RP-HPLC analysis of phenolic compounds and flavonoids in beverages and plant extracts using a CoulArray detector

Methods were developed for the analysis of natural antioxidants including phenolic compounds and flavonoids in beverages and plant extracts using gradient HPLC with multi-channel electrochemical coulometric detection. Suitability of various reversed-phase columns for this purpose was compared; pH and mobile phase gradients were optimized with respect to the separation selectivity and sensitivity of detection. Because of different target compounds in various sample types, the overlapping resolution maps and the normalized resolution product approaches described earlier were used to select optimum columns and gradients to suit the analysis of the individual sample types. The methods were applied to the analysis of phenolic compounds and flavonoids in beer, wine, tea, and yacon extracts. 32 phenolic compounds were identified and determined, including derivatives of benzoic and cinnamic acids, flavones, and a few related glycosides. Eight-channel CoulArray detection offers high selectivity and sensitivity with limits of detection in the low microg L(-1) range, at least an order of magnitude lower than single-channel coulometric detection using the Coulochem detector. No special sample pretreatment is necessary and, because of the compatibility of the CoulArray detector with gradient elution, phenolic antioxidants of different polarities can be determined in a single run. In addition to the retention times, the ratios of the areas of the pre-dominant and post-dominant peaks to the area of the dominant peak can be used for improved identification of natural antioxidants.     

Conformational transitions of calixphyrin derivatives monitored by temperature-dependent NMR spectroscopy. Ab initio interpretation of the spectra

Eight meso-aryl calixphyrin derivatives were synthesized and their conformational equilibria and transitions studied with temperature-dependent NMR spectroscopy. On the basis of density functional computations, several conformer species could be identified and observed changes in chemical shifts explained. In some compounds, the aryl group rotation and porphyrin ring flipping could be monitored independently, as their NMR coalescence temperatures were well-separated. Calculated relative conformer energies, transition barriers, and isotropic shieldings agree well with the experimental data. In the meso-substituted porhyrins (calixphyrins) the sp3 carbon atoms perturb their pi-electron system and significantly modify the molecular shape and the flexibility. Even when the conjugation of the pi-electron system was destroyed by the nonplanarity, far-range electronic induction effects still exist and influence chemical shielding and molecular geometry. The aryl functional groups moderately modify the structure of the calixphyrin ring and thus can be used for fine-tuning of the mechanical and chemical properties of these compounds.     

Rapid and simple method for determination of Nepsilon-(carboxymethyl)lysine and Nepsilon-(carboxyethyl)lysine in urine using gas chromatography/mass spectrometry

A new procedure was developed to determine in urine the concentrations of N(epsilon)-(carboxymethyl)lysine (CML) and N(epsilon)-(carboxyethyl)lysine (CEL), the major products of oxidative modification of glycated proteins, to assess levels of oxidative stress in physiological systems. The urine samples were acetonitrile-deproteinized, then derivatized by ethylchloroformate, and N(O,S)-ethoxycarbonyl ethyl esters of amino acids were analysed by isotope dilution gas chromatography/mass spectrometry. Recovery averaged 89%. Linearity was excellent (r = 0.998-0.999) in the 0.5-25 micromol/L range for CML and CEL. The limit of detection of this assay was 0.1 micromol/L (corresponding to 0.20 pmol of CML or CEL on column). Intra-day and inter-day precisions were likewise excellent, with relative standard deviations <4.63 and <6.15%, respectively. Accuracy of CML and CEL determination (15 micromol/L) was 2.9 and 5.9% of the estimated theoretical value. The time from obtaining the urine sample to determination of the concentration from the chromatographic peak was 80 min or less. This method is sensitive, reproducible, accurate, relatively cheap and very simple. It can be useful for laboratories involved in the diagnosis and monitoring of age-related chronic diseases.     

