[go: up one dir, main page]

WO2012060620A2 - Réseau ssq/peg anti-encrassement biologique et son procédé de préparation - Google Patents

Réseau ssq/peg anti-encrassement biologique et son procédé de préparation Download PDF

Info

Publication number
WO2012060620A2
WO2012060620A2 PCT/KR2011/008278 KR2011008278W WO2012060620A2 WO 2012060620 A2 WO2012060620 A2 WO 2012060620A2 KR 2011008278 W KR2011008278 W KR 2011008278W WO 2012060620 A2 WO2012060620 A2 WO 2012060620A2
Authority
WO
WIPO (PCT)
Prior art keywords
ssq
peg
network
peg network
polyethylene glycol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2011/008278
Other languages
English (en)
Korean (ko)
Other versions
WO2012060620A3 (fr
Inventor
정봉현
이봉국
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Korea Research Institute of Bioscience and Biotechnology KRIBB
Original Assignee
Korea Research Institute of Bioscience and Biotechnology KRIBB
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Korea Research Institute of Bioscience and Biotechnology KRIBB filed Critical Korea Research Institute of Bioscience and Biotechnology KRIBB
Publication of WO2012060620A2 publication Critical patent/WO2012060620A2/fr
Publication of WO2012060620A3 publication Critical patent/WO2012060620A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28—Materials for coating prostheses
    • A61L27/34—Macromolecular materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • 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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • 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
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D171/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/045—Polysiloxanes containing less than 25 silicon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/05—Polymer mixtures characterised by other features containing polymer components which can react with one another

