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Abstract Many individuals with psychotic symptoms have less complex language than healthy individuals. Word etymology is a lexical feature that has not yet been studied in clinical populations, but among healthy individuals, words of Old French origin are chosen over Germanic-origin words to convey formality (e.g. “inquire” vs. “ask”). Differences in language complexity among individuals with psychotic symptoms may relate to differences in etymological content in speech. Here, we determined the proportion of Germanic-origin word use and Old-French-origin word use in a large cohort of individuals with recent-onset psychosis or at clinically high risk for psychosis, hypothesizing that individuals with recent onset psychosis would have increased use of Germanic-origin words and decreased use of Old-French-origin words. This hypothesis was borne out, even after adjusting for sex, age, recruitment site, education, racial identity, and for a subset, IQ. Etymology proportions were associated with role but not social functioning in individuals with psychotic symptoms, consistent with the premise that they reflect speech formality. Understanding speech differences in the psychosis spectrum through the lens of etymology may lead to new interventions to improve role functioning.

The surfaces of many minerals are covered by naturally occurring cations that become partially hydrated and can be replaced by hydronium or other cations when the surface is exposed to water or an aqueous solution. These ion exchange processes are relevant to various chemical and transport phenomena, yet elucidating their microscopic details is challenging for both experiments and simulations. In this work, we make a first step in this direction by investigating the behavior of the native K+ ions at the interface between neat water and the muscovite mica (001) surface with ab-initio-based machine learning molecular dynamics and enhanced sampling simulations. Our results show that the desorption of the surface K+ ions in pure ion-free water has a significant free energy barrier irrespective of their local surface arrangement. In contrast, facile K+ diffusion between mica's ditrigonal cavities characterized by different Al/Si orderings is observed. This behavior suggests that the K+ ions may favor a dynamic disordered surface arrangement rather than complete desorption when exposed to deionized water. [ABSTRACT FROM AUTHOR]

Abstract Background Approximately 115,000 young adults will experience their first episode of psychosis (FEP) each year in the USA. Coordinated specialty care (CSC) for early psychosis is an evidence-based early intervention model that has demonstrated effectiveness by improving quality of life and reducing psychiatric symptoms for many individuals. Over the last decade, there has significant increase in the implementation of CSC programs throughout the USA. However, prior research has revealed difficulties among individuals and their family members accessing CSC. Research has also shown that CSC programs often report the limited reach of their program to underserved populations and communities (e.g., ethnoracial minorities, rural and low socioeconomic neighborhoods). Dissemination and implementation research focused on the equitable reach and implementation of CSC is needed to address disparities at the individual level. Methods The proposed study will create a novel integrative multi-level geospatial database of CSC programs implemented throughout the USA that will include program-level data (e.g., geocoded location, capacity, setting, role availability), provider-level data (race, ethnicity, professional credentials), and neighborhood-level census data (e.g., residential segregation, ethnic density, area deprivation, rural-urban continua, public transit time). This database will be used to characterize variations in CSC programs by geographical location and examine the overall reach CSC programs to specific communities. The quantitative data will be combined with qualitative data from state administrators, providers, and service users that will inform the development of dissemination tools, such as an interactive dashboard, that can aid decision making. Discussion Findings from this study will highlight the impact of outer contextual determinants on implementation and reach of mental health services, and will serve to inform the future implementation of CSC programs with a primary focus on equity.

Resolving the orbital structure of single atoms is challenging and of great importance for understanding basic chemistry. Here, the authors demonstrate that the orbital occupation difference of single Fe/Co atoms within molecules can be distinguished with high resolution AFM imaging and spectroscopy.

The structure and dynamics of water on solid surfaces critically affect the chemistry of materials in ambient and aqueous environments. Here, we investigate the hydrogen bonding network of water adsorbed on the majority (101) surface of anatase TiO2, a widely used photocatalyst, using polarization- and azimuth-resolved infrared spectroscopy combined with neural network potential molecular dynamics simulations. Our results show that one monolayer of water saturates the undercoordinated titanium (Ti5c) sites, forming one-dimensional chains of molecule hydrogen bonded to surface undercoordinated bridging oxygen (O2c) atoms. As the coverage increases, water adsorption on O2c sites leads to significant restructuring of the water monolayer and the formation of a two-dimensional hydrogen bond network characterized by tightly bound pairs of water molecules on adjacent Ti5c and O2c sites. This structural motif likely persists at ambient conditions, influencing the reactions occurring there. The results reported here provide critical details of the structure of the water–anatase (101) interface that were previously hypothesized but unconfirmed experimentally. [ABSTRACT FROM AUTHOR]

