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Lyotropic liquid crystal phases (LCPs) are widely studied for diverse applications, including protein crystallization and drug delivery. The structure and properties of LCPs vary widely depending on the composition, concentration, temperature, pH, and pressure. High-throughput structural characterization approaches, such as small-angle x-ray scattering (SAXS), are important to cover meaningfully large compositional spaces. However, high-throughput LCP phase analysis for SAXS data is currently lacking, particularly for patterns of multiphase mixtures. In this paper, we develop semi-automated software for high throughput LCP phase identification from SAXS data. We validate the accuracy and time-savings of this software on a total of 668 SAXS patterns for the LCPs of the amphiphile hexadecyltrimethylammonium bromide (CTAB) in 53 acidic or basic ionic liquid derived solvents, within a temperature range of 25–75 °C. The solvents were derived from stoichiometric ethylammonium nitrate (EAN) or ethanolammonium nitrate (EtAN) by adding water to vary the ionicity, and adding precursor ions of ethylamine, ethanolamine, and nitric acid to vary the pH. The thermal stability ranges and lattice parameters for CTAB-based LCPs obtained from the semi-automated analysis showed equivalent accuracy to manual analysis, the results of which were previously published. A time comparison of 40 CTAB systems demonstrated that the automated phase identification procedure was more than 20 times faster than manual analysis. Moreover, the high throughput identification procedure was also applied to 300 unpublished scattering patterns of sodium dodecyl-sulfate in the same EAN and EtAN based solvents in this study, to construct phase diagrams that exhibit phase transitions from micellar, to hexagonal, cubic, and lamellar LCPs. The accuracy and significantly low analysis time of the high throughput identification procedure validates a new, rapid, unrestricted analytical method for the determination of LCPs. [ABSTRACT FROM AUTHOR]

Intermetallic lithium compounds have found a wide range of applications owing to their light mass and desirable electronic and mechanical properties. Here, by compressing pure lithium and zinc mixtures in a diamond-anvil cell, we observe a direct reaction forming the stoichiometric compound LiZn, at pressures below 1 GPa. On further compression above 10 GPa, we observe the formation of Li2Zn, which is the highest lithium content compound to be discovered in the Li–Zn system. Our results constrain the structures of these compounds and their evolution with pressure, furthering our understanding of potentially useful light volume-efficient energy storage materials. [ABSTRACT FROM AUTHOR]

The observation of high-temperature superconductivity in hydride sulfide (H2S) at high pressures has generated considerable interest in compressed hydrogen-rich compounds. High-pressure hydrogen selenide (H2Se) has also been predicted to be superconducting at high temperatures; however, its behaviour and stability upon compression remains unknown. In this study, we synthesize H2Se in situ from elemental Se and molecular H2 at pressures of 0.4 GPa and temperatures of 473 K. On compression at 300 K, we observe the high-pressure solid phase sequence (I-I0-IV) of H2Se through Raman spectroscopy and x-ray diffraction measurements, before dissociation into its constituent elements. Through the compression of H2Se in H2 media, we also observe the formation of a host-guest structure, (H2Se)2H2, which is stable at the same conditions as H2Se, with respect to decomposition. These measurements showthat the behaviour ofH2Se is remarkably similar to that ofH2S and provides further understanding of the hydrogen chalcogenides under pressure. [ABSTRACT FROM AUTHOR]

The binary Xe–Ar system has been studied in a series of high pressure diamond anvil cell experiments up to 60 GPa at 300 K. In-situ x-ray powder diffraction and Raman spectroscopy indicate the formation of a van der Waals compound, XeAr2, at above 3.5 GPa. Powder x-ray diffraction analysis demonstrates that XeAr2 adopts a Laves MgZn2-type structure with space group P63/mmc and cell parameters a = 6.595 Å and c = 10.716 Å at 4 GPa. Density functional theory calculations support the structure determination, with agreement between experimental and calculated Raman spectra. Our DFT calculations suggest that XeAr2 would remain stable without a structural transformation or decomposition into elemental Xe and Ar up to at least 80 GPa. [ABSTRACT FROM AUTHOR]

The pair angle distribution function (PADF) is a three‐ and four‐atom correlation function that characterizes the local angular structure of disordered materials, particles or nanocrystalline materials. The PADF can be measured using X‐ray or electron fluctuation diffraction data, which can be collected by scanning or flowing a structurally disordered sample through a focused beam. It is a natural generalization of established pair distribution methods, which do not provide angular information. The software package pypadf provides tools to calculate the PADF from fluctuation diffraction data. The package includes tools for calculating the intensity correlation function, which is a necessary step in the PADF calculation and also the basis for other fluctuation scattering analysis techniques. [ABSTRACT FROM AUTHOR]

