Deposition products predicted from conceptual DFT: The hydrolysis reactions of MoF6, WF6, and UF6.

Metal hexafluorides hydrolyze at ambient temperature to deposit compounds having fluorine-to-oxygen ratios that depend upon the identity of the metal. Uranium-hexafluoride hydrolysis, for example, deposits uranyl fluoride (UO2F2), whereas molybdenum hexafluoride (MoF6) and tungsten hexafluoride deposit trioxides. Here, we pursue general strategies enabling the prediction of depositing compounds resulting from multi-step gas-phase reactions. To compare among the three metal-hexafluoride hydrolyses, we first investigate the mechanism of MoF6 hydrolysis using hybrid density functional theory (DFT). Intermediates are then validated by performing anharmonic vibrational simulations and comparing with infrared spectra [McNamara et al., Phys. Chem. Chem. Phys. 25, 2990 (2023)]. Conceptual DFT, which is leveraged here to quantitatively evaluate site-specific electrophilicity and nucleophilicity metrics, is found to reliably predict qualitative deposition propensities for each intermediate. In addition to the nucleophilic potential of the oxygen ligands, several other contributing characteristics are discussed, including amphoterism, polyvalency, fluxionality, steric hindrance, dipolar strength, and solubility. To investigate the structure and composition of pre-nucleation clusters, an automated workflow is presented for the simulation of particle growth. The workflow entails a conformer search at the density functional tight-binding level, structural refinement at the hybrid DFT level, and computation of a composite free-energy profile. Such profiles can be used to estimate particle nucleation kinetics. Droplet formation is also considered, which helps to rationalize the different UO2F2 particle morphologies observed under varying levels of humidity. Development of predictive methods for simulating physical and chemical deposition processes is important for the advancement of material manufacturing involving coatings and thin films.

Solvent free, catalytic and diastereoselective preparation of aryl and alkyl thioglycosides as key components for oligosaccharide synthesis.

A new and environmentally friendly protocol for the conversion of sugar per-acetates into thioglycosides under solvent free and catalytic conditions is presented. The procedure involves heating in the presence of InCl3 and various aryl thiols. For alkyl thioglycoside synthesis, cyclohexane thiol was found to give good results and yield a glycosyl donor with reactivity similar to a thioethyl congener. The established optimum reaction conditions were found to provide the desired thioglycoside products in an easy and highly diastereoselective manner even when conducted on a multigram scale.

A theoretical investigation of the hydrolysis of uranium hexafluoride: the initiation mechanism and vibrational spectroscopy.

Depleted uranium hexafluoride (UF6), a stockpiled byproduct of the nuclear fuel cycle, reacts readily with atmospheric humidity, but the mechanism is poorly understood. We compare several potential initiation steps at a consistent level of theory, generating underlying structures and vibrational modes using hybrid density functional theory (DFT) and computing relative energies of stationary points with double-hybrid (DH) DFT. A benchmark comparison is performed to assess the quality of DH-DFT data using reference energy differences obtained using a complete-basis-limit coupled-cluster (CC) composite method. The associated large-basis CC computations were enabled by a new general-purpose pseudopotential capability implemented as part of this work. Dispersion-corrected parameter-free DH-DFT methods, namely PBE0-DH-D3(BJ) and PBE-QIDH-D3(BJ), provided mean unsigned errors within chemical accuracy (1 kcal mol-1) for a set of barrier heights corresponding to the most energetically favorable initiation steps. The hydrolysis mechanism is found to proceed via intermolecular hydrogen transfer within van der Waals complexes involving UF6, UF5OH, and UOF4, in agreement with previous studies, followed by the formation of a previously unappreciated dihydroxide intermediate, UF4(OH)2. The dihydroxide is predicted to form under both kinetic and thermodynamic control, and, unlike the alternate pathway leading to the UO2F2 monomer, its reaction energy is exothermic, in agreement with observation. Finally, harmonic and anharmonic vibrational simulations are performed to reinterpret literature infrared spectroscopy in light of this newly identified species.

A unifying model of weakly nonlinear elastic waves; large on large theory.