Amorphous titanium dioxide (a-TiO2) is widely used as a coating material in applications such as electrochemistry and self-cleaning surfaces where its interface with water has a central role. However, little is known about the structures of the a-TiO2 surface and aqueous interface, particularly at the microscopic level. In this work, we construct a model of the a-TiO2 surface via a cut-melt-and-quench procedure based on molecular dynamics simulations with deep neural network potentials (DPs) trained on density functional theory data. After interfacing the a-TiO2 surface with water, we investigate the structure and dynamics of the resulting system using a combination of DP-based molecular dynamics (DPMD) and ab initio molecular dynamics (AIMD) simulations. Both AIMD and DPMD simulations reveal that the distribution of water on the a-TiO2 surface lacks distinct layers normally found at the aqueous interface of crystalline TiO2, leading to an ∼10 times faster diffusion of water at the interface. Bridging hydroxyls (Ti2–ObH) resulting from water dissociation decay several times more slowly than terminal hydroxyls (Ti–OwH) due to fast Ti–OwH2 → Ti–OwH proton exchange events. These results provide a basis for a detailed understanding of the properties of a-TiO2 in electrochemical environments. Moreover, the procedure of generating the a-TiO2-interface employed here is generally applicable to studying the aqueous interfaces of amorphous metal oxides. [ABSTRACT FROM AUTHOR]

Controlled breaking of a chemical bond by mechanical forces can provide key insight into reaction mechanisms. Here the authors, using atomic force microscopy and computations, measure the forces involved in breaking a single dative bond between a CO molecule and a ferrous phthalocyanine complex.

Nickel–iron (Ni–Fe) hydroxides have received much attention as abundant and efficient electrocatalysts for the oxygen evolution reaction (OER) under alkaline conditions. However, the behavior of Fe dopants during the reaction is still under debate. Herein, we use first-principles calculations to investigate the dehydrogenation of the basal (0001) surface of 25% Fe-doped Ni hydroxide from Ni3/4Fe1/4(OH)2 to Ni3/4Fe1/4OOH, which is generally considered to be the active phase. Our calculations show that the high valence Fe ions tend to form domains by undergoing double-exchange processes with the neighboring Ni ions, while the oxidation states of the Ni ions do not increase steadily but fluctuate between Ni2+ and Ni3+ during the dehydrogenation. The boundaries of domains between high-valence Fe3+ and Fe4+ ions are the most reactive sites for the OER, with overpotentials as low as 0.36 V. This finding not only suggests that the abundant (0001) facet, often considered catalytically inactive in previous studies, can actually make an important contribution to the catalytic performance of nickel–iron hydroxides, but is also relevant to the design of more effective and efficient catalysts for the OER. [ABSTRACT FROM AUTHOR]

The formation of ice in the atmosphere affects precipitation and cloud properties, and plays a key role in the climate of our planet. Although ice can form directly from liquid water under deeply supercooled conditions, the presence of foreign particles can aid ice formation at much warmer temperatures. Over the past decade, experiments have highlighted the remarkable efficiency of feldspar minerals as ice nuclei compared to other particles present in the atmosphere. However, the exact mechanism of ice formation on feldspar surfaces has yet to be fully understood. Here, we develop a first-principles machine-learning model for the potential energy surface aimed at studying ice nucleation at microcline feldspar surfaces. The model is able to reproduce with high-fidelity the energies and forces derived from density-functional theory (DFT) based on the SCAN exchange and correlation functional. Our training set includes configurations of bulk supercooled water, hexagonal and cubic ice, microcline, and fully-hydroxylated feldspar surfaces exposed to a vacuum, liquid water, and ice. We apply the machine-learning force field to study different fully-hydroxylated terminations of the (100), (010), and (001) surfaces of microcline exposed to a vacuum. Our calculations suggest that terminations that do not minimize the number of broken bonds are preferred in a vacuum. We also study the structure of supercooled liquid water in contact with microcline surfaces, and find that water density correlations extend up to around 10 Å from the surfaces. Finally, we show that the force field maintains a high accuracy during the simulation of ice formation at microcline surfaces, even for large systems of around 30 000 atoms. Future work will be directed towards the calculation of nucleation free-energy barriers and rates using the force field developed herein, and understanding the role of different microcline surfaces in ice nucleation. [ABSTRACT FROM AUTHOR]

Photocatalytic water splitting on TiO2 is a promising route to H2 fuel production, but the mechanistic pathway at the water–TiO2 interface remains poorly understood. Here, using liquid environmental TEM and first-principles calculations, the authors unveil the formation of a self-hydrogenated shell on the TiO2 surface that further promotes H2 production.

