Composition-dependent morphologies of CeO2 nanoparticles in the presence of Co-adsorbed H2O and CO2: a density functional theory study.

Catalytic activity is affected by surface morphology, and specific surfaces display greater activity than others. A key challenge is to define synthetic strategies to enhance the expression of more active surfaces and to maintain their stability during the lifespan of the catalyst. In this work, we outline an ab initio approach, based on density functional theory, to predict surface composition and particle morphology as a function of environmental conditions, and we apply this to CeO2 nanoparticles in the presence of co-adsorbed H2O and CO2 as an industrially relevant test case. We find that dissociative adsorption of both molecules is generally the most favourable, and that the presence of H2O can stabilise co-adsorbed CO2. We show that changes in adsorption strength with temperature and adsorbate partial pressure lead to significant changes in surface stability, and in particular that co-adsorption of H2O and CO2 stabilizes the {100} and {110} surfaces over the {111} surface. Based on the changes in surface free energy induced by the adsorbed species, we predict that cuboidal nanoparticles are favoured in the presence of co-adsorbed H2O and CO2, suggesting that cuboidal particles should experience a lower thermodynamic driving force to reconstruct and thus be more stable as catalysts for processes involving these species.

Fragment contribution models for predicting skin permeability using HuskinDB.

Mathematical models to predict skin permeation tend to be based on animal derived experimental data as well as knowing physicochemical properties of the compound under investigation, such as molecular volume, polarity and lipophilicity. This paper presents a strikingly contrasting model to predict permeability, formed entirely from simple chemical fragment (functional group) data and a recently released, freely accessible human (i.e. non-animal) skin permeation database, known as the 'Human Skin Database - HuskinDB'. Data from within the database allowed development of several fragment-based models, each including a calculable effect for all of the most commonly encountered functional groups present in compounds within the database. The developed models can be applied to predict human skin permeability (logKp) for any compound containing one or more of the functional groups analysed from the dataset with no need to know any other physicochemical properties, solely the type and number of each functional group within the chemical structure itself. This approach simplifies mathematical prediction of permeability for compounds with similar properties to those used in this study.

Infrared and Raman Diagnostic Modeling of Phosphate Adsorption on Ceria Nanoparticles.

Cerium dioxide (CeO2; ceria) nanoparticles (CeNPs) are promising nanozymes that show a variety of biological activity. Effective nanozymes need to retain their activity in the face of surface speciation in biological environments, and characterizing surface speciation is therefore critical to understanding and controlling the therapeutic capabilities of CeNPs. In particular, adsorbed phosphates can impact the enzymatic activity exploited to convert phosphate prodrugs into therapeutics in vivo and also define the early stages of the phosphate-scavenging processes that lead to the transformation of active CeO2 into inactive CePO4. In this work, we utilize ab initio lattice-dynamics calculations to study the interaction of phosphates with the three major surfaces of ceria and to predict the infrared (IR) and Raman spectral signatures of adsorbed phosphate species. We find that phosphates adsorb strongly to CeO2 surfaces in a range of stable binding configurations, of which 5-fold coordinated P species in a trigonal bipyramidal coordination may represent a stable intermediate in the early stages of phosphate scavenging. We find that the phosphate species show characteristic spectral fingerprints between 500 and 1500 cm-1, whereas the bare CeO2 surfaces show no active modes above 600 cm-1, and the 5-fold coordinated P species in particular show potential diagnostic P-O stretching modes between 650 and 700 cm-1 in both IR and Raman spectra. This comprehensive exploration of different binding modes for phosphates on CeO2 and the set of reference spectra provides an important step toward the experimental characterization of phosphate speciation and, ultimately, control of its impact on the performance of ceria nanozymes.

A Review of Key Properties of Thermoelectric Composites of Polymers and Inorganic Materials.