This article reconsiders traditional topics in nonlinear elastic waves and nonlinear ultrasonics. Herein, higher-order coupling between finite initial deformation and finite amplitude waves are considered. To allow for coupling, a large-on-large deformation model is developed and used to generate the equations of motion relative to the deformed and undeformed material configurations. Thus, the equations of motion provide a single setting to describe topics in nonlinear elastic waves such as acoustoelasticity, second harmonic generation, and coupling relations between these topics. The model is evaluated to recover the traditional linearized acoustoelastic relations and predicted second harmonic amplitudes. Then, the so-called large acoustoelasticity theory is developed for anisotropic materials with specific results given for isotropic materials. Last, the stress influence on second harmonic generation is presented.

Goal management training for adults with ADHD - clients' experiences with a group-based intervention.

BACKGROUND: There is growing evidence for the efficacy of group-based interventions for adults with ADHD. However, there is still a lack of research investigating how clients experience participating in such interventions. The aim of the current study was to explore how adults with ADHD experience participating in a group-based intervention (Goal Management Training) for ADHD. METHOD: We conducted individual, semi-structured, interviews with ten adults with ADHD who had participated in Goal Management Training administered as a group intervention. The interviews were transcribed verbatim and analyzed using thematic analysis within a hermeneutic phenomenological framework. RESULTS: Our analysis identified three main themes. The participants' starting point captured the participants' motivation and expectations prior to treatment. The ambiguity of the group - the various meanings of the group consisted of three sub-themes (The group created a sense of belonging - "I am not alone"; The personal cost of participating in the group - "At times it was a hot mess"; and The group supported the learning experience - "We worked with it together"). The group promoted positive change - How the group affected the participants' everyday lives consisted of two sub-themes (Managing ADHD in daily life - "It's much easier to handle everyday life", and Personal growth - "Gaining new perspectives"). CONCLUSION: The group format was experienced as a valuable aspect of treatment. The structure provided by Goal Management Training allowed participants to expand their perspectives and experience improved management of ADHD, as well as personal growth. The opportunity to exchange experiences with others in similar situations was seen as particularly beneficial and brought feelings of recognition and belonging. However, some also experienced the group as a burden at times, for instance by stealing one's focus. This study expands existing knowledge by exploring clients' experiences of participating in group-based interventions for ADHD and shows how the group format provided participants with more than they had hoped for. While expecting a more instrumental outcome of treatment, such as tools to manage ADHD, participants also gained a welcomed, but unexpected outcome of personal growth.

Clinical evaluation and in-vivo analysis of the performance of a fractional infrared 1550 nm laser system for skin rejuvenation.

Background: This study was done to demonstrate the safety and efficacy of a novel fractional 1550 nm laser device with a rolling mechanism (FRAX1550 Ellipse Medical, Horsholm, Denmark). Objectives: To evaluated the effectiveness of the 1550 nm device for improvement in wrinkles, pigmentation, and texture on a six point (-1 to 4) global improvement scale. Methods: Five female subjects between the ages of 44 and 71 years, with visible wrinkles and/or dyspigmentation were enrolled in the study. Two full face treatments were performed four weeks apart Follow-up visits at 1 and 3 months posttreatment were scheduled for photographic assessments. Assessment of improvement were performed by the investigators and two blinded evaluators through use of a six-point scale. Results: All subjects demonstrated improvement in all monitored parameters. The mean improvement scores were: wrinkles 1.6, skin texture 1.8, and pigmentation 1.7. All score improvements were statistically significant. Biopsy was performed on one patient immediately post-treatment and showed 800 µ penetration depth at a treatment level of 88 mJ and 400 µ at 44 mJ. Conclusions: The new rolling fractional 1550 nm laser device from this study offers improvement of aging facial skin with short downtime and minimal side effects.

Rochester Epidemiology Project Data Exploration Portal.

