CIDEP studies of the photolysis of the lignin model compound α-guaiacoxylacetoveratrone: the role of triplet reactions in aqueous and hydroxylic solvents

Free radical reactions induced by the photolysis of the lignin model compound α-guaiacoxylacetoveratrone have been studied by conventional and time-resolved ESR spectroscopy. In the presence of efficient hydrogen donors such as aqueous and hydroxylic solvents the primary reaction involves photoreduction of the triplet phenacyl ether to form the ketyl radical followed by rapid cleavage to the phenacyl radical and guaiacol. Subsequent formation of polarized guaiacoxyl radicals is due to secondary photo-oxidation. The cleavage of the ketyl radical is retarded in basic media and accelerated in acetic acid. Minor reaction pathways involving excited singlets cannot be ruled out by the current CIDEP observations.     

Determination of total chlorine in waste oil

Summary A simple method has been developed to determine the concentration of organic chlorine in waste oil. The determination is based on the conversion of organic chlorine to inorganic chloride by reaction with sodium biphenyl followed by extraction with nitric acid and a mixture of nitric acid and water. The concentration of chloride is determined by direct potentiometry with an ion-selective electrode. The limit of determination amounts to 3·10^–5 mol·l^–1 chloride ions with a standard deviation of 3.5%. Different samples of waste oil have been analyzed and the results have been compared to those obtained by combustion in a H₂/O₂ flame followed by potentiometric titration with silver nitrate.     

The thermal degradation of poly(diethyl fumarate)

The kinetics and mechanism of the thermal degradation of poly(diethyl fumarate) (PDEF) were studied by thermogravimetry, as well as by analysis of the thermolysis volatiles and polymer residue. The characteristic mass loss temperatures were determined, as were the overall thermal degradation activation energies of three PDEF samples of varying molar mass. Ethylene and ethanol were present in the thermolysis volatiles at degradation temperatures below 300 °C, while diethyl fumarate was also evidenced at higher degradation temperatures. The amount of monomer increased with increasing degradation temperature. The dependence of the molar mass of the residual polymer on the degradation time and temperature was established and the number of main-chain scissions per monomer unit, s/P₀, calculated. A thermal degradation mechanism including de-esterification and random main-chain scission is proposed. The thermal degradation of PDEF was compared to the thermolysis of poly(ethyl methacrylate) (PEMA), poly(diethyl itaconate) (PDEI) and poly(ethyl acrylate) (PEA).     

Comprehensive two-dimensional gas chromatography with isotope dilution time-of-flight mass spectrometry for the measurement of dioxins and polychlorinated biphenyls in foodstuffs. Comparison with other methods

A comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry (GC x GC-TOF-MS) experimental setup was tested for the measurement of seven 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins (PCDDs), ten 2,3,7,8-substituted polychlorinated dibenzofurans (PCDFs), four non-ortho-polychlorinated biphenyls (PCBs), eight mono-ortho-PCBs, and six indicator PCBs (Aroclor 1260) in foodstuff samples. A 40m RTX-500 (0.18mm I.D., 0.10 microm df) was used as the first dimension (1D) and a 1.5 m BPX-50 (0.10mm I.D., 0.10 microm df) as the second dimension (2D). The GC x GC chromatographic separation was completed in 45 min. Quantification was performed using 13C-label isotope dilution (ID). Isotope ratios of the selected quantification ions were checked against theoretical values prior to peak assignment and quantification. The dynamic working range spanned three orders of magnitude. The lowest detectable amount of 2,3,7,8-TCDD was 0.2 pg. Fish, pork, and milk samples were considered. On a congener basis, the GC x GC-ID-TOF-MS method was compared to the reference GC-ID high resolution mass spectrometry (HRMS) method and to the alternative GC-ID tandem-in-time quadrupole ion storage mass spectrometry (QIST-MS/MS). PCB levels ranged from low picogram (pg) to low nanogram (ng) per gram of sample and data compared very well between the different methods. For all matrices, PCDD/Fs were at a low pg level (0.05-3 pg) on a fresh weight basis. Although congener profiles were accurately described, RSDs of GC x GC-ID-TOF-MS and GC-QIST-MS/MS were much higher than for GC-ID-HRMS, especially for low level pork and milk. On a toxic equivalent (TEQ) basis, all methods, including the dioxin-responsive chemically activated luciferase gene expression (DR-CALUX) assay, produced similar responses. A cost comparison is also presented.     

The transitional isoelectric focusing process

The transitional isoelectric focusing (IEF) process (the course of pH gradient formation by carrier ampholytes (CAs) and the correlation of the focusing time with CA concentration) were investigated using a whole-column detection capillary isoelectric focusing (CIEF) system. The transitional double-peak phenomenon in IEF was explained as a result of migration of protons from the anodic end and hydroxyl ions from the cathodic end into the separation channel and the higher electric field at both acidic and basic sides of the separation channel. It was observed that focusing times increase logarithmically with CA concentration under a constant applied voltage. The correlation of focusing time with CA concentration was explained by the dependence of the charge-transfer rate on the amount of charged CAs within the separation channel during focusing.     

