Finite-size effects in lead scandium tantalate relaxor thin films

Large electromechanical effects in relaxor ferroelectrics are generally attributed to the collective response of an ensemble of correlated, nanometer-sized polar structures induced by chemical and charge disorder. Here, we study finite-size effects on such polar order (i.e., how it evolves when sample dimensions approach the polarization correlation length) in 7-70-nm-thick films of the relaxor ferroelectric PbSc0.5Ta0.5O3. Temperature-dependent polarization studies reveal a linear suppression of the polarization and nonlinearity associated with relaxor order as the film thickness decreases to ≈30 nm. Below this thickness, however, the suppression rapidly accelerates, and polarization is completely absent by film thicknesses of ≈7 nm, despite the continued observation of a broad peak in dielectric permittivity and frequency dispersion. Diffuse-scattering measurements reveal the diffuse-scattering symmetry, and analysis suggests the films have a polarization correlation length of ≈23 nm. Taken together, it is apparent that reduction of sample size and the resulting distribution of polar structures drive suppression and eventual quenching of the electrical response of relaxors, which may be attributed to increasing dipole-dipole and dipole-interface interactions

The largest oxigen bearing organic molecule repository

We present the first detection of complex aldehydes and isomers in three typical molecular clouds located within 200pc of the center of our Galaxy. We find very large abundances of these complex organic molecules (COMs) in the central molecular zone (CMZ), which we attribute to the ejection of COMs from grain mantles by shocks. The relative abundances of the different COMs with respect to that of CH3OH are strikingly similar for the three sources, located in very different environments in the CMZ. The similar relative abundances point toward a unique grain mantle composition in the CMZ. Studying the Galactic center clouds and objects in the Galactic disk having large abundances of COMs, we find that more saturated molecules are more abundant than the non-saturated ones. We also find differences between the relative abundance between COMs in the CMZ and the Galactic disk, suggesting different chemical histories of the grain mantles between the two regions in the Galaxy for the complex aldehydes. Different possibilities for the grain chemistry on the icy mantles in the GC clouds are briefly discussed. Cosmic rays can play an important role in the grain chemistry. With these new detections, the molecular clouds in the Galactic center appear to be one of the best laboratories for studying the formation of COMs in the Galaxy.Comment: 20 pages, 4 figures, accepted in Ap

Large Polarization and Susceptibilities in Artificial Morphotropic Phase Boundary PbZr1−xTixO3 Superlattices

The ability to produce atomically precise, artificial oxide heterostructures allows for the possibility of producing exotic phases and enhanced susceptibilities not found in parent materials. Typical ferroelectric materials either exhibit large saturation polarization away from a phase boundary or large dielectric susceptibility near a phase boundary. Both large ferroelectric polarization and dielectric permittivity are attained wherein fully epitaxial (PbZr0.8Ti0.2O3)n/(PbZr0.4Ti0.6O3)2n (n = 2, 4, 6, 8, 16 unit cells) superlattices are produced such that the overall film chemistry is at the morphotropic phase boundary, but constitutive layers are not. Long- (n ≥ 6) and short-period (n = 2) superlattices reveal large ferroelectric saturation polarization (Ps = 64 µC cm−2) and small dielectric permittivity (εr ≈ 400 at 10 kHz). Intermediate-period (n = 4) superlattices, however, exhibit both large ferroelectric saturation polarization (Ps = 64 µC cm−2) and dielectric permittivity (εr = 776 at 10 kHz). First-order reversal curve analysis reveals the presence of switching distributions for each parent layer and a third, interfacial layer wherein superlattice periodicity modulates the volume fraction of each switching distribution and thus the overall material response. This reveals that deterministic creation of artificial superlattices is an effective pathway for designing materials with enhanced responses to applied bias

Cultivation and anaerobic digestion of Scenedesmus spp. grown in a pilot-scale open raceway

Digestibility of a micro-algal mixture was evaluated by mesophilic anaerobic digestion in continuously-stirred tank reactors. The culture consisted primarily of Scenedesmus spp. continuously cultivated over a 6-month period in a 100 m2 raceway reactor instrumented to record pH, dissolved oxygen and temperature. The raceway received supplementary carbon in the form of flue gas from a diesel boiler (10% CO2) injected into a 1-m deep sump to control pH in the range 7.8–8.0. Dilution was optimised to biomass productivity and gave values of 10–15 and 20–25 g total suspended solids (TSS) m? 2 day? 1 in winter (December–February) and spring (April–May), respectively. The culture for the anaerobic digestion trial was harvested in February by centrifugation to give an algal paste containing 4.3% volatile solids (VS). Semi-continuous digestion at organic loading rates of 2.00, 2.75 and 3.50 g VS l? 1 day? 1 gave volumetric biogas productions of ~ 0.66, ~ 0.83 and ~ 0.99 l l? 1 day? 1, respectively. Specific methane yield ranged from 0.13 to 0.14 l CH4 g? 1 VSadded with biogas methane content ~ 62%. Overall the digestion process was stable, but only ~ 30% VS destruction was achieved indicating low biodegradability, due to the short retention times and the recalcitrant nature of this type of biomas

