Faulknerynes A-C from a Bahamian sponge Diplastrella sp.: stereoassignment by critical application of two exciton coupled CD methods

Long-chain polyacetylene alcohols, faulknerynes A-C, along with known compounds diplynes A, C and E, were isolated from two specimens of the encrusting sponge, Diplastrella sp., collected from the surface of coral in the Bahamas. Two CD methods were critically evaluated for their suitability to terminal propargylic glycols and applied to assignment of configurations of faulkneryne A and diplyne C.     

Positive solutions for second order impulsive differential equations involving Stieltjes integral conditions

In this paper, the existence of at least three positive solutions to impulsive second order differential equations is investigated. Sufficient conditions which guarantee the existence of positive solutions are obtained, by using the Avery-Peterson theorem. An example is added to illustrate the results.     

Asymptotically stable equilibrium and limit cycles in the Rock–Paper–Scissors game in a population of players with complex personalities

We investigate a population of individuals who play the Rock–Paper–Scissors (RPS) game. The players choose strategies not only by optimizing their payoffs, but also taking into account the popularity of the strategies. For the standard RPS game, we find an asymptotically stable polymorphism with coexistence of all strategies. For the general RPS game we find the limit cycles. Their stability depends exclusively on two model parameters: the sum of the entries of the RPS payoff matrix, and a sensitivity parameter which characterizes the personality of the players. Apart from the supercritical Hopf bifurcation, we found the subcritical bifurcation numerically for some intervals of the parameters of the model.     

k0-INAA of Venezuelan ceramics and complete statistical analysis to establish their provenance

A group of 46 archaeological figurines samples (ad 1300 and 1500) from Venezuelan mainland and northern island were analyzed by k0-instrumental neutron activation analysis (k0-INAA) to obtain their elemental content and give a step ahead to establish the provenance of the island figurines. In total 37 elemental concentrations were measured with uncertainties between 3 and 20 %. To make the study of provenance, a complete statistical analysis was achieved; Fisher linear discriminant, principal component analysis, hierarchical clustering and the Hotelling T² test were used to this end. Furthermore, not only the 46 samples analyzed in this work by k0-INAA were used, but also 40 samples analyzed by PGNAA and reported by Sajo-Bohus et al. (JRNC 265(2):247–256, 2005) were included in the statistical analysis. It was done in order to increase the size of the data set, and then to obtain from the statistical techniques more reliable results. It was found that a very good differentiation exits between the figurines from the island and from the mainland supporting the idea that the raw materials of the figurines come from different places.     

Detection of Prunus Necrotic Ringspot Virus in Plant Extracts with Impedimetric Immunosensor based on Glassy Carbon Electrode

This paper concerns the development of an immunosensor for detection of Prunus necrotic ringspot virus (PNRSV) in plant extracts. The immunosensor fabrication consists of successive modification steps of glassy carbon electrodes: (i) creation of COOH groups, (ii) covalent immobilization of protein A with EDC/NHS coupling reaction, (iii) immobilization of anti‐PNRSV IgG polyclonal antibody, (iiii) filling free spaces with BSA. Each step was controlled with cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The immunosensor was applied for the determination of the PNRSV virus in extracts from cucumber leaves using EIS technique. It was capable of discriminating between samples consisting of extracts from healthy plants and consisting of leaf extracts from infected plants diluted 10 000 times with extract from healthy plants.     

Amphiphilic copolymers with poly(meth)acrylic acid chains “grafted from” caprolactone 2‐(methacryloyloxy)ethyl ester‐based backbone

Well‐defined amphiphilic graft copolymers containing hydrophilic poly((meth)acrylic acid) (PMAA) or poly(acrylic acid) (PAA) side chains with gradient and statistical distributions were synthesized. For this purpose, the hydroxy‐functionalized copolymers with various gradient degrees, in which 2‐(6‐hydroxyhexanoyloxy)ethyl (meth)acrylate units (caprolactone 2‐[methacryloyloxy]ethyl ester, CLMA) formed strong gradient with tert‐butyl acrylate (tBA), slight gradient copolymers with tert‐butyl (meth)acrylate (tBMA), and statistical copolymers with methyl (meth)acrylate (MMA) were modified to bromoester multifunctional macroinitiators, P(tBMA‐grad‐BrCLMA), P(BrCLMA‐grad‐tBA), and P(BrCLMA‐co‐MMA). In the next step, they were applied in controlled radical polymerization of tBMA and tBA yielding graft copolymers with various lengths of side chains as well as graft densities. Further, the tert‐butyl groups in copolymers were successfully removed via acidolysis in the presence of trifluoracetic acid, which caused transformation of the hydrophobic graft copolymers into amphiphilic ones with ability of self‐assembly for the future biomedical applications. Copyright © 2013 John Wiley & Sons, Ltd.     

