The formation of flouride complexes of titanium(IV)

The complex formation equilibria between titanium(IV) and fluoride ions have been studied at 25°C in 3 M(Na)Cl ionic medium by measuring, with an ion selective electrode for F^?, the free HF concentration in acid Ti(IV) solutions. The [H⁺] was kept within 0.25 and I M where the predominant form of uncomplexed metal is the dihydroxotitanium(IV) ion, Ti(OH)²⁺₂. The potentiometric data have been explained by assuming Ti(OH)₂F⁺, TiF₄ and HTiF^?₆, with equilibrium constants given in Table 3. Within the accuracy of the present e.m.f. study, ±0.2 mV, no evidence for intermediate complexes bearing 2, 3 and 5 F^? was found.From a special series of measurements, carried out by replacing a large part of the Cl^? with ClO^?₄, it is concluded that no appreciable amount of Ti(IV)Cl complexes is formed at the 3 M level employed as ionic medium.     

Coiling, entrainment, and hydrodynamic coupling of decelerated fluid jets

From algal suspensions to magma upwellings, one finds jets which exhibit complex symmetry-breaking instabilities as they are decelerated by their surroundings. We consider here a model system--a saline jet descending through a salinity gradient--which produces dynamics unlike those of standard momentum jets or plumes. The jet coils like a corkscrew within a conduit of viscously entrained fluid, whose upward recirculation braids the jet, and nearly confines transverse mixing to the narrow conduit. We show that the underlying jet structure and certain scaling relations follow from similarity solutions to the fluid equations and the physics of Kelvin-Helmholtz instabilities.     

Spectral study on the molecular orientation of a tetracationic porphyrin dye on the surface of layered silicates

Tetracationic porphyrin dyes TMPyP and ZnPyP were intercalated into hydrophobized layered silicate films of three smectites. The smectites represented the layered silicate specimens of high (Fluorohectorite, Corning; FHT), medium (Kunipia F montmorillonite; KF) and low layer charge (Laponite, Laporte; LAP). The molecular orientations of the dye cations were studied by means of linearly-polarized ultraviolet-visible (UV-VIS) spectroscopy. The spectral analysis and consequent calculations of tilting angles of the transition moments at the wavelengths of Soret band transitions were in the range of 25°-35°. The determined angles indicated molecular orientation of the dye cations being almost parallel to the surface of the silicates. Slightly higher values (above 35°), determined for a FHT film, indicated either a slightly tilted orientation of the dye cations or the change of molecular comformation after the intercalation of the dye. Presented at 5-th International Conference Solid State Surfaces and Interfaces, November 19–24, 2006, Smolenice Castle, Slovakia     

Stereoregular poly‐O‐methyl [m,n]‐polyurethanes derived from D‐mannitol

Novel linear carbohydrate‐derived [m,n]‐polyurethanes are successfully prepared using D ‐mannitol as renewable and low cost starting material. The key comonomer, 1,6‐di‐O‐phenylcarbonyl‐2,3,4,5‐tetra‐O‐methyl‐D ‐mannitol is polymerized with a diamine synthesized from D ‐mannitol or with alkylenediamines. These polymerization reactions afford, respectively, a [6,6]‐polyurethane entirely based on a carbohydrate derivative or [m,n]‐polyurethanes constituted by a poly‐O‐methyl substituted unit alternating with a polymethylene chain. All these polymers are stereoregular, as result of the C₂ axis of symmetry of mannitol. The optically active polyurethanes are characterized by standard methods (FTIR, RMN, GPC, TGA, and DSC). Thus, GPC analysis reveals weight‐average molecular weights between 18,000 and 25,000 Da. Thermal studies (DSC) indicate that the polymers obtained are amorphous materials with T_g values dependent on the structure and chain length of the diamine constituent. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Long range correlation of hydrophilicity and flexibility along the calcium binding protein chains

Long range correlation concerning hydrophilicity and flexibility along a number of 80 calcium binding protein sequences is confirmed by using spectral analysis and detrended fluctuations analysis methods, as well as by Hurst exponent calculations. There are no significant differences between the correlation properties concerning these properties for the two structural subfamilies, extended and compact, of the calcium binding proteins and they are also similar with the correlation properties revealed by other investigated proteins. This result sustains the hypothesis that the long range correlation of hydrophilicity and flexibility along the chain is a common feature of proteins.     

