The PtAl(-) and PtAl2(-) anions: theoretical and photoelectron spectroscopic characterization.

We report a joint photoelectron spectroscopic and theoretical study of the PtAl(-) and PtAl2(-) anions. The ground state structures and electronic configurations of these species were identified to be C∞v, (1)Σ(+) for PtAl(-), and C2v, (2)B1 for PtAl2(-). Structured anion photoelectron spectra of these clusters were recorded and interpreted using ab initio calculations.

PtZnH5(-), A σ-Aromatic Cluster.

We report a joint photoelectron spectroscopic and theoretical study of the PtZnH5(-) cluster anion. This cluster exhibited an unprecedented planar pentagonal coordination for Pt and an unusual stability and high intensity in the mass spectrum. Both are due to the σ-aromaticity found in the H5-cycle supported by the 5d orbitals on the Pt atom.

The viability of aluminum Zintl anion moieties within magnesium-aluminum clusters.

Through a synergetic combination of anion photoelectron spectroscopy and density functional theory based calculations, we have investigated the extent to which the aluminum moieties within selected magnesium-aluminum clusters are Zintl anions. Magnesium-aluminum cluster anions were generated in a pulsed arc discharge source. After mass selection, photoelectron spectra of MgmAln (-) (m, n = 1,6; 2,5; 2,12; and 3,11) were measured by a magnetic bottle, electron energy analyzer.

Young Offenders' Emotion Recognition Dysfunction Across Emotion Intensities: Explaining Variation Using Psychopathic Traits, Conduct Disorder and Offense Severity.

Antisocial individuals have problems recognizing negative emotions (e.g. Marsh & Blair in Neuroscience and Biobehavioral Reviews 32:454-465, 2009); however, due to issues with sampling and different methods used, previous findings have been varied.

Very small "window of opportunity" for generating CO oxidation-active Au(n) on TiO2.

Recent research in heterogeneous catalysis, especially on size-selected model systems under UHV conditions and also in realistic catalytic environments, has proved that it is necessary to think in terms of the exact number of atoms when it comes to catalyst design. This is of utmost importance if the amount of noble metal, gold in particular, is to be reduced for practical reactions like CO oxidation. Here it is shown that on TiO2 only Au6 and Au7 clusters are active for CO oxidation which holds for the single crystal, thin films, and titania clusters deposited on HOPG.

The reaction rates of O2 with closed-shell and open-shell Al(x)⁻ and Ga(x)⁻ clusters under single-collision conditions: experimental and theoretical investigations toward a generally valid model for the hindered reactions of O2 with metal atom clusters.

In order to characterize the oxidation of metallic surfaces, the reactions of O2 with a number of Al(x)(-) and, for the first time, Ga(x)(-) clusters as molecular models have been investigated, and the results are presented here for x = 9-14. The rate coefficients were determined with FT-ICR mass spectrometry under single-collision conditions at O2 pressures of ~10(-8) mbar. In this way, the qualitatively known differences in the reactivities of the even- and odd-numbered clusters toward O2 could be quantified experimentally.

Alanate anion, AlH4(-): photoelectron spectrum and computations.

The alanate anion, AlH4(-), was generated in the gas phase using a pulsed arc cluster ionization source. Its photoelectron spectrum was then measured with 193 nm photons. The spectrum consists of a broad feature, spanning electron binding energies from 3.

Aluminum Zintl anion moieties within sodium aluminum clusters.

Through a synergetic combination of anion photoelectron spectroscopy and density functional theory based calculations, we have established that aluminum moieties within selected sodium-aluminum clusters are Zintl anions. Sodium-aluminum cluster anions, Na(m)Al(n)(-), were generated in a pulsed arc discharge source. After mass selection, their photoelectron spectra were measured by a magnetic bottle, electron energy analyzer.

Using social network analysis to evaluate health-related adaptation decision-making in Cambodia.

