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WO2016209064A1 - Three-dimensional mesh structure, impeller having three-dimensional mesh structure, and method for producing same - Google Patents

Three-dimensional mesh structure, impeller having three-dimensional mesh structure, and method for producing same Download PDF

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Publication number
WO2016209064A1
WO2016209064A1 PCT/KR2016/006865 KR2016006865W WO2016209064A1 WO 2016209064 A1 WO2016209064 A1 WO 2016209064A1 KR 2016006865 W KR2016006865 W KR 2016006865W WO 2016209064 A1 WO2016209064 A1 WO 2016209064A1
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WIPO (PCT)
Prior art keywords
mesh structure
dimensional mesh
group
support
cells
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Ceased
Application number
PCT/KR2016/006865
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French (fr)
Korean (ko)
Inventor
김중배
홍성길
김한솔
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Korea University Research and Business Foundation
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Korea University Research and Business Foundation
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Priority claimed from KR1020160066446A external-priority patent/KR101869350B1/en
Priority claimed from KR1020160066338A external-priority patent/KR101830198B1/en
Application filed by Korea University Research and Business Foundation filed Critical Korea University Research and Business Foundation
Publication of WO2016209064A1 publication Critical patent/WO2016209064A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12NMICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N11/00Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
    • C12N11/02Enzymes or microbial cells immobilised on or in an organic carrier
    • C12N11/08Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a synthetic polymer
    • C12N11/089Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a synthetic polymer obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F27/00Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F27/00Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • B01F27/80Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07KPEPTIDES
    • C07K17/00Carrier-bound or immobilised peptides; Preparation thereof
    • C07K17/02Peptides being immobilised on, or in, an organic carrier
    • C07K17/08Peptides being immobilised on, or in, an organic carrier the carrier being a synthetic polymer
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/02Polyamines

Definitions

  • the present invention relates to a three-dimensional mesh structure in which materials such as organic catalysts, inorganic catalysts and biomolecules are highly integrated, an impeller having a three-dimensional mesh structure, and a method of manufacturing the same.
  • Impeller is a device that regulates the flow and mixing of the fluid by rotating the fluid using external power. Impellers have been developed in various ways according to their purpose and use, and there are representative propeller type, turbine type, and screw type impellers.
  • impellers For practical applications, a number of impellers have been developed for various applications, such as industrial applications requiring precise control of fluid flow to households for simple mixing. In general, the impeller is mainly used for the uniform mixing of the fluid in the reactor or stirred tank.
  • the impeller uniformly mixes the reactants in the fluid and at the same time, useful materials such as catalysts attached to the impeller surface play an important role in improving the overall reaction efficiency.
  • useful materials such as catalysts attached to the impeller can be easily reused, thereby simplifying the process.
  • the present invention provides a three-dimensional mesh structure, an impeller having a three-dimensional mesh structure, and a three-dimensional mesh structure that can promote reactivity by highly integrating materials such as an organic catalyst, an inorganic catalyst, and a biomolecule into a mesh structure having a three-dimensional shape. It is an object to provide a manufacturing method.
  • a support having a three-dimensional mesh structure; And a media provided on a surface of the support and capable of bonding with the first material.
  • the support may include a plate-like structure including a plurality of first mesh lines formed in a first direction and spaced apart from each other, and a plurality of second mesh lines spaced apart from each other in a direction crossing the plurality of first mesh lines. can do.
  • the plate-like structure may be provided with one or more stacked.
  • the first material may include an organic catalyst, an inorganic catalyst, and a biomolecule
  • the media may include a functional group bonded to the first material, and at least one of the organic catalyst, an inorganic catalyst, and a biomolecule may be adsorbed or ionized. It may be bound to the support or the media by a bond, covalent bond, crosslink or adhesive material.
  • the functional group is a carboxyl group, amine group, imine group, epoxy group, hydroxyl group, aldehyde group, carbonyl group, ester group, methoxy group, ethoxy group, peroxy group, ether group, acetal group, sulfide group, phosphate group and iodine group It may include at least one of.
  • the media may include at least one of polymer fibers, porous particles, carbon tubes, polymer tubes, wires, pillars, graphene, fullerenes, polydopamines, and spherical particles, and the media may be adsorbed, ionically bonded, covalently bonded or adhered to. It may be bound to the support by a material.
  • the media may include a plurality of pillars protruding out of the surface of the support having a three-dimensional mesh structure.
  • the polymer fibers are polyaniline, polypyrrole, polythiophene, acrylonitrile-butadiene-styrene, polylactic acid, polyvinyl alcohol, polyacrylonitrile, polyester, polyethylene, polyethyleneimine, polypropylene oxide, poly Vinylidene fluoride, polyurethane, polyvinyl chloride, polystyrene, polycaprolactam, polylactic-co-glycolic acid, polyglycolic acid, polycaprolactone, polyethylene terephthalate, polymethylmethacrylate, polydimethylsiloxane, It may be a polymer fiber comprising at least one selected from teflon, collagen, polystyrene-co-maleic anhydride, nylon, cellulose, chitosan, and silicone, and a polymer fiber formed by modifying the functional group.
  • the polymer fibers may be aniline (pyrrole), lactic acid (lactic acid), vinyl alcohol (vinyl alcohol), acrylonitrile (acrylonitrile), ethylene (ethylene), ethylene imine (ethyleneimine), propylene oxide (propylene oxide), urethane, vinyl chloride, styrene, caprolactam, caprolactone, aprolactone, ethylene terephthalate, methyl methacrylate
  • a first monomer comprising at least one selected from dimethylsiloxane, teflon, collagen, nylon, cellulose, cellulose, chitosan and silicon; ; And aminobenzoic acid (1-aminobenzoic acid), 2-aminobenzoic acid, 3-aminobenzoic acid, 3-aminobenzoic acid, 1-phenylenediamine, 2-phenyl 2-phenylenediamine, 3-phenylenediamine, pyrrole-1-carbaldehyde, pyrrole-2-carbaldehyde
  • the support may be acrylonitrile-butadiene-styrene, polyaniline, polypyrrole, polythiophene, polylactic acid, polyvinyl alcohol, polycaprolactam, polycaprolactone, polylactic-co-glycolic acid, polyacrylo Nitrile, polyester, polyethylene, polyethyleneimine, polypropylene oxide, polyurethane, polyglycolic acid, polyethylene terephthalate, polymethylmethacrylate, polystyrene, polydimethylsiloxane, polystyrene-co-maleic anhydride, teflon, collagen, nylon , Cellulose, chitosan, glass, gold, silver, aluminum, iron, copper and silicon, the organic catalyst comprising carbonic anhydrase, glycosylating enzyme, trypsin, chymotrypsin, subtilisin, papain , Thermolysine, lipase, peroxidase, acylase, lact
  • the cells include stem It may include one or more selected from cells, immune cells, epithelial cells, muscle cells, neurons, hepatocytes, lung cells, cardiovascular cells, pancreatic cells, heart cells, bone cells and cancer cells.
  • the coupling portion is coupled to the rotation axis in the center; And an impeller coupled to the coupling part and including one or more three-dimensional mesh structures according to the above-described features.
  • the three-dimensional mesh structure may be a single body.
  • the three-dimensional mesh structure may be provided with a connection portion to be detachable to the coupling portion.
  • different materials may be fixed to each of the one or more three-dimensional mesh structures.
  • the organic catalyst, inorganic catalyst and biomolecules are highly integrated on the surface of the mesh structure of the three-dimensional shape, and reacts with the fluid, compared to the prior art There is an advantage that the reaction can proceed at a high rate.
  • the mesh structure is formed in a 3D mesh structure and the reaction fluid passes to the inside, the overall reaction area can be widened, and the highly integrated organic catalyst, inorganic catalyst, and biomolecule can react at a higher speed than the prior art. This has the advantage that it can proceed.
  • the three-dimensional mesh structure by making the impeller detachable from the coupling portion is easy to replace as necessary, there is an advantage that can be easily reused after the reaction is finished.
  • FIG. 1 is a perspective view schematically showing a three-dimensional mesh structure according to an embodiment of the present invention.
  • FIG. 2 is an exploded perspective view of a three-dimensional mesh structure according to an embodiment of the present invention.
  • FIG. 3A and 3B are plan views illustrating a three-dimensional mesh structure according to an exemplary embodiment of the present invention.
  • FIG. 3A is a plan view viewed from the direction A in FIG. 2
  • FIG. 3B is a plan view viewed from the direction B in FIG. 2.
  • FIG. 4 is a perspective view showing an impeller having a three-dimensional mesh structure according to an embodiment of the present invention.
  • FIG. 5 is an exploded perspective view of an impeller having a three-dimensional mesh structure according to an embodiment of the present invention.
  • FIG. 6 is a schematic diagram showing a process of manufacturing a three-dimensional mesh structure of the present invention as a preferred embodiment of the present invention.
  • FIG. 7 (a) to 7 (f) are SEM images of the shape of the column of fibers formed in the media of each of the supports of Examples 1 to 6 performed in Experimental Example 1.
  • FIG. (g) ⁇ (h) is a SEM image of the cross section taken by tilting and removing part of the fiber column synthesized in (c).
  • Example 8 is a graph showing the FTIR spectrum of the carboxy polyaniline fibers of the support of Example 1 to Example 6 carried out in Experimental Example 2.
  • the term "vertical direction” used in the expression of "protruding out of the surface of the support having a three-dimensional mesh structure in the vertical direction of the polymer fibers” does not mean only 90 being vertical, Assuming that the surface of the support having a dimensional mesh structure is a plane, it means that the polymer fibers protrude in the direction of the baseline perpendicular to the plane, and the polymer fibers protrude at an angle of 10 to 170 with the plane. It is also meant to include.
  • fiber column is meant to include both strands and / or multiple strands of polymer fibers protruding in a vertical direction from the surface of a support having a three-dimensional mesh structure.
  • 3D mesh structure 120 may include a support 121 and the media 150, as shown in FIG.
  • the support 121 includes a plate-like structure 125 having a mesh structure, and the plate-like structure 125 may be formed by stacking one or more as shown in FIG. 2.
  • the plate-like structure 125 extends in a first direction and is spaced apart from the plurality of first mesh lines 126, and the plurality of agents spaced apart from each other in a direction crossing the first mesh lines 126. It may include two mesh lines (127).
  • first mesh lines 126 may be formed along the length direction of the plate-like structure 125, and the second mesh lines 127 are disposed to intersect the first mesh lines 126.
  • the plate-like structure 125 may be formed by the cross arrangement of the plurality of first mesh lines 126 and the second mesh lines 127 on the same plane.
  • a plurality of porous holes 128 are formed in the plate-like structure 125 in an intersecting arrangement of the first mesh line 126 and the second mesh line 127.
  • the support 121 has a structure in which a plurality of plate-like structures 125 in which the first mesh line 126 and the second mesh line 127 are arranged to cross each other are stacked in an up / down direction, and thus a porous hole 128. ) Are also uniformly arranged in the up / down direction.
  • the support 121 may be formed in a rectangular parallelepiped shape, and since the inside and the outside of the three-dimensional mesh structure 120 are formed in a mesh shape, the three-dimensional mesh structure according to the size of the reaction apparatus and the shape of the reactant ( 120) The overall size can be adjusted.
  • the interval between the first mesh line 126 and the second mesh line may be adjusted according to the size or shape of the molecules reacting in the reactor. That is, the size of the porous hole 128 can be adjusted.
  • the first mesh line 126 may be formed to extend in a linear direction along the first direction, and the second mesh line 127 may be formed in FIG. 2.
  • the B direction as shown in Figure 3b may be formed in the circumferential direction of one side of the support 121.
  • Materials such as organic catalysts, inorganic catalysts and biomolecules may be fixed to the surface of the support 121, wherein the organic catalysts, inorganic catalysts and biomolecules may be fixed to the surface of the support. Can be used.
  • the organic catalyst, the inorganic catalyst, and the biomolecule may be fixed to the surface of the support 121 by adsorption, ionic bonding, covalent bonding, crosslinking, or an adhesive material.
  • the organic catalyst, the inorganic catalyst and the biomolecule when the organic catalyst, the inorganic catalyst and the biomolecule are fixed through the functional group, the organic catalyst, the inorganic catalyst, and the biomolecule may be fixed to the surface of the support 121 using one or a mixed method of covalent bonds, ionic bonds and crosslinking, If it is not fixed through, it is fixed to the surface of the support 121 using one of catechol-based adhesive materials such as polydopamine, polynorepinephrine, and physically simple adsorption. Can be.
  • the media 150 may be formed on the surface of the support 121 to fix the organic catalyst, the inorganic catalyst and the biomolecule (see FIG. 1). That is, the organic catalyst, the inorganic catalyst, and the biomolecule are combined with the media 150 to be fixed to the surface of the support 121.
  • the media 150 may be a polymer fiber assembly including a plurality of polymer fibers, or porous particles, carbon tubes, polymer tubes, wires, pillars, graphene, fullerenes, polydopamine, polynorepinephrine, and spheres. Note that at least one of the particles can be used.
  • the media 150 will be described as a polymer fiber aggregate.
  • the media 150 may protrude out of the support surface of the support 121 in a vertical direction in a polymer fiber assembly to form a fiber pillar (see 151 of FIG. 6).
  • the fiber column includes a variety of forms, such as straight, streamlined, S-shaped, preferably, the majority of the fiber pillar may be formed in a direction perpendicular to the long direction of the media.
  • the lower end of the fiber column (see D of FIG. 6) may form a network structure in which polymer fibers are intricately intersected with each other.
  • the organic catalyst, the inorganic catalyst, and the biomolecule may be fixed to the support 121 through the fiber pillar 151 formed on the media 150.
  • the organic catalyst, the inorganic catalyst and the biomolecules may be directly or indirectly bonded to the media 150.
  • the organic catalyst, the inorganic catalyst and the biomolecule may be directly fixed to the fiber column of the media by adsorption, ionic bond, covalent bond, crosslinking and adhesive material, preferably the organic catalyst, inorganic catalyst And the biomolecule may be directly bonded through a covalent bond with a functional group of the media.
  • the functional group of the polymer fiber and the biomolecule are specifically bound by heterogeneous biomolecules, so that the functional group and the biomolecule are indirectly bound through heterogeneous biomolecules serving as a linker, thereby forming the bio-molecule on the polymer fiber.
  • Molecules may be immobilized, more specifically, the specific binding is antibody-antigen, protein A-antibody, protein G-antibody, nucleic acid-nucleic acid hybrid, aptamer-biomolecule, avidin-biotin ), Through the specific binding of streptavidin-biotin, lectin-carbohydrate, lectin-glycoprotein, etc., between the functional group and the biomolecule.
  • the molecule may act as a linker so that the functional group of the polymer fiber and the biomolecule may be indirectly bonded.
  • the organic catalyst is a carbonic anhydrase, glycosylation enzyme, trypsin, chymotrypsin, subtilisin, papain, thermolysine, lipase, peroxidase, acylase, lactonase, protease, tyrosinase, At least one of enzymes including at least one of laccase, cellulase, xylanase, organophosphohydrolase, cholinesterase, formic acid dehydrogenase, aldehyde dehydrogenase, alcohol dehydrogenase, glucose dehydrogenase, and glucose isomerase can do.
  • the inorganic catalyst is platinum, platinum, rhodium, palladium, lead, iridium, rubidium, iron, nickel, zinc, cobalt, copper, manganese, titanium, ruthenium, silver, molybdenum, tungsten, aluminum, iron, antimony, tin, It may include at least one of bismuth, barium, osmium, nitric oxide, copper oxide, manganese oxide, titanium oxide, vananium oxide, and zinc oxide.
  • the biomolecule may include at least one of albumin, insulin, collagen, antibody, antigen, protein A, protein G, avidin, streptavidin, biotin, nucleic acid, peptide, lectin, carbohydrate.
  • the three-dimensional mesh structure 120 having such a structure is highly integrated with the catalyst material or the biomolecule on the surface and inside of the support having the three-dimensional mesh structure, the overall reaction area can be widened, and the catalyst and the biomolecule are highly integrated. The reaction yield can be improved by this.
  • the organic catalyst, the inorganic catalyst and the biomolecules are highly integrated on the surface and the inside of the three-dimensional mesh structure and react with the fluid, there is an advantage that the reaction may proceed at a high speed as compared with the prior art.
  • the three-dimensional mesh structure 120 is illustrated and described as being provided with a plurality of layers, but the present invention is not limited thereto, and the three-dimensional mesh structure 120 is one. Note that it can be formed as a single unit of.
  • the three-dimensional mesh structure 120 having the configuration as described above can be a variety of applications depending on the first material to be bonded.
  • biomolecules may be attached to the support 121 and the media 150 immobilized on the support to selectively bind microorganisms and cells, and to culture and activate them.
  • the microorganism is Bacillus subtilis, Bacillus licheniformis, Bacillus polyfermenticus, Bacillus mesentericus, Saccharomyces cerevises cerevisiae, Clostridium butyricum, Streptococcus faecalis, Streptococcus faecium, Micrococcus caseolyticus, Staphylococcus aureus auretaloclocus ), Lactobacillus casei, Lactobacillus plantarum, Leuconostoc Mesenteroides, Saccharomyces cerevisiae, Debariomyses nicotiana nicotianae), Acinetobacter calcoaceticus, alkali Alcaligenesodorans, Aromatoleum aromaticum, Geobacter metallireduc
  • Alkanivolas bors It may include one or more selected from the cumulus (Alcanivorax borkumensis). And, the cells may include one or more selected from stem cells, immune cells, epithelial cells, muscle cells, nerve cells, hepatocytes, lung cells, cardiovascular cells, pancreas cells, heart cells, bone cells and cancer cells.
  • the three-dimensional mesh structure 120 having the above configuration may be provided in plural to form the impeller 100.
  • Impeller 100 having a three-dimensional mesh structure 120 may include a coupling portion 110 and the three-dimensional mesh structure 120.
  • the coupling part 110 is for rotating one or more three-dimensional mesh structure 120 in one direction, and has a cube shape.
  • a rotating shaft 130 for rotating the three-dimensional mesh structure 120 in one direction may be coupled to the upper portion of the coupling part 110, and as shown in FIG. 5, the three-dimensional mesh structure ( Coupling holes 111 for coupling 120 may be formed.
  • the shape of the coupling portion 110 is described and illustrated as being formed in a cube shape, but is not limited thereto. Specifically, it may be formed in a hexahedral shape or a spherical shape, and may be formed in any shape as long as it is combined with the one or more three-dimensional mesh structures to rotate in one direction.
  • the three-dimensional mesh structure 120 is provided with one or more may be coupled to the side portion of the coupling portion 110, more specifically is coupled to the coupling hole 111 formed in the side portion of the coupling portion 110. .
  • one end of the three-dimensional mesh structure 120 may be provided with a connection portion 140 for coupling to the coupling hole 111.
  • connection portion 140 may be provided to protrude from one end of the three-dimensional mesh structure 120 having a predetermined length, the one or more three-dimensional mesh structure 120 is the coupling portion by the connection portion 140 Detachable at 110 may be installed.
  • connection portion 140 and the coupling hole 111 is formed in a shape and size corresponding to each other.
  • one or more of the three-dimensional mesh structure 120 may be spaced apart at equal intervals on a plane perpendicular to the axis of rotation (130).
  • four three-dimensional mesh structures are arranged at intervals of 90 degrees, but the number and placement angle are not limited thereto.
  • the one or more three-dimensional mesh structure (120, 120 ') is detachably installed from the coupling portion (110, 110'), it can be easily replaced as necessary.
  • a chain reaction can occur because different materials can be attached to each of the one or more three-dimensional mesh structures in the impeller.
  • the enzyme may be immobilized on any one of the plurality of three-dimensional mesh structures 120 coupled to the impeller 100, and the antibody may be immobilized on the other arbitrary second mesh structure to react with the antibody. .
  • the support is formed in a three-dimensional mesh structure and the catalyst material or biomolecule is highly integrated in the three-dimensional mesh structure, the overall reaction area may be widened.
  • the reaction may be simultaneously performed with stirring.
  • the three-dimensional mesh structure 120 having the above configuration can be manufactured by the following method. At this time, it will be described as an example that the organic catalyst is bonded to the media 150 through a covalent bond.
  • the functional group It can be prepared by selecting and immobilizing one of an organic catalyst, an inorganic catalyst and a biomolecule.
  • the three-dimensional mesh structure 120 has a shape in which the polymer fibers including the functional groups constituting the media 150 formed on the surface of the support 121 are grown straight or obliquely in a direction perpendicular to the surface of the support.
  • the amount of polymer fibers grown in the direction can be maximized, and the media have a very high specific surface area.
  • the organic catalyst can be immobilized very stably to the functional groups of the polymer fibers grown in the vertical direction, and the organic catalyst can be immobilized in a large amount, thereby improving thermal stability and long-term stability of the organic catalyst.
  • the three-dimensional mesh structure 120 of the present invention includes one step of supporting a support in a polymer fiber polymerization solution; Performing a polymerization reaction on the polymer fiber polymerization solution to grow a polymer fiber including a functional group on the surface of the support to form a media on which the polymer fiber aggregate forms a three-dimensional mesh structure on the surface of the support; And immobilizing the organic catalyst on the functional group of the polymer fiber forming the media.
  • the polymer fiber polymerization solution in one step may include a monomer and a polymerization initiator or a second monomer and a polymerization initiator. In this case, it is possible to polymerize a polymer other than a copolymer.
  • the polymer fiber polymerization solution of the first step includes a first monomer, a second monomer and a polymerization initiator, in which case, copolymerization for forming a copolymer is possible.
  • the first monomer is aniline (pyrrole), thiophene (thiophene), lactic acid (lactic acid), vinyl alcohol (vinyl alcohol), acrylonitrile (acrylonitrile), ethylene (ethylene), ethylene Ethyleneimine, propylene oxide, urethane, vinyl chloride, styrene, caprolactam, caprolactone, aprolactone, ethylene terephthalate, methyl One selected from methacrylate, dimethylsiloxane, teflon, collagen, nylon, cellulose, cellulose, chitosan, and silicon It may include the above, and preferably may include one or more selected from aniline (aniline) and pyrrole (pyrrole).
  • the second monomer may be a carboxyl group, an amine group, an imine group, an epoxy group, a hydroxyl group, an aldehyde group, a carbonyl group, an ester group, a methoxy group, an ethoxy group, a peroxy group, an ether group, an acetal group, a sulfide group, a phosphate group, or an eye It is a compound containing at least one functional group selected from an ode group, preferably 1-aminobenzoic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, or 3-aminobenzoic acid.
  • the second monomer is preferably used in a molar ratio of 0.05 to 0.95, preferably 0.2 to 0.8 molar ratio, more preferably 0.25 to 0.75 molar ratio with respect to 1 mole of the first monomer. If the molar ratio exceeds 1, the number of polymer fibers (fiber columns) formed in a direction perpendicular to the media may be reduced. If the molar ratio is less than 0.05, the functional groups may be added to the polymer fibers that are copolymers of the first monomer and the second monomer. It is recommended to use the biomolecule within the above range because too little or no biomolecules may be too small or immobilized.
  • the polymerization initiator is amino persulfate, potassium persulfate, sodium persulfate, hydrogen peroxide, benzoyl peroxide, acetyl peroxide and acetyl peroxide. It may include one or more selected from azobisisobutyronitrile (azobisisobutyronitrile).
  • the amount of the polymerization initiator is preferably used in a molar ratio of 0.05 to 1, preferably 0.3 to 0.85 mole ratio, more preferably 0.4 to 0.8 molar ratio with respect to 1 mole of the first monomer, wherein the amount of the polymerization initiator is If the molar ratio is less than 0.05, the polymerization reaction may be too slow and the polymer fibers formed by the polymerization reaction may not grow sufficiently to form a media having a three-dimensional mesh structure, and it is uneconomical to use the polymerization initiator in excess of 1 molar ratio. Due to this, there may be a problem in that the number of polymer fibers (fiber columns) formed in a direction perpendicular to the media is reduced.
  • the support 121 of the first stage may be used as long as it can grow a polymer fiber containing a functional group on the surface, preferably ABS (Acrylonitrile-butadiene-styrene) polymer, polylactic acid, poly Vinyl alcohol, polycaprolactam, polycaprolactone, polylactic-co-glycolic acid, polyacrylonitrile, polyester, polyethylene, polyethyleneimine, polypropylene oxide, polyurethane, polyglycolic acid, polyethylene terephthalate, polymethylmetha Acrylate, polystyrene, polydimethylsiloxane, teflon, filter paper, glass, gold plated, silicon wafer and the like can be used, but the present invention is not particularly limited thereto.
  • ABS Acrylonitrile-butadiene-styrene
  • polylactic acid poly Vinyl alcohol
  • polycaprolactam polycaprolactone
  • polylactic-co-glycolic acid polyacrylonitrile
  • polyester polyethylene,
  • the second step is to polymerize the polymer fiber polymerization solution to form a polymer or copolymer and at the same time to grow it to produce a polymer fiber. Then, as the polymer fibers grow, a polymer fiber aggregate is formed on the surface of the support, and the polymer fiber aggregate is entangled with a plurality of polymer fibers constituting the polymer fiber to form a media having a three-dimensional mesh structure (see FIG. 6A). ).
  • the media is fixed to the support surface.
  • the polymerization reaction can be carried out for 0 minutes to 48 hours, preferably 30 minutes to 36 hours under 0 °C ⁇ 80 °C, preferably 0 °C ⁇ 30 °C, more preferably 2 °C ⁇ 10 °C. have.
  • the stirring speed may be performed while stirring at a speed of 100 to 300 rpm, preferably at a speed of 150 to 250 rpm, and more preferably at a speed of 170 to 230 rpm.
  • the polymerization temperature is 0 ° C or less, the polymerization may not proceed, and if it exceeds 80 ° C, the fiber pillar may not be sufficiently formed due to excessive polymerization.
  • the stirring speed is less than 100 rpm, the polymer fibers grown in a lying shape may increase, and when the stirring speed exceeds 300 rpm, the fixing force to the support may be decreased, and the long-term stability of the manufactured three-dimensional mesh structure may be deteriorated. have.
  • the copolymer formed by polymerization forms a polymer fiber including a functional group.
  • the polymer fiber including the functional group may be a polymer fiber including a carboxyl group, a polymer fiber including an amine group and a polymer fiber including an aldehyde group.
  • the polymer fiber containing the carboxyl group may be a copolymer of aniline and 1-aminobenzoic acid, 2-aminobenzoic acid, or 3-aminobenzoic acid, and the polymer fiber containing the amine group is aniline And it may be a copolymer of 1-phenylenediamine, 2-phenylenediamine or 3-phenylenediamine, wherein the polymer fiber comprising the aldehyde group is pyron or pyrrole; and pyrrole-1-carbaldehyde, pyrrole-2 It may be a copolymer of -carbaldehyde or pyrrole-3-carbaldehyde.
  • the polymer fiber containing the functional group is polyaniline, polypyrrole, acrylonitrile-butadiene-styrene, polylactic acid, polyvinyl alcohol, polyacrylonitrile, polyester, polyethylene, polyethyleneimine, polypropylene oxide, poly Vinylidene fluoride, polyurethane, polyvinyl chloride, polystyrene, polycaprolactam, polylactic-co-glycolic acid, polyglycolic acid, polycaprolactone, polyethylene terephthalate, polymethylmethacrylate, polydimethylsiloxane, Polymers such as Teflon, collagen, polystyrene-co-maleic anhydride, nylon, cellulose, chitosan, and silicone may be used to form functional groups on the polymer fibers through modification.
  • the media according to the present invention are illustrated and described as using polymer fibers, but the present invention is not limited thereto. That is, it is noted that the media may use at least one of porous particles, carbon tubes, polymer tubes, wires, pillars, graphene, fullerenes, polydopamine, polynorpinephrine and spherical particles.
  • Step 3 is a process of fixing the organic catalyst to the media fixed to the surface of the support, specifically, the organic catalyst is reacted (or adsorbed) to the functional groups of the polymer fibers forming the media to fix the organic catalyst with the media as shown in FIG. (Or bonding).
  • the organic catalyst when used, the organic catalyst may be reacted with and immobilized with a functional group of the polymer fiber by a precipitation coating method.
  • the media formed on the surface of the support may be functionalized ( performing a funcnalization reaction; Step 3-2 of combining the functional group and the organic catalyst of the polymer fibers constituting the functional group reaction media; Step 3-3 to precipitate the organic catalyst; And 3-4 step of crosslinking the precipitated organic catalyst.
  • step 3 may further include 3-5 steps of capping the unreacted functional groups after the crosslinking and washing.
  • the functionalization reaction of step 3-1 may be performed through an EDC-NHS coupling reaction.
  • the media immobilized on the surface of the support prepared in step 2 was subjected to EDC (1-Ethyl-3- (3-dimethylaminopropyl) -carbodiimide) at a concentration of 5 to 20 mg / ml and NHS (N- at a concentration of 35 to 70 mg / ml).
  • Hydroxysuccinimide) in an EDC-NHS coupling solution containing 10 °C ⁇ 35 °C it is carried out for 30 minutes to 2 hours and stirred about 20 ⁇ 100 rpm, it can be carried out by washing it out.
  • the functionalization reaction of step 3-1 may be performed through a reaction with glutaraldehyde.
  • glutaraldehyde When the media fixed on the support surface prepared in step 2 is immersed in 0.01-1% glutaaldehyde solution for about 30 minutes to 2 hours, an aldehyde functional group is formed on the surface, and the organic catalyst can be immobilized by taking it out and washing it. .
  • the polymer fiber surface includes an aldehyde group as a functional group
  • a special treatment is not necessary and the protein may be immobilized by being supported in the organic catalyst solution as it is.
  • step 3-2 the functionalized media may be added to a solution containing an organic catalyst, and then a coupling reaction may be performed to combine the functional group of the polymer fiber with the organic catalyst.
  • step 3-3 the precipitation of step 3-3 is carried out in the solution containing the precipitation agent to the media containing the organic catalyst of step 3-2 bound to the solution containing the precipitation agent, and then the precipitation reaction for 10 minutes to 1 hour under 10 °C ⁇ 35 °C
  • biomolecules agglomerate to one another and increase in size, which eventually precipitates between the surface of the fibers or the voids (spaces) formed between the fibers.
  • the precipitation agent may be used without limitation as long as it can precipitate biomolecules with little effect on the activity of the organic catalyst, but preferably methanol, ethanol, 1-propanol, 2-propanol, butyl alcohol, acetone , PEG, ammonium sulfate, sodium chloride, sodium sulfate, sodium phosphate, potassium chloride, potassium sulfate, potassium phosphate and aqueous solutions thereof may be used alone or in combination, but is not limited thereto.
  • a crosslinking agent was added to the solution (including the media) in which the precipitation reaction of step 3-4 was performed to induce crosslinking for 10 minutes to 1 hour under 10 ° C. to 35 ° C., followed by 2 ° C. to 8 ° C.
  • the amount of the organic catalyst fixed to the media by crosslinking with one or more organic catalysts adjacent to the organic catalyst fixed to the functional group is close to each other. It can increase and the fixing force of an organic catalyst can be increased.
  • the crosslinking agent may be used without limitation as long as it can form a crosslink without inhibiting the activity of the organic catalyst, preferably diisocyanate, dianhydride, diepoxide, dialdehyde, diimide, 1-ethyl
  • One or more selected from -3-dimethyl aminopropylcarbodiimide, glutaraldehyde, bis (imido ester), bis (succinimidyl ester), genepine and diacid chloride may be used, more preferably 1
  • One or more selected from -ethyl-3-dimethyl aminopropylcarbodiimide, glutaraldehyde, genepin, bis (imido ester), bis (succinimidyl ester) and diacid chloride can be used.
  • the cross-linking reaction of step 3-4 is preferably performed later than the precipitation reaction of step 3-3, which is a void formed between the fiber column and the fiber column, or the polymer fiber and the polymer when the crosslinking of the organic catalyst is performed first. Even if the organic catalyst cannot fill or substantially fill the interior of the pores formed between the fibers, the concentration of the organic catalysts becomes equal to the ambient concentration. This is because the organic catalyst of the same concentration crosslinks and does not form a larger mass than the inlet of the pores in the pores in the fiber, so that the cross-linked organic catalyst is likely to leak out during the washing process.
  • the organic catalysts forcibly fill the pores formed between the columnar columns and the polymer fibers more densely, and the organic catalysts filled in the pores form a large mass through crosslinking with each other. (ship in a bottle) minimizes losses during washing.
  • Steps 3-3 and 3-4 are steps for increasing the amount of organic catalyst to be immobilized and improving stability. Steps 3-3 and 3-4 may be omitted depending on the type and purpose of the organic catalyst to be immobilized.
  • the copolymer represented by the following formula (1) containing a carboxyl group was polymerized and formed into a three-dimensional mesh structure made of carboxylated polyaniline nanofibers (cPANFs) to be fixed on an ABS (acrylonitrile-butadiene-styrene) polymer surface.
  • Media was prepared to prepare a support.
  • the concentration of aniline (aniline) was fixed to 10 mM, and the polymer nanofiber polymerization solution was prepared by varying the concentration of 3-ABA (3-aminobenzoic acid) as shown in Table 1 below. At this time, the concentration of ammonium persulfate, a polymerization initiator, in the polymer nanofiber polymerization solution was adjusted to 6.7 mM.
  • ABS polymer as a support was added to the polymer nanofiber polymerization solution, followed by stirring at 200 rpm at 4 ° C. to proceed with the polymerization reaction.
  • Example 1 10 mM 0 mM 6.7 mM
  • Example 2 10 mM 1 mM 6.7 mM
  • Example 3 10 mM 3 mM 6.7 mM
  • Example 4 10 mM 5 mM 6.7 mM
  • Example 5 10 mM 10 mM 6.7 mM
  • Example 6 10 mM 20 mM 6.7 mM
  • the support prepared in Examples 1 to 6 was observed using a scanning electron microscope (SEM, Quanta 250 FEG), and the results are shown in (a) to (h) of FIG. Respectively.
  • Example 7 in the case of Example 1 (a of FIG. 7), the fiber column is not sufficiently formed, and in the case of Examples 5 and 6 (e, f of FIG. 7), the nanofibers are in a vertical direction. It could be confirmed that it is produced in the form of lying sideways without growing.
  • the support layer is formed at the lower end of the fiber column, a part of which is grown in a vertical direction upward.
  • the wavelength peak of 1690 ⁇ 1750 cm - 1 is a carboxyl group which is a functional group, when the concentration of 3-aminobenzoic acid is 0 mM, 10 mM and 20 mM it can be seen that the peak is very weak or does not appear. . This may be inferred that the growth of the nanofibers containing the carboxyl group was not properly performed during the polymerization (polymerization).
  • the organic catalyst was immobilized on the support of Example 3 through an enzyme precipitate coating (EPC) method. At this time, the organic catalyst was used (glucose oxidase, GOx).
  • EPC enzyme precipitate coating
  • the EDC-NHS coupling reaction was performed at room temperature (24 ° C. to 25 ° C.) for 1 hour in order to covalently bind a glycosylation enzyme to a carboxyl group, which is a functional group of the support of Example 3.
  • the concentration of EDC was 10 mg / ml
  • NHS was 50 mg / ml.
  • the cPANF-grown scaffold was added to the mixed solution of EDC and NHS, followed by stirring at 50 rpm for 1 hour.
  • washed support was added with 10 mg / ml of an organic catalyst solution and tilt shaking was performed at 50 rpm for 1 hour to covalently bind the glycosylating enzyme to the functional group.
  • ammonium sulfate is added to the final concentration of 55%, and then tilt shaking at 50 rpm for 30 minutes at room temperature (24 ° C. to 25 ° C.) to glycosylate.
  • the enzyme was induced to precipitate.
  • glutaraldehyde is added as a crosslinking agent so that the final concentration is 0.5%, and tilt shaking is performed at 50 rpm for 30 minutes at room temperature (24 ° C. to 25 ° C.) to precipitate.
  • Crosslinking was induced between the glycosylating enzymes, and then tilt shaking was performed at 50 rpm for 4 hours at 4 ° C.
  • HRP horseradish peroxidase
  • the three-dimensional mesh structure prepared in Preparation Examples 1 to 4 and each of the enzymes of Comparative Examples 1 to 3 were stored at 50 ° C. for 12 hours, and then activity was measured. The enzyme was stored and measured for 12 hours at 45 °C, the results are shown in Figure 10.
  • Activity measurements were optically measured for the color change of the solution using a substrate appropriate for each enzyme.
  • glucose and TMB (3,3 ', 5,5'-Tetramethylbenzidine) were used as substrates
  • TP N-Succinyl-Ala-Ala-Pro-Phe p-nitroanilide
  • 4-nitrophenyl butyrate was used as the substrate for LP
  • TMB (3,3 ', 5,5'-Tetramethylbenzidine
  • the enzyme and the substrate were mixed, and the activity was measured by detecting the color change by spectroscopy at 410 nm wavelength in the case of GOx and HRP, 410 nm wavelength in the case of CT and LP.
  • the three-dimensional mesh structure of the present invention is excellent in thermal stability.
  • Impellers were fabricated using ABS (acrylonitrile-butadiene-styrene) polymers for the application of a three-dimensional mesh structure. Enzyme (GOx) was fixed.
  • Hydrogen peroxide (H 2 O 2 ) is produced by GOx of the prepared organic catalyst-nanofiber three-dimensional mesh structure (GOx impeller), thereby killing the microorganisms, using the microbial contamination prevention effect experiment proceeds as follows It was.
  • Impellers were fabricated using ABS (acrylonitrile-butadiene-styrene) polymers for the application of a three-dimensional mesh structure. Enzyme (GOx) and horseradish peroxidase (HRP) were immobilized.
  • ABS acrylonitrile-butadiene-styrene
  • Glucose produced hydrogen peroxide by GOx, and horseradish peroxidase (HRP) was used to decompose azo dyes using hydrogen peroxide.
  • HRP horseradish peroxidase
  • the three-dimensional mesh structure of the impeller according to the embodiment of the present invention is a three-dimensional mesh shape, the organic catalyst, inorganic catalyst and biomolecules are highly integrated on the surface and inside of the three-dimensional mesh structure to react with the fluid Therefore, there is an advantage that the reaction can proceed at a high rate compared to the prior art.
  • the entire 3D mesh structure is formed as a 3D mesh structure, catalyst materials or biomolecules are highly accumulated on the surface and inside, and the fluid passes through the inside of the 3D mesh structure, thereby increasing the overall reaction area.
  • the yield of the reaction can be improved by using the prepared catalyst and biomolecules.
  • a chain reaction may occur by attaching a different material to each of the one or more three-dimensional mesh structures.

