Identification of chlorinated sulfur compounds in pulp mill effluents by GC-MS and GC-AED

Summary Three chlorinated dimethyl sulfones and five chlorinated thiophenes have been identified in the alkaline extraction liquor from a bleach plant by gas chromatography with atomic emission detection (GC-AED) and with mass spectrometry (GC-MS). The information on elemental content obtained by GC-AED enabled a rapid screening of the sulfur compounds and provided important structural information complementary to the mass spectral data. Quantitation was accomplished by GC-AED based on universal calibration.     

A new method to study antioxidant capability: hydrogen transfer from phenols to a prefluorescent nitroxide

[reaction: see text]. Rate constants for hydrogen abstraction from phenols by a prefluorescent-TEMPO probe are reported. The nitroxide is employed as a potential model of peroxyl radicals. The probe works by nitroxide suppression of the fluorescence of the chromophore. The fluorescence is restored when the nitroxide abstracts a hydrogen atom to produce the diamagnetic hydroxylamine. The phenols studied in this project exhibited rate constants between 0.003 and 0.2 M(-1) s(-1). A deuterium isotope effect of 10 for TROLOX confirms that the mechanism is dominated by hydrogen transfer.     

Observation of Δn=1 dielectronic recombination resonances of boronlike argon

We report here an observation ofn=1 dielectronic recombination resonances of boron-like argon in the energy region 140–195 eV. With the cooler's electron beam as a target, a resolution of approximately 0.6 eV FWHM was obtained in the observed energy range. The energies of the doubly excited states were estimated with a Hartree-Fock calculation, which indicates that the observed resonances are from Ar¹³⁺(1s²2s²2p) to Ar¹²⁺(1s²2s²3l3l) and Ar¹²⁺(1s²2s2p3l3l) transitions.     

Electrodes based on zeolites modified with cobalt and/or molybdenum for pesticide degradation: part II—2,4,6-trichlorophenol degradation

Journal of Solid State Electrochemistry - 2,4,6-trichlorophenol (TCP) is a persistent pollutant introduced in water by industrial processes and pesticides. We have studied the electrooxidation of...     

Using an OPO laser system for recombination studies in a storage ring: LIR to n=3 states of deuterium

We have investigated the use of a one-stage optical parametric oscillator (OPO) laser system for studies of laser induced radiative recombination (LIR) of stored ions. For the test case considered, LIR into n = 3 states of deuterium, we find that the energy resolution is limited by the broad linewidth of the OPO. Within this resolution, our LIR results are in good agreement with a theoretical average field induced threshold shift model. This revised version was published online in August 2006 with corrections to the Cover Date.     

Photophysical properties of the prefluorescent nitroxide probes QT and C343T

The photophysical properties of the nitroxide prefluorescent probes 4-(3-hydroxy-2-methyl-4-quinolinoyloxy)-2,2,6,6-tetramethyl-piperidin-4-yl) ester free radical (QT) and 2,3,4,6,7,8-hexahydro-quinolizino [1,10,9-gh] coumarin-3-carboxylic acid (1-oxyl-2,2,6,6-tetramethyl-piperidin-4-yl) ester free radical (C343T) were evaluated as a function of pH and solvent properties. The absorbance of QT showed high pH sensitivity. The pKa values for the different ionization forms involved in the acid-base equilibrium of the quinoline chromophore were determined in the ground and excited states. The fluorescence lifetimes of QT, and N-hydroxylamine (QTH) and quinoline methyl ester (QMe) derivatives, showed that the intramolecular quenching efficiency by the nitroxide moiety is independent of the quinoline ionization form. The fluorescence and absorbance of C343T were highly sensitive to solvent polarity in agreement with a charged transfer excited state of the chromophore. However, we noted a decrease in the intramolecular fluorescence quenching efficiency by the nitroxide moiety when changing the polarity of the solvent from hexane to water. This behavior has been attributed to a suppression of an energy transfer mechanism in the nitroxide quenching process in very polar solvents. The results obtained in micelles allow us to propose QT and C343T as sensors for pH and micropolarity, respectively, in addition to their role as monitors for free radicals or hydrogen transfer from phenols.     

