Valence isomerization of 2-phospha-4-silabicyclo[1.1.0]butane: a high-level ab initio study

The rearrangements for 2-phospha-4-silabicyclo[1.1.0]butane, analogous to the valence isomerization of the hydrocarbons bicyclobutane, 1,3-butadiene, and cyclobutene, were studied at the (U)QCISD(T)/6-311+G**//(U)QCISD/6-31G* level of theory. The monocyclic 1,2-dihydro-1,2-phosphasiletes are shown to be the thermodynamically preferred product, in contrast to the isomerization of the hydrocarbons, which favors the 1,3-butadiene structure. Furthermore, an unprecedented direct isomerization pathway to the 1,2-dihydro-1,2-phosphasiletes was identified. This pathway is competitive with the isomerization via the open-chain butadienes and becomes favorable when electron-donating substituents are present on silicon

From adversity to psychosis: pathways and mechanisms from specific adversities to specific symptoms

Purpose Although there is considerable evidence that adversities in childhood such as social deprivation, sexual abuse, separation from parents, neglect and exposure to deviant parental communication are associated with psychosis in later life, most studies have considered broad diagnoses as outcomes. In this review we consider evidence for pathways between specific types of adversity and specific symptoms of psychosis. Methods We present theoretical arguments for expecting some degree of specificity (although by no means perfect specificity) between different kinds of adversity and different symptoms of psychosis. We review studies that have investigated social–environmental risk factors for thought disorder, auditory–verbal hallucinations and paranoid delusions, and consider how these risk factors may impact on specific psychological and biological mechanisms. Results Communication deviance in parents has been implicated in the development of thought disorder in offspring, childhood sexual abuse has been particularly implicated in auditory–verbal hallucinations, and attachment-disrupting events (e.g. neglect, being brought up in an institution) may have particular potency for the development of paranoid symptoms. Current research on psychological mechanisms underlying these symptoms suggests a number of symptom-specific mechanisms that may explain these associations. Conclusions Few studies have considered symptoms, underlying mechanisms and different kinds of adversity at the same time. Future research along these lines will have the potential to elucidate the mechanisms that lead to severe mental illness, and may have considerable clinical implications

Accelerating the discovery of materials for clean energy in the era of smart automation

The discovery and development of novel materials in the field of energy are essential to accelerate the transition to a low-carbon economy. Bringing recent technological innovations in automation, robotics and computer science together with current approaches in chemistry, materials synthesis and characterization will act as a catalyst for revolutionizing traditional research and development in both industry and academia. This Perspective provides a vision for an integrated artificial intelligence approach towards autonomous materials discovery, which, in our opinion, will emerge within the next 5 to 10 years. The approach we discuss requires the integration of the following tools, which have already seen substantial development to date: high-throughput virtual screening, automated synthesis planning, automated laboratories and machine learning algorithms. In addition to reducing the time to deployment of new materials by an order of magnitude, this integrated approach is expected to lower the cost associated with the initial discovery. Thus, the price of the final products (for example, solar panels, batteries and electric vehicles) will also decrease. This in turn will enable industries and governments to meet more ambitious targets in terms of reducing greenhouse gas emissions at a faster pace