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Abstract

Provided are a three-dimensional mesh structure, an impeller having the three-dimensional mesh structure, and a method for producing same. The mesh structure according to one embodiment of the present invention may comprise: a support having a three-dimensional mesh structure; and media provided on the surface of the support and capable of bonding with a first substance.

Description

3차원 메쉬 구조체, 3차원 메쉬 구조체를 갖는 임펠러 및 이의 제조방법Three-dimensional mesh structure, impeller having a three-dimensional mesh structure and a manufacturing method thereof

본 발명은 유기 촉매, 무기 촉매 및 바이오분자와 같은 물질이 고집적된 3차원 메쉬 구조체, 3차원 메쉬 구조체를 갖는 임펠러 및 이의 제조방법에 관한 것이다.The present invention relates to a three-dimensional mesh structure in which materials such as organic catalysts, inorganic catalysts and biomolecules are highly integrated, an impeller having a three-dimensional mesh structure, and a method of manufacturing the same.

임펠러는 외부 동력을 이용하여 유체를 회전시킴으로써 유체의 흐름 및 혼합을 조절하는 장치이다. 임펠러는 그 목적과 용도에 따라 다양하게 개발되어 왔고, 대표적으로 프로펠러형, 터빈형, 스크류형의 임펠러가 있다. An impeller is a device that regulates the flow and mixing of the fluid by rotating the fluid using external power. Impellers have been developed in various ways according to their purpose and use, and there are representative propeller type, turbine type, and screw type impellers.

실제 응용을 위하여, 유체 흐름의 정밀한 조절이 필요한 산업용부터 단순 혼합을 위한 가정용 등 다양한 응용을 위하여 수 많은 임펠러가 개발되어 있는 실정이다. 일반적으로 임펠러는 반응기 혹은 교반 탱크에서 유체의 균일한 혼합을 위하여 주로 사용된다. For practical applications, a number of impellers have been developed for various applications, such as industrial applications requiring precise control of fluid flow to households for simple mixing. In general, the impeller is mainly used for the uniform mixing of the fluid in the reactor or stirred tank.

임펠러를 이용한 교반으로 인해 반응기 내부에서 서로 다른 반응 물질들간의 균일한 혼합이 이루어지고, 이는 결국 전체 반응속도 향상 및 생산성 향상으로 이어지게 된다. 특히 촉매와 같이 유용한 물질과 함께 반응을 진행 시킬 경우, 그 효과는 더욱 극대화 될 수 있다. Agitation with an impeller results in uniform mixing between different reactants within the reactor, which in turn leads to an increase in overall reaction rate and productivity. In particular, when the reaction proceeds with a useful material such as a catalyst, the effect can be further maximized.

하지만, 이러한 종래의 시스템은 촉매와 같이 유용한 물질들을 반응 종료 후 회수하는데 어려움이 있다. 이를 해결하기 위한 방법으로, 임펠러 표면에 촉매와 같은 유용한 물질을 부착시켜 반응시키는 형태의 임펠러 제작이 가능하다. However, these conventional systems have difficulty recovering useful materials such as catalysts after the reaction has ended. As a method for solving this problem, it is possible to manufacture an impeller in which a useful material such as a catalyst is attached to the impeller surface and reacted.

이러한 임펠러는 유체 내의 반응물질들을 균일하게 혼합함과 동시에, 임펠러 표면에 부착된 촉매 등의 유용한 물질이 전체 반응효율을 향상시키는데 중요한 역할을 하게 된다. 또한 반응이 종료한 이후에 임펠러에 부착된 촉매 등의 유용한 물질들을 쉽게 재사용할 수 있어 공정이 단순해지는 장점이 있다. The impeller uniformly mixes the reactants in the fluid and at the same time, useful materials such as catalysts attached to the impeller surface play an important role in improving the overall reaction efficiency. In addition, after the reaction is finished, useful materials such as catalysts attached to the impeller can be easily reused, thereby simplifying the process.

나아가 촉매와 같은 유용한 물질이 고집적(高集積)된다면, 전체적인 반응속도 및 생산물의 수율이 향상되고, 이는 공정 비용의 감소를 가져오는 긍정적인 효과가 있다. 하지만, 종래의 임펠러는 대부분이 판상 형태로, 비표면적이 작아 촉매와 같은 유용한 물질을 고집적 하는 것에 어려움이 있는 실정이다.Furthermore, if useful materials such as catalysts are highly integrated, the overall reaction rate and the yield of the product are improved, which has the positive effect of reducing the process cost. However, most of the conventional impeller is in the form of a plate, the specific surface area is small, it is difficult to high-density useful materials such as catalysts.

