KR101283355B1 - Fabrication and characterization of hybrid pvac/mulberry fibers composite nanofibrous mats as scaffold for tissue enginnering - Google Patents

Abstract

PURPOSE: A manufacturing method of a carrier for regenerating a PVAc polymer/dak fiber tissue in which an organic particle and an inorganic particle are hybridized is provided to effectively induce a growth of hydroxyapatite which has a same component with a bone because a silicon particle is evenly dispersed and a crystallization is excellent. CONSTITUTION: A manufacturing method of a carrier for regenerating a PVAc polymer/dak fiber tissue in which an organic particle and an inorganic particle are hybridized includes following steps. A complex is obtained by directly electrospinning a PVAc solution which includes a polyhedral oligomeric silsesquioxane (POSS) nano particle on a surface of a dak fiber paper. The complex is siliconized. The PVAs solution which includes the POSS nano particle is made by mixing a dispersed POSS with a tetrahydrofuran in the PVAc solution.

Description

Fabrication and Characterization of Hybrid PVAc / Mulberry Fibers Composite Nanofibrous Mats as Scaffold for Tissue Enginnering}

The present invention relates to a method for preparing an organic-inorganic hybridized PVAc polymer / dough fiber tissue regeneration carrier which can be used for various purposes such as a scaffold.

Bio-tissue engineering is to restore the function of the human body by applying the concepts and techniques of bioscience and engineering to understand the structure and function of biological tissues and to transplant the alternative tissues into damaged biological tissues. There are three elements of tissue engineering: cells, scaffolds, and activating factors. To construct tissues artificially, it is necessary to create a human-like environment that can regulate the physiological activities of cells based on cells and scaffolds. Recently, support for tissue regeneration has been developed in various fields such as nerves, skin, skeleton, cartilage and teeth due to the development of biotissue engineering technology.

Tissue engineering to help bone growth is an important technique in biotissue engineering. In regeneration of bone tissue, scaffolds play a very important role as scaffolds for cell growth. In general, scaffolds should be suitable for biocompatibility, biodegradation, control of degradation rate, and cell proliferation and differentiation. It must also have interconnected porous networks and three-dimensional porous structures.

Bone can self-renew when damage is small, but large damage requires a scaffold to induce bone cells and support bone tissue. As a biomaterial for inducing the growth of bone cells, hydroxyapatite having the same structure as the main component of bones and teeth of the human body has been used, and silica is also being actively researched as an important mineral for bone formation.

The polymers used in scarbold include chitosan, polylactic acid (PLA), polyglycolic acid (PGA), and polyvinyl acetate (PVAc).

Research on hybrid composite materials using conventional nonwoven fabrics has been developed to improve the chemical and mechanical properties of each material. Hybrid composite materials can be classified into metal-inorganic, metal-organic and organic-inorganic composites. The composite research trend can be seen in terms of structural materials and functional materials. In terms of structural materials, there are studies related to the mechanical, thermal, and chemical properties of nanotubes, nanoclays, nano inorganics, metal fibers, and nano inorganic particle-polymer reinforced composites. In terms of functional materials, the material itself is a study on smart materials such as self-recovery, self-diagnosis, stimulus response, etc. There is research on the synthesis of nanocomposites. One of the attempts to make smart materials is to control the size of the dispersed phase of the composite material at the nano level or the molecular level to impart high functionality to the material. Is attracting attention as a new technology.

According to the present invention, silicon particles are evenly distributed and excellent in crystallinity, which can effectively induce the growth of hydroxyapatite having the same component as bone, and thus can produce siliconized Doc fiber composites that can be used for various purposes such as scaffolds. An object of the present invention is to provide a method for preparing an organic-inorganic hybridized PVAc polymer / dough fiber tissue regeneration.

According to an aspect of the present invention,

Obtaining a complex by directly electrospinning a PVAc solution containing polyhedral oligomeric silsesquioxane (POSS) nanoparticles on the surface of a paper mulberry paper;

It provides a method for producing a carrier for organic-inorganic hybridized PVAc polymer / dough fiber tissue regeneration, characterized in that it comprises a; siliconizing the complex.