The phase transition sequences of two members of the tetramethylammonium tetrachlorometallate(III) family of hybrid organic-inorganic salts have been determined and structurally characterized as a function of temperature for the first time. Unusually, a reduction in point-group symmetry with increasing temperature until reaching a cubic prototype phase is observed. Two additional intermediate phases are observed for Fe3+. First-principles calculations and the presence of short Cl...Cl contacts for Ga3+ suggest the [GaCl4]− anion to be conformationally hindered due to stronger lone-pair-σ-hole interactions. The conformationally more flexible Fe3+ structures show sublattice melting with the onset of rotational disorder in the [NMe4]+ cations occurring 40 K below the corresponding onset of rotational disorder in the [FeCl4]− sublattice. [ABSTRACT FROM AUTHOR]

The structure of the primary amino acid l-leucine has been determined for the first time by neutron diffraction. This was made possible by the use of modern neutron Laue diffraction to overcome the previously prohibitive effects of crystal size and quality. The packing of the structure into hydrophobic and hydrophilic layers is explained by the intermolecular interaction energies calculated using the PIXEL method. Variable-temperature data collections confirmed the absence of phase transitions between 120 and 300 K in the singlecrystal form. [ABSTRACT FROM AUTHOR]

The pressure- and temperature-dependent phase transitions in the ferroelectric material rubidium hydrogen sulfate (RbHSO4) are investigated by a combination of neutron Laue diffraction and high-pressure X-ray diffraction. The observation of disordered O-atom positions in the hydrogen sulfate anions is in agreement with previous spectroscopic measurements in the literature. Contrary to the mechanism observed in other hydrogen-bonded ferroelectric materials, H-atom positions are well defined and ordered in the paraelectric phase. Under applied pressure RbHSO4 undergoes a ferroelectric transition before transforming to a third, high-pressure phase. The symmetry of this phase is revised to the centrosymmetric space group P21/c, resulting in the suppression of ferroelectricity at high pressure. [ABSTRACT FROM AUTHOR]

Negative linear compressibility (NLC), the increase in a unit cell length with pressure, is a rare phenomenon in which hydrostatic compression of a structure promotes expansion along one dimension. It is usually a consequence of crystal structure topology. We show that the source of NLC in the Co(ii) citrate metal–organic framework UTSA-16 lies not in framework topology, but in the relative torsional flexibility of Co(ii)-centred tetrahedra compared to more rigid octahedra. [ABSTRACT FROM AUTHOR]

In situ high-pressure high-temperature X-ray powder diffraction studies of the cobalt-hydrogen system reveal the direct synthesis of both the binary cobalt hydride (CoH) and a novel cobalt dihydride (CoH2). We observe the formation of fcc CoH at pressures of 4 GPa, which persists to pressures of 45 GPa. At this pressure, we see the emergence with time of a further expanded fcc lattice, which we identify as CoH2, where the hydrogen atoms occupy the tetrahedral vacancies. We have explored alternative synthesis routes of CoH2 and can lower the synthesis pressure to 35 GPa by the application of high temperature. CoH2 is stable to at least 55 GPa and decomposes into CoH below 10 GPa, releasing molecular hydrogen before further decomposing completely into its constituent elements below 3 GPa. As a first-row transition metal, cobalt has a relatively lower mass than other hydride-forming transition metals, and as a result, CoH2 has a high hydrogen content of 3.3 wt. % and a volumetric hydrogen density of 214 g/l. [ABSTRACT FROM AUTHOR]

This paper assesses the performance of plane-wave density functional theory calculations at returning reliable structural information for molecular crystal structures where the primary intermolecular interactions are either hydrogen bonding or dispersion interactions. The computed structures are compared with input structures obtained from the Cambridge Structural Database, and assessed in terms of crystal packing similarities, unit-cell volume and shape, short contact distances and hydrogen-bond distances. The results demonstrate that the PBE functional [Perdew, Burke & Ernzerhof (1996). Phys. Rev. Lett. 77, 3865-3868] with Tkatchenko and Scheffler's 'TS' dispersion correction [Tkatchenko & Scheffler (2009). Phys. Rev. Lett. 102, 073005] is capable of returning reliable full structural optimizations, in which both atomic positions and unit-cell vectors are free to optimize simultaneously. [ABSTRACT FROM AUTHOR]

