Stable, while Still Active? A DFT Study of Cu, Ag, and Au Single Atoms at the C3N4/TiO2 Interface.

Hybrid DFT calculations are employed to compare the adsorption and stabilization of Cu, Ag, and Au atoms on graphitic C3N4 and on the heterojunction formed by g- C3N4 and TiO2. While Cu and Ag can be strongly chemisorbed in form of cations on g- C3N4, Au is only weakly physisorbed. On g- C3N4/TiO2, all coinage metal adatoms can be strongly chemisorbed, but, while Cu and Ag forms cations, Au form an Au- species. Ab Initio Molecular Dynamics simulations confirm that the metal adatoms on g-C3N4 are highly mobile at room temperature, while they remain confined in the interfacial spacing between C3N4 and TiO2 on the heterojunction, being both stably bound and reachable for the reactants in a catalytic cycle. Doping g-C3N4/TiO2 with metal single atoms permits thus to generate catalytic systems with tunable charge and chemical properties and improved stability with respect to bare C3N4. Moreover, the changes in the electronic structure of g-C3N4/TiO2 induced by the presence of the metal single atoms are beneficial also for photocatalytic applications.

[The diagnostic challenge of autoimmune encephalitis]. / Le défi diagnostique des encéphalites auto-immunes.

Autoimmune encephalitis encompasses a spectrum of neurological disorders characterized by an autoimmune response directed against neurons and glia. Around two-thirds of cases exhibit autoantibodies targeting neuronal or glial antigens in the cerebrospinal fluid and/or serum. The diagnosis is based on specific criteria combining a subacute clinical presentation and complementary test results. However, approximately one-quarter of patients do not present any paraclinical abnormalities, making the diagnosis complex. Testing for anti-antibodies is pivotal for diagnosis, and their interpretation should be contextual. Best practices for anti-neural antibody detection involve appropriate sample collection and confirmation of positive results in relation to the clinical picture.

L'encéphalite auto-immune comprend un spectre de troubles neurologiques caractérisés par une réponse auto-immunitaire dirigée contre les neurones et les cellules gliales. Environ deux tiers des cas présentent des autoanticorps dirigés contre des antigènes neuronaux et gliaux dans le liquide céphalorachidien et/ou le sérum. Le diagnostic repose sur des critères spécifiques combinant une présentation clinique subaiguë et des résultats d'examens complémentaires. Environ un quart des patients ne présente pas d'anomalie paraclinique, rendant le diagnostic complexe. La recherche des autoanticorps est cruciale pour le diagnostic de certitude et son interprétation doit être contextuelle. Les bonnes pratiques pour leur dosage impliquent le prélèvement d'échantillons appropriés et la confirmation des résultats positifs par rapport au tableau clinique.

CO2 electroreduction on single atom catalysts: the role of the DFT functional.

One key process involving single atom catalysts (SACs) is the electroreduction of CO2 to fuels. The chemistry of SACs differs largely from that of extended catalytic surfaces, presenting an opportunity to improve the ability to activate very stable molecules, such as CO2. In this work, we performed a density functional theory (DFT) study of CO2 activation on a series of SACs, focusing on the role played by the adopted functional in activity predictions. The role of the exchange-correlation functional has been widely investigated in heterogenous catalysts, but it is less explored in SACs. We tested the widely used PBE and the PBE+U corrected functionals against the more robust hybrid PBE0 functional. The results show that PBE is reliable if one is interested in qualitative predictions, but it leads to some inaccuracies in other cases. A possible way to attenuate this effect is by adopting the PBE+U framework, as it gives results that are very similar to PBE0 at an acceptable computational cost. The results of this study further underline the importance of the computational framework adopted in predicting the activity of SACs. The work suggests that one needs to go beyond PBE for quantitative estimates, an important consideration when performing screening and high-throughput calculations.

Copper Single Atoms Chelated on Ligand-Modified Carbon for Ullmann-Type C-O Coupling.

Invited for this month's cover is the group of Gianvito Vilé at the Politecnico di Milano. The ChemSusChem cover image depicts in an artistic manner the concept of ligand entrapping of isolated metals to design single-atom catalysts. The Research Article itself is available at 10.1002/cssc.202301529.

