Influences of Coal Ash Leachates and Emergent Macrophytes on Water Quality in Wetland Microcosms.

The storage of coal combustion residue (CCR) in surface water impoundments may have an impact on nearby water quality and aquatic ecosystems. CCR contains leachable trace elements that can enter nearby waters through spills and monitored discharge. It is important, therefore, to understand their environmental fate in affected systems.

Anger Expression Style Predicts the Domain of the First Smoking Relapse After a Quit Attempt.

Background: Risk for smoking relapse may be associated with context-dependent social and behavioral cues. However, lack of research examining the role of trait negative mood such as anger in this relationship and assessment of objective indices related to smoking status (e.g.

Life adversity is associated with smoking relapse after a quit attempt.

Multiple cross-sectional studies have linked adverse childhood events and adult adversities to current smoking, lifetime smoking, and former smoking. To date, however, there have been no direct observational studies assessing the influence of adversities on smoking relapse. We prospectively followed 123 participants, 86 of whom were habitual smokers, from pre-quit ad libitum smoking to four weeks post-quit.

Mitochondrial biotransformation of omega-(phenoxy)alkanoic acids, 3-(phenoxy)acrylic acids, and omega-(1-methyl-1H-imidazol-2-ylthio)alkanoic acids: a prodrug strategy for targeting cytoprotective antioxidants to mitochondria.

Mitochondrial reactive oxygen species (ROS) generation and the attendant mitochondrial dysfunction are implicated in a range of disease states. The objective of the present studies was to test the hypothesis that the mitochondrial beta-oxidation pathway could be exploited to deliver and biotransform the prodrugs omega-(phenoxy)alkanoic acids, 3-(phenoxy)acrylic acids, and omega-(1-methyl-1H-imidazol-2-ylthio)alkanoic acids to the corresponding phenolic antioxidants or methimazole. 3- and 5-(Phenoxy)alkanoic acids and methyl-substituted analogs were biotransformed to phenols; rates of biotransformation decreased markedly with methyl-group substitution on the phenoxy moiety.

Ring currents in tangentially p-p bonded sigma-aromatic systems.

We report a theoretical study of ring systems that delocalize electrons in a cyclic array of p orbitals arranged tangentially in sigma-bonding fashion. Sigma-bonded arrays are compared to conventional pi-bonded analogues with respect to orbital symmetry and aromatic/antiaromatic behavior. In a one-to-one correspondence between pi and tangential molecular orbitals of a cycle, local rotation turns each pi to a tangential basis function, changing bonding interactions to antibonding and inverting the order of filling of molecular orbitals.

Theoretical studies of quantum amplified isomerizations for imaging systems involving hexamethyl Dewar benzene and related systems.

The ring-opening reactions of the radical cations of hexamethyl Dewar benzene (1) and Dewar benzene have been studied using density functional theory (DFT) and complete active-space self-consistent field (CASSCF) calculations. Compound 1 is known to undergo photoinitiated ring opening by a radical cation chain mechanism, termed "quantum amplified isomerization" (QAI), which is due to the high quantum yield. Why QAI is efficient for 1 but not other reactions is explained computationally.

Peroxynitrate and peroxynitrite: a complete basis set investigation of similarities and differences between these NOx species.

Peroxynitric acid/peroxynitrate (PNA) rivals peroxynitrous acid/peroxynitrite (PNI) in importance as a reactive oxygen species. These species possess similar two-electron oxidative behavior. On the other hand, stark differences exist in the stability of these molecules as a function of pH and in the presence of CO(2), and also in the types of bond homolysis reactions that PNA and PNI may undergo.

Conformation-dependent state selectivity in O-O cleavage of ONOONO: an "inorganic cope rearrangement" helps explain the observed negative activation energy in the oxidation of nitric oxide by dioxygen.

ONOONO has been proposed as an intermediate in the oxidation of nitric oxide by dioxygen to yield nitrogen dioxide. The O-O bond breaking reactions of this unusual peroxide, and subsequent rearrangements, were evaluated using CBS-QB3 and B3LYP/6-311G hybrid density functional theory. The three stable conformers (cis,cis-, cis,trans-, and trans,trans-ONOONO, based on the O-N-O-O dihedral angles of either approximately 0 degrees or approximately 180 degrees ) are predicted to have very different O-O cleavage barriers: 2.