Coumarin 314 free radical cation: formation, properties, and reactivity toward phenolic antioxidants

We have explored the photogeneration of the coumarin 314 radical cation by using nanosecond laser excitation at wavelengths longer than 400 nm in benzene, acetonitrile, dichloromethane, and aqueous media. In addition, time-resolved absorption spectroscopy measurements allowed detection of the triplet excited state of coumarin 314 (C(314)) with a maximum absorption at 550 nm in benzene. The triplet excited state has a lifetime of 90 μs in benzene. It is readily quenched by oxygen (k(q) = 5.0 × 10(9) M(-1) s(-1)). From triplet-triplet energy transfer quenching experiments, it is shown that the energy of this triplet excited state is higher than 35 kcal/mol, in accord with the relatively large singlet oxygen quantum yield (Φ(Δ) = 0.25). However, in aqueous media, the coumarin triplet was no longer observed, and instead of that, a long-lived (160 μs in air-equilibrated solutions) free radical cation with a maximum absorbance at 370 nm was detected. The free radical cation generation, which has a quantum yield of 0.2, occurs by electron photoejection. Moreover, density functional theory (DFT) calculations indicate that at least 40% of the electronic density is placed on the nitrogen atom in aqueous media, which explains its lack of reactivity toward oxygen. On the other hand, rate constant values close to the diffusion rate limit in water (>10(9) M(-1) s(-1)) were found for the quenching of the C(314) free radical cation by phenolic antioxidants. The results have been interpreted by an electron-transfer reaction between the phenolic antioxidant and the radical cation where ion pair formation could be involved.     

Dielectronic recombination of Li-like neon and argon

We have measured dielectronic recombination rates and energies for n=0 transitions of Ne⁷⁺ and Ar¹⁵⁺ beams stored in CRYRING. The energy resolution was in the order of 10^–2 eV FWHM; the absolute accuracy in the position of the resonances is in the same order. The energy positions of the dielectronic recombination resonances are compared to theoretical calculations of the fine-structure splittings.     

Generation,Spectroscopic Characterization by EPR,and Decay of a Pyranine‐Derived Radical

The pyraninoxyl radical is readily formed from the MnO₂‐promoted oxidation of pyranine. The free radical can be formed in high concentrations (mM ), and presents a characteristic EPR spectrum that indicates a high spin‐density delocalization. It is relatively stable under nitrogen (half‐life ca. 50 min) but readily decays in presence of O₂. In spite of its high stability, the radical readily reacts with antioxidants (phenols and ascorbic acid) with a partial recovery of the parent pyranine. High concentrations of the pyraninoxyl radical (ca. 9 μM ) are present when pyranine is exposed to a free radical source (10 mM 2,2′‐azobis[2‐amidinopropane], 37°). The fact that these radicals readily react with antioxidants (ascorbic acid and caffeic acid) supports the proposal that protection by antioxidants of peroxyl radical‐promoted pyranine bleaching is mainly due to the occurrence of a repair mechanism.     

Driving matrix liquid crystal displays

Liquid crystal displays had a humble beginning with wrist watches in the seventies. Continued research and development in this multi-disciplinary field have resulted in displays with increased size and complexity. After three decades of growth in performance, LCDs now offer a formidable challenge to the cathode ray tubes (CRT). A major contribution to the growth of LCD technology has come from the developments in addressing techniques used for driving matrix LCDs. There are several approaches like passive matrix addressing, active matrix addressing and plasma addressing to drive a matrix display. Passive matrix LCD has a simple construction and uses the intrinsic non-linear characteristic of the LCD for driving. Departure from conventional line by line addressing of a passive matrix has resulted in improved performance of the display. Orthogonal functions have played a crucial role in the development of passive matrix addressing. Simple orthogonal functions that are useful for driving a matrix LCD are introduced. The basics of driving several rows simultaneously (multi-line addressing) are discussed by drawing analogies from multiplexing in communication. The impact of multi-line addressing techniques on the performance of the passive matrix LCDs in comparison with the conventional technique will be discussed.