CS). Figure 2 (b) is the surface image of the composite nanofiber three-dimensional coating; Figure 2 (c) is the cross-sectional SEM image of the composite nanofiber three-dimensional coating; Figure 2 The study showed that drug-loaded nanoparticles were integrated into nanofibers, and a composite nanofiber three-dimensional coating was constructed on zinc with a coating thickness of about 42 microns.

[0039] Combined with Figure 3 , Figure 3 it shows that from the perspective of short-term transient, the composite nanofiber three-dimensional coating has a certain protective effect on the zinc substrate; combined with Figure 4 , Figure 4 (a) is the optical microscope image of the corrosion situation of the Zn and the composite nanofiber three-dimensional coating modified Zn (PCS&AL@CS) samples after being soaked for 21 days; Figure 4 (b) is the SEM image;

[0040] Figure 4 (c) is the Zn 2+ release diagram; it can be seen from Figure 4 that the composite nanofiber three-dimensional coating reduces the local corrosion of zinc during long-term soaking and reduces the release of zinc ions.

[0041] Combined with Figure 5 it shows that the composite nanofiber three-dimensional coating enables zinc to have better ability to induce CaP deposition and osteogenic differentiation. It can be seen from Figure 6 that the zinc substrate with the surface composite nanofiber three-dimensional coating has better antibacterial properties against Escherichia coli and Staphylococcus epidermidis.

[0042] Example 2

[0043] S1: First, 3.3 g of cetyltrimethylammonium bromide (CTAB) with a concentration of 10 g / ml and 6 mL of ammonia water are added to 300 mL of deionized water, stirred for 30 min, then 15 mL of tetraethyl orthosilicate (TEOS) and 15.60 g of CaCl2 are added, and stirring is continued for 3 hours; filtered and washed three times with deionized water and ethanol respectively. Then, under the conditions of 25 °C and 8500 rpm, centrifuged for 10 minutes with a centrifuge. The collected powder is dried at 60 °C, ground with a mortar, and finally calcined in a tube furnace at 550 °C for 2 hours to obtain calcium nanosilicate particles;

[0044] S2: The calcium nanosilicate particles obtained in S1 are dispersed in water, ethanol, dichloromethane and their mixed solutions, dexamethasone with a concentration of 300 μmol / L is added, the pH value is adjusted to 12, shaken well and centrifuged, the centrifugation rate is 8000 rpm, and the centrifugation temperature is 25 °C; after centrifugation, taken out and dried for standby to obtain drug-loaded calcium nanosilicate particles;

[0045] S3: Grind the metal zinc with sandpaper, then wash it three times with deionized water, ethanol and acetone. Dry the washed sample in a vacuum dryer to obtain a substrate, then add 5g of PCL to 1g of chitosan, and then add 5% drug-loaded nano-calcium silicate particles, mix and dissolve them thoroughly to obtain a configured electrospinning solution, and then adjust the positive voltage of electrospinning to 20kV, the negative voltage to 2kV, the speed to 0.15mm / h, and the spinning time to 3h. After the electrospinning is completed, vacuum drying is performed to obtain organic-inorganic hybrid nanostructured fibers and functional coatings with a near-equal diameter and ultra-high inorganic phase ratio.

[0046] Example 3

[0047] S1: First, add 3.3g of 5g / ml hexadecyltrimethylammonium bromide (CTAB) and 6mL of ammonia water into 300mL of deionized water, stir for 30min, then add 15mL of tetraethylorthosilicate (TEOS) and 15.60gCaCl2, and continue stirring for 3 hours; filter and wash with deionized water and ethanol three times each. Then, centrifuge at 25°C and 8500rpm for 10 minutes. The collected powder is dried at 60°C and ground with a grinding mortar, and finally calcined in a tubular furnace at 550°C for 2 hours to obtain nano calcium silicate particles;

[0048] S2: Disperse the nano calcium silicate particles obtained in S1 in water, ethanol, dichloromethane and a mixed solution thereof, add doxorubicin at a concentration of 300umol / L, adjust the pH value to 3, shake well and centrifuge at a centrifugal speed of 8000rpm and a centrifugal temperature of 25°C; after centrifugation, take out and dry for later use, to obtain drug-loaded nano calcium silicate particles;

[0049] S3: The metal iron was polished with sandpaper, and then washed with deionized water, ethanol, and acetone three times. The washed sample was dried in a vacuum dryer to obtain a substrate, and then 7g of PCL was added to 1g of chitosan, and then 10% of drug-loaded nano-calcium silicate particles were added, and the mixture was fully mixed and dissolved to obtain a configured electrospinning solution. The positive voltage of the electrospinning was adjusted to 20kV, the negative voltage was 2kV, the speed was 0.15mm / h, and the spinning time was 3h. After the electrospinning was completed, vacuum drying was performed to obtain organic-inorganic hybrid nanostructured fibers and functional coatings with a near-equal diameter and ultra-high inorganic phase ratio.

