In the quest for low-molecular-weight metal sulfur complexes that bind nitrogenase-relevant small molecules and can serve as model complexes for nitrogenase, compounds with the [Ru(PiPr(3))('N(2)Me(2)S(2)')] fragment were found ('N(2)Me(2)S(2)'(2-)=1,2-ethanediamine-N,N'-dimethyl-N,N'-bis(2-benzenethiolate)(2-)). This fragment enabled the synthesis of a first series of chiral metal sulfur complexes, [Ru(L)(PiPr(3))('N(2)Me(2)S(2)')] with L=N(2), N(2)H(2), N(2)H(4), and NH(3), that meet the biological constraint of forming under mild conditions. The reaction of [Ru(NCCH(3))(PiPr(3))('N(2)Me(2)S(2)')] (1) with NH(3) gave the ammonia complex [Ru(NH(3))(PiPr(3))('N(2)Me(2)S(2)')] (4), which readily exchanged NH(3) for N(2) to yield the mononuclear dinitrogen complex [Ru(N(2))(PiPr(3))('N(2)Me(2)S(2)')] (2) in almost quantitative yield. Complex 2, obtained by this new efficient synthesis, was the starting material for the synthesis of dinuclear (R,R)- and (S,S)-[micro-N(2)[Ru(PiPr(3))('N(2)Me(2)S(2)')](2)] ((R,R)-/(S,S)-3). (Both 2 and 3 have been reported previously.) The as-yet inexplicable behavior of complex 3 to form also the R,S isomer in solution has been revealed by DFT calculations and (2)D NMR spectroscopy studies. The reaction of 1 or 2 with anhydrous hydrazine yielded the hydrazine complex [Ru(N(2)H(4))(PiPr(3))('N(2)Me(2)S(2)')] (6), which is a highly reactive intermediate. Disproportionation of 6 resulted in the formation of mononuclear diazene complexes, the ammonia complex 4, and finally the dinuclear diazene complex [micro-N(2)H(2)[Ru(PiPr(3))('N(2)Me(2)S(2)')](2)] (5). Dinuclear complex 5 could also be obtained directly in an independent synthesis from 1 and N(2)H(2), which was generated in situ by acidolysis of K(2)N(2)(CO(2))(2). Treatment of 6 with CH(2)Cl(2), however, formed a chloromethylated diazene species [[Ru(PiPr(3))('N(2)Me(2)S(2)')]-micro-N(2)H(2)[Ru(Cl)('N(2)Me(2)S(2)CH(2)Cl')]] (9) ('N(2)Me(2)S(2)CH(2)Cl'(2-) =1,2-ethanediamine-N,N'-dimethyl-N-(2-benzenethiolate)(1-)-N'-(2-benzenechloromethylthioether)(1-)]. The molecular structures of 4, 5, and 9 were determined by X-ray crystal structure analysis, and the labile N(2)H(4) complex 6 was characterized by NMR spectroscopy.

No abstract

Hurricane Sandy caused extensive physical and economic damage; the long-term mental health consequences are unknown. Flooding is a central component of hurricane exposure, influencing mental health through multiple pathways that unfold over months after flooding recedes. Here we assess the concordance in self-reported and Federal Emergency Management (FEMA) flood exposure after Hurricane Sandy and determine the associations between flooding and anxiety, depression, and post-traumatic stress disorder (PTSD). Self-reported flood data and mental health symptoms were obtained through validated questionnaires from New York City and Long Island residents (N = 1231) following Sandy. Self-reported flood data was compared to FEMA data obtained from the FEMA Modeling Task Force Hurricane Sandy Impact Analysis. Multivariable logistic regressions were performed to determine the relationship between flooding exposure and mental health outcomes. There were significant discrepancies between self-reported and FEMA flood exposure data. Self-reported dichotomous flooding was positively associated with anxiety (ORadj: 1.5 [95% CI: 1.1–1.9]), depression (ORadj: 1.7 [1.3–2.2]), and PTSD (ORadj: 2.5 [1.8–3.4]), while self-reported continuous flooding was associated with depression (ORadj: 1.1 [1.01–1.12]) and PTSD (ORadj: 1.2 [1.1–1.2]). Models with FEMA dichotomous flooding (ORadj: 2.1 [1.5–2.8]) or FEMA continuous flooding (ORadj: 1.1 [1.1–1.2]) were only significantly associated with PTSD. Associations between mental health and flooding vary according to type of flood exposure measure utilized. Future hurricane preparedness and recovery efforts must integrate micro and macro-level flood exposures in order to accurately determine flood exposure risk during storms and realize the long-term importance of flooding on these three mental health symptoms.

Road dust resuspension is a major source of particulate matter in many urban centers, especially those in which traction materials are applied to roadways in winter. Although many studies have investigated the composition and toxicity of road dust, nothing is currently known regarding its photochemical reactivity. Here, we show for the first time that road dust is photochemically active: in particular, we use a molecular probe technique to show that the illumination of aqueous road dust suspensions leads to the production of singlet oxygen (1O2), an important environmental oxidant. In experiments conducted using size-fractionated road dust, we found that the surface area-normalized steady-state 1O2 concentration ([1O2]ss) increased with decreasing particle size. We also observed correlations between [1O2]ss and the dissolved organic carbon content and ultraviolet absorbance properties of dust extracts, which suggests the involvement of chromophoric water-soluble organic carbon in the observed photochemistry. Interestingly, [1O2]ss in aqueous road dust extracts was lower than in the corresponding particle-containing samples, which implies that the particle surface itself also participated in 1O2 production. This work provides evidence that road dust photochemistry may influence the lifetime of urban pollutants that react via 1O2-mediated pathways.

Results suggest that participants with higher PTSD symptoms were more likely to grow from the impact of the storm, indicating resilience. Highly exposed participants were more likely to experience PTG. A decrease in PTG was found among those with both PTSD and depression symptoms. The development and implementation of interventions fostering PTG could be beneficial in clinical disaster response work. (PsycINFO Database Record