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The generation of above-bandgap photovoltage, referred to as the anomalous photovoltaic effect (APV), is an extraordinary characteristic sought after property in bulk ferroelectric photovoltaic devices. Despite the fact that the relatively narrow bandgap of BiFeO3 (BFO) (2.7 eV) induces a comparatively larger generation of photocurrent than other ferroelectric photovoltaic, it falls short in producing an anomalous photovoltage (Eg ≪ Voc) and exhibits leaky ferroelectric hysteresis due to unavoidable oxygen vacancies. This work revealed a reduction in oxygen vacancies through the substitution of Ba(Fe1/2Nb1/2)O3 in BFO, leading to improved structural, morphological, synchrotron XPS, and electrical properties. This reduction in oxygen vacancies has resulted in an impressive above-bandgap photovoltage (APV) of 4.41 V for 80BFO–20BFN with greater ferroelectric polarization (Pr = 20.45 μC/cm2) observed at the co-existence of polar and non-polar phases. Moreover, both theoretical and experimental optical analyses have demonstrated a significant decrease in the bandgap to 1.92 eV, effectively extending the visible region close to 653 nm. As a result, a larger population of photoexcited charge carriers is generated, enabling the attainment of a high current density (Jsc) of 0.75 μA/cm2 under 100 mW/cm2 light irradiation. [ABSTRACT FROM AUTHOR]

Strain engineering using ion beams is a current topic of research interest in semiconductor materials. Synchrotron-based high-resolution x-ray diffraction has been utilized for strain-depth analysis in GaAs irradiated with 300 keV Ar and 4H-SiC and GaAs irradiated with 100 MeV Ag ions. The direct displacement-related defect formation, anticipated from the elastic energy loss of Ar ions, can well explain the irradiation-induced strain depth profiles. The maximum strain in GaAs is evaluated to be 0.88% after Ar irradiation. The unique energy loss depth profile of 100 MeV Ag (swift heavy ions; SHIs) and resistance of pristine 4H-SiC and GaAs to form amorphous/highly disordered ion tracks by ionization energy loss of monatomic ions allow us to examine strain buildup due to the concentrated displacement damage by the elastic energy loss near the end of ion range (∼ 12 μ m). Interestingly, for the case of SHIs, the strain-depth evolution requires consideration of recovery by ionization energy loss component in addition to the elastic displacement damage. For GaAs, strain builds up throughout the ion range, and the maximum strain increases and then saturates at 0.37% above an ion fluence of 3 × 10 13 Ag/cm 2. For 4H-SiC, the maximum strain reaches 4.6% and then starts to recover for fluences above 1 × 10 13 Ag/cm 2. Finally, the contribution of irradiation defects and the purely mechanical contribution to the total strain have been considered to understand the response of different compounds to ion irradiation. [ABSTRACT FROM AUTHOR]

In the continuity of a previous jet-cooled rovibrational study of trans and cis conformers of 2-furfural in the mid-infrared region (700–1750 cm−1) [Chawananon et al., Molecules 28 (10), 4165 (2023)], the present work investigates the far-infrared spectroscopy of 2-furfural using a long path absorption cell coupled to a high-resolution Fourier transform spectrometer and synchrotron radiation at the AILES beamline of the SOLEIL synchrotron. Guided by anharmonic calculations, vibrational energy levels and excited-state rotational constants are sufficiently predictive for a complete assignment of all fundamental and combination bands up to 700 cm−1, as well as the rovibrational analysis of 4 (1) low-frequency modes of trans-(cis-)2-furfural. A global rovibrational simulation, including far-infrared rovibrational lines and microwave and millimeter-wave rotational lines assigned in a previous study [Motiyenko et al., J. Mol. Spectrosc., 244, 9 (2007)] provides a reliable set of ground- and excited-state rotational parameters involving ring torsion, bending, and ring puckering modes of 2-furfural. In a second step, a rovibrational analysis of several hot band sequences, mainly involving the lowest frequency ring CHO torsion mode, is carried out. Reliable values of some anharmonic coefficients are obtained experimentally and could serve as a benchmark for validating advanced anharmonic calculations related to these large amplitude motions of flexible molecules. [ABSTRACT FROM AUTHOR]

Developing highly efficient methane (CH4) hydrate storage methods and understanding the hydrate dissociation kinetics can contribute to advancing CH4 gas storage and transport. The effects of tetrabutylammonium bromide (TBAB) (a thermodynamic promoter) addition on the kinetics of CH4 hydrate were evaluated on the microscopic scale using synchrotron x-ray computed tomography (CT) and powder x-ray diffraction. Microscopic observations showed that a 5 wt. % TBAB solution facilitated the nucleation of CH4 hydrate owing to the initial growth of TBAB semi-clathrate hydrate particles. The CH4 hydrate crystals in the CH4 + TBAB hydrate sample were sponge-like with many internal pores and exhibited slightly enhanced self-preservation compared to the pure CH4 hydrate, both in the bulk and after pulverization to a fine powder. This study demonstrates the feasibility of controlling the rate of CH4 hydrate formation and preservation by using aqueous TBAB solutions in CH4 hydrate formation. [ABSTRACT FROM AUTHOR]

The present study focuses on the oxygen (O)-ion implantation-induced structural and electronic modifications in the single crystals of strontium-titanate (s-STO) using synchrotron-based x-ray diffraction (XRD), x-ray photoemission spectroscopy (XPS), and resonant x-ray photoemission spectroscopy. The crystallinity of the epitaxially aligned phases of s-STO is confirmed through XRD. This direct evidence of heavy ion implantation is supported by the Monte Carlo-based simulation of stopping and range of ions in matter/transport of ions in matter. XPS at different core levels is performed to detect the exact oxidation state of Ti ions in s-STO. The dominance of Ti3+ over Ti4+ upon oxygen implantation suggests the disorder in the perovskite material, primarily in the form of oxygen vacancies (VO). The confirmation of VO is explicitly shown by the enhancement in the spectral area of the assigned peak in the O 1s XPS. Resonant photoemission spectroscopy measurements were performed by varying photon energy from 32 to 46 eV to understand the nature of the valence band electronic structure of s-STO. The resonance in the different hybridized states of s-STO is confirmed by the spectral features of constant initial state plots. There is a correlation between the defective state of Ti and the oxygen-deficient state. The transformation from SrTiO3 to SrTiO2.5, partially or completely, is essentially required to underline any modification in the electronic properties of s-STO. s-STO is in a mixed state of an ionic conductor and an electronic conductor. This study outlines the creation of VO due to O-ion implantation and investigates the changes in the electronic structures of s-STO. [ABSTRACT FROM AUTHOR]

