Barium zinc borosilicate glasses with a molar composition xBaO-(60-x)ZnO-30B 2O 3-10SiO 2, where x ranged from 0 to 60 mol%, were prepared using melt-quenching method. The effect of BaO substitution for ZnO on the sintering, crystallization, and dielectric characteristics has been investigated. The behavior of the studied barium zinc borosilicate glasses was mainly determined by the relative amount of the structural modifier oxides (BaO and ZnO) and the ionic size, and field strength of the modifying cations (Ba 2+, Zn 2+). Increased amounts of BaO decreased both glass transition temperature and crystallization temperature, while increasing the relative dielectric constant. Sintering occurred before crystallization for glasses where substitution of BaO for ZnO was up to 30 mol%, but for higher substitution levels, crystallization occurred during the sintering process hindering densification. © 2012 The American Ceramic Society.

Ferritins are ubiquitous and can be found in practically all organisms that utilize Fe. They are composed of 24 subunits forming a hollow sphere with an inner cavity of similar to 80 angstrom in diameter. The main function of ferritin is to oxidize the cytotoxic Fe2+ ions and store the oxidized Fe in the inner cavity. It has been established that the initial step of rapid oxidation of Fe2+ (ferroxidation) by H-type ferritins, found in vertebrates, occurs at a diiron binding center, termed the ferroxidase center. In bacterial ferritins, however, X-ray crystallographic evidence and amino acid sequence analysis revealed a trinuclear Fe binding center comprising a binuclear Fe binding center (sites A and B), homologous to the ferroxidase center of H-type ferritin, and an adjacent mononuclear Fe binding site (site C). In an effort to obtain further evidence supporting the presence of a trinuclear Fe binding center in bacterial ferritins and to gain information on the states of the iron bound to the trinuclear center, bacterial ferritin from Desulfovibrio vulgaris (DvFtn) and its E130A variant was loaded with substoichiometric amounts of Fe2+, and the products were characterized by Mossbauer and EPR spectroscopy. Four distinct Fe species were identified: a paramagnetic diferrous species, a diamagnetic diferrous species, a mixed valence Fe2+Fe3+ species, and a mononuclear Fe2+ species. The latter three species were detected in the wild-type DvFtn, while the paramagnetic diferrous species was detected in the E130A variant. These observations can be rationally explained by the presence of a trinuclear Fe binding center, and the four Fe species can be properly assigned to the three Fe binding sites. Further, our spectroscopic data suggest that (1) the fully occupied trinuclear center supports an all ferrous state, (2) sites B and C are bridged by a mu-OH group forming a diiron subcenter within the trinuclear center, and (3) this subcenter can afford both a mixed valence Fe2+Fe3+ state and a diferrous state. Mechanistic insights provided by these new findings are discussed and a minimal mechanistic scheme involving O-O bond cleavage is proposed.

Borosilicate glass-alumina composites with (1 - x) Glass + x Al 2O 3 (x = 0, 5, 10, 25 vol.%) were prepared and the effect of Al 2O 3 addition on the structural, electrical and thermal characteristics was investigated. XRD patterns revealed the presence of cristobalite (SiO 2) in sintered borosilicate glass and that the addition of Al 2O 3 hinders cristobalite formation. This behavior is due to the diffusion of some Al 3+ ions from alumina to glass, which leads to changes in glass structure and composition as identified by SEM/EDS. Cristobalite was undetected in composites containing 10% Al 2O 3 that attained the lowest thermal expansion coefficient value (∼4.6 × 10 -6 °C -1). Conductivity (dc and ac) increased with the amount of Al 3+ ions present in the glass structure as modifiers and formers. Dielectric constant values, in the range 5.0-7.2, increased with Al 2O 3 addition and the values of loss tan δ (1.5-2.1 × 10 -2) indicate that these materials are good insulators. © 2012 Elsevier B.V. All rights reserved.

The enzymatic (tyrosinase) and chemical (NaIO4, Ag2O or Fremys's salt) oxidation of biologically relevant catecholamines, such as dopamine (DA), N-acetyldopamine (NADA) and the Ecstasy metabolites (alpha-MeDA and N-Me-alpha-MeDA) generates the corresponding o-quinone which can be trapped with nitrogen bionucleophiles such as N-acetyl-histidine and imidazole in a regioselective reaction that takes place predominantly at the 6-position of the catecholamine. (C) 2012 Elsevier Inc. All rights reserved.

