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

Pemphigus vulgaris autoantibodies induce apoptosis in HaCaT keratinocytes

Pemphigus vulgaris (PV) is an autoimmune disease characterized by binding of IgG autoantibodies to epidermal keratinocyte desmosomes. IgG autoantibodies obtained from a patient with mucocutaneous PV reacted with plakoglobin (Plkg) in addition to desmoglein-3 (Dsg3) and Dsg1. Immunofluorescence analysis confirmed that IgG autoantibodies, unlike antibodies from a healthy volunteer, caused disruption of cell-cell contacts in HaCaT keratinocytes. Moreover, apoptosis was enhanced in cells treated with autoantibodies compared to those treated with normal antibodies. The apoptotic process induced by IgG autoantibodies was characterized by caspase-3 activation, Bcl-2 depletion and Bax expression. The present report demonstrates that PV IgG autoantibodies promote apoptosis in HaCaT keratinocytes

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

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

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