PVDF-HFP Based, Quasi-Solid Nanocomposite Electrolytes for Lithium Metal Batteries.

Composite polymer electrolytes are systems of choice for future solid-state lithium metal batteries (LMBs). Poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) is among the most interesting matrices to develop new generation quasi-solid electrolytes (QSEs). Here it is reported on nanocomposites made of PVDF-HFP and pegylated SiO2 nanoparticles. Silica-based hybrid nanofillers are obtained by grafting chains of poly(ethylene glycol) methyl ether (PEG) with different molecular weight on the surface of silica nanoparticles. The functionalized nanofiller improves the mechanical, transport and electrochemical properties of the QSEs, which show good ionic conductivity values and high resistance against dendrite penetration, ensuring boosted long and safe device operation. The most promising result is obtained by dispersing 5 wt% of SiO2 functionalized with short PEG chains (PEG750 , Mw = 750 g mol-1 ) in the PVDF-HFP matrix with an ease solvent-casting procedure. It shows ionic conductivity of 0.1 mS cm-1 at 25 °C, more than 250 h resistance to stripping/plating, and impressive results during cycling tests in LMB with LiFePO4 cathode.

Pt Single Atoms Supported on Defect Ceria as an Active and Stable Dual-Site Catalyst for Alkaline Hydrogen Evolution.

This work evaluates the feasibility of alkaline hydrogen evolution reaction (HER) using Pt single-atoms (1.0 wt %) on defect-rich ceria (Pt1/CeOx) as an active and stable dual-site catalyst. The catalyst displayed a low overpotential and a small Tafel slope in an alkaline medium. Moreover, Pt1/CeOx presented a high mass activity and excellent durability, competing with those of the commercial Pt/C (20 wt %). In this picture, the defective CeOx is active for water adsorption and dissociation to create H* intermediates, providing the first site where the reaction occurs. The H* intermediate species then migrate to adsorb and react on the Pt2+ isolated atoms, the site where H2 is formed and released. DFT calculations were also performed to obtain mechanistic insight on the Pt1/CeOx catalyst for the HER. The results indicate a new possibility to improve the state-of-the-art alkaline HER catalysts via a combined effect of the O vacancies on the ceria support and Pt2+ single atoms.

A standardised open science framework for sharing and re-analysing neural data acquired to continuous stimuli.

Neurophysiology research has demonstrated that it is possible and valuable to investigate sensory processing in scenarios involving continuous sensory streams, such as speech and music. Over the past 10 years or so, novel analytic frameworks combined with the growing participation in data sharing has led to a surge of publicly available datasets involving continuous sensory experiments. However, open science efforts in this domain of research remain scattered, lacking a cohesive set of guidelines. This paper presents an end-to-end open science framework for the storage, analysis, sharing, and re-analysis of neural data recorded during continuous sensory experiments. The framework has been designed to interface easily with existing toolboxes, such as EelBrain, NapLib, MNE, and the mTRF-Toolbox. We present guidelines by taking both the user view (how to rapidly re-analyse existing data) and the experimenter view (how to store, analyse, and share), making the process as straightforward and accessible as possible for all users. Additionally, we introduce a web-based data browser that enables the effortless replication of published results and data re-analysis.

Copper Single Atoms Chelated on Ligand-Modified Carbon for Ullmann-type C-O Coupling.

Cross-coupling reactions are of great importance in chemistry due to their ability to facilitate the construction of complex organic molecules. Among these reactions, the Ullmann-type C-O coupling between phenols and aryl halides is particularly noteworthy and useful for preparing diarylethers. However, this reaction typically relies on homogeneous catalysts that rapidly deactivate under harsh reaction conditions. In this study, we introduce a novel heterogeneous catalyst for the Ullmann-type C-O coupling reaction, comprised of isolated Cu atoms chelated to a tetraethylenepentamine-pyrrole ligand that is immobilized on graphite nanoplatelets. The catalytic study reveals the recyclability of the material, and demonstrates the crucial role of the pyrrole linker in stabilizing the Cu sites. The work expands the potential of single-atom catalyst nanoarchitectures and underscores the significance of ligands in stabilizing metals in cationic forms, providing a novel, tailored catalyst for cross-coupling chemistries.

