Polyhedral cage-containing mesoporous metal-organic frameworks as platform for biocatalysis, methods of making these frameworks, and methods of using these frameworks

Patent metadata

Field	Value
Publication number	US-9404105-B2
Application number	US-201214124849-A
Country	US
Kind code	B2
Filing date	Jun 15, 2012
Priority date	Jun 16, 2011
Publication date	Aug 2, 2016
Grant date	Aug 2, 2016

Abstract

Embodiments of the present disclosure provide compositions including polyhedral mesoporous metal-organic framework including a biomolecule (e.g., enzyme), methods of making these compositions, methods of use, and the like.

First claim

We claim:

1. A composition comprising:
a mesoporous metal-organic framework (MOF) having at least one nanoscopic cage, wherein at least one nanoscopic cage includes a biomolecule, wherein the biomolecule is myoglobin or is selected from the group consisting of: microperoxidase, alcohol dehydrogenase, α-amylase, chloroperoxidase, α-chymotrypsin, glucose oxidase, horseradish peroxidase, laccase, lipase, manganese peroxidase, soybean peroxidase, trypsin, glycosylase, lysozyme, and a combination thereof, wherein the MOFs are coordination polymers with an inorganic-organic hybrid frame comprising metal ions or clusters of metal ions and organic ligands coordinated with the metal ions and/or clusters, wherein the MOFs are organized in a one-, two- or three-dimensional frameworks in which the metal clusters are linked to one another periodically by bridging ligands, pillar ligands, or a combination thereof, wherein the metal ions are selected from the group consisting of: Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb, Bi, or di-metals thereof, wherein the metal ion has a 1+, 2+, 3+, 4+, 5+, 6+, 7+, or 8+ charge, wherein the bridging ligands and the pillar ligands include one or more functional groups that coordinate with the metal(s), link metal containing groups, or both, wherein the functional group is selected from the group consisting of —CO 2 H, —CS 2 H, —NO 2 , —B(OH) 2 , and —SO 3 H, wherein the functional groups are bonded to the organic compound so to from the coordinative bond and of producing the framework material of the MOF, wherein the organic compound is selected from the group consisting of a polycarboxylated ligand, a polypyridyl ligand, a polycyano ligand, a polyphosphonate ligand, a polyhydroxyl ligand, a polysulfonate ligand, a polyimidazolate, ligand, a polytriazolate (both 1,2,3 and 1,2,4) ligand, polytetrazolate ligand, polypyrazolate ligand, and mixtures and combinations thereof.

2. The composition of claim 1 , wherein the enzyme is microperoxidase.

3. The composition of claim 1 , wherein the biomolecule is myoglobin.

4. The composition of claim 1 , wherein the mesoporous MOF is a MOF with pore sizes larger than about 1.5 nm and cage diameters larger than about 2 nm.

5. The composition of claim 1 , wherein the mesoporous MOF has a pore size of about 2 nm to 50 nm.

6. The composition of claim 1 , wherein the mesoporous MOF is stable in water.

7. The composition of claim 1 , wherein the nanoscopic cage of the mesoporous MOF has a diameter of about 3.9 to 4.7 nm.

8. The composition of claim 1 , wherein the mesoporous MOF is loaded with the biomolecule in amount of about 1 to 1000 μmol/g.

9. A mesoporous metal-organic framework (MOF), comprising:
at least one nanoscopic cage, wherein at least one nanoscopic cage includes a enzyme, wherein a nanoscopic cage has pore sizes larger than about 1.5 nm and a nanoscopic cage diameter larger than about 2 nm, and wherein the mesoporous MOF is stable in water, wherein the biomolecule is selected from the group consisting of:
microperoxidase, alcohol dehydrogenase, α-amylase, chloroperoxidase, α-chymotrypsin, glucose oxidase, horseradish peroxidase, laccase, lipase, manganese peroxidase, soybean peroxidase, trypsin, glycosylase, lysozyme, and a combination thereof, wherein the MOFs are coordination polymers with an inorganic-organic hybrid frame comprising metal ions or clusters of metal ions and organic ligands coordinated with the metal ions and/or clusters, wherein the MOFs are organized in a one-, two- or three-dimensional frameworks in which the metal clusters are linked to one another periodically by bridging ligands, pillar ligands, or a combination thereof, wherein the metal ions are selected from the group consisting of: Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, TI, Si, Ge, Sn, Pb, As, Sb, Bi, or di-metals thereof, wherein the metal ion has a 1+, 2+, 3+, 4+, 5+, 6+, 7+, or 8+ charge, wherein the bridging ligands and the pillar ligands include one or more functional groups that coordinate with the metal(s), link metal containing groups, or both, wherein the functional group is selected from the group consisting of —CO 2 H, —CS 2 H, —NO 2 , —B(OH) 2 , and —SO 3 H, wherein the functional groups are bonded to the organic compound so to from the coordinative bond and of producing the framework material of the MOF, wherein the organic compound is selected from the group consisting of a polycarboxylated ligand, a polypyridyl ligand, a polycyano ligand, a polyphosphonate ligand, a polyhydroxyl ligand, a polysulfonate ligand, a polyimidazolate, ligand, a polytriazolate (both 1,2,3 and 1,2,4) ligand, polytetrazolate ligand, polypyrazolate ligand, and mixtures and combinations thereof.

10. The MOF of claim 9 , wherein the mesoporous MOF is loaded with the biomolecule in amount of about 1 to 1000 μmol/g.

11. The MOF of claim 9 , wherein the enzyme is microperoxidase.

12. The MOF of claim 9 , wherein the mesoporous MOF has a pore size of about 2 nm to 50 nm.

13. The MOF of claim 9 , wherein the mesoporous MOF is stable in water.

14. The MOF of claim 9 , wherein the nanoscopic cage of the mesoporous MOF has a diameter of about 3.9 to 4.7 nm.

Assignees

• Ma Shengqian
• Ming Li-June
• Chen Yao
• Lykourinou Vasiliki
• Univ South Florida

Inventors

• Ma Shengqian
• Ming Li-June
• Chen Yao
• Lykourinou Vasiliki

Classifications

• C12N9/96 Primary

  Stabilising an enzyme by forming an adduct or a composition; Forming enzyme conjugates · CPC title

• C12N9/0065

  acting on hydrogen peroxide as acceptor (1.11) · CPC title

• C12N11/14

  Enzymes or microbial cells immobilised on or in an inorganic carrier · CPC title