1,546 research outputs found
Characterization of Structural and Electronic Transitions During Reduction and Oxidation of Ru(acac)3 Flow Battery Electrolytes by using Xâray Absorption Spectroscopy
Metal acetylacetonates possess several very attractive electrochemical properties; however, their cyclabilities fall short of targets for use in nonaqueous redox flow batteries. This paper describes structural and compositional changes during the reduction and oxidation of ruthenium(III) acetylacetonate [Ru(acac)3], a representative acetylacetonate. Voltammetry, bulk electrolysis, and inâ
situ Xâray absorption spectroscopy (XAS) results are complemented by those from density functional theory (DFT) calculations. The reduction of Ru(acac)3 in acetonitrile is highly reversible, producing a couple at â1.1â
V versus Ag/Ag+. Inâ
situ XAS and DFT indicate the formation of [Ru(acac)3]â with RuâO bonds lengthened relative to Ru(acac)3, nearly all of the charge localized on Ru, and no ligand shedding. The oxidation of Ru(acac)3 is quasireversible, with a couple at 0.7â
V. The initial product is likely [Ru(acac)3]+; however, this species is shortâlived, converting to a product with a couple at â0.2â
V, a structure that is nearly identical to that of Ru(acac)3 within 3â
Ă
of Ru, and approximately 70â% of the charge extracted from Ru (balance from acetylacetone). This nonâinnocence likely contributes to the instability of [Ru(acac)3]+. Taken together, the results suggest that the stabilities and cyclabilities of acetylacetonates are determined by the degree of charge transfer to/from the metal.Track changes: The structural and electronic changes of Ru(acac)3 during oxidation and reduction are characterized using bulk electrolysis and inâ
situ Xâray absorption spectroscopy. Reduction is found to be reversible with minimal structural changes, and the electrons being stored entirely on the ruthenium. Oxidation results in a rapid side reaction as a result of electrons extracted from the ligand.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/134821/1/celc201600360-sup-0001-misc_information.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/134821/2/celc201600360_am.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/134821/3/celc201600360.pd
Saguenay Youth Study : a multi-generational approach to studying virtual trajectories of the brain and cardio-metabolic health
This paper provides an overview of the Saguenay Youth Study (SYS) and its parental arm. The overarching goal of this effort is to develop trans-generational models of developmental cascades contributing to the emergence of common chronic disorders, such as depression, addictions, dementia and cardio-metabolic diseases. Over the past 10 years, we have acquired detailed brain and cardio-metabolic phenotypes, and genome-wide genotypes, in 1029 adolescents recruited in a population with a known genetic founder effect. At present, we are extending this dataset to acquire comparable phenotypes and genotypes in the biological parents of these individuals. After providing conceptual background for this work (transactions across time, systems and organs), we describe briefly the tools employed in the adolescent arm of this cohort and highlight some of the initial accomplishments. We then outline in detail the phenotyping protocol used to acquire comparable data in the parents
Considering Abundance, Affinity, and Binding Site Availability in the NF-ÎșB Target Selection Puzzle
The NF-ÎșB transcription regulation system governs a diverse set of responses to various cytokine stimuli. With tools from in vitro biochemical characterizations, to omics-based whole genome investigations, great strides have been made in understanding how NF-ÎșB transcription factors control the expression of specific sets of genes. Nonetheless, these efforts have also revealed a very large number of potential binding sites for NF-ÎșB in the human genome, and a puzzle emerges when trying to explain how NF-ÎșB selects from these many binding sites to direct cell-type- and stimulus-specific gene expression patterns. In this review, we surmise that target gene transcription can broadly be thought of as a function of the nuclear abundance of the various NF-ÎșB dimers, the affinity of NF-ÎșB dimers for the regulatory sequence and the availability of this regulatory site. We use this framework to place quantitative information that has been gathered about the NF-ÎșB transcription regulation system into context and thus consider questions it answers, and questions it raises. We end with a brief discussion of some of the future prospects that new approaches could bring to our understanding of how NF-ÎșB transcription factors orchestrate diverse responses in different biological contexts
Biocurators and Biocuration: surveying the 21st century challenges