Chemistry in isolation: High CCH/HCO+ line ratio in the AMIGA galaxy CIG 638

Multi-molecule observations towards an increasing variety of galaxies have been showing that the relative molecular abundances are affected by the type of activity. However, these studies are biased towards bright active galaxies, which are typically in interaction. We study the molecular composition of one of the most isolated galaxies in the local Universe where the physical and chemical properties of their molecular clouds have been determined by intrinsic mechanisms. We present 3 mm broad band observations of the galaxy CIG 638, extracted from the AMIGA sample of isolated galaxies. The emission of the J=1-0 transitions of CCH, HCN, HCO+, and HNC are detected. Integrated intensity ratios between these line are compared with similar observations from the literature towards active galaxies including starburst galaxies (SB), active galactic nuclei (AGN), luminous infrared galaxies (LIRG), and GMCs in M33. A significantly high ratio of CCH with respect to HCN, HCO+, and HNC is found towards CIG 638 when compared with all other galaxies where these species have been detected. This points to either an overabundance of CCH or to a relative lack of dense molecular gas as supported by the low HCN/CO ratio, or both. The data suggest that the CIG 638 is naturally a less perturbed galaxy where a lower fraction of dense molecular gas, as well as a more even distribution could explain the measured ratios. In this scenario the dense gas tracers would be naturally dimmer, while the UV enhanced CCH, would be overproduced in a less shielded medium.Comment: Letter accepted for publication in A&

Cell-autonomous programming of rat adipose tissue insulin signalling proteins by maternal nutrition.

AIMS/HYPOTHESIS: Individuals with a low birthweight have an increased risk of developing type 2 diabetes mellitus in adulthood. This is associated with peripheral insulin resistance. Here, we aimed to determine whether changes in insulin signalling proteins in white adipose tissue (WAT) can be detected prior to the onset of impaired glucose tolerance, determine whether these changes are cell-autonomous and identify the underlying mechanisms involved. METHODS: Fourteen-month-old male rat offspring born to dams fed a standard protein (20%) diet or a low (8%) protein diet throughout gestation and lactation were studied. Fat distribution and adipocyte size were determined. Protein content and mRNA expression of key insulin signalling molecules were analysed in epididymal WAT and in pre-adipocytes that had undergone in vitro differentiation. RESULTS: The offspring of low protein fed dams (LP offspring) had reduced visceral WAT mass, altered fat distribution and a higher percentage of small adipocytes in epididymal WAT. This was associated with reduced levels of IRS1, PI3K p110β, Akt1 and PKCζ proteins and of phospho-Akt Ser473. Corresponding mRNA transcript levels were unchanged. Similarly, in vitro differentiated adipocytes from LP offspring showed reduced protein levels of IRβ, IRS1, PI3K p85α and p110β subunits, and Akt1. Levels of Akt Ser473 and IRS1 Tyr612 phosphorylation were reduced, while IRS1 Ser307 phosphorylation was increased. CONCLUSIONS/INTERPRETATION: Maternal protein restriction during gestation and lactation changes the distribution and morphology of WAT and reduces the levels of key insulin signalling proteins in the male offspring. This phenotype is retained in in vitro differentiated adipocytes, suggesting that programming occurs via cell-autonomous mechanism(s).This work was supported by Diabetes UK (MSM-G; no. 12/0004508), the British Heart Foundation (SEO; no. FS/09/029/27902) and the UK Medical Research Council (SEO; no. MC_UU_12012/4)This is the accepted manuscript. It is currently embargoed pending publication

Novel domain architectures and functional determinants in atypical annexins revealed by phylogenomic analysis.