This review focusses on the development of thermoelectric composites made of oxide or conventional inorganic materials, and polymers, with specific emphasis on those containing oxides. Discussion of the current state-of-the-art thermoelectric materials, including the individual constituent materials, i.e., conventional materials, oxides and polymers, is firstly presented to provide the reader with a comparison of the top-performing thermoelectric materials. Then, individual materials used in the inorganic/polymer composites are discussed to provide a comparison of the performance of the composites themselves. Finally, the addition of carbon-based compounds is discussed as a route to improving the thermoelectric performance. For each topic discussed, key thermoelectric properties are tabulated and comparative figures are presented for a wide array of materials.

Evaluating the Test Validity of the Comprehensive Assessment of Psychopathic Personality Symptom Rating Sale (CAPP SRS).

The Comprehensive Assessment of Psychopathic Personality Symptom Rating Scale (CAPP SRS) is a relatively new measure of psychopathic personality disorder (PPD) based on the CAPP concept map of psychopathy. To investigate the CAPP SRS, we identified the most plausible formal test structure for the test using the framework proposed by Slaney and Maraun, identified an appropriate quantitative characterization of that test structure, and then statistically evaluated it based on analysis of CAPP SRS data collected from a multisite sample of 314 adult male correctional offenders and secure hospital patients in Scotland and England. Overall, the CAPP SRS survived falsification when observed test data were compared to expectations based on the unidimensional monotone latent variable or UMLV model of Holland and Rosenbaum. CAPP SRS composite scores calculated consistent with the UMLV model had good measurement precision and good external validity with respect to scores on an established test of PPD. The findings provide provisional support for the test validity of the CAPP SRS and highlight the importance of theory-driven evaluations of test validity.

Unraveling the Impact of Graphene Addition to Thermoelectric SrTiO3 and La-Doped SrTiO3 Materials: A Density Functional Theory Study.

We present a detailed theoretical investigation of the interaction of graphene with the SrO-terminated (001) surface of pristine and La-doped SrTiO3. The adsorption of graphene is thermodynamically favorable with interfacial adsorption energies of -0.08 and -0.32 J/m2 to pristine SrTiO3 and La-doped SrTiO3 surfaces, respectively. We find that graphene introduces C 2p states at the Fermi level, rendering the composite semimetallic, and thus the electrical properties are predicted to be highly sensitive to the amount and quality of the graphene. An investigation of the lattice dynamics predicts that graphene adsorption may lead to a 60-90% reduction in the thermal conductivity due to a reduction in the phonon group velocities, accounting for the reduced thermal conductivity of the composite materials observed experimentally. This effect is enhanced by La doping. We also find evidence that both La dopant ions and adsorbed graphene introduce low-frequency modes that may scatter heat-carrying acoustic phonons, and that, if present, these effects likely arise from stronger phonon-phonon interactions.

Factor structure of the Comprehensive Assessment of Psychopathic Personality-Self-Report (CAPP-SR) in community and offender samples.

The Comprehensive Assessment of Psychopathic Personality-Self-Report (CAPP-SR) is a recent operationalization of the CAPP model, which conceptualizes psychopathy in terms of 33 symptoms that can be thematically organized according to six theoretical domains. The current study examined the higher order factor structure of the CAPP-SR symptom scales in community, university, and offender samples derived from three separate countries. Exploratory factor analysis (EFA) indicated that a three-factor model (Antagonism/Meanness, Disinhibition, and Fearless Grandiosity) was optimal in a large population-representative U.S. community sample. EFA with targeted rotation confirmed this three-factor structure in New Zealand university and Lithuanian prison samples. Furthermore, construct validity analyses against other psychopathy measures and psychopathy-relevant criteria provided initial support for the three CAPP-SR latent factors. For instance, CAPP-SR Antagonism/Meanness was associated with other psychopathy scales reflective of antagonism, meanness, callous affect; CAPP-SR Disinhibition with other psychopathy scales reflective of behavioral psychopathy traits (e.g., impulsivity, irresponsibility), antisocial behavior, substance abuse; and CAPP-SR Fearless Grandiosity with narcissism, emotional stability, and boldness. These findings suggest that a three-factor structure provides for an alternative (to the traditional thematic domains) hierarchical interpretation of CAPP-SR scores. (PsycInfo Database Record (c) 2021 APA, all rights reserved).