본 발명은 3차원 형상을 가지는 메쉬 구조체에 유기 촉매, 무기 촉매 및 바이오분자와 같은 물질을 고집적(高集積)시킴으로써, 반응성을 촉진할 수 있는 3차원 메쉬 구조체, 3차원 메쉬 구조체를 갖는 임펠러 및 이의 제조방법을 제공하는데 목적이 있다.The present invention provides a three-dimensional mesh structure, an impeller having a three-dimensional mesh structure, and a three-dimensional mesh structure that can promote reactivity by highly integrating materials such as an organic catalyst, an inorganic catalyst, and a biomolecule into a mesh structure having a three-dimensional shape. It is an object to provide a manufacturing method.

상술한 과제를 해결하기 위하여 본 발명의 일 측면에 따르면, 3차원 메쉬 구조를 갖는 지지체; 및 상기 지지체의 표면에 구비되며, 제1물질과 결합가능한 미디어;를 포함하는 3차원 메쉬 구조체를 제공한다.According to an aspect of the present invention to solve the above problems, a support having a three-dimensional mesh structure; And a media provided on a surface of the support and capable of bonding with the first material.

또한, 상기 지지체는 제1방향으로 형성되며 서로 이격 배치되는 복수 개의 제1메쉬선과, 상기 복수 개의 제1메쉬선과 교차되는 방향으로 서로 이격 배치되는 복수 개의 제2메쉬선을 포함하는 판상 구조물을 포함할 수 있다.In addition, the support may include a plate-like structure including a plurality of first mesh lines formed in a first direction and spaced apart from each other, and a plurality of second mesh lines spaced apart from each other in a direction crossing the plurality of first mesh lines. can do.

또한, 상기 판상 구조물은 하나 이상 구비되어 적층될 수 있다.In addition, the plate-like structure may be provided with one or more stacked.

또한, 상기 제1물질은 유기촉매, 무기촉매 및 바이오 분자를 포함하고, 상기 미디어는 상기 제1물질과 결합되는 작용기를 포함하며, 상기 유기촉매, 무기촉매 및 바이오분자 중 적어도 하나는 흡착, 이온결합, 공유결합, 가교결합 또는 접착성 물질에 의해 상기 지지체 또는 상기 미디어에 결합될 수 있다.In addition, the first material may include an organic catalyst, an inorganic catalyst, and a biomolecule, and the media may include a functional group bonded to the first material, and at least one of the organic catalyst, an inorganic catalyst, and a biomolecule may be adsorbed or ionized. It may be bound to the support or the media by a bond, covalent bond, crosslink or adhesive material.

또한, 상기 작용기는 카르복시기, 아민기, 이민기, 에폭시기, 하이드록시기, 알데하이드기, 카르보닐기, 에스터기, 메톡시기, 에톡시기, 페록시기, 에테르기, 아세탈기, 설파이드기, 포스페이트기 및 아이오드기 중 적어도 하나를 포함할 수 있다.In addition, the functional group is a carboxyl group, amine group, imine group, epoxy group, hydroxyl group, aldehyde group, carbonyl group, ester group, methoxy group, ethoxy group, peroxy group, ether group, acetal group, sulfide group, phosphate group and iodine group It may include at least one of.

또한, 상기 미디어는 고분자 섬유, 다공성 입자, 탄소 튜브, 고분자 튜브, 와이어, 필라, 그래핀, 풀러렌, 폴리도파민 및 구형입자 중 적어도 하나를 포함하며, 상기 미디어는 흡착, 이온결합, 공유결합 또는 접착성 물질에 의해 상기 지지체에 결합될 수 있다.In addition, the media may include at least one of polymer fibers, porous particles, carbon tubes, polymer tubes, wires, pillars, graphene, fullerenes, polydopamines, and spherical particles, and the media may be adsorbed, ionically bonded, covalently bonded or adhered to. It may be bound to the support by a material.

또한, 상기 미디어는 3차원 메쉬 구조를 가지는 지지체의 표면 외부로 돌출되어 형성되는 복수 개의 기둥을 포함할 수 있다.In addition, the media may include a plurality of pillars protruding out of the surface of the support having a three-dimensional mesh structure.

또한, 상기 고분자 섬유는 폴리아닐린, 폴리피롤, 폴리티오펜, 아크릴로나이트릴-뷰타디엔-스티렌, 폴리락틱산, 폴리비닐알콜, 폴리아크릴로니트릴, 폴리에스테르, 폴리에틸렌, 폴리에틸렌이민, 폴리프로필렌옥사이드, 폴리비닐리데인 플로라이드, 폴리우레탄, 폴리염화비닐, 폴리스티렌, 폴리카프로락탐, 폴리락틱-co-글리콜산, 폴리글리콜산, 폴리카프로락톤, 폴리에틸렌 테레프탈레이트, 폴리메틸메타크릴레이트, 폴리다이메틸실록산, 테플론, 콜라겐, 폴리스티렌-co-무수말레산, 나일론, 셀룰로우즈, 키토산 및 실리콘 중에서 선택된 1종 이상을 포함하는 고분자 섬유 및 이를 개질시켜 작용기를 형성한 고분자 섬유일 수 있다.In addition, the polymer fibers are polyaniline, polypyrrole, polythiophene, acrylonitrile-butadiene-styrene, polylactic acid, polyvinyl alcohol, polyacrylonitrile, polyester, polyethylene, polyethyleneimine, polypropylene oxide, poly Vinylidene fluoride, polyurethane, polyvinyl chloride, polystyrene, polycaprolactam, polylactic-co-glycolic acid, polyglycolic acid, polycaprolactone, polyethylene terephthalate, polymethylmethacrylate, polydimethylsiloxane, It may be a polymer fiber comprising at least one selected from teflon, collagen, polystyrene-co-maleic anhydride, nylon, cellulose, chitosan, and silicone, and a polymer fiber formed by modifying the functional group.

또한, 상기 고분자 섬유는 아닐린(aniline), 피롤(pyrrole), 락틱산(lactic acid), 비닐알콜(vinyl alcohol), 아크릴로니트릴(acrylonitrile), 에틸렌(ethylene), 에틸렌이민(ethyleneimine), 프로필렌옥사이드(propylene oxide), 우레탄(urethane), 염화비닐(vinyl chloride), 스티렌(styrene), 카프로락탐(caprolactam), 카프로락톤(aprolactone), 에틸렌 테레프탈레이트(ethylene terephthalate), 메틸메타크릴레이트(methyl methacrylate), 다이메틸실록산(dimethysiloxane), 테플론(teflon), 콜라겐(collagen), 나일론(nylon), 셀룰로우즈(cellulose), 키토산(chitosan) 및 실리콘(silicon) 중에서 선택된 1종 이상을 포함하는 제1단량체; 및 아미노벤조익산(1-aminobenzoic acid), 2-아미노벤조익산(2-aminobenzoic acid), 3-아미노벤조익산(3-aminobenzoic acid), 1-페닐렌다이아민(1-phenylenediamine), 2-페닐렌다이아민(2-phenylenediamine), 3-페닐렌다이아민(3-phenylenediamine), 피롤-1-카브알데하이드(pyrrole-1-carbaldehyde), 피롤-2-카브알데하이드(pyrrole-2-carbaldehyde) 및 피롤-3-카브알데하이드(pyrrole-3-carbaldehyde) 중에서 선택된 1종 이상을 포함하는 제2단량체;가 공중합된 공중합체 및 이를 개질시켜 작용기를 형성한 공중합체일 수 있다.In addition, the polymer fibers may be aniline (pyrrole), lactic acid (lactic acid), vinyl alcohol (vinyl alcohol), acrylonitrile (acrylonitrile), ethylene (ethylene), ethylene imine (ethyleneimine), propylene oxide (propylene oxide), urethane, vinyl chloride, styrene, caprolactam, caprolactone, aprolactone, ethylene terephthalate, methyl methacrylate A first monomer comprising at least one selected from dimethylsiloxane, teflon, collagen, nylon, cellulose, cellulose, chitosan and silicon; ; And aminobenzoic acid (1-aminobenzoic acid), 2-aminobenzoic acid, 3-aminobenzoic acid, 3-aminobenzoic acid, 1-phenylenediamine, 2-phenyl 2-phenylenediamine, 3-phenylenediamine, pyrrole-1-carbaldehyde, pyrrole-2-carbaldehyde and pyrrole A second monomer comprising at least one selected from -3-carbaldehyde (pyrrole-3-carbaldehyde); may be a copolymer copolymerized and a copolymer formed by modifying the functional group.

또한, 상기 지지체는 아크릴로나이트릴-뷰타디엔-스티렌, 폴리아닐린, 폴리피롤, 폴리티오펜, 폴리락틱산, 폴리비닐알콜, 폴리카프로락탐, 폴리카프로락톤, 폴리락틱-co-글리콜산, 폴리아크릴로니트릴, 폴리에스테르, 폴리에틸렌, 폴리에틸렌이민, 폴리프로필렌옥사이드, 폴리우레탄, 폴리글리콜산, 폴리에틸렌테레프탈레이트, 폴리메틸메타크릴레이트, 폴리스티렌, 폴리디메틸실록산, 폴리스티렌-co-무수말레산, 테플론, 콜라겐, 나일론, 셀룰로우즈, 키토산, 유리, 금, 은, 알루미늄, 철, 구리 및 실리콘 중 적어도 하나를 포함하며, 상기 유기 촉매는 탄산무수화 효소, 당산화 효소, 트립신, 키모트립신, 서브틸리신, 파파인, 서몰리신, 리파아제, 페록시다아제, 아실라아제, 락토나제, 프로테아제, 티로시나아제, 라카아제, 셀룰라아제, 자일라나제, 유기포스포하이드롤레이즈, 콜린에스테라아제, 포름산 탈수소 효소, 알데히드 탈수소 효소, 알코올 탈수소 효소, 포도당 탈수소 효소, 및 포도당 이성화 효소 중 적어도 하나를 포함하고, 상기 무기 촉매는 플래티늄, 백금, 로듐, 팔라듐, 납, 이리듐, 루비듐, 철, 니켈, 아연, 코발트, 구리, 망간, 티타늄, 루테늄, 은, 몰리브덴, 텅스텐, 알루미늄, 철, 안티몬, 주석, 비스무트, 바륨, 오스뮴, 산화질소, 산화구리, 산화망간, 산화티타늄, 산화바나늄, 산화아연 중 적어도 하나를 포함하며, 상기 바이오분자는 알부민, 인슐린, 콜라겐, 항체, 항원, 프로테인A, 프로테인G, 아비딘, 스트렙타비딘, 바이오틴, 핵산, 펩타이드, 렉틴, 탄수화물 중 적어도 하나를 포함할 수 있다.In addition, the support may be acrylonitrile-butadiene-styrene, polyaniline, polypyrrole, polythiophene, polylactic acid, polyvinyl alcohol, polycaprolactam, polycaprolactone, polylactic-co-glycolic acid, polyacrylo Nitrile, polyester, polyethylene, polyethyleneimine, polypropylene oxide, polyurethane, polyglycolic acid, polyethylene terephthalate, polymethylmethacrylate, polystyrene, polydimethylsiloxane, polystyrene-co-maleic anhydride, teflon, collagen, nylon , Cellulose, chitosan, glass, gold, silver, aluminum, iron, copper and silicon, the organic catalyst comprising carbonic anhydrase, glycosylating enzyme, trypsin, chymotrypsin, subtilisin, papain , Thermolysine, lipase, peroxidase, acylase, lactonase, protease, tyrosinase, laccase, cellulase, xylanase, organofoam Phosphohydrolase, cholinesterase, formic acid dehydrogenase, aldehyde dehydrogenase, alcohol dehydrogenase, glucose dehydrogenase, and glucose isomerase, and the inorganic catalyst comprises platinum, platinum, rhodium, palladium, lead, iridium, Rubidium, iron, nickel, zinc, cobalt, copper, manganese, titanium, ruthenium, silver, molybdenum, tungsten, aluminum, iron, antimony, tin, bismuth, barium, osmium, nitric oxide, copper oxide, manganese oxide, titanium oxide, At least one of vanadium oxide and zinc oxide, wherein the biomolecule is at least one of albumin, insulin, collagen, antibody, antigen, protein A, protein G, avidin, streptavidin, biotin, nucleic acid, peptide, lectin, carbohydrate It may include one.

또한, 상기 지지체의 표면 및 상기 미디어에 상기 바이오분자를 부착하여 미생물 및 세포를 선택적으로 결합시키고, 이를 배양 및 활성화시키며, 상기 미생물은 바실러스 서브틸리스(Bacillus subtilis), 바실러스 리케니포미스(Bacillus licheniformis), 바실러스 폴리퍼멘티커스(Bacillus polyfermenticus), 바실러스 메센테리커스(Bacillus mesentericus), 사카로마이세스 세레비제(Saccharomyces cerevisiae), 클로스트리디움 부티리컴(Clostridium butyricum), 스트렙토코커스 패칼리스(Streptococcus faecalis), 스트렙토코커스 패시움(Streptococcus faecium), 마이크로코커스 카세리티쿠스(Micrococcus caseolyticus), 스테필로코커스 아우레우스 (Staphylococcus aureus), 락토바실러스 카제이(Lactobacillus casei), 락토바실러스 프라타륨(lactobacillus plantarum), 루코노스톡 메세테로이데스 (Leuconostoc Mesenteroides), 사카로마이세스 세르비시아(saccharomyces cerevisiae), 데바리오마이세스 니코티아나(Debaryomyces nicotianae), 아시네토박터 칼코아세티쿠스(Acinetobactercalcoaceticus), 알칼리게네스 균(Alcaligenesodorans), 아로매토리움 아로매티쿰(Aromatoleum aromaticum), 지오박터 메탈리듀센(Geobacter metallireducens), 디클로로모나스 아로마틱(Dechloromonas aromatic), 아스로박터속(Arthrobacter sp.) 및 알카니보락스 보르쿠멘시스(Alcanivorax borkumensis) 중에서 선택된 1종 이상을 포함하고, 상기 세포는 줄기세포, 면역세포, 상피세포, 근육세포, 신경세포, 간세포, 폐세포, 심혈관세포, 췌장세포, 심장세포, 뼈세포 및 암세포 중에서 선택된 1종 이상을 포함할 수 있다.In addition, by attaching the biomolecule to the surface of the support and the media to selectively bind the microorganisms and cells, incubating and activating the microorganisms, Bacillus subtilis, Bacillus rikenimomis (Bacillus) licheniformis, Bacillus polyfermenticus, Bacillus mesentericus, Saccharomyces cerevisiae, Clostridium butyricum, Streptococcus faecalis ), Streptococcus faecium, Micrococcus caseolyticus, Staphylococcus aureus, Lactobacillus casei, Lactobacillus pratium (lactobacillus plantarum) Leukonostoc Mesenteroides, Saccharomycete Saccharomyces cerevisiae, Debaryomyces nicotianae, Acinetobacter calcoaceticus, Alcaligenesodorans, Aromatium Aromabacterium, Aromatoleum aromaticum It comprises one or more selected from Geobacter metallireducens, Dechloromonas aromatic, Arthrobacter sp. And Alcanivorax borkumensis, the cells include stem It may include one or more selected from cells, immune cells, epithelial cells, muscle cells, neurons, hepatocytes, lung cells, cardiovascular cells, pancreatic cells, heart cells, bone cells and cancer cells.

한편, 본 발명의 다른 예에 따르면, 중심에 회전축이 결합되는 결합부; 및 상기 결합부에 결합되며, 전술한 특징에 따른 3차원 메쉬 구조체를 하나 이상 포함하는 임펠러를 제공한다.On the other hand, according to another example of the invention, the coupling portion is coupled to the rotation axis in the center; And an impeller coupled to the coupling part and including one or more three-dimensional mesh structures according to the above-described features.

또한, 상기 3차원 메쉬 구조체는 단일체일 수 있다.In addition, the three-dimensional mesh structure may be a single body.

또한, 상기 3차원 메쉬 구조체는 상기 결합부에 탈착 가능하도록 연결부가 구비될 수 있다.In addition, the three-dimensional mesh structure may be provided with a connection portion to be detachable to the coupling portion.

또한, 상기 하나 이상의 3차원 메쉬 구조체의 각각에는 서로 다른 물질이 고정될 수 있다.In addition, different materials may be fixed to each of the one or more three-dimensional mesh structures.

본 발명의 일 실시예에 따른 3차원 메쉬 구조체 및 이를 포함하는 메쉬 임펠러에 따르면, 3차원 형상의 메쉬 구조체 표면에 유기 촉매, 무기 촉매 및 바이오분자들이 고집적 되어 유체와 반응하기 때문에, 종래기술에 비하여 높은 속도로 반응이 진행될 수 있는 장점이 있다.According to the three-dimensional mesh structure and the mesh impeller including the same according to an embodiment of the present invention, since the organic catalyst, inorganic catalyst and biomolecules are highly integrated on the surface of the mesh structure of the three-dimensional shape, and reacts with the fluid, compared to the prior art There is an advantage that the reaction can proceed at a high rate.

또한, 메쉬 구조체가 3D 메쉬 구조로 형성되어 반응 유체가 내부까지 통과하기 때문에, 전체적인 반응 면적이 넓어질 수 있으며, 고집적된 유기 촉매, 무기촉매 및 바이오분자에 의해, 종래기술에 비하여 높은 속도로 반응이 진행될 수 있는 장점이 있다.In addition, since the mesh structure is formed in a 3D mesh structure and the reaction fluid passes to the inside, the overall reaction area can be widened, and the highly integrated organic catalyst, inorganic catalyst, and biomolecule can react at a higher speed than the prior art. This has the advantage that it can proceed.

또한, 3차원 메쉬 구조체가 결합부에서 탈부착 가능하도록 임펠러를 제작함으로써 필요에 따라 교체가 용이하고, 반응이 종료한 이후에 쉽게 재사용할 수 있는 장점이 있다.In addition, the three-dimensional mesh structure by making the impeller detachable from the coupling portion is easy to replace as necessary, there is an advantage that can be easily reused after the reaction is finished.

또한, 적어도 하나 이상 구비되는 3차원 메쉬 구조체의 각각에 다른 물질을 담지하여 연쇄 반응이 일어나도록 할 수 있으며, 이를 통해 다양한 응용이 가능하다. 특히 선택적 결합이 가능한 항체 등의 다양한 바이오분자를 메쉬 구조체에 고정화하여 미생물이나 세포를 특이적으로 결합시킨 후, 3차원 메쉬 구조체를 탈착하여 결합된 미생물과 세포를 배양 및 활성화함으로써, 진단, 면역세포치료, 세포칩 개발 등 다양한 의학분야에서 새로운 응용을 창출할 수 있다.In addition, it is possible to carry out a chain reaction by supporting a different material on each of the three-dimensional mesh structure provided with at least one, through which various applications are possible. In particular, various biomolecules, such as antibodies capable of selective binding, are immobilized on the mesh structure to specifically bind microorganisms or cells, and then the three-dimensional mesh structure is desorbed to culture and activate the bound microorganisms and cells, thereby diagnosing the immune cells. It can create new applications in various medical fields, such as treatment and cell chip development.

도 1은 본 발명의 일 실시예에 따른 3차원 메쉬 구조체를 개략적으로 도시한 사시도이다.1 is a perspective view schematically showing a three-dimensional mesh structure according to an embodiment of the present invention.

도 2는 본 발명의 일 실시예에 따른 3차원 메쉬 구조체의 분해 사시도이다.2 is an exploded perspective view of a three-dimensional mesh structure according to an embodiment of the present invention.

도 3a 및 도 3b는 본 발명의 일 실시예에 따른 3차원 메쉬 구조체를 도시한 평면도로써, 도 3a는 도 2에서 A 방향에서 본 평면도이며, 도 3b는 도 2에서 B 방향을 본 평면도이다.3A and 3B are plan views illustrating a three-dimensional mesh structure according to an exemplary embodiment of the present invention. FIG. 3A is a plan view viewed from the direction A in FIG. 2, and FIG. 3B is a plan view viewed from the direction B in FIG. 2.

도 4는 본 발명의 일 실시예에 따른 3차원 메쉬 구조체를 갖는 임펠러를 도시한 사시도이다.4 is a perspective view showing an impeller having a three-dimensional mesh structure according to an embodiment of the present invention.

도 5는 본 발명의 일 실시예에 따른 3차원 메쉬 구조체를 갖는 임펠러의 분해사시도이다.5 is an exploded perspective view of an impeller having a three-dimensional mesh structure according to an embodiment of the present invention.

도 6은 본 발명의 바람직한 일 예로서, 본 발명의 3차원 메쉬 구조체를 제조하는 과정을 나타낸 개략도이다.6 is a schematic diagram showing a process of manufacturing a three-dimensional mesh structure of the present invention as a preferred embodiment of the present invention.

도 7의 (a) ~ (f) 각각은 실험예 1에서 수행한 실시예 1 ~ 실시예 6의 지지체 각각의 미디어에 형성된 섬유기둥의 형상을 관찰한 SEM 이미지이다. (g) ~ (h)는 (c)에서 합성된 섬유기둥을 일부 제거하고 기울여서 단면을 찍은 SEM 이미지이다.7 (a) to 7 (f) are SEM images of the shape of the column of fibers formed in the media of each of the supports of Examples 1 to 6 performed in Experimental Example 1. FIG. (g) ~ (h) is a SEM image of the cross section taken by tilting and removing part of the fiber column synthesized in (c).

도 8은 실험예 2에서 수행한 실시예 1 ~ 실시예 6의 지지체의 따른 카르복시 폴리아닐린 섬유의 FTIR 스펙트럼을 나타낸 그래프이다.8 is a graph showing the FTIR spectrum of the carboxy polyaniline fibers of the support of Example 1 to Example 6 carried out in Experimental Example 2.

도 9의 (a)는 실시예 3의 지지체의 SEM 측정 사진이고, 도 9의(b) ~ (c) 각각은 제조예 1 ~ 제조예 3에서 제조한 메쉬 구조체 각각의 SEM 측정 사진이다.9 (a) is a SEM measurement picture of the support of Example 3, Figure 9 (b) ~ (c) is a SEM measurement picture of each of the mesh structure prepared in Preparation Examples 1 to 3.

