A new binucleating ligand incorporating four oxime groups and its copper(II), manganese(II) and cobalt(III) complexes

A new binucleating ligand incorporating four oxime groups, butane-2,3-dione O-[4-aminooxy-2,3-bis-(2-hydroxyimino-1-methyl-propylideneaminooxymethyl)-but-2-enyl]-dioxime, (H₄mto), has been synthesized and its dinuclear cobalt(III), copper(II), and homo- and hetero-tetranuclear copper(II)–manganese(II) complexes have been prepared and characterized by ¹H- and ¹³C-n.m.r., i.r., magnetic moments and mass spectral studies. Elemental analyses, stoichiometric and spectroscopic data indicate that the metal ions in the complexes are coordinated to the oxime nitrogen atoms (C=N) and the data support the proposed structure for H₄mto and its complexes. Moreover, dinuclear cobalt(III) and copper(II) complexes of H₄mto have a 2:1 metal:ligand ratio.     

Experiments and Identifications for Finite Polymer Inelasticity

The constitutive theories intended to quantitatively account for the complicated material response exhibited by polymers include, in general, adjustable material parameters. These must be identified from experimental data obtained from the material under consideration. This contribution presents the complete procedure studying the behavior of polymers at large strains in three basic steps: i) Accomplishment of homogeneous and 3-D inhomogeneous experiments under different deformation conditions. ii) Identification of the material parameters of a constitutive model by means of gradient–based optimization methods with respect to the homogeneous experimental data. iii) Validation of the identified material parameters by comparing 3-D FE simulations to the inhomogeneous experimental data. (© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Polarized absorption spectra of highly oriented two-dimensional aggregates of tetrachlorobenzimidazolocarbocyanine in thin films

Reaching a control on the mesoscopic morphology and internal molecular arrangement of cyanine aggregates is an important step for realization of devices with tailor-made optical properties. Despite a wealth of research, understanding of the relationship between molecular organization, excitonic states and dynamics of aggregates is still preliminary. To this end, we have employed polarized absorption spectroscopy to investigate the relationship between internal molecular organization and excitonic states of J-aggregates in 1,1′,3,3′tetraethyl-5,5′,6,6′-tetrachlorobenzimidazolocarbocyanine (TTBC) thin films in poly-vinyl alcohol (PVA). Angular dependence of the UV–vis spectra has been measured at 11 different orientations between the electric field polarization and the macroscopic alignment axis. Aggregate spectral response consisted of an asymmetrically split Davydov pair of bands exhibiting opposite polarization: an H-band (505 nm, Lorentzian-like, polarized along the macroscopic film axis) and a J-band (594 nm, one-dimensional J-aggregate like band shape, polarized perpendicular to the macroscopic film axis). The polarized absorption observations were found to be consistent with a herringbone model for which the internal molecular arrangement, the excited state structure and dynamics have recently been detailed by us upon interpretation of isotropic absorption data in ionic aqueous solution.     

Ordinary and penalized minimum power-divergence estimators in two-way contingency tables

Basu and Basu (Statistica Sinica 8:841–860, 1998) have proposed an empty cell penalty for the minimum power-divergence estimators which can lead to improvements in the small sample properties of these estimators. In this paper, we study the small and moderate sample performances of the ordinary and penalized minimum power-divergence estimators in terms of efficiency and robustness for the log-linear models in two-way contingency tables under the assumptions of multinomial sampling. Calculations made by enumerating all possible sample combinations show that the penalized estimators are competitive with the ordinary estimators for the moderate samples and definitely better for the smallest sample considered for both efficiency and robustness under the considered models. The results also reveal that the bigger the main effects the more need for penalization.     

Market selection decisions for inventory models with price-sensitive demand

In the majority of classical inventory theory literature, demand arises from exogenous sources upon which the firm has little or no control. In many practical contexts, however, aggregate demand is comprised of individual demands from a number of distinct customers or markets. This introduces new dimensions to supply chain planning problems involving the selection of markets or customers to include in the demand portfolio. We present a nonlinear, combinatorial optimization model to address planning decisions in both deterministic and stochastic settings, where a firm constructs a demand portfolio from a set of potential markets having price-sensitive demands. We first consider a pricing strategy that dictates a single price throughout all markets and provide an efficient algorithm for maximizing total profit. We also analyze the model under a market-specific pricing policy and describe its optimal solution. An extensive computational study characterizes the effects of key system parameters on the optimal value of expected profit, and provides some interesting insights on how a given market’s characteristics can affect optimal pricing decisions in other markets.     

