Formal hydride transfer mechanism for photoreduction of 3-phenylquinoxalin-2-ones by amines. Association Of 3-phenylquinoxalin-2-one with aliphatic amines

The photophysical and photochemical behavior of 1-methyl-3-phenylquinoxalin-2-one (MeNQ) and 3-phenylquinoxalin-2-one (HNQ) in the presence of amines is reported. While HNQ fluorescence shows an auxochromic effect and a bathochromic shift with added amines, explained by association of HNQ with amine in the ground state and emission from both excited species HNQ and [HNQ-amine], both MeNQ and HNQ are photoreduced efficiently on irradiation in the presence of amines, leading to the semireduced quinoxalin-2-ones, MeNQH(-) and HNQH(-), respectively, via an electron-proton-electron transfer, with unit quantum yields at high amine concentrations. The semireduced quinoxalin-2-ones XNQH(-) (X = H, Me) revert almost quantitatively to the parent XNQ in a dark thermal reaction with an activation free energy for MeNQH(-) of 17.4 and 25.9 kcal/mol in acetonitrile and benzene, respectively. Kinetic and spectroscopic (UV and NMR) evidence supports the proposed reaction mechanism for the reversible photoreduction.     

Excited State Properties of the Siderophore Pyochelin and its Complex with Zinc Ions

Abstract— The critical effects of pH on the electronic absorption and fluorescence characteristics of the siderophore, pyochelin, are investigated. A single anionic species is shown to be sufficient to explain the data obtained under alkaline conditions. In acidic solutions, several competing ground- and excited-state equilibria are present, which lead to fluorescence emissions from both the protonated form of pyochelin and its phenolate ion. From the spectroscopic data we are also able to show that pyochelin interacts with zinc ions in the ground state via its anionic form, thereby confirming that this siderophore does not bind Fe(III) ions uniquely.     

ABSORPTION AND EMISSION STUDIES OF ELECTRONIC STATES OF N-ARYLBENZAMIDES

Abstract— Absorption and emission spectra of several N-arylbenzamides have been measured. The quantum yields for their fluorescence were found to be dependent on matrix viscosity and temperature. Singlet-triplet splittings for these compounds were determined from their emission spectra and found to be abnormally small for π. π* states (˜ 1500 cm^-1). Indeed, the phosphorescence maxima of N-arylbenzamides occur slightly to the blue relative to their fluorescence maxima. Intersystem crossing efficiencies were determined for several of these compounds and are consistent with S₁→ S ₀ radiationless decay.     

Potential role of the nitroacidium ion on HONO emissions from the snowpack

The effects of photolysis on frozen, thin films of water-ice containing nitrogen dioxide (as its dimer dinitrogen tetroxide) have been investigated using a combination of Fourier transform reflection-absorption infrared (FT-RAIR) spectroscopy and mass spectrometry. The release of HONO is ascribed to a mechanism in which nitrosonium nitrate (NO+NO3-) is formed. Subsequent solvation of the cation leads to the nitroacidium ion, H2ONO+, i.e., protonated nitrous acid. The pathway proposed explains why the field measurement of HONO at different polar sites is often contradictory.     

Freeze-induced reactions: formation of iodine-bromine interhalogen species from aqueous halide ion solutions

Interhalide ion formation resulting from the freezing of dilute solutions containing components found in natural sea salt are investigated as a potential mechanism for the release of interhalogens to the polar atmosphere. Acidified solutions containing iodide, bromide, and nitrite ions have been frozen and then thawed, with changes in speciation analyzed using UV-visible spectrophotometry. The freezing process is shown to induce the formation of the important interhalide ion, IBr(2)(-). This species has previously been predicted to be a precursor of iodine monobromide, IBr, and represents a potentially important source of halogen atoms in the polar marine boundary layer. The reaction mechanisms that lead to the formation of IBr(2)(-) under freezing conditions are explored using both experimental and computational methodologies. The chemistry involved was subsequently modified in order to mimic naturally occurring conditions more closely and also incorporated the use of hydrogen peroxide as an oxidant. In contrast to previous studies, the freeze-induced production of IBr(2)(-) was thereby observed to occur up to pH <5.1, where the acidity levels are comparable to those found in the polar snowpack.     

