Anomalous Impact of Mechanochemical Treatment on the Na-ion Conductivity of Sodium Closo-Carbadodecaborate Probed by X-Ray Raman Scattering Spectroscopy.

Solid-state sodium ion conductors are crucial for the next generation of all-solid-state sodium batteries with high capacity, low cost, and improved safety. Sodium closo-carbadodecaborate (NaCB11 H12 ) is an attractive Na-ion conductor owing to its high thermal, electrochemical, and interfacial stability. Mechanical milling has recently been shown to increase conductivity by five orders of magnitude at room temperature, making it appealing for application in all-solid-state sodium batteries. Intriguingly, milling longer than 2 h led to a significant decrease in conductivity. In this study, X-ray Raman scattering (XRS) spectroscopy is used to probe the origin of the anomalous impact of mechanical treatment on the ionic conductivity of NaCB11 H12 . The B, C, and Na K-edge XRS spectra are successfully measured for the first time, and ab initio calculations are employed to interpret the results. The experimental and computational results reveal that the decrease in ionic conductivity upon prolonged milling is due to the increased proximity of Na to the CB11 H12 cage, caused by severe distortion of the long-range structure. Overall, this work demonstrates how the XRS technique, allowing investigation of low Z elements such as C and B in the bulk, can be used to acquire valuable information on the electronic structure of solid electrolytes and battery materials in general.

Interface Diffusion and Compatibility of (Ba,La)FeO3-δ Perovskite Electrodes in Contact with Barium Zirconate and Ceria.

Ba1-xLaxFeO3-δ perovskites (BLF) capable of conducting electrons, protons, and oxygen ions are promising oxygen electrodes for efficient solid oxide cells (fuel cells or electrolyzers), an integral part of prospected large-scale power-to-gas energy storage systems. We investigated the compatibility of BLF with lanthanum content between 5 and 50%, in contact with oxide-ion-conducting Ce0.8Gd0.2O2-δ and proton-conducting BaZr0.825Y0.175O3-δ electrolytes, annealing the electrode-electrolyte bilayers at high temperature to simulate thermal stresses of fabrication and prolonged operation. By employing both bulk X-ray diffraction and synchrotron X-ray microspectroscopy, we present a space-resolved picture of the interaction between electrode and electrolyte as what concerns cation interdiffusion, exsolution, and phase stability. We found that the phase stability of BLF in contact with other phases is correlated with the Goldschmidt tolerance factor, in turn determined by the La/Ba ratio, and appropriate doping strategies with oversized cations (Zn2+, Y3+) could improve structural stability. While extensive reactivity and/or interdiffusion was often observed, we put forward that most products of interfacial reactions, including proton-conducting Ba(Ce,Gd)O3-δ and mixed-conducting (Ba,La)(Fe,Zr,Y)O3-δ, may not be very detrimental for practical cell operation.

Modelling the structural disorder in trigonal-prismatic coordinated transition metal dichalcogenides.

Trigonal-prismatic coordinated transition metal dichalcogenides (TMDCs) are formed from stacked (chalcogen)-(transition metal)-(chalcogen) triple layers, where the chemical bond is covalent within the triple layers and van der Waals (vdW) forces are effective between the layers. Bonding is at the origin of the great interest in these compounds, which are used as 2D materials in applications such as catalysis, electronics, photoelectronics, sensors, batteries and thermoelectricity. This paper addresses the issue of modelling the structural disorder in multilayer TMDCs. The structural model takes into account stacking faults, correlated displacement of atoms and average crystallite size/shape, and is assessed by simulation of the X-ray diffraction pattern and fitting to the experimental data relative to a powdered sample of MoS2 exfoliated and restacked via lithiation. From fitting, an average crystallite size of about 50 Å, nearly spherical crystallites and a definite probability of deviation from the fully eclipsed atomic arrangement present in the ordered structure are determined. The increased interlayer distance and correlated intralayer and interlayer atomic displacement are attributed to the presence of lithium intercalated in the vdW gap between triple layers (Li/Mo molar ratio of about 0.06). The model holds for the whole class of trigonal-prismatic coordinated TMDCs, and is suitably flexible to take into account different preparation routes.

