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WO2024248354A1 - Adhésif sensible à la pression fonctionnel d'acide boronique et son procédé de fabrication - Google Patents

Adhésif sensible à la pression fonctionnel d'acide boronique et son procédé de fabrication Download PDF

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WO2024248354A1
WO2024248354A1 PCT/KR2024/006225 KR2024006225W WO2024248354A1 WO 2024248354 A1 WO2024248354 A1 WO 2024248354A1 KR 2024006225 W KR2024006225 W KR 2024006225W WO 2024248354 A1 WO2024248354 A1 WO 2024248354A1
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sensitive adhesive
boronic acid
pressure
acid functional
scaffold
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Korean (ko)
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이규의
강주미
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Kyungpook National University Hospital
Industry Academic Cooperation Foundation of KNU
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Kyungpook National University Hospital
Industry Academic Cooperation Foundation of KNU
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/34—Introducing sulfur atoms or sulfur-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/42—Introducing metal atoms or metal-containing groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J143/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C

Definitions

  • the present invention relates to a boronic acid functional pressure-sensitive adhesive, and more specifically, to a boronic acid functional pressure-sensitive adhesive and a method for producing the same, wherein a pressure-sensitive adhesive (PSA) is produced by synthesizing butyl acrylate (BA) and glycidyl methacrylate (GMA), and the pressure-sensitive adhesive is functionalized with boronic acid (4-Mercaptophenylboronic acid, 4-pMPBA).
  • PSA pressure-sensitive adhesive
  • BA butyl acrylate
  • GMA glycidyl methacrylate
  • interface properties are as important as body properties. This is because the surface of the biomaterial directly interacts with the external substrate.
  • biocompatible materials such as metals, ceramics, and polysaccharides are non-functional and have limited availability.
  • Surface modification technology can maximize the functionality of biomaterials by upgrading the properties of biomaterials or imparting new capabilities. Representative abilities include: (1) antibacterial and antifouling properties, (2) cell adhesion and growth promotion, (3) immune response suppression, and (4) improved mechanical properties of materials.
  • dopamine which contains both amine and catechol groups, interacts with the surrounding substrate while undergoing spontaneous oxidative polymerization in a weakly basic state. Since catechol can undergo various chemical interactions such as hydrogen bonding, electrostatic interaction, and pi-related bonding, the polymer structure of dopamine (i.e., polydopamine) can be successfully coated on the target substrate.
  • the polydopamine coating layer acts as a molecular bonding agent that can chemically conjugate nucleophiles (e.g., -NH2, -SH) through Michael-type addition and Schiff-base formation on the coated substrate due to the remaining unreacted catechol groups.
  • nucleophiles e.g., -NH2, -SH
  • This enables the introduction of additional functional materials with nucleophilic groups, thereby enabling easy secondary modification.
  • galol (1,2,3-trihydroxybenzene)-functionalized coating materials such as poly(carboxylic acid) and poly(pyrogallol) have been found to play a similar role, and related materials have attracted considerable attention due to their versatility in various applications.
  • polyphenol coatings have the following disadvantages: (1) the functionality is limited to catechol and galol, (2) the molar composition of unreacted functional groups is difficult to control and varies from batch to batch, and (3) they are not transparent, which limits their applications requiring transparency.
  • boronic acid is an interesting functional group that is continuously being adopted in various applications, especially in the field of biomaterials.
  • the advantage of boronic acid group lies in the dynamic covalent bond formation with diol groups that are abundant in natural molecules (e.g., glucose) and polymers (e.g., polysaccharides).
  • diol groups that are abundant in natural molecules (e.g., glucose) and polymers (e.g., polysaccharides).
  • boronic acid group can rapidly form boronic acid-diol complexes to form cross-linked structures, and the bond dissociation can be easily controlled by adjusting the pH.
  • pH-sensitive drug delivery systems and biosensors have been successfully developed.
  • boronic acid-containing biopolymers cannot be applied to surface functionalization.
  • the present invention has been completed to provide a surface modification method for boric acid functionalization.
  • the present invention has been made to solve the above problems, and an object of the present invention is to provide a boronic acid functional pressure-sensitive adhesive composed of a butyl group and a boronic acid group for surface functionalization on various substrates, and a one-step boronic acid functionalization method using the same.
