Impact of anion polarizability on ion pairing in microhydrated salt clusters

Despite longstanding interest in the mechanism of salt dissolution in aqueous media, a molecular level understanding remains incomplete. Here, cryogenic ion trap vibrational action spectroscopy is combined with electronic structure calculations to track salt hydration in a gas phase model system one water molecule at a time. The infrared photodissociation spectra of microhydrated lithium dihalide anions [LiXX′(H2O)n]- (XX′ = I2, ClI and Cl2; n = 1–3) in the OH stretching region (3800–2800 cm-1) provide a detailed picture of how anion polarizability influences the competition among ion–ion, ion–water and water–water interactions. While exclusively contact ion pairs are observed for n = 1, the formation of solvent-shared ion pairs, identified by markedly red-shifted OH stretching bands (-1), originating from the bridging water molecules, is favored already for n = 2. For n = 3, Li+ reaches its maximum coordination number of four only in [LiI2(H2O)3]-, in accordance with the hard and soft Lewis acid and base principle. Water–water hydrogen bond formation leads to a different solvent-shared ion pair motif in [LiI2(H2O)3]- and network formation even restabilizes the contact ion pair motif in [LiCl2(H2O)3]-. Structural assignments are exclusively possible after the consideration of anharmonic effects. Molecular dynamics simulations confirm that the significance of large amplitude motion (of the water molecules) increases with increasing anion polarizability and that needs to be considered already at cryogenic temperatures

Demultiplexing 160 Gbit/s OTDM signal to 40 Gbit/s by FWM in SOA

Error-free demultiplexing of 40 Gbit/s channels out of a 160 Gbit/s optical time-division signal is demonstrated using four-wave mixing in a semiconductor optical amplifier

Evaluating socio-economic and environmental sustainability of the sheep farming activity in Greece: a whole-farm mathematical programming approach

Ruminant livestock farming is an important agricultural activity, mainly located in less favoured areas. Furthermore, ruminants have been identi fi ed as a signi fi cant source of GHG emissions. In this study, a whole-farm optimization model is used to assess the socio-economic and environmental performance of the dairy sheep farming activity in Greece. The analysis is undertaken in two sheep farms that represent the extensive and the semi-intensive farming systems. Gross margin and labour are regarded as socio-economic indicators and GHG emissions as environmental indicators. The issue of the marginal abatement cost is also addressed. The results indicate that the semi-intensive system yields a higher gross margin/ewe (179 €) than the extensive system (117 €) and requires less labour. The extensive system causes higher emissions/kg of milk than the semi-intensive system (5.45 and 2.99 kg of CO2 equivalents, respectively). In both production systems, abatement is achieved primarily via reduction of the fl ock size and switch to cash crops. However, the marginal abatement cost is much higher in the case of the semi-intensive farms, due to their high productivity

Excitation and relaxation in atom-cluster collisions

Electronic and vibrational degrees of freedom in atom-cluster collisions are treated simultaneously and self-consistently by combining time-dependent density functional theory with classical molecular dynamics. The gradual change of the excitation mechanisms (electronic and vibrational) as well as the related relaxation phenomena (phase transitions and fragmentation) are studied in a common framework as a function of the impact energy (eV...MeV). Cluster "transparency" characterized by practically undisturbed atom-cluster penetration is predicted to be an important reaction mechanism within a particular window of impact energies.Comment: RevTeX (4 pages, 4 figures included with epsf

Importance of non-CO2 emissions in carbon management

Background: GHG budgets highlight a need for urgency, yet analyses are often CO2-focused, with less attention paid to non-CO2. Results: In this paper, scenarios are used to explore non-CO2 drivers and barriers to their mitigation, drawing out implications for CO2 management. Results suggest that even optimistic technological and consumption-related developments lead to on-going increases in global N2O, largely to improve food security within a changing climate. This contrasts with existing analysis, where lower levels of N2O by 2050 are projected. Conclusions: As avoiding '2°C' limits the emissions budget, constraints on reducing non-CO2 add pressure to energy system decarbonization. Overlooking how a changing climate and rising consumption restricts efforts to curb non-CO2 will result in policies aiming to avoid 2°C falling short of the mark

E. coli Histidine Triad Nucleotide Binding Protein 1 (ecHinT) Is a Catalytic Regulator of D-Alanine Dehydrogenase (DadA) Activity In Vivo

Histidine triad nucleotide binding proteins (Hints) are highly conserved members of the histidine triad (HIT) protein superfamily. Hints comprise the most ancient branch of this superfamily and can be found in Archaea, Bacteria, and Eukaryota. Prokaryotic genomes, including a wide diversity of both Gram-negative and Gram-positive bacteria, typically have one Hint gene encoded by hinT (ycfF in E. coli). Despite their ubiquity, the foundational reason for the wide-spread conservation of Hints across all kingdoms of life remains a mystery. In this study, we used a combination of phenotypic screening and complementation analyses with wild-type and hinT knock-out Escherichia coli strains to show that catalytically active ecHinT is required in E. coli for growth on D-alanine as a sole carbon source. We demonstrate that the expression of catalytically active ecHinT is essential for the activity of the enzyme D-alanine dehydrogenase (DadA) (equivalent to D-amino acid oxidase in eukaryotes), a necessary component of the D-alanine catabolic pathway. Site-directed mutagenesis studies revealed that catalytically active C-terminal mutants of ecHinT are unable to activate DadA activity. In addition, we have designed and synthesized the first cell-permeable inhibitor of ecHinT and demonstrated that the wild-type E. coli treated with the inhibitor exhibited the same phenotype observed for the hinT knock-out strain. These results reveal that the catalytic activity and structure of ecHinT is essential for DadA function and therefore alanine metabolism in E. coli. Moreover, they provide the first biochemical evidence linking the catalytic activity of this ubiquitous protein to the biological function of Hints in Escherichia coli

