Iron Complexes for Cyclic Carbonate and Polycarbonate Formation: Selectivity Control from Ligand Design and Metal-Center Geometry.

A family of 17 iron(III) aminobis(phenolate) complexes possessing different phenolate substituents, coordination geometries, and donor arrangements were used as catalysts for the reaction of carbon dioxide (CO2) with epoxides. Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry of the iron complexes with a bis(triphenylphosphine)iminium chloride cocatalyst in negative mode revealed the formation of six-coordinate iron "ate" species. Under low catalyst loadings (0.025 mol % Fe and 0.1 mol % chloride cocatalyst), all complexes showed good-to-excellent activity for converting propylene oxide to propylene carbonate under 20 bar of CO2. The most active complex possessed electron-withdrawing dichlorophenolate groups and for a 2 h reaction time gave a turnover frequency of 1240 h-1. Epichlorohydrin, styrene oxide, phenyl glycidyl ether, and allyl glycidyl ether could also be transformed to their respective cyclic carbonates with good-to-excellent conversions. Selectivity for polycarbonate formation was observed using cyclohexene oxide, where the best activity was displayed by trigonal-bipyramidal iron(III) complexes having electron-rich phenolate groups and sterically unencumbering tertiary amino donors. Those containing bulky tertiary amino ligands or those with square-pyramidal geometries around iron showed no activity for polycarbonate formation. While the overall conversions declined with decreasing CO2 pressure, CO2 incorporation remained high, giving a completely alternating copolymer. The difference in the optimum catalyst reactivity for cyclic carbonate versus polycarbonate formation is particularly noteworthy; that is, electron-withdrawing-group-containing phenolates give the most active catalysts for propylene carbonate formation, whereas catalysts with electron-donating-group-containing phenolates are the most active for polycyclohexene carbonate formation. This study demonstrates that the highly modifiable aminophenolate ligands can be tailored to yield iron complexes for both CO2/epoxide coupling and ring-opening copolymerization activity.

Emergence of the arterial worm Elaeophora schneideri in moose (Alces alces) and tabanid fly vectors in northeastern Minnesota, USA.

BACKGROUND: Moose (Alces alces) are a culturally and economically valued species in Minnesota. However, the moose population has experienced a sudden, marked decline in their range, including extirpation in the northwest and a 66% decline in the last decade in the northeast portions of the state. Although the exact cause of this decline is unclear, parasitic metastrongylid and filarioid nematode infections are known causes of morbidity and mortality in moose across North America. METHODS: To determine if these parasitic nematodes could be contributing to the Minnesota moose population decline, we molecularly examined banked tissues obtained from moose that died of known and unknown causes for the presence of nematode DNA. Extracted brain DNA of 34 individual moose was amplified utilizing primers targeting the 18S rRNA gene and internal transcribed spacer regions of nematodes. RESULTS: DNA sequencing revealed that PCR products obtained from 15 (44.1%) of the moose were 99% identical to Parelaphostrongylus tenuis, a metastrongylid known to cause neurological disease and death. Additionally, brain tissue from 20 (58.8%) individuals yielded sequences that most closely aligned with Elaeophora schneideri, a parasite associated with neurological impairment but previously unreported in Minnesota. Setaria yehi, a common filarioid parasite of deer, was also detected in the brain tissue of 5 (14.7%) moose. Molecular screening of 618 captured tabanid flies from four trapping sites revealed E. schneideri was present (6%) in the Minnesota environment and transmission could occur locally. Prevalence rates among the flies ranged between 0-100% per trapping site, with Chrysops spp. and Hybomitra spp. implicated as the vectors. CONCLUSIONS: Ultimately, these data confirm that P. tenuis is widespread in the Minnesota moose population and raises the question of the significance of E. schneideri as a contributing factor to morbidity and mortality in moose.

Necropsy findings in 62 opportunistically collected free-ranging moose (Alces alces) from Minnesota, USA (2003-13).

The Minnesota, US moose population has declined dramatically since the 1990s. All 54 carcasses of moose that died of unknown cause or were euthanized by gun shot by tribal or Department of Natural Resources personnel because of perceived signs of illness between 2003 and 2013 and eight carcasses of moose that died from vehicular accidents between 2009 and 2013 were submitted to the Minnesota Veterinary Diagnostic Laboratory and included in our study. The majority of the animals were underweight or cachectic (n = 53; 85%). Neural migration presumably by Parelaphostrongylus tenuis was a common finding (n = 28; 45%). Moderate to marked Dermacentor albipictus ("winter tick") ectoparasitism with widespread alopecia was the cause or a contributing cause of death in 14 (23%) cases in which grossly apparent anemia was associated with exhaustion of hepatic iron stores. Hepatic lesions associated with Fascioloides magna were common (n = 37; 60%) but were unlikely to be the cause of death. Environmental factors favoring winter tick survival, habitat expansion of white-tailed deer (Odocoileus virginianus), and the survival of terrestrial and aquatic snails (serving as intermediate hosts for P. tenuis and F. magna), might contribute to the seemingly severe parasitic burden in Minnesota's moose population.