Few-mode metal-free perovskite optical fiber with second-order optical nonlinearity

Semiconductor core optical fibers are highly desirable for fiber-based photonic and optoelectronic applications as they can combine strong optical nonlinearities, tight light confinement, wide transmission bands, and electronic functionality within a single platform. Perovskites have emerged as particularly exciting materials for semiconductor photonics as they have strong optical nonlinearities and tunable optoelectronic bandgaps. However, lead-based perovskites contain toxic elements and are, therefore, not environmentally friendly. Furthermore, in fiber form, their core-size is prohibitively large, making them unsuitable for nonlinear optics and applications that require single-mode guidance, such as telecommunications. Here, we report a metal-free perovskite core optical fiber where lead has been substituted for an ammonium cation in the perovskite structure. The core material has a wide bandgap greater than 5 eV, a high laser damage threshold, and a core diameter that can be produced as small as 5 \ub5m. At this core size, the fiber supports just six modes, and the fundamental mode can readily be excited and isolated. Moreover, the metal-free perovskite has a second-order susceptibility that is absent in the archetypal lead-based perovskites and many other semiconductor core materials, such as silicon and germanium. The second-order susceptibility is important for many nonlinear optics applications, such as second-harmonic generation and quantum optics

Intramuscular vaccination of Atlantic lumpfish (Cyclopterus lumpus L.) induces inflammatory reactions and local immunoglobulin M production at the vaccine administration site

Atlantic lumpfish were vaccinated by intramuscular (im) or intraperitoneal (ip) injection with a multivalent oil‐based vaccine, while control fish were injected with phosphate‐buffered saline. Four lumpfish per group were sampled for skin/muscle and head kidney tissue at 0, 2, 7, 21 and 42 days post‐immunization (dpi) for histopathology and immunohistochemistry (IHC). Gene expressions of secretory IgM, membrane‐bound IgM, IgD, TCRα, CD3ε and MHC class IIβ were studied in tissues by using qPCR. Im. vaccinated fish showed vaccine‐induced inflammation with formation of granulomas and increasing number of eosinophilic granulocyte‐like cells over time. On IHC sections, we observed diffuse intercellular staining of secretory IgM at the injection site at 2 dpi, while IgM + cells appeared in small numbers at 21 and 42 dpi. Skin/muscle samples from im. vaccinated fish demonstrated an increase in gene expression of IgM mRNA (secretory and membrane‐bound) at 21 and 42 dpi and small changes for other genes. Our results indicated that im. vaccination of lumpfish induced local IgM production at the vaccine injection site, with no apparent proliferation of IgM + cells. Eosinophilic granulocyte‐like cells appeared shortly after im. injection and increased in numbers as the inflammation progressed.publishedVersio

Comfort radicalism and NEETs: a conservative praxis

Young people who are not in education, employment or training (NEET) are construed by policy makers as a pressing problem about which something should be done. Such young people's lack of employment is thought to pose difficulties for wider society in relation to social cohesion and inclusion and it is feared that they will become a 'lost generation'. This paper(1) draws upon English research, seeking to historicise the debate whilst acknowledging that these issues have a much wider purchase. The notion of NEETs rests alongside longstanding concerns of the English state and middle classes, addressing unruly male working class youth as well as the moral turpitude of working class girls. Waged labour and domesticity are seen as a means to integrate such groups into society thereby generating social cohesion. The paper places the debate within it socio-economic context and draws on theorisations of cognitive capitalism, Italian workerism, as well as emerging theories of antiwork to analyse these. It concludes by arguing that ‘radical’ approaches to NEETs that point towards inequities embedded in the social structure and call for social democratic solutions veer towards a form of comfort radicalism. Such approaches leave in place the dominance of capitalist relations as well as productivist orientations that celebrate waged labour

Synthesis and biological evaluation of benzodiazepines containing a pentafluorosulfanyl group

The widely used pentafluorosulfanyl group (SF5) was deployed as a bioisosteric replacement for a chloro-group in the benzodiazepine diazepam (Valium™). Reaction of 2-amino-5-pentafluorosulfanyl-benzophenone with chloroacetyl chloride followed by hexamethylenetetramine, in the presence of ammonia, led to 7-sulfurpentafluoro-5-phenyl-1H-benzo[1,4]diazepin-2(3H)-one (2c). The latter was able to undergo a Pd-catalysed ortho-arylation, demonstrating that these highly fluorinated benzodiazepines can be further modified to form more complicated scaffolds. The replacement of Cl by the SF5 group, led to a loss of potency for potentiating GABAA receptor activation, most likely because of a lost ligand interaction with His102 in the GABAA receptor α subunit. Dedicated to Professor Jonathan Williams, an inspirational and humble pioneer, a colleague and mentor in chemistry