The high-entropy alloy with composition AlCoCrFeNi2.1, additively manufactured with the laser powder-bed fusion technique, has a far-from-equilibrium BCC/FCC eutectic nanolamellar structure. We studied the high-pressure response of this alloy under both static compression and high-strain rate shock compression. The response to static compression using a diamond anvil cell was studied at pressures up to 302 GPa with synchrotron x-ray diffraction at the advanced photon source. The high-pressure FCC-only phase of the EHEA previously observed by Pope et al. [AIP Adv. 13, 035124 (2023)] is found to be stable up to the highest pressure achieved in this study with a volume compression of V/V0 = 0.587 at ambient temperature. The shock experiments were performed by using GEKKO XII lasers at the Institute of Laser Engineering, Osaka University. The principal Hugoniot equation-of-state of the EHEA was measured up to a pressure of 515 GPa and a compression of V/V0 = 0.613. Additionally, the thermal equation of state of the EHEA was measured up to 6.2 GPa and 1623 K using a large-volume Paris–Edinburgh cell to obtain the temperature dependence of bulk modulus and thermal expansion coefficients. The melting temperature for EHEA AlCoCrFeNi2.1 at a pressure of 5.6 GPa was measured to be 1648 ± 25 K. These results can be used to refine stochastic (or special) quasi-random structure (SQS) models for high-pressure high-temperature behavior of high-entropy alloys. [ABSTRACT FROM AUTHOR]

In this study, we observed natural methane (CH4) hydrate sediments, which are a type of unconventional natural gas resources, using x-ray computed tomography (CT). Because CH4 hydrates are formed by hydrogen bonding of water molecules with CH4, material decomposition becomes challenging when CH4 hydrates coexist with liquid or solid water in natural sediments. Tri-contrast (absorption, refraction, and scattering) imaging was performed via diffraction enhanced x-ray CT optics using monochromatic synchrotron x rays. The quantitative characterization of the contrast changes successfully enabled the decomposition of CH4 hydrates coexisting with frozen seawater (ice) in natural sediments obtained from the Okhotsk Sea. This study reveals complementary structural information about the microtexture and spatial relation among CH4 hydrates, ice, and pores by utilizing the distinct physical properties of x rays when passing through the materials. These results highlight the exceptional capabilities of high-resolution multicontrast x-ray tomography in materials science and geoscience applications. [ABSTRACT FROM AUTHOR]

In this paper we study a self-consistent Vlasov-Fokker-Planck equations which describes the longitudinal dynamics of an electron bunch in the storage ring of a synchrotron particle accelerator. We show existence and uniqueness of global classical solutions under physical hypotheses on the initial data. The proof relies on a mild formulation of the equation and hypoelliptic regularization estimates. We also address the problem of the long-time behavior of solutions. We prove the existence of steady states, called Haissinski solutions, given implicitly by a nonlinear integral equation. When the beam current (i.e. the nonlinearity) is small enough, we show uniqueness of steady state and local asymptotic nonlinear stability of solutions in appropriate weighted Lebesgue spaces. The proof is based on hypocoercivity estimates. Finally, we discuss the physical derivation of the equation and its particular asymmetric interaction potential. [ABSTRACT FROM AUTHOR]

The monoclinic polymorph of Co3P2O8 (space group P21/c), isomorphic to farringtonite (Mg3P2O8) type orthophosphates, was studied up to 21 GPa using synchrotron powder X-ray diffraction and density-functional theory simulations to investigate the influence of pressure in the crystal structure. This study revealed a pressure induced structural phase transition for monoclinic cobalt phosphate, Co3P2O8, and the details of crystal structure of the new high-pressure polymorph were delineated. The evolution of XRD pattern with pressure indicate that the onset of a phase transition occurs around 2.90(5) GPa, and the low- and high- pressure phases coexist up to 10.3(1) GPa. The high-pressure phase also has a mono- clinic lattice (space group P21/c), and a discontinuous change of unit-cell volume of about 6.5% occurs at the transition. A reorganization of atomic positions with a change in the cobalt coordination sphere occurs in the phase transition. Notably, the high-pressure polymorph has a defect-olivine-type structure like chopinite-type orthophosphates. Using a third-order Birch--Murnaghan equation of state, the bulk moduli of the low pressure (LP) phase (75(2) GPa) and high-pressure (HP) phase (92(2) GPa) were deter- mined. For the low-pressure polymorph, the principal axes of compression and their compressibility were also determined. Density-functional theory calculations also provided the frequencies of Raman- and infrared-active modes which can be used for mode assignment in future experiments. [ABSTRACT FROM AUTHOR]

Neutron and X-ray computed tomography (NCT and XCT, respectively) are imaging techniques that are increasingly applied in geomechanics research. They are used to non-destructively reveal different microstructural aspects of geomaterials: XCT is often used to observe/quantify differences in density or porosity, while NCT reveals the presence and distribution of hydrogenous materials such as water. The correlated use of NCT and XCT for geomechanics and geotechnics research is in its infancy. To this date, very few experiments have been carried out that combine both techniques, and none has been used to investigate geomaterial–structure interaction. This paper presents the first correlative NCT–XCT imaging study of pile installation. A scaled model pile was installed in an unsaturated intact chalk cylinder and in situ NCT and ex-situ XCT synchrotron-based imaging was applied consecutively. Chalk was used because the behaviour of displacement piles installed in this material is still subject to considerable uncertainty. Results reveal for the first time the interaction between installation-induced changes in chalk density and water distribution variations, with evidence of water displacement into the densified material in the vicinity of the installed pile. A straightforward method for correlative bulk density–moisture content determination from NCT–XCT images of geomaterials is presented and their limitations are discussed. [ABSTRACT FROM AUTHOR]

We present a time-lapse 4-D high-resolution synchrotron imaging study of the morphological evolution of methane gas bubbles and hydrate film growth on these bubbles. Methane gas and partially water-saturated sand were used to form hydrate with a maximum hydrate saturation of 60%. We investigated the transient evolution of gas bubble size distribution during hydrate formation and observed three distinct stages: a) nucleation and hydrate film formation, b) rapid bubble break-up, c) gas bubble coalescence and hydrate framework formation. Our results show that the average gas bubble size distribution decreases from 34.17 μιτι (during hydrate nucleation) to 8.87 μιτι (during secondary bubble formation). The small-size methane bubble population (mean diameter below 10 μm) initially increases at the expense of the larger methane bubble population (mean diameter above 50 μη) due to breakage of the larger bubbles and coalescence of the smaller bubbles. We quantified that the average hydrate film thickness increases from 3.51 to 14.7 μ!! by tracking the evolution of a particular gas bubble. This thickness increase agrees with an analytical model with an average deviation error of 3.3%. This study provides insights into gas bubble distribution and hydrate film growth during hydrate formation, both of which impact the geophysical and mechanical properties of hydrate-bearing sediments. [ABSTRACT FROM AUTHOR]

