235 research outputs found
Characterization of Erbium-Doped Nanoparticles in Transparent Glass Ceramic Optical Fibres
We report on using nanometric mass spectroscopy and molecular dynamics modelling to characterize the composition and structure of self-grown erbium-doped nanoparticles in transparent glass ceramic optical fibres fabricated by modified chemical vapour deposition without post-ceramming
Erbium-doped transparent glass ceramic optical fibres: Characterization using mass spectroscopy and molecular dynamics modeling
Rare earth (RE) doped silica-based optical fibres with transparent glass ceramic (TGC) core were fabricated through the well-known modified chemical vapor deposition (MCVD) process without going through the commonly used stage of post-ceramming. The main characteristics of the RE-doped
dielectric nanoparticles (DNP), their density and mean diameter in thefibres are dictated by various parameters. This paper reports on progresses in the fine characterization of the nanopaticles, particularly their dimensions and composition, using nanosclae mass spectroscpy and molecular dynamics modeling, and alteration of the spectroscopic properties of the erbium ions embedded within the phospho-silicate DNP. These results permit to get more insight into the complex process of the
DNP self-nucleation and growth during the fibre fabrication process. This fabrication route could have important potentials in improving rare-earth-doped fibre amplifiers and laser sources
Co3O4 Nanocrystals on Graphene as a Synergistic Catalyst for Oxygen Reduction Reaction
Catalysts for oxygen reduction and evolution reactions are at the heart of
key renewable energy technologies including fuel cells and water splitting.
Despite tremendous efforts, developing oxygen electrode catalysts with high
activity at low costs remains a grand challenge. Here, we report a hybrid
material of Co3O4 nanocrystals grown on reduced graphene oxide (GO) as a
high-performance bi-functional catalyst for oxygen reduction reaction (ORR) and
oxygen evolution reaction (OER). While Co3O4 or graphene oxide alone has little
catalytic activity, their hybrid exhibits an unexpected, surprisingly high ORR
activity that is further enhanced by nitrogen-doping of graphene. The
Co3O4/N-doped graphene hybrid exhibits similar catalytic activity but superior
stability to Pt in alkaline solutions. The same hybrid is also highly active
for OER, making it a high performance non-precious metal based bi-catalyst for
both ORR and OER. The unusual catalytic activity arises from synergetic
chemical coupling effects between Co3O4 and graphene.Comment: published in Nature Material
Lipodystrophy-Linked LMNA p.R482W Mutation Induces Clinical Early Atherosclerosis and In Vitro Endothelial Dysfunction
Objective—Some mutations in LMNA, encoding A-type lamins, are responsible for Dunnigan-type-familial partial lipodystrophy (FPLD2), with altered fat distribution and metabolism. The high prevalence of early and severe cardiovascular outcomes in these patients suggests that, in addition to metabolic risk factors, FPLD2-associated LMNA mutations could have a direct role on the vascular wall cells.
Approach and Results—We analyzed the cardiovascular phenotype of 19 FPLD2 patients aged >30 years with LMNA p.R482 heterozygous substitutions, and the effects of p.R482W-prelamin-A overexpression in human coronary artery endothelial cells. In 68% of FPLD2 patients, early atherosclerosis was attested by clinical cardiovascular events, occurring before the age of 45 in most cases. In transduced endothelial cells, exogenous wild-type-prelamin-A was correctly processed and localized, whereas p.R482W-prelamin-A accumulated abnormally at the nuclear envelope. Patients’ fibroblasts also showed a predominant nuclear envelope distribution with a decreased rate of prelamin-A maturation. Only p.R482W-prelamin-A induced endothelial dysfunction, with decreased production of NO, increased endothelial adhesion of peripheral blood mononuclear cells, and cellular senescence. p.R482W-prelamin-A also induced oxidative stress, DNA damages, and inflammation. These alterations were prevented by treatment of endothelial cells with pravastatin, which inhibits prelamin-A farnesylation, or with antioxidants. In addition, pravastatin allowed the correct relocalization of p.R482W-prelamin-A within the endothelial cell nucleus. These data suggest that farnesylated p.R482W-prelamin-A accumulation at the nuclear envelope is a toxic event, leading to cellular oxidative stress and endothelial dysfunction.
