Identification of radicals spin-trapped in autoxidized linoleic acids: A high performance liquid chromatography and electron spin resonance study

Radicals generated in linoleic acid and deuterated linoleic acid have been trapped by the spin trap 2-methyl-2-nitroso-propane (MNP) and identified by electron spin resonance (ESR) and ENDOR spectroscopy. The formation of two distinct secondary alkyl radical adducts (one conjugated, the other non-conjugated, as shown by their UV absorption spectra) was demonstrated by 11, 11-dideuterio-9-cis-12-cis-linoleic acid using HPLC and ESR spectroscopy.     

An electron spin resonance study of radicals from chloramine-t-1 : Spin trapping of radicals produced in acid media

Under acid conditions aqueous solutions of chloramine-T form nitrogen-centred radicals via loss of the chlorine atom. The nitrogen radicals produced have been studied by ESR spectroscopy using the spintrapping method. Adducts of the spin trap phenyl-t-butyl nitrone are oxidized by chloramine-T in acid media to give a paramagnetic product in which the unpaired electron interacts with two inequivalent nitrogen atoms. The spin trap 5,5-dimethyl-2-pyrrolidine-1 -oxide is oxidized rapidly to 5,5-dimethyl-2-pyrrolidone-1-oxyl by chloramine-T under acid onditions. The water soluble trap α-4-pyridyl-1-oxide-N-t-butyl nitrone forms a stable nitroxide adduct with a nitrogen radical of chloramine-T in acid solution. Identical results were obtained with chloramine-B (sodium salt of N-chlorobenzene sulfonamide), indicating the involvement of the N-chloramine group in radical formation.     

Covalent binding of human serum albumin and ovalbumin by chloramine-T and chemical modification of the proteins

The covalent binding of ³⁵S-chloramine-T to human resum albumin (HSA) and ovalbumin is described. At pH 6.5, up to 24 chloramine-T molecules were found to be covalently bound per molecule of HSA; with ovalbumin the binding was only 5–7 molecule per protein molecule. Binding was accompanied by extensive modification of methionine, cysteine, histidine, tyrosine and lysine. Three new peaks appeared in the amino acid profiles of the modified proteins; two were identified as 1-aminoadipic acid (oxidation of lysine) and 3-chlorotyrosine. The most sites for covalent binding are lysine residues.     

An endor and ESR study of the radical cation of N,N′-bis-(4-fluorophenyl)-4,4′-bipyridylium dichloride

The ESR and ENDOR spectra of the radical cation of N,N′-bis-(4-fluoro-phenyl)-4-4′-bipyridylium dichloride (fluorophenylquat FPQ) in methanol was studied over a temperature range from +_40° to ?90°. The ENDOR technique was used to obtain accurately the splitting constans for a highly complicated ESR spectrum and computer simulation showed excellent agreement. Fluorine ENDOR resonance was clearly observed with a line width similar to that of the protons. On decreasing the temperature the concentration of the radical cation decreases until at ?90° the ESR intensity was very small. This process is reversible and concentration studies indicate that the radical cation is in equilibrium with a diamagnetic dimer species. The thermodynamic parameters ΔH°, ΔG° and ΔS° for the process are reported.     

Determination of bile acids and their conjugates in serum by HPLC using immobilized 3 alpha-hydroxysteroid dehydrogenase for detection

A method is described for the separation of unconjugated bile acids and their glycine and taurine conjugates in a single step with adequate sensitivity for analysis of serum samples. Separation was carried out over a period of 80 min using a linear gradient with increasing concentrations of methanol in aqueous ammonium dihydrogen phosphate buffer, on an ODS Spherisorb column. Spectrofluorometric detection of NADH, formed as the column eluate passed through a column of immobilized 3 alpha-hydroxysteroid dehydrogenase, enabled amounts less than 40 pmol to be quantified. The reaction was carried out at neutral pH so that the lifetime of the enzyme column was increased, compared to other methods where a pH nearer 9.0 is commonly used. Flow rates were optimized to give comparable peak area for both primary and secondary bile acids.     

Differentiation along arbitrary orientations

A prevalent problem of mechanics is the differentiation of experimental information with respect to various directions, including the determination of cross derivatives. Simple methods for evaluating such derivatives along straight and curved directions are described. The concepts are demoinstrated at boundary and internal locations of in-plane and transversely loaded plates.     

Rapid Prototyping of Low‐Loss IR Chalcogenide‐Glass Waveguides by Controlled Remelting

A method for fabricating infrared‐transmitting waveguides that yields low optical losses and strong confinement of light is presented. The method minimises the number of fabrication steps by exploiting the photosensitivity of arsenic trisulfide glass, using it both as a photoresist and as a waveguiding material. Controlled annealing/remelting of the waveguides minimises scattering due to fluctuations in refractive index at the interface between the waveguide and the surrounding medium, allowing low losses to be realised. Bends and Y‐splitter structures have been realised, as well as the longest As₂S₃ serpentine planar waveguides yet reported.     

Fracture process zone analysis of concrete using moiré interferometry

The fracture process zone (FPZ) ahead of a crack tip in concrete and mortar beams subjected to threepoint bending was studied using moiré interferometry. A large FPZ can occur in concrete before the external load reaches its maximum value. Comparing the experimental results between concrete and mortar suggests that the aggregate contributes to the formation of the large FPZ in concrete. The formation of this large FPZ makes concrete less brittle than mortar. The effect of the FPZ on the fracture property, such as stress intensity factor, is investigated by combining moiré interferometry measured displacements with the smoothing FEM method. The study shows that a large FPZ significantly affects the value of the stress intensity factor.     

Analytical-experimental correlation of polyaxial states of stress in Thornel-epoxy laminates

The observed strength and stress-strain response of [O₂/±45] _s Thornel-epoxy laminates under varying biaxial-stress ratios are compared with those predicted numerically. Both flat and ring-type off-axis composite specimens are employed by which to generate experimentally the biaxial data. While the numerical predictions tend to overestimate the observed laminate strengths, the several predicted stress-strain curves agree well with each other and with experiment. The off-axis ring specimens produced significantly higher strengths than did the corresponding flat specimens.