Water–metal oxide interfaces are central to many phenomena and applications, ranging from material corrosion and dissolution to photoelectrochemistry and bioengineering. In particular, the discovery of photocatalytic water splitting on TiO2 has motivated intensive studies of water-TiO2 interfaces for decades. So far, a broad understanding of the interaction of water vapor with several TiO2 surfaces has been obtained. However, much less is known about liquid water–TiO2 interfaces, which are more relevant to many practical applications. Probing these complex systems at the molecular level is experimentally challenging and is sometimes possible only through computational studies. This review summarizes recent advances in the atomistic understanding, mostly through computational simulations, of the structure and dynamics of interfacial water on TiO2 surfaces. The main focus is on the nature, molecular or dissociated, of water in direct contact with low-index defect-free crystalline surfaces. The hydroxyls resulting from water dissociation are essential in the photooxidation of water and critically affect the surface chemistry of TiO2. [ABSTRACT FROM AUTHOR]

The chemical equilibrium between self-ionized and molecular water dictates the acid-base chemistry in aqueous solutions, yet understanding the microscopic mechanisms of water self-ionization remains experimentally and computationally challenging. Herein, Density Functional Theory (DFT)-based deep neural network (DNN) potentials are combined with enhanced sampling techniques and a global acid-base collective variable to perform extensive atomistic simulations of water self-ionization for model systems of increasing size. The explicit inclusion of long-range electrostatic interactions in the DNN potential is found to be crucial to accurately reproduce the DFT free energy profile of solvated water ion pairs in small (64 and 128 H2O) cells. The reversible work to separate the hydroxide and hydronium to a distance S is found to converge for simulation cells containing more than 500H2O, and a distance of -8Åis the threshold beyond which the work to further separate the two ions becomes approximately zero. The slow convergence of the potential of mean force with system size is related to a restructuring of water and an increase of the local order around the water ions. Calculation of the dissociation equilibrium constant illustrates the key role of longrange electrostatics and entropic effects in the water autoionization process. [ABSTRACT FROM AUTHOR]

This paper explores the concept of design for urban commons and its role in placemaking strategies that cater to community needs and aspirations. Placemaking is viewed as a collaborative process that involves early engagement with stakeholders to create shared visions. Design, particularly through co-design methodologies, scenario building and service design, can play a role in shaping public spaces for communal value and sustainability. This paper presents and discusses three case studies from Italy to introduce the concept of Service Master Planning, a methodology that combines co-design and service-centred scenarios to facilitate top-down actions that encourage bottom-up activation. It aims to co-create a vision for the future of a place involving the various actors of complex service ecosystems. Unlike traditional urban planning, which focuses mainly on the physical infrastructure, Service Master Planning emphasises services and social ecosystems. The methodology results in a strategic document, the Service Master Plan, outlining future scenarios based on contextual needs and aspirations. The successful adoption of Service Master Plan relies on inspiring spatial design and attracting community interest for co-producing the envisioned services. The challenge lies in transitioning scenarios into concrete actions, involving architectural and urban designers, and facilitating stakeholder consultations for service provision. [ABSTRACT FROM AUTHOR]

We investigate the solvation structure of flat and stepped MgO(001) in neutral liquid water using ab initio molecular dynamics based on a hybrid density functional with dispersion corrections. Our simulations show that the MgO surface is covered by a densely packed layer of mixed intact and dissociated adsorbed water molecules in a planar arrangement with strong intermolecular H-bonds. The water dissociation fractions in this layer are >20% and >30% on the flat and stepped surfaces, respectively. Slightly above the first water layer, we observe metastable OH groups perpendicular to the interface, similar to those reported in low temperature studies of water monolayers on MgO. These species receive hydrogen bonds from four nearby water molecules in the first layer and have their hydrophobic H end directed toward bulk water, while their associated protons are bound to surface oxygens. The formation of these OH species is attributed to the strong basicity of the MgO surface and can be relevant for understanding various phenomena from morphology evolution and growth of (nano)crystalline MgO particles to heterogeneous catalysis. [ABSTRACT FROM AUTHOR]

Titanium oxide structures featuring highly reduced TiOx films on top of nearly stoichiometric TiO2 hold promise for applications ranging from photocatalysis to resistance switching devices. Here, we focus on titanium monoxide (TiO) layers on anatase TiO2 (001) and use first principles calculations to investigate their structure and properties as well as their interface with liquid water. We find that only a single TiO layer can grow epitaxially on anatase (001) and subsequent growth leads to the formation of TiO islands. The TiO layers decrease the work function and enhance the surface conductivity in comparison to pure anatase, two features that can improve the TiO2 performance in photocatalytic hydrogen evolution but are thermodynamically unstable relative to pure TiO2 in humid/aqueous environment. Furthermore, first principles molecular dynamics simulations of the TiO (001)-water and anatase (001)-water interfaces show that unlike the multilayer structure of interfacial water on the anatase surface, a very dense and tightly packed first water layer is present on the surface of TiO, which could represent the first stage of partial surface reoxidation. [ABSTRACT FROM AUTHOR]