Definitions

  • the present invention relates to an anti-bioadhesive SSQ / PEG network and a method for manufacturing the same, and more specifically, polyethylene glycol (PEG) and photocurable silsesquioxane (SSQ) are mixed and prepared by UV curing, and a solid substrate.
  • PEG polyethylene glycol
  • SSQ photocurable silsesquioxane
  • the present invention relates to an SSQ / PEG network having high resistance to non-specific adsorption used for coating a film and capable of direct nano-patterning and a method of manufacturing the same.
  • the problem of nonspecific adsorption can be prevented by precoating the surface with a material that is resistant to the adsorption of biomaterials, and can be avoided by poly (vinylalcohol), polyethylene glycol (PEG, poly (ethyleneglycol)), poly Various polymeric materials, such as acrylamide, dextran, and methacrylated phosphatidylcholine, have been used as coatings for the prevention or minimization of nonspecific adsorption (Amanda A. etal. Mallapragada, Biotechnol. Prog. , 17: 917, 2001; Harris J. M. et al., Poly (ethyleneglycol) chemistry. Biotechnicaland Biomedical Applications, 1992; Park S.
  • the coating material was used in the form of self-assembled monolayer (SAM), polymer brush, hydrogel, and immobilized on the solid surface by covalent bonds such as physical adsorption and chemical coupling.
  • SAM self-assembled monolayer
  • Poly (ethyleneglycol) chemistry Biotechnicaland Biomedical Applications, 1992; Park S. etal., J. Biomed. Mater. Res. 53: 568 , 2000; Masson J. F. et al., Talanta , 67: 918 , 2005; Ishihara K., Sci. Technol. Adv. Mater.
  • precoatings such as antimicrobial self-assembled monolayers, polymer brushes, or hydrogels on the solid surface
  • precoatings there is a disadvantage to stability.
  • PEG based SAMs are unstable and have been reported to oxidize rapidly, especially in the presence of oxygen and transition metal ions (Ostuni et al., Langmuir , 17: 5605,2001; Chen S. et al., J. Am. Chem. Soc. , 127: 14473,2005; Crouzet C. et al., Makromol. Chem .
  • biomedical devices, biosensors, and lab-on-a-chips is important because the instability of antimicrobial materials is directly related to accuracy, sensitivity, and reproducibility in biosensing. This requires the development of stable antimicrobial materials.
  • stable anti-bioadhesive materials should be made of nanostructures by appropriate patterning methods with high productivity, low cost and high reproducibility for the production and production of biomedical devices, nanobiosensors, and lab-on-a-chips.
  • direct nanopatterning of antimicrobial materials is much more efficient than indirect patterning methods (Revzin A et al., Langmuir , 19: 9855,2003; Lee B.K. etal., Small , 4: 342, 2008; Lee B. K. et al., Lab Chip , 9: 132 , 2009; Kim P. et al., Adv. Mater. , 20:31 , 2008).
  • a sufficiently hard material with a tensile modulus of 100 MPa or more is required (Palmieri F. et al., ACSNano , 1: 307, 2007).
  • the ideal anti-bioadhesive material for advanced performance in a wide range of biomedical applications is not only high anti-biofouling property (Revzin A et al., Langmuir , 19: 9855,2003; Lee B.K. et al., Small , 4: 342, 2008; Lee B. K. etal., LabChip , 9: 132, 2009; Kim P. et al., Adv. Mater. , 20:31, 2008), low viscosity, high optical transparency , High hydrophilicity (Jeong HE et al., Small , 3: 778,2007), high resistance to swelling in organic / aqueous solutions (Kim P.
  • the present inventors have made intensive efforts to develop an ideal anti-bioadhesive material having various properties for the above-mentioned wide range of biomedical applications, and thus photocurable silsesquioxane in photocurable PEG that can be directly patterned into an anti-bioadhesive material.
  • SSQ low viscosity photocurable SSQ / PEG mixture with improved PEG's unstable thermal stability, mechanical strength, insulation, swelling, and the like
  • 2 wt% UV initiator added to the mixture
  • simple UV Irradiation crosslinks the low viscosity photocurable SSQ / PEG mixture to produce an SSQ / PEG network, wherein the prepared SSQ / PEG network has a high anti-biofouling of less than 4.6%.
