Electrochemistry and Spectroscopy of Sulfate and Thiosulfate Complexes of Iron Porphyrins

The electrochemical and spectroscopic properties of the complex formed by the addition of thiosulfate to ferric porphyrins were examined. The NMR spectrum of the thiosulfate–ferric porphyrin complex was consistent with a high-spin ferric complex, while the EPR spectrum at liquid nitrogen temperatures indicated that the complex under these conditions was low-spin. Such behavior has been previously observed for other ferric porphyrin complexes. The visible spectra were characterized by a shift in the Soret band to higher energies, with smaller changes in the longer wavelength region. The complex was reasonably stable in DMF, but slowly reduced over several hours to FeII(TPP) and S4O6 2−. The voltammetric behavior of the thiosulfate complex in DMF consists of two waves, the first of which was irreversible. The ferric/ferrous reduction in the presence of thiosulfate was shifted negatively about 400 mV, compared to the Fe(TPP)(Cl) reduction. The visible, NMR and EPR spectra were most consistent with a Fe–S bonded ferric porphyrin–thiosulfate complex, Fe(P)(SSO3)−. The kinetics of the reduction of ferric porphyrin by thiosulfate in DMSO indicated an autocatalytic mechanism, where the first step is the formation of the catalyst. The identity of the catalyst could not be determined because it must be present at low concentrations, but it is formed from the reaction of the ferric complex with thiosulfate. Coordination of thiosulfate to the porphyrin was not necessary for the reduction to occur, and the reduction of Fe(TPP)(Cl) by thiosulfate was accelerated by the addition of sulfate. Under these conditions, sulfate had replaced thiosulfate as the axial ligand for the ferric porphyrin. In the presence of sulfate, the reduction occurred in a single kinetic pseudo-first order step. The voltammetry, spectroelectrochemistry and kinetics for the reaction of thiosulfate with ferric porphyrins were examined. A rapid reaction between ferric porphyrins and thiosulfate was observed in DMF. The reaction was complex, involving the formation of a catalytic intermediate. Window factor analysis and multivariate curve resolution were used to deconvolute the kinetic data

Defining ecologically relevant scales for spatial protection with long-term data on an endangered seabird and local prey availability

This is the author accepted manuscript. The final version is available from Wiley via the DOI in this record.Human activities are important drivers of marine ecosystem functioning. However, separating the synergistic effects of fishing and environmental variability on the prey base of nontarget predators is difficult, often because prey availability estimates on appropriate scales are lacking. Understandi ng how prey abundance at different spatial scales links to population change can help integrate the needs of nontarget predators into fisheries management by defining ecologically relevant areas for spatial protection. We investigated the local population response (number of breeders) of the Bank Cormorant (Phalacrocorax neglectus), a range-restricted endangered seabird, to the availability of its prey, the heavily fished west coast rock lobster (Jasus lalandii). Using Bayesian state-space modeled cormorant counts at 3 colonies, 22 years of fisheries-independent data on local lobster abundance, and generalized additive modeling, we determined the spatial scale pertinent to these relationships in areas with different lobster availability. Cormorant numbers responded positively to lobster availability in the regions with intermediate and high abundance but not where regime shifts and fishing pressure had depleted lobster stocks. The relationships were strongest when lobsters 20–30 km offshore of the colony were considered, a distance greater than the Bank Cormorant's foraging range when breeding, and may have been influenced by prey availability for nonbreeding birds, prey switching, or prey ecology. Our results highlight the importance of considering the scale of ecological relationships in marine spatial planning and suggest that designing spatial protection around focal species can benefit marine predators across their full life cycle. We propose the precautionary implementation of small-scale marine protected areas, followed by robust assessment and adaptive-management, to confirm population-level benefits for the cormorants, their prey, and the wider ecosystem, without negative impacts on local fisheries.The National Research Foundation (NRF) SEAChange Grant 79735 and an incentive grant to R.J.M.C., Leiden Conservation Foundation, Claude Leon Foundation, and our institutions provided funding

Biological survey of the Prince Edward Islands, December 2008

A biological survey of the Prince Edward Islands took place in December 2008. The survey repeated an earlier survey of the populations of surface-nesting seabirds on both islands and of fur seals (Arctocephalus spp.) and alien plants on Prince Edward Island in December 2001. Observations on burrowing seabirds, macro-invertebrates and plant communities on Prince Edward Island and an oceanographic survey of surrounding waters were also included. The survey confirmed many of the observations made on the earlier survey and permitted an assessment of trends in the abundance and distribution of biota since 2001

Dystrophic Microglia Are Associated with Neurodegenerative Disease and not Healthy Aging in the Human Brain