Preparation and Characterisation of Nano-Structured WO<Subscript>3</Subscript>-TiO<Subscript>2</Subscript> Layers for Photoelectrochromic Devices

Nano-structured WO₃-TiO₂ layers were prepared by the sol-gel route. To obtain transparent, porous and crack free layers up to 0.8 μ m with a single dipping cycle a templating strategy was used. As a template three-dimensionally network based on organically modified silane was introduced to the WO₃ and TiO₂ sols. The WO₃ layers were dip-coated onto the conductive glass substrate (TCO) and the TiO₂ layers on the top of the WO₃ layer. The morphology and the structure of the layers were determined by Scanning Electron Microscopy (SEM), High Resolution Transmission Electron Microscopy (HR-TEM), Energy Dispersive X-Ray Spectroscopy (EDXS), Auger and Infrared spectroscopy. SEM image of the WO₃-TiO₂ layer confirmed the nano-porosity of the layers and give the size of the particles of about 10 nm for TiO₂ and 30 nm for WO₃ layer. Further analysis indicated that the titanium sol penetrates the WO₃ layer. Particles in the WO₃ layer consist of a crystalline monoclinic WO₃ core surrounded by a 5–10 nm amorphous phase consisting of WO₃, TiO₂ and SiO₂. The WO₃-TiO₂ layers were used to assemble all solid state photoelectrochromic (PE) devices. Under 1 sun irradiation (1000 W/m²) the visible transmittance of the PE device changes from 62% to 1.6%. The colouring and bleaching processes last about 10 minutes.     

Formation of a [2 + 2]-heterotetranuclear macrocycle from reaction of a platina-homoditopic ligand with iron(II)

Reaction of 4'-(2-propyn-1-oxy)-2,2':6',2'-terpyridine (HC triple bond CCH2Oterpy) with trans-[PtI2(PEt3)2] regioselectively metallates the alkyne to give trans-[Pt(C triple bond CCH2Oterpy)2(PEt3)2] which, when treated with Fe(II), gives a [2 + 2]-metallocycle.     

Oxygen transport in La<Subscript>0.6</Subscript>Sr<Subscript>0.4</Subscript>Co<Subscript>1−<Emphasis Type="Italic">y</Emphasis></Subscript>Fe<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript>O<Subscript>3−δ</Subscript>

The surface exchange coefficient and chemical diffusion coefficient of oxygen for the perovskites La_0.6Sr_0.4Co_1–yFe_yO_3– (y=0.2, 0.5 and 0.8) were measured using the conductivity relaxation technique. Measurements were performed between 600 and 800 °C in an oxygen partial pressure range between 10^–4 and 1 bar. Both transport coefficients decrease markedly with decreasing oxygen partial pressure below about 10^–2 bar at all temperatures. This is attributed to ordering of oxygen vacancies. Implications for using La_0.6Sr_0.4Co_1–yFe_yO_3– as an oxygen separation membrane are discussed.Presented at the OSSEP Workshop Ionic and Mixed Conductors: Methods and Processes, Aveiro, Portugal, 10-12 April 2003     

Electrostatic interactions between amphoteric latex particles and proteins

The electrostatic interactions between amphoteric polymethyl methacrylate latex particles and proteins with different pI values were investigated. These latex particles possess a net positive charge at low pH, but they become negatively charged at high pH. The nature and degree of interactions between these polymer particles and proteins are primarily controlled by the electrostatic characteristics of the particles and proteins under the experimental conditions. The self-promoting adsorption process from the charge neutralization of latex particles by the proteins, which have the opposite net charge to that of the particles, leads to a rapid reduction in the zeta potential of the particles (in other words colloidal stability), and so strong flocculation occurs. On the other hand, the electrostatic repulsion forces between similarly charged latex particles and the proteins retard the adsorption of protein molecules onto the surfaces of the particles. Therefore, latex particles exhibit excellent colloidal stability over a wide range of protein concentrations. A transition from net negative charge to net positive charge, and vice versa (charge reversal), was observed when the particle surface charge density was not high enough to be predominant in the protein adsorption process.     

Separation of fatty acid methyl esters by comprehensive two-dimensional supercritical fluid chromatography with packed columns and programming of sampling duration

Fatty acid methyl esters from various fats and oils were separated by comprehensive two-dimensional supercritical fluid chromatography with conventional packed columns and FID detection. The first dimension was a silica gel column and the second dimension was an ODS column. This combination was largely orthogonal for the separation of fatty acid methyl esters. The first dimension separations were primarily based on the number of double bonds while the second dimension separations were based on the chain length. The highly-ordered chromatograms and improved resolution allowed the easy detection and identification of minor components. Although the first dimension separations were performed under isobaric conditions where the peak width increased in proportion to the retention, the programming of the sampling duration allowed us to maintain the optimum re-injection frequency (3–4 times) per peak into the second dimension and so to minimize the total analysis time without deteriorating the resolution.