WO2006025592A1 - 薄膜状高分子構造体とその調製方法 - Google Patents
薄膜状高分子構造体とその調製方法 Download PDFInfo
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- WO2006025592A1 WO2006025592A1 PCT/JP2005/016371 JP2005016371W WO2006025592A1 WO 2006025592 A1 WO2006025592 A1 WO 2006025592A1 JP 2005016371 W JP2005016371 W JP 2005016371W WO 2006025592 A1 WO2006025592 A1 WO 2006025592A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
- B29C41/12—Spreading-out the material on a substrate, e.g. on the surface of a liquid
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L89/00—Compositions of proteins; Compositions of derivatives thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
Definitions
- the present invention relates to a method for preparing an arbitrary-shaped thin film polymer structure.
- LB Langmuir-Blodgett
- the target molecule to which this method can be applied must be one that can be developed on the water surface as a monomolecular film, and is limited only to amphiphilic molecules that are insoluble in water.
- the LB method is not efficient, and the equipment used is expensive and not easy to handle.
- SAMs self-assembled monolayers
- metals such as gold and platinum
- inorganic materials such as silicon, silica, and glass.
- SAMs self-assembled monolayers
- the feature of this technology is that the monomolecular film is stable due to its strong bonding force with the substrate ⁇ point, and because the monomolecular film can be constructed just by submerging the substrate in the solution, it does not require special equipment and is inexpensive. This is a simple point. Furthermore, it can cope with a substrate having a complicated shape.
- stacking molecules on a two-dimensional plane for example, electrostatic interaction of polyelectrolytes Attempts have also been made to construct a three-dimensional structure in a bottom-up manner using the alternating lamination method.
- This lamination method is based on the following principle.
- the polymer electrolyte solution is immersed in the surface of the substrate having the opposite charge, and only one layer is adsorbed by electrostatic interaction. At that time, the charge on the substrate becomes a new opposite charge due to the excessive charge of the adsorbed polyelectrolyte.
- a polymer electrolyte having a charge opposite to that of the previous polymer electrolyte is further adsorbed on the surface.
- these structures are a method of constructing a functional thin film including a substrate as a scaffold, and no attempt has been made to peel the structure from the substrate and use it.
- a hollow structure having a bowl shape can be obtained by forming a polyelectrolyte complex on the surface of inorganic or metal fine particles or cells, and then dissolving the bowl.
- Silica, latex beads, melamine resin, etc. are used for the fine particles of the vertical type, and the vertical type is dissolved by HF (hydrogen fluoride), organic solvent, acid, and the like.
- HF hydrogen fluoride
- a molecular assembly constructed by introducing a polymerizable group into an amphiphilic molecule.
- micelles, vesicles, ribbons, tubes, disks, sheets, etc. are dispersed in water and polymerized to polymerize them, but the synthesis of polymerizable amphiphilic molecules is complicated. Because the aggregate structure is determined by the structure of the amphiphilic molecule, it is difficult to control the aggregate structure. Disclosure of the invention
- An object of the present invention is to provide a thin film polymer structure having an arbitrary shape and a preparation method thereof.
- the present inventor for example, after forming a self-assembled monolayer on a circular gold substrate, adsorbing and crosslinking albumin as a polyfunctional molecule, it was found that a thin albumin polymer thin film was peeled from the gold substrate to obtain a thin film polymer structure, and the present invention was completed. Further, before the thin film high molecular structure is peeled from the gold substrate, the recognition protein is bound to the surface of the structure and then peeled off. Further, when the above-described thin film structure is allowed to act on a substrate having molecules recognized by the recognition protein immobilized on the surface, the structure adheres with the back surface facing the top surface.
- the present invention is as follows.
- a thin film polymer structure comprising the following steps:
- a thin-film polymer structure having a functional substance on one side of the film which has the following steps: (a) adsorbing multifunctional molecules in an arbitrarily shaped region at the interface with the liquid phase of the substrate;
- a thin-film polymer structure having a functional substance on one side of the film which has the following steps:
- a multifunctional molecule containing the functional substance is bonded to an area of an arbitrary shape at the interface with the liquid phase of the substrate and containing a substance that recognizes the functional substance
- a thin film polymer structure having a functional substance on one side of the membrane and having an arbitrary modification on the other side comprising the following steps:
- a method for preparing a thin film polymer structure having a functional substance on one side of a membrane comprising the following steps:
- a method for preparing a thin film polymer structure having a functional substance on one side of a film comprising the following steps:
- a multifunctional molecule containing the functional substance is bonded to an area of an arbitrary shape at the interface with the liquid phase of the substrate and containing a substance that recognizes the functional substance
- a method for preparing a thin film polymer structure having a functional substance on one side of a membrane and an arbitrary modification on the other side comprising the following steps:
- the step of polymerizing and crosslinking or crosslinking the polyfunctional molecule may further include a step of charge-crosslinking by alternately laminating oppositely charged polymer electrolytes.
- the multifunctional molecule include a multifunctional monomer and / or a multifunctional macromer.
- protein, a polyelectrolyte, or a polymer bead can be illustrated, for example.
- the cross-linking of the polyfunctional macromer is performed by physical cross-linking such as heat denaturation or thermoplasticity, or melting.
- examples of the modification include a modification with a polymer compound such as polyethylene glycol, a protein, a peptide, a sugar chain, and a Z or piotin derivative.