도 10은 실험예 4에서 제조예 1 ~ 제조예 4 및 비교제조예 1 ~ 비교제조예 4의 메쉬 구조체 각각에 대한 열안정성 측정 결과이다.10 is a thermal stability measurement results for each of the mesh structures of Preparation Examples 1 to 4 and Comparative Preparation Examples 1 to 4 in Experimental Example 4.

도11은 실험예 5에서 실시한 제조예 1의 복합체를 이용한 미생물 사멸 응용 실험 결과이다.11 is a microbial killing application experiment results using the complex of Preparation Example 1 carried out in Experimental Example 5.

도 12는 실험예 6에서 실시한 제조예 1의 복합체 및 제조예 4의 메쉬 구조체를 이용한 아조 계열의 염료 분해 및 장기사용안정성 측정 결과이다.12 is a result of dye degradation and long-term stability measurement of the azo series using the composite of Preparation Example 1 carried out in Experimental Example 6 and the mesh structure of Preparation Example 4.

이하, 첨부한 도면을 참고로 하여 본 발명의 실시예에 대하여 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 상세히 설명한다. 본 발명은 여러 가지 상이한 형태로 구현될 수 있으며 여기에서 설명하는 실시예에 한정되지 않는다. 도면에서 본 발명을 명확하게 설명하기 위해서 설명과 관계없는 부분은 생략하였으며, 명세서 전체를 통하여 동일 또는 유사한 구성요소에 대해서는 동일한 참조부호를 붙였다.Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement the present invention. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. In the drawings, parts irrelevant to the description are omitted in order to clearly describe the present invention, and like reference numerals designate like elements throughout the specification.

또한, 본 발명에서 “고분자 섬유가 수직한 방향으로 3차원 메쉬 구조를 가지는 지지체의 표면 외부로 돌출~”의 표현에서 사용하는 용어인 “수직한 방향”은 90인 수직만을 의미하는 것이 아니라, 3차원 메쉬 구조를 가지는 지지체의 표면을 평면으로 가정할 때, 이 평면과 수직을 이루는 기준선 방향으로 고분자 섬유가 돌출되어 있음을 의미하는 것으로서, 상기 평면과 10 ~ 170의 각도로 고분자 섬유가 돌출되어 있는 것도 포함하는 의미이다.In addition, in the present invention, the term "vertical direction" used in the expression of "protruding out of the surface of the support having a three-dimensional mesh structure in the vertical direction of the polymer fibers" does not mean only 90 being vertical, Assuming that the surface of the support having a dimensional mesh structure is a plane, it means that the polymer fibers protrude in the direction of the baseline perpendicular to the plane, and the polymer fibers protrude at an angle of 10 to 170 with the plane. It is also meant to include.

본 발명에서 사용하는 용어인 "섬유기둥"은 3차원 메쉬 구조를 가지는 지지체의 표면으로부터 수직 방향으로 돌출된 고분자 섬유의 한 가닥 및/또는 다수 가닥이 꼬이거나 뭉친 형태를 모두 포함하는 의미이다.As used herein, the term "fiber column" is meant to include both strands and / or multiple strands of polymer fibers protruding in a vertical direction from the surface of a support having a three-dimensional mesh structure.

본 발명의 일 실시예에 따른 3차원 메쉬 구조체(120)는 도 1에 도시된 바와 같이, 지지체(121) 및 미디어(150)를 포함할 수 있다.3D mesh structure 120 according to an embodiment of the present invention may include a support 121 and the media 150, as shown in FIG.

상기 지지체(121)는 메쉬 구조를 갖는 판상 구조물(125)을 포함하며, 상기 판상 구조물(125)은 도 2에서와 같이, 하나 이상 구비되어 적층됨으로써 형성될 수 있다.The support 121 includes a plate-like structure 125 having a mesh structure, and the plate-like structure 125 may be formed by stacking one or more as shown in FIG. 2.

이때, 상기 판상 구조물(125)은 제1방향을 따라 연장되며 이격 배치되는 복수 개의 제1메쉬선(126)과, 상기 제1메쉬선(126)들과 교차되는 방향으로 이격 배치되는 복수 개의 제2메쉬선(127)을 포함할 수 있다.In this case, the plate-like structure 125 extends in a first direction and is spaced apart from the plurality of first mesh lines 126, and the plurality of agents spaced apart from each other in a direction crossing the first mesh lines 126. It may include two mesh lines (127).

이때, 상기 제1메쉬선(126)들은 판상구조물(125)의 길이 방향을 따라 형성될 수 있고, 상기 제2메쉬선(127)들은 제1메쉬선(126)들에 교차되어 배치된다.In this case, the first mesh lines 126 may be formed along the length direction of the plate-like structure 125, and the second mesh lines 127 are disposed to intersect the first mesh lines 126.

즉, 판상구조물(125)은 동일 평면 상에 복수 개의 제1메쉬선(126) 및 상기 제2메쉬선(127)의 교차 배열에 의해 형성될 수 있다. 그리고 판상구조물(125)에는 상기 제1메쉬선(126) 및 상기 제2메쉬선(127)의 교차 배열로 다수 개의 다공홀(128)이 형성된다.That is, the plate-like structure 125 may be formed by the cross arrangement of the plurality of first mesh lines 126 and the second mesh lines 127 on the same plane. In addition, a plurality of porous holes 128 are formed in the plate-like structure 125 in an intersecting arrangement of the first mesh line 126 and the second mesh line 127.

이때, 지지체(121)는 상기 제1메쉬선(126) 및 상기 제2메쉬선(127)이 교차 배열되는 복수 개의 판상구조물(125)이 상/하 방향으로 적층된 구조이므로, 다공홀(128)들도 상/하 방향으로 균일하게 배열된다.In this case, the support 121 has a structure in which a plurality of plate-like structures 125 in which the first mesh line 126 and the second mesh line 127 are arranged to cross each other are stacked in an up / down direction, and thus a porous hole 128. ) Are also uniformly arranged in the up / down direction.

또한, 상기 지지체(121)는 직육면체 형상으로 형성될 수 있으며, 상기 3차원 메쉬 구조체(120)의 내부 및 외부가 메쉬 형태로 형성되므로 반응장치의 크기와 반응물의 형상에 따라 상기 3차원 메쉬 구조체(120) 전체적인 크기를 조절할 수 있다.In addition, the support 121 may be formed in a rectangular parallelepiped shape, and since the inside and the outside of the three-dimensional mesh structure 120 are formed in a mesh shape, the three-dimensional mesh structure according to the size of the reaction apparatus and the shape of the reactant ( 120) The overall size can be adjusted.

아울러, 상기 제1메쉬선(126) 및 제2메쉬선 사이의 간격은 반응장치 내에서 반응하는 분자의 크기나 형상에 따라 조절할 수 있다. 즉, 다공홀(128)의 크기를 조절할 수 있다.In addition, the interval between the first mesh line 126 and the second mesh line may be adjusted according to the size or shape of the molecules reacting in the reactor. That is, the size of the porous hole 128 can be adjusted.

한편, 제1메쉬선(126)은 도 2의 A 방향에서 보면 도 3a에 도시된 바와 같이 제1방향을 따라 직선 방향으로 연장되어 형성될 수 있으며, 제2메쉬선(127)은 도 2의 B 방향에서 보면 도 3b에 도시된 바와 같이 지지체(121)의 일 측면의 원주 방향으로 만곡되어 형성될 수 있다.Meanwhile, when viewed from the direction A of FIG. 2, the first mesh line 126 may be formed to extend in a linear direction along the first direction, and the second mesh line 127 may be formed in FIG. 2. When viewed in the B direction as shown in Figure 3b may be formed in the circumferential direction of one side of the support 121.

이러한 상기 지지체(121)의 표면에는 유기 촉매, 무기 촉매 및 바이오 분자들과 같은 물질들이 고정될 수 있으며, 이때, 상기 유기 촉매, 무기 촉매 및 바이오 분자들은 지지체의 표면에 고정될 때 여러가지 화학적 접착 기술을 사용할 수 있다. Materials such as organic catalysts, inorganic catalysts and biomolecules may be fixed to the surface of the support 121, wherein the organic catalysts, inorganic catalysts and biomolecules may be fixed to the surface of the support. Can be used.

구체적으로, 상기 유기 촉매, 무기 촉매 및 바이오 분자는 흡착, 이온결합, 공유결합, 가교결합 또는 접착성 물질에 의해 지지체(121)의 표면에 고정될 수 있다. 이때, 상기 유기 촉매, 무기 촉매 및 바이오 분자가 작용기를 통하여 고정되는 경우에는 공유결합, 이온결합 및 가교결합 중 하나 혹은 혼합된 방법을 사용하여 지지체(121)의 표면에 고정될 수 있고, 작용기를 통하여 고정되지 않는 경우에는 폴리도파민(polydopamine), 폴리노레피네프린(polynorepinephrine)과 같이 카테콜(catechol)기를 기반으로 하는 접착성 물질 및 물리적 단순 흡착 중 하나를 사용하여 지지체(121)의 표면에 고정될 수 있다.In detail, the organic catalyst, the inorganic catalyst, and the biomolecule may be fixed to the surface of the support 121 by adsorption, ionic bonding, covalent bonding, crosslinking, or an adhesive material. In this case, when the organic catalyst, the inorganic catalyst and the biomolecule are fixed through the functional group, the organic catalyst, the inorganic catalyst, and the biomolecule may be fixed to the surface of the support 121 using one or a mixed method of covalent bonds, ionic bonds and crosslinking, If it is not fixed through, it is fixed to the surface of the support 121 using one of catechol-based adhesive materials such as polydopamine, polynorepinephrine, and physically simple adsorption. Can be.

한편, 본 발명의 일 실시예에 따르면, 상기 지지체(121)의 표면에는 유기 촉매, 무기 촉매 및 바이오 분자를 고정하기 위하여 미디어(150)가 형성될 수 있다(도 1 참조). 즉, 미디어(150)에 상기 유기 촉매, 무기 촉매 및 바이오 분자가 결합되어 지지체(121)의 표면에 고정된다.Meanwhile, according to an embodiment of the present invention, the media 150 may be formed on the surface of the support 121 to fix the organic catalyst, the inorganic catalyst and the biomolecule (see FIG. 1). That is, the organic catalyst, the inorganic catalyst, and the biomolecule are combined with the media 150 to be fixed to the surface of the support 121.

이러한, 상기 미디어(150)는 복수 개의 고분자 섬유를 포함하는 고분자 섬유 집합체일 수 있으며, 또는 다공성 입자, 탄소 튜브, 고분자 튜브, 와이어, 필라, 그래핀, 풀러렌, 폴리도파민, 폴리노레피네프린 및 구형입자 중 적어도 하나를 사용할 수 있음을 밝혀둔다.The media 150 may be a polymer fiber assembly including a plurality of polymer fibers, or porous particles, carbon tubes, polymer tubes, wires, pillars, graphene, fullerenes, polydopamine, polynorepinephrine, and spheres. Note that at least one of the particles can be used.

한편, 본 발명의 일 실시예에 따른 3차원 메쉬 구조체(120)에 대한 용이한 설명을 위하여, 상기 미디어(150)는 고분자 섬유 집합체인 것으로 설명한다. On the other hand, for easy description of the three-dimensional mesh structure 120 according to an embodiment of the present invention, the media 150 will be described as a polymer fiber aggregate.

상기 미디어(150)는 고분자 섬유 집합체 중 일부의 고분자 섬유가 수직한 방향으로 지지체(121)의 지지체 표면 외부로 돌출되어 섬유 기둥(도 6의 151 참조)을 형성할 수 있다. 이때, 상기 섬유기둥은 직선형, 유선형, S자형 등 다양한 형태를 포함하는데, 바람직하게는 섬유기둥의 대다수가 미디어의 장방향과 수직한 방향으로 형성될 수 있다. 또한, 섬유기둥의 하단부(도 6의 D 참조)는 고분자 섬유가 서로 복잡하게 교차된 형태의 네트워크 구조를 형성할 수 있다.The media 150 may protrude out of the support surface of the support 121 in a vertical direction in a polymer fiber assembly to form a fiber pillar (see 151 of FIG. 6). At this time, the fiber column includes a variety of forms, such as straight, streamlined, S-shaped, preferably, the majority of the fiber pillar may be formed in a direction perpendicular to the long direction of the media. In addition, the lower end of the fiber column (see D of FIG. 6) may form a network structure in which polymer fibers are intricately intersected with each other.

그리고, 상기 유기 촉매, 무기 촉매 및 바이오 분자는 미디어(150)에 형성되는 섬유 기둥(151)을 통하여 지지체(121)에 고정될 수 있다.In addition, the organic catalyst, the inorganic catalyst, and the biomolecule may be fixed to the support 121 through the fiber pillar 151 formed on the media 150.

여기서, 상기 유기 촉매, 무기 촉매 및 바이오 분자들은 미디어(150)에 직접적으로 결합되거나 또는 간접적으로 결합될 수 있다.Herein, the organic catalyst, the inorganic catalyst and the biomolecules may be directly or indirectly bonded to the media 150.

구체적으로, 상기 유기 촉매, 무기 촉매 및 바이오 분자는 흡착, 이온결합, 공유결합, 가교결합 및 접착성 물질에 의해 미디어의 섬유 기둥에 직접적으로 고정될 수 있으며, 바람직하게는 상기 유기 촉매, 무기 촉매 및 바이오 분자는 미디어의 작용기와 공유결합을 통해 직접적으로 결합될 수 있다.Specifically, the organic catalyst, the inorganic catalyst and the biomolecule may be directly fixed to the fiber column of the media by adsorption, ionic bond, covalent bond, crosslinking and adhesive material, preferably the organic catalyst, inorganic catalyst And the biomolecule may be directly bonded through a covalent bond with a functional group of the media.

또는, 고분자 섬유의 상기 작용기와 상기 바이오분자는 이종의 바이오분자에 의해 특이적 결합되어, 작용기와 바이오 분자가 링커(linker) 역할을 하는 이종의 바이오 분자들을 통해 간접적으로 결합되어 고분자섬유에 상기 바이오분자가 고정되어 있을 수 있는데, 좀 더 구체적으로는 상기 특이적 결합은 항체-항원, 프로테인A-항체, 프로테인G-항체, 핵산-핵산 하이브리드, 앱타머-바이오분자, 아비딘-비오틴(Avidin-biotin), 스트렙타비딘-비오틴(Streptavidin-biotin), 렉틴-탄수화물(Lectins-carbohydrate), 렉틴-글리코실단백질(Lectin-glycoprotein) 등의 특이적 결합을 통해 상기 작용기와 바이오 분자 사이에 상기 이종의 바이오 분자가 링커(linker) 역할을 하여 고분자 섬유의 작용기와 바이오 분자가 간접적으로 결합되어 있을 수 있다.Alternatively, the functional group of the polymer fiber and the biomolecule are specifically bound by heterogeneous biomolecules, so that the functional group and the biomolecule are indirectly bound through heterogeneous biomolecules serving as a linker, thereby forming the bio-molecule on the polymer fiber. Molecules may be immobilized, more specifically, the specific binding is antibody-antigen, protein A-antibody, protein G-antibody, nucleic acid-nucleic acid hybrid, aptamer-biomolecule, avidin-biotin ), Through the specific binding of streptavidin-biotin, lectin-carbohydrate, lectin-glycoprotein, etc., between the functional group and the biomolecule. The molecule may act as a linker so that the functional group of the polymer fiber and the biomolecule may be indirectly bonded.

여기서, 상기 유기 촉매는 탄산무수화 효소, 당산화 효소, 트립신, 키모트립신, 서브틸리신, 파파인, 서몰리신, 리파아제, 페록시다아제, 아실라아제, 락토나제, 프로테아제, 티로시나아제, 라카아제, 셀룰라아제, 자일라나제, 유기포스포하이드롤레이즈, 콜린에스테라아제, 포름산 탈수소 효소, 알데히드 탈수소 효소, 알코올 탈수소 효소, 포도당 탈수소 효소, 및 포도당 이성화 효소 중 적어도 하나를 포함하는 효소 중 적어도 하나를 포함할 수 있다.Here, the organic catalyst is a carbonic anhydrase, glycosylation enzyme, trypsin, chymotrypsin, subtilisin, papain, thermolysine, lipase, peroxidase, acylase, lactonase, protease, tyrosinase, At least one of enzymes including at least one of laccase, cellulase, xylanase, organophosphohydrolase, cholinesterase, formic acid dehydrogenase, aldehyde dehydrogenase, alcohol dehydrogenase, glucose dehydrogenase, and glucose isomerase can do.

또한, 상기 무기 촉매는 플래티늄, 백금, 로듐, 팔라듐, 납, 이리듐, 루비듐, 철, 니켈, 아연, 코발트, 구리, 망간, 티타늄, 루테늄, 은, 몰리브덴, 텅스텐, 알루미늄, 철, 안티몬, 주석, 비스무트, 바륨, 오스뮴, 산화질소, 산화구리, 산화망간, 산화티타늄, 산화바나늄, 산화아연 중 적어도 하나를 포함할 수 있다.In addition, the inorganic catalyst is platinum, platinum, rhodium, palladium, lead, iridium, rubidium, iron, nickel, zinc, cobalt, copper, manganese, titanium, ruthenium, silver, molybdenum, tungsten, aluminum, iron, antimony, tin, It may include at least one of bismuth, barium, osmium, nitric oxide, copper oxide, manganese oxide, titanium oxide, vananium oxide, and zinc oxide.

또한 상기 바이오 분자는 알부민, 인슐린, 콜라겐, 항체, 항원, 프로테인A, 프로테인G, 아비딘, 스트렙타비딘, 바이오틴, 핵산, 펩타이드, 렉틴, 탄수화물 중 적어도 하나를 포함할 수 있다.In addition, the biomolecule may include at least one of albumin, insulin, collagen, antibody, antigen, protein A, protein G, avidin, streptavidin, biotin, nucleic acid, peptide, lectin, carbohydrate.

이러한 구성을 갖는 3차원 메쉬 구조체(120)는 3차원 메쉬 구조를 갖는 지지체의 표면 및 내부 전체적으로 촉매물질이나 바이오분자가 고집적되기 때문에, 전체적인 반응 면적이 넓어질 수 있으며, 고집적된 촉매 및 바이오분자에 의해 반응 수율이 향상될 수 있다. Since the three-dimensional mesh structure 120 having such a structure is highly integrated with the catalyst material or the biomolecule on the surface and inside of the support having the three-dimensional mesh structure, the overall reaction area can be widened, and the catalyst and the biomolecule are highly integrated. The reaction yield can be improved by this.

또한, 3차원 메쉬 구조체의 표면 및 내부에 유기 촉매, 무기 촉매 및 바이오분자들이 고집적(集積) 되어 유체와 반응하기 때문에, 종래기술에 비하여 높은 속도로 반응이 진행될 수 있는 장점이 있다.In addition, since the organic catalyst, the inorganic catalyst and the biomolecules are highly integrated on the surface and the inside of the three-dimensional mesh structure and react with the fluid, there is an advantage that the reaction may proceed at a high speed as compared with the prior art.

한편, 본 발명의 상세한 설명 및 도면에서는 상기 3차원 메쉬 구조체(120)가 복수 개로 구비되어 적층되는 것으로 도시 및 설명하고 있으나, 본 발명이 이로 제한되지 않으며, 상기 3차원 메쉬 구조체(120)는 하나의 단일체로 형성될 수 있음을 밝혀둔다.Meanwhile, in the detailed description and drawings of the present invention, the three-dimensional mesh structure 120 is illustrated and described as being provided with a plurality of layers, but the present invention is not limited thereto, and the three-dimensional mesh structure 120 is one. Note that it can be formed as a single unit of.

한편, 상기와 같은 구성을 갖는 3차원 메쉬 구조체(120)는 결합되는 제1물질에 따라 다양한 응용이 가능하다.On the other hand, the three-dimensional mesh structure 120 having the configuration as described above can be a variety of applications depending on the first material to be bonded.

일례로, 지지체(121) 및 지지체에 고정화된 미디어(150)에 바이오분자를 부착시켜, 미생물 및 세포를 선택적으로 결합시키고, 이를 배양 및 활성화할 수 있다. 이때, 미생물은 바실러스 서브틸리스(Bacillus subtilis), 바실러스 리케니포미스(Bacillus licheniformis), 바실러스 폴리퍼멘티커스(Bacillus polyfermenticus), 바실러스 메센테리커스(Bacillus mesentericus), 사카로마이세스 세레비제(Saccharomyces cerevisiae), 클로스트리디움 부티리컴(Clostridium butyricum), 스트렙토코커스 패칼리스(Streptococcus faecalis), 스트렙토코커스 패시움(Streptococcus faecium), 마이크로코커스 카세리티쿠스(Micrococcus caseolyticus), 스테필로코커스 아우레우스(Staphylococcus aureus), 락토바실러스 카제이(Lactobacillus casei), 락토바실러스 프라타륨(Lactobacillus plantarum), 루코노스톡 메세테로이데스 (Leuconostoc Mesenteroides), 사카로마이세스 세르비시아(Saccharomyces cerevisiae), 데바리오마이세스 니코티아나(Debaryomyces nicotianae), 아시네토박터 칼코아세티쿠스(Acinetobactercalcoaceticus), 알칼리게네스 균(Alcaligenesodorans), 아로매토리움 아로매티쿰(Aromatoleum aromaticum), 지오박터 메탈리듀센(Geobacter metallireducens), 디클로로모나스 아로마틱(Dechloromonas aromatic), 아스로박터속(Arthrobacter sp.) 및 알카니보락스 보르쿠멘시스(Alcanivorax borkumensis) 중에서 선택된 1종 이상을 포함할 수 있다. 그리고, 상기 세포는 줄기세포, 면역세포, 상피세포, 근육세포, 신경세포, 간세포, 폐세포, 심혈관세포, 췌장세포, 심장세포, 뼈세포 및 암세포 중에서 선택된 1종 이상을 포함할 수 있다.For example, biomolecules may be attached to the support 121 and the media 150 immobilized on the support to selectively bind microorganisms and cells, and to culture and activate them. At this time, the microorganism is Bacillus subtilis, Bacillus licheniformis, Bacillus polyfermenticus, Bacillus mesentericus, Saccharomyces cerevises cerevisiae, Clostridium butyricum, Streptococcus faecalis, Streptococcus faecium, Micrococcus caseolyticus, Staphylococcus aureus auretaloclocus ), Lactobacillus casei, Lactobacillus plantarum, Leuconostoc Mesenteroides, Saccharomyces cerevisiae, Debariomyses nicotiana nicotianae), Acinetobacter calcoaceticus, alkali Alcaligenesodorans, Aromatoleum aromaticum, Geobacter metallireducens, Dechloromonas aromatic, Arthrobacter sp. And Alkanivolas bors It may include one or more selected from the cumulus (Alcanivorax borkumensis). And, the cells may include one or more selected from stem cells, immune cells, epithelial cells, muscle cells, nerve cells, hepatocytes, lung cells, cardiovascular cells, pancreas cells, heart cells, bone cells and cancer cells.

