Optical classification of random image fields using spectral synthetic discriminant functions

It is shown that the problem of classification of images that have the perfectly random nature may be solved with the help of synthetic discriminant functions being synthesized by least-squares technique to separate linearly the power spectra of the corresponding random image fields. The realization of the proposed method by means of an optical technique is discussed, and its efficiency is illustrated by two examples of real-life texture classification.     

High-field vs. low-field magneto-transport in a percolating medium

Recent theoretical and numerical work on high-field magneto-transport in a percolating medium is described and compared to earlier work on weak-field magneto-transport in such systems. While the weak-field behavior is well described by the simple nodes-links picture, which ignores blobs and loops on a scale smaller than the percolation correlation length ξ_p, the strong-field behavior is extremely sensitive to those features. The critical behavior at strong magnetic fields H near the percolation threshold is governed by competition between the usual H=0 fixed point and a new H=∞ fixed point. Which of those fixed points dominates the behavior is determined by the relative sizes of two characteristic lenghts: the percolation correlation length ξ_p and a new, magnetic field dependent length ξ_H.     

X-ray and magnetic birefringence studies of some lanthanide metallomesogens with Schiff's base ligands

Low angle X-ray scattering studies have been used to identify the mesophase of some calamitic lanthanide mesogens as smectic A, while magnetic birefringence studies have shown a huge magnetic anisotropy for these complexes.     

Morphology changes in the evolution of liquid two-layer films

We consider a thin film consisting of two layers of immiscible liquids on a solid horizontal (heated) substrate. Both the free liquid-liquid and the liquid-gas interface of such a bilayer liquid film may be unstable due to effective molecular interactions relevant for ultrathin layers below 100-nm thickness, or due to temperature-gradient-caused Marangoni flows in the heated case. Using a long-wave approximation, we derive coupled evolution equations for the interface profiles for the general nonisothermal situation allowing for slip at the substrate. Linear and nonlinear analyses of the short- and long-time film evolution are performed for isothermal ultrathin layers, taking into account destabilizing long-range and stabilizing short-range molecular interactions. It is shown that the initial instability can be of a varicose, zigzag, or mixed type. However, in the nonlinear stage of the evolution the mode type, and therefore the pattern morphology, can change via switching between two different branches of stationary solutions or via coarsening along a single branch.     

Porphyrins bearing mono or tripodal benzylphosphonic acid tethers for attachment to oxide surfaces

The ability to attach redox-active molecules to oxide surfaces in controlled architectures (distance, orientation, packing density) is essential for the design of a variety of molecular-based information storage devices. We describe the synthesis of a series of redox-active molecules wherein each molecule bears a benzylphosphonic acid tether. The redox-active molecules include zinc porphyrins, a cobalt porphyrin, and a ferrocene-zinc porphyrin. An analogous tripodal tether has been prepared that is based on a tris[4-(dihydroxyphosphorylmethyl)phenyl]-derivatized methane. A zinc porphyrin is linked to the methane vertex by a 1,4-phenylene unit. The tripodal systems are designed to improve monolayer stability and ensure vertical orientation of the redox-active porphyrin on the electroactive surface. For comparison purposes, a zinc porphyrin bearing a hexylphosphonic acid tether also has been prepared. The synthetic approaches for introduction of the phosphonic acid group include derivatization of a bromoalkyl porphyrin or use of a dimethyl or diethyl phosphonate substituted precursor in a porphyrin-forming reaction. The latter approach makes use of dipyrromethane building blocks bearing mono or tripodal dialkyl phosphonate groups. The zinc porphyrin-tripodal compound bearing benzylphosphonic acid legs tethered to a SiO(2) surface (grown on doped Si) was electrically well-behaved and exhibited characteristic porphyrin oxidation/reduction waves. Collectively, a variety of porphyrinic molecules can now be prepared with tethers of different length, composition, and structure (mono or tripodal) for studies of molecular-based information storage on oxide surfaces.     

