On the formation of propylene oxide from propylene in space: gas-phase reactions

In the present article, we have investigated the possibility of forming propylene oxide (PO) from propylene (PE) by bi-molecular reactions. Propylene oxide is the first chiral molecule observed in the interstellar medium, and studying the thermodynamics and kinetics of formation can suggest possible synthetic routes. We have focused our attention on gas-phase reactions, and the presence of an environment is discussed in particular for the possibility of forming it by association reactions. In particular, we have considered radical and ion–molecule reactions. Results show that the main gas-phase route to PO formation is represented by ion–molecule reactions which turn out to be compatible with astrophysical conditions, notably: PE + O + and PE+HO2+. Their final product is not PO, but its ionized variant PO + that can be neutralized by electron capture. The only thermodynamically and kinetically allowed reaction which can directly lead to neutral PO is a collision of PE with a singlet-excited OH + but two competing reactions (leading to PE + and PO +) are thermodynamically favored and thus more plausible in space

Gene silencing of endothelial von Willebrand factor reduces the susceptibility of human endothelial cells to SARS-CoV-2 infection

Mechanisms underlying vascular endothelial susceptibility to infection by severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) are not fully understood. Emerging evidence indicates that patients lacking von Willebrand factor (vWF), an endothelial hallmark, are less severely affected by SARS-CoV-2 infection, yet the precise role of endothelial vWF in modulating coronavirus entry into endothelial cells is unknown. In the present study, we demonstrated that effective gene silencing by short interfering RNA (siRNA) for vWF expression in resting human umbilical vein endothelial cells (HUVECs) significantly reduced by 56% the cellular levels of SARS-CoV-2 genomic RNA. Similar reduction of intracellular SARS-CoV-2 genomic RNA levels was observed in non-activated HUVECs treated with siRNA targeting angiotensin-converting enzyme 2 (ACE2), the cellular gateway to coronavirus. By integrating quantitative information from real-time PCR and high-resolution confocal imaging, we demonstrated that ACE2 gene expression and its plasma membrane localization in HUVECs were both markedly reduced after treatment with siRNA anti-vWF or anti-ACE2. Conversely, siRNA anti-ACE2 did not reduce endothelial vWF gene expression and protein levels. Finally, SARS-CoV-2 infection of viable HUVECs was enhanced by overexpression of vWF, which increased ACE2 levels. Of note, we found a similar increase in interferon-β mRNA levels following transfection with untargeted, anti-vWF or anti-ACE2 siRNA and pcDNA3.1-WT-VWF. We envision that siRNA targeting endothelial vWF will protect against productive endothelial infection by SARS-CoV-2 through downregulation of ACE2 expression and might serve as a novel tool to induce disease resistance by modulating the regulatory role of vWF on ACE2 expression

Singlet oxygen from cation driven superoxide disproportionation and consequences for aprotic metal-O2 batteries

Aprotic alkali metal-oxygen batteries require reversible formation of metal superoxide or peroxide on cycling. Severe parasitic reactions cause poor rechargeability, efficiency, and cycle life and have been shown to be caused by singlet oxygen (1O2) that forms at all stages of cycling. However, its formation mechanism remains unclear. We show that disproportionation of superoxide, the product or intermediate on discharge and charge, to peroxide and oxygen is responsible for 1O2 formation. While the overall reaction is driven by the stability of peroxide and thus favored by stronger Lewis acidic cations such as Li+, the 1O2 fraction is enhanced by weak Lewis acids such as organic cations. Concurrently, the metal peroxide yield drops with increasing 1O2. The results explain a major parasitic pathway during cell cycling and the growing severity in K-, Na-, and Li-O2 cells based on the growing propensity for disproportionation. High capacities and rates with peroxides are now realized to require solution processes, which form peroxide or release O2via disproportionation. The results therefore establish the central dilemma that disproportionation is required for high capacity but also responsible for irreversible reactions. Highly reversible cell operation requires hence finding reaction routes that avoid disproportionation

