KR101104775B1 - A Method for Modifying a Solid Substrate Surface Using One-Pot Process - Google Patents

Abstract

The present invention provides a method of modifying a solid substrate surface using a one-pot process. The method for modifying a solid substrate surface according to the present invention introduces an adhesive material such as dopamine and a functional target material into the solid substrate surface in a one-port process. The functionalized surface can then be used as is or as an intermediate surface for the introduction of another functional material. According to the method for modifying the surface of a solid substrate according to the present invention, it is possible to introduce various functionalities to various kinds of solid substrates, and thus it is not only applicable to a wide variety of fields such as medical, pharmaceutical, semiconductor, and catalyst, but also to introduce functional introduction. The coating of the solid substrate is performed by a one-port process, which has the advantage of modifying the surface of the solid substrate in a very simple process.

Dopamine, functional targets, one-pot process, surface modification

Description

A method for modifying a solid substrate surface using one-pot process

The present invention relates to a method of modifying a solid substrate surface using a one-pot process for simplicity of the process.

The field of chemical modification of solid substrates plays an important role in the recent fields of chemistry, chemical engineering, biology and materials engineering. Chemical modification of solid substrates has been studied by interfacial chemistry and other physical chemistries using organothiol-metals, enidiol-oxides, or silane-oxides. It is to be modified to have the desired characteristics. The materials used for solid surface modification mainly have bifunctional end groups that adhere one end to the substrate and the other end provides chemical functionality to the substrate surface.

Known methods for modifying solid substrates include methods such as SAM formation (self-assembled monolayer (SAM) formation), functionalized silanes, Langmuir-blojet deposition, and multilayer-by-layer assembly. have. Although these methods are widely used in research fields, they are not practically widely used. For example, chemical specificity between surface modifiers and solid surfaces is required, such as alkane thiols for noble metal surfaces, and silanes for oxide surfaces, complex devices for modification, and substrates for Langmuir-Bjetjet deposition. Is limited in size and shape, and sometimes many steps are required for surface modification. A further problem with known surface modification methods is that the type of solid substrate that can be modified is limited.

Mussels contain a kind of natural adhesive material that is independent of the type of surface. That is, mussels are adherent organics that can adhere to virtually all kinds of inorganic and organic substrates, including polytetrafluoroethylene (PTFE), which is classically known as a non-adhesive material. This adhesive property of mussels appears to be due to the amino acids of 3,4-dihydroxy-L-phenylalanine (DOPA) and lysine amino acids, which are found near the plaque-substrate interface. DOPA not only participates in reactions that lead to the solidification of the adhesive, but also forms strong covalent or non-covalent bonds with the substrate.

Dopamine is a particulate compound containing both catechol (DOPA) and amine groups. Dopamine can be electropolymerized on conductive substrates (Y. Li, M. Liu, C. Xiang, Q. Xie, S. Yao, Thin Solid Films, 497, 270, 2006). Haeshin Lee et al. (2006, 2007) studied mussels that have adhesion in water and on water, as well as on organic and inorganic surfaces, and found that the basic unit of adhesion is dopamine. Has been successfully coated on various surfaces including polytetrafluoroethylene (PTFE).

The present inventors completed the present invention by studying a method that can not only modify the substrate regardless of the type of substrate, but also simplify the modification process in order to impart specific functionality on the solid substrate.

SUMMARY OF THE INVENTION An object of the present invention is to provide a method of modifying a solid substrate surface that can not only modify the substrate surface regardless of the type of substrate, but can also simplify the modification process.

In order to achieve the above object, the present invention provides a method of modifying the surface of a solid substrate for coating the adhesive material and the functional target material using a one-pot process.

According to the present invention, unlike the known method, the surface can be modified without being restricted by the type of substrate, and the modification is performed by a one-port process, which is a process of coating an adhesive material and a target material on the surface of the substrate. The effect is to simplify the process.

