Selenium Valence-to-Core X-ray Emission Spectroscopy and Kβ HERFD X-ray Absorption Spectroscopy as Complementary Probes of Chemical and Electronic Structure

Selenium X-ray absorption spectroscopy (XAS) has found widespread use in investigations of Se-containing materials, geochemical processes, and biological active sites. In contrast to sulfur Kβ X-ray emission spectroscopy (XES), which has been found to contain electronic and structural information complementary to S XAS, Se Kβ XES remains comparatively under-explored. Herein, we present the first Se Valence-to-Core (VtC) XES studies of reduced Se-containing compounds and FeSe dimers. Se VtC XES is found to be sensitive to changes in covalent Se bonding interactions (Se–Se/Se–C/Se–H bonding) while relatively insensitive to changes in Fe oxidation states as selenide bridges in FeSe dimers ([Fe2Se2]2+ vs [Fe2Se2]+). Contrastingly, Se Kβ HERFD XAS is demonstrated to be quite sensitive to changes in Fe-oxidation state, with Se Kβ HERFD XAS demonstrating experimental resolution equivalent to K𝛼 HERFD XAS. Additionally, computational studies reveal both Se VtC XES and XAS to be sensitive to selenium protonation in FeSe complexes.

The Functional Nanopore (FuN) Screen: A Versatile Genetic Assay to Study and Engineer Protein Nanopores in Escherichia coli

Nanopores comprise a versatile class of membrane proteins that carry out a range of key physiological functions and are increasingly exploited in many biotechnological applications. Yet, a capacity to study and engineer nanopores in the context of live cells has so far been hampered by a lack of suitable assays that provide sufficient experimental resolution and throughput. Addressing this technological gap, a newly developed Functional Nanopore (FuN) Screen now provides a highly quantitative read-out of nanopore function in E. coli. The assay is based on genetically-encoded fluorescent protein (FP) sensors that resolve the nanopore-dependent influx of Ca2+ across the inner membrane of E. coli. The FuN Screen is subsequently applied to dissect the molecular features that underlie the formation of nanopores by the S2168 holin. This membrane peptide plays a critical role in the S21 bacteriophage life cycle as it assembles into defined nm-sized nanopores to initiate lysis of the host cell. Genetic mapping experiments complemented with high-resolution electrical recordings shedding detailed light on the molecular determinants that underlie the formation of S2168 nanopores in the inner membrane. Overall, the FuN Screen is anticipated to facilitate both fundamental studies of nanopore functions and the construction of nanopores with tailored properties and function in E. coli.

Continuous-variable tomography of solitary electrons

A method for characterising the wave-function of freely-propagating particles would provide a useful tool for developing quantum-information technologies with single electronic excitations. Previous continuous-variable quantum tomography techniques developed to analyse electronic excitations in the energy-time domain have been limited to energies close to the Fermi level. We show that a wide-band tomography of single-particle distributions is possible using energy-time filtering and that the Wigner representation of the mixed-state density matrix can be reconstructed for solitary electrons emitted by an on-demand single-electron source. These are highly localised distributions, isolated from the Fermi sea. While we cannot resolve the pure state Wigner function of our excitations due to classical fluctuations, we can partially resolve the chirp and squeezing of the Wigner function imposed by emission conditions and quantify the quantumness of the source. This tomography scheme, when implemented with sufficient experimental resolution, will enable quantum-limited measurements, providing information on electron coherence and entanglement at the individual particle level.

Unbiased atomistic insight in the competing nucleation mechanisms of methane hydrates

Methane hydrates have important industrial and climate implications, yet their formation via homogeneous nucleation under natural, moderate conditions is poorly understood. Obtaining such understanding could lead to improved control of crystallization, as well as insight into polymorph selection in general, but is hampered by limited experimental resolution. Direct molecular dynamics simulations using atomistic force fields could provide such insight, but are not feasible for moderate undercooling, due to the rare event nature of nucleation. Instead, we harvest ensembles of the rare unbiased nucleation trajectories by employing transition path sampling. We find that with decreasing undercooling the mechanism shifts from amorphous to crystalline polymorph formation. At intermediate temperature the 2 mechanisms compete. Reaction coordinate analysis reveals the amount of a specific methane cage type is crucial for crystallization, while irrelevant for amorphous solids. Polymorph selection is thus governed by kinetic accessibility of the correct cage type and, moreover, occurs at precritical nucleus sizes, apparently against Ostwald’s step rule. We argue that these results are still in line with classical nucleation theory. Our findings illuminate how selection between competing methane hydrate polymorphs occurs and might generalize to other hydrates and molecular crystal formation.

Humic surface waters of frozen peat bogs (permafrost zone) are highly resistant to bio- and photodegradation

In contrast to the large number of studies on humic waters from permafrost-free regions and oligotrophic waters from permafrost-bearing regions, the bio- and photolability of DOM from the humic surface waters of permafrost-bearing regions has not been thoroughly evaluated. Following standardized protocol, we measured biodegradation (at low, intermediate and high temperatures) and photodegradation (at one intermediate temperature) of DOM in surface waters along the hydrological continuum (depression → stream → thermokarst lake → Pechora River) within a frozen peatland in European Russia. In all systems, within the experimental resolution of 5 % to 10 %, there was no bio- or photodegradation of DOM over a 1-month incubation period. It is possible that the main cause of the lack of degradation is the dominance of allochthonous refractory (soil, peat) DOM in all waters studied. However, all surface waters were supersaturated with CO2. Thus, this study suggests that, rather than bio- and photodegradation of DOM in the water column, other factors such as peat pore-water DOM processing and respiration of sediments are the main drivers of elevated pCO2 and CO2 emission in humic boreal waters of frozen peat bogs.

Multimode Fabry–Perot Interferometer Probe Based on Vernier Effect for Enhanced Temperature Sensing

New miniaturized sensors for biological and medical applications must be adapted to the measuring environments and they should provide a high measurement resolution to sense small changes. The Vernier effect is an effective way of magnifying the sensitivity of a device, allowing for higher resolution sensing. We applied this concept to the development of a small-size optical fiber Fabry–Perot interferometer probe that presents more than 60-fold higher sensitivity to temperature than the normal Fabry–Perot interferometer without the Vernier effect. This enables the sensor to reach higher temperature resolutions. The silica Fabry–Perot interferometer is created by focused ion beam milling of the end of a tapered multimode fiber. Multiple Fabry–Perot interferometers with shifted frequencies are generated in the cavity due to the presence of multiple modes. The reflection spectrum shows two main components in the Fast Fourier transform that give rise to the Vernier effect. The superposition of these components presents an enhancement of sensitivity to temperature. The same effect is also obtained by monitoring the reflection spectrum node without any filtering. A temperature sensitivity of -654 pm/°C was obtained between 30 °C and 120 °C, with an experimental resolution of 0.14 °C. Stability measurements are also reported.

Biomolecular coevolution and its applications: Going from structure prediction toward signaling, epistasis, and function

Evolution leads to considerable changes in the sequence of biomolecules, while their overall structure and function remain quite conserved. The wealth of genomic sequences, the ‘Biological Big Data’, modern sequencing techniques provide allows us to investigate biomolecular evolution with unprecedented detail. Sophisticated statistical models can infer residue pair mutations resulting from spatial proximity. The introduction of predicted spatial adjacencies as constraints in biomolecular structure prediction workflows has transformed the field of protein and RNA structure prediction toward accuracies approaching the experimental resolution limit. Going beyond structure prediction, the same mathematical framework allows mimicking evolutionary fitness landscapes to infer signaling interactions, epistasis, or mutational landscapes.