  • UV embossing enables the fabrication of direct micropatterns of 25 nm or less.
  • the present invention comprises the steps of (a) mixing polyethylene glycol (PEG) and photocurable silsesquioxane (SSQ); And (b) curing the mixture (a) by irradiating UV in the presence of a UV initiator to obtain an SSQ / PEG network.
  • PEG polyethylene glycol
  • SSQ photocurable silsesquioxane
  • the present invention also provides an SSQ / PEG network produced by the above method.
  • the present invention also provides a method of manufacturing a nanopattern, characterized in that using the SSQ / PEG network.
  • the present invention also provides nanodevices having high resistance to nonspecific adsorption including nanopatterns prepared by the above method.
  • Figure 1 shows the anti-bioadhesive SSQ / PEG network components and reaction schemes capable of free radical polymerization.
  • FIG. 3 shows UV-Vis transmission spectra of SSQ / PEG networks polymerized by free radical polymerization on a quartz substrate.
  • Figure 5 graphically shows the expansion rate of SSQ / PEG network for toluene and PBS.
  • FIG. 7 is a schematic diagram of a nanostructure fabrication process of SSQ / PEG mixture using UV embossing (a), Si master (b) with 50 nm features, Si master (c) with 25 nm features, 50 nm FE-SEM images of 50SSQMA / 50PEGDMA330 (d) nano patterned with features and 50SSQMA / 50PEGDMA330 (e) nano patterned with 25 nm features are shown.
  • Figure 8 shows the AFM height images and shrinkage of NIM-80L master mold (a), UV-embossed 50SSQMA / 50PEGDMA330 (b), UV-embossed 50SSQMA / 50PEGDMA550 (c) and UV-embossed 50SSQMA / 50PEGDMA750 (d). .
  • Figure 9 shows the optical image of the glass (a), 50SSQMA / 50PEGDMA330 network (b) and 50SSQOG / PEGGDG526 network (c) and component (d) of the 50SSQOG / 50PEGDG526 network capable of cationic polymerization.
  • FIG. 10 shows liposomes (ac) and EGFP (optionally adsorbed on 50SSQMA / 50PEGDMA330 (b, e) and 50SSQOG / 50PEGDG526 (c, f) prepared on glass (a, d), PET film) df) fluorescence image.
  • FIG. 11 shows a non-adhesive SSQ / PEG network prepared by free radical polymerization for biomedical applications up to 25 nm in size.
  • the present invention in order to increase the crosslinking density of the PEG network, a photocurable SSQ was mixed and a photoinitiator was added to prepare an SSQ / PEG network using free radical polymerization.
  • a photocurable SSQ was mixed and a photoinitiator was added to prepare an SSQ / PEG network using free radical polymerization.
  • the present invention in one aspect, (a) mixing polyethylene glycol (PEG) and photocurable silsesquioxane (SSQ); And (b) curing the mixture (a) by irradiating UV in the presence of a UV initiator to obtain an SSQ / PEG network.
  • PEG polyethylene glycol
  • SSQ photocurable silsesquioxane
  • the polyethylene glycol may be selected from the group consisting of polyethylene glycol dimethacrylate (PEGDMA) and polyethylene glycol diacrylate (PEGDA), the photocurable silsesquioxane (SSQ) can be characterized as functionalized with methacrylate or acrylate.
  • PEGDMA polyethylene glycol dimethacrylate
  • PEGDA polyethylene glycol diacrylate
  • SSQ photocurable silsesquioxane
  • the UV initiator is 2,2'-dimethoxy-2-phenylacetophenone (DMPA, 2,2'-dimethoxy-2-phenylacetophenone), 2-hydroxy-2-methyl-1-phenyl- Propane-1-one (HMPP, 2-hydroxy-2-methyl-1-phenyl-propane-1-one), 2,4,6-trimethylbenzoyl diphenylphosphine oxide (2,4,6-Trimethylbenzoyl-diphenylphosphine Oxide) and diphenyl 2,4,6-trimethylbenzoyl phosphine oxide (Diphenyl 2,4,6-trimethylbenzoyl phosphine oxide) may be selected from the group consisting of.
  • DMPA 2,2'-dimethoxy-2-phenylacetophenone
  • HMPP 2-hydroxy-2-methyl-1-phenyl- Propane-1-one
  • HMPP 2-hydroxy-2-methyl-1-phenyl-propane-1-one
  • the present invention confirmed the UV-Vis permeability, surface hydrophilicity, swelling and mechanical properties of the SSQ / PEG network.
  • the present invention relates to an SSQ / PEG network produced by the above method.
