Porous membrane having immobilized enzyme, porous membrane composite including the same, and preparation method thereof

Patent metadata

Field	Value
Publication number	US-9840701-B2
Application number	US-201615158590-A
Country	US
Kind code	B2
Filing date	May 19, 2016
Priority date	Apr 10, 2013
Publication date	Dec 12, 2017
Grant date	Dec 12, 2017

Abstract

Disclosed herein is a porous membrane having an immobilized enzyme wherein the enzyme is immobilized within pores which are three-dimensionally connected to each other. The porous membrane having the immobilized enzyme is three-dimensionally crosslinked in a molecular level wherein nanopores of 5 to 100 nm are interconnected, so that the immobilized enzyme may be in contact with a reactant in all directions, and the reaction solution may be easily diffused, thereby proceeding with the catalytic reaction fast and conveniently without deterioration of material transport.

First claim

What is claimed is:

1. A method of preparing a porous membrane for immobilizing an enzyme, the method comprising:
polymerizing a first monomer having 2 to 4 amino groups and a second monomer having 2 to 4 isocyanate groups, acyl halide groups, or ester groups to obtain an organic sol, wherein at least one of the first monomer and the second monomer has 4 functional groups;
adding a polymer solution to the organic sol to form a mixed solution;
depositing the mixed solution on a substrate and curing the mixed solution to form a porous membrane; and
removing the polymer using a solvent by passing the solvent through the porous membrane or precipitating the porous membrane with the solvent,
wherein
at least one of the first monomer or the second monomer is based on one of the following Chemical Formulae 1 to 9, wherein R is an amino group, an isocyanate group, an acyl halide group, or an ester group;
at least one of the first monomer or the second monomer is based on Chemical Formula 10, wherein R is an amino group, an isocyanate group, an acyl halide group, or an ester group; and n is 0 or 1;
at least one of the first monomer is represented by the following Chemical Formula 11 and the second monomer has 2 isocyanate groups, wherein X is a carbon or silicon atom;
the first monomer has 2 amino groups and the second monomer is represented by the following Chemical Formula 12: wherein X is a carbon or silicon atom;
polymerizing the first monomer comprises polymerizing one or more of tetratis(4-aminophenyl)methane (TAPM), p-phenylene diamine (PDA), or oxydianiline (4,4′-oxydianiline) (ODA); or
polymerizing the first monomer comprises polymerizing one or more of p-phenylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), or tetrakis(4-isocyanatophenyl)methane (TIPM):

2. A method of preparing a porous membrane containing an immobilized enzyme, the method comprising:
passing a solution containing an enzyme through the porous membrane, the porous membrane being a three-dimensionally crosslinked structure interconnected by pores having a size of 5 to 100 nm; and
capturing the enzyme in one or more of the pores of the porous membrane,
wherein a framework of the porous membrane is a three-dimensional network formed by:
polymerizing a first monomer having 2 to 4 amino groups and a second monomer having 2 to 4 isocyanate groups, acyl halide groups or ester groups to obtain an organic sol;
mixing the organic sol with a solvent soluble polymer;
gelating the organic sol;
forming a phase-separated structure including the organic sol and the solvent soluble polymer; and
removing the solvent soluble polymer from the phase-separated structure with a solvent, wherein

at least one of the first monomer or the second monomer is based on one of the following Chemical Formulae 1 to 9, wherein R is an amino group, an isocyanate group, an acyl halide group, or an ester group,
at least one of the first monomer or the second monomer is based on one of the following Chemical Formula 10, wherein R is an amino group, an isocyanate group, an acyl halide group, or an ester group; and n is 0 or 1;
at least one of the first monomer is represented by the following Chemical Formula 11 and the second monomer has 2 isocyanate groups, wherein X is a carbon or silicon atom;
the first monomer has 2 amino groups and the second monomer is represented by the following Chemical Formula 12: wherein X is a carbon or silicon atom;
polymerizing the first monomer comprises polymerizing one or more of tetratis(4-aminophenyl)methane (TAPM), p-phenylene diamine (PDA), or oxydianiline (4,4′-oxydianiline) (ODA); or
polymerizing the first monomer comprises polymerizing one or more of p-phenylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), or tetrakis(4-isocyanatophenyl)methane (TIPM):

3. The method of claim 2 , wherein the passing of the solution is carried out by one or more of dead-end flow, cross flow filtration, or a combination thereof.