Atypical speech production of multisyllabic words and phrases by children with developmental dyslexia.

The prevalent "core phonological deficit" model of dyslexia proposes that the reading and spelling difficulties characterizing affected children stem from prior developmental difficulties in processing speech sound structure, for example, perceiving and identifying syllable stress patterns, syllables, rhymes and phonemes. Yet spoken word production appears normal. This suggests an unexpected disconnect between speech input and speech output processes. Here we investigated the output side of this disconnect from a speech rhythm perspective by measuring the speech amplitude envelope (AE) of multisyllabic spoken phrases. The speech AE contains crucial information regarding stress patterns, speech rate, tonal contrasts and intonational information. We created a novel computerized speech copying task in which participants copied aloud familiar spoken targets like "Aladdin." Seventy-five children with and without dyslexia were tested, some of whom were also receiving an oral intervention designed to enhance multi-syllabic processing. Similarity of the child's productions to the target AE was computed using correlation and mutual information metrics. Similarity of pitch contour, another acoustic cue to speech rhythm, was used for control analyses. Children with dyslexia were significantly worse at producing the multi-syllabic targets as indexed by both similarity metrics for computing the AE. However, children with dyslexia were not different from control children in producing pitch contours. Accordingly, the spoken production of multisyllabic phrases by children with dyslexia is atypical regarding the AE. Children with dyslexia may not appear to listeners to exhibit speech production difficulties because their pitch contours are intact. RESEARCH HIGHLIGHTS: Speech production of syllable stress patterns is atypical in children with dyslexia. Children with dyslexia are significantly worse at producing the amplitude envelope of multi-syllabic targets compared to both age-matched and reading-level-matched control children. No group differences were found for pitch contour production between children with dyslexia and age-matched control children. It may be difficult to detect speech output problems in dyslexia as pitch contours are relatively accurate.

Emergence of the cortical encoding of phonetic features in the first year of life.

Even prior to producing their first words, infants are developing a sophisticated speech processing system, with robust word recognition present by 4-6 months of age. These emergent linguistic skills, observed with behavioural investigations, are likely to rely on increasingly sophisticated neural underpinnings. The infant brain is known to robustly track the speech envelope, however previous cortical tracking studies were unable to demonstrate the presence of phonetic feature encoding. Here we utilise temporal response functions computed from electrophysiological responses to nursery rhymes to investigate the cortical encoding of phonetic features in a longitudinal cohort of infants when aged 4, 7 and 11 months, as well as adults. The analyses reveal an increasingly detailed and acoustically invariant phonetic encoding emerging over the first year of life, providing neurophysiological evidence that the pre-verbal human cortex learns phonetic categories. By contrast, we found no credible evidence for age-related increases in cortical tracking of the acoustic spectrogram.

MicroRNA-92a-CPEB3 axis protects neurons against inflammatory neurodegeneration.

Neuroinflammation causes neuronal injury in multiple sclerosis (MS) and other neurological diseases. MicroRNAs (miRNAs) are important modulators of neuronal stress responses, but knowledge about their contribution to neuronal protection or damage during inflammation is limited. Here, we constructed a regulatory miRNA-mRNA network of inflamed motor neurons by leveraging cell type-specific miRNA and mRNA sequencing of mice undergoing experimental autoimmune encephalomyelitis (EAE). We found robust induction of miR-92a in inflamed spinal cord neurons and identified cytoplasmic polyadenylation element-binding protein 3 (Cpeb3) as a key target of miR-92a-mediated posttranscriptional silencing. We detected CPEB3 repression in inflamed neurons in murine EAE and human MS. Moreover, both miR-92a delivery and Cpeb3 deletion protected neuronal cultures against excitotoxicity. Supporting a detrimental effect of Cpeb3 in vivo, neuron-specific deletion in conditional Cpeb3 knockout animals led to reduced inflammation-induced clinical disability in EAE. Together, we identified a neuroprotective miR-92a-Cpeb3 axis in neuroinflammation that might serve as potential treatment target to limit inflammation-induced neuronal damage.

Modeling Single-Atom Catalysis.

