Speech Reception in Young Children with Autism Is Selectively Indexed by a Neural Oscillation Coupling Anomaly.

Communication difficulties are one of the core criteria in diagnosing autism spectrum disorder (ASD), and are often characterized by speech reception difficulties, whose biological underpinnings are not yet identified. This deficit could denote atypical neuronal ensemble activity, as reflected by neural oscillations. Atypical cross-frequency oscillation coupling, in particular, could disrupt the joint tracking and prediction of dynamic acoustic stimuli, a dual process that is essential for speech comprehension. Whether such oscillatory anomalies already exist in very young children with ASD, and with what specificity they relate to individual language reception capacity is unknown. We collected neural activity data using electroencephalography (EEG) in 64 very young children with and without ASD (mean age 3; 17 females, 47 males) while they were exposed to naturalistic-continuous speech. EEG power of frequency bands typically associated with phrase-level chunking (δ, 1-3 Hz), phonemic encoding (low-γ, 25-35 Hz), and top-down control (ß, 12-20 Hz) were markedly reduced in ASD relative to typically developing (TD) children. Speech neural tracking by δ and θ (4-8 Hz) oscillations was also weaker in ASD compared with TD children. After controlling gaze-pattern differences, we found that the classical θ/γ coupling was replaced by an atypical ß/γ coupling in children with ASD. This anomaly was the single most specific predictor of individual speech reception difficulties in ASD children. These findings suggest that early interventions (e.g., neurostimulation) targeting the disruption of ß/γ coupling and the upregulation of θ/γ coupling could improve speech processing coordination in young children with ASD and help them engage in oral interactions.SIGNIFICANCE STATEMENT Very young children already present marked alterations of neural oscillatory activity in response to natural speech at the time of autism spectrum disorder (ASD) diagnosis. Hierarchical processing of phonemic-range and syllabic-range information (θ/γ coupling) is disrupted in ASD children. Abnormal bottom-up (low-γ) and top-down (low-ß) coordination specifically predicts speech reception deficits in very young ASD children, and no other cognitive deficit.

Fitting Multiplet Simulations to L-Edge XAS Spectra of Transition-Metal Complexes Using an Adaptive Grid Algorithm.

A new methodology based on an adaptive grid algorithm followed by an analysis of the ground state from the fit parameters is presented to analyze and interpret experimental XAS L2,3-edge data. The fitting method is tested first in a series of multiplet calculations for d0-d7 systems and for which the solution is known. In most cases, the algorithm is able to find the solution, except for a mixed-spin Co2+ Oh complex, where it instead revealed a correlation between the crystal field and the electron repulsion parameters near spin-crossover transition points. Furthermore, the results for the fitting of previously published experimental data sets on CaO, CaF2, MnO, LiMnO2, and Mn2O3 are presented and their solution discussed. The presented methodology has allowed the evaluation of the Jahn-Teller distortion in LiMnO2, which is consistent with the observed implications in the development of batteries, which use this material. Moreover, a follow-up analysis of the ground state in Mn2O3 has demonstrated an unusual ground state for the highly distorted site which would be impossible to optimize in a perfect octahedral environment. Ultimately, the presented methodology can be used in the analysis of X-ray absorption spectroscopy data measured at the L2,3-edge for a large number of materials and molecular complexes of first-row transition metals and can be expanded to the analysis of other X-ray spectroscopic data in future studies.

Millisecond timescale reactions observed via X-ray spectroscopy in a 3D microfabricated fused silica mixer. Corrigendum.

A figure in the article by Huyke et al. [(2021), J. Synchrotron Rad. 28, 1100-1113] is corrected.

Brain functional connectivity dynamics at rest in the aftermath of affective and cognitive challenges.