Relationship between lumbar lordosis, pelvic parameters, PI-LL mismatch and outcome after short fusion surgery for lumbar degenerative disease. Literature review, rational and presentation of public study protocol: RELApSE study (registry for evaluation of lumbar artrodesis sagittal alignEment).

Background: Vertebral arthrodesis for degenerative pathology of the lumbar spine still remains burdened by clinical problems with significant negative results. The introduction of the sagittal balance assessment with the evaluation of the meaning of pelvic parameters and spinopelvic (PI-LL) mismatch offered new evaluation criteria for this widespread pathology, but there is a lack of consistent evidence on long-term outcome. Methods: The authors performed an extensive systematic review of literature, with the aim to identify all potentially relevant studies about the role and usefulness of the restoration or the assessment of Sagittal balance in lumbar degenerative disease. They present the study protocol RELApSE (NCT05448092 ID) and discuss the rationale through a comprehensive literature review. Results: From the 237 papers on this topic, a total of 176 articles were selected in this review. The analysis of these literature data shows sparse and variable evidence. There are no observations or guidelines about the value of lordosis restoration or PI-LL mismatch. Most of the works in the literature are retrospective, monocentric, based on small populations, and often address the topic evaluation partially. Conclusions: The RELApSE study is based on the possibility of comparing a heterogeneous population by pathology and different surgical technical options on some homogeneous clinical and anatomic-radiological measures aiming to understanding the value that global lumbar and segmental lordosis, distribution of lordosis, pelvic tilt, and PI-LL mismatch may have on clinical outcome in lumbar degenerative pathology and on the occurrence of adjacent segment disease.

Ionogels Derived from Fluorinated Ionic Liquids to Enhance Aqueous Drug Solubility for Local Drug Administration.

Gelatin is a popular biopolymer for biomedical applications due to its harmless impact with a negligible inflammatory response in the host organism. Gelatin interacts with soluble molecules in aqueous media as ionic counterparts such as ionic liquids (ILs) to be used as cosolvents to generate the so-called Ionogels. The perfluorinated IL (FIL), 1-ethyl-3-methylpyridinium perfluorobutanesulfonate, has been selected as co-hydrosolvent for fish gelatin due to its low cytotoxicity and hydrophobicity aprotic polar structure to improve the drug aqueous solubility. A series of FIL/water emulsions with different FIL content and their corresponding shark gelatin/FIL Ionogel has been designed to enhance the drug solubility whilst retaining the mechanical structure and their nanostructure was probed by simultaneous SAXS/WAXS, FTIR and Raman spectroscopy, DSC and rheological experiments. Likewise, the FIL assisted the solubility of the antitumoural Doxorubicin whilst retaining the performing mechanical properties of the drug delivery system network for the drug storage as well as the local administration by a syringe. In addition, the different controlled release mechanisms of two different antitumoral such as Doxorubicin and Mithramycin from two different Ionogels formulations were compared to previous gelatin hydrogels which proved the key structure correlation required to attain specific therapeutic dosages.

Modeling bismuth insertion in 1D hybrid lead halide TMSO(PbxBiy)I3pseudo-perovskites.

The structures of the disordered 1D (pseudo-)perovskites of general TMSO(PbxBiy)I3formulation [TMSO = (CH3)3SO+], obtained by doping the TMSOPbI3species with Bi3+ions, are investigated through the formulation of a statistical model of correlated disorder, which addresses the sequences of differently occupied BI6face-sharing octahedra (B = Pb, Bi or vacant site) within ideally infinite [(BI3)-]nchains. The x-ray diffraction patterns simulated on the basis of the model are matched to the experimental traces, which show many broad peaks with awkward (nearly trapezoidal) shapes, under the assumption that the charge balance is fully accomplished within each chain. The analysis allowed to establish a definite tendency of the metal species to cluster as pure Pb and Bi sequences. The application of the model is discussed critically, in particular as what concerns the possibility that further B-site neighbors beyond the second may influence the overall B-site occupancies.