Sintered silicon nitride (Si3N4) ceramic substrates were investigated as dielectric substrates for the growth of metal-like boron-doped nanocrystalline diamond (NCD) and microcrystalline diamond coatings via the Hot Filament Chemical Vapor Deposition (HFCVD) technique. The structural, electrical and chemical properties of both the ceramic substrates and the diamond coatings may potentiate their applicability in particular in harsh environments and highly demanding situations. Boron doping was achieved via a boron oxide solution in ethanol dragged into the reaction chamber with argon. The coatings were characterized by scanning elec- tron microscopy, UV $μ$-Raman scattering, X-ray diffraction, time-of-flight secondary ion mass spectroscopy, Brale indentation for adhesion evaluation and two-point contact probe for resistivity measurements. The HFCVD technique led to a maximal growth rate of about 1 $μ$m/h. Several metal-like boron doped diamond coatings were obtained. It was found that at lower substrate temperature, lower system pressure and higher methane concentration, the resistivity of the conducting NCD coatings is about 3 orders of magnitude higher when compared with samples obtained with higher substrate temperature, higher system pressure and lower methane concentration. Nevertheless, for every metal-like boron-doped coating the use of the Si3N4 ceramic substrate guaranteed a superior adhesion level. ©

Human articular cartilage functions under a wide range of mechanical loads in synovial joints, where hydrostatic pressure (HP) is the prevalent actuating force. We hypothesized that the formation of engineered cartilage can be augmented by applying such physiologic stimuli to chondrogenic cells or stem cells, cultured in hydrogels, using custom-designed HP bioreactors. To test this hypothesis, we investigated the effects of distinct HP regimens on cartilage formation in vitro by either human nasal chondrocytes (HNCs) or human adipose stem cells (hASCs) encapsulated in gellan gum (GG) hydrogels. To this end, we varied the frequency of low HP, by applying pulsatile hydrostatic pressure or a steady hydrostatic pressure load to HNC-GG constructs over a period of 3 weeks, and evaluated their effects on cartilage tissue-engineering outcomes. HNCs (10×10 6 cells/mL) were encapsulated in GG hydrogels (1.5{%}) and cultured in a chondrogenic medium under three regimens for 3 weeks: (1) 0.4 MPa Pulsatile HP; (2) 0.4 MPa Steady HP; and (3) Static. Subsequently, we applied the pulsatile regimen to hASC-GG constructs and varied the amplitude of loading, by generating both low (0.4 MPa) and physiologic (5 MPa) HP levels. hASCs (10×10 6 cells/mL) were encapsulated in GG hydrogels (1.5{%}) and cultured in a chondrogenic medium under three regimens for 4 weeks: (1) 0.4 MPa Pulsatile HP; (2) 5 MPa Pulsatile HP; and (3) Static. In the HNC study, the best tissue development was achieved by the pulsatile HP regimen, whereas in the hASC study, greater chondrogenic differentiation and matrix deposition were obtained for physiologic loading, as evidenced by gene expression of aggrecan, collagen type II, and sox-9; metachromatic staining of cartilage extracellular matrix; and immunolocalization of collagens. We thus propose that both HNCs and hASCs detect and respond to physical forces, thus resembling joint loading, by enhancing cartilage tissue development in a frequency- and amplitude-dependant manner. © Copyright 2012, Mary Ann Liebert, Inc.

Thin-films of copper oxide @Cu OA were sputtered from a metallic copper (Cu) target and studied as a function of oxygen partial pressure @O??A. A metallic Cu film with cubic structure obtained from 0{%} O?? has been transformed to cubic CuPO phase for the increase in O?? to 9{%} but then changed to monoclinic CuO phase (for O?? PS7). The variation in crystallite size (calculated from x-ray diffraction data) was further substantiated by the variation in grain size (surface microstruc- tures). The Cu O films produced with O?? ranging between 9{%} and 75{%} showed p-type behavior, which were successfully applied to produce thin-film transistors.