• The effect of ethylammonium nitrate on lysozyme aggregation was identified using three different SAXS approaches. • The changes in protein size, shape and aggregation are dependent on the IL concentration, with aggregation above 10 mol%. • Protein aggregation was evaluated by pseudo- R g values from SAXS approaches. • Less protein aggregation in ethylammonium nitrate than ethanolammonium nitrate. • The lysozyme aggregation was suppressed by the specific IL+ additive combinations. Solvents play a crucial role in protein instability and aggregation, which are undesirable in biomedical applications. The development of quantitative, high throughput methods of evaluating protein aggregation is important in the search for novel solvent mixtures/systems, such as ionic liquids (ILs). In this study, three different small-angle X-ray scattering setups were employed to determine lysozyme size, shape, and aggregation in IL-water mixtures, including a high throughput plate approach, capillary autoloader, and size-exclusion setup, in order of increasing measurement time and scattering data quality. Protein size and shape were determined in low concentrations of ethylammonium nitrate, and the degree of protein aggregation was evaluated by a pseudo-radius of gyration (pseudo- R g). The short collection time, and wide viscosity tolerance render the plate setup ideal for high throughput screening of protein aggregation in complex IL systems. We then investigated the effect of five additives, known to stabilize proteins, on lysozyme in 144 different IL-water mixtures. We showed that lysozyme lost its shape and had increased aggregation with over 17 mol% IL present, though lysozyme was less aggregated in ethylammonium nitrate (EAN) and ethanolammonium formate (EtAF) solutions. Further, lysozyme aggregation was slightly suppressed by glycerol in EAN-water mixtures, and by trimethylamine N -oxide in EtAF and ethylammonium formate aqueous solutions. This work develops a new quantitative and high throughput approach for evaluating protein aggregation in solvent systems, including viscous solvents. [ABSTRACT FROM AUTHOR]

[Display omitted] Ions are important to modulate protein properties, including solubility and stability, through specific ion effects. Ionic liquids (ILs) are designer salts with versatile ion combinations with great potential to control protein properties. Although protein-ion binding of common metals is well-known, the IL effect on proteins is not well understood. Here, we employ the model protein lysozyme in dilute and concentrated IL solutions to determine the specific ion binding effect on protein phase behaviour, activity, size and conformational change, aggregation and intermolecular interactions. A combination of spectroscopic techniques, activity assays, small-angle X-ray scattering, and crystallography highlights that ILs, particularly their anions, bind to specific sites in the protein hydration layer via polar contacts on charged, polar and aromatic residues. The specific ion binding can induce more flexible loop regions in lysozyme, while the ion binding in the bulk phase can be more dynamic in solution. Overall, the protein behaviour in ILs depends on the net effect of nonspecific interactions and specific ion binding. Compared to formate, the nitrate anion induced high protein solubility, low activity, elongated shape and aggregation, which is largely owing to its higher propensity for ion binding. These findings provide new insights into protein-IL binding interactions and using ILs to modulate protein properties. [ABSTRACT FROM AUTHOR]

We have used synchrotron x-ray and Raman spectroscopic studies combined with molecular dynamics to investigate the I2 - H2 system at high pressure. By laser heating the mixture above 25 GPa we synthesized the molecular compound HI ( H2 )13 , with the A B 13 structure type and unusually high volumetric hydrogen content. The isolation of HI molecules by ( H2 )13 supramolecular clusters stabilizes the compound over a remarkable pressure range from 9 to at least 130 GPa. At lower pressures and 300 K another compound, hydrogen diiodane H2 ( HI)2 , spontaneously forms, being stable up to 12.5 GPa. [ABSTRACT FROM AUTHOR]

Through high-pressure Raman spectroscopy and x-ray diffraction experiments, we have investigated the formation, stability field, and structure of hydrogen iodide (HI). Hydrogen iodide is synthesized by the reaction of molecular hydrogen and iodine at room temperature and at a pressure of 0.2 GPa. Upon compression, HI solidifies into cubic phase I, and we present evidence for the emergence of a phase I' above 3.8 GPa. Across the wide temperature regime presented here, HI is unstable under compression (11 GPa at 300 K, 18 GPa at 77 K), decomposing into its constituent elements, after which no further reaction between hydrogen and iodine was observed up to pressures of 60 GPa. This study provides both the constraints on the phase diagram of HI and its kinetic stability. [ABSTRACT FROM AUTHOR]