Carry-over effects on brain states have been reported following emotional and cognitive events, persisting even during subsequent rest. Here, we investigated such effects by identifying recurring co-activation patterns (CAPs) in neural networks at rest with functional magnetic resonance imaging (fMRI). We compared carry-over effects on brain-wide CAPs at rest and their modulation after both affective and cognitive challenges. Healthy participants underwent fMRI scanning during emotional induction with negative valence and performed cognitive control tasks, each followed by resting periods. Several CAPs, overlapping with the default-mode (DMN), salience, dorsal attention, and social cognition networks were impacted by both the preceding events (movie or task) and the emotional valence of the experimental contexts (neutral or negative), with differential dynamic fluctuations over time. Temporal metrics of DMN-related CAPs were altered after exposure to negative emotional content (compared to neutral) and predicted changes in subjective affect on self-reported scores. In parallel, duration rates of another attention-related CAP increased with greater task difficulty during the preceding cognitive control condition, specifically in the negative context. These findings provide new insights on the anatomical organization and temporal inertia of functional brain networks, whose expression is differentially shaped by emotional states, presumably mediating adaptive homeostatic processes subsequent to behaviorally challenging events.

Millisecond timescale reactions observed via X-ray spectroscopy in a 3D microfabricated fused silica mixer.

Determination of electronic structures during chemical reactions remains challenging in studies which involve reactions in the millisecond timescale, toxic chemicals, and/or anaerobic conditions. In this study, a three-dimensionally (3D) microfabricated microfluidic mixer platform that is compatible with time-resolved X-ray absorption and emission spectroscopy (XAS and XES, respectively) is presented. This platform, to initiate reactions and study their progression, mixes a high flow rate (0.50-1.5 ml min-1) sheath stream with a low-flow-rate (5-90 µl min-1) sample stream within a monolithic fused silica chip. The chip geometry enables hydrodynamic focusing of the sample stream in 3D and sample widths as small as 5 µm. The chip is also connected to a polyimide capillary downstream to enable sample stream deceleration, expansion, and X-ray detection. In this capillary, sample widths of 50 µm are demonstrated. Further, convection-diffusion-reaction models of the mixer are presented. The models are experimentally validated using confocal epifluorescence microscopy and XAS/XES measurements of a ferricyanide and ascorbic acid reaction. The models additionally enable prediction of the residence time and residence time uncertainty of reactive species as well as mixing times. Residence times (from initiation of mixing to the point of X-ray detection) during sample stream expansion as small as 2.1 ± 0.3 ms are also demonstrated. Importantly, an exploration of the mixer operational space reveals a theoretical minimum mixing time of 0.91 ms. The proposed platform is applicable to the determination of the electronic structure of conventionally inaccessible reaction intermediates.

Sociodemographic Characteristics, Gender Identification, and Gender Affirmation Pathways in Transgender People: A Survey Study in Chile.

Understanding the internal diversity of transgender communities is essential for developing optimal, inclusive policies and service provision. To date, research on this topic remains scarce in Chile. We conducted a survey study describing sociodemographic characteristics (age, sex assigned at birth, onset age, nationality, education, sex work, having a partner, having children, sexual orientation, religiousness, gender identification, and gender affirmation pathways). A snowball sample of 377 self-identified transgender adults living in Chile (Mage = 31.88, rangeage = 18-67) was collected for the purpose of this study. According to their sex assigned at birth, 139 participants were female and 238 male. Results revealed that sex assigned at birth was significantly associated with almost all the sociodemographic variables. Eight gender self-identification categories were obtained based on self-declaration. These gender identification categories varied according to sex assigned at birth. Finally, four patterns (clusters) of gender affirmative actions were identified among participants. These patterns indicated that the longer the gender affirmation pathway time, the greater the invasiveness level of the medical procedures used. Sex assigned at birth moderated the association between gender affirmation pathways and gender identity categories. Results were discussed highlighting the heterogeneity found in terms of sociodemographic characteristics, gender identification, and gender affirmation pathways.

The clinical relevance of the microbiome when managing paediatric infectious diseases-Narrative review.