  • the SSQ / PEG network is (a) at least 90% UV transmission at a wavelength of 365nm or more; (b) a positive contact angle of 42.2-54.5 °; (c) mechanical strength of 1.898 to 2.815GPa; (d) an expansion ratio of 1.3 to 20.5 wt% based on the organic solvent and the aqueous solution; (e) shrinkage of 3% or less; And (f) less than 4.6% antimicrobial adhesion.
  • the SSQ / PEG network may be characterized by direct nanopatterning, direct nanopatterning is UV nanoimprint (UV nanoimprint), UV embossing (UV embossing) and UV replica molding (UV replica molding) It may be characterized in that it is performed by any one method selected from the group consisting of.
  • the present invention provides an SSQ / PEG mixture using a UV embossing method from a master mold to a high line-to-space density (1: 1), high aspect ratio (4: 1) and low shrinkage ( ⁇ SSQ / PEG networks were patterned with relief nanostructures of 25-nm or smaller features with 3%).
  • the present invention confirmed the anti-bioadhesion of the nano patterned SSQ / PEG network using a fluorescence method.
  • the SSQ / PEG network strongly prevented the adsorption of negatively charged liposomes and confirmed that they have long-term stability against chemical stress, thermal stress and biological stress.
  • the present invention relates to a method of manufacturing a nanopattern, which uses an SSQ / PEG network.
  • the size of the nanopattern may be characterized in that less than 25nm.
  • the present invention relates to a nanodevice having high resistance to nonspecific adsorption including a nanopattern produced by the above method.
  • the nanodevice may be selected from the group consisting of biomedical devices, biosensors, diagnostic arrays, implantation and delivery systems, and lab-on-a-chips.
  • SSQ multifunctionalized with methacrylate a mixture of various SSQMAs [(C 7 H 11 O 2 ) n (SiO 1.5 ) n ], where n is 8, 10 or 12: the weight ratio of PEG is 2: 8 and 5: 5
  • SSQ SSQMA, Methacrylate multi-functionalized SSQ; Hybrid Plastics
  • PEGDMA330 Sigma Aldrich
  • PEGDMA550 Sigma Aldrich
  • PEGDMA750 Sigma Aldrich
  • PEGDA575 Sigma Aldrich
  • the SSQ / PEG network was prepared by curing the SSQ / PEG mixture by irradiating 365 nm of UV (ultraviolet dose: 1000 mJ / cm 2 ) for 30 minutes using a UV lamp (Toscure251; Toshiba) in a vacuum state ( 1).
  • the viscosity of the SSQ / PEG mixture was measured using a Brookfield viscometer Model DV-II Pro (Brookfield Engineering Labs Inc.) at 25 ° C., as shown in FIG. 2, depending on the SSQ / PEG mixture, ranging from 20.8 to 175 cP. Low viscosity.
  • UV-Vis transmittance of the 50SSQ / 50PEG network was measured in a wavelength range of 200 to 800 nm using a spectrophotometer (UVmini-1420; Shimadzu). Measured.
  • Surface hydrophilicity is a desirable property for preventing nonspecific adsorption of biomolecules, especially in micro / nanofluid channel applications, which allows for the introduction of biological reagents without a pump (Jeong HE et al., Small , 3: 778, 2007).
  • the surface hydrophilic static contact angle of SSQ / PEG network was measured and confirmed.
  • the SSQ / PEG mixture was dispensed into small droplets on a Si wafer modified with PFOS (trichloro (1H, 1H, 2H, 2H-perfluorooctyl) silane; Sigma Aldrich).
  • PFOS trichloro (1H, 1H, 2H, 2H-perfluorooctyl
  • the transparent support made of 188 ⁇ m thick PET (poly (ethylene terephthalate) film was placed on the surface and a 1 ⁇ m thick SSQ / PEG mixture was placed under vacuum using a UV lamp (Toscure251; Toshiba) for 30 minutes.
  • UV ultraviolet (ultraviolet dose: 1000 mJ / cm 2 ) was irradiated to cure the SSQ / PEG mixture to prepare a flat SSQ / PEG network
  • a 5 ⁇ l drop of distilled water was placed on a flat SSQ / PEG network using a contact angle analyzer (Mouse-X; SurfaceTech Co.).
  • SCA initial static contact angle
  • the equilibrium static contact angle of all networks was measured from 42.2 to 54.5 °, and the equilibrium static contact angle of all networks was slightly smaller than the initial static contact angle by surface hydration by continuous exposure to water. Lowered.
  • the positive contact angle of PEGDMA330 decreased as the ratio of SSQMA increased, whereas the positive contact angle of PEGDMA550, PEGDMA575 and PEGDMA750 increased as the ratio of SSQMA increased.