On the rising demand for eco‐friendly refractories, reducing the use of likely toxic magnesia‐chromium aggregates remains a challenge. Previous studies by some of the authors have proposed Cr‐free alternative compositions, although the morphology of the spinel precipitates has varied across the different suggested systems. The mechanisms involved in the formation of these distinct morphologies were unclear and, therefore, are the focus of this work. In all compositions, SEM/electron backscatter diffraction revealed cube–cube orientation relationships between matrix and precipitates, indicating that their formation is influenced by the lattice parameter misfit (δ), which was measured using synchrotron X‐ray diffraction. It could be concluded that coarser and spherical precipitates form to minimize their surface‐to‐volume ratio in compositions with high absolute δ‐values. Conversely, low‐misfit systems enable the spinel to form a 3D‐network. The potential use of this knowledge to tailor the microstructure of novel compositions was demonstrated by a small Nb2O5 addition into one of the proposed compositions. [ABSTRACT FROM AUTHOR]

The pressure-induced structural changes in the perovskite-type (ABO 3 ) ferroelectric solid solution (1-x)Na 0.5 Bi 0.5 TiO 3 -xBaTiO 3 (NBT-xBT) at the morphotropic phase boundary (MPB) ( x MPB = 0.048 ) have been analyzed up to 12.3 GPa by single-crystal x-ray diffraction with synchrotron radiation. A pressure-induced phase transition takes place between 4.4 and 5.0 GPa, where the pseudocubic low-pressure phase transforms into an orthorhombic high-pressure phase with space group Pnma. The high-pressure phase is comprised of mixed BO 6 tilts and anti-polar A-cation displacements, without exhibiting coherent off-centered shifts of the B-site Ti 4 + cations that can be detected by synchrotron x-ray diffraction. Our results reveal that at ambient pressure and room temperature the NBT- x MPB BT structure possesses anti-phase BO 6 tilts with a relatively large correlation length and the same type of polar distortions as those present in pure NBT, but with strongly violated correlation length due to Ba 2 + -induced local elastic-stress fields. For x MPB the effect of Ba on the mesoscopic-scale structure is compensated by a mild external pressure of only 0.7 GPa, resulting in structural features resembling those of pure NBT at ambient conditions. [ABSTRACT FROM AUTHOR]

Compound semiconductors are playing a major role in the production of X-ray pixel detectors for the application in laboratories and beamlines at photon sources. The performance of these detectors has constantly been improved for the last decades but experiments are still limited by the properties of the detector material, especially under high flux illumination. The fast development of perovskite crystals opens the possibility for new materials to be used as highly efficient X-ray pixel detectors. The published data until now, of the transport properties, demonstrate the large potential of perovskite semiconductors. The achieved values are comparable with the ones of CdTe-based detectors. This paper presents potential perovskite-based detector materials and compares their performance with the state-of-the-art CdTe-based detectors. The perspectives of perovskite semiconductors are promising for the production of large area X-ray detectors but still some challenges remain. [ABSTRACT FROM AUTHOR]

A limited understanding regarding the underlying dynamics and mechanisms of material removal during continuous wave laser drilling has presented significant challenges in achieving precision and process control. To address this, we employed high-fidelity, in situ synchrotron x-ray imaging to reveal previously unknown material behaviors during continuous wave laser drilling with power modulation. Our findings highlight that high-aspect ratio drill holes are achieved when the laser modulation frequency falls within the range of 8–12 kHz, provided that the laser average power and modulation amplitude levels meet the specified limits. Under these conditions, we identified a material removal mechanism driven by incremental accumulation of recoil pressure that gradually pushes material upward from deep within the substrate to the surface. This mechanism manifested as a low-frequency fluctuation in the vapor depression depth, resulting in periodic instances of material ejection. Furthermore, our study underscores that rapid expansion of the melt pool and the widening of the drill hole opening can impede effective material removal by redirecting energy from material ejection to increasing the melt pool size. This investigation contributes essential insights into the subsurface dynamics involved in the drilling of high-aspect ratio holes, furthering our fundamental understanding of this intricate process. [ABSTRACT FROM AUTHOR]

The podiform chromitites in the Luobusha ophiolite have been thought to experience a very deep formation, but the maximum depth is still an open issue. Here, we have investigated the structural stability of natural magnesiochromite using the synchrotron-based powder X-ray diffraction and diamond anvil cells up to 48.6 GPa and 2 450 K. The results have shown that spinel-type magnesiochromite first decomposes into corundum-type 'Cr2O3' + B1-type 'MgO' at 11–14 GPa and 1 250–1 450 K, then modified ludwigite (mLd)-type 'Mg2Cr2O5' + corundum-type 'Cr2O3' at 14.3–20.5 GPa and 1 300–2 000 K, and finally CaTi2O4-type phase at 24.5 GPa. During the quenching procession from high-temperature-pressure conditions, the mLd-type phase appeared again and was kept at ambient conditions. We also obtained the isothermal equation states of spinel-type and CaTi2O4-type phases, revealing the composition effect on their elasticities. Based on the updated results, we propose chromitites could not experience pressure exceeding ∼14.3 GPa (approximate maximum depth ∼400 km) in the subduction-recycling genesis model. [ABSTRACT FROM AUTHOR]

A compact and versatile tensile apparatus for polymer materials is designed and fabricated. Three distinct stretching modes are developed: constant speed, cyclic, and sinusoidal, with adjustable speeds ranging from 0.001 to 120 mm/s. To capture the true strain of the central region, a high-speed camera has been integrated into the apparatus. The temperature of the sample chamber is controlled by flowing air, enabling a homogeneous temperature in the range of RT ∼200 °C. The apparatus is particularly suitable for a synchrotron beamline. The structural evolution of natural rubber during sinusoidal stretching is investigated by in situ wide-angle x-ray scattering. Scattering patterns, force, clamp position, and sample images are saved simultaneously during stretching. Notably, the results reveal a sinusoidal variation in the crystallinity of crosslinked natural rubber when a sinusoidal strain was applied to the sample. The integration of advanced measurement techniques and controlled experimental conditions ensures the acquisition of reliable and accurate data, providing valuable insights into the structural evolution of materials under dynamic deformation conditions. [ABSTRACT FROM AUTHOR]

Preparation of biomacromolecules for structural biology studies is a complex and time‐consuming process. The goal is to produce a highly concentrated, highly pure product that is often shipped to large facilities with tools to prepare the samples for crystallization trials or for measurements at synchrotrons and cryoEM centers. The aim of this article is to provide guidance and to discuss general considerations for shipping biomacromolecular samples. Details are also provided about shipping samples for specific experiment types, including solution‐ and cryogenic‐based techniques. These guidelines are provided with the hope that the time and energy invested in sample preparation is not lost due to shipping logistics. [ABSTRACT FROM AUTHOR]