- a polymer compound such as polyethylene glycol, a protein, a peptide, a sugar chain, and a Z or piotin derivative.
- the region is a region having a structure of a self-assembled monolayer or a self-assembled bilayer membrane.
- the self-assembled monomolecular film include those formed from a linear hydrophobic molecule having an SH group, a closed alkylsilyl group, an alkoxyalkylsilyl group, or a vinyl group at the terminal.
- the self-assembled bilayer membrane includes one or more selected from the group consisting of phospholipid, amino acid type lipid, glycolipid, or cationic lipid.
- the above region is preferably a region modified with a temperature-responsive polymer, and peeling is due to a temperature drop.
- the whole or a part of the substrate is made of a metal or its oxide film, silicon, silica or glass, a strong material such as my strength, graphite, or a calcium compound such as a parameter. .
- peeling can be performed by treating with a surfactant or an organic solvent, or by adding an aqueous solution containing a compound that competes with a functional substance.
- FIG. 1 is a conceptual diagram of production of the thin film polymer structure of the present invention.
- Figure 2 is a schematic diagram of the preparation of albumin nanosheets.
- FIG. 3 is a diagram showing the measurement results of the contact angle at each stage of preparing the albumin nanosheet.
- Fig. 4 is a graph showing the change in frequency in the quartz crystal microbalance method.
- Fig. 5 is a photograph showing the observation results of albumin nanosheets with a fluorescence microscope.
- Figure 7 is a diagram showing the observation results of rHSA adsorbed to the ODMS-Si0 2 substrate by fluorescence microscopy.
- Figure 8 is a schematic diagram of a fabrication of a rHSA sheet on ODMS-Si0 2 substrate.
- FIG. 9 is a diagram showing the results of observation of rHSA-SH or rHSA with a fluorescence microscope before and after addition of C 12 E 1 Q to (a) ODMS-SiO 2 substrate. (B) It is a figure which shows the observation result of the rHSA sheet
- FIG. 10 is a diagram showing an SEM image of (rHSA) LB on an ODMS substrate.
- Figure 11 shows the (rHSA) LB sheet on an ODMS substrate formed by fusing.
- Embodiments of the present invention will be described below, but they are examples for explaining the present invention, and the present invention is not limited to these embodiments.
- the present invention can be implemented in various forms without departing from the gist thereof.
- a polyfunctional molecule is adsorbed on a region of an arbitrary shape on the interface with a liquid phase on a substrate (hereinafter also referred to as “substrate”), and then polymerized. And a thin film is formed by cross-linking or cross-linking, and the thin film is peeled off from the substrate.
- substrate a liquid phase on a substrate
- the method of the present invention makes it possible to easily peel off a thin film from a substrate (or a fixed carrier).
- the thin film polymer structure of the present invention is a single layer or a laminated thin film in which polyfunctional molecules are polymerized and / or crosslinked.
- the thin film polymer structure of the present invention may have a functional substance on one side of the film, or may have a functional substance on one side of the film, and an arbitrary modification is applied to the other side. May be.
- the structure can be obtained as a polymer thin film dispersion.
- a dispersion in which the thin film polymer structure of the present invention is dispersed in a liquid is also included in the present invention.
- the “interface with the liquid phase of the substrate” means an interface where the solid substrate is in contact with a liquid such as water, an aqueous solution or an organic solvent.
- the shape of the region that adsorbs the multifunctional molecule is an arbitrary shape and is not particularly limited. Examples thereof include a circle, a rectangle, an ellipse, a ribbon, a string, a multi-branch, and a star.
- a self-assembled monolayer (SAM) or a self-assembled bilayer (SAB) is formed at the interface with the liquid phase on the substrate. It is preferable.
- the interface is preferably modified with a temperature-responsive polymer.
- “Self-assembled monolayer” means a membrane composed of linear hydrophobic molecules having a functional group capable of binding to the substrate at the end, and is fixed to the surface of the metal substrate by the functional group. A film is formed ( Figure 1A).
- “Self-assembled bilayer membrane” (SAB) is a bilayer membrane constructed by an amphiphilic molecule containing a hydrophobic hydrocarbon chain such as a lipid and a hydrophilic polar head. It is a bilayer film formed by self-organization in a hydrophilic region or a region having a charge opposite to that of the polar head of an amphiphilic molecule.
- SAM Self-assembled monolayer
- the “self-assembled film” means a film that spontaneously forms.
- the substrate is not particularly limited as long as it can adsorb polyfunctional molecules.
- the substrate for forming SAM or SAB is not particularly limited as long as SAM or SAB can be formed.
- the substrate is not particularly limited as long as it can be modified.
- a metal plate such as gold, silver, platinum, copper, iron, aluminum, titanium, or zinc, or a flat plate on which these metals are deposited can be used.
- the substrate the above-mentioned metals or oxide film thereof, silicon, oxidized silicon (Si0 2), silica or glass, My power, carbon materials such as graphs eye DOO, calcium compounds such as Apatai bets
- silicon oxidized silicon (Si0 2)
- silica or glass oxidized silicon (Si0 2)
- My power carbon materials such as graphs eye DOO
- calcium compounds such as Apatai bets
- the hydrophobic part in the hydrophobic molecule forming SAM is a straight chain having an SH group, a closed alkylsilyl group, an alkoxyloleolsilyl group, a vinyl group, an amino group, a carbonyl group, etc. at the terminal. In general, it is a saturated hydrocarbon chain having 4 to 40 carbon atoms, preferably 8 to 18 carbon atoms.