In particular, the PVAc solution containing the POSS nanoparticles is preferably made by mixing POSS dispersed in tetrahydrofuran with PVAc solution dissolved in N, N-dimethylformamide (DMF).

In addition, the complex is preferably immersed in a silicic acid solution to be silicified, and in particular, the complex is preferably immersed in a silicic acid solution and left at least 12 hours in a high temperature and high humidity atmosphere to be silicified.

Hereinafter, a method for preparing the organic-inorganic hybridized PVAc polymer / dough fiber tissue regeneration carrier of the present invention will be described in detail.

The method for preparing an organic-inorganic hybridized PVAc polymer / dough fiber tissue regeneration carrier of the present invention comprises a complex forming step and a siliconization step.

First, in the complex forming step, a PVAc solution containing organic-inorganic hybrid nanoparticles is directly electrospun onto the surface of a paper fiber to obtain a composite.

The PVAc solution containing the organic-inorganic hybrid nanoparticles is preferably a PVAc solution in which polyhedral oligomeric silsesquioxane (POSS) nanoparticles are dispersed.

The POSS nanoparticles are cage-type having a basic structure of Si, O and R, and are organic-inorganic hybrid nanoparticles having a size of 1 to 3 nm. As the POSS nanoparticles are dispersed in the PVAc solution, the electrical conductivity of the PVAc solution may be increased to form thinner and more uniform nanofibers during electrospinning. Not only can it promote crystal formation, but also it can prevent shrinkage of PVAc nanofibers and maintain pores after siliconization treatment.

Since the POSS nanoparticles do not have good dispersibility, the POSS nanoparticles were dispersed using a PVAc solution having good dispersibility of POSS nanoparticles and easy electrospinning.

On the other hand, in order to improve the dispersibility of the POSS nanoparticles, POSS nanoparticles and PVAc may be used after being dispersed or dissolved by using an organic solvent, respectively. In this case, Tetrahydrofuran (THF) may be used as the organic solvent of the POSS nanoparticles, and N, N-dimethylformamdie (DMF) may be used as the organic solvent of the PVAc.

In addition, the mulberry fiber paper is composed of cellulose, lignin and other minor components as a main component, and the content of cellulose is high among natural bast fibers. In particular, the paper mulberry paper has excellent properties such as breathability and biocompatibility, nontoxic.

The PVAc solution containing the organic-inorganic hybrid nanoparticles is directly electrospun onto the surface of the paper fiber to prepare a composite.

In this case, the composite is prepared by directly electrospinning the PVAc solution containing the organic-inorganic hybrid nanoparticles to the mulberry fiber paper while the mulberry fiber is seated or continuously supplied to the collector of the electrospinning apparatus. At this time, the doc fiber paper is supplied to the collector of the electrospinning apparatus in a wet state.

Next, the siliconization step is a step for increasing the Si crystal formation of the composite. The method of siliconization of the complex is not particularly limited, but it is preferable that the complex is immersed in a silicic acid solution and subjected to siliconization. As a silicic acid solution, Tetrahydroxysilan (THOS) solution prepared by adding tetramethyl orthosilicate (TMOS) to an aqueous HCl solution can be used.

In order to improve the siliconization effect of the composite, it is preferable to leave the composite in a silicic acid solution and then leave it for 12 hours or more in a high temperature and high humidity atmosphere.

On the other hand, the attraction between the Si of the POSS contained in the composite and Si of the silicic acid solution in the siliconization step has the advantage that the Si crystal formation is further promoted to increase.

The method for preparing the organic-inorganic hybridized PVAc polymer / dough fiber tissue regenerating carrier according to the present invention is capable of effectively inducing the growth of hydroxyapatite having the same components as bone because silicon particles are evenly distributed and excellent in crystallinity. There is an effect that can be produced a siliconized mulberry fiber composite can be used for a variety of uses.