Nano-satellites, which are following the CubeSat standard have established for demanding industrial and scientific applications with critical requirements on reliability and radiation tolerance. The employment of commercial off-the-shelf components enables a state-of-the-art performance but requires extensive testing to avoid and mitigate malefunctions due to the space environment. The CubeSat mission CLIMB is representative for future missions with a complex payload, a high power budget and a harsh radiation exposure. For this reason, a comprehensive irradiation study of its on-board-computer was done. The total ionizing dose damage of 50 krad was evaluated at a 60 Co source. As a consequence of this test, specific components were exchanged before performing single event effect studies at the synchrotron accelerator MedAustron. A board-level test revealed that the majority of effects concern the central micro controller wherefore was followed by a component-level test. Those irradiation tests make use of a pencil beam to map the device under test, which provides additional information to localize effects - by the timestamp - at the expense of an increased irradiation time compared to a homogeneous exposure. In this paper, we summarize the major findings of the test campaign and mitigation means and present a procedure for single event effect studies at medical accelerators. [ABSTRACT FROM AUTHOR]

TiO2 nanoparticles (TiO2NPs) were directly conjugated with the phototherapeutic prodrug, 5‐aminolevulinic acid (ALA), using a mild and green approach. The resultant TiO2NPs‐ALA nanoconjugates were characterized by different techniques, including HPLC, UV‐Vis, FTIR‐ATR, 1H‐NMR, FESEM‐EDS, TEM, DLS, and synchrotron radiation‐induced XPS (SR‐XPS) to assess the successful loading of 15 % and the chemical stability of ALA on the TiO2NPs. More importantly, the SR‐XPS results showed the stabilizing effect of TiO2 nanosurface on the ALA molecules (against structural change) in neutral and alkaline pHs, which is of great significance in the potential therapeutic applications of ALA. The FESEM and TEM results exhibited the grain‐like TiO2NPs‐ALA particles with a 20–50 nm size distribution, indicating size‐controlling effect of ALA on the TiO2NPs during the conjugation process and the presence of the organic molecule layer onto the surface. TiO2NPs‐ALA represents a promising candidate for studies in photodynamic therapy considering the stabilization effect observed by spectroscopic characterizations. [ABSTRACT FROM AUTHOR]

Aprotic lithium–oxygen batteries (LOBs) may deliver exceptionally high energy density but struggle to attain rapid reversibility and substantial capacity simultaneously, due to typical surface or solution‐formed insulating solid Li2O2. Tuning the structure of Li2O2 to create a large‐area amorphous layer on the cathode is predicted to overcome the multiperformance limitations. Here, an isolated nickel single atom to nitrogen‐doped graphene as a cathode catalyst (Ni─NG SAC) for LOBs is presented via a green click‐trapping strategy. Derived from the maximized exposure of atomic active sites of the cathode, the formation/decomposition mechanisms of Li2O2 are tailored, and a large area of thin Li2O2 amorphous film is achieved. The structure and functions of Ni─NG SAC are explored by theoretical computation and synchrotron radiational investigation. Consequently, the abundant Ni─N4 sites enhance redox kinetics and stand out to deliver an impressive specific discharge/charge capacity of 24 248/17 656 mAh g−1 at 200 mA g−1, together with a long cycle life of over 500 cycles. This study contributes helpful insights to achieve high‐capacity LOBs with long lifespans, by constructing unique single‐atom catalysts to optimize the formation of amorphous discharge Li2O2 products. [ABSTRACT FROM AUTHOR]

The cellular response to cisplatin was assessed in human osteosarcoma cells, using synchrotron-based (SR) Fourier Transform InfraRed nanospectroscopy (nano-FTIR) at the MIRIAM beamline B22 of Diamond Light Source (UK). This label-free mapping method delivered simultaneous morphological and biochemical information on a subcellular level (i.e. 100 s nanometer or better). Based on specific spectral biomarkers, the main biochemical constituents affected by the drug were identified at distinct locations within the cell´s inner body. Cisplatin was shown to have a noteworthy effect on proteins, mostly within the cytoplasm. A clear drug impact on cellular lipids was also observed. Within current literature on s-SNOM, this nanospectroscopy work represents a first successful application in life sciences providing full fingerprint nano-FTIR spectra across intact human cancer cells. [ABSTRACT FROM AUTHOR]

The SYRMA-3D project is dedicated to carrying out basic research to lay the groundwork for implementing breast computed tomography (bCT) using synchrotron radiation, in routine clinical settings in the near future (bCT-SR). This article focuses on the optimization of studies (image quality vs. patient dose). Three ex vivo samples were scanned at the SYRMEP station of the ELETTRA Synchrotron (Trieste, Italy) with the free space propagation technique with monochromatic beam and phase contrast, for 64 different acquisition conditions. So, for each of the energies used (25, 28, 32 and 35 keV); acquisitions were made at four distances from the sample to the detector, (0.2 m, 1.65 m, 3.7 m and 9 m), and for each of these conditions, four conditions of average glandular dose (MGD) imparted were used 20, 5, 2 and 1 mGy. Images were acquired with a photon-counting PIXIRAD detector. The Contrast-Noise ratio and Image Contrast, as indicators of image quality, were evaluated for the 5 central slices of the 64 tomographic acquisitions, in the variant that includes phase recovery (PhR). The results indicated that several protocols provided relevant three-dimensional information about the breast at clinically appropriate doses. [ABSTRACT FROM AUTHOR]

Context. Radio surveys of early-type stars have revealed a number of non-thermal emitters. Most of these have been shown to be binaries, where the collision between the two stellar winds is responsible for the non-thermal emission. Aims. HD 168112 is a non-thermal radio emitter, whose binary nature has only recently been confirmed spectroscopically. We obtained independent spectroscopic observations to determine its orbit, in addition to radio observations to see if the thermal or non-thermal nature of the emission changes during the periastron passage. Methods. We monitored HD 168112 spectroscopically for a 13 yr time span. From these data, we determined the orbital parameters, which we compared to the previous results in the literature. The stellar parameters of both components were determined by comparing the spectra to TLUSTY models. From the spectral index of the radio observations, we found how the nature of the emission changes as the system goes through periastron. Combining our results with other literature data allowed us to further constrain the orbital and stellar parameters. Results. We find HD 168112 to have an orbital period of P = 512.17−0.11+0.41 days, an eccentricity of e = 0.7533−0.0124+0.0053, and a mass ratio close to one. From our spectroscopic modelling, we derived the stellar parameters, but we had difficulty arriving at a spectroscopic mass ratio of one. The radio observations around periastron show only thermal emission, suggesting that most of the synchrotron photons are absorbed in the two stellar winds at that phase. Combining our data with the optical interferometry detection, we could constrain the inclination angle to i ~ 63°, and the mass of each component to ~26 M⊙. Conclusions. We have provided an independent spectroscopic confirmation of the binary nature of HD 168112. Although detected as a non-thermal radio emitter, near periastron the radio emission of this highly eccentric system is thermal and is mainly formed in the colliding-wind region. This effect will also occur in other colliding-wind binaries. [ABSTRACT FROM AUTHOR]