INTRODUCTION: The goal of this project was to develop an interactive, web-based tool to explore patterns of prevalence and co-occurrence of diseases using data from the expanded Rochester Epidemiology Project (E-REP) medical records-linkage system. METHODS: We designed the REP Data Exploration Portal (REP DEP) to include summary information for people who lived in a 27-county region of southern Minnesota and western Wisconsin on January 1, 2014 (n = 694,506; 61% of the entire population). We obtained diagnostic codes of the International Classification of Diseases, 9th edition, from the medical records-linkage system in 2009 through 2013 (5 years) and grouped them into 717 disease categories. For each condition or combination of 2 conditions (dyad), we calculated prevalence by dividing the number of persons with a specified condition (numerator) by the total number of persons in the population (denominator). We calculated observed-to-expected ratios (OERs) to test whether 2 conditions co-occur more frequently than would co-occur as a result of chance alone. RESULTS: We launched the first version of the REP DEP in May 2017. The REP DEP can be accessed at http://rochesterproject.org/portal/. Users can select 2 conditions of interest, and the REP DEP displays the overall prevalence, age-specific prevalence, and sex-specific prevalence for each condition and dyad. Also displayed are OERs overall and by age and sex and maps of county-specific prevalence of each condition and OER. CONCLUSION: The REP DEP draws upon a medical records-linkage system to provide an innovative, rapid, interactive, free-of-charge method to examine the prevalence and co-occurrence of 717 diseases and conditions in a geographically defined population.

Numerical density-to-potential inversions in time-dependent density functional theory.

We treat the density-to-potential inverse problem of time-dependent density functional theory as an optimization problem with a partial differential equation constraint. The unknown potential is recovered from a target density by applying a multilevel optimization method controlled by error estimates. We employ a classical optimization routine using gradients efficiently computed by the discrete adjoint method. The inverted potential has both a real and imaginary part to reduce reflections at the boundaries and other numerical artifacts. We demonstrate this method on model one-dimensional systems. The method can be straightforwardly extended to a variety of numerical solvers of the time-dependent Kohn-Sham equations and to systems in higher dimensions.

Phenotypic and genetic characterization of Piscirickettsia salmonis from Chilean and Canadian salmonids.

BACKGROUND: The study presents the phenotypic and genetic characterization of selected P. salmonis isolates from Atlantic salmon and rainbow trout suffering from SRS (salmonid rickettsial septicemia) in Chile and in Canada. The phenotypic characterization of the P. salmonis isolates were based on growth on different agar media (including a newly developed medium), different growth temperatures, antibiotics susceptibility and biochemical tests. RESULTS: This is the first study differentiating Chilean P. salmonis isolates into two separate genetic groups. Genotyping, based on 16S rRNA-ITS and concatenated housekeeping genes grouped the selected isolates into two clades, constituted by the Chilean strains, while the Canadian isolates form a branch in the phylogenetic tree. The latter consisted of two isolates that were different in both genetic and phenotypic characteristics. The phylogenies and the MLST do not reflect the origin of the isolates with respect to host species. The isolates included were heterogeneous in phenotypic tests. CONCLUSIONS: The genotyping methods developed in this study provided a tool for separation of P. salmonis isolates into distinct clades. The SRS outbreaks in Chile are caused by minimum two different genetic groups of P. salmonis. This heterogeneity should be considered in future development of vaccines against this bacterium in Chile. Two different strains of P. salmonis, in regards to genetic and phenotypic characteristics, can occur in the same contemporary outbreak of SRS.

Probabilistic inference and ranking of gene regulatory pathways as a shortest-path problem.

BACKGROUND: Since the advent of microarray technology, numerous methods have been devised to infer gene regulatory relationships from gene expression data. Many approaches that infer entire regulatory networks. This produces results that are rich in information and yet so complex that they are often of limited usefulness for researchers. One alternative unit of regulatory interactions is a linear path between genes. Linear paths are more comprehensible than networks and still contain important information. Such paths can be extracted from inferred regulatory networks or inferred directly. Since criteria for inferring networks generally differs from criteria for inferring paths, indirect and direct inference of paths may achieve different results. RESULTS: This paper explores a strategy to infer linear pathways by converting the path inference problem into a shortest-path problem. The edge weights used are the negative log-transformed probabilities of directness derived from the posterior joint distributions of pairwise mutual information between gene expression levels. Directness is inferred using the data processing inequality. The method was designed with two goals. One is to achieve better accuracy in path inference than extraction of paths from inferred networks. The other is to facilitate priorization of interactions for laboratory validation. A method is proposed for achieving this by ranking paths according to the joint probability of directness of each path's edges. The algorithm is evaluated using simulated expression data and is compared to extraction of shortest paths from networks inferred by two alternative methods, ARACNe and a minimum spanning tree algorithm. CONCLUSIONS: Direct path inference appears to achieve accuracy competitive with that obtained by extracting paths from networks inferred by the other methods. Preliminary exploration of the use of joint edge probabilities to rank paths is largely inconclusive. Suggestions for a better framework for such comparisons are discussed.