Ireland: Submerged Prehistoric Sites and Landscapes

Evidence of Ireland's drowned landscapes and settlements presently comprises 50 sites spread across the entire island. These comprise mainly intertidal find spots or small collections of flint artefacts. A handful of fully subtidal sites are known, generally from nearshore regions and consisting, with one exception, of isolated single finds. Evidence of organic remains is also sparse, with the exception of Mesolithic and Neolithic wooden fish traps buried in estuarine sediments under Dublin. The relatively small number of sites is probably due to lack of research as much as taphonomic issues, and thus the current evidence hints at the potential archaeological record which may be found underwater. Such evidence could contribute to knowledge of the coastal adaptations and seafaring abilities of Ireland's earliest inhabitants. Nonetheless, taphonomic considerations, specifically relating to Ireland's history of glaciation, sea-level change and also modern oceanographic conditions likely limit the preservation of submerged landscapes and their associated archaeology. Realistically, the Irish shelf is likely characterised by pockets of preservation, which makes detection and study of submerged landscapes difficult but not impossible. A range of potential routes of investigation are identifiable, including site-scale archaeological survey, landscape-scale seabed mapping, archival research and community engagement

Mechanical Analysis of Feeding Behavior in the Extinct “Terror Bird” Andalgalornis steulleti (Gruiformes: Phorusrhacidae)

The South American phorusrhacid bird radiation comprised at least 18 species of small to gigantic terrestrial predators for which there are no close modern analogs. Here we perform functional analyses of the skull of the medium-sized (∼40 kg) patagornithine phorusrhacid Andalgalornis steulleti (upper Miocene–lower Pliocene, Andalgalá Formation, Catamarca, Argentina) to assess its mechanical performance in a comparative context. Based on computed tomographic (CT) scanning and morphological analysis, the skull of Andalgalornis steulleti is interpreted as showing features reflecting loss of intracranial immobility. Discrete anatomical attributes permitting such cranial kinesis are widespread phorusrhacids outgroups, but this is the first clear evidence of loss of cranial kinesis in a gruiform bird and may be among the best documented cases among all birds. This apomorphic loss is interpreted as an adaptation for enhanced craniofacial rigidity, particularly with regard to sagittal loading. We apply a Finite Element approach to a three-dimensional (3D) model of the skull. Based on regression analysis we estimate the bite force of Andalgalornis at the bill tip to be 133 N. Relative to results obtained from Finite Element Analysis of one of its closest living relatives (seriema) and a large predatory bird (eagle), the phorusrhacid's skull shows relatively high stress under lateral loadings, but low stress where force is applied dorsoventrally (sagittally) and in “pullback” simulations. Given the relative weakness of the skull mediolaterally, it seems unlikely that Andalgalornis engaged in potentially risky behaviors that involved subduing large, struggling prey with its beak. We suggest that it either consumed smaller prey that could be killed and consumed more safely (e.g., swallowed whole) or that it used multiple well-targeted sagittal strikes with the beak in a repetitive attack-and-retreat strategy

Great Britain: the intertidal and underwater archaeology of Britain’s submerged landscapes

The submerged landscapes around Great Britain are extensive and would have offered productive territory for hunting, gathering, exploitation of aquatic and marine resources, and—in the final stages of postglacial sea-level rise—opportunities for agriculture. They would also have provided land connections to continental Europe and opportunities for communication by sea travel along now-submerged palaeocoastlines and river estuaries. Most of the archaeological material has been discovered in intertidal or shallow water conditions, but there are also discoveries in deeper water, with dates ranging from earliest human presence nearly one million years ago up to the establishment of modern sea level. Some later material is present where coastlines have continued to sink in more recent millennia. Intertidal sites are especially well represented because of relatively large tidal ranges and shallow offshore gradients on many coastlines. These are often associated with remains of submerged forests, which are periodically exposed at low tide and then covered up again by movements of sand. Some of the most distinctive intertidal finds are the human and animal footprints preserved in intertidal sediments in many locations, especially at Goldcliff East. The earliest, at Happisburgh, are dated between 0.78 and 1 Ma. Fully submerged sites include the Mesolithic site of Bouldnor Cliff with its worked timbers, and the Middle Stone Age artefacts from offshore aggregate Area 240 along with well-preserved ice age fauna and environmental indicators. Pioneering work using oil industry seismic records has produced detailed reconstructions of the submerged landscape, and this is being followed up by new work involving targeted acoustic survey and coring of sediments

Sulfur-Directed Olefin Oxidations: Observation of Divergent Reaction Mechanisms in the Palladium-Mediated Acetoxylation of Unsaturated Thioacetals

The Pd-mediated oxidation of unsaturated thioacetals gives either allyl or vinyl esters, depending on the substrate structure. We report the characterization of a range of sulfur-stabilized palladium intermediates via a combined computational and experimental NMR approach, demonstrating that the oxidation proceeds via two divergent reaction mechanisms. We were also able to synthesize an unusual sigma-bound Pd complex, via acetoxypalladation of an unsaturated dithiane, which was characterized by X-ray crystallography