Stepwise cycloreversion of oxetane radical cations with initial C-O bond cleavage

2,4,6-Triaryl(thia)pyrylium salts have been used as electron-transfer photosensitizers for the cycloreversion of the oxetane ring system. The radical cation of 2,3-diphenyl-4-hydroxymethyloxetane (1) undergoes stepwise splitting via initial O-C2 cleavage. Spin and charge in the resulting intermediate are located in the oxygen and carbon atoms, respectively. Subsequent intramolecular nucleophilic attack produces 2,3-diphenyl-4-hydroxytetrahydrofuran (4a). Formation of this product occurs in the submicrosecond time scale, competing with C3-C4 cleavage to the detectable (lambdamax = 470 nm) trans-stilbene radical cation.     

Erratum to: Determination of metal ion content of beverages and estimation of target hazard quotients: a comparative study

This is a correction to the following paper: Hague T, Petroczi A, Andrews PR, Barker J, Naughton DP: Determination of metal ion content of beverages and estimation of target hazard quotients: a comparative study. Chem Central J 2008, 2:13.     

Vascular endothelial and smooth muscle cell culture on NaOH-treated poly(epsilon-caprolactone) films: a preliminary study for vascular graft development

Tissue engineering offers the potential of providing vessels that can be used to replace diseased and damaged native blood vessels. The endothelization of a synthetic vascular graft minimizes the failures associated with blood clotting and platelet activation. The aim of this study was to culture vascular-derived endothelial and smooth muscle cells on both untreated and NaOH-treated poly(epsilon-caprolactone) (PCL) films, a biocompatible and bio-resorbable polymer, and to evaluate the behavior of both cell types as a preliminary study for vascular graft development. PCL films were prepared by hot pressing; characterized by DSC, IR, SEM, and scanning force microscopy; and treated with NaOH to increase the surface hydrophilicity before cell culture. Endothelial and smooth muscle cells, isolated from pig cava vein, were characterized by immunofluorescence and confocal microscopy studies of endothelial nitric oxide synthase and alpha-smooth muscle actin. Good adhesion, growth, viability and morphology of both the endothelial and smooth muscle cells on PCL films were obtained, but a light stimulation of mitochondrial activity was observed during short culture times. NaOH treatment improved the adhesion and enhanced the proliferation in both cell types. This verified the possible use of this modified polymer as a support in the preparation of a synthetic vascular graft. [Diagram: see text] SEM micrograph of smooth muscle cells cultured on NaOH-treated PCL film. (Original magnification: 1000x).     

Conformational study of N-substituted 8-azabicyclo[3.2.1]octan-3-ones

N-Substituted 8-azabicyclo[3.2.1]octan-3-ones have been studied by ¹H and ¹³C NMR spectroscopy. In CDCl₃ solutions, these ketones display the same preferred conformation. The pyrrolidine and piperidone rings adopt a flattened N-8 envelope and distorted chair conformation, puckered at N-8 and flattened at C-3, respectively, with the N-substituent in axial position with respect to the piperidone ring.     

Potentiometric dissociation constants and analytical properties of α-mercaptobenzeneacetic acid

The α-mercaptobenzeneacetic acid has been synthesized and screened for its properties as an analytical reagent. The acid dissociation constants have been determined potentiometrically in 0.1 M KNO₃ and 0.5 M KNO₃ ethanol-water 20% (v/v) solutions at 25 ± 0.1 °C.     

Spectrofluorimetric determination of clioquinol in pharmaceutical preparations

Summary The absorption spectrum of the nitrate radical (NO₃) in aqueous solution and the kinetic of the reactions with Cl^– and OH^– have been determined using laser-spectrometric techniques. The maximum absorption was found at 635 nm with a decadic absorption coefficient of =(530±110) l/mol·cm. At 298 K rate constants of k₁=(1.0±0.2)·10⁷ l/mol·s for the reaction with chloride and of k₂=(8.2±0.9)·10⁷ l/mol·s for the reaction with hydroxide were obtained.     

Estimation of the aggregation number and core radius of microemulsions

Summary A simple working method for the estimation of the aggregation numbers and core radii from weight measurements of sodium bis-2-ethylhexylsulphosuccinate (aerosol-OT orAOT)/decane/water microemulsions of several compositions is proposed.Starting out from the hypotheses that (i) the density of the water inside the droplets is the same as that of free water, (ii) all the surfactant is localized as interface, and (iii) the penetration of the organic phase into the interface is negligible, values for the aggregation number and core radii comparable to those determined using more sophisticated methods were obtained.The results/methodological simplicity ratio may be of great advantage in kinetic work on reaction mechanisms in microemulsions.

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Abschätzung von Aggregationszahl und Radius von Mikroemulsionen

Zusammenfassung Es wird eine einfache Methode zur Abschätzung von Aggregationszahl und Core-Radius von Mikroemulsionen aus Gewichtsmessungen von Natriumbis-2-ethylhexylsulphosuccinat (aerosol-OT oderAOT)/Decan/Wasser-Mikroemulsionen verschiedener Zusammensetzung vorgeschlagen. Unter den Annahmen, daß (i) die Dichte von Wasser innerhalb der Aggregationen die gleiche als bei freiem Wasser ist, (ii) das ganze Emulsionsmittel in der Grenzfläche vorliegt und (iii) das Eindringen der organischen Phase in die Grenzfläche vernachlässigbar ist, können Werte für Aggregationszahlen und Core-Radien erhalten werden, die durchaus mit entsprechenden Werten aus aufwendigeren Methoden vergleichbar sind. Das Leistungsverhältnis (Ergebnisse/geringer Aufwand) ist sehr vorteilhaft und macht die Methode für kinetische Arbeiten zur Bestimmung von Reaktionsmechanismen in Mikroemulsionen interessant.

     

Application of vernier thinning techniques to segmented annular arrays

Due to the aperture periodicity, the inter-element spacing of two-dimensional squared arrays is maintained near lambda/2 in order to avoid grating lobes. This condition gives rise to severe problems derived from the huge number of array elements and from their little size that causes the signal to noise ratio to bring down. Vernier techniques have been proposed to lower the number of active elements, but the drastic reduction of the ultrasonic energy is still a great problem for the image contrast. In this work, vernier techniques for segmented annular (SA) arrays are theoretically studied. SA arrays produce lower grating lobes than squared arrays and, therefore, allow the element size to be increased beyond the lambda/2 constraint. Using larger elements, SA arrays have advantage to squared arrays because they have larger active area and smaller thinning order for the same complexity (number of channels) of the image system. Theoretical results of the vernier techniques applied to SA arrays in both radial and tangential directions are presented and compared with the equivalent squared array.     

Reductive PET cycloreversion of oxetanes: singlet multiplicity, regioselectivity, and detection of olefin radical anion

Cycloreversion of 2-(p-cyanophenyl)-4-methyl-3-phenyloxetane (1) is achieved using 1-methoxynaphthalene (2) as electron-transfer photosensitizer. The experimental results are consistent with the reaction taking place from the singlet excited state of the sensitizer. Ring splitting of the radical anion 1*- occurs with cleavage of O-C2 and C3-C4 bonds, leading to products (acetaldehyde and p-cyanostilbene) different from the reagents used in the Paterno-Büchi synthesis of 1. The olefin radical anion involved in the electron-transfer process has been detected by means of laser flash photolysis.