Through a series of high-pressure x-ray diffraction experiments combined with in situ laser heating, we explore the pressure–temperature phase diagram of germanium (Ge) at pressures up to 110 GPa and temperatures exceeding 3000 K. In the pressure range of 64–90 GPa, we observe orthorhombic Ge-IV transforming above 1500 K to a previously unobserved high-temperature phase, which we denote as Ge-VIII. This high-temperature phase is characterized by a tetragonal crystal structure, space group I4/mmm. Density functional theory simulations confirm that Ge-IV becomes unstable at high temperatures and that Ge-VIII is highly competitive and dynamically stable at these conditions. The existence of Ge-VIII has profound implications for the pressure–temperature phase diagram, with melting conditions increasing to much higher temperatures than previous extrapolations would imply. [ABSTRACT FROM AUTHOR]

Serial crystallography of membrane proteins often employs high-viscosity injectors (HVIs) to deliver micrometre-sized crystals to the X-ray beam. Typically, the carrier medium is a lipidic cubic phase (LCP) media, which can also be used to nucleate and grow the crystals. However, despite the fact that the LCP is widely used with HVIs, the potential impact of the injection process on the LCP structure has not been reported and hence is not yet well understood. The self-assembled structure of the LCP can be affected by pressure, dehydration and temperature changes, all of which occur during continuous flow injection. These changes to the LCP structure may in turn impact the results of X-ray diffraction measurements from membrane protein crystals. To investigate the influence of HVIs on the structure of the LCP we conducted a study of the phase changes in monoolein/water and monoolein/buffer mixtures during continuous flow injection, at both atmospheric pressure and under vacuum. The reservoir pressure in the HVI was tracked to determine if there is any correlation with the phase behaviour of the LCP. The results indicated that, even though the reservoir pressure underwent (at times) significant variation, this did not appear to correlate with observed phase changes in the sample stream or correspond to shifts in the LCP lattice parameter. During vacuum injection, there was a three-way coexistence of the gyroid cubic phase, diamond cubic phase and lamellar phase. During injection at atmospheric pressure, the coexistence of a cubic phase and lamellar phase in the monoolein/water mixtures was also observed. The degree to which the lamellar phase is formed was found to be strongly dependent on the co-flowing gas conditions used to stabilize the LCP stream. A combination of laboratory-based optical polarization microscopy and simulation studies was used to investigate these observations. [ABSTRACT FROM AUTHOR]

[Display omitted] Continuous flow injection is a key technology for serial crystallography measurements of protein crystals suspended in the lipidic cubic phase (LCP). To date, there has been little discussion in the literature regarding the impact of the injection process itself on the structure of the lipidic phase. This is despite the fact that the phase of the injection matrix is critical for the flow properties of the stream and potentially for sample stability. Here we report small-angle X-ray scattering measurements of a monoolein:water mixture during continuous delivery using a high viscosity injector. We observe both an alignment and modification of the LCP as a direct result of the injection process. The orientation of the cubic lattice with respect to the beam was estimated based on the anisotropy of the diffraction pattern and does not correspond to a single low order zone axis. The solvent fraction was also observed to impact the stability of the cubic phase during injection. In addition, depending on the distance traveled by the lipid after exiting the needle, the phase is observed to transition from a pure diamond phase (Pn 3 m) to a mixture containing both gyriod (Ia 3 d) and lamellar ( L α ) phases. Finite element modelling of the observed phase behaviour during injection indicates that the pressure exerted on the lipid stream during extrusion accounts for the variations in the phase composition of the monoolein:water mixture. [ABSTRACT FROM AUTHOR]

Molecular hydrogen forms the archetypical quantum solid. Its quantum nature is revealed by behavior which is classically impossible and by very strong isotope effects. Isotope effects between H2, D2, and HD molecules come from mass difference and the different quantum exchange effects: fermionic H2 molecules have antisymmetric wavefunctions, while bosonic D2 molecules have symmetric wavefunctions, and HD molecules have no exchange symmetry. To investigate how the phase diagram depends on quantum-nuclear effects, we use high-pressure and low-temperature in situ Raman spectroscopy to map out the phase diagrams of H2-HD-D2 with various isotope concentrations over a wide pressure-temperature (P-T) range. We find that mixtures of H2, HD, and D2 behave as an isotopic molecular alloy (ideal solution) and exhibit symmetry-breaking phase transitions between phases I and II and phase III. Surprisingly, all transitions occur at higher pressures for the alloys than either pure H2 or D2. This runs counter to any quantum effects based on isotope mass but can be explained by quantum trapping of high-kinetic energy states by the exchange interaction. [ABSTRACT FROM AUTHOR]