In recent years, the field of infectious diseases has been hit by the overwhelming amount of information generated while the human microbiome is being disentangled. Based on the interaction between the microbiota and the immune system, the implications regarding infectious diseases are probably major and remain a challenge. AIMS: This review was conceived as a comprehensive tool to provide an overview of the available evidence regarding the influence of the microbiome on infectious diseases in children. METHODS: We present the main findings aroused from microbiome research in prevention, diagnosis and treatment of infectious disease under a paediatric perspective, to inform clinicians of the potential relevance of microbiome-related knowledge for translation to clinical practice. RESULTS AND CONCLUSION: The evidence shown in this review highlights the numerous research gaps ahead and supports the need to move forward to integrating the so-called microbiome thinking into our routine clinical practice.

Nature of cobalt species during the in situ sulfurization of Co(Ni)Mo/Al2O3 hydrodesulfurization catalysts.

The evolution in local structure and electronic properties of cobalt was investigated during in situ sulfurization. Using a combination of 1s X-ray absorption (XAS) and 1s3p resonant inelastic X-ray scattering (RIXS), the valence, coordination and symmetry of cobalt ions were tracked in two cobalt-promoted molybdenum oxide precursors of the hydrodesulfurization catalyst system, namely Co-Mo/Al2O3 and Co-Ni-Mo/Al2O3. Extended X-ray absorption fine structure shows that the Co-O bonds were replaced with Co-S bonds as a function of reaction temperature. The cobalt K pre-edge intensity shows that the symmetry of cobalt was modified from Co3+ Oh and Co2+ Oh to a Co2+ ion where the inversion symmetry is broken, in agreement with a square-pyramidal site. The 1s3p RIXS data revealed the presence of an intermediate cobalt oxy-sulfide species. This species was not detected from XAS and was determined from the increased information obtained from the 1s3p RIXS data. The cobalt XAS and RIXS data show that nickel has a significant influence on the formation of the cobalt oxy-sulfide intermediate species prior to achieving the fully sulfided state at T > 400°C.

Strain-Engineered Oxygen Vacancies in CaMnO3 Thin Films.

We demonstrate a novel pathway to control and stabilize oxygen vacancies in complex transition-metal oxide thin films. Using atomic layer-by-layer pulsed laser deposition (PLD) from two separate targets, we synthesize high-quality single-crystalline CaMnO3 films with systematically varying oxygen vacancy defect formation energies as controlled by coherent tensile strain. The systematic increase of the oxygen vacancy content in CaMnO3 as a function of applied in-plane strain is observed and confirmed experimentally using high-resolution soft X-ray absorption spectroscopy (XAS) in conjunction with bulk-sensitive hard X-ray photoemission spectroscopy (HAXPES). The relevant defect states in the densities of states are identified and the vacancy content in the films quantified using the combination of first-principles theory and core-hole multiplet calculations with holistic fitting. Our findings open up a promising avenue for designing and controlling new ionically active properties and functionalities of complex transition-metal oxides via strain-induced oxygen-vacancy formation and ordering.

Local vs Nonlocal States in FeTiO3 Probed with 1s2pRIXS: Implications for Photochemistry.

Metal-metal charge transfer (MMCT) is expected to be the main mechanism that enables the harvesting of solar light by iron-titanium oxides for photocatalysis. We have studied FeTiO3 as a model compound for MMCT with 1s2pRIXS at the Fe K-edge. The high-energy resolution XANES enables distinguishing five pre-edge features. The three first well distinct RIXS features are assigned to electric quadrupole transitions to the localized Fe* 3d states, shifted to lower energy by the 1s core-hole. Crystal field multiplet calculations confirm the speciation of divalent iron. The contribution of electric dipole absorption due to local p-d mixing allowed by the trigonal distortion of the cation site is supported by DFT and CFM calculations. The two other nonlocal features are assigned to electric dipole transitions to excited Fe* 4p states mixed with the neighboring Ti 3d states. The comparison with DFT calculations demonstrates that MMCT in ilmenite is favored by the hybridization between the Fe 4p and delocalized Ti 3d orbitals via the O 2p orbitals.