The present invention comprises the steps of dissolving the adhesive material and the target material in the solvent in a one-pot process under the basic conditions (step 1);

Coating the solid substrate by dipping the solution of step 1 (step 2); And

It provides a method of modifying the surface of the solid substrate comprising the step (step 3) of removing the solid substrate coated in step 2 and washed.

Hereinafter, the present invention will be described in detail for each step.

Step 1 of the present invention is a step of dissolving the adhesive material and the target material represented by the following formula (1) in a solvent in a one-pot process under basic conditions:

Wherein R ¹ is one selected from the group consisting of thiol, amine, nitrile, aldehyde, sulfidyl, imidazole, and azide, and R ² is one selected from the group consisting of H, OH, and COOH. ).

In the present invention, the adhesive material is a material used for adhesion between the solid substrate and the target material, and the target material refers to a material that is introduced to the non-functional solid surface and coated to modify the solid surface by functionalizing the surface. In addition, in the present invention, the one-port process refers to a process of mixing an adhesive material and a target material in a single process and then coating the solid material on a solid substrate after the adhesive material is coated on the solid substrate. it means.

The reforming method is
Dissolving a dopamine adhesive material and a target material represented by Chemical Formula 2 under a basic condition in a solvent by a one-pot process (step A);
Coating the solid substrate by dipping the solution of step A (step B); And
It is preferable that the method of modifying the surface of the solid substrate comprising the step of removing and washing the solid substrate coated in step B (step C):

.

.

Dopamine is a bifunctional compound containing both hydroxyl and amine groups. The hydroxyl group is considered to be involved in the bonding action to the solid substrate, and the amine group is involved in the binding reaction with the target material. do.

In order to facilitate the oxidation polymerization of dopamine, step 1 is preferably performed under basic conditions, and the pH of the solution is preferably 7 to 12. It is possible to use a pH buffer such as Tris buffer (Pris), phosphate buffer (PBS) to maintain the pH of the solution as described above.

In addition, the solvent used in the step 1 is preferably water or methanol alone solvent, or a mixed solvent thereof. Since such a single solvent or a mixed solvent has an effect of increasing the solubility in the process of melting the adhesive material and the target material together, it is preferable to use such a solvent.

)인 경우는 몰비율로 1 : 1 ~ 1 : 2(도파민 : 2-(다이메틸아미노)에탄티올), 각각 도파민과 2-브로모-N-(3,4-다이하이드록시펜에틸)-2-메틸프로판아미드(

)인 경우는 몰비율로 1 : 3 ~ 1 : 5(도파민 : 2-브로모-N-(3,4-다이하이드록시펜에틸)-2-메틸프로판아미드), 및 각각 도파민과 세틸트리메틸암모늄 브로마이드인 경우는 몰비율로 3 : 1 ~ 5 : 1(도파민 : 세틸트리메틸암모늄 브로마이드)인 것이 바람직하다. 상기와 같은 접착물질과 타겟물질의 혼합비율은 각각의 물질에 따른 코팅 효율을 고려한 것으로, 혼합비율이 상기 범위를 벗어나는 경우 코팅 효율이 낮아지는 문제점이 있어 바람직하지 않다.In the step 1 of the present invention, the mixing ratio of the adhesive material and the target material is 1: 9 to 1: 11 (dopamine: hyaluronic acid) by weight ratio when the adhesive material and the target material are dopamine and hyaluronic acid, respectively, and dopamine and 2- (Dimethylamino) ethanethiol (

) In the molar ratio of 1: 1 to 1: 2 (dopamine: 2- (dimethylamino) ethanethiol), dopamine and 2-bromo-N- (3,4-dihydroxyphenethyl)-, respectively. 2-methylpropanamide (

) In the molar ratio of 1: 3 to 1: 5 (dopamine: 2-bromo-N- (3,4-dihydroxyphenethyl) -2-methylpropanamide), and dopamine and cetyltrimethylammonium, respectively. In the case of bromide, the molar ratio is preferably 3: 1 to 5: 1 (dopamine: cetyltrimethylammonium bromide). The mixing ratio of the adhesive material and the target material as described above is to consider the coating efficiency according to each material, it is not preferable because the coating efficiency is lowered when the mixing ratio is out of the above range.