  • the present invention provides a method for producing a boronic acid functional pressure-sensitive adhesive, comprising the steps of: synthesizing a scaffold pressure-sensitive adhesive by reacting butyl acrylate and glycidyl methacrylate; and synthesizing a boronic acid pressure-sensitive adhesive by reacting the scaffold pressure-sensitive adhesive with 4-mercaptophenylboronic acid.
  • the molar ratio of the glycidyl methacrylate to the butyl acrylate may be 1:12 to 15.
  • azobisisobutyronitrile and dimethylformamide can be added and reacted at 50 to 70 °C.
  • the hydroxyl group of the above 4-mercaptophenylboronic acid can be protected using pinacol.
  • the step of reacting the scaffold pressure-sensitive adhesive with the 4-mercaptophenylboronic acid to synthesize a boronic acid pressure-sensitive adhesive may include the steps of: dissolving the scaffold pressure-sensitive adhesive and the 4-mercaptophenylboronic acid in tetrahydrofuran, respectively; adding the 4-mercaptophenylboronic acid solution to the scaffold pressure-sensitive adhesive solution; adding DBU (1,8-Diazabicyclo[5.4.0]undec-7-ene) as a catalyst to the mixed solution and reacting at 50 to 60 °C for 22 to 26 hours; and after the reaction step, precipitating the mixed solution using a methanol/water common solvent and then centrifuging the obtained mixture and dissolving the obtained mixture in tetrahydrofuran.
  • a step of deprotecting the pinacol group may be additionally included.
  • the present invention provides a boronic acid functional pressure-sensitive adhesive comprising a boronic acid group and a butyl group.
  • the above-mentioned boronic acid functional pressure-sensitive adhesive can be manufactured by polymerizing butyl acrylate and glycidyl methacrylate.
  • the above-mentioned boronic acid functional pressure-sensitive adhesive can be applied to one or more substrates selected from the group consisting of polymers, metals, and ceramics.
  • the present invention provides an antifouling coating composition comprising a boronic acid functional pressure-sensitive adhesive manufactured by the manufacturing method of claims 1 to 6.
  • the present invention can provide a boronic acid functional pressure-sensitive adhesive composed of a butyl group and a boronic acid group for surface functionalization on various substrates and a method for producing the same.
  • the present invention can provide a one-step boronic acid functionalization method using the pressure-sensitive adhesive.
  • the boronic acid functional pressure-sensitive adhesive according to the present invention can be utilized as an implant coating material, and more specifically, the synthesized alginate-catechol (Alg-Ca), known as an antifouling natural polymer, can be reversibly bonded to a substrate functionalized with boronic acid through catechol-boronate complexation.
  • Alg-Ca synthesized alginate-catechol
  • the boronic acid functional pressure-sensitive adhesive according to the present invention can introduce a boronic acid functional group onto the surface of a specific material and can be utilized in various application fields.
  • Figure 1 is a 1 H NMR spectrum of a scaffold pressure-sensitive adhesive (PSA).
  • Figure 2 is the 1 H NMR spectrum of 4-pMPBA (4-Mercaptophenylboronic acid).
  • Figure 3 is a 1 H NMR spectrum after the reaction between phenyl boronic acid and the scaffold pressure-sensitive adhesive is completed.
  • Figure 4 shows (A) the 1 H NMR spectrum of PSA-BA, (B) the 1 H NMR spectrum comparing the pinacol peaks of PSA-pBA before and after deprotection, and (C) the UV-vis spectra of PSA-pBA and PSA-BA.
  • Figure 5 shows XPS peaks of a bare silicon wafer and a PSA-BA coated silicon wafer.
  • Figure 6 shows the contact angle patterns before and after PSA-BA coating on various substrates (PLLA, PDMS, Au, Aluminum).
  • Figure 7 shows (A) a schematic diagram of Alg-Ca synthesis, (B) 1 H NMR spectrum of Alg-Ca, (C) the degree of catechol substitution of alginate, and the results of measuring ultraviolet absorbance at 280 nm (A280) using a UV-vis spectrophotometer.
  • Figure 8 shows the results of in vitro cytotoxicity tests on bare glass, PSA-BA primary-coated glass, and PSA-BA/Alg-Ca secondary-coated glass.
  • Figure 9 shows (A) a schematic diagram of repeated Alg-Ca coating on a boric acid-functionalized substrate, (B) changes in the atomic percentage of Si2p when PSA-BA (first coating) and Alg-Ca (second coating) are sequentially applied to a bare substrate (silicon wafer), and (C, D, E, F, G, H) fluorescent images of stained bacteria, live and dead bacteria, on each substrate.