The discovery of ferroelectricity in HfO2 ultrathin films has gathered considerable interest from the microelectronic industry owing to their compatibility with complementary metal oxide semiconductor technology. However, a significant challenge in utilizing HfO2 thin films for commercial devices is the wakeup effect, which is an increase in polarization with the number of electric field cycles in HfO2-based capacitors. Despite efforts to develop wakeup-free HfO2 thin films, the root cause of this effect remains elusive. Some studies attribute it to the tetragonal (T) to orthorhombic (O) phase transformation, while others suggest it is due to the redistribution of oxygen vacancies within the HfO2 layer during electric field cycling. This study investigated the phase transformation dynamics and oxygen vacancy distributions in TiN/Hf0.5Zr0.5O2/TiN capacitors subjected to electric field cycling using in situ grazing incidence synchrotron x-ray diffraction and ex situ x-ray photoelectron spectroscopy. The as-grown HZO films were crystallized in a mixed phase consisting of monoclinic (M), tetragonal, and orthorhombic fractions. The T-phase volume fraction decreased continuously up to 10k electric field cycles. In contrast, the O-phase fraction increased within the first 100 cycles and then stabilized with further cycling. The redistribution of oxygen vacancies occurred continuously throughout the cycling process. The results revealed that continuous oxygen vacancy redistribution during electric field cycling resulted in phase transformation between the T-, O-, and M-phases. The study provides insight into the phase transformation dynamics and oxygen vacancy redistribution in TiN/Hf0.5Zr0.5O2/TiN capacitors during electric field cycling, shedding light on the underlying mechanisms of the wakeup effect. [ABSTRACT FROM AUTHOR]

Elektrocateres rappsilberi gen. et sp. nov. is described from Bitterfeld or Saxonian amber. It is the first representative of the superfamily Cleroidea (Coleoptera) recorded in this amber, from which only 10 families of beetles were known until now. The new genus and species was studied using classical stereomicroscopy, as well as digital microscopy and synchrotron-radiation-based micro-computed tomography. The fossil is related to the rare extant monotypic genera Trichocateres Kolibáč, 2010 and Carinicateres Kolibáč, 2021 from tropical forests of Southeastern Asia. It is assumed that Elektrocateres rappsilberi gen. et sp. nov. would be predatory, hunting other arthropods on tree branches and trunks; however, its mouthparts are probably still on halfway between herbivory or fungivory and predatory. [ABSTRACT FROM AUTHOR]

The users of synchrotron light are now tens of thousands throughout the world. Paradoxically, many of them do not know much about the early history of their domain. This is regrettable, since education about the initial developments makes it easier to fully understand synchrotron radiation and effectively use its amazing features. Scarcely known, in particular, is the key role of scientists working in Frascati, Italy. Partly based on his personal experiences, the author reports here relevant aspects of this story, including a pioneering French–Italian experiment that started in the early 1960s, and the Frascati contributions in the 1970s and 1980s to the birth of synchrotron light research. Finally, the unwise strategic decisions that prevented Italy from achieving absolute leadership in this domain – in spite of its unique initial advantages – are analyzed. [ABSTRACT FROM AUTHOR]

This study introduces a compact, portable femtosecond fibre laser system designed for synchronization with SPring‐8 synchrotron X‐ray pulses in a uniform filling mode. Unlike traditional titanium–sapphire mode‐locked lasers, which are fixed installations, our system utilizes fibre laser technology to provide a practical alternative for time‐resolved spectroscopy, striking a balance between usability, portability and cost‐efficiency. Comprehensive evaluations, including pulse characterization, timing jitter and frequency stability tests revealed a centre wavelength of 1600 nm, a pulse energy of 4.5 nJ, a pulse duration of 35 fs with a timing jitter of less than 9 ps, confirming the suitability of the system for time‐resolved spectroscopic studies. This development enhances the feasibility of experiments that combine synchrotron X‐rays and laser pulses, offering significant scientific contributions by enabling more flexible and diverse research applications. [ABSTRACT FROM AUTHOR]

X‐ray ptychography and ptychographic computed tomography have seen a rapid rise since the advent of fourth‐generation synchrotrons with a high degree of coherent radiation. In addition to quantitative multiscale structural analysis, ptychography with spectral capabilities has been developed, allowing for spatial‐localized multiscale structural and spectral information of samples. The SWING beamline of Synchrotron SOLEIL has recently developed a nanoprobe setup where the endstation's first spectral and resonant ptychographic measurements have been successfully conducted. A metallic nickel wire sample was measured using 2D spectral ptychography in XANES mode and resonant ptychographic tomography. From the 2D spectral ptychography measurements, the spectra of the components of the sample's complex‐valued refractive index, δ and β, were extracted, integrated along the sample thickness. By performing resonance ptychographic tomography at two photon energies, 3D maps of the refractive index decrement, δ, were obtained at the Ni K‐edge energy and another energy above the edge. These maps allowed the detection of impurities in the Ni wire. The significance of accounting for the atomic scattering factor is demonstrated in the calculation of electron density near a resonance through the use of the δ values. These results indicate that at the SWING beamline it is possible to conduct state‐of‐the‐art spectral and resonant ptychography experiments using the nanoprobe setup. [ABSTRACT FROM AUTHOR]

The demand for powder X‐ray diffraction analysis continues to increase in a variety of scientific fields, as the excellent beam quality of high‐brightness synchrotron light sources enables the acquisition of high‐quality measurement data with high intensity and angular resolution. Synchrotron powder diffraction has enabled the rapid measurement of many samples and various in situ/operando experiments in nonambient sample environments. To meet the demands for even higher throughput measurements using high‐energy X‐rays at SPring‐8, a high‐throughput and high‐resolution powder diffraction system has been developed. This system is combined with six sets of two‐dimensional (2D) CdTe detectors for high‐energy X‐rays, and various automation systems, including a system for automatic switching among large sample environmental equipment, have been developed in the third experimental hutch of the insertion device beamline BL13XU at SPring‐8. In this diffractometer system, high‐brilliance and high‐energy X‐rays ranging from 16 to 72 keV are available. The powder diffraction data measured under ambient and various nonambient conditions can be analysed using Rietveld refinement and the pair distribution function. Using the 2D CdTe detectors with variable sample‐to‐detector distance, three types of scan modes have been established: standard, single‐step and high‐resolution. A major feature is the ability to measure a whole powder pattern with millisecond resolution. Equally important, this system can measure powder diffraction data with high Q exceeding 30 Å−1 within several tens of seconds. This capability is expected to contribute significantly to new research avenues using machine learning and artificial intelligence by utilizing the large amount of data obtained from high‐throughput measurements. [ABSTRACT FROM AUTHOR]

We conducted in-situ X-ray diffraction to study the crystalline phase evolution in hydroxyapatite-zirconia composites during both conventional and flash sintering processes. Additionally, we examined the thermal history and microstructure of the composite under these sintering conditions. Despite both sintering methods reaching similar average temperatures, they yielded distinct results in terms of crystalline phase composition and microstructure. In the flash sintered samples, we observed a complete transformation of hydroxyapatite into α- tricalcium phosphate and a complete tetragonal to cubic phase transition in zirconia. Conversely, the conventionally sintered samples remained practically stable. Notably, the flash sintered samples exhibited needle-like microstructures, which were absent in their conventionally sintered counterparts. This divergence suggests that the application of an electric field plays a role in generating athermal effects during the sintering of hydroxyapatite-zirconia composites. [ABSTRACT FROM AUTHOR]