[0050] Example 4

[0051] S1: First, add 3.3g of 7g / ml hexadecyltrimethylammonium bromide (CTAB) and 6mL of ammonia water into 300mL of deionized water, stir for 30min, then add 15mL of tetraethylorthosilicate (TEOS) and 15.60gCaCl2, and continue stirring for 3 hours; filter and wash with deionized water and ethanol three times each. Then, centrifuge for 10 minutes at 25°C and 8500rpm. The collected powder is dried at 60°C and ground with a grinding mortar, and finally calcined in a tubular furnace at 550°C for 2 hours to obtain nano calcium silicate particles;

[0052] S2: Disperse the nano calcium silicate particles obtained in S1 in water, ethanol, dichloromethane and a mixed solution thereof, add cisplatin at a concentration of 300umol / L, adjust the pH value to 11, shake well and centrifuge at a centrifugal speed of 8000rpm and a centrifugal temperature of 25°C; after centrifugation, take out and dry for later use, to obtain drug-loaded nano calcium silicate particles;

[0053] S3: The metal iron was polished with sandpaper, and then washed with deionized water, ethanol, and acetone three times. The washed sample was dried in a vacuum dryer to obtain a substrate, and then 10g of PCL was added to 1g of chitosan, and then 20% of drug-loaded nano-calcium silicate particles were added, and the mixture was fully mixed and dissolved to obtain a configured electrospinning solution. The positive voltage of the electrospinning was adjusted to 20kV, the negative voltage was 2kV, the speed was 0.15mm / h, and the spinning time was 3h. After the electrospinning was completed, vacuum drying was performed to obtain an organic-inorganic hybrid nanostructured fiber and a functional coating with a near-equal diameter and ultra-high inorganic phase ratio.

[0054] The present invention provides an organic-inorganic hybrid nanostructured fiber with a near-equal diameter and ultra-high inorganic phase ratio and a functional coating.

[0055] The organic-inorganic hybrid nanostructured fiber and functional coating with near-equal diameter and ultra-high inorganic phase ratio provided by the present invention realizes a significant increase in the inorganic phase ratio by innovatively constructing a near-equal diameter composite system of spherical calcium silicate nanoparticles and an organic fiber matrix, breaking through the limitation of about 10%-20% of the traditional non-equal diameter composite structure. Its preparation method adopts drug-preloaded calcium silicate nanoparticles and fiber equal diameter distribution technology, thereby effectively solving the technical bottleneck of large-sized inorganic components being difficult to spin.

[0056] Moreover, the functional synergistic effect was fully exerted through the synergistic optimization of the inorganic-organic phases. Specifically, nanoscale spherical inorganic nanoparticles were synthesized, and the Zeta potentials of the inorganic nanoparticles and the drug were changed by pH adjustment, so that the two were adsorbed together through electrostatic interaction. Then, the inorganic nanoparticles were modified to improve their compatibility with organic fibers. Natural molecules were added to the main-phase polymer with good spinnability and blended with the main-phase polymer to adjust the properties of the spinning solution, so as to obtain a fiber matrix that matches the size of the inorganic functional particles. The addition of the auxiliary molecule was entangled and compatible with the main phase on one side and had polar-polar interactions with the modified inorganic nanoparticles on the other side, enhancing the overall compatibility to ensure the mechanical properties. The functionalized inorganic nanoparticles were mixed with the spinning solution and electrospun by a suitable process to obtain a structure in which the functionalized inorganic nanoparticles and the organic fibers were nearly equidiameter organic-inorganic composites, enabling the proportion of the blended inorganic phase to reach 30% to over 50%.