The energetics of carbonated PuO2 surfaces affects nanoparticle morphology: a DFT+U study.

Radiolytic corrosion of actinide materials represent an issue for the long term storage and disposal of nuclear materials. Molecular species adsorbed at the surface of the actinides may impact the rate of radiolysis, and as the surfaces corrode, the soluble toxic and radioactive species leach into groundwater. It is therefore critical to characterise the surface composition of actinides. Here, we employ ab initio modelling to determine the surface composition of PuO2 with respect to adsorbed CO2. We found that CO2 interacts strongly with the surface forming carbonate species. By mapping the energetics of this interaction, we then calculate the temperature of desorption, finding that surface morphology has a strong impact on the adsorption of CO2, with the {100} being the most and the {111} the least affected by carbonation. Finally, we predict the effect of carbonation on the morphology of PuO2 nanoparticles as a function of temperature and pressure, finding that truncated octahedral is the preferred morphology. This modelling strategy helps characterise surface compensition and nanoparticle morphology, and we discuss the implication for radiolytically driven dispersal of material into the environment.

Comparison between the Psychopathy Checklist-Revised and the Comprehensive Assessment of Psychopathic Personality in a representative sample of Spanish prison inmates.

In the field of psychopathy, there is an ongoing debate about the core traits that define the disorder, and that therefore must be present to some extent in all psychopaths. The main controversy of this debate concerns criminal behaviour, as some researchers consider it a defining trait, while others disagree. Using a representative sample of 204 Spanish convicted inmates incarcerated at the Pereiro de Aguiar Penitentiary in Ourense, Spain, we tested two competing models, the Psychopathy Checklist-Revised (PCL-R), which includes criminal behaviour items, versus the Comprehensive Assessment of Psychopathic Personality (CAPP), which does not. We used two different PCL-R models, one that includes criminal items and another that does not. PCL-R factors, facets, and testlets from both models and CAPP dimensions were correlated and compared. Two different PCL-R cut-off scores, 25 or more and 30 or more, were used for the analysis. Overall, a strong correlation was found between PCL-R and CAPP scores in the whole sample, but as scores increased and inmates became more psychopathic, the correlations weakened. All these data indicate that psychopathy, understood to mean having high scores on the PCL-R and CAPP, is a multidimensional entity, and inmates can develop the disorder and then receive the diagnosis through different dimensions. The CAPP domains showed better correlations when compared with the PCL-R factors from both models, showing that an instrument for the assessment of psychopathy without a criminal dimension is valuable for clinical assessment and research purposes.

Development and initial validation of the Comprehensive Assessment of Psychopathic Personality-Self-Report (CAPP-SR).

The Comprehensive Assessment of Psychopathic Personality (CAPP; Cooke, Hart, Logan, & Michie, 2012) is a concept map that entails 33 personality traits; it integrates historical and contemporary conceptualizations and operationalizations of psychopathy. The current project sought to develop and validate a self-report inventory to operationalize this concept map. Study 1 reported on the development of a CAPP Self-Report (CAPP-SR) inventory using expert ratings to select items for an experimental version. Next, these experimental items were evaluated in an online sample of 550 community-dwelling U.S. participants who were carefully recruited to match current U.S. census data on gender, age, and race/ethnicity. The application of various latent modeling and classical test theory procedures resulted in the 99-item CAPP-SR measure. In Study 2, two samples from the United States and New Zealand were used for initial validation purposes. CAPP scales showed a promising pattern of convergent validity with other self-report psychopathy scales. The new CAPP-SR inventory is promising for furthering research on this emerging psychopathy model in correctional, forensic, business, and other settings in which this clinical construct is of high importance. (PsycINFO Database Record (c) 2019 APA, all rights reserved).

An examination of Psychopathy Checklist-Revised latent factor structure via exploratory structural equation modeling.