Catalytic strategies based on main group metals are significantly less advanced than those of transition metal catalysis, leaving untapped areas of potentially fruitful research. We here demonstrate an effective approach for the modulation of Bi 6p energy levels during the construction of atomically dispersed clusters of amorphous BiOx. Bi oxidation state is proposed to strongly affects the nitrogen fixation activity, with the half‐occupied pz orbitals of the Bi2+ ions being highly efficient toward electron injection into the inert N2 molecule. With sufficient catalytic sites to adsorb and activate N2, the bonding between N2 and catalyst is able to be in situ identified. The catalyst shows an outstanding Faraday efficiency (≈30 %) and high yield (≈113 μg h−1 mg−1cat) in NH3 production, outperforming most of the existing catalysts in aqueous solution. These results lay the basis for developing the potential of p‐block elements for catalysis of multi‐electron reactions. [ABSTRACT FROM AUTHOR]

The interaction of water with TiO2 surfaces is of crucial importance in various scientific fields and applications, from photocatalysis for hydrogen production and the photooxidation of organic pollutants to self-cleaning surfaces and bio-medical devices. In particular, the equilibrium fraction of water dissociation at the TiO2–water interface has a critical role in the surface chemistry of TiO2, but is difficult to determine both experimentally and computationally. Among TiO2 surfaces, rutile TiO2(110) is of special interest as the most abundant surface of TiO2’s stable rutile phase. While surface-science studies have provided detailed information on the interaction of rutile TiO2(110) with gas-phase water, much less is known about the TiO2(110)–water interface, which is more relevant to many applications. In this work, we characterize the structure of the aqueous TiO2(110) interface using nanosecond timescale molecular dynamics simulations with ab initio-based deep neural network potentials that accurately describe water/TiO2(110) interactions over a wide range of water coverages. Simulations on TiO2(110) slab models of increasing thickness provide insight into the dynamic equilibrium between molecular and dissociated adsorbed water at the interface and allow us to obtain a reliable estimate of the equilibrium fraction of water dissociation. We find a dissociation fraction of 22 ± 6% with an associated average hydroxyl lifetime of 7.6 ± 1.8 ns. These quantities are both much larger than corresponding estimates for the aqueous anatase TiO2(101) interface, consistent with the higher water photooxidation activity that is observed for rutile relative to anatase. [ABSTRACT FROM AUTHOR]

COVID-19 and technological advances have made online communication more common, which has increased the number of online communities. However, online communities tend to rise and fall rapidly, and maintaining active participants is vital to online community survival and development. While online communities connect many diverse participants, they also add to the complexity of the network and challenge participants to collaborate and participate. Despite the widespread use of service design and co-design for collaborating and participating in offline communities, there have been few studies examining their application and contribution online. This study uses participatory action research as a methodology. It takes China's online community, Chinese Service Design Community (CSDC), as a research object, analyses its development process from 2019 to 2022, and combines the online community life cycle proposed by Iriberri and Leroy as an analytical model to illustrate how service design and co-design activities can contribute to the community's transition from "inception" to "maturity" (Iriberri & Leroy, 2009). In addition, it also explores how service design and codesign can help to produce the ‘legacy’ for the long-term development of online communities by reflecting on the influences of the 'heroes' of online communities. [ABSTRACT FROM AUTHOR]

The liberalisation of cannabis laws, the increasing availability and potency of cannabis has renewed concern about the risk of psychosis with cannabis. The objective of the WFSBP task force was to review the literature about this relationship. Converging lines of evidence suggest that exposure to cannabis increases the risk for psychoses ranging from transient psychotic states to chronic recurrent psychosis. The greater the dose, and the earlier the age of exposure, the greater the risk. For some psychosis outcomes, the evidence supports some of the criteria of causality. However, alternate explanations including reverse causality and confounders cannot be conclusively excluded. Furthermore, cannabis is neither necessary nor sufficient to cause psychosis. More likely it is one of the multiple causal components. In those with established psychosis, cannabis has a negative impact on the course and expression of the illness. Emerging evidence also suggests alterations in the endocannabinoid system in psychotic disorders. Given that exposure to cannabis and cannabinoids is modifiable, delaying or eliminating exposure to cannabis or cannabinoids, could potentially impact the rates of psychosis related to cannabis, especially in those who are at high risk for developing the disorder. [ABSTRACT FROM AUTHOR]

Density functional theory is used for calculating the adsorption properties of Au and Pt metal nanoclusters on Ti[O.sub.2] anatase (101). Oxygen vacancies have affected the growth of Au, while the nucleation behavior of Pt is less affected.