Electronic structure calculations represent an essential complement of experiments to characterize single-atom catalysts (SACs), consisting of isolated metal atoms stabilized on a support, but also to predict new catalysts. However, simulating SACs with quantum chemistry approaches is not as simple as often assumed. In this work, the essential factors that characterize a reliable simulation of SACs activity are examined. The Perspective focuses on the importance of precise atomistic characterization of the active site, since even small changes in the metal atom's surroundings can result in large changes in reactivity. The dynamical behavior and stability of SACs under working conditions, as well as the importance of adopting appropriate methods to solve the Schrödinger equation for a quantitative evaluation of reaction energies are addressed. The Perspective also focuses on the relevance of the model adopted. For electrocatalysis this must include the effects of the solvent, the presence of electrolytes, the pH, and the external potential. Finally, it is discussed how the similarities between SACs and coordination compounds may result in reaction intermediates that usually are not observed on metal electrodes. When these aspects are not adequately considered, the predictive power of electronic structure calculations is quite limited.

Seeing a Talking Face Matters: Gaze Behavior and the Auditory-Visual Speech Benefit in Adults' Cortical Tracking of Infant-directed Speech.

In face-to-face conversations, listeners gather visual speech information from a speaker's talking face that enhances their perception of the incoming auditory speech signal. This auditory-visual (AV) speech benefit is evident even in quiet environments but is stronger in situations that require greater listening effort such as when the speech signal itself deviates from listeners' expectations. One example is infant-directed speech (IDS) presented to adults. IDS has exaggerated acoustic properties that are easily discriminable from adult-directed speech (ADS). Although IDS is a speech register that adults typically use with infants, no previous neurophysiological study has directly examined whether adult listeners process IDS differently from ADS. To address this, the current study simultaneously recorded EEG and eye-tracking data from adult participants as they were presented with auditory-only (AO), visual-only, and AV recordings of IDS and ADS. Eye-tracking data were recorded because looking behavior to the speaker's eyes and mouth modulates the extent of AV speech benefit experienced. Analyses of cortical tracking accuracy revealed that cortical tracking of the speech envelope was significant in AO and AV modalities for IDS and ADS. However, the AV speech benefit [i.e., AV > (A + V)] was only present for IDS trials. Gaze behavior analyses indicated differences in looking behavior during IDS and ADS trials. Surprisingly, looking behavior to the speaker's eyes and mouth was not correlated with cortical tracking accuracy. Additional exploratory analyses indicated that attention to the whole display was negatively correlated with cortical tracking accuracy of AO and visual-only trials in IDS. Our results underscore the nuances involved in the relationship between neurophysiological AV speech benefit and looking behavior.

Bridging the Gap: Immunotherapy in Progressive Multifocal Leukoencephalopathy: A New Hope?

Progressive multifocal leukoencephalopathy (PML) is a severe infection of the CNS occurring in immunocompromised individuals in which large demyelinating lesions are induced by polyomavirus JC (JCV). In the absence of effective antiviral treatment, control of the infection relies on restoring anti-JCV immunity. Thus, particularly in long-standing immunocompromising conditions such as organ transplantation, lymphoproliferative disorders, or idiopathic lymphopenia, new strategies to boost anti-JCV immune responses are needed. Here, we report the case of a patient developing PML in the context of kidney transplantation who received recombinant human interleukin 7 to foster immune responses against JCV. We give an overview of the immunologic mechanisms underlying the development of PML and immune restoration within the CNS after JCV infection. Immunotherapeutic strategies developed based on current understanding of the disease hold promise in managing patients with PML.

Increased top-down semantic processing in natural speech linked to better reading in dyslexia.

Early research proposed that individuals with developmental dyslexia use contextual information to facilitate lexical access and compensate for phonological deficits. Yet at present there is no corroborating neuro-cognitive evidence. We explored this with a novel combination of magnetoencephalography (MEG), neural encoding and grey matter volume analyses. We analysed MEG data from 41 adult native Spanish speakers (14 with dyslexic symptoms) who passively listened to naturalistic sentences. We used multivariate Temporal Response Function analysis to capture online cortical tracking of both auditory (speech envelope) and contextual information. To compute contextual information tracking we used word-level Semantic Surprisal derived using a Transformer Neural Network language model. We related online information tracking to participants' reading scores and grey matter volumes within the reading-linked cortical network. We found that right hemisphere envelope tracking was related to better phonological decoding (pseudoword reading) for both groups, with dyslexic readers performing worse overall at this task. Consistently, grey matter volume in the superior temporal and bilateral inferior frontal areas increased with better envelope tracking abilities. Critically, for dyslexic readers only, stronger Semantic Surprisal tracking in the right hemisphere was related to better word reading. These findings further support the notion of a speech envelope tracking deficit in dyslexia and provide novel evidence for top-down semantic compensatory mechanisms.

pH- and Facet-Dependent Surface Chemistry of TiO2 in Aqueous Environment from First Principles.

