Cellular Disulfide Bond Formation in Bioactive Peptides and Proteins

Bioactive peptides play important roles in metabolic regulation and modulation and many are used as therapeutics. These peptides often possess disulfide bonds, which are important for their structure, function and stability. A systematic network of enzymes—a disulfide bond generating enzyme, a disulfide bond donor enzyme and a redox cofactor—that function inside the cell dictates the formation and maintenance of disulfide bonds. The main pathways that catalyze disulfide bond formation in peptides and proteins in prokaryotes and eukaryotes are remarkably similar and share several mechanistic features. This review summarizes the formation of disulfide bonds in peptides and proteins by cellular and recombinant machinery.     

Magnetic properties of new manganese ferrites submicron particles

New manganese defect metastable ferrites with spinal structure were prepared by oxidation at a temperature lower than 500°C of submicron manganese substituted magnetites, Fe3-xMNxO4(0 leq x < 1). X-ray diffraction measurements and thermal analysis studies have been carried out on these systems. Low-temperature magnetic measurements have also been carried out. With these studies, it has been possible to depict the cation distribution in substituted magnetites and oxidized compounds, and to understand the complex process of oxidation. In defect spinels, vacancies are formed not only from oxidation of Fe²⁺ions, but also of Mn²⁺and Mn³⁺ions. Manganese-rich compound with x = 0.97 having high content of Mn³⁺and Mn⁴⁺ions show an important increase in coercive force, which exceeds 700 Oe at 4.2 K.     

Study by thermogravimetry,electrical conductivity and IR spectrometry of the phase transition for manganese cation deficient spinels

Thermogravimetry, electrical conductivity and IR spectrometry were used to study the crystal structure change of the metastable manganese cation deficient spinels that occur during the oxidation of manganese ions above 500° C. The kinetic of the transformation is found to be governed by a nucleation growth mechanism with an activation energy varying with the amount of Mn³⁺ ions. The nature of the inversion products depends on the manganese substitution extent. We observe for a substitution extent x<0.72 a phase with a corundum structure which is a solid solution of -(MnFe)₂O₃ and for x>0.72 a mixture of two phases -(MnFe)₂O₃ + Mn₂O₃ of orthorhombic structure.     

Electrical conductivity study of oxidation process in manganese-substituted magnetites

During oxidation in air of finely-grained manganese-substituted magnetites (Mn _0.8x ²⁺ Fe _1–0.8x ³⁺ )_A– (Fe _1+0.6x ³⁺ Fe _1–0.8x ²⁺ Mn _0.2x ³⁺ )_BO ₄ ^2– (A=tetrahedral, B=octahedral) the temperature dependence of the electrical conductivity over a temperature range of 100 to 700° C was investigated. Below 500° C the evolution of electrical conductivity might be closely associated with the position and nature of cations in the spinel lattice. The profile of the =f(t) curves show that the mechanism of electrical conduction in the temperature range 150 to 300° C can be explained in terms of the oxidation of Fe²⁺ to Fe³⁺ ions at octahedral sites. For the temperature range 300 to 400° C the conductivity involves the hopping of electrons from tetrahedral-site Mn²⁺ ions to tetrahedral-site Mn³⁺ ions. Above 500° C the oxidation of Mn²⁺ ions leads to an increase in conductivity with the generation of new phases of -Fe₂O₃, Mn₂O₃ and -(MnFe)₂O₃.     

Understanding the Glycopeptide Antibiotic Crosslinking Cascade: In Vitro Approaches Reveal the Details of a Complex Biosynthesis Pathway

The glycopeptide antibiotics (GPAs) are a fascinating example of complex natural product biosynthesis, with the nonribosomal synthesis of the peptide core coupled to a cytochrome P450-mediated cyclisation cascade that crosslinks aromatic side chains within this peptide. Given that the challenges associated with the synthesis of GPAs stems from their highly crosslinked structure, there is great interest in understanding how biosynthesis accomplishes this challenging set of transformations. In this regard, the use of in vitro experiments has delivered important insights into this process, including the identification of the unique role of the X-domain as a platform for P450 recruitment. In this minireview, we present an analysis of the results of in vitro studies into the GPA cyclisation cascade that have demonstrated both the tolerances and limitations of this process for modified substrates, and in turn developed rules for the future reengineering of this important antibiotic class.     

