Enzyme-assisted ATRP procedures

Patent metadata

Field	Value
Publication number	US-11472894-B2
Application number	US-201916520008-A
Country	US
Kind code	B2
Filing date	Jul 23, 2019
Priority date	Jul 23, 2018
Publication date	Oct 18, 2022
Grant date	Oct 18, 2022

Abstract

Materials and methods for conducting an atom transfer radical polymerization in the presence of oxygen by interlocking enzymatic activities are provided herein.

First claim

What is claimed is:

1. A method for polymerizing free radically copolymerizable monomers, comprising combining the monomers with:
(a) a deoxygenated, aqueous polymerization medium comprising (i) a transition metal catalyst, and (ii) an initiator comprising one or more redox transferable atoms or groups;
(b) an oxygen scavenger comprising glucose and glucose oxidase (GOx); and
(c) a reactive oxygen species (ROS) scavenger comprising pyruvate,
to form a conjugate.

2. The method of claim 1 , wherein the method is carried out in a reactor with a limited head space comprising air.

3. The method of claim 1 , wherein the method is carried out in a reactor open to the atmosphere.

4. The method of claim 1 , wherein the initiator is a biomolecule with one or more functional initiators.

5. The method of claim 4 , wherein the biomolecule comprises a protein, polypeptide, polynucleotide, aptamer, nucleic acid, or other biomolecule that is incorporated into the formed conjugate with the polymer grown from the incorporated initiator site(s).

6. The method of claim 1 , comprising transition metal-mediated controlled polymerizing of vinyl monomers in an aqueous based polymerization medium.

7. The method of claim 1 , wherein the method is an Initiators for Continuous Activator Regeneration (ICAR) atom transfer radical polymerization (ATRP), and wherein a free radical source is generated in situ by reaction of an enzyme with the product of the oxygen scavenging reaction.

8. The method of claim 1 , wherein the method is a photo-ATRP, wherein a free radical source is generated in situ by photo-based reaction of a reducing agent, and wherein oxygen is removed by reaction of an enzyme with the product of the oxygen scavenging reaction.

9. The method of claim 1 , wherein the method is an activator regenerated by electron transfer (ARGET) ATRP, wherein a free radical source is generated in situ by reaction of a reducing agent, and wherein oxygen is removed by reaction of an enzyme with the product of the oxygen scavenging reaction.

10. The method of claim 9 , wherein the method is a surface-initiated polymerization.

11. The method of claim 1 , wherein the GOx is immobilized on a solid surface.

12. The method of claim 11 , wherein the solid surface comprises glass, metal, or plastic.

13. An oxygen-driven atom transfer radical polymerization (ATRP) method, wherein the method comprises combining:
(a) a deoxygenated, aqueous polymerization medium comprising (i) copper at a concentration less than 1500 ppm, wherein the copper is capable of participating in a redox reaction, and (ii) a halogen-containing initiator comprising one or more redox transferable atoms or groups;
(b) an oxygen scavenger comprising glucose and glucose oxidase (GOx); and
(c) a reactive oxygen species (ROS) scavenger comprising pyruvate,
wherein the concentrations of the oxygen scavenger and the ROS scavenger are sufficient to provide a continuous source of radicals for controlled polymerization from the halogen-containing initiator.

14. The method of claim 13 , wherein the method is carried out in a reactor with a limited head space comprising air.

15. The method of claim 13 , wherein the method is carried out in a reactor open to the atmosphere.

16. The method of claim 13 , wherein the GOx is immobilized on a solid surface.

17. The method of claim 16 , wherein the solid surface comprises glass, metal, or plastic.

18. A method for polymerizing free radically copolymerizable monomers to form a conjugate, comprising combining the monomers with:
(a) a deoxygenated, aqueous polymerization medium comprising (i) a transition metal catalyst and (ii) an initiator comprising one or more redox transferable atoms or groups;
(b) glucose and glucose oxidase (GOx); and
(c) pyruvate,
to form the conjugate.

Assignees

• Univ Carnegie Mellon

Inventors

• Matyjaszewski Krzysztof
• Barros Alan Enciso
• Fu Liye
• Russell Alan J

Classifications

• C12P13/02

  Amides, e.g. chloramphenicol {or polyamides; Imides or polyimides; Urethanes, i.e. compounds comprising N-C=O structural element or polyurethanes (peptides C12P21/00 or C07K)} · CPC title

• C08F2438/01

  Atom Transfer Radical Polymerization [ATRP] or reverse ATRP · CPC title

• C08F220/286

  and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate · CPC title

• C08F220/28

  containing no aromatic rings in the alcohol moiety · CPC title

• C12Y101/03004

  Glucose oxidase (1.1.3.4) · CPC title