The structural and electronic properties of nanostructured Ce1–x–yZrxTbyO2 ternary oxides: Unusual concentration of Tb3+ and metal_oxygen_metal interactions

10 pages, 12 figures, 1 table.Ceria-based ternary oxides are widely used in many areas of chemistry, physics, and materials science. Synchrotron-based time-resolved x-ray diffraction, x-ray absorption near-edge spectroscopy (XANES), Raman spectroscopy, and density-functional calculations were used to study the structural and electronic properties of Ce–Zr–Tb oxide nanoparticles. The nanoparticles were synthesized following a novel microemulsion method and had sizes in the range of 4–7 nm. The Ce1–x–yZrxTbyO2 ternary systems exhibit a complex behavior that cannot be predicted as a simple extrapolation of the properties of Ce1–xZrxO2, Ce1–xTbxO2, or the individual oxides (CeO2, ZrO2, and TbO2). The doping of ceria with Zr and Tb induces a decrease in the unit cell, but there are large positive deviations with respect to the cell parameters predicted by Vegard's rule for ideal solid solutions. The presence of Zr and Tb generates strain in the ceria lattice through the creation of crystal imperfections and O vacancies. The O K-edge and Tb LIII-edge XANES spectra for the Ce1–x–yZrxTbyO2 nanoparticles point to the existence of distinctive electronic properties. In Ce1–x–yZrxTbyO2 there is an unexpected high concentration of Tb3+, which is not seen in TbO2 or Ce1–xTbxO2 and enhances the chemical reactivity of the ternary oxide. Tb_O_Zr interactions produce a stabilization of the Tb(4f,5d) states that is responsible for the high concentration of Tb3+ cations. The behavior of Ce1–x–yZrxTbyO2 illustrates how important can be metal_oxygen_metal interactions for determining the structural, electronic, and chemical properties of a ternary oxide.The research carried out at the Chemistry Department of Brookhaven National Laboratory was financed through Contract No. DE-AC02-98CH10886 with the US Department of Energy (Division of Chemical Sciences). The NSLS is supported by the Divisions of Materials and Chemical Sciences of DOE. Work at the “Instituto de Catálisis y Petroleoquímica (CSIC)” was done with financial support from CICYT (Project No. MAT2000-1467).Peer reviewe

Bimodal distribution of RNA expression levels in human skeletal muscle tissue

<p>Abstract</p> <p>Background</p> <p>Many human diseases and phenotypes are related to RNA expression, levels of which are influenced by a wide spectrum of genetic and exposure-related factors. In a large genome-wide study of muscle tissue expression, we found that some genes exhibited a bimodal distribution of RNA expression, in contrast to what is usually assumed in studies of a single healthy tissue. As bimodality has classically been considered a hallmark of genetic control, we assessed the genome-wide prevalence, cause, and association of this phenomenon with diabetes-related phenotypes in skeletal muscle tissue from 225 healthy Pima Indians using exon array expression chips.</p> <p>Results</p> <p>Two independent batches of microarrays were used for bimodal assessment and comparison. Of the 17,881 genes analyzed, eight (<it>GSTM1, HLA-DRB1, ERAP2, HLA-DRB5, MAOA, ACTN3, NR4A2</it>, and <it>THNSL2</it>) were found to have bimodal expression replicated in the separate batch groups, while 24 other genes had evidence of bimodality in only one group. Some bimodally expressed genes had modest associations with pre-diabetic phenotypes, of note <it>ACTN3 </it>with insulin resistance. Most of the other bimodal genes have been reported to be involved with various other diseases and characteristics. Association of expression with <it>cis </it>genetic variation in a subset of 149 individuals found all but one of the confirmed bimodal genes and nearly half of all potential ones to be highly significant expression quantitative trait loci (eQTL). The rare prevalence of these bimodally expressed genes found after controlling for batch effects was much lower than the prevalence reported in other studies. Additional validation in data from separate muscle expression studies confirmed the low prevalence of bimodality we observed.</p> <p>Conclusions</p> <p>We conclude that the prevalence of bimodal gene expression is quite rare in healthy muscle tissue (<0.2%), and is much lower than limited reports from other studies. The major cause of these clearly bimodal expression patterns in homogeneous tissue appears to be <it>cis</it>-polymorphisms, indicating that such bimodal genes are, for the most part, eQTL. The high frequency of disease associations reported with these genes gives hope that this unique feature may identify or actually be an underlying factor responsible for disease development.</p

How do older people with sight loss manage their general health? A qualitative study