Climate change adaptation in the health sector requires decisions across sectors, levels of government, and organisations. The networks that link these different institutions, and the relationships among people within these networks, are therefore critical influences on the nature of adaptive responses to climate change in the health sector. This study uses social network research to identify key organisational players engaged in developing health-related adaptation activities in Cambodia.

IFNγ/IL-10 co-producing cells dominate the CD4 response to malaria in highly exposed children.

Although evidence suggests that T cells are critical for immunity to malaria, reliable T cell correlates of exposure to and protection from malaria among children living in endemic areas are lacking. We used multiparameter flow cytometry to perform a detailed functional characterization of malaria-specific T cells in 78 four-year-old children enrolled in a longitudinal cohort study in Tororo, Uganda, a highly malaria-endemic region. More than 1800 episodes of malaria were observed in this cohort, with no cases of severe malaria.

Strong, low-barrier hydrogen bonds may be available to enzymes.

The debate over the possible role of strong, low-barrier hydrogen bonds in stabilizing reaction intermediates at enzyme active sites has taken place in the absence of an awareness of the upper limits to the strengths of low-barrier hydrogen bonds involving amino acid side chains. Hydrogen bonds exhibit their maximal strengths in isolation, i.e.

Combined photoelectron, collision-induced dissociation, and computational studies of parent and fragment anions of N-paranitrophenylsulfonylalanine and N-paranitrophenylalanine.

After synthesizing the compounds N-paranitrophenylsulfonylalanine (NPNPSA) and N-paranitrophenylalanine (NPNPA), the photoelectron spectrum of the valence anion of N-paranitrophenylsulfonylalanine (NPNPSA)(-), was measured and the collision-induced dissociation (CID) pathways of deprotonated N-paranitrophenylsulfonylalanine (NPNPSA-H)(-) and deprotonated N-paranitrophenylalanine (NPNPA-H)(-) were determined. Pertinent calculations were conducted to analyze both sets of experimental data. From the valence anion photoelectron spectrum of (NPNPSA)(-), the adiabatic electron affinity (AEA) of NPNPSA was determined to be 1.

The stress-buffering effects of functional social support on ambulatory blood pressure.

Objective: Social support is a reliable predictor of cardiovascular health. According to the buffering hypothesis, stress is 1 mechanism by which support is able to affect physiological processes. However, most of the experimental evidence for the hypothesis comes from laboratory studies.

Aluminium(III) amidinates formed from reactions of `AlCl' with lithium amidinates.

The disproportionation of AlCl(THF)n (THF is tetrahydrofuran) in the presence of lithium amidinate species gives aluminium(III) amidinate complexes with partial or full chloride substitution. Three aluminium amidinate complexes formed during the reaction between aluminium monochloride and lithium amidinates are presented. The homoleptic complex tris(N,N'-diisopropylbenzimidamido)aluminium(III), [Al(C13H19N2)3] or Al{PhC[N(i-Pr)]2}3, (I), crystallizes from the same solution as the heteroleptic complex chloridobis(N,N'-diisopropylbenzimidamido)aluminium(III), [Al(C13H19N2)2Cl] or Al{PhC[N(i-Pr)]2}2Cl, (II).

Communication: In search of four-atom chiral metal clusters.

A combined study utilizing anion photoelectron spectroscopy and density functional theory was conducted to search for four-atom, chiral, metal, and mostly metal clusters. The clusters considered were AuCoMnBi(-/0), AlAuMnO(-/0), AgMnOAl(-/0), and AuAlPtAg(-/0), where the superscripts, (-/0), refer to anionic and neutral cluster species, respectively. Based on the agreement of experimentally and theoretically determined values of both electron affinities and vertical detachment energies, the calculated cluster geometries were validated and examined for chirality.

A multi-layered governance framework for incorporating social science insights into adapting to the health impacts of climate change.

Background: Addressing climate change and its associated effects is a multi-dimensional and ongoing challenge. This includes recognizing that climate change will affect the health and wellbeing of all populations over short and longer terms, albeit in varied ways and intensities. That recognition has drawn attention to the need to take adaptive actions to lessen adverse impacts over the next few decades from unavoidable climate change, particularly in developing country settings.