CTM4DOC: electronic structure analysis from X-ray spectroscopy.

Two electronic structure descriptions, one based on orbitals and the other based on term symbols, have been implemented in a new Matlab-based program, CTM4DOC. The program includes a graphical user interface that allows the user to explore the dependence of details of electronic structure in transition metal systems, both in the ground and core-hole excited states, on intra-atomic electron-electron, crystal-field and charge-transfer interactions. The program can also track the evolution of electronic structure features as the crystal-field parameters are systematically varied, generating Tanabe-Sugano-type diagrams. Examples on first-row transition metal systems are presented and the implications on the interpretation of X-ray spectra and on the understanding of low-spin, high-spin and mixed-spin systems are discussed.

Kß Valence to Core X-ray Emission Studies of Cu(I) Binding Proteins with Mixed Methionine - Histidine Coordination. Relevance to the Reactivity of the M- and H-sites of Peptidylglycine Monooxygenase.

Biological systems use copper as a redox center in many metalloproteins, where the role of the metal is to cycle between its +1 and +2 oxidation states. This chemistry requires the redox potential to be in a range that can stabilize both Cu(I) and Cu(II) states and often involves protein-derived ligand sets involving mixed histidine-methionine coordination that balance the preferences of both oxidation states. Transport proteins, on the other hand, utilize copper in the Cu(I) state and often contain sites comprised predominately of the cuprophilic residue methionine. The electronic factors that allow enzymes and transporters to balance their redox requirements are complex and are often elusive due to the dearth of spectroscopic probes of the Cu(I) state. Here we present the novel application of X-ray emission spectroscopy to copper proteins via a study of a series of mixed His-Met copper sites where the ligand set varies in a systematic way between the His3 and Met3 limits. The sites are derived from the wild-type peptidylglycine monooxygenase (PHM), two single-site variants which replicate each of its two copper sites (CuM-site and CuH-site), and the transporters CusF and CusB. Clear differences are observed in the Kß2,5 region at the Met3 and His3 limits. CusB (Met3) has a distinct peak at 8978.4 eV with a broad shoulder at 8975.6 eV, whereas CuH (His3) has two well-resolved features: a more intense feature at 8974.8 eV and a second at 8977.2 eV. The mixed coordination sphere CusF (Met2His) and the PHM CuM variant (Met1His2) have very similar spectra consisting of two features at 8975.2 and 8977.8 eV. An analysis of DFT calculated spectra indicate that the intensity of the higher energy peak near 8978 eV is mediated by mixing of ligand-based orbitals into the Cu d(10) manifold, with S from Met providing more intensity by facilitating increased Cu p-d mixing. Furthermore, reaction of WT PHM with CO (an oxygen analogue) produced the M site CO complex, which showed a unique XES spectrum that could be computationally reproduced by including interactions between Cu(I) and the CO ligand. The study suggests that the valence-to-core (VtC) region can not only serve as a probe of ligand speciation but also offer insight into the coordination geometry, in a fashion similar to XAS pre-edges, and may be sufficiently sensitive to the coordination of exogenous ligands to be useful in the study of reaction mechanisms.

In search of metal hydrides: an X-ray absorption and emission study of [NiFe] hydrogenase model complexes.