Solid-state structure dependence of the molecular distortion and spectroscopic properties of the Cu(I) bis(2,9-dimethyl-1,10-phenanthroline) ion

The relation between the geometry and spectroscopic properties of a series of salts of the Cu(I) bis(2,9-dimethyl-1,10-phenanthroline) ion, (Cu((I))(dmp)(2))(+), is explored. The distortions from the idealized D(2)(d)() geometry, which include flattening, rocking of the dmp ligands, and displacement of the Cu atoms out of the dmp planes, show considerable variation, indicating the importance of packing forces in the crystalline environment. The change in the absorption spectra upon flattening of the complex, expressed as the variation of the angle between the dmp planes, which varies from 88 degrees in the BF(4) and tosylate salts to 73 degrees in the picrate, agrees qualitatively with parallel DFT calculations. No correlation is found between ground state geometry and luminescence lifetimes, recorded both at room temperature and at 16 K. The low temperature lifetimes vary by a factor of 8 among the (Cu((I))(dmp)(2))(+) salts examined, the longest lifetime (2.4 micros at 16 K) being observed for the tosylate salt.     

Manganese(II) chemistry of a new N3O-donor chelate ligand: synthesis, X-ray structures, and magnetic properties of solvent- and oxalate-bound complexes

The synthesis and characterization of a new N3O donor ligand N-benzyl-N-((6-pivaloylamido-2-pyridyl)methyl)-N-(2-pyridylmethyl)amine (bpppa) is reported. Treatment of bpppa with Mn(II)(ClO4)2.6H2O in acetonitrile solution yielded the mononuclear [(bpppa)Mn(CH3CN)(H2O)](ClO4)2 (1) which was characterized by X-ray crystallography, elemental analysis, IR spectroscopy, mass spectrometry, and a solution magnetic moment measurement. Admixture of equimolar equivalents of bpppa and Mn(II)(ClO4)2.6H2O in methanol solution, followed by addition of 0.5 or 1 equivalents of sodium oxalate, yielded the binuclear complex [{(bpppa)Mn}2([mu]-C2O4)](ClO4)2 (2), which was characterized by X-ray crystallography, elemental analysis, IR spectroscopy, mass spectrometry, and solid-state magnetic measurements. While 1 is mononuclear, the formation of the binuclear oxalate derivative indicates that use of the bpppa ligand does not enable isolation of a complex that is structurally relevant to a proposed 1:1 Mn(II)-oxalate adduct in the catalytic cycle of the oxalate degrading enzyme oxalate decarboxylase.     

Multisensor system for determination of polyoxometalates containing vanadium at its different oxidation states

The electronic tongue (ET) multisensor system has been employed for the detection of metal-oxygen cluster anions (polyoxometalates) containing vanadium (IV/V) atoms. Sensitivity of a variety of potentiometric chemical sensors with plasticized polyvinyl chloride and chalcogenide glass membranes was evaluated with respect to vanadyl/vanadate ions, decavanadate and a series of Keggin-type polyoxometalates (POM) such as α-[SiW₁₁V^IVO₄₀]⁶⁻, α-[SiW₁₁V^VO₄₀]⁵⁻, α-[BW₁₁V^IVO₄₀]⁷⁻, α-[BW₁₁V^VO₄₀]⁶⁻, α-[PW₁₁V^IVO₄₀]⁵⁻ and α-[PW_12−nV_n^VO₄₀]⁽³⁺ⁿ⁾⁻ (n = 1, 2, 3). Sensor's responses to vanadium complexes were evaluated in the pH range of 2.4-6.5 and a set of sensors appropriate for detecting a variety of vanadium species was selected. Such sensor array was able to distinguish different vanadium complexes allowing their simultaneous quantification in binary (V(IV)/V(V)) mixtures. The vanillyl alcohol oxidation with α-[SiW₁₁V^VO₄₀]⁵⁻ was monitored using ET to evaluate the capacity of proposed analytic system to detect simultaneously V(IV)/V(V) in POM under dynamic equilibrium. ET was demonstrated to be a promising tool for the discrimination and quantification of vanadium-containing POMs at different oxidation states. In particular, such a system could represent a significant interest for the mechanistic studies of redox reactions with POMs.