The fundamental cellular role and molecular interactions of annexins in vesicle trafficking and membrane remodeling remain to be further clarified in order to better understand and exploit their contributions to health and disease. We focused on distinctive features of atypical annexins from all domains of life using phylogenomic, molecular systematic and experimental approaches, to extend the current paradigm and better account for annexin diversity of structure, function and mechanistic role in membrane homeostasis. The analysis of gene duplications, organization of domain architectures and profile hidden Markov models of subfamily orthologs defined conserved structural features relevant to molecular interactions and functional divergence of seven family clades ANXA-G. Single domain annexins of bacteria, including cyanobacteria, were frequently coupled to enzymatic units conceivably related to membrane metabolism and remodeling. Multiple ANX domains (up to 20) and various distinct functional domains were observed in unique annexins. Canonical type 2 calcium binding ligands were well-preserved in roughly half of all ANX domains, but alternative structural motifs comprised of 'KGD', cysteine or tryptophan residues were prominently conserved in the same strategic interhelical loops. Selective evolutionary constraint, site-specific location and co-occurrence in all kingdoms identify alternative modes of fundamental binding interactions for annexins

Insulin secretion profiles are modified by overexpression of glutamate dehydrogenase in pancreatic islets

Aims/hypothesis: Glutamate dehydrogenase (GDH) is a mitochondrial enzyme playing a key role in the control of insulin secretion. However, it is not known whether GDH expression levels in beta cells are rate-limiting for the secretory response to glucose. GDH also controls glutamine and glutamate oxidative metabolism, which is only weak in islets if GDH is not allosterically activated by L-leucine or (+/−)-2-aminobicyclo-[2,2,1]heptane-2-carboxylic acid (BCH). Methods: We constructed an adenovirus encoding for GDH to overexpress the enzyme in the beta-cell line INS-1E, as well as in isolated rat and mouse pancreatic islets. The secretory responses to glucose and glutamine were studied in static and perifusion experiments. Amino acid concentrations and metabolic parameters were measured in parallel. Results: GDH overexpression in rat islets did not change insulin release at basal or intermediate glucose (2.8 and 8.3mmol/l respectively), but potentiated the secretory response at high glucose concentrations (16.7mmol/l) compared to controls (+35%). Control islets exposed to 5mmol/l glutamine at basal glucose did not increase insulin release, unless BCH was added with a resulting 2.5-fold response. In islets overexpressing GDH glutamine alone stimulated insulin secretion (2.7-fold), which was potentiated 2.2-fold by adding BCH. The secretory responses evoked by glutamine under these conditions correlated with enhanced cellular metabolism. Conclusions/interpretation: GDH could be rate-limiting in glucose-induced insulin secretion, as GDH overexpression enhanced secretory responses. Moreover, GDH overexpression made islets responsive to glutamine, indicating that under physiological conditions this enzyme acts as a gatekeeper to prevent amino acids from being inappropriate efficient secretagogue

Dietary nitrate increases arginine availability and protects mitochondrial complex I and energetics in the hypoxic rat heart

This is the final version. It was first published by Wiley in The Journal of Physiology at http://onlinelibrary.wiley.com/doi/10.1113/jphysiol.2014.275263/abstract.Hypoxic exposure is associated with impaired cardiac energetics in humans and altered mitochondrial function, with suppressed complex I-supported respiration, in rat heart. This response might limit reactive oxygen species (ROS) generation, but at the cost of impaired electron transport chain (ETC) activity. Dietary nitrate supplementation improves mitochondrial efficiency and can promote tissue oxygenation by enhancing blood flow. We therefore hypothesised that ETC dysfunction, impaired energetics and oxidative damage in the hearts of rats exposed to chronic hypoxia could be alleviated by sustained administration of a moderate dose of dietary nitrate. Male Wistar rats (n=40) were given water supplemented with 0.7 mmol/L NaCl (as control) or 0.7 mmol/L NaNO3, elevating plasma nitrate levels by 80%, and were exposed to 13% O2 (hypoxia) or normoxia (n=10 per group) for 14 days. Respiration rates, ETC protein levels, mitochondrial density, ATP content and protein carbonylation were measured in cardiac muscle. Complex I respiration rates and protein levels were 33% lower in hypoxic/NaCl rats compared with normoxic/NaCl controls. Protein carbonylation was 65% higher in hearts of hypoxic rats compared with controls, indicating increased oxidative stress, whilst ATP levels were 62% lower. Respiration rates, complex I protein and activity, protein carbonylation and ATP levels were all fully protected in the hearts of nitrate-supplemented hypoxic rats. Both in normoxia and hypoxia, dietary nitrate suppressed cardiac arginase expression and activity and markedly elevated cardiac L-arginine concentrations, unmasking a novel mechanism of action by which nitrate enhances tissue NO bioavailability. Dietary nitrate therefore alleviates metabolic abnormalities in the hypoxic heart, improving myocardial energetics