Steps 2 and B of the present invention are a step of coating a solid substrate by immersing the solid substrate for surface modification in the reactant-target material solution prepared by the one-pot process. At this time, it is preferable to immerse the solid substrate in the solution for 10 minutes to 24 hours in order to sufficiently coat the solid substrate by the solution. The material of the solid substrate used in step 2 of the present invention is a polymer material, a noble metal material, a metal material, a metal oxide material, a ceramic material, a nonmetallic material and a group 3-5 (III-V), group 2-6 ( II-VI) is preferably selected from the group containing the compound.

Steps 3 and C of the present invention are the steps of removing and washing the solid substrate coated in steps 2 and B. The coated solid substrate can be washed with distilled water and a hydrophilic solvent. Through this cleaning process, the adhesive-target material solution that is not coated on the solid substrate is removed from the solid substrate.

When hyaluronic acid is used as the target material while modifying the surface of the solid substrate in the above manner, the modified solid substrate is modified to have adsorption to non-adsorbable cells such as M07e and blood cells. In addition, when cetyltrimethylammonium bromide is used as the target material, the modified solid substrate is modified to inhibit cell proliferation due to the antimicrobial properties of the material.

The method for modifying a solid substrate surface according to the present invention may further include the step of immersing the washed substrate in a solution in which the fixing material is dissolved, thereby fixing the fixing material to the substrate.

The fixing step of the present invention is a step for fixing and using a suitable fixing material according to the application on the modified solid substrate. Depending on the application, the method of immobilizing the fixing material on the modified solid substrate surface may vary depending on the type of target material coated, which may be performed by a method well known to those skilled in the art.

For example, when using a compound having a molecular weight of 1,000 or less having a tertiary amine such as 2- (dimethylamino) ethanethiol as the target material, the surface of the solid substrate is modified so that a silica layer can be formed on the solid substrate, When a polymer polymerization initiator having a molecular weight of 1,000 or less having a tertiary or secondary bromine functional group such as 2-bromo-N- (3,4-dihydroxyphenethyl) -2-methylpropanamide is used as a target material, The solid substrate surface is modified to allow polymer polymerization on the substrate. In this case, the polymer polymerization is preferably an atomic transition radical polymer polymerization reaction using a transition metal catalyst, the transition metal catalyst is preferably a copper complex compound. In addition, the monomer of the polymer polymerization may be an acrylic monomer, the acrylic monomer is preferably dimethylaminoethyl methacrylate.

Hereinafter, the present invention will be described in detail by Examples and Experimental Examples. However, the following Examples and Experimental Examples are intended to describe the present invention in detail, and the scope of the present invention is not limited by the following Examples and Experimental Examples.

≪ Example 1 >

silicon On a substrate  Hyaluronic acid coating

5 mg of dopamine and 50 mg of hyaluronic acid were dissolved together in 5 mL of Tris buffer at pH 8.5. The solution was stirred at room temperature for 10 minutes to uniformly mix dopamine and hyaluronic acid in the solvent. After sufficient stirring, the silicon substrate was immersed in solution and left for 18 hours to allow sufficient coating. After the coated silicon substrate was taken out, the hyaluronic acid was coated on the silicon substrate by washing the substrate with distilled water and drying with nitrogen to remove the uncoated dopamine and hyaluronic acid solution from the substrate.