TiO2 is a relevant catalytic material, and its chemistry in aqueous environment is a challenging aspect to address. Also, the morphology of TiO2 particles at the nanoscale is often complex, spanning from faceted to spherical. In this work, we study the pH- and facet-dependent surface chemistry of TiO2/water interfaces by performing ab initio molecular dynamics simulations with the grand canonical formulation of species in solution. We first determined the acid-base equilibrium constants at the interface, which allows us to estimate the pH at the point of zero charge, an important experimental observable. Then, based on simulated equilibrium constants, we predict the amount of H+, OH-, and adsorbed H2O species present on the surfaces as a function of the pH, a relevant aspect for water splitting semi-reactions. We approximated the complex morphology of TiO2 particles by considering the rutile (110) and (011), and anatase (101), (001), and (100) surfaces.

Identification of Intermediates in the Reaction Pathway of SO2 on the CaO Surface: From Physisorption to Sulfite to Sulfate.

The interaction of CaO and Ca(OH)2 with solvated or gaseous SO2 plays a crucial role in the corrosion of urban infrastructure by acid rain or in the removal of SO2 from flue gas. We carried out a combined spectroscopic and theoretical investigation on the interaction of SO2 with a CaO(001) single crystal. First, the surface chemistry of SO2 was investigated at different temperatures using polarization-resolved IR reflection absorption spectroscopy. Three species were identified, and an in-depth density functional theory study was carried out, which allowed deriving a consistent picture. Unexpectedly, low temperature exposure to SO2 solely yields a physisorbed species. Only above 100 K, the transformation of this weakly bound adsorbate first to a chemisorbed sulfite and then to a sulfate occurs, effectively passivatating the surface. Our results provide the basis for more efficient strategies in corrosion protection of urban infrastructure and in lime-based desulfurization of flue gas.

Band Edges Engineering of 2D/2D Heterostructures: The C3 N4 /Phosphorene Interface.

We investigate the interface between carbon nitride (C3 N4 ) and phosphorene nanosheets (P-ene) by means of Density Functional Theory (DFT) calculations. C3 N4 /P-ene composites have been recently obtained experimentally showing excellent photoactivity. Our results indicate that the formation of the interface is a favorable process driven by Van der Waals forces. The thickness of P-ene nanosheets determines the band edges offsets and the charge carriers' separation. The system is predicted to pass from a nearly type-II to a type-I junction when the thickness of P-ene increases, and the conduction band offset is particularly sensitive. Last, we apply the Transfer Matrix Method to estimate the efficiency for charge carriers' migration as a function of the P-ene thickness.

An unconstrained approach to systematic structural and energetic screening of materials interfaces.

From grain boundaries and heterojunctions to manipulating 2D materials, solid-solid interfaces play a key role in many technological applications. Understanding and predicting properties of these complex systems present an ongoing and increasingly important challenge. Over the last few decades computer simulation of interfaces has become vastly more powerful and sophisticated. However, theoretical interface screening remains based on largely heuristic methods and is strongly biased to systems that are amenable to modelling within constrained periodic cell approaches. Here we present an unconstrained and generally applicable non-periodic screening approach for systematic exploration of material's interfaces based on extracting and aligning disks from periodic reference slabs. Our disk interface method directly and accurately describes how interface structure and energetic stability depends on arbitrary relative displacements and twist angles of two interacting surfaces. The resultant detailed and comprehensive energetic stability maps provide a global perspective for understanding and designing interfaces. We confirm the power and utility of our method with respect to the catalytically important TiO2 anatase (101)/(001) and TiO2 anatase (101)/rutile (110) interfaces.