Loss of physiological microglial function may increase the propagation of neurodegenerative diseases. Cellular senescence is a hallmark of aging; thus, we hypothesized age could be a cause of dystrophic microglia. Stereological counts were performed for total microglia, 2 microglia morphologies (hypertrophic and dystrophic) across the human lifespan. An age-associated increase in the number of dystrophic microglia was found in the hippocampus and frontal cortex. However, the increase in dystrophic microglia was proportional to the age-related increase in the total number of microglia. Thus, aging alone does not explain the presence of dystrophic microglia. We next tested if dystrophic microglia could be a disease-associated microglia morphology. Compared with controls, the number of dystrophic microglia was greater in cases with either Alzheimer\u27s disease, dementia with Lewy bodies, or limbic-predominant age-related TDP-43 encephalopathy. These results demonstrate that microglia dystrophy, and not hypertrophic microglia, are the disease-associated microglia morphology. Finally, we found strong evidence for iron homeostasis changes in dystrophic microglia, providing a possible molecular mechanism driving the degeneration of microglia in neurodegenerative disease

Implantable Cardioverter Defibrillator Therapy in Patients with Cardiac Sarcoidosis

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/93643/1/j.1540-8167.2012.02350.x.pd

Managing marine disease emergencies in an era of rapid change

Infectious marine diseases can decimate populations and are increasing among some taxa due to global change and our increasing reliance on marine environments. Marine diseases become emergencies when significant ecological, economic or social impacts occur. We can prepare for and manage these emergencies through improved surveillance, and the development and iterative refinement of approaches to mitigate disease and its impacts. Improving surveillance requires fast, accurate diagnoses, forecasting disease risk and real-time monitoring of disease-promoting environmental conditions. Diversifying impact mitigation involves increasing host resilience to disease, reducing pathogen abundance and managing environmental factors that facilitate disease. Disease surveillance and mitigation can be adaptive if informed by research advances and catalysed by communication among observers, researchers and decision-makers using information-sharing platforms. Recent increases in the awareness of the threats posed by marine diseases may lead to policy frameworks that facilitate the responses and management that marine disease emergencies require

Pan-viral serology implicates enteroviruses in acute flaccid myelitis.

Since 2012, the United States of America has experienced a biennial spike in pediatric acute flaccid myelitis (AFM)1-6. Epidemiologic evidence suggests non-polio enteroviruses (EVs) are a potential etiology, yet EV RNA is rarely detected in cerebrospinal fluid (CSF)2. CSF from children with AFM (n = 42) and other pediatric neurologic disease controls (n = 58) were investigated for intrathecal antiviral antibodies, using a phage display library expressing 481,966 overlapping peptides derived from all known vertebrate and arboviruses (VirScan). Metagenomic next-generation sequencing (mNGS) of AFM CSF RNA (n = 20 cases) was also performed, both unbiased sequencing and with targeted enrichment for EVs. Using VirScan, the viral family significantly enriched by the CSF of AFM cases relative to controls was Picornaviridae, with the most enriched Picornaviridae peptides belonging to the genus Enterovirus (n = 29/42 cases versus 4/58 controls). EV VP1 ELISA confirmed this finding (n = 22/26 cases versus 7/50 controls). mNGS did not detect additional EV RNA. Despite rare detection of EV RNA, pan-viral serology frequently identified high levels of CSF EV-specific antibodies in AFM compared with controls, providing further evidence for a causal role of non-polio EVs in AFM

The Atacama Cosmology Telescope: Extragalactic Sources at 148 GHz in the 2008 Survey

We report on extragalactic sources detected in a 455 square-degree map of the southern sky made with data at a frequency of 148 GHz from the Atacama Cosmology Telescope 2008 observing season. We provide a catalog of 157 sources with flux densities spanning two orders of magnitude: from 15 to 1500 mJy. Comparison to other catalogs shows that 98% of the ACT detections correspond to sources detected at lower radio frequencies. Three of the sources appear to be associated with the brightest cluster galaxies of low redshift X-ray selected galaxy clusters. Estimates of the radio to mm-wave spectral indices and differential counts of the sources further bolster the hypothesis that they are nearly all radio sources, and that their emission is not dominated by re-emission from warm dust. In a bright (>50 mJy) 148 GHz-selected sample with complete cross-identifications from the Australia Telescope 20 GHz survey, we observe an average steepening of the spectra between 5, 20, and 148 GHz with median spectral indices of $\alpha_{\rm 5-20} = -0.07 \pm 0.06$, $\alpha_{\rm 20-148} = -0.39 \pm0.04$, and $\alpha_{\rm 5-148} = -0.20 \pm 0.03$. When the measured spectral indices are taken into account, the 148 GHz differential source counts are consistent with previous measurements at 30 GHz in the context of a source count model dominated by radio sources. Extrapolating with an appropriately rescaled model for the radio source counts, the Poisson contribution to the spatial power spectrum from synchrotron-dominated sources with flux density less than 20 mJy is C^{\rm Sync} = (2.8 \pm 0.3) \times 10^{-6} \micro\kelvin^2.Comment: Accepted to Ap