- linear hydrophobic molecules having SH groups include alkanethiols. Arcanci Examples of all include undecanethiol, dodecanethiol, and tetradecanethiol.
- the hydrophobic molecule may be an alkene or alkyne containing an unsaturated bond, an isoprenoid skeleton having a branched structure, or a molecule having a steroid ring.
- the SAM can be spontaneously formed by dissolving the hydrophobic molecule having an SH group on a gold substrate in a solvent such as ethanol and contacting or immersing this solution in the gold substrate.
- SAMs can be obtained from long-chain molecules with vinyl groups on silicon substrates, and long-chain molecules with silica- and alkylalkylsilyl groups on silica and metal substrate surfaces.
- long-chain hydrophobic molecules having these groups include octadecyldimethylchlorosilane, trialkoxyhexadecylsilane, octadecyltrimethoxysilane
- the amphipathic molecule constituting SAB may be any molecule containing a hydrophobic part and a hydrophilic part in the molecule.
- SAB can easily form a film having a bilayer structure by coating an organic solvent in which amphipathic molecules such as lipids are dissolved on a substrate. After that, the region having a bilayer structure can be formed by decomposing and removing the dilayer structure of the region that has not been masked by electron beam irradiation.
- a substrate having an anionic or cationic region by surface treatment is contacted or immersed in a dispersion of a cationic lipid or an anionic lipid, whereby SAB can be spontaneously formed in the region. .
- the SAB is spontaneously formed by contacting or immersing a substrate having a SAM-formed region with a solution or dispersion of an amphiphilic molecule. be able to.
- the substrate may be modified with a temperature-responsive polymer.
- the temperature-responsive polymer is such that the polymer chain contracts above the phase transition temperature and becomes a gel state due to the hydrophobic interaction, and below the phase transition temperature, the polymer chain swells and becomes a fluid state.
- poly (N-isopropyl chloride) (PIPAAm) or a copolymer thereof can be used.
- PIPAAm poly (N-isopropyl chloride)
- the interface with the aqueous phase of the temperature-responsive polymer modified on the substrate is hydrophobic above the phase transition temperature, whereas the interface is hydrophilic below the phase transition temperature.
- the method of modifying and adsorbing the temperature-responsive polymer on the substrate may be simply applying PIPAAm on the substrate and drying it.
- PIPAAm on a polystyrene substrate
- light irradiation polymerization may be used. It may be grafted.
- These polymers can be adsorbed or chemically modified on an arbitrary region of the substrate by using a masking technique described later.
- the region of the surface-treated substrate that is, the region of the SAM forming substrate, SAB forming substrate, or temperature-responsive polymer film forming substrate can be formed into a region of an arbitrary shape using masking. it can.
- a photomask method will be described. However, those skilled in the art can appropriately select and implement the method, and the method is not limited to the following.
- a resist is formed on the surface-treated substrate.
- a positive photoresist can be applied to a surface-treated substrate with a spin coater at 800 rpm for 3 seconds, followed by 7000 rpm for 20 seconds, and then heated and dried at, for example, 110 ° C for 90 seconds. Les. If the rotation speed and rotation time are increased, the film thickness of the photoresist ⁇ decreases, and the heating temperature and heating time are not limited to the methods described above as long as the resist solvent evaporates.
- the resist is exposed through a photomask. For exposure, electron beam irradiation, ultraviolet irradiation, X-ray irradiation, etc. may be performed for 1 to 60 seconds, preferably 5 to 20 seconds.
- the photomask can be, for example, a 10 / zm X 30; um rectangle or a 3 m diameter circle.
- display the resist on the photosensitive substrate The image is allowed to dry, while the unexposed areas of the resist are removed.
- 0 2 plasma treatment, CO plasma treatment, SAM not protected by Regis Bok by reactive ion etch ing treatment using a halogen gas to remove the SAB or temperature-responsive polymer film.
- the resist is removed with a resist-soluble solvent such as acetone, THF, or dichloromethane. Accordingly, a region having a desired shape (for example, a micro pattern) having a film structure or modified with a temperature-responsive polymer can be formed.
- Examples of the substance that is a constituent element of the thin film to be adsorbed on the region of the boundary surface with the liquid phase of the substrate include, for example, a polyfunctional monomer or a polyfunctional macromer. A multifunctional molecule is mentioned.
- a polyfunctional monomer or macromer is a molecule having two or more same or different functional groups in one molecule.
- the multifunctional monomer include amino acids, sugars and other amino monomers, carboxyl groups, hydroxyl groups, mercapto groups, isocyanato groups, aldehyde groups, epoxy groups, cyanur groups, divinylolbenzene And monomers having a plurality of bur groups such as divinino ethenole, divininole sulfone and bismaleimide.
- multifunctional macromers include proteins, polylysine, polyglutamic acid, hydrolysates of polystyrene-free water-free maleic acid copolymer, chitosan, alginic acid, and polymer beads.
- the monomer or macromer is monofunctional, it can be used in combination with a polyfunctional one.
- a polymer such as polystyrene or poly (Nippon Prolacton), or a polyfunctional molecule (such as albumin) adsorbed or chemically modified on the surface of a bead made of a copolymer of L-lactic acid and dalicholic acid is used. It can also be done.