Electron spin resonance studies of 199HgH, 201HgH, 199HgD and 201HgD isolated in neon and argon matrices at 4K: an electronic structure investigation

Various isotopomers of the mercury hydride radical (HgH) have been generated in a microwave discharge and trapped in neon and argon matrices at 4 K for electron spin resonance (ESR) investigations. Both the dipolar (A_dip) and isotropic (A_iso) components of the nuclear hyperfine interactions have been directly measured for ¹⁹⁹Hg, ²⁰¹Hg, H and D. Electronic structure information for HgH in its X²Σ ground state obtained from the hyperfine data is compared with theoretical results from several different computational methods. The hyperfine interactions in HgH are unusually large with A_iso(¹⁹⁹Hg) = 6859(3), A_dip(¹⁹⁹Hg) = 446(3), A_iso(H) = 730(2) and A_dip(H) = 0(2) MHz. A standard analysis of the hyperfine interactions demonstrates the need for a more in-depth theoretical treatment of HgH that should include relativistic effects. An interesting shift in spin density is observed when deuterium replaces hydrogen in HgH. The decreased spin density on deuterium, which was demonstrated in earlier studies, can now be more fully investigated since these new measurements confirm an associated increase in spin density on mercury     

Improved models for the phase behaviour of hydrogen fluoride: chain and ring aggregates in the SAFT approach and the AEOS model

Hydrogen fluoride presents one of the strongest hydrogen bonds known. Ring aggregates exist both in the vapour and liquid phases at low temperatures resulting in an anomalously high low-temperature vapour pressure. The effect of ring-like aggregates on the vapour—liquid phase equilibria of associating fluids is studied within the framework of the statistical associating fluid theory (SAFT) and in the chemical model of Lencka and Anderko (AEOS). The SAFT approach incorporates separate contributions to describe chain formation, association (hydrogen bonding), and long range dispersion forces. The treatment of the association interactions stems from the thermodynamic perturbation theory of Wertheim. At the first level of approximation the contribution of ring-like aggregates is neglected and only chain- and treelike structures are treated. In this work an earlier extension of the approach to incorporate ring aggregates is used to model the phase behaviour of hydrogen fluoride. The chemical model of Lencka and Anderko for associating fluids is also considered together with a modification that takes into account the formation of ring aggregates. Vapour pressures and coexistence densities are examined together with heats of vapourization, and the calculations are compared with experimental data.     

Assessment of Temporal Variability Trends for Inorganic Parameters in Ground Water

Abstract

The passage of environmental legislation in the United States has dramatically increased ground-water monitoring in the vicinity of point sources such as abandoned waste disposal sites, operational waste disposal sites, and municipal landfills. Even though these programs require sufficient sampling to define background conditions as part of the site characterization process, there is still a general absence of quantitative information on the magnitude and periodicity of temporal fluctuations for inorganic constituents in ground water. This paper presents an approach that has been used to develop an initial characterization of these temporal trends.

A search if on-going site investigation reports identified 18 facilities across the United States that had monthly monitoring data at a frequency of at least monthly for a period of one and a half years or longer (15 RCRA-C hazardous waste disposal facilities with monthly data for a period of 2–3 years, 2 research monitoring locations with biweekly monitoring data for a period of one and a half years, and a precious metal mining operation with daily monitoring data for a limited number of parameters for a period of one and a half years). The data from these site investigations were used to describe the temporal variability of several ground-water constituents including pH, specific conductance, sulfate, sodium, chloride, alkalinity, silica, iron, and manganese. An assessment of these data suggests that the magnitude of temporal ground-water fluctuations are on the order of 20 percent of the average concentration for chloride, 10 percent of the average concentration for sodium, manganese and specific conductance, 5 percent of the average concentration for alkalinity and pH, and essentially zero for silica. The apparent periodicities of these temporal fluctuations ranged from 40 weeks to approximately 2 years. The magnitude and periodicities in ground water are substantially smaller than those that have been reported and documented for the same constituents in surface waters. These differences are due to the fact that sunlight and wind, two energy factors that drive temporal cycles in surface water, do not exert a similar influence on the environmental chemistry of ground-water constituents.