상기와 같은 구성을 갖는 3차원 메쉬 구조체(120)는 도 4에 도시된 바와 같이, 복수 개로 구비하여 임펠러(100)를 형성할 수 있다.As shown in FIG. 4, the three-dimensional mesh structure 120 having the above configuration may be provided in plural to form the impeller 100.

본 발명의 일 실시예에 따른 3차원 메쉬 구조체(120)를 갖는 임펠러(100)는 결합부(110) 및 3차원 메쉬 구조체(120)를 포함할 수 있다.Impeller 100 having a three-dimensional mesh structure 120 according to an embodiment of the present invention may include a coupling portion 110 and the three-dimensional mesh structure 120.

상기 결합부(110)는 하나 이상의 3차원 메쉬 구조체(120)를 일 방향으로 회전시키기 위한 것으로, 정육면체 형상을 갖는다.The coupling part 110 is for rotating one or more three-dimensional mesh structure 120 in one direction, and has a cube shape.

또한, 상기 결합부(110)의 상부에는 3차원 메쉬 구조체(120)를 일 방향으로 회전시키기 위한 회전축(130)이 결합될 수 있으며, 도 5에 도시된 바와 같이, 측면부에는 3차원 메쉬 구조체(120)가 결합되기 위한 결합홀(111)이 형성될 수 있다.In addition, a rotating shaft 130 for rotating the three-dimensional mesh structure 120 in one direction may be coupled to the upper portion of the coupling part 110, and as shown in FIG. 5, the three-dimensional mesh structure ( Coupling holes 111 for coupling 120 may be formed.

한편, 본원발명의 상세한 설명 및 도면에서는 결합부(110)의 형상이 정육면체 형상으로 형성되는 것으로 설명 및 도시하고 있으나 이로 제한되지는 않는다. 구체적으로, 육면체 형상 또는 구 형상으로 형성될 수 있으며, 상기 하나 이상의 3차원 메쉬 구조체와 결합되어 일 방향으로 회전할 수 있는 형상이라면 어떠한 형상으로도 형성될 수 있다.On the other hand, in the detailed description and drawings of the present invention, the shape of the coupling portion 110 is described and illustrated as being formed in a cube shape, but is not limited thereto. Specifically, it may be formed in a hexahedral shape or a spherical shape, and may be formed in any shape as long as it is combined with the one or more three-dimensional mesh structures to rotate in one direction.

상기 3차원 메쉬 구조체(120)는 하나 이상 구비되어 상기 결합부(110)의 측면부에 결합될 수 있으며, 보다 상세하게는 상기 결합부(110)의 측면부에 형성되는 결합홀(111)에 결합된다.The three-dimensional mesh structure 120 is provided with one or more may be coupled to the side portion of the coupling portion 110, more specifically is coupled to the coupling hole 111 formed in the side portion of the coupling portion 110. .

이때, 상기 3차원 메쉬 구조체(120)의 일단에는 상기 결합홀(111)에 결합되기 위한 연결부(140)가 구비될 수 있다.At this time, one end of the three-dimensional mesh structure 120 may be provided with a connection portion 140 for coupling to the coupling hole 111.

상기 연결부(140)는 소정의 길이를 가지고 상기 3차원 메쉬 구조체(120)의 일단에서 돌출되게 구비될 수 있으며, 상기 하나 이상의 3차원 메쉬 구조체(120)는 상기 연결부(140)에 의해 상기 결합부(110)에서 착탈 가능하게 설치될 수 있다.The connection portion 140 may be provided to protrude from one end of the three-dimensional mesh structure 120 having a predetermined length, the one or more three-dimensional mesh structure 120 is the coupling portion by the connection portion 140 Detachable at 110 may be installed.

또한, 상기 연결부(140)와 상기 결합홀(111)은 서로 대응되는 형상 및 크기로 형성된다.In addition, the connection portion 140 and the coupling hole 111 is formed in a shape and size corresponding to each other.

한편, 하나 이상의 상기 3차원 메쉬 구조체(120)는 상기 회전축(130)에 수직한 평면 상에 동일 간격으로 이격 배치될 수 있다. 본 실시예에서는 4 개의 3차원 메쉬 구조체가 90도 간격으로 배치된 것을 예시하였으나, 그 수 및 배치 각도가 이에 제한된 것은 아니다.On the other hand, one or more of the three-dimensional mesh structure 120 may be spaced apart at equal intervals on a plane perpendicular to the axis of rotation (130). In the present exemplary embodiment, four three-dimensional mesh structures are arranged at intervals of 90 degrees, but the number and placement angle are not limited thereto.

이와 같은 구성에 따르면, 상기 하나 이상의 3차원 메쉬 구조체(120, 120')가 결합부(110, 110')로부터 착탈 가능하게 설치됨으로써, 필요에 따라 교체가 용이할 수 있다. According to this configuration, the one or more three-dimensional mesh structure (120, 120 ') is detachably installed from the coupling portion (110, 110'), it can be easily replaced as necessary.

또한, 임펠러에 하나 이상의 3차원 메쉬 구조체 각각에 다른 물질을 부착할 수 있으므로 연쇄 반응이 일어날 수 있다. In addition, a chain reaction can occur because different materials can be attached to each of the one or more three-dimensional mesh structures in the impeller.

즉, 일례로, 임펠러(100)에 결합된 복수 개의 3차원 메쉬 구조체(120) 중 임의의 제1메쉬 구조체에는 효소를 고정시키고, 다른 임의의 제2메쉬 구조체에는 항체를 고정시켜 반응시킬 수 있다.That is, for example, the enzyme may be immobilized on any one of the plurality of three-dimensional mesh structures 120 coupled to the impeller 100, and the antibody may be immobilized on the other arbitrary second mesh structure to react with the antibody. .

또한, 지지체가 3차원 메쉬 구조로 형성되어 3차원 메쉬 구조체 전체에 촉매물질이나 바이오분자가 고집적되기 때문에, 전체적인 반응 면적이 넓어질 수 있다.In addition, since the support is formed in a three-dimensional mesh structure and the catalyst material or biomolecule is highly integrated in the three-dimensional mesh structure, the overall reaction area may be widened.

아울러, 임펠러가 반응기 내에서 회전되기 때문에 교반과 함께 반응이 동시에 이루어질 수 있다.In addition, since the impeller is rotated in the reactor, the reaction may be simultaneously performed with stirring.

한편, 상기와 같은 구성을 갖는 3차원 메쉬 구조체(120)는 다음과 같은 방법으로 제조될 수 있다. 이때, 상기 미디어(150)에는 공유결합을 통하여 유기촉매가 결합되는 것을 일례로 설명한다.On the other hand, the three-dimensional mesh structure 120 having the above configuration can be manufactured by the following method. At this time, it will be described as an example that the organic catalyst is bonded to the media 150 through a covalent bond.

본 발명의 일 실시예에 따른 3차원 메쉬 구조체(120)는 도 6에 도시된 바와 같이, 지지체(121) 표면에 작용기가 포함된 고분자 섬유를 성장시켜서 미디어(150)를 형성시킨 후, 상기 작용기에 유기 촉매, 무기 촉매 및 바이오 분자 중 하나를 선택하여 고정화시켜서 제조할 수 있다. In the three-dimensional mesh structure 120 according to an embodiment of the present invention, as shown in Figure 6, by growing a polymer fiber containing a functional group on the surface of the support 121 to form a media 150, the functional group It can be prepared by selecting and immobilizing one of an organic catalyst, an inorganic catalyst and a biomolecule.

즉, 3차원 메쉬 구조체(120)는 지지체(121)의 표면에 형성된 미디어(150)를 구성하는 작용기를 포함하는 고분자 섬유가 지지체 표면으로부터 수직한 방향으로 곧게 또는 비스듬히 성장한 형태를 가짐으로써, 수직한 방향으로 성장한 고분자 섬유 양을 극대화시킬 수 있고, 미디어가 매우 높은 비표면적을 가지게 된다. 그리고, 상기 수직한 방향으로 성장된 고분자 섬유의 작용기에 유기촉매가 매우 안정적으로 고정화시키고, 많은 양의 유기 촉매를 고정화시킬 수 있게 되어, 유기 촉매의 열안정성 및 장기사용 안정성을 향상시킬 수 있다. That is, the three-dimensional mesh structure 120 has a shape in which the polymer fibers including the functional groups constituting the media 150 formed on the surface of the support 121 are grown straight or obliquely in a direction perpendicular to the surface of the support. The amount of polymer fibers grown in the direction can be maximized, and the media have a very high specific surface area. In addition, the organic catalyst can be immobilized very stably to the functional groups of the polymer fibers grown in the vertical direction, and the organic catalyst can be immobilized in a large amount, thereby improving thermal stability and long-term stability of the organic catalyst.

이러한, 본 발명의 3차원 메쉬 구조체(120)를 제조하는 방법에 대하여 좀 더 구체적으로 설명하면, 본 발명의 3차원 메쉬 구조체(120)는 고분자 섬유 중합용액에 지지체를 담지하는 1단계; 상기 고분자 섬유 중합용액을 중합반응을 수행하여, 지지체 표면에 작용기가 포함된 고분자 섬유를 성장시켜서 고분자 섬유 집합체가 3차원 메쉬 구조를 형성하고 있는 미디어를 지지체 표면에 형성시키는 2단계; 및 미디어를 형성하는 고분자 섬유의 작용기에 유기 촉매를 고정화시키는 3단계;를 포함하는 공정을 수행하여 제조할 수 있다. Such a method of manufacturing the three-dimensional mesh structure 120 of the present invention will be described in more detail. The three-dimensional mesh structure 120 of the present invention includes one step of supporting a support in a polymer fiber polymerization solution; Performing a polymerization reaction on the polymer fiber polymerization solution to grow a polymer fiber including a functional group on the surface of the support to form a media on which the polymer fiber aggregate forms a three-dimensional mesh structure on the surface of the support; And immobilizing the organic catalyst on the functional group of the polymer fiber forming the media.

1단계의 상기 고분자 섬유 중합용액은 1단량체와 중합개시제 또는 제2단량체와 중합개시제를 포함할 수 있다. 이 경우, 공중합체(copolymer)가 아닌 중합체(polymer)를 중합이 가능하다.The polymer fiber polymerization solution in one step may include a monomer and a polymerization initiator or a second monomer and a polymerization initiator. In this case, it is possible to polymerize a polymer other than a copolymer.

1단계의 상기 고분자 섬유 중합용액은 제1단량체, 제2단량체 및 중합개시제를 포함하며, 이 경우, 공중합체(copolymer) 형성을 위한 공중합이 가능하다.The polymer fiber polymerization solution of the first step includes a first monomer, a second monomer and a polymerization initiator, in which case, copolymerization for forming a copolymer is possible.

이때, 상기 제1단량체는 아닐린(aniline), 피롤(pyrrole), 티오펜 (thiophene), 락틱산(lactic acid), 비닐알콜(vinyl alcohol), 아크릴로니트릴(acrylonitrile), 에틸렌(ethylene), 에틸렌이민(ethyleneimine), 프로필렌옥사이드(propylene oxide), 우레탄(urethane), 염화비닐(vinyl chloride), 스티렌(styrene), 카프로락탐(caprolactam), 카프로락톤(aprolactone), 에틸렌 테레프탈레이트(ethylene terephthalate), 메틸메타크릴레이트(methyl methacrylate), 다이메틸실록산(dimethysiloxane), 테플론(teflon), 콜라겐(collagen), 나일론(nylon), 셀룰로우즈(cellulose), 키토산(chitosan) 및 실리콘(silicon) 중에서 선택된 1종 이상을 포함할 수 있고, 바람직하게는 아닐린(aniline) 및 피롤(pyrrole) 중에서 선택된 1종 이상을 포함할 수 있다.In this case, the first monomer is aniline (pyrrole), thiophene (thiophene), lactic acid (lactic acid), vinyl alcohol (vinyl alcohol), acrylonitrile (acrylonitrile), ethylene (ethylene), ethylene Ethyleneimine, propylene oxide, urethane, vinyl chloride, styrene, caprolactam, caprolactone, aprolactone, ethylene terephthalate, methyl One selected from methacrylate, dimethylsiloxane, teflon, collagen, nylon, cellulose, cellulose, chitosan, and silicon It may include the above, and preferably may include one or more selected from aniline (aniline) and pyrrole (pyrrole).

그리고, 상기 제2단량체는 카르복시기, 아민기, 이민기, 에폭시기, 하이드록시기, 알데하이드기, 카르보닐기, 에스터기, 메톡시기, 에톡시기, 페록시기, 에테르기, 아세탈기, 설파이드기, 포스페이트기 및 아이오드기 중에서 선택된 1종 이상의 작용기를 포함하는 화합물이며, 바람직하게는 1-아미노벤조익산(1-aminobenzoic acid), 2-아미노벤조익산(2-aminobenzoic acid), 3-아미노벤조익산(3-aminobenzoic acid), 1-페닐렌다이아민(1-phenylenediamine), 2-페닐렌다이아민(2-phenylenediamine), 3-페닐렌다이아민(3-phenylenediamine), 피롤-1-카브알데하이드(pyrrole-1-carbaldehyde), 피롤-2-카브알데하이드(pyrrole-2-carbaldehyde) 및 피롤-3-카브알데하이드(pyrrole-3-carbaldehyde), 티오펜-2-카브알데하이드(thiophene-2-carbaldehyde) 및 3-티오펜카복사알데하이드(3-thiophenecarboxaldehyde) 중에서 선택된 1종 이상을 포함할 수 있다.The second monomer may be a carboxyl group, an amine group, an imine group, an epoxy group, a hydroxyl group, an aldehyde group, a carbonyl group, an ester group, a methoxy group, an ethoxy group, a peroxy group, an ether group, an acetal group, a sulfide group, a phosphate group, or an eye It is a compound containing at least one functional group selected from an ode group, preferably 1-aminobenzoic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, or 3-aminobenzoic acid. acid), 1-phenylenediamine, 2-phenylenediamine, 3-phenylenediamine, pyrrole-1-carbaldehyde carbaldehyde), pyrrole-2-carbaldehyde and pyrrole-3-carbaldehyde, thiophene-2-carbaldehyde and 3-thiophene Carboxaldehyde (3-thiophenecarboxaldehyde) containing at least one selected from There.

이때, 상기 제2단량체는 제1단량체 1 몰에 대하여, 0.05 ~ 0.95 몰비로, 바람직하게는 0.2 ~ 0.8 몰비로, 더욱 바람직하게는 0.25 ~ 0.75 몰비로 사용하는 것이 좋은데, 이때, 제2단량체 사용량이 1 몰비를 초과하면 미디어에 수직한 방향으로 형성되는 고분자 섬유(섬유기둥)의 수가 줄어드는 문제가 있을 수 있으며, 0.05 몰비 미만으로 사용하면 제1단량체와 제2단량체의 공중합체인 고분자 섬유에 작용기가 너무 적거나 없어서 바이오 분자를 고정량이 너무 적거나 바이오 분자 고정이 불가능할 수 있으므로 상기 범위 내로 사용하는 것이 좋다. In this case, the second monomer is preferably used in a molar ratio of 0.05 to 0.95, preferably 0.2 to 0.8 molar ratio, more preferably 0.25 to 0.75 molar ratio with respect to 1 mole of the first monomer. If the molar ratio exceeds 1, the number of polymer fibers (fiber columns) formed in a direction perpendicular to the media may be reduced. If the molar ratio is less than 0.05, the functional groups may be added to the polymer fibers that are copolymers of the first monomer and the second monomer. It is recommended to use the biomolecule within the above range because too little or no biomolecules may be too small or immobilized.

그리고, 상기 중합개시제는 아미노 퍼설페이트(amino persulfate), 포타슘 퍼설페이트(potassium persulfate), 소듐 퍼설페이트(sodium persulfate), 과산화수소(hydrogen peroxide), 과산화벤조일(benzoyl peroxide), 과산화아세틸(acetyl peroxide) 및 아조비스이소뷰티로니트릴(azobisisobutyronitrile) 중에서 선택된 1종 이상을 포함할 수 있다. 이때, 중합개시제의 사용량은 제1단량체 1 몰에 대하여, 0.05 ~ 1 몰비로, 바람직하게는 0.3 ~ 0.85 몰비로, 더욱 바람직하게는 0.4 ~ 0.8 몰비로 사용하는 것이 좋은데, 이때, 중합개시제 사용량이 0.05 몰비 미만이면 중합 반응이 너무 더디고 중합 반응에 의해 형성된 고분자 섬유가 충분히 성장하지 못해서 3차원 메쉬 구조의 미디어 형성이 어려울 수 있으며, 중합개시제 사용량이 1 몰비를 초과하는 것은 비경제적이고, 과도한 중합반응으로 인해 미디어에 수직한 방향으로 형성되는 고분자 섬유(섬유기둥)의 수가 줄어드는 문제가 있을 수 있다.In addition, the polymerization initiator is amino persulfate, potassium persulfate, sodium persulfate, hydrogen peroxide, benzoyl peroxide, acetyl peroxide and acetyl peroxide. It may include one or more selected from azobisisobutyronitrile (azobisisobutyronitrile). At this time, the amount of the polymerization initiator is preferably used in a molar ratio of 0.05 to 1, preferably 0.3 to 0.85 mole ratio, more preferably 0.4 to 0.8 molar ratio with respect to 1 mole of the first monomer, wherein the amount of the polymerization initiator is If the molar ratio is less than 0.05, the polymerization reaction may be too slow and the polymer fibers formed by the polymerization reaction may not grow sufficiently to form a media having a three-dimensional mesh structure, and it is uneconomical to use the polymerization initiator in excess of 1 molar ratio. Due to this, there may be a problem in that the number of polymer fibers (fiber columns) formed in a direction perpendicular to the media is reduced.

또한, 1단계의 상기 지지체(121)는 표면에 작용기를 포함하는 고분자 섬유를 성장시킬 수 있는 것이라면 어느 것이든 사용 가능하며, 바람직하게는 ABS(Acrylonitrile-butadiene-styrene) 폴리머, 폴리락틱산, 폴리비닐알콜, 폴리카프로락탐, 폴리카프로락톤, 폴리락틱-co-글리콜산, 폴리아크릴로니트릴, 폴리에스테르, 폴리에틸렌, 폴리에틸렌이민, 폴리프로필렌옥사이드, 폴리우레탄, 폴리글리콜산, 폴리에틸렌테레프탈레이트, 폴리메틸메타크릴레이트, 폴리스티렌, 폴리디메틸실록산, 테플론, 여과지, 유리, 금도금, 실리콘 웨이퍼 등을 사용할 수 있으며, 본 발명이 이에 특별히 한정되는 것은 아니다. In addition, the support 121 of the first stage may be used as long as it can grow a polymer fiber containing a functional group on the surface, preferably ABS (Acrylonitrile-butadiene-styrene) polymer, polylactic acid, poly Vinyl alcohol, polycaprolactam, polycaprolactone, polylactic-co-glycolic acid, polyacrylonitrile, polyester, polyethylene, polyethyleneimine, polypropylene oxide, polyurethane, polyglycolic acid, polyethylene terephthalate, polymethylmetha Acrylate, polystyrene, polydimethylsiloxane, teflon, filter paper, glass, gold plated, silicon wafer and the like can be used, but the present invention is not particularly limited thereto.

상기 2단계는 고분자 섬유 중합용액을 중합반응시켜서 중합체 또는 공중합체를 형성시킴과 동시에 이를 성장시켜서 고분자 섬유를 제조한다. 그리고, 고분자 섬유가 성장하면서 지지체 표면 상에 고분자 섬유 집합체가 형성되고, 상기 고분자 섬유 집합체는 이를 구성하는 다수 개의 고분자 섬유가 서로 얽혀서 3차원 메쉬 구조의 미디어가 형성된다(도 6의 (A) 참조). The second step is to polymerize the polymer fiber polymerization solution to form a polymer or copolymer and at the same time to grow it to produce a polymer fiber. Then, as the polymer fibers grow, a polymer fiber aggregate is formed on the surface of the support, and the polymer fiber aggregate is entangled with a plurality of polymer fibers constituting the polymer fiber to form a media having a three-dimensional mesh structure (see FIG. 6A). ).

그리고, 작용기를 포함하는 공중합체와 달리, 작용기를 포함하지 않는 중합체로 성장된 고분자 섬유인 경우, 별도의 개질반응을 수행하여 고분자 섬유에 작용기를 형성시킬 수도 있다.And, unlike the copolymer containing a functional group, in the case of a polymer fiber grown with a polymer containing no functional group, it is also possible to form a functional group on the polymer fiber by performing a separate reforming reaction.

