Easter, Quinn T. Garcia, Antonio Blum, Suzanne A. Single-Polymer–Particle Growth Kinetics with Molecular Catalyst Speciation and Single-Turnover Imaging The dynamics of the local environments surrounding molecular polymerization catalysts plausibly impact turnover kinetics, but the impact of and nature of such dynamics have previously been obscured by ensemble averaging. With Grubbs’ second generation ruthenium metathesis catalyst and a precipitation polymerization system, studies at the single-particle and -turnover level establish that (1) an inverse correlation exists between rate and duration of single-polymer–particle growth of aggregates, consistent with a local environment density model for the time-variable kinetics; (2) cross-linking additives produced a small, but detectible, reduction in overall monomer incorporation; (3) total ruthenium quantity within the polymer particles (as characterized by energy dispersive X-ray spectroscopy) is differentiable from the quantity that is catalytically active (as characterized by in situ fluorescence microscopy), providing catalyst speciation information; and (4) time-resolved enyne metathesis reactions can be imaged, corresponding to single turnovers at individual molecular catalysts during polymer growth under synthetically relevant conditions. These findings identify and characterize reactivity distributions likely arising from the dynamics of local environments. As such, these data provide reactivity information that is unavailable through traditional ensemble analytical methods that obscure this type of information through averaging. dynamic;environment density model;polymerization catalysts;precipitation polymerization system;catalyst speciation information;energy dispersive X-ray spectroscopy;Molecular Catalyst Speciation;generation ruthenium metathesis catalyst;reactivity information;impact turnover kinetics;polymer growth;time-variable kinetics;turnover level;reactivity distributions;Single-Turnover Imaging;monomer incorporation;ruthenium quantity;ensemble;polymer particles 2019-03-04
    https://acs.figshare.com/articles/media/Single-Polymer_Particle_Growth_Kinetics_with_Molecular_Catalyst_Speciation_and_Single-Turnover_Imaging/7853249
10.1021/acscatal.9b00095.s006