Surface-modified magnetic colloids for affinity adsorption of immunoglobulins

This work describes the preparation, characterization and in vitro adsorption tests of surface-modified magnetoliposomes for affinity binding of (i) anticardiolipin (isotype G) antibodies and (ii) specific isotype E antibodies generated by hypersensitivity reactions in humans with respiratory allergy. In the first case, cardiolipin embedded in the bilayer of magnetoliposomes was used as specific ligand. In the second case, antigenic proteins present in an extract of Dermatophagoids pteronyssinus and Blomia tropicalis mites were covalently coupled on the surface of magnetoliposomes via a diglycolic spacer arm, and used as specific ligands for IgE. Antibody adsorption was performed in a high-gradient magnetophoresis system, using either sera of healthy individuals or a pool of sera from autoimmune or allergic patients. The selectivity and capacity of the system were quantified by a frontal analysis in a capillary column, and by constructing breakthrough curves. The results show that the highest yield and selectivity were obtained if the ligand was extended into the aqueous layer surrounding the magnetoliposome surface. A 100% selectivity was obtained for adsorption of specific IgE, and 8% for IgG. These results demonstrate the potentialities of both types of surface-modified magnetic biocolloids in the field of in vitro diagnosis tests for allergic or autoimmune conditions.     

Dielectric relaxation studies and electro‐optical measurements in poly(triethylene glycol dimethacrylate)/nematic E7 composites exhibiting an anchoring breaking transition

Electric field driven anchoring breakage in poly(triethylene glycol dimethacrylate)/nematic E7 composites was studied using dielectric spectroscopy and transmittance measurements. The transmittance hysteresis observed on increasing and decreasing an applied electric field, associated with different alignment states of the liquid crystal (LC), was monitored through dielectric loss. Essential changes are felt mainly in the δ‐peak, i.e. the dielectric response of the nematic when the director lies parallel to the applied electric field. An irreversible effect persists after the field had exceeded a critical value, which was manifest in a higher transmittance and a higher dielectric strength of the δ‐peak in the OFF state. The initial scattering/opaque state of the sample can only be recovered by heating to the clearing temperature of the nematic LC. The effect referred, commonly called memory effect, is rationalized in terms of anchoring breakage of the LC at the polymer–LC interfaces. The electro‐optical response was tested for different poly(triethylene glycol dimethacrylate)/nematic E7 composites in different composition ratios prepared by polymerisation‐induced phase separation. The lowest threshold field was observed for the 30:70 composite.     

Differentiation of Lippia gracilis Schauer Genotypes by LC Fingerprint and Chemometrics Analyses

A liquid chromatographic method with photodiode-array detection has been developed for differentiation of seven genotypes of Lippia gracilis Schauer, originated from Sergipe state (named 106 to 110) and from Bahia state (201 and 202), cultivated and collected in the rural campus of the Federal University of Sergipe. For a comparative analysis of the fingerprint chromatograms, chemometric tools were applied with exploratory methods. The genotypes were differentiated and their relationship with original place was established (Sergipe and Bahia states) by principal component analysis of the fingerprint chromatograms of both leaves and stem samples.     

Preparation of glutamine films on silicon substrates

Amino acids and polypeptides thin films, pure or attached to polymers, present large application as sensors and biosensors. The interactions between such films and the supports, their sensorial properties, as well as the development of techniques to produce thin regular films, are still challenges in the area. In this work, we present the preparation of L ‐glutamine thin films on silicon substrates, the factors that determine amino acid/silicon substrate interaction, and the morphology of the films. For this purpose, a 2⁴ factorial design is used, taking into account the effects of the solvent system, the glutamine concentration, the temperature, as well as the pretreatment of the substrate surface. The contact angles between a drop of glutamine solution and the silicon substrate were taken for the preliminary evaluation of the affinity between the amino acid and the substrate. The results have shown six promising experimental combinations with oxidized silicon as substrate to improve the solution/substrate interaction. Three of these promising conditions involved aqueous solution of L ‐glutamine and three alkalis solution. The obtained films were characterized by scanning electron microscopy (SEM), Rutherford backscattering (RBS), and Fourier transform infrared (FTIR) spectroscopy. The selected experimental conditions permitted to prepare a variety of films with L ‐glutamine, like small crystals, lamellas, needles, and smoothed regular films. The systems prepared in presence of alkalis solution yielded regular and smooth films. Copyright © 2008 John Wiley & Sons, Ltd.     

