Effect of Sb and MnO2-Doping on Phase Transitions, Crystal Structure, Thermal, Dielectric, Ferroelectric and Piezoelectric Properties of Na0.5K0.5NbO3 Ceramics

Lead-free ceramics of Na0.5K0.5Nb1-xSbxO3 (NKNS) and Na0.5K0.5Nb1-xSbxO3 + 0.5 mol%MnO2 (NKNS + 0.5 mol%MnO2) (0 < x < 0.06) ceramics were prepared by a conventional solid-state hot pressing method. The ceramics possess a single-phase perovskite structure with orthorhombic symmetry. Microstructural examination revealed that Mn doping of NKNS leads to improvement of densification. The cubic-tetragonal and tetragonal-orthorhombic phase transitions of NKNS shifted to higher and lower temperature, respectively after introduction of Mn ion. Besides, ferroelectric and piezoelectric properties were improved. The results were discussed in term of difference in both ionic size and electronegativity of Nb5+ and Sb5+ and improvement of densification after Mn ion doping

Neutron-Capture Elements in the Early Galaxy: Insights from a Large Sample of Metal-Poor Giants

New abundances for neutron-capture (n-capture) elements in a large sample of metal-poor giants from the Bond survey are presented. The spectra were acquired with the KPNO 4-m echelle and coude feed spectrographs, and have been analyzed using LTE fine-analysis techniques with both line analysis and spectral synthesis. Abundances of eight n-capture elements (Sr, Y, Zr, Ba, La, Nd, Eu, Dy) in 43 stars have been derived from blue (lambda = 4070--4710, R~20,000, S/N ratio~100-200) echelle spectra and red (lambda = 6100--6180, R~22,000, S/N ratio~100-200) coude spectra, and the abundance of Ba only has been derived from the red spectra for an additional 27 stars. Overall, the abundances show clear evidence for a large star-to-star dispersion in the heavy element-to-iron ratios. The new data also confirm that at metallicities [Fe/H] <~ --2.4, the abundance pattern of the heavy (Z >= 56) n-capture elements in most giants is well-matched to a scaled Solar System r-process nucleosynthesis pattern. The onset of the main r-process can be seen at [Fe/H] ~ --2.9. Contributions from the s-process can first be seen in some stars with metallicities as low as [Fe/H] ~ --2.75, and are present in most stars with metallicities [Fe/H] > --2.3. The lighter n-capture elements (Sr-Y-Zr) are enhanced relative to the heavier r-process element abundances. Their production cannot be attributed solely to any combination of the Solar System r- and main s-processes, but requires a mixture of material from the r-process and from an additional n-capture process which can operate at early Galactic time.Comment: Text + 5 Tables and 11 Figures: Submitted to the Astrophysical Journa

The Chemical Composition and Age of the Metal-Poor Halo Star BD +17^\circ 3248

We have combined new high-resolution spectra obtained with the Hubble Space Telescope (HST) and ground-based facilities to make a comprehensive new abundance analysis of the metal-poor, halo star BD +17^\circ 3248. We have detected the third r-process peak elements osmium, platinum, and (for the first time in a metal-poor star) gold, elements whose abundances can only be reliably determined using HST. Our observations illustrate a pattern seen in other similar halo stars with the abundances of the heavier neutron-capture elements, including the third r-process peak elements, consistent with a scaled solar system r-process distribution. The abundances of the lighter neutron-capture elements, including germanium and silver, fall below that same scaled solar r-process curve, a result similar to that seen in the ultra-metal-poor star CS 22892--052. A single site with two regimes or sets of conditions, or perhaps two different sites for the lighter and heavier neutron-capture elements, might explain the abundance pattern seen in this star. In addition we have derived a reliable abundance for the radioactive element thorium. We tentatively identify U II at 3859 A in the spectrum of BD +17^\circ 3248, which makes this the second detection of uranium in a very metal-poor halo star. Our combined observations cover the widest range in proton number (from germanium to uranium) thus far of neutron-capture elements in metal-poor Galactic halo stars. Employing the thorium and uranium abundances in comparison with each other and with several stable elements, we determine an average cosmochronological age for BD +17^\circ 3248 of 13.8 +/- 4 Gyr, consistent with that found for other similar metal-poor halo stars.Comment: 58 pages, 4 tables, 11 figures; To appear in ApJ Typo correcte