4. A method of preparing a porous membrane containing an immobilized enzyme, the method comprising:
polymerizing a first monomer having 2 to 4 amino groups and a second monomer having 2 to 4 isocyanate groups, acyl halide groups, or ester groups to obtain an organic sol;
adding a polymer solution to the organic sol to obtain a mixed solution;
applying the mixed solution to a substrate and curing the mixed solution;
forming a phase-separated structure including the polymer and an organic sol from the mixed solution;
passing a solvent through the phase-separated structure or immersing the phase-separated structure in a solvent to remove the polymer from the phase-separated structure; and
obtaining a porous membrane having a three-dimensionally interconnected framework comprising pores having a size of 5 nm to 100 nm; and
passing a solution containing an enzyme through the porous membrane,
wherein
at least one of the first monomer or the second monomer is based on one of the following Chemical Formulae 1 to 9, wherein R is an amino group, an isocyanate group, an acyl halide group, or an ester group,
at least one of the first monomer or the second monomer is based on Chemical Formula 10, wherein R is an amino group, an isocyanate group, an acyl halide group, or an ester group; and n is 0 or 1;
at least one of the first monomer is represented by the following Chemical Formula 11 and the second monomer has 2 isocyanate groups, wherein X is a carbon or silicon atom;
the first monomer has 2 amino groups and the second monomer is represented by the following Chemical Formula 12: wherein X is a carbon or silicon atom;
polymerizing the first monomer comprises polymerizing one or more of tetratis(4-aminophenyl)methane (TAPM), p-phenylene diamine (PDA), or oxydianiline (4,4′-oxydianiline) (ODA); or
polymerizing the first monomer comprises polymerizing one or more of p-phenylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), or tetrakis(4-isocyanatophenyl)methane (TIPM):

5. The method of claim 4 , wherein the polymer solution comprises one or more of polyethyleneglycol, polysulfone, polyethersulfone, polyacrylonitrile, polyimide, polyetherimide, polybenzimidazole, polymethylmethacrylate, polystyrene, polyetheretherketone or polyvinylidenefluoride.

6. The method of claim 2 , wherein the porous membrane is formed as a flat membrane or a hollow fiber membrane.

7. The method of claim 2 , wherein the solvent is a first solvent, and the method further comprises:
passing a second solvent though the porous membrane having the enzyme captured therein to further immobilize the enzyme.

8. The method of claim 7 , wherein the second solvent passing though the porous membrane is water.

9. The method of claim 2 , wherein passing the solution containing the enzyme through the porous membrane comprises using one or more enzymes comprising one or more of lipase, amylase, protease, trypsin, papain, brinase, peroxidase, horseradish peroxidase (HRP), carbonic anhydrase, aquaporin, motrypsin, subtilisin, soybean peroxidase, chloroperoxidase, manganese peroxidase, tyrosinase, laccase, cellulase, xylanase, lactase, sucrase, organophosphohydrolase, chlorinesteras

Assignees

• Gwangju Inst Science & Tech

Inventors

• Park Ji-Woong
• Han Sun-Young
• Bae Jae-Sung

Classifications

• C12N11/08

  the carrier being a synthetic polymer · CPC title

• B01D71/64

  Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors · CPC title

• C12P7/649

  Biodiesel, i.e. fatty acid alkyl esters · CPC title

• C12P13/00

  Preparation of nitrogen-containing organic compounds · CPC title

• C12N11/04 Primary

  entrapped within the carrier, e.g. gel or hollow fibres · CPC title