  • the present invention provides a method for producing a boronic acid functional pressure-sensitive adhesive, comprising the steps of: synthesizing a scaffold pressure-sensitive adhesive by reacting butyl acrylate and glycidyl methacrylate; and synthesizing a boronic acid pressure-sensitive adhesive by reacting the scaffold pressure-sensitive adhesive with 4-mercaptophenylboronic acid.
  • the above scaffold pressure-sensitive adhesive can be obtained through free radical polymerization of the butyl acrylate and the glycidyl methacrylate.
  • butyl acrylate can induce a low glass transition temperature (Tg) of the pressure-sensitive adhesive, thereby improving flexibility and facilitating chemical interaction with the surface.
  • glycidyl methacrylate can act as a block for introducing special functional molecules.
  • the molar ratio of the glycidyl methacrylate: the butyl acrylate may be 1:12 to 15, more preferably 1:13 to 14, but is not limited thereto.
  • the molar ratio of the glycidyl methacrylate and the butyl acrylate may be set to maximize the functionality while minimizing the influence on the unique glass transition temperature (Tg) ( ⁇ -30°C) required for use as a pressure-sensitive adhesive.
  • azobisisobutyronitrile and dimethylformamide are added and the reaction can be performed at 50 to 70 °C. More specifically, the reaction can be performed at 60 °C, but is not limited thereto.
  • the above 4-mercaptophenylboronic acid can protect the hydroxyl group using pinacol.
  • a nucleophile having a thiol group can be easily covalently bonded to a scaffold by a ring-opening reaction of an epoxide.
  • the ring-opening of the epoxide can be activated not only by the thiol but also by the boronic acid, which may cause unexpected competition.
  • the reaction rate between unprotected phenyl boronic acid and the scaffold pressure-sensitive adhesive may be significantly reduced.
  • the hydroxyl group of 4-mercaptophenylboronic acid can be protected using pinacol in the present invention.
  • the step of reacting the scaffold pressure-sensitive adhesive with the 4-mercaptophenylboronic acid to synthesize a boronic acid pressure-sensitive adhesive may include the steps of: dissolving the scaffold pressure-sensitive adhesive and the 4-mercaptophenylboronic acid in tetrahydrofuran, respectively; adding the 4-mercaptophenylboronic acid solution to the scaffold pressure-sensitive adhesive solution; adding DBU (1,8-Diazabicyclo[5.4.0]undec-7-ene) as a catalyst to the mixed solution and reacting at 50 to 60 °C for 22 to 26 hours; and after the reaction step, precipitating the mixed solution using a methanol/water common solvent and then centrifuging the obtained mixture and dissolving the obtained mixture in tetrahydrofuran.
  • a step of deprotecting the pinacol group may be additionally included.
  • the step of deprotecting the pinacol group of the above boronic acid pressure-sensitive adhesive can obtain the final product, a boronic acid functional pressure-sensitive adhesive, by deprotecting the pinacol group by treating with 5% TFA and MeB(OH) 2 .
  • MeB(OH) 2 can act as a sacrificial molecule because it has a higher binding affinity than phenyl boronic acid.
  • the pinacol group bonded to the original position is removed and can be replaced by phenyl boronic acid through ester exchange (Fig. 4).
  • the present invention provides a boronic acid functional pressure-sensitive adhesive comprising a boronic acid group and a butyl group.
  • the above-mentioned boronic acid functional pressure-sensitive adhesive can be manufactured by polymerizing butyl acrylate and glycidyl methacrylate.
  • the above-mentioned boronic acid functional pressure-sensitive adhesive can be applied to one or more substrates selected from the group consisting of polymers, metals, and ceramics.
  • the coating possibility of a boronic acid functional pressure-sensitive adhesive on not only a silicon substrate but also various polymer and metal substrates can be evaluated using contact angle measurements, and it can be confirmed that the boronic acid functional pressure-sensitive adhesive is successfully coated on all substrates, thereby changing the polarity of the surface.
  • the present invention provides an antifouling coating composition utilizing a boronic acid functional pressure-sensitive adhesive manufactured by the manufacturing method of claims 1 to 6.
  • a new repetitive antifouling technology can be developed by focusing on the reversible bonding characteristics between catechol and boronic acid functional groups.
  • the reason why repetitive coating is necessary is that surrounding organic substances continuously accumulate on the surface over time. For example, if an implant material is continuously used in a physiological environment, even if it exhibits anti-biofouling properties, it will eventually be covered with an organic layer over time.