Purpose: Older people with sight loss experience a number of barriers to managing their health. The purpose of this qualitative study was to explore how older people with sight loss manage their general health and explore the techniques used and strategies employed for health management. Methods: Semi-structured face-to-face interviews were conducted with 30 participants. Interviews were audio-recorded, transcribed verbatim and analysed using thematic analysis. Results: Health management challenges experienced included: managing multiple health conditions; accessing information; engaging in health behaviours and maintaining wellbeing. Positive strategies included: joining support groups, clubs and societies; using low vision aids; seeking support from family and friends and accessing support through health and social care services. Conclusion: Healthcare professionals need to be more aware of the challenges faced by older people with sight loss. Improved promotion of group support and charity services which are best placed to share information, provide fora to learn about coping techniques and strategies, and give older people social support to prevent isolation is needed. Rehabilitation and support services and equipment can only be beneficial if patients know what is available and how to access them. Over-reliance on self-advocacy in current healthcare systems is not conducive to patient-centred care. Implications for Rehabilitation Sight loss in older people can impact on many factors including health management. This study identifies challenges to health management and highlights strategies used by older people with sight loss to manage their health. Access to support often relies on patients seeking information for themselves. However, self-advocacy is challenging due to information accessibility barriers. Informal groups and charities play an important role in educating patients about their condition and advising on available support to facilitate health management

Performance of a constructed wetland in Grand Marais, Manitoba, Canada : removal of nutrients, pharmaceuticals, and antibiotic resistance genes from municipal wastewater

Background The discharge of complex mixtures of nutrients, organic micropollutants, and antibiotic resistance genes from treated municipal wastewater into freshwater systems are global concerns for human health and aquatic organisms. Antibiotic resistance genes (ARGs) are genes that have the ability to impart resistance to antibiotics and reduce the efficacy of antibiotics in the systems in which they are found. In the rural community of Grand Marais, Manitoba, Canada, wastewater is treated passively in a sewage lagoon prior to passage through a treatment wetland and subsequent release into surface waters. Using this facility as a model system for the Canadian Prairies, the two aims of this study were to assess: (a) the presence of nutrients, micropollutants (i.e., pesticides, pharmaceuticals), and ARGs in lagoon outputs, and (b) their potential removal by the treatment wetland prior to release to surface waters in 2012. Results As expected, concentrations of nitrogen and phosphorus species were greatest in the lagoon and declined with movement through the wetland treatment system. Pharmaceutical and agricultural chemicals were detected at concentrations in the ng/L range. Concentrations of these compounds spiked downstream of the lagoon following discharge and attenuation was observed as the effluent migrated through the wetland system. Hazard quotients calculated for micropollutants of interest indicated minimal toxicological risk to aquatic biota, and results suggest that the wetland attenuated atrazine and carbamazepine significantly. There was no significant targeted removal of ARGs in the wetland and our data suggest that the bacterial population in this system may have genes imparting antibiotic resistance. Conclusions The results of this study indicate that while the treatment wetland may effectively attenuate excess nutrients and remove some micropollutants and bacteria, it does not specifically target ARGs for removal. Additional studies would be beneficial to determine whether upgrades to extend retention time or alter plant community structure within the wetland would optimize removal of micropollutants and ARGs to fully characterize the utility of these systems on the Canadian Prairies.

Reduced fetal vitamin D status by maternal undernutrition during discrete gestational windows in sheep

Placental transport of vitamin D and other nutrients (e.g. amino acids, fats and glucose) to the fetus is sensitive to maternal and fetal nutritional cues. We studied the effect of maternal calorific restriction on fetal vitamin D status and the placental expression of genes for nutrient transport (aromatic T-type amino acid transporter-1 [TAT-1]; triglyceride hydrolase / lipoprotein uptake facilitator lipoprotein lipase [LPL]) and vitamin D homeostasis (CYP27B1; vitamin D receptor [VDR]), and their association with markers of fetal cardiovascular function and skeletal muscle growth. Pregnant sheep received 100% total metabolizable energy (ME) requirements (control), 40% total ME requirements peri-implantation (PI40, 1–31 days of gestation [dGA]) or 50% total ME requirements in late gestation (L, 104–127 dGA). Fetal, but not maternal, plasma 25-hydroxy-vitamin D (25OHD) concentration was lower in PI40 and L maternal undernutrition groups (p<0.01) compared with the control group at 0.86 gestation. PI40 group placental CYP27B1 mRNA levels were increased (p<0.05) compared with the control group. Across all groups, higher fetal plasma 25OHD concentration was associated with higher skeletal muscle myofibre and capillary density (p<0.05). In the placenta, higher VDR mRNA levels were associated with higher TAT-1 (p<0.05) and LPL (p<0.01) mRNA levels. In the PI40 maternal undernutrition group only, reduced fetal plasma 25OHD concentration may be mediated in part by altered placental CYP27B1. The association between placental mRNA levels of VDR and nutrient transport genes suggests a way in which the placenta may integrate nutritional cues in the face of maternal dietary challenges and alter fetal physiology

