New lipophilic 3-hydroxy-4-pyridinonate iron(III) complexes: synthesis and EXAFS structural characterisation

New tris-iron(III) chelates of 3-hydroxy-4-pyridinone ligands derived from maltol (3-hydroxy-2-methyl-4-pyrone) or ethylmaltol (2-ethyl-3-hydroxy-4-pyrone), including a variety of N-aryl (phenyl, 4'-tolyl, 4'-(n-butyl)phenyl, 4'-(n-hexyl)phenyl) and N-benzyl (4'-methylbenzyl, 4'-fluorobenzyl and 4'-(trifluoromethyl)benzylamine) substituents on the nitrogen atom of the pyridinone ring, have been prepared. Characterization by C,H,N elemental analysis and thermogravimetric measurements indicates that most of the complexes are obtained as hydrates of general formula ML3.xH2O. Structural characterization of these difficult to crystallize lipophilic complexes has been achieved by EXAFS spectroscopy. Solutions of iron(III) complexes of maltol, ethylmaltol, 1,2-dimethyl-3-hydroxy-4-pyridinone and 1-phenyl-2-methyl-3-hydroxy-4-pyridinone in methanol-water mixtures were also examined by EXAFS. Distances from the central atom to ligand atoms, within 6 A of the metal, have been determined in the solid and solution samples and the results show that the structure observed in the powder is maintained in solution. The local structure around the metal centre, bond distances and bond angles, does not change significantly with variable lipophilicity, thus indicating that ligands may be tailored according to specific needs without altering their chelation properties. EXAFS data analysis for this set of tris-iron(III) compounds illustrates the important contribution of both intra-ligand and inter-ligand multiple scattering pathways through the metal centre to a peak observed in the FT spectrum at twice the metal ligand distance (approximately 4 A). The present results demonstrate that EXAFS features at twice the metal-ligand distance are valuable in the assignment of molecular geometry and that location of hydration water molecules, by EXAFS analysis, is limited by the geometry of the complexes, in particular for those in which ligands containing phenyl rings are present.     

Synthesis of niobia nanocrystals with controlled morphology

In this work, TT niobia-phase nanocrystals with controlled morphology were obtained by the hydrothermal treatment of a niobium peroxo complex precursor at very low temperatures. The materials obtained by this route presented a very high surface area (ranging from 79 to 327 m(2)/g), disordered NbO(6), NbO(7), and NbO(8) polyhedra, Nb-O superficial sites, and a superficial OH group, which must have ensured the acidic characteristics of this oxide.     

Resonant Raman scattering characterization of carbon nanotubes grown with different catalysts

Single-walled carbon nanotube samples produced in the presence of different combinations of metal catalysts have been studied by resonant Raman spectroscopy. The diameter distribution of different samples has been determined by analysis of the laser excitation energy dependence of the tangential modes associated with metallic nanotubes. These modes are resonantly enhanced over a narrow range of the exciting energies, which shifts for different samples. The Raman cross-section expression has been used to fit the experimental Raman excitation profiles. This procedure was used to determine the mean value and the width of the distribution of diameters within each sample.     

Low-Loss Photopatternable Hybrid Sol–Gel Materials

Hybrid sol–gel technology has proved its usefulness in the field of micro-optics. Indeed, it makes it possible to manufacture optical microcomponents by processes much simpler than those currently used, particularly when photopatternable materials are employed. However, for wavelengths in the near infrared window (NIR), this process is confronted with a major problem which results from the significant optical absorption of this type of materials, in particular around 1550 nm. The aim of this paper is to describe the origin of the losses of some hybrid sol–gel materials of direct interest in micro-device fabrication in order to propose solutions to achieve a greater transparency in the NIR region. The intrinsic absorption of the precursors was first of all considered since it is crucial to pursue the final goal of decreased losses. Then, the principal parameters of the sol–gel synthesis were studied. Among them, the thermal treatment conditions, the hydrolysis ratio and the controlled addition of transition metal alkoxides allow an improvement of the material transparency, at 1550 nm most particularly. This last point was considered with the highest attention, and NIR and NMR spectroscopies were employed to explain how the addition of zirconium alkoxides at the end of the reaction makes it possible to considerably decrease the losses in the material.     