  • an implant material is continuously used in a physiological environment, even if it exhibits anti-biofouling properties, it will eventually be covered with an organic layer over time.
  • dental implant materials they can be easily coated with polyphenol substances when food is consumed. After being covered with an organic layer, external pathogens such as bacteria can attach to the surface and grow.
  • the anti-biofouling function of the existing surface can be disabled by being covered with an additional layer.
  • This problem can be solved by repeatedly switching and attaching the bio-fouling prevention layer. Even if an organic layer is deposited on the surface, it can be naturally removed by removing the bio-fouling prevention layer underneath. After that, the existing surface can be re-coated with a contamination prevention material to restore the bio-fouling prevention function.
  • PSAs Scaffold pressure-sensitive adhesives
  • BA butyl acrylate
  • GMA glycidyl methacrylate
  • AIBN azobisisobutyronitrile
  • the polymer was precipitated with a common solvent of methanol/water 95:5 (%, v/v) to remove the residual reactants.
  • the precipitate was centrifuged, and the polymer was redissolved in tetrahydrofuran (THF). After repeating this precipitation process three times, the polymer was dried under high vacuum to remove the solvent.
  • the synthesis of the scaffold PSA was confirmed by 1 H NMR spectroscopy.
  • PSA-pBA 4-pMPBA was introduced into the epoxide ring of the scaffold PSA.
  • scaffold PSA (2 g, 1.24 mmol, 1 eq.) was dissolved in anhydrous THF (18 mL) in a round bottom flask, and then purged with inert nitrogen gas.
  • 4-pMPBA (0.388 g, 1.64 mmol, 1.33 eq.) was also dissolved in anhydrous THF (2 mL) and then slowly added dropwise to the PSA solution.
  • Step 4 Production of PSA-BA by removing pinacol from PSA-pBA
  • PSA-pBA Pinacol deprotection of PSA-pBA was performed.
  • PSA-pBA 230 mg
  • anhydrous THF 2.75 mL
  • a solution of methylboronic acid (MeB(OH) 2 ; 1 eq, 60 mg) dissolved in anhydrous THF (2 mL) was added dropwise to the mixture with stirring.
  • trifluoroacetic acid (TFA; 250 ⁇ L) was slowly added dropwise to the mixture, and the reaction was carried out at room temperature for 2 h.
  • the polymer was precipitated with a common solvent of methanol/water 95:5 (%, v/v). After centrifugation of the precipitate, the polymer was redissolved in tetrahydrofuran (THF). Finally, the obtained polymer was solvent-removed using a Schlenk line.
  • the unprotected pinacol group in PSA-pBA was confirmed by 1 H NMR and UV-Vis spectroscopy (UV-1800, Shimadzu, Japan). The conversion was calculated by comparing the integrals of the pinacol peaks before and after the deprotection step, and the distinct peak right next to the pinacol peak was used as a standard.
  • Alg-Ca was synthesized via EDC/NHS coupling reaction.
  • alginate (1 g, approximately 5 mmol) was dissolved in 100 mL of 0.1 M MES buffer (pH 5.2), and the mixture was purged with inert N 2 gas.
  • EDC-HCl (5 mmol, 0.9585 g) and NHS (5 mmol, 0.575 g) were individually added dropwise to the alginate solution at 10 min intervals.
  • PSA-BA was coated on a Si wafer (1 cm ⁇ 1 cm) using a spin coater (SC-300, EHC.Co., Ltd, Japan). Specifically, a PSA-BA solution (20 mg/mL) was dissolved in THF in an oil bath at 50°C. Then, the completely dissolved PSA-BA solution (60 ⁇ L) was dropped all at once onto the Si wafer, and the substrate was spin-coated. Specifically, the first and second coating steps were performed at 1000 rpm for 10 s and 4000 rpm for 20 s, respectively. Finally, the coating was confirmed by contact angle and X-ray photoelectron spectroscopy (see Figure 12).
  • Example 2 The same procedure as Example 1 was followed, except that a PLLA substrate was used instead of a Si wafer.
  • Example 2 The same procedure as in Example 1 was followed except that a PDMS substrate was used instead of a Si wafer.
  • Example 2 The same procedure as in Example 1 was followed except that an Au substrate was used instead of a Si wafer.
  • Example 2 The same procedure as Example 1 was followed, except that an aluminum substrate was used instead of a Si wafer.