  • the static contact angle values of all kinds of SSQ / PEG networks were smaller than the static contact angle values of PEGDMA330 homopolymers, which means that all kinds of SSQ / PEG networks remain hydrophilic.
  • the expansion ratio of the PEG / SSQ network in toluene and PBS was measured to be 1.3 ⁇ 20.5 wt%, the expansion ratio of the PEG homopolymer increased with increasing the molecular weight of the PEG, PEG expansion rate of the homopolymer It was confirmed that the relative concentration of the SSQ increases, and decreases as the molecular weight of the PEG homopolymer decreases. This result is due to the increased crosslinking density of the network by SSQMA.
  • the 50SSQMA / 50PEGDMA330 network exhibited negligible water expansion (1.3 wt .-%).
  • Non-swellable 50SSQMA / 50PEGDMA330 networks can be used as insulating films for electrochemical biosensors because redox agents, such as ferricyanide compounds dissolved in buffer solutions, cannot pass through non-swellable films.
  • Nanopatterning up to 25 nm with high line-to-space ratio (1: 1) and high aspect ratio (4: 1) is possible when the polymer network has sufficient mechanical strength to maintain the structure.
  • the Young's modulus of the crosslinked PEGDMA330 is 1GPa
  • the Young's modulus of the PEGDMA550 is 40.3 MPa
  • the PEGDMA750 Young's modulus is 16.5 MPa.
  • the smallest Young's modulus for the 50SSQMA / 50PEGDMA330, 50SSQMA / 50PEGDMA550 and 50SSQMA / 50PEGDMA750 networks were measured to be 2.815, 2.038 and 1.898 GPa, respectively. These results are significantly higher than the Young's modulus of PEG homopolymers and higher than the Young's modulus values of previously studied polymer materials used as anti-bioadhesive materials (Amanda A. etal., Biotechnol. Prog. , 17: 917,2001; Kim A. et al., Lab Chip , 6: 1432,2006; HuZ. Et al., J. Am. Chem. Soc. , 130: 14244, 2008).
  • SSQ / PEG networks with high Young's modulus are capable of direct nanopatterning up to 25nm.
  • UV embossing method with high productivity, low cost and high reproducibility was used for direct nanopatterning of the 50SSQ / 50PEG mixture (FIG. 7A).
  • SSQ / PEG mixture was dispensed drop by drop onto a silicone master modified with PFOS as a release agent.
  • the silicon master mold was used by purchasing NIM25L / 100, NIM-80L, and NIM-100H having a line-to-space ratio of 1: 1 and a height of 100 nm in a size of 25-200 nm in NTT-AT Coporation.
  • a transparent support such as glass or PET film modified with TMSPM was carefully transferred onto the surface and in vacuum the support was compressed at an imprinting pressure of 0.1 MPa for 10 seconds.
  • the 50SSQ / 50PEG mixture was UV irradiated for 3 minutes from the top of the transparent substrate while the pressure was maintained by a nanoimprinter system (NM-401; Meisyo Kiko Co., Ltd) equipped with a UV lamp (Toscure251; Toshiba) under vacuum. UV dose: 200 mJ / cm 2 ), and then the mold was separated from the substrate.
  • NM-401 Meisyo Kiko Co., Ltd
  • UV lamp Toscure251; Toshiba
  • FE-SEM Field emission scanning electron microscopy, S-4300 type microscope; Hitachi Co.
  • the 50SSQ / 50PEG network was coated with a 10 nm gold layer before analysis using the Quick Coater SC-701HMC (Sanyu Electron Co., Ltd.), and the patterned nanostructures were vibrated at ambient temperature (tapping mode). Photographs were taken with a Digital Instruments NanoScope III atomic force microscope (Veeco Instruments). Data was processed using SPIP V3.3.7.0 software.
  • the low viscosity 50SSQMA / 50PEGDMA330 mixture was replicated from the silicon master to the nanostructures using UV embossing at a relatively short time of 190 seconds at room temperature and low pressure of 0.1 MPa.
  • the pattern of uniformly replicated parallel lines with half-pitches of 50 nm and 25 nm did not differ from the silicon master and no defects were found at smaller sizes.
  • the same results as for the 50SSMQA / 50PEGDMA330 were confirmed for nanopatterning of other 50SSQ / 50PEG mixtures.