<Example 2>

titanium On a substrate  2-( Dimethylamino ) Ethanethiol  Coating and Silica Layer Formation

20 mg of dopamine was dissolved in 10 mL of pH 8.5 Tris buffer and stirred for 1 min, after which the titanium substrate was immersed in solution. After 45 minutes, 10 mL of 10 mM 2- (dimethylamino) ethanethiol solution prepared by dissolving in pH 8.5 Tris buffer was added to the dopamine solution, stirred for 1 minute, and left for 5 hours to allow sufficient coating. . After removing the coated titanium substrate, the substrate was washed with distilled water and dried with nitrogen to remove the uncoated dopamine and 2- (dimethylamino) ethanethiol solution from the substrate. 0.147 mL of tetramethyl orthosilicate (TMOS) was added to 10 mL of 1 mM HCl solution to prepare a 100 mM TMOS solution, and 5 ml of the solution was mixed with 5 ml of 100 mM phosphate buffer solution at pH 6.0 to form silica. The solution was prepared. The titanium substrate coated with 2- (dimethylamino) ethanethiol was immersed in the silica forming solution and left for 1 hour. After removing the titanium substrate on which the silica layer was formed, the substrate was washed with distilled water and dried with nitrogen.

<Examples 3 and 4>

Polyvinylchloride , Polystyrene On a substrate  2-( Dimethylamino ) Ethanethiol  Coating and Silica Layer Formation

The surface of the solid substrate was modified in the same manner as in Example 2 except that polyvinyl chloride (PVC) and polystyrene (PS) were used as the solid substrate.

Example 5

gold On a substrate  For polymer polymerization Initiator  Coating and Polymer Polymerization

2 mg of dopamine and 12 mg of 2-bromo-N- (3,4-dihydroxyphenethyl) -2-methylpropanamide were dissolved in 5 mL of methanol and a water mixed solvent (volume ratio = 3: 2). At this time, Tris buffer of pH 8.5 was used as water to satisfy basic conditions. The solution was stirred at room temperature for 1 minute to ensure uniform mixing of dopamine and 2-bromo-N- (3,4-dihydroxyphenethyl) -2-methylpropanamide in the solvent. After sufficient stirring, the gold substrate was immersed in solution and left for 18 hours to allow sufficient coating. After removing the coated gold substrate, the substrate was washed with distilled water to remove uncoated dopamine and 2-bromo-N- (3,4-dihydroxyphenethyl-2-methylpropanamide solution from the substrate. Into a Schlenk Flask, 0.014 g of CuBr and 0.031 g of 2,2'-dipyridyl were added to a vacuum, and then purged with argon gas. Subsequently, 8.4 mL of degassed water and 1.6 ml of dimethyl amino ethyl methacrylate (DMAEMA) were added to the shrink flask. Reaction for 4 hours after transferring to another shrink flask in an argon gas environment containing the gold substrate coated with 2-bromo-N- (3,4-dihydroxyphenethyl) -2-methylpropanamide Polymerization on Gold Substrates As to form a poly-dimethyl aminoethyl methacrylate polymer layer. Gold substrate is a polymer layer formed is washed with distilled water and methanol and dried with nitrogen.

<Examples 6-17>

solid On a substrate  For polymer polymerization Initiator  Coating and Polymer Polymerization

Solid substrates include indium tin oxide (ITO), glass, silicon, aluminum, platinum, titanium, poly methylmethacrylate (PMMA), polycarbonate (PC), polyvinylchloride (PVC), polystyrene (PS), cyclic olefins The surface of the solid substrate was modified in the same manner as in Example 5 except that the material of copolymer (COC) and Teflon was used.

&Lt; Example 18 >

gold On a substrate Cetyltrimethylammonium  Bromide coating

2.4 mL of 10 mM dopamine dissolved in PBS solution of pH 7.4 and 0.6 mL of 10 mM cetyltrimethylammonium bromide were mixed and 6 mL of 0.5 M sodium hydroxide solution was added to adjust the pH to 9.4. The solution was stirred at room temperature for 1 minute to uniformly mix dopamine and cetyltrimethylammonium bromide in the solvent. After sufficient stirring, the gold substrate was immersed in solution and left for 18 hours to allow sufficient coating. After the coated gold substrate was removed, the substrate was washed with distilled water and dried with nitrogen to remove uncoated dopamine and cetyltrimethylammonium bromide solution from the substrate.