Hydration in aqueous NaCl.

Atomistic details about the hydration of ions in aqueous solutions are still debated due to the disordered and statistical nature of the hydration process. However, many processes from biology, physical chemistry to materials sciences rely on the complex interplay between solute and solvent. Oxygen K-edge X-ray excitation spectra provide a sensitive probe of the local atomic and electronic surrounding of the excited sites. We used ab initio molecular dynamics simulations together with extensive spectrum calculations to relate the features found in experimental oxygen K-edge spectra of a concentration series of aqueous NaCl with the induced structural changes upon solvation of the salt and distill the spectral fingerprints of the first hydration shells around the Na+- and Cl--ions. By this combined experimental and theoretical approach, we find the strongest spectral changes to indeed result from the first hydration shells of both ions and relate the observed shift of spectral weight from the post- to the main-edge to the origin of the post-edge as a shape resonance.

Multifunctional PLA/Gelatin Bionanocomposites for Tailored Drug Delivery Systems.

A series of bionanocomposites composed of shark gelatin hydrogels and PLA nanoparticles featuring different nanostructures were designed to generate multifunctional drug delivery systems with tailored release rates required for personalized treatment approaches. The global conception of the systems was considered from the desired customization of the drug release while featuring the viscoelastic properties needed for their ease of storage and posterior local administration as well as their biocompatibility and cell growth capability for the successful administration at the biomolecular level. The hydrogel matrix offers the support to develop a direct thermal method to convert the typical kinetic trapped nanostructures afforded by the formulation method whilst avoiding the detrimental nanoparticle agglomeration that diminishes their therapeutic effect. The nanoparticles generated were successfully formulated with two different antitumoral compounds (doxorubicin and dasatinib) possessing different structures to prove the loading versatility of the drug delivery system. The bionanocomposites were characterized by several techniques (SEM, DLS, RAMAN, DSC, SAXS/WAXS and rheology) as well as their reversible sol-gel transition upon thermal treatment that occurs during the drug delivery system preparation and the thermal annealing step. In addition, the local applicability of the drug delivery system was assessed by the so-called "syringe test" to validate both the storage capability and its flow properties at simulated physiological conditions. Finally, the drug release profiles of the doxorubicin from both the PLA nanoparticles or the bionanocomposites were analyzed and correlated to the nanostructure of the drug delivery system.

Characterization of Tuna Gelatin-Based Hydrogels as a Matrix for Drug Delivery.

The skin of yellowfin tuna is one of the fishery industry solid residues with the greatest potential to add extra value to its circular economy that remains yet unexploited. Particularly, the high collagen content of fish skin allows generating gelatin by hydrolysis, which is ideal for forming hydrogels due to its biocompatibility and gelling capability. Hydrogels have been used as drug carriers for local administration due to their mechanical properties and drug loading capacity. Herein, novel tuna gelatin hydrogels were designed as drug vehicles with two structurally different antitumoral model compounds such as Doxorubicin and Crocin to be administrated locally in tissues with complex human anatomies after surgical resection. The characterization by gel permeation chromatography (GPC) of purified gelatin confirmed their heterogeneity composition, exhibiting three major bands that correspond to the ß and α chains along with high molecular weight species. In addition, the Fourier Transform Infrared (FT-IR) spectra of gelatin probed the secondary structure of the gelatin showing the simultaneous existence of α helix, ß sheet, and random coil structures. Morphological studies at different length scales were performed by a multi-technique approach using SAXS/WAXS, AFM and cryo-SEM that revealed the porous network formed by the interaction of gelatin planar aggregates. In addition, the sol-gel transition, as well as the gelation point and the hydrogel strength, were studied using dynamic rheology and differential scanning calorimetry. Likewise, the loading and release profiles followed by UV-visible spectroscopy indicated that the novel gelatin hydrogels improve the drug release of Doxorubicin and Crocin in a sustained fashion, indicating the structure-function importance in the material composition.

On the effect of metal loading on the reducibility and redox chemistry of ceria supported Pd catalysts.