Curated databases are an integral part of the tool set that researchers use on a daily basis for their work. For most users, however, how databases are maintained, and by whom, is rather obscure. The International Society for Biocuration (ISB) represents biocurators, software engineers, developers and researchers with an interest in biocuration. Its goals include fostering communication between biocurators, promoting and describing their work, and highlighting the added value of biocuration to the world. The ISB recently conducted a survey of biocurators to better understand their educational and scientific backgrounds, their motivations for choosing a curatorial job and their career goals. The results are reported here. From the responses received, it is evident that biocuration is performed by highly trained scientists and perceived to be a stimulating career, offering both intellectual challenges and the satisfaction of performing work essential to the modern scientific community. It is also apparent that the ISB has at least a dual role to play to facilitate biocuratorsâ work: (i) to promote biocuration as a career within the greater scientific community; (ii) to aid the development of resources for biomedical research through promotion of nomenclature and data-sharing standards that will allow interconnection of biological databases and better exploit the pivotal contributions that biocurators are making
Prenatal exposure to maternal cigarette smoking, amygdala volume, and fat intake in adolescence
Context : Prenatal exposure to maternal cigarette smoking is a well-established risk factor for obesity, but the underlying mechanisms are not known. Preference for fatty foods, regulated in part by the brain reward system, may contribute to the development of obesity.
Objective : To examine whether prenatal exposure to maternal cigarette smoking is associated with enhanced fat intake and risk for obesity, and whether these associations may be related to subtle structural variations in brain regions involved in reward processing.
Design : Cross-sectional study of a population-based cohort.
Setting : The Saguenay Youth Study, Quebec, Canada.
Participants : A total of 378 adolescents (aged 13 to 19 years; Tanner stage 4 and 5 of sexual maturation), half of whom were exposed prenatally to maternal cigarette smoking (mean [SD], 11.1 [6.8] cigarettes/d).
Main Outcome Measures : Fat intake was assessed with a 24-hour food recall (percentage of energy intake consumed as fat). Body adiposity was measured with anthropometry and multifrequency bioimpedance. Volumes of key brain structures involved in reward processing, namely the amygdala, nucleus accumbens, and orbitofrontal cortex, were measured with magnetic resonance imaging.
Results : Exposed vs nonexposed subjects exhibited a higher total body fat (by approximately 1.7 kg; P = .009) and fat intake (by 2.7%; P = .001). They also exhibited a lower volume of the amygdala (by 95 mm3; P < .001) but not of the other 2 brain structures. Consistent with its possible role in limiting fat intake, amygdala volume correlated inversely with fat intake (r = â0.15; P = .006).
Conclusions : Prenatal exposure to maternal cigarette smoking may promote obesity by enhancing dietary preference for fat, and this effect may be mediated in part through subtle structural variations in the amygdala
Angle of repose and segregation in cohesive granular matter
We study the effect of fluids on the angle of repose and the segregation of
granular matter poured into a silo. The experiments are conducted in two
regimes where: (i) the volume fraction of the fluid is small and it forms
liquid bridges between particles, and (ii) the particles are completely
immersed in the fluid. The data is obtained by imaging the pile formed inside a
quasi-two dimensional silo through the transparent glass side walls. In the
first series of experiments, the angle of repose is observed to increase
sharply with the volume fraction of the fluid and then saturates at a value
that depends on the size of the particles. We systematically study the effect
of viscosity by using water-glycerol mixtures to vary it over at least three
orders of magnitude while keeping the surface tension almost constant. Besides
surface tension, the viscosity of the fluid is observed to have an effect on
the angle of repose and the extent of segregation. In case of bidisperse
particles, segregation is observed to decrease and finally saturate depending
on the size ratio of the particles and the viscosity of the fluid. The sharp
initial change and the subsequent saturation in the extent of segregation and
angle of repose occurs over similar volume fraction of the fluid. In the second
series of experiments, particles are poured into a container filled with a
fluid. Although the angle of repose is observed to be unchanged, segregation is
observed to decrease with an increase in the viscosity of the fluid.Comment: 9 pages, 12 figure
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