- albumin such as BSA (cushion serum albumin) and HSA (human serum albumin)
- hemoglobin examples include bottles, myoglobin, soluble collagen, and fibrinogen.
- the protein may be purified from a biological sample by a known method, or may be a peptide synthesized by a peptide synthesizer.
- a recombinant protein produced in a host such as a mammalian cell, E.
- coli or yeast by a known method, and then purified is used.
- You can also For example, a pyridyl disulfide group, a maleimide group, or a succinimide group bonded to a functional group such as an amino group, a carboxyl group, or a hydroxyl group of a protein via a spacer having an appropriate length. Can also be used. Proteins can also be used in the form of latex beads coated with protein (see Examples 10-12).
- a polymer bead is a polymer obtained by emulsion polymerization or suspension polymerization of a monomer having a vinyl group, granulated by the 0 / W emulsion method, or a polymer obtained by ring-opening polymerization using a cyclic compound as a monomer. It means a product that is emulsified with a surfactant and granulated, and a product obtained by polymerizing a polyfunctional macromer.
- the polymer beads include latex beads composed of polystyrene-co-divinylbenzene and the like. Biodegradable beads can also be used as polymer beads.
- the polyfunctional molecule may be an amphiphilic molecule.
- amphiphilic molecules include polymerizable phospholipids, amino acid-type lipids, and glycolipids having a gen group and a bull group in the 1-acyl chain and the 2-acyl chain.
- a thin film (thin film polymer) can be formed from a single type of molecule or a combination of multiple types of molecules.
- the combination can be a combination of multiple multifunctional monomers, a combination of multiple multifunctional macromers, or a combination of multifunctional monomers and macromers.
- You can use polymer beads coated with protein as polyfunctional molecules.
- Polyfunctional polymers adsorb on SAM, SAB, or temperature-sensitive polymer film on the surface-treated substrate to form a polymer thin film.
- the molecules that form) are arranged with the hydrophobic portion oriented in SAM.
- polymerization and / or crosslinking are performed as appropriate to form a polymer thin film on the surface-treated substrate (for example, on SAM) (FIG. 1C).
- the adsorption of the polyfunctional polymer on the SAM may be performed by contacting or immersing the SAM-forming substrate in a dispersion containing the polyfunctional molecule or in a dispersion. Thereby, a thin film of polyfunctional polymer can be formed.
- a polymer electrolyte having a charge opposite to the surface charge of SAB.
- the region may be contacted or immersed in a solution or dispersion of the polyfunctional molecule.
- a polymer thin film can be formed.
- the state of the temperature-responsive polymer during bonding is preferably a gel state.
- the temperature during adsorption is preferably higher than the phase transition temperature of the temperature-responsive polymer.
- the SAM, SAB or temperature-responsive polymer membrane can also be adsorbed by repeating the operation of pulling out the polyfunctional molecule solution from the solution at an appropriate rate.
- polyfunctional molecules since the contact utilizes the surface tension at the gas-liquid interface, polyfunctional molecules may be adsorbed on the membrane more selectively than in liquid contact.
- polymerization means a polymer formation reaction
- Molecular polymerization methods include polycondensation, polyaddition, addition condensation, ring-opening polymerization, addition polymerization. (Radical force polymerization, anion polymerization, cationic polymerization), solid phase polymerization by heat, photopolymerization, radiation polymerization, plasma polymerization And so on.
- crosslinking means that a chemical bond is formed between some specific atoms in a linear polymer.
- 3D network structure is formed by cross-linking To do.
- Examples of molecular crosslinking methods include urethane bonds and urea bonds by isocyanate groups, formation of Schiff bases by aldehyde groups, and disulfide bonds by mercapto groups.
- Examples of the cross-linking agent include alkyl diimidates, acyl diazides, disoocyanates, bismaleimides, triazinyls, diazo compounds, dartal aldehyde, N-succinimidyl-3- (2-pyridyldithio) alkionate, bromocyan, and the like. be able to.
- the cross-linking between the polyfunctional macromers may be physical cross-linking such as coagulation by heat denaturation.
- the surface may be partially melted and physically crosslinked.
- the polymer beads may be completely heated and melted to form a thin film having an arbitrary shape.
- Protein processing conditions can be appropriately set according to the nature of the protein. For example, in the case of albumin, heat denaturation by treatment at 60 to 120 ° C, preferably 70 to 100 ° C for 1 to 60 minutes, preferably 10 to 30 minutes. And can be cross-linked.
- the polymer beads are used at a temperature of 1100 to 1550 ° C, preferably 1100 to 120 ° C. By treating for 2 seconds to 5 minutes, preferably 10 seconds to 60 seconds, it can be partially dissolved and made to stand. Alternatively, the polymer beads are treated at a temperature of 100 to 1550 ° C, preferably 1100 to 120 ° C for 30 to 10 minutes, preferably 1 to 5 minutes, It can be completely melted by heating. After the polymerization and crosslinking, the polyfunctional molecules that form a thin film may be adsorbed on the formation substrate such as SAM or SAB on which the thin film is already formed, and the polymerization and crosslinking may be repeated. .
- a polymer electrolyte can also be used as the polyfunctional macromer of the constituent elements of the thin film.