Unravelling the Structure of Magnus' Pink Salt

A combination of multinuclear ultra-wideline solid-state NMR, powder X-ray diffraction (pXRD), X-ray absorption fine structure experiments, and first principles calculations of platinum magnetic shielding tensors has been employed to reveal the previously unknown crystal structure of Magnus’ pink salt (MPS), [Pt(NH3)4][PtCl4], study the isomeric Magnus’ green salt (MGS), [Pt(NH3)4][PtCl4], and examine their synthetic precursors K2PtCl4 and Pt(NH3)4Cl2·H2O. A simple synthesis of MPS is detailed which produces relatively pure product in good yield. Broad 195Pt, 14N, and 35Cl SSNMR powder patterns have been acquired using the WURST-CPMG and BRAIN-CP/WURST-CPMG pulse sequences. Experimentally measured and theoretically calculated platinum magnetic shielding tensors are shown to be very sensitive to the types and arrangements of coordinating ligands as well as intermolecular Pt–Pt metallophilic interactions. High-resolution 195Pt NMR spectra of select regions of the broad 195Pt powder patterns, in conjunction with an array of 14N and 35Cl spectra, reveal clear structural differences between all compounds. Rietveld refinements of synchrotron pXRD patterns, guided by first principles geometry optimization calculations, yield the space group, unit cell parameters, and atomic positions of MPS. The crystal structure has P-1 symmetry and resides in a pseudotetragonal unit cell with a distance of >5.5 Å between Pt sites in the square-planar Pt units. The long Pt–Pt distances and nonparallel orientation of Pt square planes prohibit metallophilic interactions within MPS. The combination of ultra-wideline NMR, pXRD, and computational methods offers much promise for future investigation and characterization of Pt-containing systems

Lake-size dependency of wind shear and convection as controls on gas exchange

High-frequency physical observations from 40 temperate lakes were used to examine the relative contributions of wind shear (u*) and convection (w*) to turbulence in the surface mixed layer. Seasonal patterns of u* and w* were dissimilar; u* was often highest in the spring, while w * increased throughout the summer to a maximum in early fall. Convection was a larger mixed-layer turbulence source than wind shear (u */w*-1 for lakes* and w* differ in temporal pattern and magnitude across lakes, both convection and wind shear should be considered in future formulations of lake-air gas exchange, especially for small lakes. © 2012 by the American Geophysical Union.Jordan S. Read, David P. Hamilton, Ankur R. Desai, Kevin C. Rose, Sally MacIntyre, John D. Lenters, Robyn L. Smyth, Paul C. Hanson, Jonathan J. Cole, Peter A. Staehr, James A. Rusak, Donald C. Pierson, Justin D. Brookes, Alo Laas, and Chin H. W

GSA: A Framework for Rapid Prototyping of Smart Alarm Systems

We describe the Generic Smart Alarm, an architectural framework for the development of decision support modules for a variety of clinical applications. The need to quickly process patient vital signs and detect patient health events arises in many clinical scenarios, from clinical decision support to tele-health systems to home-care applications. The events detected during monitoring can be used as caregiver alarms, as triggers for further downstream processing or logging, or as discrete inputs to decision support systems or physiological closed-loop applications. We believe that all of these scenarios are similar, and share a common framework of design. In attempting to solve a particular instance of the problem, that of device alarm fatigue due to numerous false alarms, we devised a modular system based around this framework. This modular design allows us to easily customize the framework to address the specific needs of the various applications, and at the same time enables us to perform checking of consistency of the system. In the paper we discuss potential specific clinical applications of a generic smart alarm framework, present the proposed architecture of such a framework, and motivate the benefits of a generic framework for the development of new smart alarm or clinical decision support systems

Galactic-Scale Outflow and Supersonic Ram-Pressure Stripping in the Virgo Cluster Galaxy NGC 4388

The Hawaii Imaging Fabry-Perot Interferometer (HIFI) on the University of Hawaii 2.2m telescope was used to map the Halpha and [O III] 5007 A emission-line profiles across the entire disk of the edge-on Sb galaxy NGC 4388. We confirm a rich complex of highly ionized gas that extends ~4 kpc above the disk of this galaxy. Low-ionization gas associated with star formation is also present in the disk. Evidence for bar streaming is detected in the disk component and is discussed in a companion paper (Veilleux, Bland-Hawthorn, & Cecil 1999; hereafter VBC). Non-rotational blueshifted velocities of 50 - 250 km/s are measured in the extraplanar gas north-east of the nucleus. The brighter features in this complex tend to have more blueshifted velocities. A redshifted cloud is also detected 2 kpc south-west of the nucleus. The velocity field of the extraplanar gas of NGC 4388 appears to be unaffected by the inferred supersonic (Mach number M ~ 3) motion of this galaxy through the ICM of the Virgo cluster. We argue that this is because the galaxy and the high-|z| gas lie behind a Mach cone with opening angle ~ 80 degrees. The shocked ICM that flows near the galaxy has a velocity of ~ 500 km/s and exerts insufficient ram pressure on the extraplanar gas to perturb its kinematics. We consider several explanations of the velocity field of the extraplanar gas. Velocities, especially blueshifted velocities on the N side of the galaxy, are best explained as a bipolar outflow which is tilted by > 12 degrees from the normal to the disk. The observed offset between the extraplanar gas and the radio structure may be due to buoyancy or refractive bending by density gradients in the halo gas. Velocity substructure in the outflowing gas also suggests an interaction with ambient halo gas.Comment: 29 pages including 5 figures, Latex, requires aaspp4.sty, to appear in ApJ, 520 (July 20, 1999 issue