  • Alg-Ca was coated on Si wafers modified with PSA-BA.
  • a solution of Alg-Ca (5 mg/mL) dissolved in pH 8.5 Tris buffer was prepared.
  • the PSA-BA-coated substrates were immersed in the solution (4 mL) using a petri dish for each piece. After shaking the dish at 50 rpm for 24 h, the substrates were washed with distilled water and dried with N 2 gas. Finally, the coating of Alg-Ca was confirmed using X-ray photoelectron spectroscopy.
  • Alg-Ca After removing the Alg-Ca layer from the Si wafer modified with PSA-BA and Alg-Ca, Alg-Ca was newly coated. To remove the Alg-Ca layer, the substrate was held obliquely with tweezers and washed with pH 4 PBS buffer for 5 min. Then, the substrate was rinsed with distilled water and dried using nitrogen gas. Alg-Ca recoating of the substrate with only the PSA-BA layer remaining was performed by the previously mentioned method. Both the removal and recoating of Alg-Ca were analyzed by X-ray photoelectron spectroscopy (Nexsa, Thermo Fisher, USA).
  • Bare glass was prepared for comparison of cytotoxicity tests with PSA-BA coated glass.
  • the synthesis of the scaffold PSA was confirmed by 1 H NMR spectroscopy.
  • Figure 1 shows the 1 H NMR spectrum of the scaffold PSA synthesized in Manufacturing Example 1.
  • Figure 2 shows the 1 H NMR spectrum of 4-pMPBA synthesized in Manufacturing Example 1.
  • the synthesized 4-pMPBA can be seen to be grafted via the ring-opening reaction of epoxide.
  • a nucleophile having a thiol group can easily be covalently bonded to a scaffold by the ring-opening reaction of the epoxide group.
  • the ring-opening of the epoxide group can be activated not only by the thiol but also by the boronic acid, resulting in an unexpected competition.
  • the reaction rate of phenyl boronic acid (unprotected) and the scaffold PSA was significantly reduced, as confirmed in the 1 H NMR results (Fig. 3).
  • the final product, PSA-BA was obtained by deprotecting the pinacol group by treating PSA-pBA with 5% TFA and MeB(OH) 2 , and the conversion was about 60% calculated from the 1 H NMR results (Fig. 4 (A), (B)).
  • MeB(OH) 2 acts as a sacrificial molecule because it has a higher binding affinity than phenyl boronic acid.
  • the pinacol group conjugated to the original position was removed and replaced by phenyl boronic acid through ester exchange.
  • the surfaces of bare silicon wafers and PSA-BA-coated silicon wafers were analyzed by XPS.
  • Fig. 5 is an XPS spectrum of the surface of a bare silicon wafer and a silicon wafer coated with PSA-BA. As can be seen in Fig. 5, it can be confirmed that the Si2p peak is significantly reduced after PSA-BA coating.
  • PSA-BA can be applied to various surfaces. This is because of the presence of butyl groups in PSA, which are known to exhibit adhesion to a wide range of substrates and strong van der Waals forces.
  • the possibility of PSA-BA coating on representative polymer and metal (PLLA, PDMS, Au, aluminum) substrates was evaluated using contact angle measurements (Fig. 6). As observed in the experimental results, the contact angle values of all substrates converged to approximately 80° after PSA-BA coating. In particular, the contact angles on relatively polar surfaces (e.g., PLLA, Au, aluminum) increased after coating, whereas those on relatively nonpolar surfaces (e.g., PDMS) decreased.
  • relatively polar surfaces e.g., PLLA, Au, aluminum
  • Alg-Ca The synthesis of Alg-Ca was confirmed by 1 H NMR spectroscopy.
  • the degree of catechol substitution (DOS) of alginate was measured by UV absorbance at 280 nm (A280) using a UV-Vis spectrophotometer (UV-1800, Shimadzu, Japan).
  • a calibration curve was obtained using dopamine hydrochloride solution.
  • Figure 7(A) is a schematic diagram of the synthesis of Alg-Ca
  • Figure 7(B) is a 1 H NMR spectrum of Alg-Ca
  • Figure 7(C) shows the results of measuring the degree of catechol substitution of alginate by measuring the UV absorbance at A280 nm using a UV-vis spectrophotometer.