- a surface-treated substrate such as SAM or SAB in a dilute solution of oppositely charged polyelectrolytes (polycation and polyanion)
- the polyelectrolyte is adsorbed spontaneously on SAM or SAB, A thin film in which polycation and polyanion are laminated is formed.
- Polymers such as chitosan, polylysine, polyarginine, polyhistidine, ionene, poly (quaternized pyridine), diallyldialkylammonium salt are included in the above polycations, alginic acid, Examples thereof include polyglutamic acid, polymethacrylic acid, polyacrylic acid, polystyrene sulfonic acid, alkali metal salts thereof, and alkaline earth metal salts. Alkaline hydrolysates of alternating copolymers of maleic anhydride and styrene can also be used.
- the polycation and polyion that constitute the laminated film formed by this alternate adsorption method are cross-linked by an electrostatic force to form a thin film. Further, by dehydrating and condensing between an amino group and a carboxylic acid residue between polyion complexes, a thin film can also be formed by crosslinking as an amide group by a covalent bond.
- Thin films formed as described above are also within the scope of the present invention.
- the thin film formed at the interface with the liquid phase of the substrate may be a single layer film or a laminated film.
- the substrate may be washed before and after the polyfunctional molecule adsorption, polymerization / crosslinking treatment. Cleaning can be performed by contacting or immersing the substrate in the cleaning solution one or more times.
- the thin film polymer thus formed is peeled from the substrate (or the surface of the SAM when SAM is formed) to obtain a thin film polymer structure (Fig. 1D).
- the substrate on which the thin film is formed is brought into contact with the surfactant solution, immersed, immersed and then shaken, or repeatedly subjected to a vibration force or pulling operation, or the thin film is formed.
- the substrate is contacted, immersed, or immersed in an organic solvent, and then shaken, vibrated, or repeatedly pulled out.
- the type of the surfactant is not particularly limited.
- nonionic surfactants such as C 12 E 10 (polyoxyethylene 10'lauryl ether), Teen 20, ritorrX, sodium cholate, sodium dodecyl sulfate, Palmitic An ionic surfactant such as sodium acid can be mentioned.
- the type of the organic solvent is not particularly limited as long as the thin film can be peeled off.
- alcohols such as ethanol and methanol, THF, DMF, chloroform, dichloromethane, benzene, toluene, ethyl acetate, etc. Can be mentioned. Delamination is believed to occur between the SAM or SAB and the thin film.
- the thin film structure formed on the surface of SAB for example, a laminated film formed by the alternate adsorption method of polymer electrolyte
- the entire SAB or the structure side of the bilayer structure This occurs when the monomolecular film is dissolved in an organic solvent. Therefore, in the case of SAM, the dispersion of the peeled structure does not contain the components of SAM, and the structure is composed of multifunctional components.
- the dispersion of the peeled structure is The liquid contains SAB components, and the structure can be purified by centrifugation, filtration, or ultrafiltration.
- the substrate When peeling a polymer structure on a thin film formed on a gel-state temperature-responsive polymer modified on the surface of the substrate, the substrate is contacted and immersed in an appropriate aqueous solution, and the temperature is set to the phase transition temperature. After that, repeat shaking, shaking, or pulling out. ⁇
- a functional substance can be bound on a film obtained by polymerizing or crosslinking polyfunctional molecules (FIG. 1E), and the thin film can be peeled off from the substrate (FIG. 1F).
- a thin film polymer structure having a functional substance on one side of the film can be produced.
- a functional substance is a substance that recognizes molecules such as a recognition protein on the cell membrane, its ligand, an antigen or an antibody, a substance that promotes a specific reaction such as a catalyst or an enzyme, an antioxidant or a radical scavenger, etc. It means a substance involved in the reaction.
- a method for producing such a thin film polymer structure is as follows.
- an arbitrary shape at the interface with the liquid phase of the substrate A polyfunctional molecule is adsorbed in the region, and the adsorbed polyfunctional molecule (for example, polymer electrolyte) is polymerized and Z or crosslinked to form a polymer thin film (FIGS. 1A to C).
- the adsorbed polyfunctional molecule for example, polymer electrolyte
- FIG. 1E the thin film-like polymer structure having the functional substance can be obtained by peeling the thin film from the substrate (see FIG. 1). 1 F).
- the peeling of the thin film from the substrate can be performed in the same manner as in the above “peeling of the thin film”.
- an amino group, a carboxyl group, a hydroxyl group, a mercapto group, an isocyanate group, an aldehyde group introduced into the polyfunctional monomer or macromer constituting the thin film It can be bonded to an epoxy group, a cyanuric group, or a vinyl group via a functional group that can be bonded.
- the bonding reaction between a functional molecule and a thin film is a urethane bond or a urea bond due to a reaction between a hydroxyl group or an amino group and an isocyanate group, formation of a Schiff base due to a reaction between an amino group and an aldehyde group, mercapto A disulfide bond between groups, a reaction between a mercapto group and a pyridyldisulfide group or a maleimide group, or a reaction between a carbonyl group and a succinimide group can be used.
- Ligan can be introduced on the thin film side or the functional material side, and the functional substance can be fixed on the thin film using a complex with an acceptor introduced on the functional material side or the thin film side.
- Specific examples include a combination of piotin and avidin, sugar chain and lectin, antigen and antibody, drug and receptor, enzyme and substrate.