<Examples 19-21>

solid On a substrate Cetyltrimethylammonium  Bromide coating

The surface of the solid substrate was modified in the same manner as in Example 18 except that silicon, titanium, and silica microparticles were used as the solid substrate.

Experimental Example 1

M07e  Cell Adsorption  Confirm

M07e cells are cells that specifically adsorb the hyaluronic acid, and can be confirmed whether or not the hyaluronic acid is coated according to the adsorption of cells on the solid surface. In order to confirm the adsorption of M07e cells on the solid substrate coated with dopamine and hyaluronic acid, M07e cell adsorption experiment was performed in comparison with the dopamine-coated solid substrate, and the results are shown in FIG. 1.

Figure 1 (a) is a result for a solid substrate coated with dopamine only, Figure 1 (b) is a result for a solid substrate coated with dopamine and hyaluronic acid. Only when dopamine and hyaluronic acid are coated on the solid substrate as shown in FIG. 1, it can be seen that M07e cells are adsorbed onto the solid substrate. Thus, when the solid substrate is immersed in a solution mixed with dopamine and hyaluronic acid, It can be seen that the solid surface is coated with hyaluronic acid.

Experimental Example 2

titanium On a substrate  Silica layer Formation  Confirm

In order to confirm the coating of 2- (dimethylamino) ethanethiol and the formation of a silica layer on a titanium substrate, contact angle measurement and XPS analysis of each substrate were carried out. The results of the above experiments are shown in FIGS. 2 and 3. It was.

FIG. 2 (a) is a contact angle photograph of a titanium substrate coated with dopamine and 2- (dimethylamino) ethanethiol, and FIG. 2 (b) is a contact angle photograph of a titanium substrate having a silica layer formed on the coated substrate. . The degree of hydrophilicity and hydrophobicity of the solid surface may be determined according to the degree of contact angle between the solid surface and the water droplet. After the silica layer is formed, the contact angle is significantly reduced due to the hydrophilicity of the silica layer. FIG. 3 (a) shows the results of X-ray photoelectron spectroscopy (XPS) of a titanium substrate coated with dopamine and 2- (dimethylamino) ethanethiol, and FIG. 3 (b) shows a silica layer. XPS analysis results of the formed titanium substrate. XPS analysis of titanium substrates coated with dopamine and 2- (dimethylamino) ethanethiol showed sulfur peaks, an element present in 2- (dimethylamino) ethanethiol. In addition, when the XPS analysis was performed on the titanium substrate on which the silica layer was formed, a silicon peak, an element present in silica, was observed. Comparing the figures, it can be seen that a silica layer is formed on the coated titanium substrate.

Experimental Example 3

Silica Layers on Various Solid Substrates Formation  Confirm

Except that PVC and PS were used as the solid substrate, 2- (dimethylamino) ethanethiol was coated and silica layer was formed in the same manner as in Experimental Example 2.

(A) is a contact angle photograph of a PVC substrate coated with dopamine and 2- (dimethylamino) ethanethiol, (b) is a contact angle photograph of a PVC substrate on which a silica layer is formed, and (c) shows dopamine and A contact angle photograph of a PS substrate coated with 2- (dimethylamino) ethanethiol, and (d) is a contact angle photograph of a PS substrate on which a silica layer is formed. Figure 5 (a) is the XPS spectrum of the PVC substrate coated with dopamine and 2- (dimethylamino) ethanethiol, (b) is the XPS spectrum of the PVC substrate with a silica layer, (c) is dopamine and 2 XPS spectrum of PS substrate coated with-(dimethylamino) ethanethiol, and (d) is XPS spectrum of PS substrate having a silica layer formed on the substrate. 4 and 5, even when the material of the solid substrate is PVC or PS, it can be seen that the same results as in Experimental Example 2.

