Leveraging Triphenylphosphine-Containing Polymers to Explore Design Principles for Protein-Mimetic Catalysts

15 April 2024, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


Complex interactions between non-coordinating residues are significant yet commonly overlooked components of macromolecular catalyst function. While these interactions have been demonstrated to impact binding affinities and catalytic rates in metalloenzymes, the roles of similar structural elements in synthetic polymeric catalysts remain underexplored. Using a model Suzuki-Miyuara cross-coupling reaction, we performed a series of systematic studies to probe the interconnected effects of metal-ligand cross-links, electrostatic interactions, and local rigidity in polymer catalysts. To achieve this, a novel bi-functional triphenylphosphine acrylamide (BisTPPAm) monomer was synthesized and evaluated alongside an analogous monofunctional triphenylphosphine acrylamide (TPPAm). In model copolymer catalysts, increased initial reaction rates were observed for copolymers untethered by Pd complexation (BisTPPAm-containing) as compared to the Pd-cross-linked catalysts (TPPAm-containing). Further, incorporating local rigidity through secondary structure-like and electrostatic interactions revealed nonmonotonic relationships between composition and reaction rate, demonstrating the potential for tunable behavior through secondary sphere interactions. Finally, through rigorous cheminformatics featurization strategies and statistical modeling, we quantitated relationships between chemical descriptors of the substrate and reaction conditions on catalytic performance. Collectively, these results provide insights into relationships between composition, structure, and function of protein-mimetic catalytic copolymers.


Polymer catalysts
Structure-function relationships
Suzuki-Miyaura cross-coupling

Supplementary materials

Leveraging Triphenylphosphine-Containing Polymers to Explore Design Principles for Protein-Mimetic Catalysts Supplemental Information
Supporting information contains the experimental details, synthetic procedures, statistical modeling, and supplemental figures and tables include NMR, SEC, DLS and other characterization


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