New HPLC method for in vitro dissolution study of antihypertensive mixture amlodipine and perindopril using an experimental design

A new HPLC method was developed for the determination of amlodipine and perindopril in their binary mixture as a part of a routine control of combined formulations. For the first time an HPLC method was used for an in vitro dissolution study of tablets containing the above drugs. The presented method was validated to meet official requirements and this validation included specificity, stability, linearity, precision and accuracy. Chromatography was carried out using a LiChrospher RP-18 column, a mixture containing acetonitrile and phosphate buffer of pH 3.0 (50:50, v/v) as mobile phase and UV detection at 225 nm. The dissolution test was performed using 900 mL of phosphate buffer at pH 5.5 containing 1% cetylpyridini chloride (CPC) at 37°C and 75 rpm, using the paddle method. Robustness procedure was done according to the plan defined by the Plackett-Burman design. The effects of acetonitrile content, pH of the buffer and flow rate of the mobile phase, column temperature, pH and CPC content in the dissolution medium as well as rotation speed of the paddle were considered. After that, both graphical and statistical methods were used for identification of significant and non-significant effects.      

Corrosion depth profiles of nitrided titanium alloy in acidified sulphate solution

Thick (400 µm) glow-discharge nitrided layers, TiN+Ti₂N + αTi(N) type, have been produced on the Ti-1Al-1Mn titanium alloy. Using a progressive thinning method, the polarization characteristics at different depths of nitrided layers have been measured. From the plots of obtained potentiodynamic polarization curves the depth profiles of characteristic anodic and cathodic currents (at potentials corresponding to (a) hydride formation, (b) hydrogen evolution, (c) primary passivation, (d) oxygen evolution and (e) secondary passivation) as well as polarization resistance have been determined in 0.5 M Na₂SO₄ solution acidified to pH = 2. The anomalously high slope of the polarization curves in the cathodic region has been ascribed to the formation of titanium hydride. It has been shown that outer nitrided layers (up to 25 µm) exhibit excellent acid corrosion resistance owing to strong inhibition of the anodic process by TiN phase. Corrosion resistance of deeper situated layers gradually decreases and at depths of 250–370 µm the corrosion process is accelerated by presence of TiO₂ precipitations. Nitrided layers, unlike the alloy core, allow oxygen evolution on the oxy-nitrided surface at potential of +1.6 V and at more positive potentials gradual transformation of the surfacial film into TiO₂ takes place. Secondary passivation on nitrided titanium is less efficient than that in the absence of Ti-N species.      

Bond length interrelations in benzenoid hydrocarbons and their heteroatom analogues

The geometries of some benzenoid hydrocarbons and their analogues with XY (XY = BB, BC, BN, CN, and NN) bonds have been determined at the B3LYP/6-311++G^∗∗ level of theory. It is shown that the lengths of peripheral XY bonds are strictly correlated with the lengths of their CC counterparts in native hydrocarbons. No correlation of this type is observed for the XY bonds located inside the rings.     

Influence of the Modifier Type and its Concentration on Electroosmotic Flow of the Mobile Phase in Pressurized Planar Electrochromatography

The aim of this work was to find a relationship between electroosmotic flow (EOF) velocity of the mobile phase in pressurized planar electrochromatography (PPEC) and physicochemical properties like zeta potential, dielectric constant, and viscosity of the mobile phase as well as its composition. The study included different types of organic modifiers (acetonitrile, methanol, ethanol, acetone, formamide, N-methylformamide and N,N-dimethylformamide) in the full concentration range. In all experiments, chromatographic glass plates HPTLC RP-18 W from Merck (Darmstadt) were used as a stationary phase. During the study we found that there is no linear correlation between EOF velocity of the mobile phase and single variables such as zeta potential or dielectric constant or viscosity. However, there is quite strong linear correlation between EOF velocity of the mobile phase and variable obtained by multiplying zeta potential of the stationary phase–mobile phase interface, by dielectric constant of the mobile phase solution and dividing by viscosity of the mobile phase. Therefore, it could be concluded that the PPEC system fulfilled the Helmholtz–Smoluchowski equation.