- a SAM, SAB, temperature-responsive polymer film, or the like in which a substance capable of recognizing a functional substance (referred to as “recognition substance”) is bonded to the surface of the substrate.
- recognition substance a substance capable of recognizing a functional substance
- Figure 1G The recognition substance is the other substance that forms a pair with the “functional substance”.
- a functional substance is bound to a polyfunctional molecule (for example, a polyelectrolyte), and the polyfunctional molecule is adsorbed on the SAM, SAB or temperature-responsive polymer membrane.
- a complex is formed between the recognition substance bound to the surface of the SAM, SAB or temperature-responsive polymer film and the functional substance bound to the polyfunctional molecule.
- a method for bonding the functional substance to the polyfunctional molecule a method similar to the method for bonding the functional substance to the thin film can be used.
- the recognition substance is covalently bonded in advance to a part of the molecules constituting the SAM, SAB or temperature-responsive polymer film.
- the chemical bonding method uses the same method as the above-described method of bonding the functional substance to the thin film, and the physical bonding method includes electrostatic interaction, hydrophobic interaction, hydrogen bonding. Use intermolecular force.
- the binding density of the recognition substance to the SAM, SAB, and temperature-responsive polymer film is preferably controlled according to the density of the functional substance in the target thin film polymer structure.
- the thin film can be peeled by adding a substance that competes with the functional substance or a substance that competes with the recognition substance (for example, an aqueous solution containing a low molecular weight compound).
- a substance that competes with the functional substance for example, an aqueous solution containing a low molecular weight compound.
- the recognition substance remains on the SAM, SAB, or temperature-responsive polymer film, and is not included in the dissociated thin film polymer structure.
- Examples of combinations of a functional substance and its partner include piotin and avidin, sugar chain and lectin, antigen and antibody, drug and receptor, enzyme and substrate, and the like. Thus, one of these substances can be bound to the membrane.
- Enzymes include force tarase, horseradish peroxidase, chymotrypsin, cytochrome, ⁇ -amylase,] 3 'amylase, galactosidase, glycocelle brosidase, blood coagulation factor, peroxidase, protease, cellular And hemase ⁇ / lase, xylanase, lipase, pullulanase, isomerase, dalcoamylase, glucose isomerase, glutaminase, ⁇ -dalcanase, serine protease, and the like, but are not limited thereto.
- the present invention provides a method for preparing a thin film high molecular structure in which a surface is modified by bonding a substance to one or both surfaces of the thin film.
- the thin film polymer structure having a modified membrane surface is obtained by applying any modification to the other surface of the structure having a functional substance on one surface prepared in 2 above. is there.
- a thin-film polymer structure having a functional substance on its surface is fixed to a substrate surface having a recognition substance. Fixing to the substrate occurs spontaneously by bringing the dispersion of the structure into contact with, dipping, or shaking the substrate. Since the functional substance is bound on the thin film, the thin film is turned upside down and bound to the recognition substance via the functional substance (Fig. 1G).
- the surface of the thin film (the surface different from the bonding surface of the functional substance) is modified with an appropriate modifying substance (Fig. 1H), and the thin film is peeled off so that the functional substance is present on one side of the film.
- the other side of the membrane is made with a modifier attached ( Figure 11).
- the thin film can be peeled by adding a substance that competes with the functional substance or a substance that competes with the recognition substance (for example, an aqueous solution containing a low molecular weight compound).
- a substance that competes with the functional substance for example, an aqueous solution containing a low molecular weight compound.
- the recognition substance remains on the SAM, SAB, or temperature-responsive polymer film, and is not included in the peeled thin film polymer structure.
- a thin film obtained by the method of the present invention that is, a polymer ultrathin film (referred to as “nano jellyfish”) in which a functional substance is bonded to one surface and an arbitrary modification is applied to the other surface is also disclosed.
- a polymer ultrathin film referred to as “nano jellyfish” in which a functional substance is bonded to one surface and an arbitrary modification is applied to the other surface is also disclosed.
- Examples of the functional substance partner (recognition substance) possessed by the nano jellyfish include substances that can specifically recognize the functional substances described above, such as GPIb, GPIalla, p-selectin, but are not limited thereto. It is not something.
- the modification applied to the surface opposite to the surface to which the functional substance is bonded is not particularly limited.
- a polymer compound for example, polyethylene glycol (PEG)
- protein for example, polyethylene glycol (PEG)
- peptide for example, polypeptide
- the term “piotine derivative” means a peotine in which an active group such as an amino group or a carboxyl group, or an active ester group such as a pyridyldisulfide group or a succinimidyl group is bonded.
- the nano jellyfish can be used as a drug carrier (for example, a functional carrier or a platelet substitute in a drug delivery system).
- a drug carrier for example, a functional carrier or a platelet substitute in a drug delivery system.
- the modification includes, for example, ( a ) a drug, (b) a substance containing a site that specifically recognizes a target tissue cell (specific recognition substance), and (c) nano It may be a substance for stabilizing jellyfish in the body. Specific examples of these modifiers are as follows.
- Drugs anti-inflammatory agents, hemostatic agents, vasodilators, thrombolytic agents, anti-arteriosclerotic agents, etc.
- the method of modifying an arbitrary substance is, for example, that a hydroxyl group or an amino group of an arbitrary substance activates a carboxyl group of an arbitrary substance by urethane bonding or urea bonding by an isocyanate group of a nano jellyfish.