We present a first spectroscopic characterization of the homoatomic polyhalogen tetrabromine, Br4, in the gas phase. Photolysis of CHBr3 at 248 nm is used to generate atomic bromine radicals in a flow tube reactor. Resulting combination products are detected by photoionization mass spectrometry at the Advanced Light Source of the Lawrence Berkeley National Laboratory. Interpretation of the experimental mass spectra is informed by calculated adiabatic ionization energies carried out at the CCSD(T)/aug‐cc‐pVTZ//M06‐2X/aug‐cc‐pVTZ and CCSD(T)/aug‐cc‐pVTZ//cam‐B3LYP/6‐311++g** levels of theory. Tunable VUV synchrotron radiation enables the collection of the mass‐selected photoionization spectra by which Br4 is assigned using Franck‐Condon simulations of a Br2 dimer with a stretched tetrahedral geometry. [ABSTRACT FROM AUTHOR]

Compressibility and pressure-induced structural evolution of kokchetavite, the hexagonal polymorph of KAlSi3O8, has been studied up to 11.8 GPa using synchrotron single-crystal X-ray diffraction. Two phase transitions were observed at pressures of ~0.3 and 10.4 GPa. Kokchetavite-I (as-synthesized, P6/mcc) transforms into kokchetavite-II with the P 6 c2 space group. Kokchetavite-II → kokchetavite-III phase transition at ~10.4 GPa is accompanied by a change of symmetry to probably orthorhombic. After pressure release, kokchetavite reverts to the initial single-crystal state with P6/mcc space group. A second-order Birch-Murnaghan equation of state was calculated for phase kokchetavite-II with coefficients V0 = 1486(3) Å3, K0 = 59(2) GPa. [ABSTRACT FROM AUTHOR]

The growth behaviors of hydrogen bubbles and intermetallic compounds (IMCs) during solidification of an Al-5 wt.% Mn alloy was investigated by synchrotron radiography. Results show that bubble collapse can increase hydrogen concentration in nearby Al melt, thus facilitating the formation and growth of new bubbles. Under the interference of Al6Mn IMCs, the growth method of an individual bubble is changed from a Gaussian distribution to a linear model. Al6Mn crystal growth can be divided into three stages: first an isotropic spherical crystal appears, then it evolves into primary branches, and eventually forms an irregular octahedron. [ABSTRACT FROM AUTHOR]

Many insects feed on xylem or phloem sap of vascular plants. Although physical damage to the plant is minimal, the process of insect feeding can transmit lethal viruses and bacterial pathogens. Disparities between insect-mediated pathogen transmission efficiency have been identified among xylem sap-feeding insects; however, the mechanistic drivers of these trends are unclear. Identifying and understanding the structural factors and associated integrated functional components that may ultimately determine these disparities are critical for managing plant diseases. Here, we applied synchrotron-based X-ray microcomputed tomography to digitally reconstruct the morphology of three xylem sap-feeding insect vectors of plant pathogens: Graphocephala atropunctata (blue-green sharpshooter; Hemiptera, Cicadellidae) and Homalodisca vitripennis (glassy-winged sharpshooter; Hemiptera, Cicadellidae), and the spittlebug Philaenus spumarius (meadow spittlebug; Hemiptera, Aphrophoridae). The application of this technique revealed previously undescribed anatomical features of these organisms, such as key components of the salivary complex. The visualization of the 3D structure of the precibarial valve led to new insights into the mechanism of how this structure functions. Morphological disparities with functional implications between taxa were highlighted as well, including the morphology and volume of the cibarial dilator musculature responsible for extracting xylem sap, which has implications for force application capabilities. These morphological insights will be used to target analyses illuminating functional differences in feeding behavior.

Over the past two decades, serial X-ray crystallography has enabled the structure determination of a wide range of proteins. With the advent of X-ray free-electron lasers (XFELs), ever-smaller crystals have yielded high-resolution diffraction and structure determination. A crucial need to continue advancement is the efficient delivery of fragile and micrometre-sized crystals to the X-ray beam intersection. This paper presents an improved design of an all-polymer microfluidic `chip for room-temperature fixed-target serial crystallography that can be tailored to broadly meet the needs of users at either synchrotron or XFEL light sources. The chips are designed to be customized around different types of crystals and offer users a friendly, quick, convenient, ultra-low-cost and robust sample-delivery platform. Compared with the previous iteration of the chip [Gilbile et al. (2021), Lab Chip, 21, 4831-4845], the new design eliminates cleanroom fabrication. It has a larger imaging area to volume, while maintaining crystal hydration stability for both in situ crystallization or direct crystal slurry loading. Crystals of two model proteins, lysozyme and thaumatin, were used to validate the effectiveness of the design at both synchrotron (lysozyme and thaumatin) and XFEL (lysozyme only) facilities, yielding complete data sets with resolutions of 1.42, 1.48 and 1.70 Å, respectively. Overall, the improved chip design, ease of fabrication and high modifiability create a powerful, all-around sample-delivery tool that structural biologists can quickly adopt, especially in cases of limited sample volume and small, fragile crystals.

Aggregated and hyperphosphorylated Tau is one of the pathological hallmarks of Alzheimer's disease. Tau is a polyampholytic and intrinsically disordered protein (IDP). In this paper, we present for the first time experimental results on the ionic strength dependence of the radius of gyration (Rg) of human Tau 4RS and 4RL isoforms. Synchrotron X-ray scattering revealed that 4RS Rg is regulated from 65.4 to 58.5 Å and 4RL Rg is regulated from 70.9 to 57.9 Å by varying ionic strength from 0.01 to 0.592 M. The Rg of 4RL Tau is larger than 4RS at lower ionic strength. This result provides an insight into the ion-responsive nature of intrinsically disordered and polyampholytic Tau, and can be implicated to the further study of Tau-Tau and Tau-tubulin intermolecular structure in ionic environments.

A new generation of adaptive x-ray optics (AXO) is being installed on high-coherent-flux x-ray beamlines worldwide to correct and control the optical wavefront with sub-nm precision. These ultra-smooth mirrors achieve high reflectivities at glancing angles of incidence and can be hundreds of mm long. One type of adaptive x-ray mirror relies on piezoelectric ceramic strips which are segmented into channels and actuated to induce local, longitudinal bending, generating one-dimensional shape changes in the mirror substrate. A recently described mirror model uses a three-layer geometry with parallel actuators on the front and back surfaces of a thicker mirror substrate. By analogy to a solved problem in the thermal actuation of a tri-metal strip, we show that the achievable bending radius varies approximately as the square of the substrate thickness. We provide an analytic solution and simulate bending using a finite-element model.

