Capillary electrochromatography using polyelectrolyte multilayer coatings

This review covers recent progress in polyelectrolyte multilayer (PEM) coatings applied to analytical separations using open-tubular capillary electrochromatography (OT-CEC). The simple preparation procedure involved in the PEM approach has provided some attractive features over other modes of capillary electrophoresis-based separations including packed column capillary electrochromatography (PC-CEC) and micellar electrokinetic chromatography (MEKC). PEM coatings have been used to alleviate the adsorption of basic analytes, to improve separations, and to improve the stability of the electroosmotic flow. Fundamental aspects of PEM coatings on surfaces and analytical separation platforms are briefly outlined in this review. In addition, applications of PEM coatings to fused-silica capillaries or microchip separation devices for the separation of small achiral or chiral analytes, as well as large biomolecules, are discussed.     

The synthesis of 5,8-difluoronaphtho[2,3-c]thiophene-4,9-dione and its facile conversion to 2-[2-(dimethylamino)ethyl]- 5-[2-(dimethylamino)ethylamino]-8-fluoro-naphtho[2,3-c] pyrrole-4,9-dione

The synthesis of 5,8-difluoronaphtho[2,3-c]thiophene-4,9-dione ( 2a ) has been accomplished. Treatment of 2a with 2,2-dimethylaminoethylamine leads to 2-[2-(dimethylamino)ethyl]-5-[2-(dimethylamino)ethylamino]-8-fluoronaphtho[2,3-c]pyrrole-4,9-dione ( 6 ).     

A multitechnique surface analytical study of a segmented block copolymer poly(ether-urethane) modified through an H2O radio frequency glow discharge

Recent work in our laboratories has fully characterized the surface region of a segmented poly(ether-urethane) (PEU) extending from the air/polymer interfacial region through bulk depths in the micron range. This characterization utilized energy and angle dependent Electron Spectroscopy for Chemical Analysis (ESCA), Attenuated Total Reflectance–Fourier Transform Infrared Spectroscopy (ATR–FTIR), and Comprehensive Wettability Profiling (contact angle using a homologous series of liquids) as defined by Zisman. In this study this same multi-analytical-technique approach is used to elucidate changes in these PEU surfaces induced through an H₂O Radio Frequency Glow Discharge (RFGD) plasma. This investigation reports both qualitative and quantitative changes due to the modification treatments as well as the permanency of the changes effected on these surfaces through the plasma treatment. From our analyses, the amount of surface residing polyurethane (hard segment) is observed to increase due to a proposed plasma etching mechanism. Further, the addition of oxygen containing functionality is detected at the modified surfaces unique with respect to the unmodified PEU. These surface modifications which show large increases in wettability, are finally observed to be semi-permanent over a time period of 6 months.     

INHIBITION OF PHOTOTAXIS IN Volvox aureus BY NATURAL AND SIMULATED SOLAR ULTRAVIOLET LIGHT

Exposure to artificial UV wavelengths and the UV component of sunlight delays positive phototaxis in the green alga Volvox aureus. Broad band wavelength filters were used to modify the output from UV-B sources (280-320 nm) and natural sunlight. The delay in phototaxis by artificial UV is increased with exposure to shorter UV-B wavelengths. Natural sunlight experiments were performed with exposure to full sunlight and to its UV component only. The UV component present in summer sunlight produced long periods of inhibition in phototaxis and even lethality, while exposure to the total spectrum of sunlight had no significant effects on movement or survival. The data indicate that although this species of alga is well equipped to deal with present levels of UV exposure, increases in the short UV-B wavelengths in sunlight may force an alteration in patterns of photomovement.     

The design, synthesis and evaluation of high affinity macrocyclic carbohydrate inhibitors

Carbohydrate-protein interactions have been investigated for a model system of a monoclonal antibody, SYA/J6, which binds a trisaccharide epitope of the O-polysaccharide of the Shigella flexneri variant Y lipopolysaccharide. The thermodynamics of binding for the methyl glycoside of the native trisaccharide epitope, Rha-Rha-GlcNAc () to SYA/J6 over a range of temperatures exhibits strong, linear enthalpy-entropy compensation and a negative heat capacity change (DeltaC(p)=-152 cal mol(-1) degree(-1)). At 293 K the free energy of association is the sum of favourable enthalpy and entropy contributions (DeltaH=-3.9 kcal mol(-1) and -TDeltaS=-2.9 kcal mol(-1)). Crystal structures for SYA/J6 Fab detailed the position of the native trisaccharide epitope, Rha-Rha-GlcNAc, and facilitated a strategy to design a tighter binding, low molecular weight ligand. This involved pre-organization of the native trisaccharide in its bound conformation by addition of intramolecular constraints (a beta-alanyl or glycinyl tether). ELISA measurements indicated that the glycinyl tethered trisaccharide was not an optimal candidate for further analysis, while microcalorimetry provided data showing that the beta-alanyl tethered trisaccharide displayed a 15-fold increase in affinity for SYA/J6. Tethering resulted in a favourable entropic contribution to binding, relative to the native trisaccharide (-TDeltaDeltaS=-1.2 kcal mol(-1)). Potential energy and dynamics calculations using the AMBER Plus force fields indicated that trisaccharide adopted a rigid conformation similar to that of the bound conformation of the native trisaccharide epitope. While this strategy resulted in modest free energy gains by minimizing losses due to conformational entropy, thermodynamic data are consistent with significant contributions from solvent reorganization.     