  • the shrinkage of the nano-patterned 50SSQ / 50PEG network showed a low shrinkage of less than 3% as shown in FIG. 8, which improves the accuracy of the nanopattern and extends the life of the master mold. .
  • SSQMA / PEGDMA having an 800 nm dot pattern and SSQOG / PEGDG having an 800 nm dot pattern were prepared as a comparative group (FIG. 9).
  • SSQOG / PEGDG having the 800 nm dot pattern is a 50:50 wt .-% glycidyl ether octa-functionalized SSQ (Toagosei Co., Ltd.) / PEGDG (PEG) which is a cationic polymerizable mixture for UV embossing.
  • liposomes containing texas-red 1,2-dihexadecanoyl-sn-glycero-phosphoethanolamine (molecular probes) and enhanced green fluorescence protein (EGFP) are modeled. Used as a biomolecule.
  • POPC phospholipid 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine; Avanti Polar Lipids Inc.
  • SA stearic acid; Sigma Aldrich
  • with a molar ratio of 80: 20: 1 of 50 nm diameter 10 mM liposome suspensions of TR-DHPE were prepared using an extrusion method in PBS at pH 7.4.
  • 3 mM EGFP purified from E. coli was suspended in 10 mM PBS.
  • the liposomes and protein solution were dropped on a glass, SSQMA / PEGDMA having an 800 nm dot pattern and an SSQOG / PEGDG substrate having an 800 nm dot pattern, incubated at room temperature for 1 hour, and washed with PBS, followed by fluorescence addition apparatus (IX-FLA; Fluorescence images for each substrate were obtained using an Olympus BX51 inverted research microscope with Olympus and a high resolution digital camera (DP70; Olympus) for image acquisition. Red luminescence of 590 nm and more and green light emission of 480-550 nm were filtered using U-MWG and U-MSWG Olympus filter cubes, respectively.
  • SSQMA / PEGDMA having an 800 nm dot pattern strongly prevented nonspecific adsorption of liposomes compared to SSQOG / PEGDG having a glass and 800 nm dot pattern.
  • the fluorescence intensity of TR-DHPE and EGFP on the surface was systematically measured, and when compared with the glass at 100%, all SSQMA / PEGDMA networks were liposome and It was confirmed to prevent the adsorption of EGFP to less than 4.6%.
  • the prevention of biomolecule adsorption is due to the heavy hydration of PEG, good structural flexibility and high chain mobility.
  • hydrated PEGs with flexibility and mobility in SSQ / PEG networks can prevent nonspecific adsorption of organisms
  • SSQOG / PEGDG networks prepared by cationic polymerization react with liposomes containing negatively charged SAs and Electrostatic interactions between the EGFP and the positively charged SSQOG / PEGDG surface resulted in uniform and high adsorption of biomolecules.
  • the free radical polymerization step is more appropriate than the cationic polymerization step.
  • the pattern of the 50SSQMA / 50PEGDMA network did not degrade even after long standing for 12 hours at a high concentration of 10 mM liposomes in 10 mM PBS at pH 7.4.
  • SSQ / PEG networks with high optical transmission, low viscosity, non-swellability, hydrophilicity, high mechanical strength and high stability against chemical stress, thermal stress and biological stress can be free radical polymerized and directly nanopatterned. It can be used in a variety of biomedical applications such as nanobiodevices, nanobiosensors and lab-on-a-chips.
  • the anti-bioadhesive SSQ / PEG network according to the present invention not only has high anti-biofouling, but also low viscosity, high optical transparency, high hydrophilicity, high resistance to swelling in organic / aqueous solutions, biological and chemical And it has high stability against thermal stress and high mechanical strength, it is possible to manufacture direct micropattern up to 25nm can be easily used for advanced performance of a wide range of biomedical applications.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Dermatology (AREA)
  • Public Health (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Veterinary Medicine (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Transplantation (AREA)
  • Epidemiology (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • Polyethers (AREA)
  • Paints Or Removers (AREA)
  • Medicinal Preparation (AREA)