A brief Patient-Reported Outcomes Quality of Life (PROQOL) instrument to improve patient care.

Jeff Sloan and colleagues describe the development of the Patient-Reported Outcomes Quality of Life (PROQOL) instrument, which captures and stores patient-recorded outcomes in the medical record for patients with diabetes. Please see later in the article for the Editors' Summary.

Fragment-based time-dependent density functional theory.

Using the Runge-Gross theorem that establishes the foundation of time-dependent density functional theory, we prove that for a given electronic Hamiltonian, choice of initial state, and choice of fragmentation, there is a unique single-particle potential (dubbed time-dependent partition potential) which, when added to each of the preselected fragment potentials, forces the fragment densities to evolve in such a way that their sum equals the exact molecular density at all times. This uniqueness theorem suggests new ways of computing the time-dependent properties of electronic systems via fragment-time-dependent density functional theory calculations. We derive a formally exact relationship between the partition potential and the total density, and illustrate our approach on a simple model system for binary fragmentation in a laser field.

Endothelial protein C receptor binding induces conformational changes to severe malaria-associated group A PfEMP1.

Severe Plasmodium falciparum malaria infections are caused by microvascular sequestration of parasites binding to the human endothelial protein C receptor (EPCR) via the multi-domain P. falciparum erythrocyte membrane protein 1 (PfEMP1) adhesion ligands. Using cryogenic electron microscopy (Cryo-EM) and PfEMP1 sequence diversity analysis, we found that group A PfEMP1 CIDRα1 domains interact with the adjacent DBLα1 domain through central, conserved residues of the EPCR-binding site to adopt a compact conformation. Upon EPCR binding, the DBLα1 domain is displaced, and the EPCR-binding helix of CIDRα1 is turned, kinked, and twisted to reach a rearranged, stable EPCR-bound conformation. The unbound conformation and the required transition to the EPCR-bound conformation may represent a conformational masking mechanism of immune evasion for the PfEMP1 family.

Impact of peptide:HLA complex stability for the identification of SARS-CoV-2-specific CD8+T cells.

Induction of a lasting protective immune response is dependent on presentation of epitopes to patrolling T cells through the HLA complex. While peptide:HLA (pHLA) complex affinity alone is widely exploited for epitope selection, we demonstrate that including the pHLA complex stability as a selection parameter can significantly reduce the high false discovery rate observed with predicted affinity. In this study, pHLA complex stability was measured on three common class I alleles and 1286 overlapping 9-mer peptides derived from the SARS-CoV-2 Spike protein. Peptides were pooled based on measured stability and predicted affinity. Strikingly, stability of the pHLA complex was shown to strongly select for immunogenic epitopes able to activate functional CD8+T cells. This result was observed across the three studied alleles and in both vaccinated and convalescent COVID-19 donors. Deconvolution of peptide pools showed that specific CD8+T cells recognized one or two dominant epitopes. Moreover, SARS-CoV-2 specific CD8+T cells were detected by tetramer-staining across multiple donors. In conclusion, we show that stability analysis of pHLA is a key factor for identifying immunogenic epitopes.

Pott's puffy tumor in a 23-month-old: Youngest known case of a rare disease.

This case report describes a child who developed Pott's puffy tumor and was treated at the Children's Mercy Hospital in Kansas City. In addition to a discussion of a case, a review of the literature was completed on this topic describing the typical embryology and development of the frontal sinus, and the epidemiology, diagnosis, and treatment of Pott's puffy tumor. The patient was a 23-month-old boy who developed Pott's puffy tumor after recovery from influenza. The patient presented to the hospital with progressing edema of the unilateral eye that spread bilaterally within a few days. A CT scan demonstrated pansinusitis, developed frontal sinuses, right periorbital cellulitis, and medial forehead subperiosteal abscess. Functional endoscopic sinus surgery and transcutaneous abscess drainage were urgently performed and the patient made a full recovery following a course of ertapenem and levofloxacin. The presence of a developed frontal sinus in a 23-month-old is an unexpected radiologic finding. This case represents the youngest patient reported in the literature to develop this rare complication of frontal sinusitis.