Experimental Example 4

Polymers on Gold Substrates Polymerization  Confirm

In order to confirm 2-bromo-N- (3,4-dihydroxyphenethyl) -2-methylpropanamide coating and polymer polymerization on gold substrates, IR and XPS analyzes were performed on each substrate. The results of are shown in Figures 6 and 7.

FIG. 6 (a) is an IR spectrum of a gold substrate coated with dopamine and the target material, and FIG. 6 (b) is an IR spectrum after polymer polymerization on the coated gold substrate. As a result, after the polymer polymerization, C (O stretching) and CH stretching peaks, which are the binding vibration energy between elements specifically possessed by poly (dimethyl amino ethyl methacrylate), are respectively around 1730 cm ^-1 and 2900 cm ^-1 . Confirmed. The peaks are invisible peaks before the formation of the polymer, and it can be seen that the polymer polymerization was performed on the gold substrate according to the present invention through the formation of the peak. FIG. 7A is an XPS spectrum of a gold substrate coated with dopamine and the target material, and FIG. 7B is an XPS spectrum after polymerizing the gold substrate coated as described above. By confirming that the intensity of carbon, nitrogen, and oxygen peaks increases after polymer polymerization, it may be indirectly confirmed that the polymer is formed on the gold substrate.

Experimental Example 5

Contact angle  Polymer on various solid substrates through measurement Polymerization  Confirm

Solid prepared in Examples 5 to 17 to confirm polymer polymerization on a solid substrate coated with dopamine and 2-bromo-N- (3,4-dihydroxyphenethyl) -2-methylpropanamide The contact angle measurement experiment was performed on the board | substrate as follows.

Contact angle measurement experiment is to check the surface properties of the solid substrate by measuring the angle between the solid substrate and the water drop by dropping the water droplets on the prepared solid substrate, the contact angle measurement results according to the experiment is shown in FIG. When the polymer is sufficiently polymerized on the solid substrate, the surface properties are almost similar regardless of the type of the solid substrate, and thus the contact angles measured are similar. In Figure 8 it can be seen that the contact angle after the polymerization of the polymer for most of the solid substrate is close to 50 degrees, through which the polymer was formed on a variety of solid substrates.

<Experimental Example 6>

XPS  By analysis Cetyltrimethylammonium  Bromide Coating  Confirm

XPS analysis was performed to confirm whether cetyltrimethylammonium bromide was coated with dopamine on the gold substrate, and the results are shown in FIG. 9. Since cetyltrimethylammonium bromide contains quaternary amine groups, peaks can be observed in areas different from those of general nitrogen peaks. As can be seen in FIG. 9, the cetyltrimethylammonium bromide was formed on a gold substrate by confirming that a peak was formed at 402.5 eV. It can be seen that cetyltrimethylammonium bromide is coated.

Experimental Example 7

Check the growth of bacteria

Cetyltrimethylammonium bromide is known to have antimicrobial properties and is known to prevent the growth of bacteria when put into bacteria. Therefore, the following experiment was performed to confirm whether cetyltrimethylammonium bromide was coated on the silica microparticles prepared in Example 21 according to the present invention.

50 mg of silica microparticles coated with cetyltrimethylammonium bromide were dispersed in 0.5 mL of PBS solution at pH 7.4. The solution was then added to 2 mL of PBS solution containing 10 ⁵ E. coli and Staphylococcus. After standing at 37 ^° C. for 20 minutes, 50 mL of the supernatant was extracted and spread over agar plates. And it was left for 18 hours at 37 ^° C to observe the state of growth of bacteria, the results of the experiment is shown in Figure 10. 10 (a) shows the results of E. coli growth experiments using the untreated silica microparticles, (b) shows the E. coli growth experiments using the silica microparticles coated with cetyltrimethylammonium bromide (C) shows the results of staphylococcal growth experiments using untreated silica microparticles, and (d) shows the staphylococcal growth experiments using silica microparticles coated with cetyltrimethylammonium bromide. This is the result. In the case of Escherichia coli and Staphylococcus proliferation experiments using untreated silica microparticles, it can be seen that bacteria were widely grown on agar plates. In the case of the cocci propagation experiment, it can be seen that the bacteria hardly multiplied on the agar plate. This result shows that the fine coating of cetyltrimethylammonium bromide, which is an antimicrobial material, on the silica microparticles.

