Synthesis and spectroscopic characterization of high-spin mononuclear iron(II) p-semiquinonate complexes.

Two mononuclear iron(II) p-semiquinonate (pSQ) complexes have been generated via one-electron reduction of precursor complexes containing a substituted 1,4-naphthoquinone ligand. Detailed spectroscopic and computational analysis confirmed the presence of a coordinated pSQ radical ferromagnetically coupled to the high-spin Fe(II) center. The complexes are intended to model electronic interactions between (semi)quinone and iron cofactors in biology.

Fe(II) complexes that mimic the active site structure of acetylacetone dioxygenase: O2 and NO reactivity.

Acetylacetone dioxygenase (Dke1) is a bacterial enzyme that catalyzes the dioxygen-dependent degradation of β-dicarbonyl compounds. The Dke1 active site contains a nonheme monoiron(II) center facially ligated by three histidine residues (the 3His triad); coordination of the substrate in a bidentate manner provides a five-coordinate site for O(2) binding. Recently, we published the synthesis and characterization of a series of ferrous β-diketonato complexes that faithfully mimic the enzyme-substrate intermediate of Dke1 (Park, H.

Structural, spectroscopic, and electrochemical properties of nonheme Fe(II)-hydroquinonate complexes: synthetic models of hydroquinone dioxygenases.

Using the tris(3,5-diphenylpyrazol-1-yl)borate ((Ph2)Tp) supporting ligand, a series of mono- and dinuclear ferrous complexes containing hydroquinonate (HQate) ligands have been prepared and structurally characterized with X-ray crystallography. The monoiron(II) complexes serve as faithful mimics of the substrate-bound form of hydroquinone dioxygenases (HQDOs) - a family of nonheme Fe enzymes that catalyze the oxidative cleavage of 1,4-dihydroxybenzene units. Reflecting the variety of HQDO substrates, the synthetic complexes feature both mono- and bidentate HQate ligands.

Synthesis and characterization of Fe(II) β-diketonato complexes with relevance to acetylacetone dioxygenase: insights into the electronic properties of the 3-histidine facial triad.

A series of high-spin iron(II) β-diketonato complexes have been prepared and characterized with the intent of modeling the substrate-bound form of the enzyme acetylacetone dioxygenase (Dke1). The Dke1 active site features an Fe(II) center coordinated by three histidine residues in a facial geometry--a departure from the standard 2-histidine-1-carboxylate (2H1C) facial triad dominant among nonheme monoiron enzymes. The deprotonated β-diketone substrate binds to the Fe center in a bidentate fashion.

Nanosilver induces minimal lung toxicity or inflammation in a subacute murine inhalation model.

Background: There is increasing interest in the environmental and health consequences of silver nanoparticles as the use of this material becomes widespread. Although human exposure to nanosilver is increasing, only a few studies address possible toxic effect of inhaled nanosilver. The objective of this study was to determine whether very small commercially available nanosilver induces pulmonary toxicity in mice following inhalation exposure.

Commercially manufactured engineered nanomaterials for environmental and health studies: important insights provided by independent characterization.

Environmental and health studies on nanomaterials are appearing in the literature at a rapid pace. These studies will address important issues related to the environmental health and safety (EHS) of nanomaterials. As noted in many recent workshop and agency reports, studies devoted toward the environmental fate and transport, nanomaterial-biological interactions, toxicity, and overall risk assessment of nanomaterials should have nanomaterial characterization as a central component of the study design.

Nanorod dissolution quenched in the aggregated state.

Metal-containing nanorods are of great interest from a number of technological perspectives, and they are also present in the natural environment. Here we show that dissolution, both rate and extent, is greater for rod-shaped alpha-FeOOH particles on the nanoscale at pH 2 relative to microrods. However, when nanorods aggregate, either at lower pH and/or high ionic strength, dissolution is either completely quenched or severely quenched, by orders of magnitude.

Airborne monitoring to distinguish engineered nanomaterials from incidental particles for environmental health and safety.

Two methods were used to distinguish airborne engineered nanomaterials from other airborne particles in a facility that produces nano-structured lithium titanate metal oxide powder. The first method involved off-line analysis of filter samples collected with conventional respirable samplers at each of seven locations (six near production processes and one outdoors). Throughout most of the facility and outdoors, respirable mass concentrations were low (<0.