Abstract

La présente invention porte sur un réseau SSQ/PEG anti-encrassement biologique et sur son procédé de préparation. En particulier, la présente invention porte sur un réseau SSQ/PEG, et son procédé de préparation, le réseau étant préparé par durcissement d'un mélange de polyéthylène glycol (PEG) et de silsesquioxane (SSQ) photodurcissable à l'aide de rayons UV, ayant une haute résistance à une adsorption non spécifique qui est utilisée pour revêtir un substrat solide, et pouvant être directement soumis à une formation de motifs nanométriques. Le réseau SSQ/PEG anti-encrassement biologique selon la présente invention possède non seulement une propriété anti-encrassement biologique mais encore une faible viscosité, une haute transparence optique, une haute hydrophilicité, une propriété anti-gonflement en solution organique/aqueuse, de hautes stabilités contre des contraintes biologiques, chimiques et thermiques, et une haute résistance mécanique, et peut également subir une formation de motifs fins à une échelle inférieure à 25 nm directement afin d'être facilement utilisé pour des performances de haute technologie dans un large éventail d'applications biomédicales.
PCT/KR2011/008278 2010-11-02 2011-11-02 Réseau ssq/peg anti-encrassement biologique et son procédé de préparation Ceased WO2012060620A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2010-0108233 2010-11-02
KR1020100108233A KR20120046532A (ko) 2010-11-02 2010-11-02 항생물부착성 ｓｓｑ／ｐｅｇ 네트워크 및 그 제조방법

Publications (2)

Publication Number Publication Date
WO2012060620A2 true WO2012060620A2 (fr) 2012-05-10
WO2012060620A3 WO2012060620A3 (fr) 2012-08-02

Family

ID=46024946

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2011/008278 Ceased WO2012060620A2 (fr) 2010-11-02 2011-11-02 Réseau ssq/peg anti-encrassement biologique et son procédé de préparation

Country Status (2)

Country Link
KR (1) KR20120046532A (fr)
WO (1) WO2012060620A2 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2540786A4 (fr) * 2010-02-26 2013-08-07 Nippon Steel & Sumikin Chem Co Composition d'agent de revêtement
CN103642043A (zh) * 2013-11-04 2014-03-19 西南石油大学 一种梯形醚链聚倍半硅氧烷聚合物及其制备方法
WO2018118932A1 (fr) 2016-12-22 2018-06-28 Illumina, Inc. Appareil d'impression
US10018867B2 (en) 2015-11-30 2018-07-10 Lg Display Co., Ltd. Nano capsule liquid crystal layer and liquid crystal display device including the same
CN120022427A (zh) * 2025-02-20 2025-05-23 武汉大学中南医院 一种脱细胞猪心包与poss-peg-cho交联的生物纳米复合材料及其制备方法和应用

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5043789A (en) * 1990-03-15 1991-08-27 International Business Machines Corporation Planarizing silsesquioxane copolymer coating

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2540786A4 (fr) * 2010-02-26 2013-08-07 Nippon Steel & Sumikin Chem Co Composition d'agent de revêtement
CN103642043A (zh) * 2013-11-04 2014-03-19 西南石油大学 一种梯形醚链聚倍半硅氧烷聚合物及其制备方法
CN103642043B (zh) * 2013-11-04 2016-01-20 西南石油大学 一种梯形醚链聚倍半硅氧烷聚合物及其制备方法
US10018867B2 (en) 2015-11-30 2018-07-10 Lg Display Co., Ltd. Nano capsule liquid crystal layer and liquid crystal display device including the same
WO2018118932A1 (fr) 2016-12-22 2018-06-28 Illumina, Inc. Appareil d'impression
CN110226128A (zh) * 2016-12-22 2019-09-10 伊鲁米那股份有限公司 压印设备
EP3559745A4 (fr) * 2016-12-22 2020-11-11 Illumina, Inc. Appareil d'impression
US11213976B2 (en) 2016-12-22 2022-01-04 Illumina, Inc. Imprinting apparatus
AU2017382163B2 (en) * 2016-12-22 2022-06-09 Illumina Cambridge Limited Imprinting apparatus
CN110226128B (zh) * 2016-12-22 2024-07-02 伊鲁米那股份有限公司 压印设备
US12157252B2 (en) 2016-12-22 2024-12-03 Illumina, Inc. Imprinting apparatus including silicon master with a plurality of nanofeatures and an anti-stick layer having a cyclosiloxane and method of forming
CN120022427A (zh) * 2025-02-20 2025-05-23 武汉大学中南医院 一种脱细胞猪心包与poss-peg-cho交联的生物纳米复合材料及其制备方法和应用