Dynamics of Metal Centers Monitored by Nuclear Inelastic Scattering

Nuclear inelastic scattering of synchrotron radiation has been used now since 10 years as a tool for vibrational spectroscopy. This method has turned out especially useful in case of large molecules that contain a M\"ossbauer active metal center. Recent applications to iron-sulfur proteins, to iron(II) spin crossover complexes and to tin-DNA complexes are discussed. Special emphasis is given to the combination of nuclear inelastic scattering and density functional calculations

Changes in Dietary Intake and Adherence to the NU-AGE Diet Following a One-Year Dietary Intervention among European Older Adults—Results of the NU-AGE Randomized Trial

Background: The Mediterranean Diet has been proposed as an effective strategy to reduce inflammaging, a chronic low grade inflammatory status, and thus, to slow down the aging process. We evaluated whether a Mediterranean-like dietary pattern specifically targeting dietary recommendations of people aged over 65 years (NU-AGE diet) could be effective to shift dietary intake of older adults towards a healthful diet. Methods: Adults aged 65–80 years across five EU-centers were randomly assigned to a NU-AGE diet group or control group. The diet group followed one year of NU-AGE dietary intervention specifying consumption of 15 food groups plus the use of a vitamin D supplement. Participants in the diet group received counselling and individually tailored dietary advice, food products and a vitamin D supplement. Dietary intake was assessed by means of seven-day food records at baseline and one-year follow-up. A continuous NU-AGE index (0–160 points) was developed to assess NU-AGE diet adherence. Results: In total 1296 participants were randomized and 1141 participants completed the intervention (571 intervention, 570 control). After one year, the diet group improved mean intake of 13 out of 16 NU-AGE dietary components (p < 0.05), with a significant increase in total NU-AGE index (difference in mean change = 21.3 ± 15.9 points, p < 0.01). Conclusions: The NU-AGE dietary intervention, based on dietary recommendations for older adults, consisting of individual dietary counselling, free healthy foods and a vitamin D supplement, may be a feasible strategy to improve dietary intake in an aging European population

Theoretical investigation of the electronic structure of Fe(II) complexes at spin-state transitions

The electronic structure relevant to low spin (LS)high spin (HS) transitions in Fe(II) coordination compounds with a FeN6 core are studied. The selected [Fe(tz)6]2+(1) (tz=1H-tetrazole), [Fe(bipy)3]2+(2) (bipy=2,2’-bipyridine) and [Fe(terpy)2]2+ (3) (terpy=2,2’:6’,2’’-terpyridine) complexes have been actively studied experimentally, and with their respective mono-, bi-, and tridentate ligands, they constitute a comprehensive set for theoretical case studies. The methods in this work include density functional theory (DFT), time-dependent DFT (TD-DFT) and multiconfigurational second order perturbation theory (CASPT2). We determine the structural parameters as well as the energy splitting of the LS-HS states (ΔEHL) applying the above methods, and comparing their performance. We also determine the potential energy curves representing the ground and low-energy excited singlet, triplet, and quintet d6 states along the mode(s) that connect the LS and HS states. The results indicate that while DFT is well suited for the prediction of structural parameters, an accurate multiconfigurational approach is essential for the quantitative determination of ΔEHL. In addition, a good qualitative agreement is found between the TD-DFT and CASPT2 potential energy curves. Although the TD-DFT results might differ in some respect (in our case, we found a discrepancy at the triplet states), our results suggest that this approach, with due care, is very promising as an alternative for the very expensive CASPT2 method. Finally, the two dimensional (2D) potential energy surfaces above the plane spanned by the two relevant configuration coordinates in [Fe(terpy)2]2+ were computed both at the DFT and CASPT2 levels. These 2D surfaces indicate that the singlet-triplet and triplet-quintet states are separated along different coordinates, i.e. different vibration modes. Our results confirm that in contrast to the case of complexes with mono- and bidentate ligands, the singlet-quintet transitions in [Fe(terpy)2]2+ cannot be described using a single configuration coordinate

The gene encoding the ketogenic enzyme HMGCS2 displays a unique expression during gonad development in mice

