Recent advances in polymeric monolithic stationary phases for electrochromatography in capillaries and chips

This review article summarizes the advances made over the last two years in polymeric monoliths for capillary electrochromatography (CEC). It covers the scientific literature in the period extending form the second half of 2002 until the end of first half of 2004. Currently, there is an increasing interest in monolithic stationary phases in CEC as an alternative to particulate packed capillary columns due in major part to the simplicity of the in situ preparation of monolithic stationary phases and the availability of a wide chemistry for surface ligands, which allow for tailoring the chromatographic sorbent needed for solving a given separation problem(s). The various approaches, formats, and chemistries used for the preparation of monolithic stationary phases are described.     

Capillary zone electrophoresis of linear and branched oligosaccharides

The electrophoretic behavior of derivatized linear and branched oligosaccharides from various sources was examined in capillary zone electrophoresis with polyether-coated fused-silica capillaries. Two UV-absorbing (also fluorescent) derivatizing agents (2-amino-pyridine and 6-aminoquinoline) were utilized for the electrophoresis and sensitive dtection of neutral oligosaccharides, e.g., N-acetylchitooligosaccharides, high-mannose glycans and xyloglucan oligosaccharides. The oligosaccharides labelled with 6-aminoquinoline yielded eight times higher signal than those tagged with 2-aminopyridine. Plots of logarithmic electrophoretic mobilities of labelled N-acetylchitooligosaccharides with 6-aminoquinoline or 2-aminopyridine versus the number of sugar residues in the homologous series yielded straight lines in the size range studied, the slopes of which were independent of the tagging functions. The slopes of these lines are referred to as the N-acetylglucosaminyl group mobility decrement. The oligosaccharides were better resolved in the presence of tetrabutylammonium bromide in the running electrolyte. Furthermore, the electrophoretic mobilities of branched oligosaccharides were indexed with respect to linear homooligosaccharides, an approach that may prove valuable in correlating and predicting the mobilities of complex oligosaccharides.     

Biospecific interaction (affinity) CEC and affinity nano-LC

This review article is aimed at assessing the recent progress made in affinity nano-LC and affinity CEC performed in capillaries and microchips. A variety of biospecific interactions is covered including lectin affinity, immunoaffinity, immobilized metal affinity, sugar-based affinity, protein A affinity, protein G affinity, aptamer affinity, enzyme affinity, and other miscellanea. ACE involving affinity interaction in free solution is not covered in this review article. Also, affinity-based separations involving chiral recognition are not the subject of this review article because they are the topic of a more specialized review article on chiral separations in this special issue. A total of 31 papers published in the period 1998-2006 have been discussed in this review article.     

A Novel Electrochemical Sensor Based on Poly(1,5-diaminonaphthalene) and Poly(1,2-diaminoanthraquinone) Core-shell Composite Electrodes for Effective Voltammetric Determination of Nitrite

In this article, poly(1,2-diaminoanthraquinone) (pDAAQ) and poly(1,5-diaminonaphthalene) (pDAN) were electrochemically deposited layer by layer on a glassy carbon electrode (GCE) to generate pDAAQ/pDAN@GCE and pDAN/pDAAQ@GCE composite electrodes, respectively. The morphology and characteristics of the modified electrodes were investigated via electrochemical impedance spectroscopy)EIS), Fourier transform infrared spectroscopy (FT-IR), and scanning electron microscopy)SEM). The obtained results reveal the outstanding performance of the pDAN/pDAAQ@GCE electrode for electrochemical nitrite sensing where pDAAQ plays a vital role as the inner layer. Cyclic voltammetry (CV), linear sweep voltammetry (LSV), and differential pulse voltammetry (DPV) measurements revealed that the oxidation peak current of nitrite was proportional to its concentration. The best LSV results were obtained in a concentration range of 10–150 μM, with a limit of detection of 1.2 μM. Furthermore, the pDAN/pDAAQ@GCE composite electrode was used to determine nitrite ions in real water samples with good results.     

No slip boundary effects in non-Darcian mixed convection from a vertical wall in saturated porous media. Analytical solution

An analytical study is made for wall effects in non-Darcy mixed convection from vertical impermeable surfaces embedded in a saturated porous medium. The governing equations are transformed into a dimensionless form by non-similar transformation to cover both forced and natural convection dominated regimes. Two different dimensionless parameters that measure the strength of mixed convection were found in both regimes. The parameters of forced convection dominated regime can be related to those of natural convection dominated regime. An approximate analytical solution for the governing equations was obtained. Temperature and velocity profiles for both regimes are presented. Received on 9 September 1997     

Experimental analysis of the quasi-static and dynamic torsional behaviour of shape memory alloys

This paper investigates experimentally the quasi-static and dynamic torsional behaviour of shape memory alloys wires under cyclic loading. A specifically designed torsional pendulum made of a Ni–Ti wire is described. Results on the quasi-static behaviour of the wire obtained using this setup are presented, giving an overall view of the damping capacity of the material as function of the amplitude of the loading (imposed torsional angle), the frequency and the temperature. The dynamical behaviour is then presented through measured frequency response function between forcing angle at the top of the pendulum and the difference between top and bottom rotation angles in the vicinity of the first eigenfrequency of the wire, i.e. in the range [0.3 Hz, 1 Hz]. The softening-type non-linearity and its subsequent jump phenomenon, predicted theorically by the decrease of the effective stiffness when martensite transformation starts is clearly evidenced and analysed.     

Approximate solutions and micro-regularity in the Denjoy-Carleman classes

We begin with a sequence M of positive real numbers and we consider the Denjoy-Carleman class CM. We show how to construct M-approximate solutions for complex vector fields with CM coefficients. We then use our construction to study micro-local properties of boundary values of approximate solutions in general M-involutive structures of codimension one, where the approximate solution is defined in a wedge whose edge (where the boundary value exists) is a maximally real submanifold. We also obtain a CM version of the Edge-of-the-Wedge Theorem.     

Extraction of the Anticancer and Antimicrobial Agent,Prodigiosin, from Vibrio gazogenes PB1 and Its Identification by 1D and 2D NMR

Prodigiosin is a secondary metabolite produced in several species of bacteria. It exhibits antimicrobial and anticancer properties. Methods for the extraction and identification of prodigiosin and their related derivatives from bacterial cultures typically depend on solvent-based extractions followed by NMR spectroscopy. The estuarine bacterium, V. gazogenes PB1, was previously shown to produce prodigiosin. This conclusion, however, was based on analytical data obtained from ultraviolet-visible absorption spectrophotometry and infrared spectroscopy. Complete dependence on these techniques would be considered inadequate for the accurate identification of the various members of the prodiginine family of compounds, which possess very similar chemical structures and near-identical optical properties. In this study, we extracted prodigiosin from a culture of Vibrio gazogenes PB1 cultivated in minimal media, and for the first time, confirmed the synthesis of prodigiosin Vibrio gazogenes PB1 using NMR techniques. The chemical structure was validated by ¹H and ¹³C NMR spectroscopy, and further corroborated by 2D NMR, which included ¹H-¹H-gDQFCOSY, ¹H-¹³C-gHSQC, and ¹H-¹³C-gHMBC, as well as ¹H-¹H-homonuclear decoupling experiments. Based on this data, previous NMR spectral assignments of prodigiosin are reaffirmed and in some cases, corrected. The findings will be particularly relevant for experimental work relating to the use of V. gazogenes PB1 as a host for the synthesis of prodigiosin.