[0057] At the application level, this structure achieved precise control of drug release behavior through a three-level sequential control release mechanism (inorganic particle loading - fiber encapsulation - coating regulation), effectively overcoming the initial burst release effect existing in traditional single carriers or simple composite systems and prolonging the effective drug release period. In particular, it can regulate the bone regeneration microenvironment from multiple dimensions and multiple components, synergistically achieve anti-inflammatory, antibacterial, and "angiogenesis-osteogenesis" coupled long-term and stable promotion of bone regeneration and repair, and realize highly dynamic and adaptable bone healing ability. Similarly, this design is compatible with the flexible regulation of different drug types and loading amounts. By adjusting the pore size structure and surface properties of the inorganic phase particles, it can adapt to various functional requirements such as antibacterial, anti-tumor, tissue regeneration, and wound healing promotion, showing practical advantages in the fields of tissue engineering scaffolds, long-term and stable drug-targeted tumor treatment, medical dressings, intelligent coatings, etc.

Claims

1. A method for preparing an organic-inorganic hybrid nanostructured fiber with a near-equal diameter and ultra-high inorganic phase ratio and a functional coating, characterized in that: The following steps are involved: S1; hexadecyltrimethylammonium bromide and ammonia water are put into a solvent and stirred, tetraorthosilicate and CaCl2 are added, stirring is continued, filtered and washed, and then centrifuged to obtain a powder, which is dried and ground, and then calcined to obtain nano calcium silicate particles; S2: dispersing the nano calcium silicate particles obtained in S1 in a solvent, adding alendronate, adjusting the pH, and then centrifuging and drying to obtain drug-loaded nano calcium silicate particles; S3: grinding the degradable metal, then cleaning and drying to obtain a substrate; adding PCL to chitosan, wherein the mass ratio of PCL to chitosan is 1-10:10-1; adding the drug-loaded nano calcium silicate particles in S2, mixing to obtain a spinning solution, and then using electrospinning to prepare an organic-inorganic hybrid nanostructured fiber with a nearly equal diameter and ultra-high inorganic phase ratio and its functional coating on the substrate.

2. The method for preparing a nearly equal diameter ultra-high inorganic phase ratio organic-inorganic hybrid nanostructured fiber and functional coating according to claim 1, characterized in that: The volume ratio of the ammonia water to the solvent described in S1 is 1:10-100.

3. The method for preparing a nearly equal diameter ultra-high inorganic phase ratio organic-inorganic hybrid nanostructured fiber and functional coating according to claim 1, characterized in that: The stirring time described in S1 is 30 minutes, the temperature of the centrifugal process is 25°C, the centrifugal speed is 8500rpm, the centrifugal time is 10 minutes, the drying temperature is 60°C, the calcination temperature is 300-800°C, and the calcination time is 2 hours.

4. The method for preparing a nearly equal diameter ultra-high inorganic phase ratio organic-inorganic hybrid nanostructured fiber and functional coating according to claim 1, characterized in that: The solvent described in S2 includes water, ethanol, dichloromethane, formic acid, acetic acid and the like in a single or mixed solution; the pH value is 1 to 12, the centrifugal speed is 8000 rpm, and the centrifugal temperature is 25°C.

5. The method for preparing a nearly equal diameter ultra-high inorganic phase ratio organic-inorganic hybrid nanostructured fiber and functional coating according to claim 1, characterized in that: The spinning parameters in the electrospinning process described in S3 are positive voltage 5-20 kV negative voltage 2 kV, spinning speed 0.15 mm / h, receiving distance 15 cm, and spinning time 3 h.

6. An organic-inorganic hybrid nanostructured fiber with a near-equal diameter and ultra-high inorganic phase ratio obtained by the preparation method according to any one of claims 1 to 5, characterized in that: The fiber is an organic-inorganic composite structure with functionalized inorganic nanoparticles inside, and the diameters of the functionalized inorganic nanoparticles and the fiber are nearly equal.

7. A functional coating formed by using an organic-inorganic hybrid nanostructured fiber with a near-equal diameter and ultra-high inorganic phase ratio as claimed in claim 6, characterized in that: The functional coating is a multi-component, multi-layered three-dimensional mosaic structure.

8. The use of the functional coating formed by the organic-inorganic hybrid nanostructured fiber with a near-equal diameter and ultra-high inorganic phase ratio according to claim 7, characterized in that: The functional coating can be used for a surface functional modification layer.

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