Steric engineering of metal-halide perovskites with tunable optical band gaps

Owing to their high energy-conversion efficiency and inexpensive fabrication routes, solar cells based on metal-organic halide perovskites have rapidly gained prominence as a disruptive technology. An attractive feature of perovskite absorbers is the possibility of tailoring their properties by changing the elemental composition through the chemical precursors. In this context, rational in silico design represents a powerful tool for mapping the vast materials landscape and accelerating discovery. Here we show that the optical band gap of metal-halide perovskites, a key design parameter for solar cells, strongly correlates with a simple structural feature, the largest metal-halide-metal bond angle. Using this descriptor we suggest continuous tunability of the optical gap from the mid-infrared to the visible. Precise band gap engineering is achieved by controlling the bond angles through the steric size of the molecular cation. Based on these design principles we predict novel low-gap perovskites for optimum photovoltaic efficiency, and we demonstrate the concept of band gap modulation by synthesising and characterising novel mixed-cation perovskites.Comment: This manuscript was submitted for publication on March 6th, 2014. Many of the results presented in this manuscript were presented at the International Conference on Solution processed Semiconductor Solar Cells, held in Oxford, UK, on 10-12 September 2014. The manuscript is 37 pages long and contains 8 figure

Instability of supersymmetric microstate geometries

We investigate the classical stability of supersymmetric, asymptotically flat, microstate geometries with five non-compact dimensions. Such geometries admit an "evanescent ergosurface": a timelike hypersurface of infinite redshift. On such a surface, there are null geodesics with zero energy relative to infinity. These geodesics are stably trapped in the potential well near the ergosurface. We present a heuristic argument indicating that this feature is likely to lead to a nonlinear instability of these solutions. We argue that the precursor of such an instability can be seen in the behaviour of linear perturbations: nonlinear stability would require that all linear perturbations decay sufficiently rapidly but the stable trapping implies that some linear perturbation decay very slowly. We study this in detail for the most symmetric microstate geometries. By constructing quasinormal modes of these geometries we show that generic linear perturbations decay slower than any inverse power of time.This work was supported by European Research Council grant ERC-2011-StG279363-HiDGR.This is the final version of the article. It first appeared from Springer via https://doi.org/10.1007/JHEP10(2016)03

Congenital heart anomalies in the first trimester: From screening to diagnosis.

Congenital heart defects occur in approximately 1% of liveborn children and represent the most common form of congenital malformation. Due to the small size and complexity of the heart structures, prenatal diagnosis is most often made in the second trimester of pregnancy. Early diagnosis however offers significant advantages regarding the timing of further investigations, prenatal counseling, and access to management options. In the last decade, advances in antenatal imaging have improved the detection of cardiac malformations with increasing emphasis on earlier pregnancy screening and diagnosis. We aim to summarize current "state of the art" imaging of the fetal heart in the first trimester

Stoichiometries of U2AF35, U2AF65 and U2 snRNP reveal new early spliceosome assembly pathways

The selection of 3' splice sites (3?ss) is an essential early step in mammalian RNA splicing reactions, but the processes involved are unknown. We have used single molecule methods to test whether the major components implicated in selection, the proteins U2AF35 and U2AF65 and the U2 snRNP, are able to recognize alternative candidate sites or are restricted to one pre-specified site. In the presence of adenosine triphosphate (ATP), all three components bind in a 1:1 stoichiometry with a 3?ss. Pre-mRNA molecules with two alternative 3?ss can be bound concurrently by two molecules of U2AF or two U2 snRNPs, so none of the components are restricted. However, concurrent occupancy inhibits splicing. Stoichiometric binding requires conditions consistent with coalescence of the 5? and 3? sites in a complex (I, initial), but if this cannot form the components show unrestricted and stochastic association. In the absence of ATP, when complex E forms, U2 snRNP association is unrestricted. However, if protein dephosphorylation is prevented, an I-like complex forms with stoichiometric association of U2 snRNPs and the U2 snRNA is base-paired to the pre-mRNA. Complex I differs from complex A in that the formation of complex A is associated with the loss of U2AF65 and 3

Laparoscopic repair of vaginal vault prolapse by lateral suspension with mesh

Background: To evaluate the long-term outcomes of laparoscopic lateral suspension using mesh reinforcement for symptomatic posthysterectomy vaginal vault prolapse. Materials and methods: We analyzed in a prospective cohort study all the women treated by laparoscopic lateral suspension with mesh for symptomatic vaginal vault prolapse between January 2004 and September 2010. In this procedure, the mesh is laterally suspended to the abdominal wall, posterior to the anterior superior iliac spine. We performed systematic follow-up examinations at 4weeks, 6months and yearly postoperatively. Clinical evaluation of pelvic organ support was assessed by the pelvic organ prolapse quantification (POP-Q) grading system. Main outcome measures were recurrence rate, reoperation rate for symptomatic recurrence or de novo prolapse, mesh erosion rate, reoperation rate for mesh erosion, total reoperation rate. Observations and results: Of the 73 patients seen at a mean 17.5months follow-up, recurrent vaginal vault prolapse was registered in only one woman (success rate of 98.6%). When considering all vaginal sites, we observed a total of 13 patients with recurrent or de novo prolapse (17.8%). The non-previously treated posterior compartment was involved in eight cases (new appearance rate of 11%). Of these 13 women, only 6 were symptomatic, requiring surgical management (reoperation rate for genital prolapse of 8.2%). Four patients presented with mesh erosion into the vagina (5.5%). Two required partial vaginal excision of the mesh in the operating room (2.7%). There were no mesh-related infections. The total reoperation rate was 11%. Conclusion: Laparoscopic lateral suspension with mesh interposition is a safe and effective technique for the treatment of vaginal vault prolapse. This approach represents an alternative procedure to the laparoscopic sacrocolpopex