Figure 1 (a) is a photograph of the adsorption of M07e cells on a silicon substrate coated with dopamine only, Figure 1 (b) is a photograph of the adsorption of M07e cells on a silicon substrate coated with dopamine and hyaluronic acid.

FIG. 2A is a contact angle photograph of a titanium substrate coated with dopamine and 2- (dimethylamino) ethanethiol, and FIG. 2B is a contact angle photograph of a titanium substrate having a silica layer formed on the substrate.

FIG. 3A is an XPS spectrum of a titanium substrate coated with dopamine and 2- (dimethylamino) ethanethiol, and FIG. 3B is an XPS spectrum of a titanium substrate having a silica layer formed thereon.

4A is a contact angle photograph of a PVC substrate coated with dopamine and 2- (dimethylamino) ethanethiol, and FIG. 4B is a contact angle photograph of a PVC substrate having a silica layer formed on the substrate. 4 (c) is a contact angle photograph of a PS substrate coated with dopamine and 2- (dimethylamino) ethanethiol, and FIG. 4 (d) is a contact angle photograph of a PS substrate having a silica layer formed on the substrate.

5A is an XPS spectrum of a PVC substrate coated with dopamine and 2- (dimethylamino) ethanethiol, and FIG. 5B is an XPS spectrum of a PVC substrate having a silica layer formed on the substrate. 5 (c) is an XPS spectrum of a PS substrate coated with dopamine and 2- (dimethylamino) ethanethiol, and FIG. 5 (d) is an XPS spectrum of a PS substrate having a silica layer formed on the substrate.

FIG. 6A is an IR spectrum of a gold substrate coated with dopamine and 2-bromo-N- (3,4-dihydroxyphenethyl) -2-methylpropanamide, and FIG. IR spectrum of a gold substrate polymerized with a poly (dimethyl amino ethyl methacrylate) polymer on the substrate.

FIG. 7A is an XPS spectrum of a gold substrate coated with dopamine and 2-bromo-N- (3,4-dihydroxyphenethyl) -2-methylpropanamide, and FIG. XPS spectrum of a gold substrate polymerized with a poly (dimethyl amino ethyl methacrylate) polymer on the substrate.

8 is a graph comparing the contact angles of various solid substrates that are not treated with the contact angles of various solid substrates polymerized on a surface of a poly (dimethyl amino ethyl methacrylate) polymer.

9 is an XPS spectrum of a gold substrate coated with dopamine and cetyl trimethylammonium bromide.

Figure 10 (a) is a photograph of the agar plate after performing the E. coli growth experiment on the agar plate using the untreated silica microparticles, Figure 10 (b) is silica coated with cetyltrimethylammonium bromide Photograph of the agar plate taken after performing the E. coli growth experiment on the agar plate using the microparticles, Figure 10 (c) is a staphylococcal growth experiment on the agar plate using the untreated silica microparticles It is a photograph of the agar plate taken back, Figure 10 (d) is a photograph of the agar plate taken after performing staphylococcus aureus experiments on the agar plate using silica microparticles coated with cetyltrimethylammonium bromide.