The evaporation-induced self-assembly process of amphiphilic molecules (4POSS-DL-POM) in a mixed acetone/ n -decane solution is investigated using small-angle X-ray scattering. A series of scattering data analysis methods is employed to elucidate the structural evolution of heterocluster 4POSS-DL-POM from a fractal network to compact nanoclusters, followed by the formation of core–shell nanoclusters, and ultimately to hcp superlattice structure. [Display omitted] Self-assembly of nanoclusters (NCs) is an effective synthetic method for preparing functionalized nanomaterials. However, the assembly process and mechanisms in solutions still remain ambiguous owing to the limited strategies to monitor intermediate assembled states. Herein, the self-assembly process of amphiphilic molecule 4POSS-DL-POM (consisting of four polyhedral oligomeric silsesquioxanes, a dendritic linker, and one polyoxometalate) by evaporation of acetone in a mixed acetone/ n -decane solution is monitored by time-resolved synchrotron small-angle X-ray scattering (SAXS). Scattering data assessments, including Kratky analysis, pair distance distribution function, and model fitting, track the self-assembly process of 4POSS-DL-POM from a fractal network to compact NCs, then to core–shell NCs, and finally to superlattice structure. The calculated average aggregation number of a core–shell NC is 11 according to the parameters obtained from core-shell model fitting, in agreement with electron microscopy. The fundamental understanding of the self-assembly dynamics from heterocluster into NCs provides principles to control building block shape and guide target aggregation, which can further promote the design and construction of highly ordered cluster-assembled functional nanomaterials. [ABSTRACT FROM AUTHOR]

Processing-induced defects affect the performance and reliability of multilayered ceramics. They are introduced from the raw powder, or during tape casting, drying, thermo-compression, binder burnout, and sintering. Using synchrotron X-ray multiscale tomography, we investigated how the microstructural heterogeneities and various defects evolve in the sintering of tape-cast alumina laminate. The strength-limiting defects were identified as large defects at the layer interface and peculiar crack-like defects formed around large inclusions contained in the raw powder. Although a slurry might be uniform in colloidal processing, the particle packing in the tape was heterogeneous. This heterogeneity determined the spatial distribution of pores and formed complex pores in later stages. Moreover, we found the formation of flake-like sheets in slurry due to the self-assembly of polyhedral alumina crystals. This phenomenon has the potential to be applied in the manufacture of 2D micro-sheets controlled to the thickness of a single particle. [ABSTRACT FROM AUTHOR]

In this exploratory study, we searched for associations between the two most common diseases of the oral cavity—dental caries and periodontal diseases—taking into account additional factors, such as personalized clinical pictures (the individual risk factors of the patient), based on the method of a multivariate data analysis of the molecular changes in the composition of human gingival crevicular fluid (GCF). For this purpose, a set of synchrotron Fourier-transform infrared spectroscopy (FTIR) spectra of gingival crevicular fluid samples from patients with different demographics, levels of dental caries development and periodontal diseases, and the presence/absence of concomitant chronic diseases were obtained and analyzed. Using a set of techniques (v-, F-, Chi-square tests; a principal component analysis (PCA); and the hierarchical clustering of principal components (HCPCs)) implemented in the R package FactoMineR allowed us to assess the relationship between the principal components (PCs) and characteristics of the respondents. By identifying the features (vibrational modes in the FTIR spectra) that contribute most to the differentiation of the spectral dataset, and by taking into account the interrelationships between the patients' characteristics, we were able to match specific biological markers (specific molecular groups) to the two factors of interest—two types of oral pathologies. The results obtained show that the observed changes in the quantitative and qualitative composition of the modes in the infrared (IR) spectra of the GCF samples from patients with different dental caries developments and periodontal diseases present confirm the difficulty of identifying patient-specific spectral information. At the same time, different periodontal pathologies are more closely associated with other characteristics of the patients than the level of their caries development. The multivariate analysis performed on the spectral dataset indicates the need to take into account not only the co-occurrence of oral diseases, but also some other factors. The lack of this consideration (typical in lots of studies in this area) may lead to misinterpretations and consequently to a loss of data when searching for biological markers of certain oral diseases. [ABSTRACT FROM AUTHOR]

The correlations between the electrical behavior and microstructural properties of samples consisting of particle composites fabricated from SiC particles embedded in a silicone matrix, were investigated using X-ray computed tomography. In the voltage field range 200-1000 V/mm, the measured conductivity as a function of SiC volume fraction exhibits two distinct gaps. Upon further investigations, we attribute these observations to percolation thresholds at the microscale. The first gap, corresponding to interconnections between SiC particles that were originally disconnected, is more significant at higher voltage; while the second one, resulting from shortening conductivity pathways between the external surfaces of the samples with the increase of SiC volume fraction, seems more sensitive to lower voltages and is correlated with a decrease of the tortuosity of the percolated SiC network. [ABSTRACT FROM AUTHOR]

Hierarchical self‐assembly represents a powerful strategy for the fabrication of functional materials across various length scales. However, achieving precise formation of functional hierarchical assemblies remains a significant challenge and requires a profound understanding of molecular assembly interactions. In this study, we present a molecular‐level understanding of the hierarchical assembly of sequence‐defined peptoids into multidimensional functional materials, including twisted nanotube bundles serving as a highly efficient artificial light harvesting system. By employing synchrotron‐based powder X‐ray diffraction and analyzing single crystal structures of model compounds, we elucidated the molecular packing and mechanisms underlying the assembly of peptoids into multidimensional nanostructures. Our findings demonstrate that incorporating aromatic functional groups, such as tetraphenyl ethylene (TPE), at the termini of assembling peptoid sequences promotes the formation of twisted bundles of nanotubes and nanosheets, thus enabling the creation of a highly efficient artificial light harvesting system. This research exemplifies the potential of leveraging sequence‐defined synthetic polymers to translate microscopic molecular structures into macroscopic assemblies. It holds promise for the development of functional materials with precisely controlled hierarchical structures and designed functions. [ABSTRACT FROM AUTHOR]

(1−x)Pb(Mg1/3Nb2/3)O3-xPbTiO3 (PMN-PT) perovskite-like solid solutions are recognized for their outstanding electromechanical properties, which are of technological importance. However, some significant aspects of the crystal structures and domain assemblages in this system and the role of these characteristics in defining the functional performance of PMN-PT remain uncertain. Here, we used synchrotron x-ray diffraction to investigate the phase transition linking the paraelectric (cubic) and ferroelectric (tetragonal) phases in a single crystal of 0.65PMN-0.35PT. We analyzed the evolution of reciprocal-space maps across this transition. These maps were collected using small temperature step (1 K) and a high reciprocal-space resolution to reveal changes in the splitting of Bragg peaks caused by the formation of ferroelastic domains in the low-symmetry phase. Our results uncovered a two-phase state, cubic plus tetragonal phases, which exists over a narrow temperature range of only ≈4 K and exhibits a thermal hysteresis of ≈1.8 K. Remarkably, within this state, the lattice parameter of the cubic phase, a C , matches the orientational average of the lattice parameters for the tetragonal polymorph, 2 3 a T + 1 3 c T . We discuss the implications of this matching, highlighting the possibility of it being realized by the formation of an assemblage of tetragonal twin domains separated from the cubic phase by a strain-free {110} boundary, as in the "adaptive phase" but without domain miniaturization. [ABSTRACT FROM AUTHOR]

