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Abstract: Understanding the structure–property relationship and nanoscopic behaviour of ionic liquids is of utmost importance for their potential applications. Focusing these studies on sets of homobaric ionic liquids could provide important insight into the effects of specific chemical groups on the overall interaction profile, bringing researchers one step closer to succesfully designing ionic liquids which are tailor-made for specific applications. This work focuses on ionic liquids with 12 total carbons on their side chains, studying both their bulk physical properties (such as densities and viscosities) and their nanostructuring. The results reveal that by keeping the total number of carbons constant, but arranging them differently around the imidazolium ring, either in a linear or in a branched-chain formation, can result in compounds with quite distinct properties. Some of those (such as diffusivity) appear to be more sensitive to symmetry variations, while others (such as density) are not significantly affected. X-ray scattering is used in order to get a clearer understanding of the nanostructuring of the studied compounds and to investigate to what extent the observed macroscopic properties are directly linked to the nanoscale ordering.

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Abstract: Present understanding of protein structure dynamics trails behind that of static structures. A torsion-angle based approach, called representation of protein entities (RoPE), derives an interpretable conformational space which correlates with data collection temperature, resolution and reaction coordinate. For more complex systems, atomic coordinates fail to separate functional conformational states, which are still preserved by torsion angle-derived space. This indicates that torsion angles are often a more sensitive and biologically relevant descriptor for protein conformational dynamics than atomic coordinates.

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Abstract: Despite extensive efforts to develop high-performance H2 evolution catalysts, this remains a major challenge. Here, we demonstrate the use of Cd/Pt precursor solutions for significant photocatalytic H2 production (154.7 mmol g-1 h-1), removing the need for a pre-synthesized photocatalyst. In addition, we also report simultaneous in-situ synthesis of Pt single-atoms anchored CdS nanoparticles (PtSA-CdSIS) during photoirradiation. The highly dispersed in-situ incorporation of extensive Pt single atoms on CdSIS enables the enhancement of active sites and suppresses charge recombination, which results in exceptionally high solar-to-hydrogen conversion efficiency of ~1% and an apparent quantum yield of over 91% (365 nm) for H2 production. Our work not only provides a promising strategy for maximising H2 production efficiency but also provides a green process for H2 production and the synthesis of highly photoactive PtSA-CdSIS nanoparticles.

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Abstract: The origin of jaws and teeth remains contentious in vertebrate evolution. ‘Placoderms’ (Silurian-Devonian armoured jawed fishes) are central to debates on the origins of these anatomical structures. ‘Acanthothoracids’ are generally considered the most primitive ‘placoderms’. However, they are so far known mainly from disarticulated skeletal elements that are typically incomplete. The structure of the jaws—particularly the jaw hinge—is poorly known, leaving open questions about their jaw function and comparison with other placoderms and modern gnathostomes. Here we describe a near-complete ‘acanthothoracid’ upper jaw, allowing us to reconstruct the likely orientation and angle of the bite and compare its morphology with that of other known ‘placoderm’ groups. We clarify that the bite position is located on the upper jaw cartilage rather than on the dermal cheek and thus show that there is a highly conserved bite morphology among most groups of ‘placoderms’, regardless of their overall cranial geometry. Incorporation of the dermal skeleton appears to provide a sound biomechanical basis for jaw origins. It appears that ‘acanthothoracid’ dentitions were fundamentally similar in location to that of arthrodire ‘placoderms’, rather than resembling bony fishes. Irrespective of current phylogenetic uncertainty, the new data here resolve the likely general condition for ‘placoderms’ as a whole, and as such, ancestral morphology of known jawed vertebrates.

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Abstract: An understanding the organic matter (OM) in primitive interplanetary materials can provide us with important constraints on both the early solar system carbon cycle and incipient prebiotic synthesis before the origin of life. As a window to the past, primitive chondrites preserve the most pristine record of parent body, nebular and interstellar components and the occurrence of OM in them has been shown in both soluble (SOM) (1) and insoluble (IOM) (2) form. Total organic carbon (TOC) abundance reaches ~3-4 wt% in the most primitive carbonaceous chondrite (CCs) (3), such as Ivuna-type chondrites (CIs) – thus making them highly desirable for the OM studies, and relevant to the study of Asteroid 162173 Ryugu samples from the Hayabusa-2 mission. A combination of both SOM and IOM analysis of organic bulk meteorite separates together with in-situ analysis of OM have provided a comprehensive account of chondritic OM (4). In the case of in-situ analysis, the combination of both scanning (SEM) and transmission electron microscopy (TEM) together with soft X-Ray scanning transmission microscopy (STXM) have shown the presence of micron to submicron distinctive organic particles (OPs) (5). Carbon K-edge X-ray absorption near edge structure (XANES) has shown the aromatic-carbonyl-carboxyl chemical nature of these organic particles (5). In addition, aromatic-poorer and carboxylic-richer diffuse OM (6) within both amorphous and phyllosilicate occurs as well. As observation techniques are getting better, aberration corrected TEM coupled with electron energy loss spectroscopy (EELS) might provide the same results as carbon XANES, but with higher image magnification, rapid data acquisition and better accessibility. In this context, we present the results of a comparative carbon K-edge XANES and EELS study of CI meteorite Ivuna. An approximately 100 nm lamella of the Ivuna meteorite was prepared using focused ion beam (FIB)-SEM with the Helios 5 Hydra DualBeam (CEITEC, Masaryk University, Czechia) and analysed by TEM-EELS with the JEOL ARM200CF (ePSIC, Diamond Light Source, UK) and STXM-XANES at Beamline BL19A of the KEK Photon Factory, Japan. We observed that (I) XANES on samples that did not experience TEM-EELS are in agreement with the previous studies of aromatic-carbonyl-carboxylic macromolecular OPs and IOM, while (II) the TEM-EELS of OPs show aromatic-carbonyl functional chemistry but with amorphous carbon convoluting the carboxylic peak, and aromatic-poor spectra with a sharp carbonate peak in diffuse OM. The difference between XANES and EELS particularly in the diffuse OM can be interpreted by electron-beam damage. Thickness and e-beam damage leads to amorphous C formation in the OPs. In the case of more labile OM in the phyllosilicate, its change by heating and oxidation is expected.