Cyclopolymerization of diastereomeric diepoxides

The meso- and d,l-diastereomers of o-bis(epoxyethyl)benzene have been synthesized and identified. The diastereomers were polymerized by a variety of catalysts to give a polymer which has mainly isochroman recurring units as a result of a cyclopolymerization mechanism. Some features of the polymerization with the triisobutylaluminum catalyst system have been studied. The rates of polymerization of the monomers and the transition temperatures of the resulting polymers have been determined. The results are explained on the basis of a controlled intramolecular propagation and a stereospecific polymerization.     

Direct identification of proteins from T47D cells and murine brain tissue by matrix-assisted laser desorption/ionization post-source decay/collision-induced dissociation

The purpose of this study is to determine the feasibility of the direct matrix-assisted laser desorption/ionization (MALDI) identification of proteins in fixed T47D breast cancer cells and murine brain tissues. The ability to identify proteins from cells and tissue may lead to biomarkers that effectively predict the onset of defined disease states, and their dynamic behavior could be an important hint for drug target discoveries. Direct tissue application of trypsin allows protein identification in cells and tissues, while maintaining spatial integrity and intracellular organization. Using a chemical printer, matrix was co-registered on trypsinized human T47D breast cancer cells and cryo-preserved sections of murine brain tissue, followed by MALDI post-source decay (PSD) or MALDI collision-induced dissociation (CID), respectively. Mass-to-charge (m/z) data from the cells and brain tissues were processed using Mascot software interrogation of the National Center for Biotechnology Information (NCBI) database. Histone H2B was identified from cultured T47D human breast cancer cells. Tubulin beta2 was identified from mouse brain cortex following an induced stroke. These results suggest that MALDI PSD/CID, combined with bioinformatics, can be used for the direct identification of proteins from cells and tissues. Refinements in preparation techniques may improve this approach to provide a tool for quantitative proteomics and clinical analysis.     

EXAFS structural studies of electrodeposited Co and Ni hexacyanoferrate films

XAS (EXAFS and XANES), XPS and IR spectroscopies were used to extract redox compositional and structural information on films of electrodeposited Co and Ni hexacyanoferrates whose redox state was manipulated electrochemically. The X-ray methods provided direct information on the metal species and IR provided indirect information via the behaviour of the ligand vibration. XPS responses showed that the electrochemical response of Co hexacyanoferrate is attributable to Co (except for a small amount of Fe^II oxidation at very positive potentials), and of Ni hexacyanoferrate to Fe; XANES edge shifts confirm these deductions. Local structure around the metal atoms was extracted from EXAFS data in terms of M′–N, M′–C and M′–Fe (M′ = Co or Ni) distances and the associated Debye-Waller factors as functions of film charge state. For Co hexacyanoferrate, the redox variation of static disorder was consistent with a molecular model involving discrete Co^II and Co^III sites, whose populations respond to potential, but not with a solid-state model.     

A virtual trajectory model predicts differences in vocal fold kinematics in individuals with vocal hyperfunction

A simple, one degree of freedom virtual trajectory model of vocal fold kinematics was developed to investigate whether kinematic features of vocal fold movement confirm increased muscle stiffness. Model simulations verified that increases in stiffness were associated with changes in kinematic parameters, suggesting that increases in gesture rate would affect kinematic features to a lesser degree in vocal hyperfunction patients given the increased levels of muscle tension they typically employ to phonate. This hypothesis was tested experimentally in individuals with muscle tension dysphonia (MTD; N = 10) and vocal nodules (N = 10) relative to controls with healthy normal voice (N = 10) who were examined with trans-nasal endoscopy during a simple vocal fold abductory-adductory task. Kinematic measures in MTD patients were less affected by increased gesture rate, consistent with the hypothesis that these individuals have elevated typical laryngeal muscle tension. Group comparisons of the difference between medium and fast gesture rates (Mann-Whitney, one-tailed) showed statistically significant differences between the control and MTD individuals on the two kinematic features examined (p<0.05). Results in nodules participants were mixed and are discussed independently. The findings support the potential use of vocal fold kinematics as an objective clinical assay of vocal hyperfunction.     

Finiteness conditions and PD<Subscript><Emphasis Type="Italic">r</Emphasis></Subscript>-group covers of PD<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript>-complexes

We show that an infinite cyclic covering space M′ of a PD _n -complex M is a PD _n-1-complex if and only if χ(M) = 0, M′ is homotopy equivalent to a complex with finite [(n−1)/2]-skeleton and π₁(M′) is finitely presentable. This is best possible in terms of minimal finiteness assumptions on the covering space. We give also a corresponding result for covering spaces M _ν with covering group a PD _r -group under a slightly stricter finiteness condition.      

Chemical Structure and Biological Activities of Secondary Metabolites from Salicornia europaea L.

Salicornia europaea L. is a halophyte that grows in salt marshes and muddy seashores, which is widely used both as traditional medicine and as an edible vegetable. This salt-tolerant plant is a source of diverse secondary metabolites with several therapeutic properties, including antioxidant, antidiabetic, cytotoxic, anti-inflammatory, and anti-obesity effects. Therefore, this review summarizes the chemical structure and biological activities of secondary metabolites isolated from Salicornia europaea L.     

Electrochemical quartz crystal microbalance studies of redox polymer films

Electrochemical quartz crystal microbalance measurements are reported for redox switching of thin films of three macromolecule-metal complexes: poly(vinylferrocene) (PVF), 10% osmium-functionalized poly(vinylpyridine) (Os-PVP), and 10% osmium functionalized poly(vinylpyridine-co-styrene) (Os-PVP-co-PS). The data provide insight into the ion and solvent transfer processes associated with electron transfer between the electrode and the electroactive film. Four important parameters are identified: electrolyte composition, (co)polymer composition, prior film history and experimental time scale.