Perfect simulation for locally continuous chains of infinite order

We establish sufficient conditions for perfect simulation of chains of infinite order on a countable alphabet. The new assumption, localized continuity, is formalized with the help of the notion of context trees, and includes the traditional continuous case, probabilistic context trees and discontinuous kernels. Since our assumptions are more refined than uniform continuity, our algorithms perfectly simulate continuous chains faster than the existing algorithms of the literature. We provide several illustrative examples.     

The energy functional on the Virasoro–Bott group with the L 2-metric has no local minima

The geodesic equation for the right invariant L ²-metric (which is a weak Riemannian metric) on each Virasoro–Bott group is equivalent to the KdV-equation. We prove that the corresponding energy functional, when restricted to paths with fixed endpoints, has no local minima. In particular, solutions of KdV do not define locally length-minimizing paths.     

The nature of the N?O bond in amine oxides

Despite the ubiquitous presence of amine oxides in chemistry, there is no consensus about the nature of the N O bond in these compounds. In this work, we have used electron density analysis to investigate the nature of this bond in substituted amine oxides, R₃NO, and have compared it with the nature of the N O bond in hydroxylamines, R₂NOR, and model molecules that have well-established chemical bond character. The results showed that the N O bond length and relative stability are proportional to the inductive effect of the substituents. Quantum chemical topology, natural bond orbitals (NBO), and natural resonance theory (NRT) analyses indicated that the N O bond is polar covalent in all the studied amine oxides, but the ionic contribution is different. NBO and NRT analyses revealed that molecules with more electronegative substituents have strongly delocalized N O and N R bonds, whereas molecules with electropositive substituents have localized bonds.     

Cyclam functionalization through isocyanate insertion in Zr-N bonds

The insertion of isocyanates in (Bn(2)Cyclam)ZrX(2) is regioselective; (Bn(2)Cyclam)Zr(OR)(2) produces urea-like moieties by the insertion of RN═C═O in the Zr-N(amido) bonds of the cyclam ring. Depending on the bulkiness of the isocyanate R groups, O- and N-bound ureates are formed. (Bn(2)Cyclam)Zr(NH(t)Bu)(2) reacts with MesN═C═O at the terminal Zr-N bonds.     

Vibrational mode frequencies of silica species in SiO2-H2O liquids and glasses from ab initio molecular dynamics

Vibrational spectroscopy techniques are commonly used to probe the atomic-scale structure of silica species in aqueous solution and hydrous silica glasses. However, unequivocal assignment of individual spectroscopic features to specific vibrational modes is challenging. In this contribution, we establish a connection between experimentally observed vibrational bands and ab initio molecular dynamics (MD) of silica species in solution and in hydrous silica glass. Using the mode-projection approach, we decompose the vibrations of silica species into subspectra resulting from several fundamental structural subunits: The SiO(4) tetrahedron of symmetry T(d), the bridging oxygen (BO) Si-O-Si of symmetry C(2v), the geminal oxygen O-Si-O of symmetry C(2v), the individual Si-OH stretching, and the specific ethane-like symmetric stretching contribution of the H(6)Si(2)O(7) dimer. This allows us to study relevant vibrations of these subunits in any degree of polymerization, from the Q(0) monomer up to the fully polymerized Q(4) tetrahedra. Demonstrating the potential of this approach for supplementing the interpretation of experimental spectra, we compare the calculated frequencies to those extracted from experimental Raman spectra of hydrous silica glasses and silica species in aqueous solution. We discuss observed features such as the double-peaked contribution of the Q(2) tetrahedral symmetric stretch, the individual Si-OH stretching vibrations, the origin of the experimentally observed band at 970 cm(-1) and the ethane-like vibrational contribution of the H(6)Si(2)O(7) dimer at 870 cm(-1).