Preparation of Polymer Nanoparticles by Ring Opening Metathesis Polymerization in Aqueous Dispersed Systems with Water-Soluble Ruthenium-based Catalyst

Ring opening metathesis polymerization (ROMP) is a variant of olefin metathesis used to polymerize strained cyclic olefins. Ruthenium-based Grubbs’ catalysts are widely used in ROMP to produce industrially important products. While highly efficient in organic solvents such as dichloromethane and toluene, these hydrophobic catalysts are not typically applied in aqueous systems. With the advancements in emulsion and miniemulsion polymerization, it is promising to conduct ROMP in an aqueous dispersed phase to generate well-defined latex nanoparticles while improving heat transfer and reducing the use of volatile organic solvents (VOCs). Herein I report the efforts made using a PEGylated ruthenium alkylidene as the catalyst to initiate ROMP in an oil-in-water miniemulsion. 1H NMR revealed that the synthesized PEGylated catalyst was stable and reactive in water. Using 1,5-cyclooctadiene (COD) as monomer, we showed the highly efficient catalyst yielded colloidally stable polymer latexes with ~ 100% conversion at room temperature. Kinetic studies demonstrated first-order kinetics with good livingness as confirmed by the shift of gel permeation chromatography (GPC) traces. Depending on the surfactants used, the particle sizes ranged from 100 to 300 nm with monomodal distributions. The more strained cyclic olefin norbornene (NB) could also be efficiently polymerized with a PEGylated ruthenium alkylidene in miniemulsion to full conversion and with minimal coagulum formation.

The effects of the non-native invertebrate predator Bythotrephes longimanus and declining aqueous calcium on crustacean zooplankton communities in Canadian Shield lakes

Over the last several decades, human activities have resulted in environmental changes that have increased the number of stressors that can act on a single environment. In Canadian Shield lakes, two recent stressors, the invasion of Bythotrephes longimanus and calcium decline, have been documented. Widespread acidification of hundreds of North American lakes has resulted in the precipitous decline of lake water calcium concentration. Crustacean zooplankton with high calcium demands are likely to be vulnerable to calcium decline, especially <1.5 mg Ca/L, where survival and reproduction rates are reduced. These taxa are also vulnerable to predation by Bythotrephes that has been implicated in the loss of pelagic biodiversity in soft water lakes. Despite laboratory and field studies aimed at understanding the independent impact of these stressors, it is unclear how their co-occurrence will influence community response. Using a combination of data from a large regional lake survey and field experiments, I examined the individual and joint effects of Bythotrephes and calcium decline on native zooplankton community structure. Results demonstrated that much is known about Bythotrephes and our findings of reduced total zooplankton and species richness, due to the loss of Cladocera, are consistent with field surveys and other experimental studies. While we did not detect strong evidence for an effect of calcium on zooplankton using the lowest calcium concentration among invaded lakes (1.2 mg Ca/L), there is evidence that, as lake water calcium concentrations fall <1 mg Ca/L, per capita growth rates of a broad variety of taxa are expected to decline. At the regional scale, negative effects of Bythotrephes and calcium on abundances of small cladocerans and Daphnia pulicaria, respectively, were in agreement with my experimental observations. We also observed significant interactions between Bythotrephes and calcium for a broad variety of taxa. As Bythotrephes continues to spread and invade lakes that are also declining in aqueous calcium, both stressors are likely to amplify negative effects on Cladocera that appear the most vulnerable. Loss of these important zooplankton in response to both Bythotrephes and calcium decline, is likely to lower zooplankton productivity, with potential effects on phytoplankton and higher trophic levels.