Metal hydrides are invoked as important intermediates in both chemical and biological H2 production. In the [NiFe] hydrogenase enzymes, pulsed EPR and high-resolution crystallography have argued that the hydride interacts primarily at the Ni site. In contrast, in [NiFe] hydrogenase model complexes, it is observed that the bridging hydride interacts primarily with the Fe. Herein, we utilize a combination of Ni and Fe X-ray absorption (XAS) and emission (XES) spectroscopies to examine the contribution of the bridging hydride to the observed spectral features in [(dppe)Ni(µ-pdt)(µ-H)Fe(CO)3](+). The corresponding data on (dppe)Ni(µ-pdt)Fe(CO)3 are used as a reference for the changes that occur in the absence of a hydride bridge. For further interpretation of the observed spectral features, all experimental spectra were calculated using a density functional theory (DFT) approach, with excellent agreement between theory and experiment. It is found that the iron valence-to-core (VtC) XES spectra reveal clear signatures for the presence of a Fe-H interaction in the hydride bridged model complex. In contrast, the Ni VtC XES spectrum largely reflects changes in the local Ni geometry and shows little contribution from a Ni-H interaction. A stepwise theoretical analysis of the hydride contribution and the Ni site symmetry provides insights into the factors, which govern the different metal-hydride interactions in both the model complexes and the enzyme. Furthermore, these results establish the utility of two-color XES to reveal important insights into the electronic structure of various metal-hydride species.

Spanish Adaptation and Validation of the Posttraumatic Growth Inventory-Short Form.

The purpose of this article is to adapt and validate the short form of the Posttraumatic Growth Inventory (PTGI-SF) in Spanish. The scale consists of 10 items distributed in 5 posttraumatic growth dimensions measured in the original instrument. The psychometric properties and dimensionality of the scale are examined in a sample of college students (N = 681). Results lend support to the validity and reliability (α = .83) of the PTGI-SF. The dimensions of PTGI-SF show correlations ranging between .29 and .52. In addition, the inventory correlates significantly with deliberate rumination (r = .39) and the search for meaning in life (r = .32). The factor loadings of the items in the confirmatory factor analysis varied between .52 and .87, showing good fit indexes (comparative fit index = .97, Tucker-Lewis index = .93, relative fit index = .90, incremental fit index = .97, normed fit index = .96, and root mean square error of approximation = .05). Multi-group confirmatory factor analysis supported invariance of the PTGI-SF across the 2 groups. Finally, significantly higher PTGI-SF scores were observed in subjects who were actively looking for meaning in life, or had found it after a seeking process, than in subjects who had not looked for meaning in life or had given up because they had not been successful.

Kß mainline X-ray emission spectroscopy as an experimental probe of metal-ligand covalency.

The mainline feature in metal Kß X-ray emission spectroscopy (XES) has long been recognized as an experimental marker for the spin state of the metal center. However, even within a series of metal compounds with the same nominal oxidation and spin state, significant changes are observed that cannot be explained on the basis of overall spin. In this work, the origin of these effects is explored, both experimentally and theoretically, in order to develop the chemical information content of Kß mainline XES. Ligand field expressions are derived that describe the behavior of Kß mainlines for first row transition metals with any d(n) count, allowing for a detailed analysis of the factors governing mainline shape. Further, due to limitations associated with existing computational approaches, we have developed a new methodology for calculating Kß mainlines using restricted active space configuration interaction (RAS-CI) calculations. This approach eliminates the need for empirical parameters and provides a powerful tool for investigating the effects that chemical environment exerts on the mainline spectra. On the basis of a detailed analysis of the intermediate and final states involved in these transitions, we confirm the known sensitivity of Kß mainlines to metal spin state via the 3p-3d exchange coupling. Further, a quantitative relationship between the splitting of the Kß mainline features and the metal-ligand covalency is established. Thus, this study furthers the quantitative electronic structural information that can be extracted from Kß mainline spectroscopy.

Valence-to-core X-ray emission spectroscopy of iron-carbonyl complexes: implications for the examination of catalytic intermediates.