The Psychopathy Checklist-Revised (PCL-R; Hare, 1991, 2003) is widely used in clinical and forensic practice. Its latent factor structure has been subject to debate and controversy for almost 40 years. Various principal component and factor models have been proposed. It is argued that the use of independent cluster models has been questionable. The use of models that assume that symptoms will have zero loadings on all but one factor fails to reflect the clinical reality that symptoms of personality disorder are likely to be the consequence of multiple latent traits. This misspecification of models will lead to excessive latent factor correlations, which, in turn, have a negative impact on the nomological network of relations among latent traits and other constructs. In this study, we applied exploratory structural equation modeling (ESEM) to PCL-R data derived from a multisite U.K. sample. First, we tested models derived from the 3- and 4-factor perspectives using confirmatory factor analysis. Second, we tested ESEM models based on these two perspectives. The 3-factor model displayed stability across both analytic methods, with the latent factor correlations being smaller in the ESEM analysis. The 4-factor model displayed less stability across analytic methods, with a major crime factor accounting for a large proportion of variance in numerous items. Comprehensive Assessment of Psychopathic Personality domain ratings were used as external criteria. The concurrent validity of the 3-factor ESEM model was conceptually clearer than that for the equivalent 4-factor model. The application of ESEM may provide greater clarity to the debate regarding the latent structure of the PCL-R. (PsycINFO Database Record (c) 2019 APA, all rights reserved).

Novel validity evidence of the Psychopathy Checklist- Revised (PCL-R) in a representative sample of Spanish inmates.

Psychopathy Checklist-Revised (PCL-R) validation studies have been conducted mainly in non representative samples of North American adult male serious offenders. Research in other samples is needed to test the generalizability of PCL-R construct validity. PCL-R psychometric properties and construct validity were evaluated in a representative sample of 204 Spanish sentenced inmates. These inmates had served at least 6 months of their sentence at Pereiro de Aguiar prison. This sample was heterogeneous with respect to type of official charges and was representative, as all offenders who met the inclusion and exclusion criteria were invited to participate. Classical test theory indexes of reliability, correlations between PCL-R items, factors and facets, external correlations, and factor structure analysis demonstrated that PCL-R affective, interpersonal and lifestyle dimensions were more reliable and valid for the psychopathy than the antisocial construct in this Southern European sample.

Clinician ratings of the Comprehensive Assessment of Psychopathic Personality (CAPP) in a representative sample of Spanish prison inmates: New validity evidence.

The Comprehensive Assessment of Psychopathic Personality (CAPP) is a concept map of psychopathic personality disorder (PPD). The CAPP- Institutional Rating Scale (IRS) is a tool designed to assess CAPP symptoms in institutional settings. The CAPP contains 33 personality traits organized in six domains: attachment, behavioural, cognitive, dominance, emotional and self. Until now, much of the CAPP research has been conducted out of clinical, forensic and correctional settings using self-ratings. In the current study, the psychometric properties and construct validity of the CAPP-IRS were evaluated in a non-convenience sample of 204 Spanish convicts. Clinician ratings were employed. Participants had been imprisoned for at least 6 months at Pereiro de Aguiar Penitentiary. This group of inmates was heterogeneous with respect to type of official charges, and representative as all convicts interned for at least 6 months in this prison were screened for participation. Classical test theory indexes of reliability, correlations between CAPP items and domains and external correlations and structural analyses demonstrated that CAPP assessment is a solid and robust way of evaluating psychopathy in a correctional setting. Best fit was found for a three-factor model: attachment and emotional items associated with a callous and unemotional trait, dominance and self items associated with a pathological interpersonal style, and behavioural and residual items from other domains associated with impulsivity.

Photochemistry of [Ru(pytz)(btz)2](2+) and Characterization of a κ(1)-btz Ligand-Loss Intermediate.