상기 미디어가 형성되면서, 미디어가 지지체 표면에 고정하게 된다.As the media is formed, the media is fixed to the support surface.

이때, 상기 중합반응은 0℃ ~ 80℃, 바람직하게는 0℃ ~ 30℃, 더욱 바람직하게는 2℃ ~ 10℃ 하에서 0분 ~ 48 시간 동안, 바람직하게는 30분 ~ 36 시간 동안 수행할 수 있다. 그리고, 중합반응시, 교반 속도는 100 ~ 300 rpm의 속도로 바람직하게는 150 ~ 250 rpm의 속도로, 더욱 바람직하게는 170 ~ 230 rpm의 속도로 교반시키면서 수행할 수 있다. 이때, 중합반응온도가 0℃ 이하이면 중합반응 진행이 안될 수 있고, 80℃를 초과하면 과도한 중합반응으로 인해 섬유기둥이 충분하게 형성되지 않을 수 있다. 그리고, 교반속도가 100 rpm 미만이면 누운 형상으로 성장한 고분자 섬유가 증가할 수 있으며, 300 rpm을 초과하는 경우 지지체에 대한 고정력이 감소할 수 있고, 제조된 3차원 메쉬 구조체의 장기사용안정성이 떨어질 수 있다.At this time, the polymerization reaction can be carried out for 0 minutes to 48 hours, preferably 30 minutes to 36 hours under 0 ℃ ~ 80 ℃, preferably 0 ℃ ~ 30 ℃, more preferably 2 ℃ ~ 10 ℃. have. In addition, during the polymerization reaction, the stirring speed may be performed while stirring at a speed of 100 to 300 rpm, preferably at a speed of 150 to 250 rpm, and more preferably at a speed of 170 to 230 rpm. At this time, if the polymerization temperature is 0 ° C or less, the polymerization may not proceed, and if it exceeds 80 ° C, the fiber pillar may not be sufficiently formed due to excessive polymerization. When the stirring speed is less than 100 rpm, the polymer fibers grown in a lying shape may increase, and when the stirring speed exceeds 300 rpm, the fixing force to the support may be decreased, and the long-term stability of the manufactured three-dimensional mesh structure may be deteriorated. have.

앞서 설명한 바와 같이 중합되어 형성된 공중합체는 작용기를 포함하는 고분자 섬유를 형성하게 된다. 일례를 들면, 상기 작용기를 포함하는 고분자 섬유는 카르복시기를 포함하는 고분자 섬유, 아민기를 포함하는 고분자 섬유 및 알데하이드기를 포함하는 고분자 섬유일 수 있다. 보다 바람직한 일례를 들면, 상기 카르복시기를 포함하는 고분자 섬유는 아닐린 및 1-아미노벤조익산, 2-아미노벤조익산, 또는 3-아미노벤조익산의 공중합체일 수 있고, 상기 아민기를 포함하는 고분자 섬유는 아닐린 및 1-페닐렌다이아민, 2-페닐렌다이아민 또는 3-페닐렌다이아민의 공중합체일 수 있고, 상기 알데하이드기를 포함하는 고분자 섬유는 파이론 또는 피롤;과 피롤-1-카브알데하이드, 피롤-2-카브알데하이드 또는 피롤-3-카브알데하이드;의 공중합체 일 수 있다. As described above, the copolymer formed by polymerization forms a polymer fiber including a functional group. For example, the polymer fiber including the functional group may be a polymer fiber including a carboxyl group, a polymer fiber including an amine group and a polymer fiber including an aldehyde group. As a more preferred example, the polymer fiber containing the carboxyl group may be a copolymer of aniline and 1-aminobenzoic acid, 2-aminobenzoic acid, or 3-aminobenzoic acid, and the polymer fiber containing the amine group is aniline And it may be a copolymer of 1-phenylenediamine, 2-phenylenediamine or 3-phenylenediamine, wherein the polymer fiber comprising the aldehyde group is pyron or pyrrole; and pyrrole-1-carbaldehyde, pyrrole-2 It may be a copolymer of -carbaldehyde or pyrrole-3-carbaldehyde.

또한, 상기 작용기를 포함하는 고분자 섬유는 폴리아닐린, 폴리피롤, 아크릴로나이트릴-뷰타디엔-스티렌, 폴리락틱산, 폴리비닐알콜, 폴리아크릴로니트릴, 폴리에스테르, 폴리에틸렌, 폴리에틸렌이민, 폴리프로필렌옥사이드, 폴리비닐리데인 플로라이드, 폴리우레탄, 폴리염화비닐, 폴리스티렌, 폴리카프로락탐, 폴리락틱-co-글리콜산, 폴리글리콜산, 폴리카프로락톤, 폴리에틸렌 테레프탈레이트, 폴리메틸메타크릴레이트, 폴리다이메틸실록산, 테플론, 콜라겐, 폴리스티렌-co-무수말레산, 나일론, 셀룰로우즈, 키토산, 실리콘 등의 고분자 섬유를 개질 등을 통해서 고분자 섬유에 작용기를 형성시킨 것을 사용할 수도 있다.In addition, the polymer fiber containing the functional group is polyaniline, polypyrrole, acrylonitrile-butadiene-styrene, polylactic acid, polyvinyl alcohol, polyacrylonitrile, polyester, polyethylene, polyethyleneimine, polypropylene oxide, poly Vinylidene fluoride, polyurethane, polyvinyl chloride, polystyrene, polycaprolactam, polylactic-co-glycolic acid, polyglycolic acid, polycaprolactone, polyethylene terephthalate, polymethylmethacrylate, polydimethylsiloxane, Polymers such as Teflon, collagen, polystyrene-co-maleic anhydride, nylon, cellulose, chitosan, and silicone may be used to form functional groups on the polymer fibers through modification.

한편, 본 발명에 따른 미디어는 고분자 섬유를 사용하는 것으로 도시 및 설명하고 있으나 본 발명이 이로 제한되지 않는다. 즉, 미디어는 다공성 입자, 탄소 튜브, 고분자 튜브, 와이어, 필라, 그래핀, 풀러렌, 폴리도파민, 폴리노레피네프린 및 구형입자 중 적어도 하나를 사용할 수 있음을 밝혀둔다.Meanwhile, the media according to the present invention are illustrated and described as using polymer fibers, but the present invention is not limited thereto. That is, it is noted that the media may use at least one of porous particles, carbon tubes, polymer tubes, wires, pillars, graphene, fullerenes, polydopamine, polynorpinephrine and spherical particles.

3단계는 지지체의 표면에 고정된 미디어에 유기 촉매를 고정시키는 공정으로서, 구체적으로는 미디어를 형성하는 고분자 섬유의 작용기에 유기촉매를 반응(또는 흡착)시켜서 도 6과 같이 유기촉매를 미디어와 고정(또는 결합)시키는 공정이다.Step 3 is a process of fixing the organic catalyst to the media fixed to the surface of the support, specifically, the organic catalyst is reacted (or adsorbed) to the functional groups of the polymer fibers forming the media to fix the organic catalyst with the media as shown in FIG. (Or bonding).

그리고, 3단계는 유기 촉매를 사용하는 경우, 석출코팅법(precipitate coating)으로 유기촉매를 고분자 섬유의 작용기와 반응 및 고정화시킬 수 있는데, 이를 구체적으로 설명하면, 지지체 표면에 형성된 미디어를 작용기화(funcnalization) 반응을 수행하는 3-1단계; 작용기화 반응을 수행한 미디어를 구성하는 고분자 섬유의 작용기와 유기 촉매를 결합반응시키는 3-2단계; 유기 촉매를 석출시키는 3-3단계; 및 석출된 유기 촉매간 가교결합시키는 3-4단계;를 포함하는 공정을 수행할 수도 있다.In the third step, when the organic catalyst is used, the organic catalyst may be reacted with and immobilized with a functional group of the polymer fiber by a precipitation coating method. Specifically, the media formed on the surface of the support may be functionalized ( performing a funcnalization reaction; Step 3-2 of combining the functional group and the organic catalyst of the polymer fibers constituting the functional group reaction media; Step 3-3 to precipitate the organic catalyst; And 3-4 step of crosslinking the precipitated organic catalyst.

또한, 3단계는 가교결합시킨 후, 세척 후, 미반응 작용기를 캡핑(capping)시키는 3-5단계;를 더 포함할 수 있다.In addition, step 3 may further include 3-5 steps of capping the unreacted functional groups after the crosslinking and washing.

바람직한 일례로, 고분자 섬유 표면에 작용기로서 카르복실기를 포함할 경우 유기촉매의 아민기와 연결하기 위해서, 상기 3-1 단계의 작용기화 반응은 EDC-NHS 커플링 반응을 통해 수행될 수 있다. 2단계에서 제조한 지지체 표면에 고정된 상기 미디어를 5 ~ 20 mg/ml 농도의 EDC(1-Ethyl-3-(3-dimethylaminopropyl)-carbodiimide) 및 35 ~ 70 mg/ml 농도의 NHS(N-Hydroxysuccinimide)를 포함하는 EDC-NHS 커플링 용액에 10℃ ~ 35℃ 하에서, 30분 ~ 2시간 정도 담지하여 20~100 rpm 정도로 교반시킨 후, 이를 꺼내어 세척하여 수행할 수 있다.In a preferred embodiment, in the case of including a carboxyl group as a functional group on the surface of the polymer fiber, in order to connect with the amine group of the organic catalyst, the functionalization reaction of step 3-1 may be performed through an EDC-NHS coupling reaction. The media immobilized on the surface of the support prepared in step 2 was subjected to EDC (1-Ethyl-3- (3-dimethylaminopropyl) -carbodiimide) at a concentration of 5 to 20 mg / ml and NHS (N- at a concentration of 35 to 70 mg / ml). Hydroxysuccinimide) in an EDC-NHS coupling solution containing 10 ℃ ~ 35 ℃, it is carried out for 30 minutes to 2 hours and stirred about 20 ~ 100 rpm, it can be carried out by washing it out.

바람직한 일례로, 고분자 섬유 표면에 작용기로서 아민기를 포함할 경우 유기촉매의 아민기와 연결하기 위해서, 상기 3-1 단계의 작용기화 반응은 글루타알데하이드(glutaraldehyde)와의 반응을 통해 수행될 수 있다. 2단계에서 제조한 지지체 표면에 고정된 상기 미디어를 0.01 ~ 1%의 글루타알데하이드 용액에 30분 ~ 2시간 정도 담지하면, 표면에 알데하이드 작용기가 생기고, 이를 꺼내어 세척하여 유기촉매를 고정화할 수 있다.As a preferred example, when the polymer fiber surface contains an amine group as a functional group, the functionalization reaction of step 3-1 may be performed through a reaction with glutaraldehyde. When the media fixed on the support surface prepared in step 2 is immersed in 0.01-1% glutaaldehyde solution for about 30 minutes to 2 hours, an aldehyde functional group is formed on the surface, and the organic catalyst can be immobilized by taking it out and washing it. .

바람직한 일례로, 고분자 섬유 표면에 작용기로서 알데하이드기를 포함할 경우 유기 촉매의 아민기와 연결하기 위해서, 특별한 처리과정은 필요하지 않고 그대로 유기촉매 용액에 담지하여 단백질을 고정화할 수 있다.In a preferred embodiment, when the polymer fiber surface includes an aldehyde group as a functional group, in order to connect with the amine group of the organic catalyst, a special treatment is not necessary and the protein may be immobilized by being supported in the organic catalyst solution as it is.

그리고, 3-2단계는 작용기화시킨 미디어를 유기 촉매를 포함하는 용액에 투입한 다음, 결합반응을 수행하여 고분자 섬유의 작용기와 유기 촉매를 결합시킬 수 있다.In step 3-2, the functionalized media may be added to a solution containing an organic catalyst, and then a coupling reaction may be performed to combine the functional group of the polymer fiber with the organic catalyst.

다음으로, 3-3 단계의 석출은 3-2 단계를 수행한 유기 촉매가 결합한 미디어를 석출화제를 포함하는 용액에 투입한 후, 10℃ ~ 35℃ 하에서, 10분 ~ 1시간 동안 석출반응을 유도하면 바이오 분자들이 서로 뭉치게 되어 그 크기가 커지게 되어 결국 섬유의 표면 또는 섬유와 섬유간에 형성되는 공극(공간) 사이에서 석출하게 된다. Next, the precipitation of step 3-3 is carried out in the solution containing the precipitation agent to the media containing the organic catalyst of step 3-2 bound to the solution containing the precipitation agent, and then the precipitation reaction for 10 minutes to 1 hour under 10 ℃ ~ 35 ℃ When induced, biomolecules agglomerate to one another and increase in size, which eventually precipitates between the surface of the fibers or the voids (spaces) formed between the fibers.

이때 상기 석출화제는 유기 촉매의 활성에 거의 영향을 미치지 않으면서 바이오 분자를 석출시킬 수 있는 것이면 종류의 제한 없이 사용될 수 있지만 바람직하게는 메탄올, 에탄올, 1-프로판올, 2-프로판올, 부틸알콜, 아세톤, PEG, 암모늄 설페이트, 소듐 클로라이드, 소듐 설페이트, 소듐 포스페이트, 포타슘 클로라이드, 포타슘 설페이트, 포타슘 포스페이트 및 이들의 수용액을 단독 또는 혼합한 것일 수 있으나 이에 제한되는 것은 아니다.At this time, the precipitation agent may be used without limitation as long as it can precipitate biomolecules with little effect on the activity of the organic catalyst, but preferably methanol, ethanol, 1-propanol, 2-propanol, butyl alcohol, acetone , PEG, ammonium sulfate, sodium chloride, sodium sulfate, sodium phosphate, potassium chloride, potassium sulfate, potassium phosphate and aqueous solutions thereof may be used alone or in combination, but is not limited thereto.

다음으로, 3-4 단계의 석출반응을 수행한 용액(미디어를 포함)에 가교제를 첨가하여 10℃ ~ 35℃ 하에서, 10분 ~ 1시간 동안 가교결합을 유도한 후, 2℃ ~ 8℃ 하에서 10시간 ~ 24시간 동안 유기 촉매간 가교결합시켜서 도6에 개략도로 나타낸 바와 같이, 작용기에 고정된 유기 촉매가 근접하고 있는 단수 또는 복수 개의 유기 촉매와 서로 가교시켜서 미디어에 고정되는 유기 촉매의 양을 증대시키고, 유기 촉매의 고정력을 증대시킬 수 있다.Next, a crosslinking agent was added to the solution (including the media) in which the precipitation reaction of step 3-4 was performed to induce crosslinking for 10 minutes to 1 hour under 10 ° C. to 35 ° C., followed by 2 ° C. to 8 ° C. As shown in the schematic diagram of Fig. 6 by crosslinking between the organic catalysts for 10 to 24 hours, the amount of the organic catalyst fixed to the media by crosslinking with one or more organic catalysts adjacent to the organic catalyst fixed to the functional group is close to each other. It can increase and the fixing force of an organic catalyst can be increased.

상기 가교제는 유기 촉매의 활성을 저해하지 않고서 가교결합을 형성할 수 있는 것이면 종류의 제한없이 사용될 수 있으며, 바람직하게는 디이소시아네이트, 디안히드라이드, 디에폭사이드, 디알데하이드, 디이미드, 1-에틸-3-디메틸 아미노프로필카보디이미드, 글루타르알데하이드, 비스(이미도 에스테르), 비스(석신이미딜 에스테르), 제네핀 및 디애시드 클로라이드 중에서 선택된 1종 이상을 사용할 수 있으며, 더욱 바람직하게는 1-에틸-3-디메틸 아미노프로필카보디이미드, 글루타르알데하이드, 제네핀, 비스(이미도 에스테르), 비스(석신이미딜 에스테르) 및 디애시드 클로라이드 중에서 선택된 1종 이상을 사용할 수 있다.The crosslinking agent may be used without limitation as long as it can form a crosslink without inhibiting the activity of the organic catalyst, preferably diisocyanate, dianhydride, diepoxide, dialdehyde, diimide, 1-ethyl One or more selected from -3-dimethyl aminopropylcarbodiimide, glutaraldehyde, bis (imido ester), bis (succinimidyl ester), genepine and diacid chloride may be used, more preferably 1 One or more selected from -ethyl-3-dimethyl aminopropylcarbodiimide, glutaraldehyde, genepin, bis (imido ester), bis (succinimidyl ester) and diacid chloride can be used.

상기 3-4 단계의 가교반응은 3-3 단계의 석출반응 보다 나중에 수행하는 것이 바람직한데, 이는 유기 촉매의 가교결합을 먼저 수행하는 경우 섬유기둥과 섬유기둥 사이에 형성된 공극, 또는 고분자 섬유와 고분자 섬유간에 형성된 공극의 내부를 유기 촉매가 상당부분 채우지 못하게 되거나 가사 이를 채웠다 하더라도 유기 촉매들의 농도는 주위 농도와 같아지게 된다. 주위와 같은 농도의 유기 촉매가 가교결합을 하여 섬유안의 공극에서 공극의 입구보다 더 큰 덩어리를 이루지 못하여 세척 과정에서 가교결합된 유기촉매가 외부로 유출되는 경우가 발생할 확률이 높기 때문이다. 하지만 석출공정을 먼저 수행하면 유기 촉매들이 강제적으로 섬유기둥 사이 및 고분자 섬유간에 형성된 공극을 더욱 조밀하게 메우게 되며 공극에 채워진 유기 촉매들이 서로 가교결합을 통해 큰 덩어리를 이루기 때문에 병목현상 또는 병 속의 배(ship in a bottle) 현상으로 수세과정에서 손실을 최소화시킬 수 있다. The cross-linking reaction of step 3-4 is preferably performed later than the precipitation reaction of step 3-3, which is a void formed between the fiber column and the fiber column, or the polymer fiber and the polymer when the crosslinking of the organic catalyst is performed first. Even if the organic catalyst cannot fill or substantially fill the interior of the pores formed between the fibers, the concentration of the organic catalysts becomes equal to the ambient concentration. This is because the organic catalyst of the same concentration crosslinks and does not form a larger mass than the inlet of the pores in the pores in the fiber, so that the cross-linked organic catalyst is likely to leak out during the washing process. However, if the precipitation process is performed first, the organic catalysts forcibly fill the pores formed between the columnar columns and the polymer fibers more densely, and the organic catalysts filled in the pores form a large mass through crosslinking with each other. (ship in a bottle) minimizes losses during washing.

상기 3-3단계 및 3-4 단계는 고정화하려는 유기 촉매의 양을 늘리고, 안정성을 향상시키기 위한 단계이다. 고정화하려는 유기 촉매의 종류 및 목적에 따라 상기 3-3단계 및 3-4 단계를 생략할 수도 있다.Steps 3-3 and 3-4 are steps for increasing the amount of organic catalyst to be immobilized and improving stability. Steps 3-3 and 3-4 may be omitted depending on the type and purpose of the organic catalyst to be immobilized.

이하, 본 발명을 하기 실시예 및 실험예를 통해 보다 상세하게 설명한다. 하기 실시예 및 실험예들은 본 발명을 예시하기 위하여 제시된 것일 뿐 본 발명의 권리범위가 하기 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to the following examples and experimental examples. The following examples and experimental examples are presented to illustrate the present invention, but the scope of the present invention is not limited by the following examples.

[실시예]EXAMPLE

실시예 1 ~ 실시예 6 : 지지체의 제조Example 1-6 Example 6 Preparation of Support

카르복시기를 포함하는 하기 화학식 1로 표시되는 공중합체를 중합 및 성장된 섬유(carboxylated polyaniline nanofiber, cPANF)로 이루어진 3차원 메쉬 구조의 미디어를 형성시켜서, ABS(acrylonitrile-butadiene-styrene) 폴리머 표면에 고정된 미디어를 제조하여, 지지체를 제조하였다.The copolymer represented by the following formula (1) containing a carboxyl group was polymerized and formed into a three-dimensional mesh structure made of carboxylated polyaniline nanofibers (cPANFs) to be fixed on an ABS (acrylonitrile-butadiene-styrene) polymer surface. Media was prepared to prepare a support.

구체적으로, 아닐린(aniline)의 농도는 10 mM로 고정시키고, 3-ABA(3-aminobenzoic acid)의 농도를 하기 표 1과 같이 달리하여 고분자 나노섬유 중합용액을 제조하였다. 이때, 고분자 나노섬유 중합용액 내 중합개시제인 암모늄 퍼설페이트(ammonium persulfate)의 농도는 6.7 mM이 되도록 하였다. Specifically, the concentration of aniline (aniline) was fixed to 10 mM, and the polymer nanofiber polymerization solution was prepared by varying the concentration of 3-ABA (3-aminobenzoic acid) as shown in Table 1 below. At this time, the concentration of ammonium persulfate, a polymerization initiator, in the polymer nanofiber polymerization solution was adjusted to 6.7 mM.

다음으로, 고분자 나노섬유 중합용액에 지지체인 ABS 폴리머을 투입한 후, 4℃에서 200 rpm으로 교반시켜 중합반응을 진행시켰다. Next, the ABS polymer as a support was added to the polymer nanofiber polymerization solution, followed by stirring at 200 rpm at 4 ° C. to proceed with the polymerization reaction.

다음으로, 24 시간을 반응시킨 후에는 증류수를 이용하여 5분 동안 200 rpm에서 세척을 하였고, 이러한 세척을 3회 반복하여 지지체를 제조하여 실시예 1 ~ 실시예 6을 각각 실시하였다.Next, after the reaction for 24 hours was washed for 5 minutes at 200 rpm using distilled water, and this washing was repeated three times to prepare a support to carry out Examples 1 to 6, respectively.

