Nuclear magnetic resonance as a quantitative tool to study interactions in biomacromolecules

High-resolution nuclear magnetic resonance (NMR) has emerged as one of the most versatile tools for the quantitative study of structure, kinetics, and thermodynamics of biomolecules and their interactions at atomic resolution. Traditionally, nuclear Overhauser enhancements (NOEs) and chemical shift perturbation methods are used to determine molecular geometries and to identify contact surfaces, but more recently, weak anisotropic orientation, anisotropic diffusion, and scalar couplings across hydrogen bonds provide additional information. Examples of such technologies are shown as applied to the quantitative characterization of function and thermodynamics of several biomacromolecules. In particular, (1) the structural and dynamical changes of the TipA multidrug resistance protein are followed upon antibiotic binding, (2) the trimer-monomer equilibrium and thermal unfolding of foldon, a small and very efficient trimerization domain of the T4 phagehead, is described in atomic detail, and (3) the changes of individual protein hydrogen bonds during thermal unfolding are quantitatively followed by scalar couplings across hydrogen bond

Fundamentals of tin iodide perovskites:A promising route to highly efficient, lead-free solar cells

Hybrid tin-iodide perovskites are investigated as potential lead-free replacement of the lead-iodide perovskites; however, the intrinsic operational limit of these systems has not been described in detail, so far. In this work we combine advanced ab initio calculations with XRD and absorption measurements to lay out the fundamentals of formamidinium (FASnI3) and methylammonium (MASnI3) tin iodide perovskites, in comparison with the lead-halide MAPbI3 prototype. Our theoretical analysis reveals that the tin-based materials display an intrinsic photoconversion efficiency on a par with the lead perovskites, and even superior in the thick-layer limit, where the theoretical PCE reaches 30.5% for lead-halides, and 32.3% for tin-halides under AM1.5G illumination; this is the result of two competing factors: a smaller absorption cross section at the onset for stannates, and their smaller band gap of 1.36 eV, thus very close to the ideal Shockley-Queisser limit. We found the rate of photoluminescence emission extremely sensitive to the absorption spectral weight at the band extrema, resulting in B-factor as different as 7.6 × 10-9 s-1 cm3 for MASnI3 and 0.4 × 10-10 s-1 cm3 for FASnI3. The additional impact of Urbach energy and hole doping, giving rise to large Burstein-Moss effect, is described in detail. This journal i

Counterfeit medicines: a pilot study for chemical profiling employing a different proposal of an usual technique

Gas chromatography (GC) is a gold standard technique used in forensic laboratories, including for the characterization of counterfeit medicines. When coupled simultaneously to flame ionization (FID) and mass detector (MS) allow the identification and quantification of medicines and drugs employing a single method, besides permitting the application of chemometric tools for forensic intelligence purposes. Here is presented a pilot project that developed and applied a qualitative method for the analysis of counterfeit medicines comprised by amphetamine-type stimulants and antidepressants, through a simple extraction procedure followed by GC-FID/MS analysis, with application of exploratory tools by Hierarchical Cluster Analysis (HCA) and Principal Component Analysis (PCA). The main purpose was to identify similarities between the all compounds detected in the irregular medicines allowing the traceability of illicit producers with the creation of a common data base. Through the analyses it was verified that different producers of counterfeit medicines labeled as Sibutramine, added a mixture of Caffeine and Benzocaine in their formulation, respecting the same ratio of 2.2:1. HCA was able to confirm these results, showing the presence of both falsifications in the same cluster, representing the best tool to identify similar characteristics among the samples – when compared to PCA. Other interesting finding was the use of Fluoxetine as a falsification of counterfeit medicines labeled as Sibutramine and Diethylpropion. Another seized sample labeled as “Nobesio Forte”, marketed as a mix of stimulants, showed only Caffeine and Lidocaine in its formulation. The pilot project applied primarily to 45 samples of counterfeit medicines containing amphetamine-type stimulants and antidepressants, showed the capability of perform the chemical profiling of counterfeit medicines in the solid form - powder, capsules and tablets. Further analysis can be performed for different types of medicines in solid form using the developed method, allowing the construction of a single database to perform the chemical profiling of counterfeit medicines, enabling the traceability of illicit producers

Arbuscular cell invasion coincides with extracellular vesicles and membrane tubules

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Imaging Light-Induced Migration of Dislocations in Halide Perovskites with 3d Nanoscale Strain Mapping

In recent years, halide perovskite materials have been used to make high-performance solar cells and light-emitting devices. However, material defects still limit device performance and stability. Here, synchrotron-based Bragg coherent diffraction imaging is used to visualize nanoscale strain fields, such as those local to defects, in halide perovskite microcrystals. Significant strain heterogeneity within MAPbBr3 (MA = CH3NH3+) crystals is found in spite of their high optoelectronic quality, and both 〈100〉 and 〈110〉 edge dislocations are identified through analysis of their local strain fields. By imaging these defects and strain fields in situ under continuous illumination, dramatic light-induced dislocation migration across hundreds of nanometers is uncovered. Further, by selectively studying crystals that are damaged by the X-ray beam, large dislocation densities and increased nanoscale strains are correlated with material degradation and substantially altered optoelectronic properties assessed using photoluminescence microscopy measurements. These results demonstrate the dynamic nature of extended defects and strain in halide perovskites, which will have important consequences for device performance and operational stability