Synthetic routes to linear oligo-Tröger's bases

Derivatives of Tr?ger's base (TB) have played important roles in receptor construction due to their rigid V-shape. A new class of these compounds are the oligo-TBs, which can function as cavitands. Herein, we describe both stepwise and one-step (oligomerization) methods suitable for the preparation of linear oligo-TBs.     

Enantioseparations of non-benzenoid and oligo-Tröger’s bases by HPLC on Whelk O1 column

The separation of enantiomers of several ‘bis- and tris-Tröger’s bases’ by HPLC on commercially available chiral stationary phase Whelk O1 is described for the first time. The observed structure–enantioselectivity relationships are in agreement with the previously established molecular recognition model. For all ‘bis- and tris-Tröger’s bases’ studied, satisfactory to excellent enantioselectivities were observed.     

Communication: Experimental proof of symmetry breaking in tilted smectics composed of molecules with axial chirality

For the first time, domains with twisted structures have been established in planar samples of achiral compounds in tilted smectic C phase. This evidences separation of molecular conformers differing in the sense of axial chirality and confirms polar C(2) symmetry of these domains. A simple model considering polar surface anchoring energy and bulk energy of the twist can account for this finding. Conditions for coexistence of twisted and homogeneous domains are discussed.     

Cyclodextrin modified gold nanoparticles-based open-tubular capillary electrochromatographic separations of polyaromatic hydrocarbons

In this study, spherical gold nanoparticles (GNPs) of 14.7 nm diameter, prepared by citrate reduction of a gold(III) salt and characterized by UV–Vis absorption spectrometry and transmission electron microscopy, were modified by a covalent attachment of 6^I-O-(3-mercaptopropyl)β-cyclodextrin (β-CD-SH) or per-6-deoxy-per-6-mercapto-β-cyclodextrin (β-CD-SH7). Subsequently, via three alternative approaches, β-CD-modified GNPs were immobilized onto the inner wall of the fused-silica (FS) capillaries and applied as special stationary phases for open-tubular capillary electrochromatography (OT-CEC). The first immobilization procedure was based on pre-derivatization of a FS capillary with (3-mercaptopropyl)trimethoxysilane (MPTMS) followed by subsequent reactions with GNPs and β-CD-SH or β-CD-SH7. The other two preparation protocols took advantage of sol–gel approach gaining a significant increase in the interaction surface for solutes. In both instances, the sol–gel created 3D structure was further covalently modified with GNPs. Serving that purpose, either β-CD-SH7 modified GNPs were used for the immobilization into the sol–gel matrix (“one-step sol–gel technique”) or native GNPs were immobilized first into the sol–gel matrix and subsequently modified with β-CD-SH7 (“two-step sol–gel technique”). The separation performance of CD-GNPs modified FS capillaries was tested by OT-CEC in reversed-phase mode applied to separation of a model mixture of five polyaromatic hydrocarbons. The highest separation efficiencies were obtained with the capillaries prepared by two-step sol–gel technique. However, with respect to the relatively low reproducibility of this method, the first of the above preparation procedures, i.e., a simple pre-derivatization of the FS capillary with MPTMS ensued with β-CD-SH7-GNPs immobilization seems to be more feasible approach providing decent separation efficiency.     

On Polynomial Solutions of Generalized Moisil-Théodoresco Systems and Hodge-de Rham Systems

The aim of the paper is to study relations between polynomial solutions of generalized Moisil-Théodoresco (GMT) systems and polynomial solutions of Hodge-de Rham systems and, using these relations, to describe polynomial solutions of GMT systems. We decompose the space of homogeneous solutions of GMT system of a given homogeneity into irreducible pieces under the action of the group O(m) and we characterize individual pieces by their highest weights and we compute their dimensions.     

Local-in-space estimates near initial time for weak solutions of the Navier-Stokes equations and forward self-similar solutions

We show that the classical Cauchy problem for the incompressible 3d Navier-Stokes equations with (?1)-homogeneous initial data has a global scale-invariant solution which is smooth for positive times. Our main technical tools are local-in-space regularity estimates near the initial time, which are of independent interest.