Disorders/differences of sex development (DSD) cause profound psychological and reproductive consequences for the affected individuals, however, most are still unexplained at the molecular level. Here, we present a novel gene, 3-hydroxy-3-methylglutaryl coenzyme A synthase 2 (HMGCS2), encoding a metabolic enzyme in the liver important for energy production from fatty acids, that shows an unusual expression pattern in developing fetal mouse gonads. Shortly after gonadal sex determination it is up-regulated in the developing testes following a very similar spatial and temporal pattern as the male-determining gene Sry in Sertoli cells before switching to ovarian enriched expression. To test if Hmgcs2 is important for gonad development in mammals, we pursued two lines of investigations. Firstly, we generated Hmgcs2-null mice using CRISPR/Cas9 and found that these mice had gonads that developed normally even on a sensitized background. Secondly, we screened 46,XY DSD patients with gonadal dysgenesis and identified two unrelated patients with a deletion and a deleterious missense variant in HMGCS2 respectively. However, both variants were heterozygous, suggesting that HMGCS2 might not be the causative gene. Analysis of a larger number of patients in the future might shed more light into the possible association of HMGCS2 with human gonadal development.Stefan Bagheri-Fam, Huijun Chen, Sean Wilson, Katie Ayers, James Hughes, Frederique Sloan-Bena, Pierre Calvel, Gorjana Robevska, Beatriz Puisac, Kamila Kusz-Zamelczyk, Stefania Gimelli, Anna Spik, Jadwiga Jaruzelska, Alina Warenik-Szymankiewicz, Sultana Faradz, Serge Nef, Juan Pie, Paul Thomas, Andrew Sinclair, Dagmar Wilhel

The extreme r-element rich, iron-poor halo giant CS31082-001: Implications for the r-process site(s) and radioactive cosmochronology

We present a high-resolution spectroscopic analysis of the bright (V=11.7), extreme halo giant CS31082-001 ([Fe/H] = -2.9), obtained in an ESO-VLT Large Programme dedicated to very metal-poor stars. We find CS31082-001 to be extremely rich in r-process elements, comparable in this respect only to the similarly metal-poor, but carbon-enriched, giant CS22892-052. As a result of the extreme overabundance of the heaviest r-process elements, and negligible blending from CH and CN molecular lines, a reliable measurement is obtained of the U II line at 386 nm, for the first time in a halo star, along with numerous lines of Th II, as well as lines of 25 other r-process elements. Abundance estimates for a total of 43 elements are reported in CS31082-001, almost half of the entire periodic table. All elements with 56 \leq Z \leq 72 follow the Solar r-element pattern, reduced by about 1.25 dex ([r/Fe]=+1.7 dex, a factor 50). Pb, in contrast, seems to be below the shifted Solar r-process distribution, possibly indicating an error in the latter, while thorium is more enhanced than the lighter nuclides. Thus, while a universal production ratio for the r-process elements seems to hold in the interval 56 \leq Z \leq 72, it breaks down in the actinide region. When available, the U/Th is thus preferable to Th/Eu for radioactive dating: (i) because of its faster decay rate and smaller sensitivity to observational errors, and (ii) because the inital production ratio of the neighboring nuclides 238U and 232Th is more robustly predicted than the 151Eu/232Th ratio. Our current best estimate for the age of CS31082-001 is 14.0+/-2.4 Gyr

Membrane fluidity matters: Hyperthermia from the aspects of lipids and membranes

Hyperthermia is a promising treatment modality for cancer in combination both with radio- and chemotherapy. In spite of its great therapeutic potential, the underlying molecular mechanisms still remain to be clarified. Due to lipid imbalances and 'membrane defects' most of the tumour cells possess elevated membrane fluidity. However, further increasing membrane fluidity to sensitise to chemo-or radiotherapy could have some other effects. In fact, hyperfluidisation of cell membrane induced by membrane fluidiser initiates a stress response as the heat shock protein response, which may modulate positively or negatively apoptotic cell death. Overviewing some recent findings based on a technology allowing direct imaging of lipid rafts in live cells and lipidomics, novel aspects of the intimate relationship between the 'membrane stress' of tumour cells and the cellular heat shock response will be highlighted. Our findings lend support to both the importance of membrane remodelling and the release of lipid signals initiating stress protein response, which can operate in tandem to control the extent of the ultimate cellular thermosensitivity. Overall, we suggest that the fluidity variable of membranes should be used as an independent factor for predicting the efficacy of combinational cancer therapies