Elaboration and characterization of Fe1-xO thin films sputter deposited from magnetite target

Majority of the authors report elaboration of iron oxide thin films by reactive magnetron sputtering from an iron target with Ar-O₂ gas mixture. Instead of using the reactive sputtering of a metallic target we report here the preparation of Fe_1-xO thin films, directly sputtered from a magnetite target in a pure argon gas flow with a bias power applied. This oxide is generally obtained at very low partial oxygen pressure and high temperature. We showed that bias sputtering which can be controlled very easily can lead to reducing conditions during deposition of oxide thin film on simple glass substrates. The proportion of wustite was directly adjusted by modifying the power of the substrate polarization. Atomic force microscopy was used to observe these nanostructured layers. Mössbauer measurements and electrical properties versus bias polarization and annealing temperature are also reported.     

High performances boron doped γ-Fe2O3particles prepared from oxalic precursors

γ-Fe₂O₃ particles (L≈0.15 to 0.2 μm, L/D≈2 to 5) with coercivity up to 400 Oe have been prepared from oxalic precursors. To preserve the particle form, the oxalates were doped with boron. The effects due to this element was studied during the different thermal treatments which effect the pseudomorphous transformation of oxalate particles into spinel ferrite. ESCA spectroscopy, and X-ray measurements could point out the presence of a Fe₃BO₅ phase at the surface of γ-Fe₂O₃ particles. In spite of the important mass losses (H₂O, CO, CO₂) and the important crystallographic structure modifications occurring during the transformation of oxalate into magnetic oxide, γ-Fe₂O ₃ particles obtained by this method have very good textural characteristics. Boron-doped γ-Fe₂O₃ particles were used to make 3.5-in diskettes with standard formulation. In these conditions, media properties were comparable to trading diskettes properties     

Synthesis of La2−xNiO4+δ oxides by polymeric route: non-stoichoimetry control

The synthesis of La_2−xNiO_4+δ oxides has been done via a polymeric route. This method allows the preparation of a wide range of non-stoichoimetry values. Oxides with values as high as 0.25 have been synthesised. Correlations between processing parameters such as sol composition and heat treatment have been done with structural and microstructural properties of the oxides. In our synthesis conditions, the higher the mean grain size, the higher the non-stoichoimetry level.

Transmission electron microscopy on these oxides has shown that whatever the non-stoichoimetry level, the extra-oxygen arranges in the structure according to two superstructures which correspond to δ=0.25 and δ=0.17. This shows that our grains consist of a mixture of these compositions.     

Copper and iron based thin film nanocomposites prepared by radio frequency sputtering. Part I: elaboration and characterization of metal/oxide thin film nanocomposites using controlled in situ reduction process

Copper and iron based thin films were prepared on glass substrate by radio-frequency sputtering technique from a delafossite CuFeO₂ target. After deposition, the structure and microstructure of the films were examined using grazing incidence X-ray diffraction, Raman spectroscopy, electron probe micro-analysis and transmission electron microscopy coupled with EDS mapping. Target to substrate distance and sputtering gas pressure were varied to obtain films having different amount and distribution of copper nanoparticles and different composition of oxide matrix. The overall reaction process, which starts from CuFeO₂ target and ends with the formation of films having different proportion of copper, copper oxide and iron oxide, was described by a combination of balanced chemical reactions. A direct relationship between the composition of the metal/oxide nanocomposite thin film and the sputtering parameters was established. This empirical relationship can further be used to control the composition of the metal/oxide nanocomposite thin films, i.e. the in situ reduction of copper ions in the target.     

Synthesis and characterization of sub-micron size Co-Ni alloys using malonate as precursor

Sub-micron size (0.2-0.6 μm) particles of Co_1−xNi_x (0≤x≤1) alloys have been synthesized by the polyol method using Co-Ni malonates as precursors but without using any protective agents such as PVP or any other surfactants. The synthesized alloys are found to be homogeneous. EDX analysis of the alloys showed particle-to-particle uniformity in composition. SEM showed largely non-agglomerated, almost spherical particles, with a fairly narrow size distribution. In the first reported effort of its kind, WAXS analysis was carried out to estimate the amounts of HCP and FCC phases present in pure Co and Co_0.8Ni_0.2. Coercivity, saturation magnetization and remanent magnetization at room temperature for all the compositions are reported. These results agree well with the composition of the alloys.