Also Published As

Publication number Publication date
KR20120046532A (ko) 2012-05-10
WO2012060620A3 (fr) 2012-08-02

Similar Documents

Publication Publication Date Title
US20140010970A1 (en) Photocurable polyethylene glycol silsesquioxane, polyethylene glycol silsesquioxane network prepared therefrom, anti-biofouling device including the polyethylene glycol silsesquioxane network, and method of preparing nano-pattern
Fu et al. Preparation of cross-linked polystyrene hollow nanospheres via surface-initiated atom transfer radical polymerizations
WO2012070833A2 (fr) Composition de résine durcissable sous l'action d'un rayonnement et procédé de fabrication d'un moule auto-réplicable l'utilisant
Liu et al. Potential skin layers for membranes with tunable nanochannels
AU2006251389B2 (en) Hydrophobic coating
US7220452B2 (en) Multilayer transfer patterning using polymer-on-polymer stamping
KR101582384B1 (ko) 코드화된 고분자 미세입자
WO2012060620A2 (fr) Réseau ssq/peg anti-encrassement biologique et son procédé de préparation
KR101468817B1 (ko) 초소수성 표면의 제조방법
US8119248B2 (en) Organic-inorganic hybrid free standing film, and its production method
JPH0792695A (ja) 薄膜パターン形成法
US20220155211A1 (en) Altering flow cell signals
WO2013060087A1 (fr) Composé silsesquioxane oligomère polyédrique contenant un groupe fonctionnel mercapto, sa composition et matrice souple pour l'impression
Kalulu et al. Hydrophilic surface modification of polydimetylsiloxane‐co‐2‐hydroxyethylmethacrylate (PDMS‐HEMA) by Silwet L‐77 (heptamethyltrisiloxane) surface treatment
JP2011508712A (ja) 封入触媒を使ったゾル−ゲル法
Kohli et al. Nanostructured crosslinkable micropatterns by amphiphilic dendrimer stamping
CN118703089B (zh) 一种涂层材料、基于其的具有表面微结构阵列的防雾抗污涂层及涂层的制备方法
Lee et al. Direct nanopatterning of silsesquioxane/poly (ethylene glycol) blends with high stability and nonfouling properties
Yang et al. Stimuli‐Responsive Hybrid Coatings of Polyelectrolyte Multilayers and Nano‐Patterned Polymer Brushes
Yun et al. Silica/Ultraviolet-Cured Resin Nanocomposites for Replica Molds in Ultraviolet Nanoimprinting
Fozdar et al. Flash imprint lithography using a mask aligner: a method for printing nanostructures inphotosensitive hydrogels
JP5584872B2 (ja) 高分子ナノ構造体を表面に備える基板及びその製造方法
CN119024644B (zh) 纳米压印光刻胶及其制备方法
Shin et al. Fabrication of contact lens containing high‐performance wire grid polarizer
TWI406091B (zh) The curable composition and the preparation method of the article having the transparent protective layer using the composition

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11838225

Country of ref document: EP

Kind code of ref document: A2

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11838225

Country of ref document: EP

Kind code of ref document: A2