Conclusions—LMNA p.R482 mutations, responsible for FPLD2, exert a direct proatherogenic effect in endothelial cells, which could contribute to patients’ early atherosclerosis
Evolution of Linear Absorption and Nonlinear Optical Properties in V-Shaped Ruthenium(II)-Based Chromophores
In this article, we describe a series of complexes with electron-rich cis-{Ru^(II)(NH_3)_4}^(2+) centers coordinated to two pyridyl ligands bearing N-methyl/arylpyridinium electron-acceptor groups. These V-shaped dipolar species are new, extended members of a class of chromophores first reported by us (Coe, B. J. et al. J. Am. Chem. Soc. 2005, 127, 4845−4859). They have been isolated as their PF_6− salts and characterized by using various techniques including ^1H NMR and electronic absorption spectroscopies and cyclic voltammetry. Reversible Ru^(III/II) waves show that the new complexes are potentially redox-switchable chromophores. Single crystal X-ray structures have been obtained for four complex salts; three of these crystallize noncentrosymmetrically, but with the individual molecular dipoles aligned largely antiparallel. Very large molecular first hyperpolarizabilities β have been determined by using hyper-Rayleigh scattering (HRS) with an 800 nm laser and also via Stark (electroabsorption) spectroscopic studies on the intense, visible d → π^* metal-to-ligand charge-transfer (MLCT) and π → π^* intraligand charge-transfer (ILCT) bands. The latter measurements afford total nonresonant β_0 responses as high as ca. 600 × 10^(−30) esu. These pseudo-C_(2v) chromophores show two substantial components of the β tensor, β_(zzz) and β_(zyy), although the relative significance of these varies with the physical method applied. According to HRS, β_(zzz) dominates in all cases, whereas the Stark analyses indicate that β_(zyy) is dominant in the shorter chromophores, but β_(zzz) and β_(zyy) are similar for the extended species. In contrast, finite field calculations predict that β_(zyy) is always the major component. Time-dependent density functional theory calculations predict increasing ILCT character for the nominally MLCT transitions and accompanying blue-shifts of the visible absorptions, as the ligand π-systems are extended. Such unusual behavior has also been observed with related 1D complexes (Coe, B. J. et al. J. Am. Chem. Soc. 2004, 126, 3880−3891)
Shrinking-Hole Colloidal Lithography: Self-Aligned Nanofabrication of Complex Plasmonic Nanoantennas
Plasmonic nanoantennas create locally strongly enhanced electric fields in so-called hot spots. To place a relevant nanoobject with high accuracy in such a hot spot is crucial to fully capitalize on the potential of nanoantennas to control, detect, and enhance processes at the nanoscale. With state-of-the-art nanofabrication, in particular when several materials are to be used, small gaps between antenna elements are sought, and large surface areas are to be patterned, this is a grand challenge. Here we introduce self-aligned, bottom-up and self-assembly based Shrinking-Hole Colloidal Lithography, which provides (i) unique control of the size and position of subsequently deposited particles forming the nanoantenna itself, and (ii) allows delivery of nanoobjects consisting of a material of choice to the antenna hot spot, all in a single lithography step and, if desired, uniformly covering several square centimeters of surface. We illustrate the functionality of SHCL nanoantenna arrangements by (i) an optical hydrogen sensor exploiting the polarization dependent sensitivity of an Au-Pd nanoantenna ensemble; and (ii) single particle hydrogen sensing with an Au dimer nanoantenna with a small Pd nanoparticle in the hot spot
Colossal dielectric constants in transition-metal oxides
Many transition-metal oxides show very large ("colossal") magnitudes of the
dielectric constant and thus have immense potential for applications in modern
microelectronics and for the development of new capacitance-based
energy-storage devices. In the present work, we thoroughly discuss the
mechanisms that can lead to colossal values of the dielectric constant,
especially emphasising effects generated by external and internal interfaces,
including electronic phase separation. In addition, we provide a detailed
overview and discussion of the dielectric properties of CaCu3Ti4O12 and related
systems, which is today's most investigated material with colossal dielectric
constant. Also a variety of further transition-metal oxides with large
dielectric constants are treated in detail, among them the system La2-xSrxNiO4
where electronic phase separation may play a role in the generation of a
colossal dielectric constant.Comment: 31 pages, 18 figures, submitted to Eur. Phys. J. for publication in
the Special Topics volume "Cooperative Phenomena in Solids: Metal-Insulator
Transitions and Ordering of Microscopic Degrees of Freedom
Altered adipocyte differentiation and unbalanced autophagy in type 2 Familial Partial Lipodystrophy: an in vitro and in vivo study of adipose tissue browning
Type-2 Familial Partial Lipodystrophy is caused by LMNA mutations. Patients gradually lose subcutaneous fat from the
limbs, while they accumulate adipose tissue in the face and neck. Several studies have demonstrated that autophagy is
involved in the regulation of adipocyte differentiation and the maintenance of the balance between white and brown
adipose tissue. We identified deregulation of autophagy in laminopathic preadipocytes before induction of
differentiation. Moreover, in differentiating white adipocyte precursors, we observed impairment of large lipid droplet
formation, altered regulation of adipose tissue genes, and expression of the brown adipose tissue marker UCP1.
Conversely, in lipodystrophic brown adipocyte precursors induced to differentiate, we noticed activation of autophagy,
formation of enlarged lipid droplets typical of white adipocytes, and dysregulation of brown adipose tissue genes. In
agreement with these in vitro results indicating conversion of FPLD2 brown preadipocytes toward the white lineage,
adipose tissue from FPLD2 patient neck, an area of brown adipogenesis, showed a white phenotype reminiscent of its
brown origin. Moreover, in vivo morpho-functional evaluation of fat depots in the neck area of three FPLD2 patients by
PET/CT analysis with cold stimulation showed the absence of brown adipose tissue activity. These findings highlight a
new pathogenetic mechanism leading to improper fat distribution in lamin A-linked lipodystrophies and show that
both impaired white adipocyte turnover and failure of adipose tissue browning contribute to disease.We thank FPLD2 patients for donating biological samples. We thank the Italian
Network for Laminopathies and the European Consortium of Lipodystrophies
(ECLip) for support and helpful discussion. We thank Aurelio Valmori for the
technical support. The studies were supported by Rizzoli Orthopedic Institute
“5 per mille” 2014 project to MC, AIProSaB project 2016 and Fondazione Del
Monte di Bologna e Ravenna grant 2015–2016 “New pharmacological
approaches in bone laminopathies based on the use of antibodies neutralizing
TGF beta 2” to GL. GL is also supported by PRIN MIUR project 2015FBNB5Y.S
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