1 and 2 are SEM photographs of the nanofiber nonwoven fabrics of Example 1 and Comparative Example 1. FIG.
3 and 4 are graphs showing the measurement of the nanofiber diameter of the nanofiber nonwoven fabric of Example 1 and Comparative Example 1.
5 and 6 are photographs of the composite of Example 2 and Comparative Example 2 immersed in a silicic acid solution.
7 and 8 are SEM photographs of the composite of siliconized Example 2 and Comparative Example 2.
9 is a diagram illustrating chemical structure analysis using an infrared spectrophotometer.

Hereinafter, the method for preparing the organic-inorganic hybridized PVAc polymer / dough fiber tissue regeneration carrier according to the present invention will be described in detail with reference to the following Examples. The scope of the present invention is not limited to the following examples.

Example 1

10 wt% polyhedral oligosilsesquixane (POSS) solution dissolved in tetrahydrofuran (THF) was mixed with 17 wt% PVAc solution dissolved in N, N-dimethylformamdie (DMF) at room temperature in a weight ratio of 15: 1 to prepare a PVAc solution containing POSS. It was. POSS used opropyldimethylsilcyclohexyl POSS produced by the US Air Force Reseach Lab. PVAc used products from Aldrich, THF and DMF produced by Showa in Japan.

Nanofiber nonwoven fabric was prepared by directly spinning the PVAc solution containing the POSS to the collector of the electrospinning apparatus. The tip-to-collector distance (TCD) was fixed at 10 cm and the voltage was 15 kVf during electrospinning. The high voltage supplier used SHV 300 (ACP) with a voltage of 0-60 kV. korea co., LTD).

Comparative Example 1

A 17 wt% PVAc solution dissolved in N, N-dimethylformamdie (DMF) was electrospun onto a collector of an electrospinning apparatus to prepare a nanofiber nonwoven fabric. At this time, DMF, PVAc and electrospinning conditions were carried out in the same manner as in Example 1.

[Measurement of Diameter of Nanofiber Nonwoven Fabric]

The nanofiber nonwoven fabrics of Example 1 and Comparative Example 1 were observed with a scanning electron microscope (SEM, JSM-5900. Jeol Co., Japan), and SEM pictures are shown in FIGS. 1 and 2.

In addition, the SEM photographs of FIGS. 1 and 2 were used to measure the thickness of 100 nanofibers using image software, and the change in diameter depending on the presence or absence of POSS was illustrated in the graphs of FIGS. 3 and 4.

In the case of the nanofiber nonwoven fabric of Example 1, the average diameter of the nanofibers was 165 nm as shown in FIG. 3, and the average diameter of the nanofibers of the nanofiber nonwoven fabric of Comparative Example 1 was 450 nm as shown in FIG. 4. The average diameter of the nanofibers of Example 1 was measured to be 285 nm smaller than that of Comparative Example 1. This is believed to be able to form thinner nanofibers during electrospinning as the electrical conductivity of the PVAc solution containing POSS increases, and the electrical conductivity may be due to the Si element of POSS.

Furthermore, in the case of the nanofiber nonwoven fabric of Comparative Example 1, the diameter of the nanofibers was not uniform as shown in FIGS. 2 and 4, but the diameter of the nanofiber nonwoven fabric of Example 1 was very uniform as in FIGS. .

[Example 2]

The PVAc solution containing the POSS prepared in Example 1 was directly electrospun into water-damp Doc fiber paper supplied to the collector of the electrospinning apparatus to prepare a composite.

At this time, the used doc fiber paper was supplied from 100% doc fiber paper without refining and bleaching from Jirisan Hanji of Namwon Material, Jeonbuk.

The tip-to-collector distance (TCD) was fixed at 10 cm and the voltage was 15 kVf during electrospinning. The high voltage supplier used SHV 300 (ACP) with a voltage of 0-60 kV. korea co., LTD).

1 mM HCl aqueous solution was prepared using distilled water, and 1 M Tetramethyl orthosilicate (TMOS) was added to 200 mL HCl aqueous solution to finally obtain 500 mM Tetrahydroxysilan (THOS) solution. HCl was used as a trielectric chemistry and TMOS was manufactured by Aldrich.