Ets1 Induces Dysplastic Changes When Expressed in Terminally-Differentiating Squamous Epidermal Cells

BACKGROUND: Ets1 is an oncogene that functions as a transcription factor and regulates the activity of many genes potentially important for tumor initiation and progression. Interestingly, the Ets1 oncogene is over-expressed in many human squamous cell cancers and over-expression is highly correlated with invasion and metastasis. Thus, Ets1 is believed to mainly play a role in later stages of the oncogenic process, but not early events. METHODOLOGY/PRINCIPAL FINDINGS: To better define the role of Ets1 in squamous cell carcinogenesis, we generated a transgenic mouse model in which expression of the Ets1 oncogene could be temporally and spatially regulated. Upon Ets1 induction in differentiating cells of stratified squamous epithelium, these mice exhibited dramatic changes in epithelial organization including increased proliferation and blocked terminal differentiation. The phenotype was completely reversed when Ets1 expression was suppressed. In mice where Ets1 expression was re-induced at a later age, the phenotype was more localized and the lesions that developed were more invasive. Many potential Ets1 targets were upregulated in the skin of these mice with the most dramatic being the metalloprotease MMP13, which we demonstrate to be a direct transcriptional target of Ets1. CONCLUSIONS/SIGNIFICANCE: Collectively, our data reveal that upregulation of Ets1 can be an early event that promotes pre-neoplastic changes in epidermal tissues via its regulation of key genes driving growth and invasion. Thus, the Ets1 oncogene may be important for oncogenic processes in both early and late stages of tumor development

Association between age of cannabis initiation and gray matter covariance networks in recent onset psychosis

Cannabis use during adolescence is associated with an increased risk of developing psychosis. According to a current hypothesis, this results from detrimental effects of early cannabis use on brain maturation during this vulnerable period. However, studies investigating the interaction between early cannabis use and brain structural alterations hitherto reported inconclusive findings. We investigated effects of age of cannabis initiation on psychosis using data from the multicentric Personalized Prognostic Tools for Early Psychosis Management (PRONIA) and the Cannabis Induced Psychosis (CIP) studies, yielding a total sample of 102 clinically-relevant cannabis users with recent onset psychosis. GM covariance underlies shared maturational processes. Therefore, we performed source-based morphometry analysis with spatial constraints on structural brain networks showing significant alterations in schizophrenia in a previous multisite study, thus testing associations of these networks with the age of cannabis initiation and with confounding factors. Earlier cannabis initiation was associated with more severe positive symptoms in our cohort. Greater gray matter volume (GMV) in the previously identified cerebellar schizophrenia-related network had a significant association with early cannabis use, independent of several possibly confounding factors. Moreover, GMV in the cerebellar network was associated with lower volume in another network previously associated with schizophrenia, comprising the insula, superior temporal, and inferior frontal gyrus. These findings are in line with previous investigations in healthy cannabis users, and suggest that early initiation of cannabis perturbs the developmental trajectory of certain structural brain networks in a manner imparting risk for psychosis later in life

Greenhouse gas (N2O and CH4) fluxes under nitrogen-fertilised dryland wheat and barley on subtropical Vertosols: risk, rainfall and alternatives

The northern Australian grains industry relies on nitrogen (N) fertiliser to optimise yield and protein, but N fertiliser can increase soil fluxes of nitrous oxide (N2O) and methane (CH4). We measured soil N2O and CH4 fluxes associated with wheat (Triticum aestivum) and barley (Hordeum vulgare) using automated (Expts 1, 3) and manual chambers (Expts 2, 4, 5). Experiments were conducted on subtropical Vertosol soils fertilised with N rates of 0-160kgNha-1. In Expt 1 (2010), intense rainfall for a month before and after sowing elevated N2O emissions from N-fertilised (80kgNha-1) wheat, with 417gN2O-Nha-1 emitted compared with 80g N2O-Nha-1 for non-fertilised wheat. Once crop N uptake reduced soil mineral N, there was no further treatment difference in N2O. Expt 2 (2010) showed similar results, however, the reduced sampling frequency using manual chambers gave a lower cumulative N2O. By contrast, very low rainfall before and for several months after sowing Expt 3 (2011) resulted in no difference in N2O emissions between N-fertilised and non-fertilised barley. N2O emission factors were 0.42, 0.20 and -0.02 for Expts 1, 2 and 3, respectively. In Expts 4 and 5 (2011), N2O emissions increased with increasing rate of N fertiliser. Emissions were reduced by 45% when the N fertiliser was applied in a 50:50 split between sowing and mid-tillering, or by 70% when urea was applied with the nitrification inhibitor 3,4-dimethylpyrazole-phosphate. Methane fluxes were typically small and mostly negative in all experiments, especially in dry soils. Cumulative CH4 uptake ranged from 242 to 435g CH4-Cha-1year-1, with no effect of N fertiliser treatment. Considered in terms of CO2 equivalents, soil CH4 uptake offset 8-56% of soil N2O emissions, with larger offsets occurring in non-N-fertilised soils. The first few months from N fertiliser application to the period of rapid crop N uptake pose the main risk for N2O losses from rainfed cereal cropping on subtropical Vertosols, but the realisation of this risk is dependent on rainfall. Strategies that reduce the soil mineral N pool during this time can reduce the risk of N2O loss