The effect of Pd loading on the redox characteristics of a ceria support was examined using in situ Pd K-edge XAS, Ce L3-edge XAS and in situ X-ray diffraction techniques. Analysis of the data obtained from these techniques indicates that the onset temperature for the partial reduction of Ce(IV) to Ce(III), by exposure to H2, varies inversely with the loading of Pd. Whilst the onset and completion temperatures of the reduction of Ce(IV) to Ce(III) are different, both samples yield the same maximal fraction of Ce(III) formation independent of Pd loading. Furthermore, the partial reduction of Ce is found to be concurrent with the reduction of PdO and demonstrated that the presence of metallic Pd is necessary for the reduction of the CeO2 support. Upon passivation by room temperature oxidation, a full oxidation of the reduced ceria support was observed. However, only a mild surface oxidation of Pd was identified. The mild passivation of the Pd is found to lead to a highly reactive sample upon a second reduction by H2. The onset of the reduction of Pd and Ce has been demonstrated to be independent of the Pd loading after a mild passivation with both samples exhibiting near room temperature reduction in the presence of H2.

Understanding the Preparation and Reactivity of Mo/ZSM-5 Methane Dehydroaromatization Catalysts.

Methane dehydroaromatization is a promising reaction for the direct conversion of methane to liquid hydrocarbons. The active sites and the mechanism of this reaction remain controversial. This work is focused on the operando X-ray absorption near edge structure spectroscopy analysis of conventional Mo/ZSM-5 catalysts during their whole lifetime. Complemented by other characterization techniques, we derived spectroscopic descriptors of molybdenum precursor decomposition and its exchange with zeolite Brønsted acid sites. We found that the reduction of Mo-species proceeds in two steps and the active sites are of similar nature, regardless of the Mo content. Furthermore, the ZSM-5 unit cell contracts at the beginning of the reaction, which coincides with benzene formation and it is likely related to the formation of hydrocarbon pool intermediates. Finally, although reductive regeneration of used catalysts via methanation is less effective as compared to combustion of coke, it does not affect the structure of the catalysts.

Data Mining of Polymer Phase Transitions upon Temperature Changes by Small and Wide-Angle X-ray Scattering Combined with Raman Spectroscopy.

The complex physical transformations of polymers upon external thermodynamic changes are related to the molecular length of the polymer and its associated multifaceted energetic balance. The understanding of subtle transitions or multistep phase transformation requires real-time phenomenological studies using a multi-technique approach that covers several length-scales and chemical states. A combination of X-ray scattering techniques with Raman spectroscopy and Differential Scanning Calorimetry was conducted to correlate the structural changes from the conformational chain to the polymer crystal and mesoscale organization. Current research applications and the experimental combination of Raman spectroscopy with simultaneous SAXS/WAXS measurements coupled to a DSC is discussed. In particular, we show that in order to obtain the maximum benefit from simultaneously obtained high-quality data sets from different techniques, one should look beyond traditional analysis techniques and instead apply multivariate analysis. Data mining strategies can be applied to develop methods to control polymer processing in an industrial context. Crystallization studies of a PVDF blend with a fluoroelastomer, known to feature complex phase transitions, were used to validate the combined approach and further analyzed by MVA.

The rise of X-ray spectroscopies for unveiling the functional mechanisms in batteries.

Synchrotron-based techniques have been key tools in the discovery, understanding, and development of battery materials. In this review, some of the most suitable X-ray spectroscopy related techniques employed for addressing diverse scientific cases connected to battery science are highlighted. Furthermore, current shortcomings, intrinsic limitations, and ongoing challenges of individual techniques are pointed out, providing an outlook of future trends that are relevant to the battery research community. In particular, the ongoing development of next generation synchrotrons, machine learning algorithms for data analysis and combined theoretical/experimental approaches will enhance the already powerful assets of these advanced spectroscopic methods.

Identification of the Calcium, Aluminum, and Magnesium Distribution within Millimeter-Sized Extraterrestrial Materials Using Nonresonant X-ray Raman Spectroscopy in Preparation for the Hayabusa2 Sample Return Mission.

