WO2016209064A1 - Structure à mailles tridimensionnelle, roue la comprenant, et son procédé de production - Google Patents

Structure à mailles tridimensionnelle, roue la comprenant, et son procédé de production 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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Prior art keywords
mesh structure
dimensional mesh
group
support
cells
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PCT/KR2016/006865
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English (en)
Korean (ko)
Inventor
김중배
홍성길
김한솔
Original Assignee
고려대학교 산학협력단
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Priority claimed from KR1020160066446A external-priority patent/KR101869350B1/ko
Priority claimed from KR1020160066338A external-priority patent/KR101830198B1/ko
Application filed by 고려대학교 산학협력단 filed Critical 고려대학교 산학협력단
Publication of WO2016209064A1 publication Critical patent/WO2016209064A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
    • C12N11/02—Enzymes or microbial cells immobilised on or in an organic carrier
    • C12N11/08—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a synthetic polymer
    • C12N11/089—Enzymes 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • B01F27/80—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07K—PEPTIDES
    • C07K17/00—Carrier-bound or immobilised peptides; Preparation thereof
    • C07K17/02—Peptides being immobilised on, or in, an organic carrier
    • C07K17/08—Peptides being immobilised on, or in, an organic carrier the carrier being a synthetic polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions 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
    • C08L79/02—Polyamines

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

L'invention concerne une structure à mailles tridimensionnelle, une roue la comprenant, et son procédé de production. La structure à mailles selon un mode de réalisation de la présente invention peut comprendre : un support ayant une structure à mailles tridimensionnelle; et des milieux fournis sur la surface du support et capables de se lier à une première substance.
PCT/KR2016/006865 2015-06-25 2016-06-27 Structure à mailles tridimensionnelle, roue la comprenant, et son procédé de production WO2016209064A1 (fr)

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KR10-2015-0090713 2015-06-25
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KR20150091394 2015-06-26
KR10-2016-0066446 2016-05-30
KR1020160066446A KR101869350B1 (ko) 2015-06-26 2016-05-30 3차원 메쉬 구조체 및 이를 포함하는 메쉬 임펠러
KR1020160066338A KR101830198B1 (ko) 2015-06-25 2016-05-30 바이오분자-고분자섬유 복합체 및 이의 제조방법
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107213883A (zh) * 2017-07-21 2017-09-29 韩萌 一种氧化石墨烯‑聚乳酸微气泡复合材料及其制备方法和应用
CN109096742A (zh) * 2018-06-08 2018-12-28 东南大学 一种改性芳纶-热塑性聚氨酯复合材料的制备方法
CN109485881A (zh) * 2018-09-30 2019-03-19 山东诺威聚氨酯股份有限公司 一种高强电子防护服用tpu薄膜材料及其制备方法
CN109529953A (zh) * 2018-12-13 2019-03-29 四川农业大学 一种胶原蛋白TiO2复合催化剂及其制备方法
CN115851696A (zh) * 2023-02-17 2023-03-28 深圳先进技术研究院 铜基甲酸脱氢酶、其制备方法、包含其的电极及应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3767535A (en) * 1971-06-14 1973-10-23 Corning Glass Works Method of reacting an insolubilized enzyme in a fluid medium
US4963489A (en) * 1987-04-14 1990-10-16 Marrow-Tech, Inc. Three-dimensional cell and tissue culture system
KR20060071890A (ko) * 2004-12-22 2006-06-27 경북대학교 산학협력단 세포 배양용 나노섬유 지지체
JP2011501691A (ja) * 2007-10-08 2011-01-13 ビーエーエスエフ ソシエタス・ヨーロピア 反応器内部構造としての触媒特性を有する成形体の使用

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3767535A (en) * 1971-06-14 1973-10-23 Corning Glass Works Method of reacting an insolubilized enzyme in a fluid medium
US4963489A (en) * 1987-04-14 1990-10-16 Marrow-Tech, Inc. Three-dimensional cell and tissue culture system
KR20060071890A (ko) * 2004-12-22 2006-06-27 경북대학교 산학협력단 세포 배양용 나노섬유 지지체
JP2011501691A (ja) * 2007-10-08 2011-01-13 ビーエーエスエフ ソシエタス・ヨーロピア 反応器内部構造としての触媒特性を有する成形体の使用

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
LATHOUDER, DE ET AL.: "Structured Reactors for Enzyme Immobilization: a Monolithic Stirrer Reactor for Application in Organic Media", CHEMICAL ENGINEERING RESEARCH AND DESIGN, vol. 84, no. A5, 2006, pages 390 - 398, XP022536246 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107213883A (zh) * 2017-07-21 2017-09-29 韩萌 一种氧化石墨烯‑聚乳酸微气泡复合材料及其制备方法和应用
CN107213883B (zh) * 2017-07-21 2019-09-13 韩萌 一种氧化石墨烯-聚乳酸微气泡复合材料及其制备方法和应用
CN109096742A (zh) * 2018-06-08 2018-12-28 东南大学 一种改性芳纶-热塑性聚氨酯复合材料的制备方法
CN109485881A (zh) * 2018-09-30 2019-03-19 山东诺威聚氨酯股份有限公司 一种高强电子防护服用tpu薄膜材料及其制备方法
CN109485881B (zh) * 2018-09-30 2021-04-16 山东一诺威聚氨酯股份有限公司 一种高强电子防护服用tpu薄膜材料及其制备方法
CN109529953A (zh) * 2018-12-13 2019-03-29 四川农业大学 一种胶原蛋白TiO2复合催化剂及其制备方法
CN115851696A (zh) * 2023-02-17 2023-03-28 深圳先进技术研究院 铜基甲酸脱氢酶、其制备方法、包含其的电极及应用

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