Synthesis, structure and pyrolysis of stabilised phosphonium ylides containing saturated oxygen heterocycles

yesA range of twelve stabilised phosphonium ylides containing tetrahydrofuran, tetrahydropyran or 2,2- dimethyl-1,3-dioxolane rings have been prepared and fully characterised, including one X-ray structure determination of each type. The X-ray structures confirm the PvC and CvO functions to be syn and all the compounds undergo thermal extrusion of Ph3PO to give the corresponding alkynes. In some cases there is also competing loss of Ph3P to give different carbene-derived products and evidence has been obtained for the generation of 2-phenyloxete in this way. Raising the pyrolysis temperature leads in several cases to new secondary reactions of the alkyne products involving a sequence of alkyne to vinylidene isomerisation, intramolecular CH insertion, and retro Diels Alder reaction

The tectonic development and erosion of the knox subglacial sedimentary basin, East Antarctica

Sedimentary basins beneath the East Antarctic Ice Sheet (EAIS) have immense potential to inform models of the tectonic evolution of East Antarctica and its ice-sheet. However, even basic characteristics such as thickness and extent are often unknown. Using airborne geophysical data, we resolve the tectonic architecture of the Knox Subglacial Sedimentary Basin in western Wilkes Land. In addition, we apply an erosion restoration model to reconstruct the original basin geometry for which we resolve geometry typical of a transtensional pull-apart basin. The tectonic architecture strongly indicates formation as a consequence of the rifting of India from East Gondwana from ca. 160-130 Ma, and we suggest a spatial link with the western Mentelle Basin offshore Western Australia. The erosion restoration model shows that erosion is confined within the rift margins, suggesting that rift structure has strongly influenced the evolution of the Denman and Scott ice streams

The value of 2 J P–CO as a diagnostic parameter for the structure and thermal reactivity of carbonyl-stabilised phosphonium ylides

A survey of 20 carbonyl-stabilised phosphonium ylides with recently reported X-ray structures shows a strong correlation between the CP to CO torsion angle and the value of 2JP–CO, with high values being associated with an anti configuration and low with syn. Seven new X-ray structural determinations are reported, several for types of ylide not crystallographically characterised before, and these also conform to this pattern. The value of 2JP–CO is then correlated with whether or not thermal extrusion of Ph3PO occurs to give alkynes for over 200 ylides and an empirical rule developed that the extrusion never occurs for ylides where this value is > 11 Hz. This is used to rationalise the anomalous behaviour of some trioxo ylides and cyclic ylides, two of which afford cycloalkynes, isolated after rearrangement as the isomeric 1,3-dienes. The rule also holds for a family of novel highly fluorinated ylides which afford fluorinated alkynes in good yield upon flash vacuum pyrolysis.EPSRC (U.K.) for a DTA Studentship (Grant No. EP/P505712/1

Salivary characteristics may be associated with burning mouth syndrome?

Burning mouth syndrome (BMS) it is characterized by burning and uncomfortable sensations with no clinical alterations or laboratory findings. The evaluation of the salivary characteristics of people with BMS can help the understanding of the pathogenesi

Yellow Fever Virus Infectivity for Bolivian Aedes aegypti Mosquitoes

The absence of urban yellow fever virus (YFV) in Bolivian cities has been attributed to the lack of competent urban mosquito vectors. Experiments with Aedes aegypti from Santa Cruz, Bolivia, demonstrated infection (100%), dissemination (20%), and transmission of a Bolivian YFV strain (CENETROP-322)

Metagenomic next-generation sequencing aids the diagnosis of viral infections in febrile returning travellers

Objectives Travel-associated infections are challenging to diagnose because of the broad spectrum of potential aetiologies. As a proof-of-principle study, we used MNGS to identify viral pathogens in clinical samples from returning travellers in a single center to explore its suitability as a diagnostic tool. Methods Plasma samples from 40 returning travellers presenting with a fever of ≥38°C were sequenced using MNGS on the Illumina MiSeq platform and compared with standard-of-care diagnostic assays. Results In total, 11/40 patients were diagnosed with a viral infection. Standard of care diagnostics revealed 5 viral infections using plasma samples; dengue virus 1 (n = 2), hepatitis E (n = 1), Ebola virus (n = 1) and hepatitis A (n = 1), all of which were detected by MNGS. Three additional patients with Chikungunya virus (n = 2) and mumps virus were diagnosed by MNGS only. Respiratory infections detected by nasal/throat swabs only were not detected by MNGS of plasma. One patient had infection with malaria and mumps virus during the same admission. Conclusions MNGS analysis of plasma samples improves the sensitivity of diagnosis of viral infections and has potential as an all-in-one diagnostic test. It can be used to identify infections that have not been considered by the treating physician, co-infections and new or emerging pathogens. Summary Next generation sequencing (NGS) has potential as an all-in-one diagnostic test. In this study we used NGS to diagnose returning travellers with acute febrile illness in the UK, highlighting cases where the diagnosis was missed using standard methods