Gradient bounds for minimizers of free discontinuity problems related to cohesive zone models in fracture mechanics

In this note we consider a free discontinuity problem for a scalar function, whose energy depends also on the size of the jump. We prove that the gradient of every smooth local minimizer never exceeds a constant, determined only by the data of the problem.     

POPMUSIC for the point feature label placement problem

Point feature label placement is the problem of placing text labels adjacent to point features on a map so as to maximize legibility. The goal is to choose positions for the labels that do not give rise to label overlaps and that minimize obscuration of features. A practical goal is to minimize the number of overlaps while considering cartographic preferences. This article proposes a new heuristic for solving the point feature label placement problem based on the application of the POPMUSIC frame. Computational experiments show that the proposed heuristic outperformed other recent metaheuristics approaches in the literature. Experiments with problem instances involving up to 10 million points show that the computational time of the proposed heuristic increases almost linearly with the problem size. New problem instances based on real data with more than 13,000 labels are proposed.     

Sensitive Determination of the Diquat Herbicide in Fresh Food Samples on a Highly Boron‐Doped Diamond Electrode

The highly boron‐doped diamond electrode (HBDD) combined with square wave voltammetry (SWV) was used in the development of an analytical procedure for diquat determination in potato and sugar cane samples and lemon, orange, tangerine and pineapple juices. Preliminary experiments realised in a medium of 0.05 mol L^?1 Na₂B₄O₇ showed the presence of two voltammetric peaks around ?0.6 V and around ?1.0 V vs. Ag/AgCl/Cl^? 3.0 mol L^?1, where the first peak could be successfully used for analytical proposes due the facility in the electrode surface renovation. After the experimental and voltammetric optimisation, the calculated detection and quantification limits were 1.6×10^?10 mol L^?1 and 5.3×10^?10 mol L^?1 (0.057 µg L^?1 and 0.192 µg L^?1, respectively), which are lower than the maximum residue limit established for fresh food samples by the Brazilian Sanitary Vigilance Agency. The proposed methodology was used to determine diquat residues in potato and sugar cane samples and lemon, orange, tangerine and pineapple juices and the calculated recovery efficiencies indicated that the proposed procedure presents higher robustness, stability and sensitivity, good reproducibility, and is very adequate for diquat determination in complex samples.     

3D [Ag-Mg] polyanionic frameworks in the La4Ag10Mg3 and La4Ag10.3Mg12 new ternary compounds

The crystal structures of two new ternary phases, La₄Ag₁₀Mg₃ and La₄Ag_10.3Mg₁₂, were refined from X-ray single crystal diffraction data. La₄Ag₁₀Mg₃ crystallizes in the Ca₄Au₁₀In₃ structure type, an ordered variant of the binary Zr₇Ni₁₀ compound: orthorhombic, Cmce, oS68, a=14.173(5), b=10.266(3), c=10.354(3) Å, Z=4, wR₂=0.0826, 676 F² values, 50 variables. La₄Ag_10.3Mg₁₂ represents a new structure type: orthorhombic, Cmmm, oS116-10.32, a=9.6130(3), b=24.9663(8), c=9.6333(2) Å, Z=4, wR₂=0.0403, 1185 F² values, 101 variables. The structural analysis of both compounds, highlighting a significant contraction of the Ag-Mg distances, suggests the existence of three-dimensional [Ag-Mg] networks hosting La atoms. LMTO calculations applied to La₄Ag₁₀Mg₃ indicate that the strongest bonds occur for Ag-Ag and Ag-Mg interactions, and confirm the presence of a 3D_∞[Ag₁₀Mg₃]^δ− polyanionic framework balanced by positively charged La atoms.