Analysis of anthocyanin pigments in Lonicera (Caerulea) extracts using chromatographic fractionation followed by microcolumn liquid chromatography-mass spectrometry

Anthocyanins from the fruit Lonicera caerulea L. var. kamtschatica (blueberry honeysuckle, Caprifoliaceae) were studied via (semi)preparative chromatographic fractionation followed by MS and μLC/MS analysis. The extraction procedure was optimized with respect to analytical purposes as well as its potential use for the preparation of nutraceuticals. The highest yield of anthocyanins was obtained using acidified methanol as the extraction medium. A comparable total anthocyanin content was obtained using a mixture of methanol and acetone. However, when Lonicera anthocyanins were in contact with acetone, a condensation reaction occurred to a large extent and related 5-methylpyranoanthocyanins were found. The effect of other extraction media, including ethanol as a "green" solvent, is also discussed. The potential of two fractionation procedures for extract purification differing in their chromatographic selectivity and scale was studied (i.e. using a Sephadex LH-20 gel column and a reversed phase). Fractions obtained by both procedures were used for a detailed analysis. MS and μLC/MS(2) methods were used for monitoring anthocyanin and 5-methylpyranoderivatives content as well as identifying less common and more complex dyes (dimer of cyanidin-3-hexoside, cyanidin-ethyl-catechin-hexosides, etc.). These more complex dyes are most likely formed during fruit treatment.     

On comparison of ℓ-stable vector optimization results

Two papers with similar optimality conditions were published by I. Ginchev, and by D. Bedna?ík and K. Pastor independently in Nonlinear Analysis in 2011. We compare these results. We also show the equivalence of two definitions of ?-stability of vector functions. Moreover, we generalize another result given by I. Ginchev and V. I. Ivanov [J. Math. Anal. Appl. 340 (2008), 646–657] and compare it with the previously mentioned optimality conditions.     

On the power series expansions for the sine and cosine

In this note we give an elementary derivation for the power series expansions for the sine and the cosine function.     

Multi-objective seaport planning by MOORA decision making

An approach is needed to localize in an optimal way a seaport facing different indicators, criteria or objectives sometimes from different groups or individuals. The internal mechanical solution of a Ratio System, producing dimensionless numbers, is preferred to Cost-Benefit or to Weights which most of the time are used to equalize the different units. The ratio system creates the opportunity to use a second approach: a non-subjective Reference Point Theory based on the found ratios. The two approaches form a control on each other. This theory is called MOORA (Multi-Objective Optimization by Ratio Analysis). As an application a ranking is made for the best location of a new seaport or for the expansion of an existing one given a set of objectives to be fulfilled.     

Retention of 3,5-dinitrobenzoyl derivatives of linear alcohol polyethoxylates in reversed-phase liquid chromatographic system with acetonitrile-water mobile phase

The influence of mobile phase composition (acetonitrile-water ratio) on the separation of derivatised linear alkyl polyethoxylates (LAEs) is evaluated using thermodynamic quantities (Gibbs energy, enthalpy and entropy). In comparison to homologue series of alcohols oligomers of LAEs show irregular chromatographic behaviour that is demonstrated in irregular changes of thermodynamic quantities. It might be explained considering an influence of some of the following processes or their combinations on the retention of LAEs. These processes are solvation of oxyethylene chains in mobile phase, their interaction with silanols on silica surface of stationary phase and possibly their conformation changes. The composition of a mobile phase affects the mentioned processes and that is why the retention of LAEs is strongly (for the reversed-phase system unusually) sensitive to this composition in the studied range (volume fraction of acetonitrile phi = 0.90, 0.96 and 0.98). The experimental data also support the idea of the active role of stationary phase in the reversed-phase system.     

Aspects of trapping efficiency and matrix effects in the development of a restricted‐access‐media‐based trap‐and‐elute liquid chromatography with mass spectrometry method

Online restricted access media with liquid chromatography and tandem mass spectrometry for the direct analysis of small molecules in biological fluids represents an interesting alternative to time‐demanding traditional sample preparation techniques. In this study, important considerations concerning the development of a restricted access media with liquid chromatography and tandem mass spectrometry method for the analysis of dansylated estrogens in biological matrix are presented. Parameters influencing peak tailing and trapping efficiency were evaluated. The key factors included the ion strength of the mobile phase, a loading flow rate of the sample onto the trap column, and selection of a proper stationary phase of the trap column for a given set of analytes. These parameters have proven to be essential for minimizing any unwanted chromatographic peak tailing. The bulk derivatization of the analytes in the biological fluids and its relationship to the observed matrix effects was evaluated as well.     

Current trends in the description of lanthanum strontium manganite oxygen electrode reaction mechanism in a high-temperature solid oxide cell

This review summarizes recent progress in understanding the oxygen reduction and evolution reactions at the lanthanum strontium manganite electrode of a high-temperature solid oxide cell. Information provided here is put into the perspective of the defect chemistry of lanthanum strontium manganite and its impact on the electrode reaction mechanisms itself. After summarizing recent views on the oxygen reduction reaction mechanism, the focus turns to the oxygen evolution reaction, which is significantly less treated in the literature. A combination of the information in the literature on both reactions was the basis for modified reaction mechanism of the oxygen evolution reaction to be proposed under consideration of recent experimental observations and theoretical findings.     

A Counterexample on Sample-Path Optimality in Stable Markov Decision Chains with the Average Reward Criterion

This note deals with Markov decision chains evolving on a denumerable state space. Under standard continuity-compactness requirements, an explicit example is provided to show that, with respect to a strong sample-path average reward criterion, the Lyapunov function condition does not ensure the existence of an optimal stationary policy.     

An aperiodic set of 13 Wang tiles

A new aperiodic tile set containing only 13 tiles over 5 colors is presented. Its construction is based on a recent technique developed by Kari. The tilings simulate the behavior of sequential machines that multiply real numbers in balanced representations by real constants.     

Novel synthetic approach to alfaprostol key intermediates via Stille coupling with an alkyne

Novel intermediates based on the Corey skeleton for preparation of the ω-chain of non-halogenated unnatural prostaglandin analogues containing a triple bond at position 13–14 (PG numbering) were synthesized. The utilization of a novel synthetic approach towards a new tin intermediate, and subsequent Stille coupling opens up new possibilities for preparing these important pharmaceutical intermediates.