160 research outputs found
Characterization of the evolution of noble metal particles in a commercial threeâway catalyst: Correlation between real and simulated ageing
Ageing of automotive catalysts is associated to a loss of their functionality and ultimately to a waste of precious resources. For this reason, understanding catalyst ageing phenomena is necessary for the design of long lasting efficient catalysts. The present work has the purpose of studying in depth all the phenomena that occur during ageing, in terms of morphological modification and deactivation of the active materials: precious metal particles and oxidic support. The topic was deeply investigated using specific methodologies (FTâIR, CO chemisorption, FEâ SEM) in order to understand the behavior of metals and support, in terms of their surface properties, morphology and dispersion in the washcoat material. A series of commercial catalysts, aged in different conditions, have been analyzed, in order to find correlations between real and simulated ageing conditions. The characterization highlights a series of phenomena linked to the deactivation of the catalysts. Pd nanoparticles undergo a rapid agglomeration, exhibiting a quick loss of dispersion and of active sites with an increase of particles size. The evolution of the support allows highlighting also the contribution of chemical ageing effects. These results were also correlated with performance tests executed on synthetic gas bench, underlining a good correspondence between vehicle and laboratory aged samples and the contribution of chemical poisoning to vehicle aged ones. The collected data are crucial for the development of accelerated laboratory ageing protocols, which are instrumental for the development and testing of long lasting abatement systems
The Secondary Structure of a Major Wine Protein is Modified upon Interaction with Polyphenols
Polyphenols are an important constituent of wines and they are largely studied due to their antioxidant properties and for their effects on wine quality and stability, which is also related to their capacity to bind to proteins. The effects of some selected polyphenols, including procyanidins B1 and B2, tannic acid, quercetin, and rutin, as well as those of a total white wine procyanidin extract on the conformational properties of the major wine protein VVTL1 (Vitis vinifera Thaumatin-Like-1) were investigated by Synchrotron Radiation Circular Dichroism (SRCD). Results showed that VVTL1 interacts with polyphenols as demonstrated by the changes in the secondary (far-UV) and tertiary (near-UV) structures, which were differently affected by different polyphenols. Additionally, polyphenols modified the two melting temperatures (TM) that were found for VVTL1 (32.2 °C and 53.9 °C for the protein alone). The circular dichroism (CD) spectra in the near-UV region revealed an involvement of the aromatic side-chains of the protein in the interaction with phenolics. The data demonstrate the existence of an interaction between polyphenols and VVTL1, which results in modification of its thermal and UV denaturation pattern. This information can be useful in understanding the behavior of wine proteins in presence of polyphenols, thus giving new insights on the phenomena that are involved in wine stability
Rotational and high-resolution infrared spectrum of HCN: global ro-vibrational analysis and improved line catalogue for astrophysical observations
HCN is an ubiquitous molecule in interstellar environments, from external
galaxies, to Galactic interstellar clouds, star forming regions, and planetary
atmospheres. Observations of its rotational and vibrational transitions provide
important information on the physical and chemical structure of the above
environments. We present the most complete global analysis of the spectroscopic
data of HCN. We have recorded the high-resolution infrared spectrum from
450 to 1350 cm, a region dominated by the intense and
fundamental bands, located at 660 and 500 cm, respectively, and their
associated hot bands. Pure rotational transitions in the ground and
vibrationally excited states have been recorded in the millimetre and
sub-millimetre regions in order to extend the frequency range so far considered
in previous investigations. All the transitions from the literature and from
this work involving energy levels lower than 1000 cm have been fitted
together to an effective Hamiltonian. Because of the presence of various
anharmonic resonances, the Hamiltonian includes a number of interaction
constants, in addition to the conventional rotational and vibrational l-type
resonance terms. The data set contains about 3400 ro-vibrational lines of 13
bands and some 1500 pure rotational lines belonging to 12 vibrational states.