Valence-to-core X-ray emission spectroscopy (V2C XES) has been applied to a series of compounds relevant to both homogeneous catalysts and intermediates in heterogeneous reactions, namely [Fe(CO)5], [Fe2(CO)9], [Fe3(CO)12], [Fe(CO)3(cod)] (cod=cyclo-octadienyl), [Fe2Cp2(CO)4] (Cp=cyclo-pentadienyl), [Fe2Cp*2(CO)4] (Cp*=tetramethylcyclopentadienyl), and [FeCp(CO)2(thf)][B(ArF)4] (ArF=pentafluorophenyl). DFT calculations of the V2C XES spectra show very good agreement with experiment, which allows for an in depth analysis of the origins of the observed spectral signatures. It is demonstrated that the observed spectral features can be broken down into specific ligand and metal fragment contributions. The relative intensities of the observed features are further explained through a quantitative investigation of the metal 3p and 4p contributions to the spectra. The ability to use V2C XES to separate carbonyl, hydrocarbon, and solvent contributions is highlighted.

Experimental and computational X-ray emission spectroscopy as a direct probe of protonation states in oxo-bridged Mn(IV) dimers relevant to redox-active metalloproteins.

The protonation state of oxo bridges in nature is of profound importance for a variety of enzymes, including the Mn4CaO5 cluster of photosystem II and the Mn2O2 cluster in Mn catalase. A set of dinuclear bis-µ-oxo-bridged Mn(IV) complexes in different protonation states was studied by Kß emission spectroscopy to form the foundation for unraveling the protonation states in the native complex. The valence-to-core regions (valence-to-core XES) of the spectra show significant changes in intensity and peak position upon protonation. DFT calculations were performed to simulate the valence-to-core XES spectra and to assign the spectral features to specific transitions. The Kß(2,5) peaks arise primarily from the ligand 2p to Mn 1s transitions, with a characteristic low energy shoulder appearing upon oxo-bridge protonation. The satellite Kß" peak provides a more direct signature of the protonation state change, since the transitions originating from the 2s orbitals of protonated and unprotonated µ-oxo bridges dominate this spectral region. The energies of the Kß" features differ by ~3 eV and thus are well resolved in the experimental spectra. Additionally, our work explores the chemical resolution limits of the method, namely, whether a mixed (µ-O)(µ-OH2) motif can be distinguished from a symmetric (µ-OH)2 one. The results reported here highlight the sensitivity of Kß valence-to-core XES to single protonation state changes of bridging ligands, and form the basis for further studies of oxo-bridged polymetallic complexes and metalloenzyme active sites. In a complementary paper, the results from X-ray absorption spectroscopy of the same Mn(IV) dimer series are discussed.

An Architecture for Providing Personalized Digital Health.

Patients need mechanisms to integrate health information coming from different sources, including personal devices. This would lead to Personalized Digital Health (PDH). HIPAMS (Health Information Protection And Management System) is a modular and interoperable secure architecture that helps in achieving this objective and building a Framework for PDH. The paper presents HIPAMS and how it supports PDH.

MedSecurance Project: Advanced Security-for-Safety Assurance for Medical Device IoT (IoMT).

The MedSecurance project focus on identifying new challenges in cyber security with focus on hardware and software medical devices in the context of emerging healthcare architectures. In addition, the project will review best practice and identify gaps in the guidance, particularly the guidance stipulated by the medical device regulation and directives. Finally, the project will develop comprehensive methodology and tooling for the engineering of trustworthy networks of inter-operating medical devices, that shall have security-for-safety by design, with a strategy for device certification and certifiable dynamic network composition, ensuring that patient safety is safeguarded from malicious cyber actors and technology "accidents".

Expedited analysis of DFT outputs: introducing MOAnalyzer.

MOAnalyzer, a Matlab-based program, has been developed to facilitate the analysis of density functional theory output files from ORCA. The program allows the user to define fragments within a molecule and then provides information on the contribution of each fragment to the molecular orbitals based on the Loewdin population analysis. Correlations to spectroscopy (X-ray absorption and X-ray emission) are also obtained, and the resulting information can be visualized in tables or MO diagrams.