Pyridine-substituted oligopeptides as scaffolds for the assembly of multimetallic complexes: variation of chain length

This paper presents the synthesis and characterization of pyridine-substituted artificial oligopeptides with an aminoethylglycine backbone of varying length, which are designed to act as scaffolds for the self-assembly of multimetallic structures. The identities and purities of the oligopeptides are confirmed with mass spectrometry, (1)H NMR, HPLC, and pH titrations. The acid dissociation constants for the oligopeptides were determined and were found to decrease with increasing pyridine units. Titrations of the oligopeptides with Cu(II) and Pt(II) complexes containing the tridentate ligands 2,2':6',2'-terpyridine and pyridine 2,6-dicarboxylic acid were monitored using UV-visible absorption spectroscopy and showed stoichiometric binding based on the number of pyridines on the peptide strand. Metal titrations performed using an analogous oligopeptide with methyl substituents (in place of the pyridine ligands) showed very weak or no binding. In the case of the oligopeptides containing bound Pt(terpyridine)(2+) complexes, cyclic voltammetry reveals two sequential one-electron reductions at formal potentials that do not vary as a function of oligopeptide length. The measured diffusion coefficients were measured with chronoamperometry and were found to decrease with increasing oliopeptide length.     

Forensic classification of ballpoint pen inks using high performance liquid chromatography and infrared spectroscopy with principal components analysis and linear discriminant analysis

Several varieties of blue ballpoint pen inks were analyzed by high performance liquid chromatography (HPLC) and infrared spectroscopy (IR). The chromatographic data extracted at four wavelengths (254, 279, 370 and 400 nm) was analyzed individually and at a combination of these wavelengths by the soft independent modeling of class analogies (SIMCA) technique using principal components analysis (PCA) to estimate the separation between the pen samples. Linear discriminant analysis (LDA) measured the probability with which an observation could be assigned to a pen class. The best resolution was obtained by HPLC using data from all four wavelengths together, differentiating 96.4% pen pairs successfully using PCA and 97.9% pen samples by LDA. PCA separated 60.7% of the pen pairs and LDA provided a correct classification of 62.5% of the pens analyzed by IR. The results of this study indicate that HPLC coupled with chemometrics provided a better discrimination of ballpoint pen inks compared to IR. The need to develop a suitable IR method for analysing blue ballpoint pen inks has been emphasized and it is hoped that the development of such a method would indeed provide a valuable tool for the non-destructive analysis of blue ballpoint pen ink samples for forensic purposes.     

Unidirectional Littelmann Paths for Crystals of Type A and Rank 2

Algebras and Representation Theory - For the Kashiwara crystal of a highest weight representation of an affine Lie algebra of type A and rank e, with highest weight Λ, there is a labeling by...     

Cross-channel coupling in positron-atom scattering

Coupled-state calculations including positronium channels are reported for positron scattering by atomic hydrogen, lithium and sodium. Integrated cross sections and total cross sections are presented for all three atoms. For lithium differential cross sections are also given. Throughout, comparison is made between results calculated with and without inclusion of the positronium channels. S-wave cross sections for positron scattering by atomic hydrogen in the Ps(1s, 2s, 2p)+H(1s, 2s, 2p) approximation show the high energy resonance first observed by Higgins and Burke in the coupled-static approximation. This resonance has now moved up to 51.05 eV and narrowed in width to 2.92 eV. Other pronounced structure is seen in the S-wave cross sections between 10 and 20 eV; it is tentatively suggested that this structure may be due to the formation of a temporary pseudo-molecular collision complex. Results calculated in the Ps(1s, 2s, , 2p, ,+H(1s, 2s, , 2p, approximation show convergence towards accurate values in the energy region below and in the Ore gap. Contrary to previous work on lithium using only an atomic basis, it is found that coupling to the 3d state of lithium is not so important when positronium channels are included; this is because a mixed basis of atom and positronium states gives a more rapidly convergent approximation than an expansion based on atom states alone. The threshold behaviour of the elastic cross section and the Ps(1s) formation cross section for lithium is investigated. Results in the Ps(1s, 2s, 2p)+Na(3s, 3p) approximation for sodium show good agreement with the total cross section measurements of Kwan et al.