Versatile triphenylphosphine-containing polymeric catalysts and elucidation of structure-function relationships

Abstract

Synthetic polymers are a modular solution to bridging the two most common classes of catalysts: proteins and small molecules. Polymers offer the synthetic versatility of small molecule catalysts, while simultaneously having the ability to construct microenvironments mimicking those of natural proteins. We synthesized a panel of polymeric catalysts containing a novel triphenylphosphine acrylamide monomer (TPPAm) and investigated how their properties impact the rate of a model Suzuki-Miyaura cross-coupling reaction. Systematic variation of polymer properties, such as molecular weight, functional density, and comonomer identity, led to tunable reaction rates and solvent compatibility, including full conversion in an aqueous medium. Studies with bulky substrates revealed connections between polymer parameters and reaction conditions that were further elucidated with a regression analysis. Some connections were substrate-specific, highlighting the value of the rapidly tunable polymer catalyst. Collectively, these results aid in building structure-function relationships to guide the development of polymer catalysts with tunable substrate and environment compatibility.

Navigating the Expansive Landscapes of Soft Materials: A User Guide for High-Throughput Workflows

“…Common intrinsic descriptors of a material include composition (e.g., hydrophobic, 35 functional, 36 charged, 37 and stimuli-responsive 38 ), architecture (e.g., cross-linked, 22 branched, 23 and star 39 ), sequence patterning, 40 and molecular weight. However, descriptors that are extrinsic to the material itself, such as sample preparation protocols 41−44 or substrate choice for a polymer catalyst, 45,46 can also be important variables to probe with a library.…”

“…For instance, in recent studies on the design of polymeric catalysts, the structure and activity profiles (i.e., turnover rates and final yields) are sensitive to external reaction conditions such as solvent, temperature, and substrate identity. 45,46,260 Instrument parameters can be strategically tuned to improve the throughput of many characterization methods. In spectroscopic techniques, parameters such as the spectral width, resolution, and number of scans can be optimized to reduce acquisition times without compromising the ability to identify key features or make preliminary assessments.…”

“…236−238 Dyes not coupled to the polymer can span solvatochromic, colorimetric, or fluorogenic types, and are capable of characterizing diverse properties including conformational changes, 98,214 aggregation, 239,240 cell viability, 241,242 metal ion uptake, 105,243−245 and catalytic activity. 45,46 Characterization using dyes is both accessible and straightforward, involving minimal sample preparation and rapid throughput in well plates. For example, Nile red is a fluorescent dye used to visualize hydrophobic surfaces of proteins, 246 polymers, 247 and lipid droplets.…”

Bottle brush star block copolymer nanoreactors for efficient photooxidation catalysis: effects of chain softness

“…Building polymer catalysts containing a secondary structure, such as a-helix or b-sheet using hydrogen bonding, metal-ligand coordination, or p-p stacking, is a strategy to design unique three-dimensional pockets for selective catalysts. [17][18][19][20] These biomimetic secondary structures can enhance catalytic activity and chiral selectivity for catalytic applications. However, they are limited to specific reaction conditions, restricting their operational versatility.…”

Enhanced Efficiency of Pd(0)-Based Single Chain Polymeric Nanoparticles for in Vitro Prodrug Activation by Modulating the Polymer’s Microstructure

“…Notably, as compared to other bioorthogonal catalysts where a 5-day incubation period is required for pro-5FU activation, our system accomplished catalysis within 48 h in the presence of cells. 24 It is known that HepG2 cell lines are very resistant and are tough targets for 5FU to exert its function, 31,32 explaining why the activation of 5FU was less prone to lead to significant cell death. The resistance of HepG2 toward 5FU also helped to unveil differences in catalytic activity resulting from the different polymer microstructures in P@Pd(0).…”