[화학식 1][Formula 1]

Figure PCTKR2016006865-appb-I000001
Figure PCTKR2016006865-appb-I000001

상기 화학식 1에서 m 및 n은 몰비로서, m : n = 1 : 0 ~ 20 몰비이다.In Formula 1, m and n are molar ratios, and m: n = 1: 1 to 20 to 20 molar ratios.

구분division 아닐린 농도Aniline concentration 3-ABA 농도3-ABA concentration 중합개시제 농도Initiator Concentration 실시예 1Example 1 10 mM10 mM 0 mM0 mM 6.7 mM6.7 mM 실시예 2Example 2 10 mM10 mM 1 mM1 mM 6.7 mM6.7 mM 실시예 3Example 3 10 mM10 mM 3 mM3 mM 6.7 mM6.7 mM 실시예 4Example 4 10 mM10 mM 5 mM5 mM 6.7 mM6.7 mM 실시예 5Example 5 10 mM10 mM 10 mM10 mM 6.7 mM6.7 mM 실시예 6Example 6 10 mM10 mM 20 mM20 mM 6.7 mM6.7 mM

실험예Experimental Example 1 : 지지체의 형태 관찰 1: Observation of the shape of the support

지지체의 형태를 확인하기 위하여, 상기 실시예 1 ~ 6에서 제조된 지지체를 주사전자현미경(SEM, Quanta 250 FEG)을 이용하여 관찰하였고, 그 결과를 하기 도 7의 (a) ~ (h)에 각각 나타내었다.In order to confirm the shape of the support, the support prepared in Examples 1 to 6 was observed using a scanning electron microscope (SEM, Quanta 250 FEG), and the results are shown in (a) to (h) of FIG. Respectively.

도 7를 살펴보면, 실시예 1(도 7의 a)의 경우, 섬유기둥이 충분히 형성되지 않으며, 실시예 5 및 실시예 6의 경우(도 7의 e, f), 나노섬유가 수직한 방향으로 성장하지 않고 옆으로 누운 형태로 제조되는 것을 확인할 수 있었다.Referring to FIG. 7, in the case of Example 1 (a of FIG. 7), the fiber column is not sufficiently formed, and in the case of Examples 5 and 6 (e, f of FIG. 7), the nanofibers are in a vertical direction. It could be confirmed that it is produced in the form of lying sideways without growing.

그러나, 실시예 2 ~ 실시예 4의 경우, 3-ABA 농도가 증가할수록 섬유기둥이 증가하는 경향을 확인할 수 있었다(도 7의 b 내지 d). However, in Examples 2 to 4, as the concentration of 3-ABA was increased, it was confirmed that the fiber pillars tended to increase (b to d of FIG. 7).

도7의 (g)와 (h)를 살펴보면, 섬유기둥이 하단에 지지층이 생기면서 일부가 위쪽인 수직한 방향으로 성장한 모습을 확인할 수 있다.Looking at Figures 7 (g) and (h), it can be seen that the support layer is formed at the lower end of the fiber column, a part of which is grown in a vertical direction upward.

실험예Experimental Example 2 : 지지체의 표면 작용기 확인 2: check the surface functional groups of the support

지지체의 표면 작용기의 존부를 확인하기 위하여, 실시예 1 ~ 6에서 제조한 지지체를 라만분광기(LabRam ARAMIS IR2)를 이용하여 FT-IR 스펙트럼을 확인하였고, 그 결과를 하기 도 8에 나타내었다.In order to confirm the presence of the surface functional group of the support, the support prepared in Examples 1 to 6 was confirmed the FT-IR spectrum using a Raman spectrometer (LabRam ARAMIS IR2), the results are shown in Figure 8 below.

도 8을 살펴보면, 1690 ~ 1750 cm- 1 의 파장 피크가 작용기인 카르복시기인데, 3-아미노벤조익산의 농도가 0 mM, 10 mM 및 20 mM인 경우 피크가 매우 약하거나, 나타나지 않는 것을 확인할 수 있다. 이는 중합(polymerization)과정에서 카르복시기를 포함하는 나노섬유의 성장이 제대로 수행되지 않은 것을 유추할 수 있다. Referring to Figure 8, the wavelength peak of 1690 ~ 1750 cm - 1 is a carboxyl group which is a functional group, when the concentration of 3-aminobenzoic acid is 0 mM, 10 mM and 20 mM it can be seen that the peak is very weak or does not appear. . This may be inferred that the growth of the nanofibers containing the carboxyl group was not properly performed during the polymerization (polymerization).

이에 반해 3mM(실시예 3) 및 5mM(실시예 4)의 경우, 매우 강한 피크를 보였으며, 1 mM(실시예 2)의 경우 실시예 3 ~ 4 보다 상대적으로 약한 피크를 보였다.On the other hand, 3 mM (Example 3) and 5 mM (Example 4) showed very strong peaks, and 1 mM (Example 2) showed relatively weak peaks than Examples 3-4.

상기 실험예 1 및 실험예 2를 통하여, 미디어 형성시, 제1단량체와 제2단랑체를 1 : 0.05 ~ 0.95 몰비로 합성하는 것이 적정함을 확인할 수 있었다.Through Experimental Example 1 and Experimental Example 2, it was confirmed that it is appropriate to synthesize the first monomer and the second monomer at a molar ratio of 1: 0.05 to 0.95 when forming the media.

제조예Production Example 1 :  One : 당산화효소를Glycosylase 이용한 3차원  3D using 메쉬Mesh 구조체의 제조 Fabrication of the Structure

상기 실시예 3의 지지체에 효소석출코팅(enzyme precipitate coating, EPC) 방식을 통해 유기 촉매 고정화를 진행하였다. 이때, 유기 촉매는 당산화효소(glucose oxidase, GOx)를 사용하였다. The organic catalyst was immobilized on the support of Example 3 through an enzyme precipitate coating (EPC) method. At this time, the organic catalyst was used (glucose oxidase, GOx).

구체적으로, 실시예 3의 지지체의 작용기인 카르복시(Carboxyl)기에 당산화 효소를 공유결합시키기 위해 EDC-NHS 커플링 반응을 1시간 동안 상온(24℃ ~ 25℃)에서 진행하였다. 이때, EDC의 농도는 10 mg/ml, NHS는 50 mg/ml이었다. EDC 및 NHS 용액을 혼합한 용액에 cPANF가 성장한 지지체를 넣어주고 1시간 동안 50 rpm으로 교반하여 주었다. Specifically, the EDC-NHS coupling reaction was performed at room temperature (24 ° C. to 25 ° C.) for 1 hour in order to covalently bind a glycosylation enzyme to a carboxyl group, which is a functional group of the support of Example 3. At this time, the concentration of EDC was 10 mg / ml, NHS was 50 mg / ml. The cPANF-grown scaffold was added to the mixed solution of EDC and NHS, followed by stirring at 50 rpm for 1 hour.

EDC-NHS 커플링 반응 완료 후, 증류수를 이용하여 3회 세척하였으며, 세척은 5분 동안 200 rpm에서 교반하여 수행하였다. After completion of the EDC-NHS coupling reaction, it was washed three times with distilled water, washing was performed by stirring at 200 rpm for 5 minutes.

다음으로 세척한 지지체를 10 mg/ml의 유기 촉매 용액을 첨가하고 1시간 동안 틸트 셰이킹(tilt shaking)을 50 rpm에서 진행시켜, 당산화 효소를 작용기와 공유결합시켰다. Next, the washed support was added with 10 mg / ml of an organic catalyst solution and tilt shaking was performed at 50 rpm for 1 hour to covalently bind the glycosylating enzyme to the functional group.

다음으로, 암모늄설페이트(ammonium sulfate)를 첨가하여 최종 농도가 55%가 되도록 한 다음, 이를 30분간 상온(24℃ ~ 25℃)에서 틸트 셰이킹(tilt shaking)을 50 rpm으로 진행하여, 당산화 효소가 석출되도록 유도하였다. Next, ammonium sulfate is added to the final concentration of 55%, and then tilt shaking at 50 rpm for 30 minutes at room temperature (24 ° C. to 25 ° C.) to glycosylate. The enzyme was induced to precipitate.

다음으로, 가교제로서 글루타알데하이드(glutaraldehyde)를 첨가하여 최종 농도가 0.5%가 되도록 하고, 30분간 상온(24℃ ~ 25℃)에서 틸트 셰이킹(tilt shaking)을 50 rpm으로 진행하여, 석출된 당산화 효소간에 가교결합을 유도하였고, 이후, 17 시간 동안 4℃에서 틸트 셰이킹(tilt shaking)을 50 rpm을 진행하였다. Next, glutaraldehyde is added as a crosslinking agent so that the final concentration is 0.5%, and tilt shaking is performed at 50 rpm for 30 minutes at room temperature (24 ° C. to 25 ° C.) to precipitate. Crosslinking was induced between the glycosylating enzymes, and then tilt shaking was performed at 50 rpm for 4 hours at 4 ° C.

그리고, 가교결합을 완료한 후, 이를 완충용액을 이용하여 200 rpm으로 5분간 3회 세척하였다. And, after completing the crosslinking, it was washed three times for 5 minutes at 200 rpm using a buffer solution.

다음으로, 미반응된 알데하이드(aldehyde) 작용기를 캡핑(capping)해주기 위해, 100 mM Tris 완충용액(pH 7.0)을 넣고 상온(24℃ ~ 25℃)에서 200 rpm으로 1시간 동안 교반하여, 캡핑반응을 수행한 다음, 완충용액을 이용하여 200 rpm으로 5분동안 3회 세척하여 3차원 메쉬 구조체를 제조하였다. Next, in order to cap the unreacted aldehyde (aldehyde) functional group, 100 mM Tris buffer solution (pH 7.0) was added and stirred at room temperature (24 ° C.-25 ° C.) at 200 rpm for 1 hour. Next, using the buffer solution to wash three times for 5 minutes at 200 rpm to prepare a three-dimensional mesh structure.

제조예Production Example 2 : 키모트립신을 이용한 3차원  2: 3D using chymotrypsin 메쉬Mesh 구조체의 제조 Fabrication of the Structure

상기 제조예 1과 동일한 방법으로 제조하되, 당산화 효소 대신 키모트립신(α-chimotrypsin, CT)을 사용하고, pH 7.8의 Tris 완충용액을 사용한 것을 제외하고는 동일한 방법으로 3차원 메쉬 구조체를 제조하였다. Prepared in the same manner as in Preparation Example 1, except that instead of the glycosylation enzyme chymotrypsin (α-chimotrypsin, CT) was used, except that a tris buffer solution of pH 7.8 was used to prepare a three-dimensional mesh structure. .

제조예Production Example 3 : 리파아제를 이용한 3차원  3: 3D using lipase 메쉬Mesh 구조체의 제조 Fabrication of the Structure

상기 제조예 1과 동일한 방법으로 제조하되, 당산화 효소 대신 리파아제(LP, lipase)를 사용한 것을 제외하고는 동일한 방법으로 3차원 메쉬 구조체를 제조하였다. Prepared in the same manner as in Preparation Example 1, except that lipase (LP, lipase) instead of glycosylation enzyme was prepared in the same way three-dimensional mesh structure.

제조예Production Example 4 :  4 : 양고추냉이Horseradish 과산화효소를 이용한 3차원  3D using peroxidase 메쉬Mesh 구조체의 제조 Fabrication of the Structure

상기 제조예 1과 동일한 방법으로 제조하되, 당산화 효소 대신 양고추냉이 과산화효소(HRP, horseradish peroxidase)를 사용한 것을 제외하고는 동일한 방법으로 3차원 메쉬 구조체를 제조하였다. It was prepared in the same manner as in Preparation Example 1, except that horseradish peroxidase (HRP, horseradish peroxidase) was used instead of the glycosylation enzyme to prepare a three-dimensional mesh structure.

실험예Experimental Example 3 : 3차원3: 3D 메쉬Mesh 구조체의 형태 관찰  Observe the shape of the structure

3차원 메쉬 구조체의 형태를 관찰하기 위하여, 제조예 1 ~ 4에서 제조된 3차원 메쉬 구조체를 주사전자현미경(SEM, Quanta 250 FEG)을 이용하여 관찰하였고, 그 결과를 하기 도 9에 나타내었다. In order to observe the shape of the three-dimensional mesh structure, the three-dimensional mesh structure prepared in Preparation Examples 1 to 4 was observed using a scanning electron microscope (SEM, Quanta 250 FEG), the results are shown in Figure 9 below.

도 9(a)는 실시예 3의 지지체를 관찰한 이미지이고, (b)는 제조예 1의 3차원 메쉬 구조체 표면을 관찰한 이미지이고, (c)는 제조예 2의 3차원 메쉬 구조체 표면을 관찰한 이미지이고, (d)는 제조예 3의 3차원 메쉬 구조체 표면을 관찰한 이미지이다.9 (a) is an image of the support of Example 3, (b) is an image of the surface of the three-dimensional mesh structure of Preparation Example 1, (c) is a surface of the three-dimensional mesh structure of Preparation Example 2 It is an image observed, (d) is the image which observed the surface of the 3D mesh structure of manufacture example 3.

도 9(a)와 (b) ~ (d)를 비교해 보면, 효소가 고정되기 전의 지지체(a)에 효소를 고정화시키는 경우 지지체의 표면에 효소가 결합 및 고정되어 두께가 두꺼워진 것을 확인할 수 있었다. 9 (a) and (b) to (d), when the enzyme is immobilized on the support (a) before the enzyme is fixed, the enzyme was bound to the surface of the support and the thickness was confirmed to be thick. .

실험예Experimental Example 4 : 3차원4: 3D 메쉬Mesh 구조체의  Struct 열안정성Thermal stability 분석  analysis

3차원 메쉬 구조체의 열안정성을 확인하기 위하여 제조예 1 ~ 4에서 제조된 3차원 메쉬 구조체 및 비교예 1 ~ 3의 효소 각각을 50℃ 하에서 12시간 보관한 후, 활성을 측정하였고, 비교예 4의 효소는 45℃ 하에서 12시간 동안 보관 및 활성을 측정하였고, 그 결과를 도 10에 나타내었다.In order to confirm the thermal stability of the three-dimensional mesh structure, the three-dimensional mesh structure prepared in Preparation Examples 1 to 4 and each of the enzymes of Comparative Examples 1 to 3 were stored at 50 ° C. for 12 hours, and then activity was measured. The enzyme was stored and measured for 12 hours at 45 ℃, the results are shown in Figure 10.

활성 측정은 각각의 효소에 적합한 기질을 사용하여 광학적으로 용액의 색변화를 측정하였다. GOx의 경우, 글루코오스(glucose)와 TMB(3,3′,5,5′-Tetramethylbenzidine)를 기질로 사용하였고, CT의 경우, TP(N-Succinyl-Ala-Ala-Pro-Phe p-nitroanilide)를 기질로 사용하였고, LP의 경우, 4-나이트로페닐뷰티레이트(4-nitrophenyl butyrate)를 기질로 사용하였고, HRP의 경우, TMB(3,3′,5,5′-Tetramethylbenzidine)를 기질로 사용하였다. Activity measurements were optically measured for the color change of the solution using a substrate appropriate for each enzyme. In the case of GOx, glucose and TMB (3,3 ', 5,5'-Tetramethylbenzidine) were used as substrates, and in the case of CT, TP (N-Succinyl-Ala-Ala-Pro-Phe p-nitroanilide) Was used as the substrate, 4-nitrophenyl butyrate was used as the substrate for LP, and TMB (3,3 ', 5,5'-Tetramethylbenzidine) was used as the substrate for HRP. Used.

그리고, 효소와 기질을 섞어주고, GOx와 HRP의 경우는 410 nm 파장에서, CT와 LP는 410 nm 파장에서 색변화를 분광기로 검출하여 활성을 측정하였다.In addition, the enzyme and the substrate were mixed, and the activity was measured by detecting the color change by spectroscopy at 410 nm wavelength in the case of GOx and HRP, 410 nm wavelength in the case of CT and LP.

도 10을 살펴보면, 제조예 1 ~ 4의 3차원 메쉬 구조체는 비교예 1 ~ 4와 각각 비교할 때, 상대적 활성이 80% 이상으로 유지되는 것을 확인할 수 있고, 3차원 메쉬 구조체를 형성하지 않은 효소는 시간 경과에 따라 활성이 현저하게 저하되는 것을 확인할 수 있었다. Looking at Figure 10, the three-dimensional mesh structure of Preparation Examples 1 to 4, when compared with Comparative Examples 1 to 4, respectively, it can be seen that the relative activity is maintained at 80% or more, the enzyme does not form a three-dimensional mesh structure It was confirmed that the activity was significantly reduced over time.

이를 통하여, 본 발명의 3차원 메쉬 구조체가 열안정성이 우수함을 확인할 수 있었다.Through this, it was confirmed that the three-dimensional mesh structure of the present invention is excellent in thermal stability.

실험예Experimental Example 5 : 3차원5: 3D 메쉬Mesh 구조체의 장기사용안정성 및 미생물 사멸 효과 확인 실험 Experiment to confirm long-term stability and microbial killing effect of structure

실험예Experimental Example 5-1 : 과산화수소 생성 측정 5-1: Hydrogen Peroxide Production Measurement

3차원 메쉬 구조체의 응용으로 ABS(acrylonitrile-butadiene- styrene) 폴리머를 이용하여 임펠러를 제작하였고, 임펠러의 3차원 메쉬 구조체 표면에 실시예 1과 동일한 방법으로 미디어를 형성시킨 후, 동일한 방법으로 당산화 효소(GOx)를 고정시켰다.Impellers were fabricated using ABS (acrylonitrile-butadiene-styrene) polymers for the application of a three-dimensional mesh structure. Enzyme (GOx) was fixed.

제조한 유기 촉매-나노섬유 3차원 메쉬 구조체(GOx 임펠러)의 GOx에 의해 과산화수소(H2O2)가 생성되고, 이에 의해 미생물이 사멸하는데, 이를 이용하여 미생물 오염방지 효과 실험을 하기와 같이 진행하였다. Hydrogen peroxide (H 2 O 2 ) is produced by GOx of the prepared organic catalyst-nanofiber three-dimensional mesh structure (GOx impeller), thereby killing the microorganisms, using the microbial contamination prevention effect experiment proceeds as follows It was.

10mM의 글루코스(glucose)를 GOx 임펠러가 있는 용액에 첨가한 다음, 200 rpm으로 교반을 수행하였고, 시간에 따른 과산화수소 농도 변화를 측정하였으며, 그 결과를 도 11(a) 나타내었다. 10 mM glucose was added to the solution with the GOx impeller, followed by stirring at 200 rpm, and the change in concentration of hydrogen peroxide over time was measured, and the results are shown in FIG. 11 (a).

도 11(a)를 살펴보면, GOx가 고정화된 임펠러는 지속적으로 과산화수소를 생성하는 것을 확인하였으며, 이에 반해, GOx가 고정화되지 않은 임펠러는 과산화수소가 생성되지 않았다.Looking at Figure 11 (a), it was confirmed that the impeller GOx is immobilized to produce hydrogen peroxide continuously, on the other hand, the impeller without GOx is not produced hydrogen peroxide.

실험예Experimental Example 5-2 : 장기사용안정성 측정 5-2: Long-term stability of use

다음으로, 고정화된 GOx가 생성된 과산화수소에 의해 활성이 저해되는 효과가 있는지 확인하기 위하여, GOx 임펠러를 이용하여 과산화수소를 반복적으로 생산하는 실험을 진행하였고, 그 결과를 도 11(b)에 나타내었다. 도 11(b)를 살펴보면, GOx 임펠러를 1시간씩 10회 재사용하였음에도 초기 활성의 90% 이상을 유지하는 결과를 얻을 수 있었다. Next, in order to check whether the immobilized GOx has an effect of inhibiting activity by the generated hydrogen peroxide, an experiment was performed to repeatedly produce hydrogen peroxide using a GOx impeller, and the results are shown in FIG. 11 (b). . Looking at Figure 11 (b), even if the GOx impeller was reused 10 times for 1 hour was obtained to maintain more than 90% of the initial activity.

이를 통하여 장기사용안정성이 우수함을 확인할 수 있었다.Through this, it was confirmed that the long-term stability is excellent.

실험예Experimental Example 5-3 : 미생물 사멸 효과 측정 5-3: Microbial killing effect measurement

상기 GOx 임펠러로 과산화수소 생성 측정시, 1시간 동안 생성된 과산화수소와 2시간 동안 생성된 과산화수소를 박테리아의 일종인 Staphylococcus aureus가 존재하는 용액에 첨가하였더니, 과산화수소를 넣지 않은 경우에 비하여, 생존한 박테리아 수가 시간에 따라 급격히 감소함을 확인할 수 있었다(도11 (c) 참조). When hydrogen peroxide production was measured with the GOx impeller, hydrogen peroxide produced for 1 hour and hydrogen peroxide produced for 2 hours were added to a solution containing Staphylococcus aureus, a kind of bacteria, and the number of bacteria that survived was higher than that of hydrogen peroxide. It was confirmed that the sharp decrease with time (see Fig. 11 (c)).

GOx 임펠러가 1시간 반응한 경우에 비하여 2시간 반응한 경우가 과산화수소의 생성량이 더 많으므로, 박테리아를 더 많이 사멸시킬 수 있음을 확인할 수 있었다.When the GOx impeller reacted for 2 hours compared to the reaction for 1 hour, more hydrogen peroxide was produced, and it was confirmed that more bacteria could be killed.

실험예Experimental Example 6 : 3차원6: 3D 메쉬Mesh 구조체의 염료 분해  Dye decomposition of structures

산업용으로 사용되는 염료에는 아조(Azo)기가 포함되어 있는 경우가 많은데, 이는 환경을 심각하게 오염시킬 수 있는 물질이다. 아조 계열의 염료는 효소에 의해서 분해가 될 수 있다. 본 발명의 3차원 메쉬 구조체 기술을 통해 아조염료의 분해 실험을 진행하였다. Industrial dyes often contain Azo groups, which can seriously pollute the environment. Azo dyes can be degraded by enzymes. Through the three-dimensional mesh structure technology of the present invention, the decomposition experiment of the azo dye was carried out.

