SUPEROXIDE DISMUTASE AS AN AMPLIFIER OF THE CHEMICAL REACTIVITY OF PORPHYRIN RADICAL-CATIONS

Abstract— Porphyrin radical-cations have been produced using laser flash photolysis via oxidation of the porphyrin triplets by metronidazole. This radical-cation reacts with OJ as shown by its increased half-life in the presence of native superoxide dismutase. Comparable results are obtained when porphyrin radical-cations are formed by Br₂^-O₂^-oxidation of porphyrins produced in pulse radiolysis of oxygen-saturated aqueous solutions containing 20 mM Br^-O^-. These results provide an explanation for the enhancement by superoxide dismutase of the photosensitizing capacity of porphyrins in the presence of electrophilic nitroimidazoles (Bazin and Santus, 1986). They may also apply to porphyrin radical-cations formed by monophotonic or biphotonic photoionization processes.     

Syntheses,structure, and photoluminescence properties of the 1-dimensional chain compounds [(TPA)(2)Au][Au(CN)(2)] and (TPA)AuCl (TPA = 1,3,5-triaza-7-phosphaadamantane)

The structures and temperature-dependent photoluminescence properties of the one-dimensional compounds [(TPA)(2)Au][Au(CN)(2)], 1, and (TPA)AuCl, 2, are reported. An extended linear chain with weak Au.Au interactions along the c-axis is evident in the structure of 1, and a helical chain with a pitch of 3.271 A is seen for 2. The intrachain Au...Au separation is 3.457(1) and 3.396(2) A in 1 and 2, respectively. As a result of this weak Au...Au interaction, the physical properties of these compounds are anisotropic. Scanning electron microscopy (SEM) studies indicate that single crystals of both compounds are noninsulating. Single crystals of 1 do not luminesce visibly, but grinding the crystals finely initiates a strong green emission under UV irradiation at room temperature. Further interesting optical properties include the dependence of the emission profile of the powder on the exciting wavelength and luminescence thermochromism. When excited at wavelengths < 360 nm, the powder exhibits a blue emission at 425 nm while excitation with longer wavelengths leads to a green emission near 500 nm. While the green emission dominates at ambient temperature, cooling to cryogenic temperatures leads to the dominance of the blue emission. Fibers of 2 are luminescent at 78 K with an emission band centered at 580 nm. Compound 1 crystallizes in the orthorhombic space group Cccm (No. 66), with Z = 2, a = 6.011(1) A, b = 23.877(6) A, c = 6.914(1) A, V = 992.3(3) A(3), and R = 0.0337. Compound 2 crystallizes in the trigonal space group R3 (No. 148), with Z = 18, a = 22.587(2) A, b = 22.587(2) A, c = 9.814(2) A, V = 4336 A(3), and R = 0.0283.     

Elucidation of the mechanism of chiral selectivity in diastereomeric salt formation using organic solvent nanofiltration

Organic solvent nanofiltration (OSN) was used to investigate the mechanism of chiral selectivity in diastereomeric salt formation of alpha-phenylethylamine with D-tartaric acid and di-p-toluoyl-D-tartaric acid as resolving agents; results indicate that for these systems chiral selectivity occurs only upon crystallisation and chiral interactions in solution were negligible.     

Review of current techniques for the verification of the species origin of meat

An overview of developments that have occurred in meat species identification over the last decade is presented. It starts by noting the different requirements for speciation techniques over the period, describes the complex nature of meat in terms of chemical composition and shows how the chain of events from slaughter to retail gives rise to opportunities for deliberate adulteration or innocent contamination. The limitations of techniques such as electrophoresis and isoelectrofocusing are pointed out where the analysis of mixed meats is concerned; attention then focuses on the range of techniques based on antigen-antibody interactions: agar gel immunodiffusion, counter immuno-electrophoresis and enzyme-linked immunosorbent assay (ELISA) in three formats. The choice of analyte is discussed, firstly for the analyses of raw meat materials and secondly, for heat-processed meat products. In the first example, blood serum proteins are used almost exclusively despite the limitation that their presence does not necessarily denote the presence of the corresponding muscle tissue (meat). For cooked products, a new range of antisera are necessary, based on thermally stable components derived from the tissues. By using different formats of ELISA, it is demonstrated that different responses can be obtained for heat-processed meat versus processed offal, and that determination of a species meat content in a cooked mixed meat product is possible. Techniques for improving the specificity and performance of antisera are discussed briefly, with the future introduction of thermally stable, muscle-specific monoclonal antisera being seen as the way forward.     

Organic fuelled flames in selective ionization detectors for chromatography

Summary The selectivities of two flame-based ionization detectors identified as a Remote FID (RFID) and a Flame Thermionic Ionization Detector (FTID) have been improved by introducing methane as a fuel for the flame. Both the RFID and FTID feature a detector struture in which the ionization polarizer and collector are located several centimeters downstream of an oxygen-rich flame, rather than immediately adjacent to the flame as in a flame ionization detector. The RFID detects long-lived negative ions produced in the flame by the combustion of lead, tin, phosphorus, or silicon compounds. The FTID re-ionizes and detects neutral electronegative products generated by combustion of nitrogen, halogen, or phosphorus compounds. An organic-fuelled RFID can detect 1 pg Pb (Sn, P)/sec with a selectivity of the order of 10⁶ versus hydrocarbons. An organic fuelled FTID is applicable to detection of compounds at nanogram and higher levels. FTID selectivity for PCB compounds in a transformer oil matrix is of the order of 10⁵1. The improved selectivity achieved by using an organic-fuelled flame is also applicable to the detection of phospholipid and other non-volatile N, P, or Cl compounds using an FID/FTID detector accessory for a TLC/FID analyser.     

