Using pressure to unravel the structure-dynamic-disorder relationship in metal halide perovskites.

The exceptional optoelectronic properties of metal halide perovskites (MHPs) are presumed to arise, at least in part, from the peculiar interplay between the inorganic metal-halide sublattice and the atomic or molecular cations enclosed in the cage voids. The latter can exhibit a roto-translative dynamics, which is shown here to be at the origin of the structural behavior of MHPs as a function of temperature, pressure and composition. The application of high hydrostatic pressure allows for unraveling the nature of the interaction between both sublattices, characterized by the simultaneous action of hydrogen bonding and steric hindrance. In particular, we find that under the conditions of unleashed cation dynamics, the key factor that determines the structural stability of MHPs is the repulsive steric interaction rather than hydrogen bonding. Taking as example the results from pressure and temperature-dependent photoluminescence and Raman experiments on MAPbBr[Formula: see text] but also considering the pertinent MHP literature, we provide a general picture about the relationship between the crystal structure and the presence or absence of cationic dynamic disorder. The reason for the structural sequences observed in MHPs with increasing temperature, pressure, A-site cation size or decreasing halide ionic radius is found principally in the strengthening of the dynamic steric interaction with the increase of the dynamic disorder. In this way, we have deepened our fundamental understanding of MHPs; knowledge that could be coined to improve performance in future optoelectronic devices based on this promising class of semiconductors.

Aggregation-induced emission from silole-based lumophores embedded in organic-inorganic hybrid hosts.

Aggregation-induced emitters - or AIEgens - are often symbolised by their photoluminescence enhancement as a result of aggregation in a poor solvent. However, for some applications, it is preferable for the AIE response to be induced in the solid-state. Here, the ability of an organic-inorganic hybrid polymer host to induce the AIE response from embedded silole-based lumophores has been explored. We have focussed on understanding how the incorporation method controls the extent of lumophore aggregation and thus the associated photophysical properties. To achieve this, two sample concentration series have been prepared, based on either the parent AIEgen 1,1-dimethyl-2,3,4,5-tetraphenylsilole (DMTPS) or the silylated analogue (DMTPS-Sil), which were physically doped or covalently grafted, respectively, to dU(600) - a member of the ureasil family of poly(oxyalkylene)/siloxane hybrids. Steady-state and time-resolved photoluminescence measurements, coupled with confocal microscopy studies, revealed that covalent grafting leads to improved dispersibility of the AIEgen, reduced scattering losses, increased photoluminescence quantum yields (up to ca. 40%) and improved chemical stability. Moreover, the ureasil also functions as a photoactive host that undergoes excitation energy transfer to the embedded DMTPS-Sil with an efficiency of almost 70%. This study highlights the potential for designing complex photoluminescent hybrid polymers exhibiting an ehanced AIE response for solid-state optical applications.

Co-infection in critically ill patients with COVID-19: an observational cohort study from England.

Introduction. During previous viral pandemics, reported co-infection rates and implicated pathogens have varied. In the 1918 influenza pandemic, a large proportion of severe illness and death was complicated by bacterial co-infection, predominantly Streptococcus pneumoniae and Staphylococcus aureus.Gap statement. A better understanding of the incidence of co-infection in patients with COVID-19 infection and the pathogens involved is necessary for effective antimicrobial stewardship.Aim. To describe the incidence and nature of co-infection in critically ill adults with COVID-19 infection in England.Methodology. A retrospective cohort study of adults with COVID-19 admitted to seven intensive care units (ICUs) in England up to 18 May 2020, was performed. Patients with completed ICU stays were included. The proportion and type of organisms were determined at <48 and >48 h following hospital admission, corresponding to community and hospital-acquired co-infections.Results. Of 254 patients studied (median age 59 years (IQR 49-69); 64.6 % male), 139 clinically significant organisms were identified from 83 (32.7 %) patients. Bacterial co-infections/ co-colonisation were identified within 48 h of admission in 14 (5.5 %) patients; the commonest pathogens were Staphylococcus aureus (four patients) and Streptococcus pneumoniae (two patients). The proportion of pathogens detected increased with duration of ICU stay, consisting largely of Gram-negative bacteria, particularly Klebsiella pneumoniae and Escherichia coli. The co-infection/ co-colonisation rate >48 h after admission was 27/1000 person-days (95 % CI 21.3-34.1). Patients with co-infections/ co-colonisation were more likely to die in ICU (crude OR 1.78,95 % CI 1.03-3.08, P=0.04) compared to those without co-infections/ co-colonisation.Conclusion. We found limited evidence for community-acquired bacterial co-infection in hospitalised adults with COVID-19, but a high rate of Gram-negative infection acquired during ICU stay.

Synthetic factors affecting the stability of methylammonium lead halide perovskite nanocrystals.

Lead halide perovskite nanocrystals (PNCs) have emerged as promising candidates for use in optoelectronic devices. Significant focus has been directed towards optimising synthetic conditions to obtain PNCs with tunable emission properties. However, the reproducible production of stable PNC dispersions is also crucial for fabrication and scale-up of these devices using liquid deposition methods. Here, the stability of methylammonium lead halide (MAPbX3 where X = Br, I) PNCs produced via the ligand-assisted reprecipitation process is explored. We have focussed on understanding how different combinations of specific synthetic factors - dilution, halide source and ratio as well as capping-ligand concentration - affect the stability of the resultant PNC dispersion. Photoluminescence spectroscopy, transmission electron microscopy and dynamic light scattering studies revealed that subtle changes in the reaction conditions lead to significant changes in the particle morphology and associated optical properties, often with catastrophic consequences on stability. This study highlights the importance of designing PNC dispersions in order to make more efficient and reliable optoelectronic devices.

Equal Footing of Thermal Expansion and Electron-Phonon Interaction in the Temperature Dependence of Lead Halide Perovskite Band Gaps.

Lead halide perovskites, which are causing a paradigm shift in photovoltaics, exhibit an atypical temperature dependence of the fundamental gap: it decreases in energy with decreasing temperature. Reports ascribe such a behavior to a strong electron-phonon renormalization of the gap, neglecting contributions from thermal expansion. However, high-pressure experiments performed on the archetypal perovskite MAPbI3 (MA stands for methylammonium) yield a negative pressure coefficient for the gap of the tetragonal room-temperature phase, which speaks against the assumption of negligible thermal expansion effects. Here we show that for MAPbI3 the temperature-induced gap renormalization due to electron-phonon interaction can only account for about 40% of the total energy shift, thus implying thermal expansion to be more if not as important as electron-phonon coupling. Furthermore, this result possesses general validity, holding also for the tetragonal or cubic phase, stable at ambient conditions, of most halide perovskite counterparts.

Prolonged coexistence of humans and megafauna in Pleistocene Australia.

Recent claims for continent wide disappearance of megafauna at 46.5 thousand calendar years ago (ka) in Australia have been used to support a "blitzkrieg" model, which explains extinctions as the result of rapid overkill by human colonizers. A number of key sites with megafauna remains that significantly postdate 46.5 ka have been excluded from consideration because of questions regarding their stratigraphic integrity. Of these sites, Cuddie Springs is the only locality in Australia where megafauna and cultural remains are found together in sequential stratigraphic horizons, dated from 36-30 ka. Verifying the stratigraphic associations found here would effectively refute the rapid-overkill model and necessitate reconsideration of the regional impacts of global climatic change on megafauna and humans in the lead up to the last glacial maximum. Here, we present geochemical evidence that demonstrates the coexistence of humans and now-extinct megafaunal species on the Australian continent for a minimum of 15 ka.