Er as marker for order–disorder determination in the PbTiO3 system

Er³⁺ ions were added to the PbTiO₃ network using the polymeric precursor method to characterize the order–disorder transformation found in this material by means of experimental and theoretical approach. The disordered and ordered material structures were studied by photoluminescence measurements, X-ray diffraction (XRD) and UV–visible spectroscopy. The Er³⁺ ions served as a marker to identify the structural short-range order beginning in the PbTiO₃ matrix. From photoluminescence results it was concluded that disordered PbTiO₃ powders have a certain short range order in the network that are undetected by XRD measurements. The electronic structures were calculated by the ab initio periodic method in DFT level with the non-local B3LYP hybrid approximation for the Ti atom site interpretation using density of states (DOS) results. This analysis enabled understanding that Ti atom sphere coordination can create possible states for radioactive return and trap of electron–holes pair.     

Ceramic crucibles: a new alternative for melting of PbO-BiO1.5-GaO1.5 glasses

PbO-Bi₂O₃-Ga₂O₃ glasses present interesting properties such as good transmission in the mid-infrared region, high magnetic Verdet constant and non-linear properties. The processing of these heavy-metal-oxide (HMO) glasses is limited by the high corrosive nature of the melt, even in relation to noble metal crucibles. In this work, three kinds of ceramic crucibles (alumina, tin oxide and zirconia) were tested for melting HMO glasses. The main physical properties of the prepared glasses, such as the characteristic temperatures, optical transmission were studied in function of the crucible nature, time/temperature melting parameters. The incorporation of crucible material in the glasses was determined by ICP and atomic absorption. The maximum glass contamination from the crucible was 2.9, 1.6 and 3.6 mol% for Al₂O₃, SnO₂ and ZrO₂ crucibles, respectively, when melting was done at 900 °C/240 min, for zirconia crucibles and at 1000 °C/60 min, for the other two crucibles. The evolution of the physical properties was discussed as a function of contamination degree.     

Fragmentation experiment and model for falling mercury drops

The experiment consists of counting and measuring the size of the many fragments observed after the fall of a mercury drop on the floor. The size distribution follows a power-law for large enough fragments. We address the question of a possible crossover to a second, different power-law for small enough fragments. Two series of experiments were performed. The first uses a traditional film photographic camera, and the picture is later treated on a computer in order to count the fragments and classify them according to their sizes. The second uses a modern digital camera. The first approach has the advantage of a better resolution for small fragment sizes. The second, although with a poorer size resolution, is more reliable concerning the counting of all fragments up to its resolution limit. Both together clearly indicate the real existence of the quoted crossover.     

Modelling of self-aligned total internal reflection waveguide mirrors: an interlaboratory comparison

Results of modelling of light propagation in 45° self-aligned total internal reflection rib waveguide mirrors on InP substrate are compared. Six laboratories participated in the comparison with the following six modelling methods: the standard fast-Fouriertransform beam propagation method (BPM), the standard finite-difference (FD) BPM using the Crank-Nicholson scheme (two laboratories), the FD-BPM with the correction for the slowly varying envelope approximation, the method of lines, the eigenmode expansion and propagation method, and a simple method based on the field overlap. All the laboratories used the effective-index method to reduce the three-dimensional problem to two dimensions. The differences among the results obtained by different methods are briefly discussed and qualitatively compared to measured values.     

The geometry of hypercomplex matrices

Hypercomplex matrices realize a matrix representation for quaternions and octonions. We establish a number of interesting properties of hypercomplex matrices.     

Influence of temperature and environment humidity on the transmission spectrum of sol-gel hybrid channel waveguides

Hybrid materials produced by the hydrolytic sol-gel process reveal strong absorption in the spectral region of 1550 nm, mainly due to the high concentration of OH groups. This characteristic constitutes an obstacle to the application of these materials, in particular to telecom integrated optical devices. A simple thermal treatment applied to the device does not contribute to increase the transparency. The real-time influence of temperature and environment humidity on the optical transmission properties of sol-gel organic-inorganic raised channel waveguides is analyzed in order to achieve an understanding of the OH group’s behaviour in the materials. We demonstrate that the level of the optical losses at 1550 nm can significantly be decreased at high temperature. Cooling the sample in dry atmosphere makes it possible to reach a better transparency, which can be useful to improve the performance of hybrid sol-gel optical devices.