We report the synthesis, characterization, and photochemical reactivity of the triazole-containing complex [Ru(pytz)(btz)2](2+) (1, pytz = 1-benzyl-4-(pyrid-2-yl)-1,2,3-triazole, btz = 1,1'-dibenzyl-4,4'-bi-1,2,3-triazolyl). The UV-vis absorption spectrum of 1 exhibits pytz- and btz-centered (1)MLCT bands at 365 and 300 nm, respectively. Upon photoexcitation, acetonitrile solutions of 1 undergo conversion to the ligand-loss intermediate, trans-[Ru(pytz)(κ(2)-btz)(κ(1)-btz)(NCMe)](2+) (2, Φ363 = 0.013) and ultimately to the ligand-loss product trans-[Ru(pytz)(btz)(NCMe)2](2+) (3), both of which are observed and characterized by (1)H NMR spectroscopy. Time-dependent density functional theory calculations reveal that the S1 state of the complex has primarily HOMO → LUMO pytz-based (1)MLCT character. Data show that the (3)MLCT and (3)MC states are in close energetic proximity (≤0.11 eV to 2 d.p.) and that the T1 state from a single-point triplet state calculation at the S0 geometry suggests (3)MC character. Optimization of the T1 state of the complex starting from the ground state geometry leads to elongation of the two Ru-N(btz) bonds cis to the pytz ligand to 2.539 and 2.544 Å leading to a pseudo-4-coordinate (3)MC state rather than the (3)MLCT state. The work therefore provides additional insights into the photophysical and photochemical properties of ruthenium triazole-containing complexes and their excited state dynamics.

Ferrous Iron Binding Key to Mms6 Magnetite Biomineralisation: A Mechanistic Study to Understand Magnetite Formation Using pH Titration and NMR Spectroscopy.

Formation of magnetite nanocrystals by magnetotactic bacteria is controlled by specific proteins which regulate the particles' nucleation and growth. One such protein is Mms6. This small, amphiphilic protein can self-assemble and bind ferric ions to aid in magnetite formation. To understand the role of Mms6 during in vitro iron oxide precipitation we have performed in situ pH titrations. We find Mms6 has little effect during ferric salt precipitation, but exerts greatest influence during the incorporation of ferrous ions and conversion of this salt to mixed-valence iron minerals, suggesting Mms6 has a hitherto unrecorded ferrous iron interacting property which promotes the formation of magnetite in ferrous-rich solutions. We show ferrous binding to the DEEVE motif within the C-terminal region of Mms6 by NMR spectroscopy, and model these binding events using molecular simulations. We conclude that Mms6 functions as a magnetite nucleating protein under conditions where ferrous ions predominate.

Psychometric properties of the Hare Psychopathy Checklist-Revised (PCL-R) in a representative sample of Canadian federal offenders.

The Hare Psychopathy Checklist-Revised (PCL-R; Hare, 2003) is a commonly used psychological test for assessing traits of psychopathic personality disorder. Despite the abundance of research using the PCL-R, the vast majority of research used samples of convenience rather than systematic methods to minimize sampling bias and maximize the generalizability of findings. This potentially complicates the interpretation of test scores and research findings, including the "norms" for offenders from the United States and Canada included in the PCL-R manual. In the current study, we evaluated the psychometric properties of PCL-R scores for all male offenders admitted to a regional reception center of the Correctional Service of Canada during a 1-year period (n = 375). Because offenders were admitted for assessment prior to institutional classification, they comprise a sample that was heterogeneous with respect to correctional risks and needs yet representative of all offenders in that region of the service. We examined the distribution of PCL-R scores, classical test theory indices of its structural reliability, the factor structure of test items, and the external correlates of test scores. The findings were highly consistent with those typically reported in previous studies. We interpret these results as indicating it is unlikely any sampling limitations of past research using the PCL-R resulted in findings that were, overall, strongly biased or unrepresentative.

25-Hydroxyvitamin D C3-epimer is universally present in neonatal Western Australian samples but is unlikely to contribute to diagnostic misclassification.

