We performed laboratory studies to determine the effects of salinity on the photodegradation of dissolved organic matter (DOM) from the Great Dismal Swamp, Virginia, an important source of terrestrial DOM to the lower Chesapeake Bay. Samples were created by mixing Great Dismal Swamp water (ionic strength < 0 mol L 21 ) with modified artificial seawater solutions of differing salinities while keeping the final dissolved organic carbon (DOC) concentration constant. These samples were then irradiated for 24 h in a light box providing ultraviolet (UV) light similar to that of natural sunlight. Light absorbance and DOC concentrations decreased after photoexposure, whereas dissolved inorganic carbon (DIC) concentrations increased. Variations in salinity affected both DIC production and UV absorption, with the higher salinity samples showing lower DIC production and less photobleaching. Addition of an iron chelator eliminated the relationship between photochemistry and salinity by reducing both photobleaching and DIC production at low salinities. As terrigenous DOM transits through an estuary, its photochemical reactivity and optical properties may change significantly as a function of salinity, probably as a result of changes in DOM conformation or changes in iron-DOM photochemistry, or both.
Cu(I) coordination by organoselenium compounds was recently reported as a mechanism for their prevention of copper-mediated DNA damage. To establish whether direct Se-Cu coordination may be involved in selenium antioxidant activity, Cu(I) coordination of the selenoamino acids methyl-Se-cysteine (MeSeCys) and selenomethionine (SeMet) was investigated. NMR results in D2O indicate that Cu(I) binds to the Se atom of both MeSeCys and SeMet as well as the carboxylic acid oxygen atom(s) or amine nitrogen atoms. X-ray absorption spectroscopy (XAS) and density functional theory (DFT) results confirm Se-Cu coordination, with the identification of a 2.4 Å Se-Cu vector in both the Se- and Cu-EXAFS data. XAS studies also show Cu(I) in an unusual three-coordinate environment with the additional two ligands arising from O/N (2.0 Å). DFT models of 1:1 Cu-selenoamino acid complexes suggest that both selenoamino acids coordinate Cu(I) through the selenium and amino groups, with the third ligand assumed to be water. These compounds represent the first structurally characterized copper(I) complexes with sulfur or selenium-containing amino acids.
Ternary mixed magnetic Co 1−x Mn y Ni x-y Cl 2 •2H 2 O has as its components three well studied antiferromagnets. Each is characterized by MCl 2 MCl 2 M…chemical and structural chains, with intrachain exchange interactions antiferromagnetic for the Mn component but ferromagnetic for the other two components. Competing ferromagnetic and antiferromagnetic intrachain exchange interactions occur in two different pairwise combinations. Reported here is the magnetic behavior of an equimolar mixture of the three components. One maximum appears in the magnetic susceptibility vs temperature, at 4.85 ± 0.05 K, a quite interesting result since decidedly lower than the locations of susceptibility maxima in the pure components. A pronounced upturn in the susceptibility below 2.3 K also appears. Magnetization vs field isotherms display increasingly strong convex upward curvature and associated hysteresis with decreasing temperature. All of these characteristics differ markedly from those of the pure components.
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