Crop changes from the XVI century to the present in a hill/mountain area of eastern Liguria (Italy)

<p>Abstract</p> <p>Background</p> <p>Chronological information on the composition and structure of agrocenoses and detailed features of land cover referring to specific areas are uncommon in ethnobotanical studies, especially for periods before the XIX century. The aim of this study was to analyse the type of crop or the characteristics of soil cover from the XVI century to the present.</p> <p>Methods</p> <p>This diachronic analysis was accomplished through archival research on the inventories of the Parish of St. Mary and those of the Municipality of Pignone and from recent surveys conducted in an area of eastern Liguria (Italy).</p> <p>Results</p> <p>Archival data revealed that in study area the primary means of subsistence during the last five centuries, until the first half of the XX century, was chestnuts. In the XVIII and XIX centuries, crop diversification strongly increased in comparison with previous and subsequent periods. In more recent times, the abandonment of agricultural practices has favoured the re-colonisation of mixed woodland or cluster-pine woodland.</p> <p>Conclusion</p> <p>Ancient documents in the ecclesiastic or municipal inventories can be a very useful tool for enhancing the knowledge of agricultural practice, as well as of subsistence methods favoured by local populations during a particular time and for reconstructing land use change over time.</p

Model to estimate the sampling density for establishment of yield mapping

Yield mapping represents the spatial variability concerning the features of a productive area and allows intervening on the next year production, for example, on a site-specific input application. The trial aimed at verifying the influence of a sampling density and the type of interpolator on yield mapping precision to be produced by a manual sampling of grains. This solution is usually adopted when a combine with yield monitor can not be used. An yield map was developed using data obtained from a combine equipped with yield monitor during corn harvesting. From this map, 84 sample grids were established and through three interpolators: inverse of square distance, inverse of distance and ordinary kriging, 252 yield maps were created. Then they were compared with the original one using the coefficient of relative deviation (CRD) and the kappa index. The loss regarding yield mapping information increased as the sampling density decreased. Besides, it was also dependent on the interpolation method used. A multiple regression model was adjusted to the variable CRD, according to the following variables: spatial variability index and sampling density. This model aimed at aiding the farmer to define the sampling density, thus, allowing to obtain the manual yield mapping, during eventual problems in the yield monitor.O mapa de produtividade representa a variabilidade espacial das características de uma área cultivada e permite intervir na produção dos anos posteriores, na aplicação diferenciada de insumos. Este trabalho teve por objetivo verificar a influência da densidade amostral e do tipo de interpolação na exatidão dos mapas de produtividade, gerados a partir da amostragem manual de grãos, solução que pode ser adotada quando um monitor não pode ser utilizado. Um mapa de produtividade foi obtido com monitor de colheita comercial em lavoura de milho, a partir do qual foram estabelecidas 84 grades e, por meio de três interpoladores, o inverso da distância ao quadrado, inverso da distância e krigagem geraram-se, assim, 252 mapas de produtividade, que foram então comparados com o original, utilizando-se o coeficiente de desvio relativo (CDR) e o índice kappa. A perda de informação do mapa de produtividade aumentou à medida em que se diminuiu a densidade amostral e foi dependente do método de interpolação utilizado. Um modelo de regressão múltipla foi ajustado à variável CDR, em função das variáveis: índice de variabilidade espacial e densidade amostral. Este modelo teve a finalidade de auxiliar o agricultor na definição da densidade amostral e permitir obter-se, manualmente, o mapa de produtividade, caso ocorram problemas eventuais no monitor de colheita.Coordenacao de Aperfeicoamento de Pessoal de Nivel (CAPES)Coordenacao de Aperfeicoamento de Pessoal de Nivel (CAPES)Conselho Nacional de Desenvolvimento Cientifico e Tecnologico (CNPq)Conselho Nacional de Desenvolvimento Cientifico e Tecnologico (CNPq