- Amide bond with amino group of nano jellyfish, bond between amino group of any substance and amino group of nano jellyfish with Schiff base by dartal aldehyde, Lü's amino group is a hydroxyl group and an amide bond or an ester bond.
- Any substance is a polysaccharide, and after forming an imido carbonate with cyanogen bromide, the amino group of nano jellyfish
- the mercapto group of any substance include disulfide bonds between activated mercapto groups of nano jellyfish.
- alkyl diimidates, acyl diazides, diisocynates, bismaleimides, triazinyls, diazo compounds, dartal aldehyde, N-succinimidinore-3- (2-pyridyldithio) alkionate, bromocyan, Etc. can be used to crosslink with the corresponding functional group.
- any substance is hydrophobic, it is hydrophobic interaction in the hydrophobic region of the jellyfish, if it is hydrogen-bonded, it is hydrogen-bonded in the hydrogen-bonded region of the nano jellyfish, and if it has a charge, the opposite charge of the nano jellyfish It can be bonded to the region of
- albumin nanosheets were prepared by the following steps (FIG. 2).
- the gold substrate was immersed in an ethanol solution of ImM undecanethiol and allowed to stand at room temperature for 18 hours to form SAM. Next, the SAM forming gold substrate was cleaned.
- the washed SAM-forming gold substrate was immersed in 2.5 mg / mL rHSA acetate buffer (pH 5.0) and allowed to stand at room temperature for 1 hour to adsorb rHSA onto the SAM. Subsequently, the substrate was cleaned.
- the washed substrate was immersed in 25% (v / v) glutaldehyde and allowed to stand at room temperature for 30 minutes to crosslink rHSA. (4) rHSA sheet peeling
- albumin nanosheet rHSA sheet
- rHSA sheet rHSA sheet
- C 12 E 10 polyoxyethylene 10-lauryl ether
- FIG. 4 shows a graph of the frequency change results. From Fig. 4, it is clear that the frequency change is 86 Hz. Considering that the 1 Hz change in frequency corresponds to 0.86 ng of rHSA adsorption, it was calculated that 74 ng of rHSA was adsorbed.
- Example 4 Observation of albumin nanosheets with a fluorescence microscope
- the purpose of this example is to examine the presence or absence of a change in the shape of albumin by peeling a nanosheet using a surfactant.
- the shape of the albumin nanosheet on the gold substrate before peeling and the shape of the albumin nanosheet on the glass substrate were peeled off from the gold substrate with a surfactant, and observed with a fluorescence microscope.
- a positive photoresist was applied using Subinko one coater (800 rpm, 3 s + 7000 rpm, 20 s), the heating Dry (110 ° C, 90 s). After applying a photomask (rectangle; 10 ⁇ m X 30 ⁇ ) and UV irradiation (7 s), a resist pattern was obtained on the substrate through development and drying operations.
- ODMS O Kuta decyl trimethinecyanine Tokishishiran
- LC-SPDP succinimidyl 6- [3 '-(2-pyridyldithio) propionamido] hexanoate
- rHSA crosslinking agent
- GPC gel permeation matrix
- PD pyridyl disulfide
- rHSA-SH was obtained.
- Example 9 Fluorescence microscopy of rHSA thin film polymer structure fabricated on ODMS-Si0 2 substrate
- the thin film formation microphone port patterned ODMS-Si0 2 substrate prepared in Example 8 was observed by fluorescence microscopy, only ODMS region is fluoresce, confirmed rHSA-SH channel selection ⁇ adsorption did it. Therefore, when immersed in a C 12 E 10 aqueous solution (conditions where rHSA can be peeled off the substrate) (room temperature, 1 hour), rHSA-SH does not peel off, stays on the substrate, and is immersed for 6 hours. It peeled off (Fig. 8, Fig. 9 (a)).
- a thin film-like polymer with the structure is peeled Te carefully transferred convex on the cover glass (room temperature, 6 hours) was fluorescence microscopy, substantially the same sheet as the shape observed with ODMS-Si0 2 substrate The shape was observed (Fig. 9 (b)). It was thought that the out of focus was due to the curvature of the sheet in the liquid phase.
- Example 1 Preparation of rHSA Coated Latex Beads (rHSA Coated LB, (rHSA) LB) Disperse ⁇ ( ⁇ 200 nm) in rHSA solution (20 mg / mL, lmL), shake (room temperature, 2 hours), LB RHSA was physically adsorbed on the surface.
- Example 1 2 ODMS-Si0 2 Adsorption of rHSA-coated LB
- ODMS- The operation of pulling out the Si0 2 substrate (Example 6) was repeated several times in a short time to adsorb rHSA on the substrate.
- the substrate was washed with ultrapure water, dried, and observed by scanning electron microscope.
- Fig. 10 (a) selective adsorption of rHSA-coated LB to the hydrophobic ODMS region was confirmed (Fig. 10 (a)). Almost all LBs were densely packed in the region and were in point contact (Fig. 10 (b)).
- a thin film polymer structure having an arbitrary shape and a preparation method thereof are provided.
- the structure of the present invention can be used as a functional carrier or a platelet substitute in a drug delivery system by binding a target recognition site or the like to the structure.