  • Cytotoxicity tests were performed according to the ISO 10993-5 guideline. L929 cells were used for cytotoxicity tests to confirm the biocompatibility of the samples (Bare glass, PSA-BA primary coating, PSA-BA/Alg-Ca secondary coating). The cells were maintained in a medium at 37°C in a 5% CO 2 humidified incubator. Cells that were passaged twice were harvested and seeded in a 24-well plate at a density of 0.05 x 10 5 cells per well. The samples cut into 10 mm ⁇ 10 mm pieces were placed in the well plates, and the cell suspension was slowly dispensed. After that, they were cultured for 24 h in a 5% CO 2 humidified incubator at 37°C.
  • CCK-8 assay solution For cytotoxicity tests, one drop of CCK-8 assay solution was added to each well, and 100 ⁇ L of the supernatant from each well was transferred to a 96-well plate. Absorbance was read at 450 nm using a microplate reader (Infinite 200 Pro, Tecan, Mannedorf, Switzerland).
  • both modified surfaces showed biocompatibility and similar cell viability compared to the bare substrate (Fig. 8).
  • the antifouling properties of the coated glass were evaluated based on the degree of adhesion of E. coil (KRIBB, Korea). Specifically, the modified substrate was placed in a 24-well plate, and the bacterial solution (5.3 ⁇ 10 9 CFU/mL) was dispensed. The plate was then incubated at 37°C for 24 h. After overnight, the plate was removed from the incubator, and the substrate was washed three times with sterile PBS. The washed sample was then transferred to a new 24-well plate, and 1 mL of sterile PBS was dispensed into each well.
  • KRIBB E. coil
  • the bacterial live/dead reagent (3 ⁇ L per mL, Invitrogen, USA) was added to each well, and the plate was placed back into the 37°C incubator for 15 min. After incubation, the substrate surface was covered with a bare glass substrate, and fluorescence images were observed using a confocal microscope (ECLIPSE Ts2-FL, Nikon, Japan).
  • Figure 9(C, D, E, F, G, H) shows the results of bacterial attachment based on sequential coating (1, 2, 1', 2' coating).
  • the area of the exposed substrate (SiO 2 ) was set as 1, and the degrees of attachment of the remaining substrates were compared and analyzed using ImageJ. After functionalizing the bare substrate with PSA-BA (1 coating), the degree of bacterial attachment was reduced to 92.0%.
  • Acrylic adhesives are generally resistant to microbial communities due to their smooth texture and nutrient-poor properties. However, the adhesive alone cannot completely prevent bacterial attachment. The observation results showed that bacteria attached to the surface and began to form an organic layer during 24 hours of incubation.
  • the antifouling coating surface (2 coating) was exposed to a tank containing living marine life (squid) for a week. Then, bacteria were cultured on the surface according to the same procedure as before. As a result, it was confirmed that the bacterial adhesion ability was significantly increased by about 3.4 times (Fig. 9(G)). After treatment with a pH 4 PBS solution for 5 min to remove the antifouling and organic layers, when the Alg-Ca coating was reapplied, it was confirmed that the adhesion rate decreased again to 99.8% compared to the bare surface. In other words, it was proven that repetitive modification of a biofouling surface is possible through PSA-BA functionalization (see Fig. 14).

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Abstract

La présente invention concerne un adhésif sensible à la pression fonctionnel d'acide boronique. Plus spécifiquement, la présente invention concerne un procédé de fabrication d'un adhésif sensible à la pression fonctionnel d'acide boronique, le procédé comprenant les étapes consistant à : synthétiser un adhésif sensible à la pression d'échafaudage par réaction d'acrylate de butyle avec du méthacrylate de glycidyle; et synthétiser un adhésif sensible à la pression d'acide boronique par réaction d'un adhésif sensible à la pression d'échafaudage avec de l'acide 4-mercaptophénylboronique. De plus, la présente invention concerne un adhésif sensible à la pression fonctionnel d'acide boronique comprenant un groupe acide boronique et un groupe butyle. De plus, la présente invention concerne un matériau de revêtement fonctionnel et une composition de revêtement antisalissure, comprenant l'adhésif sensible à la pression d'acide boronique selon la présente invention.
PCT/KR2024/006225 2023-05-30 2024-05-09 Adhésif sensible à la pression fonctionnel d'acide boronique et son procédé de fabrication Pending WO2024248354A1 (fr)

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KR20150139286A (ko) * 2014-06-03 2015-12-11 포항공과대학교 산학협력단 카테콜기와 티올기를 함유하는 화합물, 이의 제조방법 및 용도
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