Monoterpenoid glucoindole alkaloids and iridoids from Pterocephalus pinardii

A new secondary metabolite, pterocephaline, along with the known cantleyoside, 7α‐morroniside, 3β,5α‐tetrahydrodesoxycordifoline lactam, 5S‐5‐carboxyvincoside, sweroside, and loganin have been isolated from the aerial parts of P. pinardii (Dipsacaceae). Moreover, cantleyoside‐methyl‐hemiacetal and cantleyoside‐dimethyl‐acetal were obtained as seco‐iridoid artifacts. The structures were elucidated by extensive spectroscopic methods including 1D‐(¹H, ¹³C and TOCSY) and 2D‐NMR (DQF‐COSY, HSQC and HMBC). Monoterpenoid glucoindole alkaloids were encountered for the first time in Dipsacaceae family. Copyright © 2010 John Wiley & Sons, Ltd.     

An analysis of dielectric relaxation using the fractional master equation of the stochastic Ising model

In this paper, we begin introducing some basic definitions and mathematical preliminaries of the fractional calculus theory. By using the fractional calculus technique (that is, calculus of derivatives and integrals of any arbitrary real or complex order) a solution of the fractional master equation derived from the stochastic Ising model of Glauber has been obtained and the result is applied to an analysis of the dielectric relaxation processes. From the solution of the equation, the Cole-Cole dispersion relation, KWW (Kohlrausch-William-Watts) equation and algebraic decay relaxation functions are obtained easily. Then these functions are compared with Bozdemir's earlier analysis of the stochastic Ising model.     

Biocentri-voltammetric biosensor for acetylcholine and choline

We report on the determination of choline and acetylcholine via biocentrivoltammetry. This method combines centrifugation and voltammetry and is based on a carbon paste electrode modified with acetylcholinesterase and choline oxidase. The electrode was placed at the bottom of a biocentrivoltammetric cell. Acetylcholine and choline are accumulated on the enzyme electrode via centrifugative forces, upon which a direct voltammetric scan is applied. Reaction time, pH values, quantities of enzyme and centrifugation parameters were optimized. A linear response is obtained in the 0.07 to 10?μM concentration range of acetylcholine, and a limit of detection as low as 0.5?μM. The linear range is between 0.1 and 500?μM for choline. The method was applied to the determination of acetylcholine and choline in spiked serum samples.

Tin oxide nanoparticles-polymer modified single-use sensors for electrochemical monitoring of label-free DNA hybridization

In this study, SnO₂ nanoparticles (SNPs)-poly(vinylferrocenium) (PVF⁺) modified single-use graphite electrodes were developed for electrochemical monitoring of DNA hybridization. The surfaces of polymer modified and polymer-SNP modified pencil graphite electrodes (PGEs) were firstly characterized by using SEM analysis. The electrochemical behaviours of these electrodes were also investigated using the differential pulse voltammetry (DPV) and electrochemical impedance spectroscopy (EIS) techniques. The polymer-SNP modified PGEs were then tested for the electrochemical sensing of DNA based on the changes at the guanine oxidation signals. Experimental parameters, such as; different modifications in DNA oligonucleotides, DNA probe concentrations were examined to obtain more sensitive and selective electrochemical signals for nucleic acid hybridization. After optimization studies, DNA hybridization was investigated in the case of complementary of hepatitis B virus (HBV) probe, mismatch (MM), and noncomplementary (NC) sequences.     

Photo-Fries-based photosensitive polymeric interlayers for patterned organic devices

This work reports on the investigation of the photosensitive polymer poly(diphenyl bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate) (PPNB), which undergoes the photo-Fries rearrangement upon illumination with UV-light, used as interfacial layers in organic electronic devices. Two cases were investigated: the use of a blend of PPNB with poly-vinylcarbazole (PVK) as an interlayer in para-sexiphenyl (PSP) based organic light emitting diodes (OLEDs) and the use of PPNB as gate dielectric layer in organic field effect transistors (OFETs). The photo-Fries rearrangement reaction causes a change of the polymer chemical structure resulting in a change of its physical and chemical properties. The electroluminescence spectra and emission of the PSP OLEDs are not affected when fabricated with a non-UV-illuminated PPNB:PVK blend. However, the electroluminescence is totally quenched in those OLEDs fabricated with UV-illuminated PPNB:PVK blend. Although the dielectric constant of PPNB increases upon UV-treatment, it is demonstrated that those OFETs built with UV-treated PPNB as gate dielectric have lower performance than those OFETs built with non-UV-treated PPNB. Furthermore, the effect of the UV-illumination of PPNB and PPNB:PVK blend on the growth of the small molecules C₆₀ and PSP has been studied by atomic force microscopy. Using photolithography, this kind of photochemistry can be performed to spatially control and tune the optical and electrical performance of organic electronic devices.