Photoelectron spectroscopic and density functional theoretical studies of the 2'-deoxycytidine homodimer radical anion.

The intact (parent) 2'-deoxycytidine homodimer anion, (dC)2 (●-), was generated in the gas phase (in vacuo) using an infrared desorption∕photoemission source and its photoelectron spectrum was recorded using a pulsed, magnetic bottle photoelectron spectrometer. The photoelectron spectrum (PES) revealed a broad peak with the maximum at an electron binding energy between 1.6 and 1.

Relationships and cardiovascular risk: perceived spousal ambivalence in specific relationship contexts and its links to inflammation.

Objectives: Although perceiving one's social ties as sources of ambivalence has been linked to negative health outcomes, the more specific contexts by which such relationships influence health remain less studied. We thus examined if perceived spousal relationship quality in three theoretically important contexts (i.e.

Characterization of a nitrite reductase involved in nitrifier denitrification.

Nitrifier denitrification is the conversion of nitrite to nitrous oxide by ammonia-oxidizing organisms. This process, which is distinct from denitrification, is active under aerobic conditions in the model nitrifier Nitrosomonas europaea. The central enzyme of the nitrifier dentrification pathway is a copper nitrite reductase (CuNIR).

Negative ions of p-nitroaniline: photodetachment, collisions, and ab initio calculations.

The structures of parent anion, M(-), and deprotonated molecule, [M-H](-), anions of the highly polar p-nitroaniline (pNA) molecule are studied experimentally and theoretically. Photoelectron spectroscopy (PES) of the parent anion is employed to estimate the adiabatic electron affinity (EAa = 0.75 ± 0.

Photoelectron spectroscopy of the aluminum hydride anions: AlH2(-), AlH3(-), Al2H6(-), Al3H9(-), and Al4H12(-).

We report measurements of the negative ion photoelectron spectra of the simple aluminum hydride anions: AlH2(-), AlH3(-), Al2H6(-), Al3H9(-), and Al4H12(-). From these spectra, we measured the vertical detachment energies of the anions, and we estimated the electron affinities of their neutral counterparts. Our results for AlH2(-), AlH3(-), and Al2H6(-) were also compared with previous predictions by theory.

On the existence of designer magnetic superatoms.

The quantum states in small, compact metal clusters are bunched into electronic shells with electronic orbitals resembling those in atoms, enabling classification of stable clusters as superatoms. The filling of superatomic orbitals, however, does not generally follow Hund's rule, and it has been proposed that magnetic superatoms can be stabilized by doping simple metal clusters with magnetic atoms. Here, we present evidence of the existence of a magnetic superatom and the determination of its spin moment.

Tumor necrosis factor-related apoptosis-inducing ligand promotes microvascular endothelial cell hyperpermeability through phosphatidylinositol 3-kinase pathway.

Background: Microvascular hyperpermeability that occurs in hemorrhagic shock and burn trauma is regulated by the apoptotic signaling pathway. We hypothesized that tumor necrosis factor-α (TNF-α)-related apoptosis-inducing ligand (TRAIL) would promote hyperpermeability directly or by interacting with other signaling pathways.

Methods: Rat lung microvascular endothelial cells (RLMECs) grown on Transwell membranes (Corning Life Sciences, Lowell, MA) were treated with recombinant human TRAIL (10, 50, and 100 ng/mL) for 6 hours or TRAIL (100 ng/mL) + LY294002 (a PI3K inhibitor; 20 μmol/L), Z-DEVD-FMK (a caspase-3 inhibitor; 10 μmol/L), or the inhibitors alone.

Photoelectron spectroscopy and density functional theory studies on the uridine homodimer radical anions.

We report the photoelectron spectrum (PES) of the homogeneous dimer anion radical of uridine, (rU)(2)(●-). It features a broad band consisting of an onset of ∼1.2 eV and a maximum at the electron binding energy (EBE) ranging from 2.