Relaxation of Electron Spin during High-Field Transport in GaAs Bulk

A semiclassical Monte Carlo approach is adopted to study the multivalley spin depolarization of drifting electrons in a doped n-type GaAs bulk semiconductor, in a wide range of lattice temperature ($40<T_L<300$ K) and doping density ($10^{13}<n<10^{16}$cm$^{-3}$). The decay of the initial non-equilibrium spin polarization of the conduction electrons is investigated as a function of the amplitude of the driving static electric field, ranging between 0.1 and 6 kV/cm, by considering the spin dynamics of electrons in both the $\Gamma$ and the upper valleys of the semiconductor. Doping density considerably affects spin relaxation at low temperature and weak intensity of the driving electric field. At high values of the electric field, the strong spin-orbit coupling of electrons in the $L$-valleys significantly reduces the average spin polarization lifetime, but, unexpectedly, for field amplitudes greater than 2.5 kV/cm, the spin lifetime increases with the lattice temperature. Our numerical findings are validated by a good agreement with the available experimental results and with calculations recently obtained by a different theoretical approach.Comment: 14 pages, 6 figure

Evidence of stochastic resonance in the mating behavior of Nezara viridula (L.)

We investigate the role of the noise in the mating behavior between individuals of Nezara viridula (L.), by analyzing the temporal and spectral features of the non-pulsed type female calling song emitted by single individuals. We have measured the threshold level for the signal detection, by performing experiments with the calling signal at different intensities and analyzing the insect response by directionality tests performed on a group of male individuals. By using a sub-threshold signal and an acoustic Gaussian noise source, we have investigated the insect response for different levels of noise, finding behavioral activation for suitable noise intensities. In particular, the percentage of insects which react to the sub-threshold signal, shows a non-monotonic behavior, characterized by the presence of a maximum, for increasing levels of the noise intensity. This constructive interplay between external noise and calling signal is the signature of the non-dynamical stochastic resonance phenomenon. Finally, we describe the behavioral activation statistics by a soft threshold model which shows stochastic resonance. We find that the maximum of the ensemble average of the input-output cross-correlation occurs at a value of the noise intensity very close to that for which the behavioral response has a maximum.Comment: 6 pages, 4 figures, to appear in EPJ B (2008

Association of Torquetenovirus Viremia with Physical Frailty and Cognitive Impairment in Three Independent European Cohorts

Introduction: Immunosenescence and inflammaging have been implicated in the pathophysiology of frailty. Torquetenovirus (TTV), a single-stranded DNA anellovirus, the major component of the human blood virome, shows an increased replication rate with advancing age. An elevated TTV viremia has been associated with an impaired immune function and an increased risk of mortality in the older population. The objective of this study was to analyze the relation between TTV viremia, physical frailty, and cognitive impairment. Methods: TTV viremia was measured in 1,131 nonfrail, 45 physically frail, and 113 cognitively impaired older adults recruited in the MARK-AGE study (overall mean age 64.7 ± 5.9 years), and then the results were checked in two other independent cohorts from Spain and Portugal, including 126 frail, 252 prefrail, and 141 nonfrail individuals (overall mean age: 77.5 ± 8.3 years). Results: TTV viremia ≥4log was associated with physical frailty (OR: 4.69; 95% CI: 2.06-10.67, p &lt; 0.0001) and cognitive impairment (OR: 3.49, 95% CI: 2.14-5.69, p &lt; 0.0001) in the MARK-AGE population. The association between TTV DNA load and frailty status was confirmed in the Spanish cohort, while a slight association with cognitive impairment was observed (OR: 1.33; 95% CI: 1.000-1.773), only in the unadjusted model. No association between TTV load and frailty or cognitive impairment was found in the Portuguese sample, although a negative association between TTV viremia and MMSE score was observed in Spanish and Portuguese females. Conclusions: These findings demonstrate an association between TTV viremia and physical frailty, while the association with cognitive impairment was observed only in the younger population from the MARK-AGE study. Further research is necessary to clarify TTV's clinical relevance in the onset and progression of frailty and cognitive decline in older individuals