Control over bottlebrush polymer synthesis by ring-opening metathesis polymerization (ROMP) of macromonomers (MMs) is highly dependent on the competition between the kinetics of the polymerization and the lifetime of the catalyst. We evaluated the effect of anchor group chemistry-the configuration of atoms linking the polymer to a polymerizable norbornene-on the kinetics of ROMP of polystyrene and poly(lactic acid) MMs initiated by (H2IMes)(pyr)2(Cl)2Ru═CHPh (Grubbs third generation catalyst). We observed a variance in the rate of propagation of >4-fold between similar MMs with different anchor groups. This phenomenon was conserved across all MMs tested, regardless of solvent, molecular weight (MW), or repeat unit identity. The observed >4-fold difference in propagation rate had a dramatic effect on the maximum obtainable backbone degree of polymerization, with slower propagating MMs reducing the maximum bottlebrush MW by an order of magnitude (from ∼10(6) to ∼10(5) Da). A chelation mechanism was initially proposed to explain the observed anchor group effect, but experimental and computational studies indicated that the rate differences likely resulted from a combination of varying steric demands and electronic structure among the different anchor groups. The addition of trifluoroacetic acid to the ROMP reaction substantially increased the propagation rate for all anchor groups tested, likely due to scavenging of the pyridine ligands. Based on these data, rational selection of the anchor group is critical to achieve high MM conversion and to prepare pure, high MW bottlebrush polymers by ROMP grafting-through.
Heterogeneous chemistry of the most important atmospheric oxidants, O 3 , NO 3 , and OH, plays a central role in regulating atmospheric gas concentrations, processing aerosols, and aging materials. Recent experimental and computational studies have begun to reveal the detailed reaction mechanisms and kinetics for gas-phase O 3 , NO 3 , and OH when they impinge on organic surfaces. Through new research approaches that merge the fields of traditional surface science with atmospheric chemistry, researchers are developing an understanding for how surface structure and functionality affect interfacial chemistry with this class of highly oxidizing pollutants. Together with future research initiatives, these studies will provide a more complete description of atmospheric chemistry and help others more accurately predict the properties of aerosols, the environmental impact of interfacial oxidation, and the concentrations of tropospheric gases.
We present a detailed mechanism for the hydrolysis of Sarin catalyzed by Cs 8 Nb 6 O 19 obtained using electronic structure calculations. The initial steps of the reaction involve the adsorption of water and Sarin on the hexaniobate catalyst via nonbonding interactions. Dissociation of the coordinated water molecule generates a hydroxide ion that adds nucleophilically to the coadsorbed Sarin molecule in a concerted manner, following a general base catalysis mechanism. The addition of OH − to the nerve agent generates a trigonal bipyramidal pentacoordinated phosphorus intermediate that subsequently undergoes facile dissociation forming either HF or isopropanol and a corresponding phosphonic acid. The rate-determining step of the overall reaction is found to be the dissociation of water on the catalyst in concert with the nucleophilic addition of the nascent OH − to the nerve agent. The calculated barrier for this step is considerably smaller than that measured for bulk base hydrolysis. This work represents a blueprint for future studies aimed to optimize catalysts for base hydrolysis of nerve agents at the gas−surface interface.
Ambient pressure in situ synchrotron-based spectroscopic techniques have been correlated to illuminate atomic-level details of bond breaking and formation during the hydrolysis of a chemical warfare nerve agent simulant over a polyoxometalate catalyst. Specifically, a Cs8[Nb6O19] polyoxoniobate catalyst has been shown to react readily with dimethyl methylphosphonate (DMMP). The atomic-level transformations of all reactant moieties, the [Nb6O19]8− polyanion, its Cs+ counterions, and the DMMP substrate, were tracked under ambient conditions by a combination of X-ray absorption fine structure spectroscopy, Raman spectroscopy, and X-ray diffraction. Results reveal that the reaction mechanism follows general base (in contrast to specific base) hydrolysis. Together with computational results, the work demonstrates that the ultimate fate of DMMP hydrolysis at the Cs8[Nb6O19] catalyst is strong binding of the (methyl) methylphosphonic acid ((M)MPA) product to the polyanions, which ultimately inhibits catalytic turnover.
Summary Separating rare-earth-element-rich minerals from unwanted gangue in mined ores relies on selective binding of collector molecules at the interface to facilitate froth flotation. Salicylhydroxamic acid (SHA) exhibits enhanced selectivity for bastnäsite over calcite in microflotation experiments. Through a multifaceted approach, leveraging density functional theory calculations, and advanced spectroscopic methods, we provide molecular-level mechanistic insight to this selectivity. The hydroxamic acid moiety introduces strong interactions at metal-atom surface sites and hinders subsurface-cation stabilization at vacancy-defect sites, in calcite especially. Resulting from hydrogen-bond-induced interactions, SHA lies flat on the bastnäsite surface and shows a tendency for multilayer formation at high coverages. In this conformation, SHA complexation with bastnäsite metal ions is stabilized, leading to advanced flotation performance. In contrast, SHA lies perpendicular to the calcite surface due to a difference in cationic spacing. We anticipate that these insights will motivate rational design and selection of future collector molecules for enhanced ore beneficiation.
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