The nondestructive investigation of millimeter-sized meteoritic materials is often hindered by self-absorption effects. Using X-ray-based analytical methods, the information depth for many elements (Z < 30) is in the range of up to only a few hundred micrometers, and for low-Z elements (Z < 20), this is reduced even further to only a few tens of micrometers. However, the investigation of these low-Z elements, in particular calcium, aluminum, and magnesium, is of great importance to planetary geologists and cosmochemists, as these elements are regularly used to characterize and identify specific features of interest in extraterrestrial materials, especially primitive chondritic material. In this work, nonresonant inelastic X-ray scattering from core electrons was performed at beamline ID20 of the ESRF in a direct tomography approach in order to visualize these low-Z elements within the millimeter-sized meteoritic samples. The obtained 3D elemental distribution volumes were compared to results from X-ray fluorescence-CT and absorption CT experiments and were found to be in good agreement. Additionally, several regions of interest could be identified within the inelastic scattering volumes, containing information that is not available through the other presented means. As such, the proposed approach presents a valuable tool for the nondestructive investigation of low-Z elemental distributions within millimeter-sized extraterrestrial materials, such as the samples of the Hayabusa2 sample return mission.

Augmented Reality in Medical Practice: From Spine Surgery to Remote Assistance.

Background: While performing surgeries in the OR, surgeons and assistants often need to access several information regarding surgical planning and/or procedures related to the surgery itself, or the accessory equipment to perform certain operations. The accessibility of this information often relies on the physical presence of technical and medical specialists in the OR, which is increasingly difficult due to the number of limitations imposed by the COVID emergency to avoid overcrowded environments or external personnel. Here, we analyze several scenarios where we equipped OR personnel with augmented reality (AR) glasses, allowing a remote specialist to guide OR operations through voice and ad-hoc visuals, superimposed to the field of view of the operator wearing them. Methods: This study is a preliminary case series of prospective collected data about the use of AR-assistance in spine surgery from January to July 2020. The technology has been used on a cohort of 12 patients affected by degenerative lumbar spine disease with lumbar sciatica co-morbidities. Surgeons and OR specialists were equipped with AR devices, customized with P2P videoconference commercial apps, or customized holographic apps. The devices were tested during surgeries for lumbar arthrodesis in a multicenter experience involving author's Institutions. Findings: A total number of 12 lumbar arthrodesis have been performed while using the described AR technology, with application spanning from telementoring (3), teaching (2), surgical planning superimposition and interaction with the hologram using a custom application for Microsoft hololens (1). Surgeons wearing the AR goggles reported a positive feedback as for the ergonomy, wearability and comfort during the procedure; being able to visualize a 3D reconstruction during surgery was perceived as a straightforward benefit, allowing to speed-up procedures, thus limiting post-operational complications. The possibility of remotely interacting with a specialist on the glasses was a potent added value during COVID emergency, due to limited access of non-resident personnel in the OR. Interpretation: By allowing surgeons to overlay digital medical content on actual surroundings, augmented reality surgery can be exploited easily in multiple scenarios by adapting commercially available or custom-made apps to several use cases. The possibility to observe directly the operatory theater through the eyes of the surgeon might be a game-changer, giving the chance to unexperienced surgeons to be virtually at the site of the operation, or allowing a remote experienced operator to guide wisely the unexperienced surgeon during a procedure.

Zinc determines dynamical properties and aggregation kinetics of human insulin.

Protein aggregation is a widespread process leading to deleterious consequences in the organism, with amyloid aggregates being important not only in biology but also for drug design and biomaterial production. Insulin is a protein largely used in diabetes treatment, and its amyloid aggregation is at the basis of the so-called insulin-derived amyloidosis. Here, we uncover the major role of zinc in both insulin dynamics and aggregation kinetics at low pH, in which the formation of different amyloid superstructures (fibrils and spherulites) can be thermally induced. Amyloid aggregation is accompanied by zinc release and the suppression of water-sustained insulin dynamics, as shown by particle-induced x-ray emission and x-ray absorption spectroscopy and by neutron spectroscopy, respectively. Our study shows that zinc binding stabilizes the native form of insulin by facilitating hydration of this hydrophobic protein and suggests that introducing new binding sites for zinc can improve insulin stability and tune its aggregation propensity.