A site determination for Mu* and its implications

A chain of arguments is made which draws on the experimental results ofSR, muon-pion-decay channeling, and³He channeling in deuterium-implanted silicon and which leads to a plausible site for the anomalous muonium atom Mu^* in the group-IV semiconductors. I propose that Mu^* in silicon occupies the deuterium position approximately 1.6 Å from a Si atom in a [111] anti-bonding direction and that analogous sites are occupied in Ge and diamond. Some possible implications of this site assignment are discussed.     

Excess heat capacities of ternary systems containing chlorobenzene or chloronaphthalene

Densities and heat capacities of ternary systems were determined at 25°C. The ternary systems consisted of: a polar molecule (component 1) + a mixture of alkanes (components 2 and 3) of different sizes and shapes. Five such systems were studied: chlorobenzene + cyclohexane + n-heptane; chlrobenzene + cyclohexane + n-hexadecane; chlorobenze + cyclohexane + isooctane; chlorobenzene + isooctane + n-heptane; 1-chloronaphthalene + isooctane + n-heptane. The excess molar volumes and heat capacities were obtained along dilution lines by component 1 (chlorobenzene or 1-chloronaphthalene) of mixtures of components 2 and 3 (at fixed component 2 mole fraction X₂). Unexpectedly the excess heat capacities C _p1(23) ^E of the pseudo-binaries {1+(2+3)} do not always fall between the two (limiting) curves of C _p12 ^E and C _p13 ^E corresponding to the two binaries {1+2} and {1+3}. Instead, especially for {chlorobenzene + cyclohexane + an n-alkane} the C _p1(23) ^E curves are displaced toward less negative values, even beyond the limiting values corresponding to the binaries. This correlates semi-quantitatively with the negative C _p23 ^E of the binary {2+3}.Presented at the Symposium, 76^th CSC Congress, Sherbrooke, Quebec, May 30-June 3, 1993, honoring Professor Donald Patterson on the occasion of his 65^th birthday.     

Quantification of monohydroxy-PAH metabolites in urine by solid-phase extraction with isotope dilution-GC–MS

For measurement of biomarkers from polycyclic aromatic hydrocarbon (PAH) exposure, an analytical method is described quantifying hydroxylated PAH (OH-PAH) in urine samples. This method determined monohydroxy metabolites of naphthalene, fluorene, phenanthrene, fluoranthene, pyrene, chrysene, benzo[c]phenanthrene, and benz[a]anthracene. The sample preparation consisted of enzymatic hydrolysis, solid-phase extraction and derivatization with a silylating reagent. Five carbon-13 labeled standards were used for isotope dilution. Analytes were separated by gas chromatography (GC) and quantified with high-resolution mass spectrometry (HRMS). This method produced good recoveries (41-70%), linearity, and specificity. Data were corrected for blank levels from the naphthalene, fluorene, and phenanthrene metabolites. Method detection limits ranged from 2 ng L(-1) for 1-hydroxypyrene to 43.5 ng L(-1) for 1-hydroxynaphthalene. Using quality control charts from two urine pools, the method can be readily applied to biomonitoring PAH exposure.     

Use of stable isotope labeling technique and mass isotopomer distribution analysis of [(13)C]palmitate isolated from surfactant disaturated phospholipids to study surfactant in vivo kinetics in a premature infant

Pulmonary surfactant is a complex mixture of phospholipids and proteins which lowers surface tension and maintains alveolar expansion at end expiration. Developmental and genetic disruption of pulmonary surfactant metabolism leads to respiratory distress in newborns. Stable isotope labeling of metabolic precursors of disaturated phospholipids, the most abundant and specific component of pulmonary surfactant, permits the measurement of the kinetics of surfactant metabolism in vivo. We measured [U-(13)C(6)]glucose incorporation into palmitic acid derived from disaturated surfactant phospholipids. A 24 h infusion of [U-(13)C(6)]glucose (140 mg kg(-1)) was administered to a premature infant who required mechanical ventilation for respiratory distress syndrome; tracheal aspirate samples were obtained at the start of the infusion and at regular intervals for the next 70 h. Each tracheal aspirate sample was incubated with osmium tetroxide to isolate disaturated surfactant phospholipids. Methyl esters of the fatty acids in the disaturated phospholipids were prepared and the enrichment of [(13)C]methyl palmitate was measured by gas chromatography/mass spectrometry (GC/MS) and gas chromatography/combination/isotope ratio mass spectrometry (GC/C/IRMS). Mass isotopomer distribution analysis (MIDA) was used to calculate the fractional synthetic rate (FSR) of palmitate synthesized from acetate. With both GC/MS and GC/C/IRMS, palmitate (13)C enrichment was first detected 12.3 h after the start of the tracer infusion. The enrichment increased in a linear fashion, reached a peak at 47 h and remained constant in the remainder of the samples. The FSR of palmitate from acetate was 5.2% per day. Stable isotope techniques and MIDA will provide insights into the kinetics of surfactant metabolism in newborns with respiratory dysfunction.