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Automated ARGET ATRP Accelerates Catalyst Optimization for the Synthesis of Thiol-Functionalized Polymers
Daniel J Siegwart1, Matthias Leiendecker, Robert Langer
1Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States ; David H. Koch Institute for Integrative Cancer Research, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States.
Macromolecules
|April 20, 2013
Summary
Automated polymerization accelerates catalyst optimization for disulfide-functionalized polymers. This high-throughput method, using ARGET ATRP, efficiently synthesizes polymers without an inert atmosphere, enabling rapid condition screening for diverse monomers.
Area of Science:
- Polymer Chemistry
- Organic Synthesis
- Materials Science
Background:
- Conventional polymer synthesis via Atom Transfer Radical Polymerization (ATRP) is often low-throughput and requires an inert atmosphere, hindering rapid optimization.
- Developing efficient and high-throughput methods for controlled polymerization is crucial for accelerating polymer discovery and production.
Purpose of the Study:
- To develop an automated, high-throughput method for controlled radical polymerization.
- To accelerate catalyst optimization and the production of disulfide-functionalized polymers.
- To demonstrate the applicability of the developed method across a range of monomers.
Main Methods:
- Utilized an automated system for Accelerated, Group-Involved, Atom Transfer Radical Polymerization (ARGET ATRP).
- Screened and optimized polymerization conditions (catalyst, reducing agent) for eight different monomers, including novel ARGET ATRP applications.
- Synthesized a library of disulfide-functionalized polymers using optimized conditions and specific initiators, ligands, and reducing agents.
Main Results:
- Successfully identified polymerization conditions for eight monomers, including 2-(diethylamino)ethyl methacrylate and di(ethylene glycol) methyl ether methacrylate, via ARGET ATRP.
- Synthesized various disulfide-functionalized polymers, including those from butyl acrylate, oligo(ethylene glycol) methacrylate, styrene, and methyl methacrylate.
- Demonstrated that the disulfide linkages could be cleaved to yield thiol-terminated chains, useful for bioconjugation.
Conclusions:
- The developed automated, high-throughput ARGET ATRP method significantly accelerates catalyst optimization and polymer synthesis.
- The method is versatile, applicable to a wide range of monomers, and eliminates the need for an inert atmosphere.
- The synthesized disulfide-functionalized polymers offer potential applications in polymer bioconjugates and can be readily cleaved.
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