More than 120 spectroscopic constants have been determined directly from the
fit, without any assumption deduced from theoretical calculations or
comparisons with similar molecules. An extensive list of highly accurate rest
frequencies has been produced to assist astronomical searches and data
interpretation. These improved data, have enabled a refined analysis of the
ALMA observations towards Sgr B2(N2).Comment: 35 pages, 14 figures, accepted for pubblication in ApJ Supplemen
Weak Lensing Study in VOICE Survey II: Shear Bias Calibrations
The VST Optical Imaging of the CDFS and ES1 Fields (VOICE) Survey is proposed
to obtain deep optical imaging of the CDFS and ES1 fields using the VLT
Survey Telescope (VST). At present, the observations for the CDFS field have
been completed, and comprise in total about 4.9 deg down to
26 mag. In the companion paper by Fu et al. (2018), we
present the weak lensing shear measurements for -band images with seeing
0.9 arcsec. In this paper, we perform image simulations to calibrate
possible biases of the measured shear signals. Statistically, the properties of
the simulated point spread function (PSF) and galaxies show good agreements
with those of observations. The multiplicative bias is calibrated to reach an
accuracy of 3.0%. We study the bias sensitivities to the undetected faint
galaxies and to the neighboring galaxies. We find that undetected galaxies
contribute to the multiplicative bias at the level of 0.3%. Further
analysis shows that galaxies with lower signal-to-noise ratio (SNR) are
impacted more significantly because the undetected galaxies skew the background
noise distribution. For the neighboring galaxies, we find that although most
have been rejected in the shape measurement procedure, about one third of them
still remain in the final shear sample. They show a larger ellipticity
dispersion and contribute to 0.2% of the multiplicative bias. Such a bias
can be removed by further eliminating these neighboring galaxies. But the
effective number density of the galaxies can be reduced considerably. Therefore
efficient methods should be developed for future weak lensing deep surveys.Comment: 11 pages, 13 figures, 2 tables. MNRAS accepte
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Metabolic control of DNA methylation in naive pluripotent cells.
Naive epiblast and embryonic stem cells (ESCs) give rise to all cells of adults. Such developmental plasticity is associated with genome hypomethylation. Here, we show that LIF-Stat3 signaling induces genomic hypomethylation via metabolic reconfiguration. Stat3-/- ESCs show decreased α-ketoglutarate production from glutamine, leading to increased Dnmt3a and Dnmt3b expression and DNA methylation. Notably, genome methylation is dynamically controlled through modulation of α-ketoglutarate availability or Stat3 activation in mitochondria. Alpha-ketoglutarate links metabolism to the epigenome by reducing the expression of Otx2 and its targets Dnmt3a and Dnmt3b. Genetic inactivation of Otx2 or Dnmt3a and Dnmt3b results in genomic hypomethylation even in the absence of active LIF-Stat3. Stat3-/- ESCs show increased methylation at imprinting control regions and altered expression of cognate transcripts. Single-cell analyses of Stat3-/- embryos confirmed the dysregulated expression of Otx2, Dnmt3a and Dnmt3b as well as imprinted genes. Several cancers display Stat3 overactivation and abnormal DNA methylation; therefore, the molecular module that we describe might be exploited under pathological conditions
Metabolic control of DNA methylation in naive pluripotent cells.
Naive epiblast and embryonic stem cells (ESCs) give rise to all cells of adults. Such developmental plasticity is associated with genome hypomethylation. Here, we show that LIF-Stat3 signaling induces genomic hypomethylation via metabolic reconfiguration. Stat3-/- ESCs show decreased α-ketoglutarate production from glutamine, leading to increased Dnmt3a and Dnmt3b expression and DNA methylation. Notably, genome methylation is dynamically controlled through modulation of α-ketoglutarate availability or Stat3 activation in mitochondria. Alpha-ketoglutarate links metabolism to the epigenome by reducing the expression of Otx2 and its targets Dnmt3a and Dnmt3b. Genetic inactivation of Otx2 or Dnmt3a and Dnmt3b results in genomic hypomethylation even in the absence of active LIF-Stat3. Stat3-/- ESCs show increased methylation at imprinting control regions and altered expression of cognate transcripts. Single-cell analyses of Stat3-/- embryos confirmed the dysregulated expression of Otx2, Dnmt3a and Dnmt3b as well as imprinted genes. Several cancers display Stat3 overactivation and abnormal DNA methylation; therefore, the molecular module that we describe might be exploited under pathological conditions
A conformational switch controlling the toxicity of the prion protein
Prion infections cause conformational changes of the cellular prion protein (PrPC) and lead to progressive neurological impairment. Here we show that toxic, prion-mimetic ligands induce an intramolecular R208-H140 hydrogen bond (âH-latchâ), altering the flexibility of the α2âα3 and ÎČ2âα2 loops of PrPC. Expression of a PrP2Cys mutant mimicking the H-latch was constitutively toxic, whereas a PrPR207A mutant unable to form the H-latch conferred resistance to prion infection. High-affinity ligands that prevented H-latch induction repressed prion-related neurodegeneration in organotypic cerebellar cultures. We then selected phage-displayed ligands binding wild-type PrPC, but not PrP2Cys. These binders depopulated H-latched conformers and conferred protection against prion toxicity. Finally, brain-specific expression of an antibody rationally designed to prevent H-latch formation prolonged the life of prion-infected mice despite unhampered prion propagation, confirming that the H-latch is an important reporter of prion neurotoxicity
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