This study reports the synthesis and crystal structure determination of a novel CrTe3 phase using various experimental and theoretical methods. The average stoichiometry and local phase separation of this quenched high‐pressure phase were characterized by ex situ synchrotron powder X‐ray diffraction and total scattering. Several structural models were obtained using simulated annealing, but all suffered from an imperfect Rietveld refinement, especially at higher diffraction angles. Finally, a novel stoichiometrically correct crystal structure model was proposed on the basis of electron diffraction data and refined against powder diffraction data using the Rietveld method. Scanning electron microscopy–energy‐dispersive X‐ray spectrometry (EDX) measurements verified the targeted 1:3 (Cr:Te) average stoichiometry for the starting compound and for the quenched high‐pressure phase within experimental errors. Scanning transmission electron microscopy (STEM)–EDX was used to examine minute variations of the Cr‐to‐Te ratio at the nanoscale. Precession electron diffraction (PED) experiments were applied for the nanoscale structure analysis of the quenched high‐pressure phase. The proposed monoclinic model from PED experiments provided an improved fit to the X‐ray patterns, especially after introducing atomic anisotropic displacement parameters and partial occupancy of Cr atoms. Atomic resolution STEM and simulations were conducted to identify variations in the Cr‐atom site‐occupancy factor. No significant variations were observed experimentally for several zone axes. The magnetic properties of the novel CrTe3 phase were investigated through temperature‐ and field‐dependent magnetization measurements. In order to understand these properties, auxiliary theoretical investigations have been performed by first‐principles electronic structure calculations and Monte Carlo simulations. The obtained results allow the observed magnetization behavior to be interpreted as the consequence of competition between the applied magnetic field and the Cr–Cr exchange interactions, leading to a decrease of the magnetization towards T = 0 K typical for antiferromagnetic systems, as well as a field‐induced enhanced magnetization around the critical temperature due to the high magnetic susceptibility in this region. [ABSTRACT FROM AUTHOR]

Template condensation of 2-acetylpyridineoxime with butyl ester of 1,3-propanediboronic acid in the presence of iron(II) affords a poorly separable mixture of complex products. Similar results were observed when Fe3+ ions were used for cross-linking in place of the diboronic acid. Prolonged crystallization of these mixtures gave crystals of perchlorate salts of a FeIIFeIIIFeII-trinuclear hexapyridineoximate cation and of an analogous FeIIFeIIFeII-intracomplex that crystallize with chloroform and dichloromethane solvent molecules, respectively. Both complexes were characterized by synchrotron single-crystal X-ray diffraction (XRD) experiments. The Fe–N distances of the two 'terminal' iron cations are virtually the same between these trinuclear complexes and unambiguously support assignments of oxidation number +2 and low-spin state (S = 0). The centers of the FeN6-coordination polyhedra adopt geometries resembling trigonal antiprisms with distortion angles φ of approximately 40°. The FeO6-coordination polyhedra possess an almost ideal Oh geometry with φ close to 60°. Each of these iron(II) or iron(III) µ3-metallocenters acts as a bifunctional Lewis acid that cross-links two pseudoclathrochelate entities, formed by the 'terminal' iron(II) ions, to give an almost linear (the corresponding intramolecular Fe(2)...Fe(1)...Fe(3) angles are close to 180°) helical cation or intracomplex. [ABSTRACT FROM AUTHOR]

The influence of the crystal synthesis method on the crystallographic structure of caffeine–citric acid cocrystals was analyzed thanks to the synthesis of a new polymorphic form of the cocrystal. In order to compare the new form to the already known forms, the crystal structure of the new cocrystal (C8H10N4O2·C6H8O7) was solved by powder X‐ray diffraction thanks to synchrotron experiments. The structure determination was performed using 'GALLOP', a recently developed hybrid approach based on a local optimization with a particle swarm optimizer, particularly powerful when applied to the structure resolution of materials of pharmaceutical interest, compared to classical Monte‐Carlo simulated annealing. The final structure was obtained through Rietveld refinement, and first‐principles density functional theory (DFT) calculations were used to locate the H atoms. The symmetry is triclinic with the space group P and contains one molecule of caffeine and one molecule of citric acid per asymmetric unit. The crystallographic structure of this cocrystal involves different hydrogen‐bond associations compared to the already known structures. The analysis of these hydrogen bonds indicates that the cocrystal obtained here is less stable than the cocrystals already identified in the literature. This analysis is confirmed by the determination of the melting point of this cocrystal, which is lower than that of the previously known cocrystals. [ABSTRACT FROM AUTHOR]

We report the studies of structure and properties of a quasi-one-dimensional (quasi-1D) compound ${\rm BaTiS}_{3}$ BaTiS 3 under pressure. The poly-crystalline samples are synthesized by solid-state reaction method and single-crystalline samples are produced by chemical vapor transport method. The XRD measurement under ambient pressure confirms the hexagonal structure, which consists of face-sharing octahedral ${\rm TiS}_{6}$ TiS 6 chains along c-axis and displays a quasi-1D feature. When applying pressure, the synchrotron X-ray diffraction experiments show that the sample undergoes a phase transition from hexagonal phase to orthorhombic phase at around 10 GPa due to the zig–zag deformation of ${\rm TiS}_{6}$ TiS 6 chains, while the quasi-1D structure is reserved. At ambient pressure, ${\rm BaTiS}_{3}$ BaTiS 3 exhibits an insulating behavior with a band gap about 0.273 eV. When applying pressure, the sample undergoes a crossover from insulator to metal due to the enhancement of inter-chain electron hopping. [ABSTRACT FROM AUTHOR]

Since synchrotron polarization fluctuations are related to the fundamental properties of the magnetic field, we propose the polarization intensity variance to measure the Galactic interstellar medium (ISM) magnetization. We confirm the method's applicability by comparing it with the polarization angle dispersion and its reliability by measuring the underlying Alfvénic Mach number of magnetohydrodynamic turbulence. With the finding of the power-law relation of A ∝ M A 2 between polarization intensity variance A and Alfvénic Mach number M A, we apply the new technique to the Canadian Galactic Plane Survey data, achieving the Alfvénic Mach number of the Galactic ISM. Our results show that the low-latitude Galactic ISM is dominated by sub-Alfénic turbulence, with M A approximately between 0.5 and 1.0. [ABSTRACT FROM AUTHOR]