Nicole S. Sampson

Nicole Sampson

Distinguished Professor
Stony Brook University
Department of Chemistry
Stony Brook, NY
USA
 631-632-7952
 nicole.sampson@stonybrook.edu

Abstract

Control of Alternating Polymer Backbones in ROMP: Toward Sequence Control

A desire to control the orientation and stereochemistry of monomer incorporation led to our design of new substrates for ruthenium-catalyzed ring-opening metathesis polymerization, ROMP. We demonstrated that cyclobutene-1-carboxylate esters, undergo alternating ROMP, AROMP or alt-ROMP, to give copolymers with precisely controlled sequence. Our alternating copolymer systems allow functionality to be placed along a polymer chain with larger than typical spacing.1


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We have used both homopolymers and alternating copolymers derived from cyclobutenes for mimicking antimicrobial peptides.2 This AROMP protocol has been expanded to bicyclo[4.2.0] alkenes and cyclohexene that gives very long, linear copolymers with rigorous sequence alternation containing alternating unsaturated amides and 1-alkylidene-2-alkylcyclohexanes in a precisely controlled sequence.3, 4, 5 We will also present new large cycloalkene6 monomers that may be used in place of cyclohexene and which provide polymers with heteroatom backbone functionalities that are degradable.

Authors

Nicole S Sampson, Jingling Zhang, Francis Boadi, Kathlyn A. Parker, Li Tan, Guofang Li, and Airong Song

Affiliations

Department of Chemistry, Stony Brook University, Stony Brook, NY 11794-3400

Citations

1. Parker, K. A.; Sampson, N. S., Precision synthesis of alternating copolymers via ring-opening polymerization of 1-substituted cyclobutenes. Acc. Chem. Res. 2016, 49, 3, 408-17
2. Song, A.; Walker, S. G.; Parker, K. A.; Sampson, N. S., Antibacterial studies of cationic polymers with alternating, random, and uniform backbones. ACS Chem. Biol. 2011, 6, 6, 590-9
3. Tan, L.; Parker, K. A.; Sampson, N. S., A Bicyclo[4.2.0]octene-derived monomer provides completely linear alternating copolymers via alternating ring-opening metathesis polymerization, AROMP. Macromolecules 2014, 47, 19, 6572-6579
4. Tan, L.; Li, G.; Parker, K. A.; Sampson, N. S., Ru-Catalyzed isomerization provides access to aternating copolymers via ring-opening metathesis polymerization. Macromolecules 2015, 48, 14, 4793-4800
5. Li, G.; Sampson, N. S., Alternating Ring-Opening Metathesis Polymerization, AROMP, of Hydrophobic and Hydrophilic Monomers Provides Oligomers with Side-Chain Sequence Control. Macromolecules 2018, 51, 11, 3932-3940
6. Zhang, J.; Li, G.; Sampson, N. S., Incorporation of Large Cycloalkene Rings into Alternating Copolymers Allows Control of Glass Transition and Hydrophobicity. ACS Macro. Lett. 2018, 7, 9, 1068-1072

Lecture Images

Nicole Sampson presenting at APS2019 Nicole Sampson presenting at APS2019 Nicole Sampson presenting at APS2019