3차원 메쉬 구조체의 응용으로 ABS(acrylonitrile-butadiene- styrene) 폴리머를 이용하여 임펠러를 제작하였고, 임펠러의 3차원 메쉬 구조체 표면에 실시예 1과 동일한 방법으로 미디어를 형성시킨 후, 동일한 방법으로 당산화 효소(GOx) 및 양고추냉이 과산화효소(HRP, horseradish peroxidase)를 고정시켰다.Impellers were fabricated using ABS (acrylonitrile-butadiene-styrene) polymers for the application of a three-dimensional mesh structure. Enzyme (GOx) and horseradish peroxidase (HRP) were immobilized.

글루코스(Glucose)가 GOx에 의해 과산화수소를 생성시키고, 양고추냉이 과산화효소(HRP)가 과산화수소를 이용하여 아조계열의 염료를 분해하는 방식을 이용하였다. Glucose produced hydrogen peroxide by GOx, and horseradish peroxidase (HRP) was used to decompose azo dyes using hydrogen peroxide.

먼저 GOx가 고정화된 3차원 메쉬 구조체 및 HRP가 고정화된 3차원 메쉬 구조체의 개수를 변화 시켜가며, 아조 계열의 염료인 Chicago Sky Blue 6B 분해 실험을 진행하였다. 이때 Chicago Sky Blue 6B 및 글루코스의 농도는 각각 2 ?M, 1mM 이었다. First, the number of 3D mesh structures immobilized with GOx and 3D mesh structures immobilized with HRP was varied, and the decomposition experiment of Chicago Sky Blue 6B, an azo dye, was performed. The concentrations of Chicago Sky Blue 6B and glucose were 2 μM and 1 mM, respectively.

실험 결과, GOx 메쉬가 2개, HRP 메쉬가 2개 장착되었을 경우가 다른 개수의 메쉬가 장착된 경우보다 최종 분해율이 가장 높았다(도12(a)). As a result of the experiment, two GOx meshes and two HRP meshes had the highest final decomposition rate than the other number of meshes (Fig. 12 (a)).

그리고, 반복 사용에 대한 안정성을 테스트하기 위해 10회의 재사용 실험을 진행한 결과, 70% 이상의 초기 활성을 유지하는 안정화된 결과를 얻을 수 있었다(도 12 (b)).In addition, as a result of 10 reuse experiments to test the stability for repeated use, it was possible to obtain a stabilized result of maintaining the initial activity of more than 70% (Fig. 12 (b)).

이를 통하여, 3차원 메쉬 구조체를 응용하여 수처리가 가능하고, 장기사용안정성이 우수함을 확인할 수 있었다.Through this, it was confirmed that the water treatment is possible by applying the three-dimensional mesh structure, and excellent long-term stability.

상술한 바와 같이, 본 발명의 일 실시예에 따른 임펠러의 3차원 메쉬 구조체가 3차원 메쉬 형상이며, 3차원 메쉬 구조체의 표면 및 내부에 유기 촉매, 무기 촉매 및 바이오분자들이 고집적 되어 유체와 반응하기 때문에, 종래기술에 비하여 높은 속도로 반응이 진행될 수 있는 장점이 있다.As described above, the three-dimensional mesh structure of the impeller according to the embodiment of the present invention is a three-dimensional mesh shape, the organic catalyst, inorganic catalyst and biomolecules are highly integrated on the surface and inside of the three-dimensional mesh structure to react with the fluid Therefore, there is an advantage that the reaction can proceed at a high rate compared to the prior art.

또한, 3차원 메쉬 구조체 전체가 3D 메쉬 구조로 형성되어 표면 및 내부에 촉매물질이나 바이오분자가 고집적되고, 유체가 3차원 메쉬 구조체의 내부까지 통과하기 때문에, 전체적인 반응 면적이 넓어질 수 있으며, 고집적된 촉매 및 바이오분자에 의해 반응 수율이 향상될 수 있다. In addition, since the entire 3D mesh structure is formed as a 3D mesh structure, catalyst materials or biomolecules are highly accumulated on the surface and inside, and the fluid passes through the inside of the 3D mesh structure, thereby increasing the overall reaction area. The yield of the reaction can be improved by using the prepared catalyst and biomolecules.

또한, 임펠러에 하나 이상의 3차원 메쉬 구조체가 탈부착가능하기 때문에, 하나 이상의 3차원 메쉬 구조체 각각에 다른 물질을 부착하여 연쇄 반응이 일어나도록 할 수 있다.In addition, since one or more three-dimensional mesh structures are detachable to the impeller, a chain reaction may occur by attaching a different material to each of the one or more three-dimensional mesh structures.

또한, 반응이 종료한 이후에, 3차원 메쉬 구조체 및 이를 포함한 임펠러를 손쉽게 재사용할 수 있는 장점이 있다.In addition, after the reaction is finished, there is an advantage that can easily reuse the three-dimensional mesh structure and the impeller including the same.

이상에서 본 발명의 일 실시예에 대하여 설명하였으나, 본 발명의 사상은 본 명세서에 제시되는 실시 예에 제한되지 아니하며, 본 발명의 사상을 이해하는 당업자는 동일한 사상의 범위 내에서, 구성요소의 부가, 변경, 삭제, 추가 등에 의해서 다른 실시 예를 용이하게 제안할 수 있을 것이나, 이 또한 본 발명의 사상범위 내에 든다고 할 것이다.Although one embodiment of the present invention has been described above, the spirit of the present invention is not limited to the embodiments set forth herein, and those skilled in the art who understand the spirit of the present invention, within the scope of the same idea, the addition of components Other embodiments may be easily proposed by changing, deleting, adding, etc., but this will also be within the scope of the present invention.

Claims (15)

3차원 메쉬 구조를 갖는 지지체; 및A support having a three-dimensional mesh structure; And 상기 지지체의 표면에 구비되며, 제1물질과 결합가능한 미디어;를 포함하는 3차원 메쉬 구조체.And a media provided on the surface of the support and bondable with the first material. 제 1 항에 있어서,The method of claim 1, 상기 지지체는 제1방향으로 형성되며 서로 이격 배치되는 복수 개의 제1메쉬선과, 상기 복수 개의 제1메쉬선과 교차되는 방향으로 서로 이격 배치되는 복수 개의 제2메쉬선을 포함하는 판상 구조물을 포함하는 3차원 메쉬 구조체.The support may include a plate-shaped structure including a plurality of first mesh lines formed in a first direction and spaced apart from each other, and a plurality of second mesh lines spaced apart from each other in a direction crossing the plurality of first mesh lines. Dimensional mesh structure. 제 2 항에 있어서,The method of claim 2, 상기 판상 구조물은 하나 이상 구비되어 적층되는 3차원 메쉬 구조체.The plate-like structure is provided with one or more three-dimensional mesh structure. 제 1 항에 있어서,The method of claim 1, 상기 제1물질은 유기촉매, 무기촉매 및 바이오 분자를 포함하고,The first material includes an organic catalyst, an inorganic catalyst and a biomolecule, 상기 미디어는 상기 제1물질과 결합되는 작용기를 포함하며,The media includes a functional group bonded to the first material, 상기 유기촉매, 무기촉매 및 바이오분자 중 적어도 하나는 흡착, 이온결합, 공유결합, 가교결합 또는 접착성 물질에 의해 상기 지지체 또는 상기 미디어에 결합되는 3차원 메쉬 구조체.At least one of the organic catalyst, the inorganic catalyst and the biomolecule is bonded to the support or the media by adsorption, ionic bonding, covalent bonding, crosslinking or adhesive material. 제 4 항에 있어서,The method of claim 4, wherein 상기 작용기는 카르복시기, 아민기, 이민기, 에폭시기, 하이드록시기, 알데하이드기, 카르보닐기, 에스터기, 메톡시기, 에톡시기, 페록시기, 에테르기, 아세탈기, 설파이드기, 포스페이트기 및 아이오드기 중 적어도 하나를 포함하는 3차원 메쉬 구조체.The functional group is at least one of a carboxyl group, an amine group, an imine group, an epoxy group, a hydroxyl group, an aldehyde group, a carbonyl group, an ester group, a methoxy group, an ethoxy group, a peroxy group, an ether group, an acetal group, a sulfide group, a phosphate group and an iodine group Three-dimensional mesh structure containing one. 제 4 항에 있어서,The method of claim 4, wherein 상기 미디어는 고분자 섬유, 다공성 입자, 탄소 튜브, 고분자 튜브, 와이어, 필라, 그래핀, 풀러렌, 폴리도파민, 폴리노레피네프린 및 구형입자 중 적어도 하나를 포함하며,The media includes at least one of polymer fibers, porous particles, carbon tubes, polymer tubes, wires, pillars, graphene, fullerenes, polydopamine, polynorepinephrine, and spherical particles, 상기 미디어는 흡착, 이온결합, 공유결합, 가교결합 또는 접착성 물질에 의해 상기 지지체에 결합되는 3차원 메쉬 구조체.Wherein said media is bonded to said support by adsorption, ionic bonding, covalent bonding, crosslinking, or an adhesive material. 제 6 항에 있어서,The method of claim 6, 상기 미디어는 3차원 메쉬 구조를 가지는 지지체의 표면 외부로 돌출되어 형성되는 복수 개의 기둥을 포함하는 3차원 메쉬 구조체.The media includes a plurality of pillars protruding out of the surface of the support having a three-dimensional mesh structure. 제 6 항에 있어서, The method of claim 6, 상기 고분자 섬유는 폴리아닐린, 폴리피롤, 폴리티오펜, 아크릴로나이트릴-뷰타디엔-스티렌, 폴리락틱산, 폴리비닐알콜, 폴리아크릴로니트릴, 폴리에스테르, 폴리에틸렌, 폴리에틸렌이민, 폴리프로필렌옥사이드, 폴리비닐리데인 플로라이드, 폴리우레탄, 폴리염화비닐, 폴리스티렌, 폴리카프로락탐, 폴리락틱-co-글리콜산, 폴리글리콜산, 폴리카프로락톤, 폴리에틸렌 테레프탈레이트, 폴리메틸메타크릴레이트, 폴리다이메틸실록산, 테플론, 콜라겐, 폴리스티렌-co-무수말레산, 나일론, 셀룰로우즈, 키토산 및 실리콘 중에서 선택된 1종 이상을 포함하는 고분자 섬유 및 이를 개질시켜 작용기를 형성한 고분자 섬유인 3차원 메쉬 구조체.The polymer fiber is polyaniline, polypyrrole, polythiophene, acrylonitrile-butadiene-styrene, polylactic acid, polyvinyl alcohol, polyacrylonitrile, polyester, polyethylene, polyethyleneimine, polypropylene oxide, polyvinyl Dane fluoride, polyurethane, polyvinyl chloride, polystyrene, polycaprolactam, polylactic-co-glycolic acid, polyglycolic acid, polycaprolactone, polyethylene terephthalate, polymethylmethacrylate, polydimethylsiloxane, teflon, A three-dimensional mesh structure, which is a polymer fiber comprising at least one selected from collagen, polystyrene-co-maleic anhydride, nylon, cellulose, chitosan, and silicon, and a polymer fiber formed by modifying the same. 제 6 항에 있어서,The method of claim 6, 상기 고분자 섬유는 The polymer fiber is 아닐린(aniline), 피롤(pyrrole), 락틱산(lactic acid), 비닐알콜(vinyl alcohol), 아크릴로니트릴(acrylonitrile), 에틸렌(ethylene), 에틸렌이민(ethyleneimine), 프로필렌옥사이드(propylene oxide), 우레탄(urethane), 염화비닐(vinyl chloride), 스티렌(styrene), 카프로락탐(caprolactam), 카프로락톤(aprolactone), 에틸렌 테레프탈레이트(ethylene terephthalate), 메틸메타크릴레이트(methyl methacrylate), 다이메틸실록산(dimethysiloxane), 테플론(teflon), 콜라겐(collagen), 나일론(nylon), 셀룰로우즈(cellulose), 키토산(chitosan) 및 실리콘(silicon) 중에서 선택된 1종 이상을 포함하는 제1단량체; 및Aniline, pyrrole, lactic acid, vinyl alcohol, acrylonitrile, ethylene, ethyleneimine, propylene oxide, urethane (urethane), vinyl chloride, styrene, caprolactam, caprolactone, aprolactone, ethylene terephthalate, methyl methacrylate, dimethylsiloxane ), A first monomer comprising at least one selected from teflon, collagen, nylon, nylon, cellulose, chitosan, and silicon; And 아미노벤조익산(1-aminobenzoic acid), 2-아미노벤조익산(2-aminobenzoic acid), 3-아미노벤조익산(3-aminobenzoic acid), 1-페닐렌다이아민(1-phenylenediamine), 2-페닐렌다이아민(2-phenylenediamine), 3-페닐렌다이아민(3-phenylenediamine), 피롤-1-카브알데하이드(pyrrole-1-carbaldehyde), 피롤-2-카브알데하이드(pyrrole-2-carbaldehyde) 및 피롤-3-카브알데하이드(pyrrole-3-carbaldehyde) 중에서 선택된 1종 이상을 포함하는 제2단량체;가 공중합된 공중합체 및 이를 개질시켜 작용기를 형성한 고중합체인 3차원 메쉬 구조체.Aminobenzoic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, 1-phenylenediamine, 2-phenylene 2-phenylenediamine, 3-phenylenediamine, pyrrole-1-carbaldehyde, pyrrole-2-carbaldehyde and pyrrole- A second monomer comprising at least one selected from 3-carbaldehyde (pyrrole-3-carbaldehyde); copolymerized copolymer and a three-dimensional mesh structure is a high polymer formed by modifying the functional group. 제 4 항에 있어서,The method of claim 4, wherein 상기 지지체는 아크릴로나이트릴-뷰타디엔-스티렌, 폴리아닐린, 폴리피롤, 폴리티오펜, 폴리락틱산, 폴리비닐알콜, 폴리카프로락탐, 폴리카프로락톤, 폴리락틱-co-글리콜산, 폴리아크릴로니트릴, 폴리에스테르, 폴리에틸렌, 폴리에틸렌이민, 폴리프로필렌옥사이드, 폴리우레탄, 폴리글리콜산, 폴리에틸렌테레프탈레이트, 폴리메틸메타크릴레이트, 폴리스티렌, 폴리디메틸실록산, 폴리스티렌-co-무수말레산, 테플론, 콜라겐, 나일론, 셀룰로우즈, 키토산, 유리, 금, 은, 알루미늄, 철, 구리 및 실리콘 중 적어도 하나를 포함하며,The support is acrylonitrile-butadiene-styrene, polyaniline, polypyrrole, polythiophene, polylactic acid, polyvinyl alcohol, polycaprolactam, polycaprolactone, polylactic-co-glycolic acid, polyacrylonitrile, Polyester, polyethylene, polyethyleneimine, polypropylene oxide, polyurethane, polyglycolic acid, polyethylene terephthalate, polymethylmethacrylate, polystyrene, polydimethylsiloxane, polystyrene-co-maleic anhydride, teflon, collagen, nylon, cellulite At least one of rose, chitosan, glass, gold, silver, aluminum, iron, copper and silicon, 상기 유기 촉매는 탄산무수화 효소, 당산화 효소, 트립신, 키모트립신, 서브틸리신, 파파인, 서몰리신, 리파아제, 페록시다아제, 아실라아제, 락토나제, 프로테아제, 티로시나아제, 라카아제, 셀룰라아제, 자일라나제, 유기포스포하이드롤레이즈, 콜린에스테라아제, 포름산 탈수소 효소, 알데히드 탈수소 효소, 알코올 탈수소 효소, 포도당 탈수소 효소, 및 포도당 이성화 효소 중 적어도 하나를 포함하고,The organic catalyst is carbonic anhydrase, glycosylating enzyme, trypsin, chymotrypsin, subtilisin, papain, thermolysine, lipase, peroxidase, acylase, lactonase, protease, tyrosinase, laccase At least one of cellulase, xylanase, organophosphohydrolase, cholinesterase, formic acid dehydrogenase, aldehyde dehydrogenase, alcohol dehydrogenase, glucose dehydrogenase, and glucose isomerization enzyme, 상기 무기 촉매는 플래티늄, 백금, 로듐, 팔라듐, 납, 이리듐, 루비듐, 철, 니켈, 아연, 코발트, 구리, 망간, 티타늄, 루테늄, 은, 몰리브덴, 텅스텐, 알루미늄, 철, 안티몬, 주석, 비스무트, 바륨, 오스뮴, 산화질소, 산화구리, 산화망간, 산화티타늄, 산화바나늄, 산화아연 중 적어도 하나를 포함하며,The inorganic catalyst may be platinum, platinum, rhodium, palladium, lead, iridium, rubidium, iron, nickel, zinc, cobalt, copper, manganese, titanium, ruthenium, silver, molybdenum, tungsten, aluminum, iron, antimony, tin, bismuth, At least one of barium, osmium, nitric oxide, copper oxide, manganese oxide, titanium oxide, vananium oxide, and zinc oxide, 상기 바이오분자는 알부민, 인슐린, 콜라겐, 항체, 항원, 프로테인A, 프로테인G, 아비딘, 스트렙타비딘, 바이오틴, 핵산, 펩타이드, 렉틴, 탄수화물 중 적어도 하나를 포함하는 3차원 메쉬 구조체.The biomolecule is a three-dimensional mesh structure comprising at least one of albumin, insulin, collagen, antibodies, antigens, protein A, protein G, avidin, streptavidin, biotin, nucleic acids, peptides, lectins, carbohydrates. 제 10 항에 있어서,The method of claim 10, 상기 지지체의 표면 및 미디어에 상기 바이오분자를 부착시켜, 미생물 및 세포를 선택적으로 결합시키고, 이를 배양 및 활성화하며,Attaching the biomolecules to the surface and media of the support to selectively bind microorganisms and cells, to culture and activate them, 상기 미생물은 바실러스 서브틸리스(Bacillus subtilis), 바실러스 리케니포미스(Bacillus licheniformis), 바실러스 폴리퍼멘티커스(Bacillus polyfermenticus), 바실러스 메센테리커스(Bacillus mesentericus), 사카로마이세스 세레비제(Saccharomyces cerevisiae), 클로스트리디움 부티리컴(Clostridium butyricum), 스트렙토코커스 패칼리스(Streptococcus faecalis), 스트렙토코커스 패시움(Streptococcus faecium), 마이크로코커스 카세리티쿠스(Micrococcus caseolyticus), 스테필로코커스 아우레우스(Staphylococcus aureus), 락토바실러스 카제이(Lactobacillus casei), 락토바실러스 프라타륨(lactobacillus plantarum), 루코노스톡 메세테로이데스 (Leuconostoc Mesenteroides), 사카로마이세스 세르비시아(saccharomyces cerevisiae), 데바리오마이세스 니코티아나(Debaryomyces nicotianae), 아시네토박터 칼코아세티쿠스(Acinetobactercalcoaceticus), 알칼리게네스 균(Alcaligenesodorans), 아로매토리움 아로매티쿰(Aromatoleum aromaticum), 지오박터 메탈리듀센(Geobacter metallireducens), 디클로로모나스 아로마틱(Dechloromonas aromatic), 아스로박터속(Arthrobacter sp.) 및 알카니보락스 보르쿠멘시스(Alcanivorax borkumensis) 중에서 선택된 1종 이상을 포함하고,The microorganism is Bacillus subtilis, Bacillus licheniformis, Bacillus polyfermenticus, Bacillus mesentericus, Saccharomyces cerevisiae ), Clostridium butyricum, Streptococcus faecalis, Streptococcus faecium, Micrococcus caseolyticus, Staphylococcus aureus , Lactobacillus casei, Lactobacillus plantarum, Leuconostoc Mesenteroides, Saccharomyces cerevisiae, Debariomyces nicotianae nicotianae ), Acinetobacter calcoaceticus, alkali Alcaligenesodorans, Aromatoleum aromaticum, Geobacter metallireducens, Dechloromonas aromatic, Arthrobacter sp. And Alkanivolas bors At least one selected from Alcanivorax borkumensis, 상기 세포는 줄기세포, 면역세포, 상피세포, 근육세포, 신경세포, 간세포, 폐세포, 심혈관세포, 췌장세포, 심장세포, 뼈세포 및 암세포 중에서 선택된 1종 이상을 포함하는 3차원 메쉬 구조체.Said cells are stem cells, immune cells, epithelial cells, muscle cells, neurons, hepatocytes, lung cells, cardiovascular cells, pancreas cells, heart cells, bone cells and cancer cells comprising a three-dimensional mesh structure comprising one or more. 중심에 회전축이 결합되는 결합부; 및Coupling portion is coupled to the rotation axis in the center; And 상기 결합부에 결합되며, 제 1 항 내지 제 11 항 중 어느 한 항에 따른 3차원 메쉬 구조체를 하나 이상 포함하는 임펠러.An impeller coupled to the coupling part, the impeller including one or more three-dimensional mesh structure according to any one of claims 1 to 11. 제 12 항에 있어서,The method of claim 12, 상기 3차원 메쉬 구조체는 단일체인 임펠러.The three-dimensional mesh structure is a single impeller. 제 12 항에 있어서,The method of claim 12, 상기 3차원 메쉬 구조체는 상기 결합부에 탈부착 가능하도록 연결부가 구비되는 임펠러.The three-dimensional mesh structure impeller is provided with a connection portion to be detachable to the coupling portion. 제 12 항에 있어서,The method of claim 12, 상기 하나 이상의 3차원 메쉬 구조체의 각각에는 서로 다른 물질이 고정되는 임펠러.An impeller to which different materials are fixed to each of the one or more three-dimensional mesh structure.
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