Solid-Solid Interfaces in Protonic Ceramic Devices: A Critical Review.

The literature concerning protonic ceramic devices is critically reviewed focusing the reader's attention on the structure, composition, and phenomena taking place at solid-solid interfaces. These interfaces play a crucial role in the overall device performance, and the relevance of understanding the phenomena taking place at the interfaces for the further improvement of electrochemical protonic ceramic devices is therefore stressed. The grain boundaries and heterostructures in electrolytic membranes, the electrode-electrolyte contacts, and the interfaces within composite anode and cathode materials are all considered, with specific concern to advanced techniques of characterization and to computational modeling by ab initio approaches. An outlook about future developments and improvements highlights the necessity of a deeper insight into the advanced analysis of what happens at the solid-solid interfaces and of in situ/operando investigations that are presently sporadic in the literature on protonic ceramic devices.

In situ observation of nanolite growth in volcanic melt: A driving force for explosive eruptions.

Although gas exsolution is a major driving force behind explosive volcanic eruptions, viscosity is critical in controlling the escape of bubbles and switching between explosive and effusive behavior. Temperature and composition control melt viscosity, but crystallization above a critical volume (>30 volume %) can lock up the magma, triggering an explosion. Here, we present an alternative to this well-established paradigm by showing how an unexpectedly small volume of nano-sized crystals can cause a disproportionate increase in magma viscosity. Our in situ observations on a basaltic melt, rheological measurements in an analog system, and modeling demonstrate how just a few volume % of nanolites results in a marked increase in viscosity above the critical value needed for explosive fragmentation, even for a low-viscosity melt. Images of nanolites from low-viscosity explosive eruptions and an experimentally produced basaltic pumice show syn-eruptive growth, possibly nucleating a high bubble number density.

On the Nature of Charge-Injecting Contacts in Organic Field-Effect Transistors.

Organic field-effect transistors (OFETs) are key enabling devices for plastic electronics technology, which has a potentially disruptive impact on a variety of application fields, such as health, safety, and communication. Despite the tremendous advancements in understanding the OFET working mechanisms and device performance, further insights into the complex correlation between the nature of the charge-injecting contacts and the electrical characteristics of devices are still necessary. Here, an in-depth study of the metal-organic interfaces that provides a direct correlation to the performance of OFET devices is reported. The combination of synchrotron X-ray spectroscopy, atomic force microscopy, electron microscopy, and theoretical simulations on two selected electron transport organic semiconductors with tailored chemical structures allows us to gain insights into the nature of the injecting contacts. This multiple analysis repeated at the different stages of contact formation provides a clear picture on the synergy between organic/metal interactions, interfacial morphology, and structural organization of the electrode. The simultaneous synchrotron X-ray experiments and electrical measurements of OFETs in operando uncovers how the nature of the charge-injecting contacts has a direct impact on the injection potential of OFETs.

Fabrication of highly ordered Cu2+/Fe3+ decorated polyhedral oligomeric silsesquioxane hybrids: How metal coordination influences structure.

Incorporation of isolated metal centers into well-organized nanostructures is a promising route in the development of the next generation of chemical, magnetic and electronic devices. In this work, a layer-by-layer protocol to grow highly ordered thin films of metal-decorated organic-inorganic cage-like polyhedral oligomeric silsesquioxane (POSS) is introduced. The key strategy is to use metal ions (Cu2+ or Fe3+) as linker for the amino-functionalized cage-like POSS, which are self-assembled between arachidic acid layers during Langmuir-Schaefer deposition. The Langmuir-Schaefer films are examined by X-ray photoelectron spectroscopy, X-ray diffraction, grazing incidence wide-angle X-ray scattering and extended X-ray absorption fine structure in order to understand how the coordination of metal ions influences the structure in the course of the layer-by-layer formation of the films.