Claims (20)

Under basic conditions, dissolving the adhesive material and the target material represented by Formula 1 in a solvent in a one-pot process (step 1); Coating the solid substrate by dipping the solution of step 1 (step 2); And Taking out and washing the solid substrate coated in step 2 Method of modifying the surface of a solid substrate comprising a system (step 3): <Formula 1>

Wherein R ¹ is one selected from the group consisting of thiol, amine, nitrile, aldehyde, sulfidyl, imidazole, and azide, and R ² is one selected from the group consisting of H, OH, and COOH. ). The method of claim 1, wherein the reforming method further comprises the step of immersing the substrate washed in the step 3 in a solution in which the fixing material interacting with the target material, the fixing material to the substrate further comprising: Modification of the surface of a solid substrate. Dissolving a dopamine adhesive material and a target material represented by Chemical Formula 2 under a basic condition in a solvent by a one-pot process (step A); Coating the solid substrate by dipping the solution of step A (step B); And Method for modifying the surface of the solid substrate comprising the step of removing the solid substrate coated in step B and washing (step C): <Formula 2>

. The method of claim 1, wherein the basic condition of step 1 is in the range of pH 7 to 12. 5. The method of claim 4, wherein the pH of the solution is maintained in the range of 7 to 12 over part or all of the reaction time. The method of claim 1, wherein the solvent of step 1 is one selected from the group consisting of water, a hydrophilic solvent, and a mixed solvent thereof. The method of claim 1, wherein the solution temperature of step 2 is in the range of a freezing point to a boiling point of the solvent used. According to claim 1, wherein the material of the solid substrate of step 2 is a polymeric material, precious metal materials, metal materials, metal oxide materials, ceramic materials, non-metal materials and Group 3-5 (III-V), 2-6 And a group (II-VI) compound. The method of modifying the surface of a solid substrate according to claim 1, wherein the hyaluronic acid is used as the target material of step 1, so that the solid substrate has adsorption to non-adsorbable cells such as M07e and blood cells. The method of claim 2, wherein the target material of step 1 2- (dimethylamino) ethanethiol (

Using a compound having a molecular weight of 1,000 or less having a tertiary amine such as) to enable a silica layer to be formed on the solid substrate. The method of claim 2, wherein the target material of step 1 is 2-bromo-N- (3,4-dihydroxyphenethyl) -2-methylpropanamide (

A method of modifying the surface of a solid substrate to enable polymer polymerization on a solid substrate by using a polymer polymerization initiator having a molecular weight of 1,000 or less having a tertiary or secondary bromine functional group, such as). 12. The method of claim 11, wherein the polymer polymerization is an atomic transition radical polymer polymerization reaction using a transition metal catalyst. 13. The method of claim 12, wherein the transition metal catalyst is a copper complex compound. 13. The method of claim 12, wherein the monomer of the polymer is an acrylic monomer. 15. The method of claim 14, wherein said acrylic monomer is dimethylaminoethyl methacrylate. The solid substrate of claim 1, wherein a compound having a molecular weight of 1,000 or less having a quaternary amine such as cetyltrimethylammonium bromide as a target material of step 1 is used to enable the introduction of antimicrobial properties that prevent bacterial growth on the solid substrate. Surface modification method. The method of claim 1, wherein when the adhesive material and the target material of step 1 are dopamine and hyaluronic acid, respectively, the weight ratio thereof is 1: 9 to 1: 11 (dopamine: hyaluronic acid) of the solid substrate surface Reforming method. The method of claim 2, wherein when the adhesive material and the target material of step 1 are compounds having a molecular weight of 1,000 or less having a tertiary amine such as dopamine and 2- (dimethylamino) ethanethiol, respectively, their molar ratio is 1: A method of modifying the surface of a solid substrate, characterized in that 1 to 1: 2 (dopamine: target material). The method of claim 2, wherein the adhesive material and the target material of step 1 are tertiary or secondary, such as dopamine and 2-bromo-N- (3,4-dihydroxyphenethyl) -2-methylpropanamide, respectively. In the case of a polymer polymerization initiator having a molecular weight of 1,000 or less having a bromine functional group, their molar ratio is 1: 3 to 1: 5 (dopamine: target substance). The method of claim 1, wherein when the adhesive material and the target material of step 1 are compounds having a molecular weight of 1,000 or less having a quaternary amine such as dopamine and cetyltrimethylammonium bromide, respectively, their molar ratio is 3: 1 to 5: 1 (Dopamine: target material) A method of modifying the surface of a solid substrate.

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