Abstract
Description
Claims
Priority Applications (7)
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US11/658,908 US20120034466A1 (en) | 2004-08-31 | 2005-08-31 | Thin-Filmy Polymeric Structure and Method of Preparing the Same |
CA 2576723 CA2576723A1 (en) | 2004-08-31 | 2005-08-31 | Thin-filmy polymeric structure and method of preparing the same |
DE200560026671 DE602005026671D1 (de) | 2004-08-31 | 2005-08-31 | Dünnschichtige polymerstruktur und verfahren zu ihrer herstellung |
EP20050782124 EP1785448B1 (en) | 2004-08-31 | 2005-08-31 | Thin-filmy polymeric structure and method of preparing the same |
AT05782124T ATE500289T1 (de) | 2004-08-31 | 2005-08-31 | Dünnschichtige polymerstruktur und verfahren zu ihrer herstellung |
JP2006532023A JPWO2006025592A1 (ja) | 2004-08-31 | 2005-08-31 | 薄膜状高分子構造体とその調製方法 |
AU2005278317A AU2005278317A1 (en) | 2004-08-31 | 2005-08-31 | Thin-filmy polymeric structure and method of preparing the same |
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JP (1) | JPWO2006025592A1 (ja) |
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CN (1) | CN101023123A (ja) |
AT (1) | ATE500289T1 (ja) |
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JP2006306759A (ja) * | 2005-04-27 | 2006-11-09 | Fujimori Kogyo Co Ltd | トロンビン医薬製剤 |
WO2008050913A1 (fr) | 2006-10-27 | 2008-05-02 | Shinji Takeoka | Structure polymère de type film et son procédé de préparation |
JP2010518436A (ja) * | 2007-02-09 | 2010-05-27 | ノバルティス アーゲー | コンタクトレンズ用架橋性ポリイオンコーティング |
WO2011046226A1 (ja) * | 2009-10-13 | 2011-04-21 | 株式会社バイオナノシータ | 高分子超薄膜分散体及びその調製方法 |
WO2012137610A1 (ja) | 2011-04-08 | 2012-10-11 | 国立大学法人山梨大学 | 医薬製剤 |
WO2013137260A1 (ja) | 2012-03-12 | 2013-09-19 | ナノシータ株式会社 | 高分子超薄膜及び多孔質高分子超薄膜 |
US9949897B2 (en) | 2012-04-11 | 2018-04-24 | L'oreal | Self-standing cosmetic sheet |
JP2018158973A (ja) * | 2017-03-22 | 2018-10-11 | リンテック株式会社 | 高分子薄膜分散体の製造方法 |
CN110548413A (zh) * | 2018-06-04 | 2019-12-10 | 宁波蓝盾新材料科技有限公司 | 一种新型纳米原子级海水淡化薄膜及其制备方法与应用 |
KR20200097715A (ko) | 2017-12-15 | 2020-08-19 | 도레이 카부시키가이샤 | 고분자 박막의 제조 장치 및 제조 방법 |
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- 2005-08-31 DE DE200560026671 patent/DE602005026671D1/de active Active
- 2005-08-31 CA CA 2576723 patent/CA2576723A1/en not_active Abandoned
- 2005-08-31 AT AT05782124T patent/ATE500289T1/de not_active IP Right Cessation
- 2005-08-31 EP EP20050782124 patent/EP1785448B1/en not_active Not-in-force
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- 2005-08-31 CN CNA2005800285344A patent/CN101023123A/zh active Pending
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JPWO2008050913A1 (ja) * | 2006-10-27 | 2010-02-25 | 武岡 真司 | 薄膜状高分子構造体とその調製方法 |
JP5028422B2 (ja) * | 2006-10-27 | 2012-09-19 | 真司 武岡 | 薄膜状高分子構造体とその調製方法 |
CN101557931B (zh) * | 2006-10-27 | 2012-10-03 | 武冈真司 | 薄膜状高分子结构体和其制备方法 |
JP2012187926A (ja) * | 2006-10-27 | 2012-10-04 | Shinji Takeoka | 薄膜状高分子構造体とその調製方法 |
EP2957423A1 (en) | 2006-10-27 | 2015-12-23 | Shinji Takeoka | Thin film-like polymer structure and method for preparing the same |
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WO2012137610A1 (ja) | 2011-04-08 | 2012-10-11 | 国立大学法人山梨大学 | 医薬製剤 |
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WO2013137260A1 (ja) | 2012-03-12 | 2013-09-19 | ナノシータ株式会社 | 高分子超薄膜及び多孔質高分子超薄膜 |
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JP2018158973A (ja) * | 2017-03-22 | 2018-10-11 | リンテック株式会社 | 高分子薄膜分散体の製造方法 |
KR20200097715A (ko) | 2017-12-15 | 2020-08-19 | 도레이 카부시키가이샤 | 고분자 박막의 제조 장치 및 제조 방법 |
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JPWO2006025592A1 (ja) | 2008-05-08 |
ATE500289T1 (de) | 2011-03-15 |
CA2576723A1 (en) | 2006-03-09 |
EP1785448A4 (en) | 2007-09-05 |
EP1785448B1 (en) | 2011-03-02 |
EP1785448A1 (en) | 2007-05-16 |
US20120034466A1 (en) | 2012-02-09 |
AU2005278317A1 (en) | 2006-03-09 |
DE602005026671D1 (de) | 2011-04-14 |
KR20070054182A (ko) | 2007-05-28 |
CN101023123A (zh) | 2007-08-22 |
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