The complex was immersed in the THOS solution for 1 hour and then rescued. The complex was placed in a desiccator so that distilled water and the sample did not come into contact with each other, and left at 60 ° C. for at least 12 hours while the lid was closed to induce silicification.

Comparative Example 2

The PVAc solution of Comparative Example 1 was directly spun onto water-soaked Doc fiber paper supplied to the collector of the electrospinning apparatus to prepare a composite. At this time, the electrospinning was performed under the same conditions as in Example 2.

And siliconization was induced in the same manner as in Example 2 using a THOS solution in the complex.

[Synthesis of nanofibers after immersion of silicic acid solution]

After immersing the composite of Example 2 and Comparative Example 2 in each silicic acid solution (THOS) for 1 hour, the state of the paper mulberry paper and nanofibers were visually observed, and each photograph is shown in Figs.

In the case of Example 2, which is a composite composed of POSS-containing nanofibers, the nanofibers were not separated from the paper fibers after siliconization as shown in FIG. 5. It can be seen that there is no morphological change such as the nanofiber not shrinking after the siliconization treatment.

In the case of Comparative Example 2, which is a composite composed of nanofibers containing no POSS, the nanofibers were separated from the duct fiber paper after the siliconization treatment as shown in FIG. 6. It is believed that the nanofibers contracted and separated from the paper fibers.

And the composite of Example 2 and Comparative Example 2 siliconized by immersion of silicic acid solution was observed with each scanning electron microscope (SEM, JSM-5900. Jeol Co., Japan), SEM pictures are shown in FIGS. same.

In the case of the composite of Example 2, it was confirmed that the form and pores of the nanofibers were maintained after siliconization as shown in FIG. 7, but in the case of the composite of Comparative Example 2, the nanofibers were dissolved by silicic acid solution as shown in FIG. I could read that.

[Infrared Spectrophotometer Measurement]

A) Doc-fiber paper (MF), b) unsiliconed composite of Comparative Example 2 (MF / PVAc), c) silicization using an infrared spectrophotometer (FT-IR, Spectrum GX, Perkin Elmer Inc., USA) Unconjugated Example 2 composite (MF / PP), d) silicified Example 2 composite (Silicificated MF / PP) and e) POSS structures were analyzed and shown in FIG. 9.

MF showed the same peak as cellulose, and the structure of POSS was confirmed through the peak of the siliconized composite of Example 2 (Silicificated MF / PP). It can be seen that 2850-2820 cm-1, 2300-2250, and 1460-1340 are the peaks of the POSS. In particular, in the case of the siliconized composite of Example 2 (Silicificated MF / PP), the peak increase was found at 860. This shows that many of the Si-O-Si atoms were attached to the composite after siliconization.

Claims (4)

Obtaining a complex by directly electrospinning a PVAc solution containing polyhedral oligomeric silsesquioxane (POSS) nanoparticles on the surface of a paper mulberry paper;
Silicifying the complex; an organic-inorganic hybridized PVAc polymer / dough fiber tissue regenerating carrier, characterized in that it comprises a.
The method of claim 1,
The PVAc solution containing the POSS nanoparticles is an organic-inorganic hybridized PVAc polymer, characterized in that the PVAc solution dissolved in N, N-dimethylformamide (DMF) is mixed with POSS dispersed in tetrahydrofuran. / Method of preparing a carrier for tissue regeneration.
The method of claim 1,
Method for producing an organic-inorganic hybridized PVAc polymer / dough fiber tissue regeneration carrier characterized in that the complex is immersed in a silicic acid solution to siliconize.
The method of claim 3,
After immersing the complex in a silicic acid solution, the complex is placed in a desiccator so that the distilled water and the sample do not touch, and the organic-inorganic hybridized PVAc polymer is characterized in that it is siliconized by leaving the lid closed at 60 ° C. for at least 12 hours. Method for producing a carrier for regenerating mulberry fibers.

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