Body Shape and Life Style of the Extinct Balearic Dormouse Hypnomys (Rodentia, Gliridae): New Evidence from the Study of Associated Skeletons

Hypnomys is a genus of Gliridae (Rodentia) that occurred in the Balearic Islands until Late Holocene. Recent finding of a complete skeleton of the chronospecies H. morpheus (Late Pleistocene-Early Holocene) and two articulated skeletons of H. cf. onicensis (Late Pliocene) allowed the inference of body size and the calculation of several postcranial indexes. We also performed a Factorial Discriminant Analysis (FDA) in order to evaluate locomotory behaviour and body shape of the taxa. Using allometric models based on skull and tooth measurements, we calculated a body weight between 173 and 284 g for H. morpheus, and direct measurements of articulated skeletons yielded a Head and Body Length (HBL) of 179 mm and a Total Body Length of 295 mm for this species. In addition to the generally higher robustness of postcranial bones already recorded by previous authors, H. morpheus, similar to Canariomys tamarani, another extinct island species, displayed elongated zygopodium bones of the limbs and a wider distal humerus and femur than in an extant related taxon, Eliomys quercinus. Indexes indicated that Hypnomys was more terrestrial and had greater fossorial abilities than E. quercinus. This was also corroborated by a Discriminant Analysis, although no clear additional inference of locomotory abilities could be calculated

Photochromism in Ruddlesden-Popper copper-based perovskites:A light-induced change of coordination number at the surface

Ruddlesden-Popper organic-inorganic hybrid copper-based perovskites have been studied for decades owing to a variety of interesting properties, such as thermochromism and piezochromism, and the mechanisms behind these phenomena have been explained. Another possible property of these materials that has seldomly been investigated is photochromism. In this work, the photochromic properties of bis(phenethylammonium) tetrachlorocuprate (also known as phenethylammonium copper chloride) are reported for the first time. This material has attracted scientific interest owing to the fact that it shows both ferroelectric and ferromagnetic behavior. This work highlights the difference in stability between two Ruddlesden-Popper copper-based perovskites - with phenethylammonium (PEA) or methylammonium (MA) as the cations - during external stimuli. Various techniques, such as Raman and X-ray photoelectron spectroscopy, and grazing-incidence wide-angle X-ray scattering, combined with optical studies, were used to investigate the underlying photochemical processes at a molecular level. It is found that for the PEA compound, ultraviolet illumination causes a color change from yellow to brown. This is the result of two independent events, namely a Cu2+ reduction reaction and a transition from an octahedral copper-chloride structure to square-planar CuCl42-. After illumination, the material (brown color) is unstable in air, which is evident from a color change back to yellow. Interestingly, the similar compound bis(methylammonium) tetrachlorocuprate does not display photochromic behavior, which is attributed to the different nature of the two organic cations

Photophysics of Two-Dimensional Perovskites—Learning from Metal Halide Substitution

Whereas their photophysics exhibits an intricate interplay of carriers with the lattice, most reports have so far relied on single compound studies. With the exception of variations of the organic spacer cations, the effect of constituent substitution on the photophysics and the nature of emitting species, in particular, has remained largely under-explored. Here PEA$_2$PbBr$_4$, PEA$_2$PbI$_4$, and PEA$_2$SnI$_4$ are studied through a variety of optical spectroscopy techniques to reveal a complex set of excitonic transitions at low temperature. We attribute the emergence of weak high energy features to a vibronic progression breaking Kasha's rule and highlight that the responsible phonons cannot be accessed through simple Raman spectroscopy. Bright peaks at lower energy are due to two distinct excitons, of which the upper is a convolution of a bright exciton and a localised state, whereas the lower is attributed to shallow defects. Our study offers deeper insights into the photophysics of two-dimensional perovskites through compositional substitution and highlights critical limits to the communities' current understanding of the photophysics of these compounds

Threats posed by the fungal kingdom to humans, wildlife, and agriculture

The fungal kingdom includes at least 6 million eukaryotic species and is remarkable with respect to its profound impact on global health, biodiversity, ecology, agriculture, manufacturing, and biomedical research. Approximately 625 fungal species have been reported to infect vertebrates, 200 of which can be human associated, either as commensals and members of our microbiome or as pathogens that cause infectious diseases. These organisms pose a growing threat to human health with the global increase in the incidence of invasive fungal infections, prevalence of fungal allergy, and the evolution of fungal pathogens resistant to some or all current classes of antifungals. More broadly, there has been an unprecedented and worldwide emergence of fungal pathogens affecting animal and plant biodiversity. Approximately 8,000 species of fungi and Oomycetes are associated with plant disease. Indeed, across agriculture, such fungal diseases of plants include new devastating epidemics of trees and jeopardize food security worldwide by causing epidemics in staple and commodity crops that feed billions. Further, ingestion of mycotoxins contributes to ill health and causes cancer. Coordinated international research efforts, enhanced technology translation, and greater policy outreach by scientists are needed to more fully understand the biology and drivers that underlie the emergence of fungal diseases and to mitigate against their impacts. Here, we focus on poignant examples of emerging fungal threats in each of three areas: human health, wildlife biodiversity, and food security