BACKGROUND: The presence of C3-epimer (C-3-epi-25-hydroxyvitamin D) in infant serum may complicate 25-hydroxyvitamin D (25(OH)D) measurement when using liquid chromatography tandem mass spectrometry assays that do not separately measure the epimer. We measured the concentration of C3-epi-25(OH)D in neonatal samples in Western Australian using umbilical cord blood samples and a liquid chromatography tandem mass spectrometry assay that separately quantifies 25(OH)D and C3-epi-25(OH)D. METHODS: A total of 120 anonymized cord blood samples were analysed using a liquid chromatography tandem mass spectrometry assay that utilizes two CSH fluoro-phenyl columns in series. Chromatography was performed on a Waters Acquity Ultra Performance Liquid system, and quantification was using a Waters Quattro Premier XE mass spectrometer. RESULTS: C3-epi-25(OH)D3 was detected in all umbilical cord blood samples (median 5.2 nmol/L, IQR 3.7-6.6 nmol/L) and contributed 6.6% (SD 2.6, 95% CI [6.1, 7.1]) of the total 25(OH)D concentration. Mean 25(OH)D3 measured in cord blood was 79.1 nmol/L (SD 22.7 nmol/L). A positive relationship (R(2 )= 0.35, P < 0.0005) between 25(OH)D3 levels and C3-epi-25(OH)D3 was noted in this cohort. No samples contained 25(OH)D2 or C3-epi-25(OH)D2. CONCLUSION: C3-epi-25(OH)D3 is present in all neonatal samples but contributes <10% of the total 25(OH)D concentration which is unlikely to be clinically significant. Liquid chromatography tandem mass spectrometry assays that do not separately quantify C3-epi-25(OH)D3 from other vitamin D metabolites may potentially overestimate neonatal 25(OH)D levels, but diagnostic misclassification in neonates is unlikely.

Domains of psychopathy: evaluating the structure of a lexical model of psychopathic personality disorder.

This study examines the structure of the Comprehensive Assessment of Psychopathic Personality (CAPP) from a card sort perspective. The CAPP is a lexically based construct map of psychopathy comprising 33 symptoms organized by its developers into 6 broad functional domains of personality (i.e., Attachment, Behavioral, Cognitive; Dominance; Emotional, Self). Groups of mental health workers and students were asked to sort the CAPP symptoms into the model's 6 proposed domains. Overall, both mental health workers and students were able to categorize the symptoms speedily and intuitively according to model. This suggests that the CAPP model's hierarchical structure is plausible, and that the lexical nature of the model is successful in facilitating people's ability to understand features of psychopathy in a way that requires limited cognitive effort. Together, these findings support the validity of the CAPP model as a lexically based concept map of psychopathy. Yet, some exceptions to the overall pattern of agreement with model were identified.

Phage display selected magnetite interacting Adhirons for shape controlled nanoparticle synthesis.

Adhirons are robust, well expressing, peptide display scaffold proteins, developed as an effective alternative to traditional antibody binding proteins for highly specific molecular recognition applications. This paper reports for the first time the use of these versatile proteins for material binding, and as tools for controlling material synthesis on the nanoscale. A phage library of Adhirons, each displaying two variable binding loops, was screened to identify specific proteins able to interact with [100] faces of cubic magnetite nanoparticles. The selected variable regions display a strong preference for basic residues such as lysine. Molecular dynamics simulations of amino acid adsorption onto a [100] magnetite surface provides a rationale for these interactions, with the lowest adsorption energy observed with lysine. These proteins direct the shape of the forming nanoparticles towards a cubic morphology in room temperature magnetite precipitation reactions, in stark contrast to the high temperature, harsh reaction conditions currently used to produce cubic nanoparticles. These effects demonstrate the utility of the selected Adhirons as novel magnetite mineralization control agents using ambient aqueous conditions. The approach we outline with artificial protein scaffolds has the potential to develop into a toolkit of novel additives for wider nanomaterial fabrication.

A Prototypicality Validation of the Comprehensive Assessment of Psychopathic Personality (CAPP) Model Spanish Version.

The Comprehensive Assessment of Psychopathic Personality (CAPP) is a newly developed, lexically based, conceptual model of psychopathy. The content validity of the Spanish language CAPP model was evaluated using prototypicality analysis. Prototypicality ratings were collected from 187 mental health experts and from samples of 143 health professionals and 282 community residents. Across the samples the majority of CAPP items were rated as highly prototypical of psychopathy. The Self, Dominance, and Attachment domains were evaluated as being more prototypical than the Behavioral and Cognitive domains. These findings are consistent with findings from similar studies in other languages and provide further support for the content validation of the CAPP model across languages and the lexical approach.