Clinical predictors of invasive fungal rhinosinusitis in a tertiary pediatric hospital.

OBJECTIVES: Invasive fungal rhinosinusitis (IFRS) is a potentially fatal disease that affects the severely immunocompromised and requires aggressive treatment. The objective of this study is to better describe predictors of biopsy positivity in patients at high risk of IFRS at a pediatric hospital. METHODS: This was a single-center case-control study of 36 patients (37 total biopsies) ≤ 21 years old with one of five high-risk oncologic/hematologic diagnoses who underwent operative endoscopy for clinical suspicion for IFRS. IFRS positivity was defined histologically. Collected information included patient demographics, primary diagnosis, oncologic relapses, time from diagnosis to biopsy, clinical characteristics, and endoscopic findings. These data were used to create a simple predictive scoring system. RESULTS: 17 patients had biopsy-proven IFRS (IFRS(+)) for an overall incidence of 2.1% in the designated high-risk population. Average time from most recent oncologic development (diagnosis, relapse, or hematopoietic stem-cell transplant) to biopsy in the IFRS(+) group was 2.09 months (SD = 2.26), and 7.28 months in the IFRS(-) group (SD = 9.17) (p = 0.009). Clinical characteristics did not differentiate between IFRS(+) and IFRS(-). Bedside endoscopy performed poorly, as it was interpreted as normal in 42.8% of IFRS(+) and 53.8% of IFRS(-). In contrast, the presence of any positive endoscopic finding intra-operatively was highly specific for IFRS(+) (94%) with moderate sensitivity (70%), and the difference in rate of positivity between groups was statistically significant (p < 0.001). CONCLUSION: Operative endoscopy with biopsy remains the gold-standard to rule-out IFRS in the setting of high clinical suspicion. Time elapsed from most recent oncologic development to clinical concern for IFRS may influence the likelihood of disease, though this requires further study. Clinical symptoms and bedside endoscopy were not predictive and should be used with caution in decision-making.

Goal management training improves executive control in adults with ADHD: an open trial employing attention network theory to examine effects on attention.

BACKGROUND: Adults with Attention-Deficit/Hyperactivity Disorder (ADHD) typically experience poorer attentional control. According to the attention network theory, attentional control relies on three interacting networks of alerting, orienting, and executive control. In ADHD, it is mainly the alerting and executive control networks that are suggested and found to be compromised. METHODS: In the current study, we investigated if a group-based metacognitive remediation program (Goal Management Training [GMT]) in adults with ADHD would enhance attentional control using an experimental measure of the attention network theory. We expected that GMT would specifically enhance the executive control and alerting networks. RESULTS: Data from post- and follow up-assessments of 21 adults (age: 39.05 [11.93]) with ADHD who had completed GMT were included. Linear mixed-effects modeling revealed significant improvements in the functioning of the executive control network for the majority of the participants, although a small subset of participants showed a negative development following the intervention. Results also showed an improvement in the orienting network at follow up, but no change in the alerting network. CONCLUSION: The results may indicate that improvements in the functioning of the executive control network are central to the positive effects of GMT reported in disorders characterized by impaired attentional control. TRIAL REGISTRATION: The study was retrospectively registered in the ISRCTN (Identifier: ISRCTN91988877) on the 18/01/2021.

Pharmacologic management of post-tonsillectomy pain in children.

Tonsillectomy is a very common procedure in children, often performed on an outpatient basis. Severe postoperative pain is common, and can be prolonged. Despite a large number of available analgesic medications, often employed in combination, achieving adequate pain control remains a persistent challenge. Research suggests a tendency among caregivers to undertreat pain, and a need for detailed care instructions and education to ensure adequate pain management. Furthermore, ongoing questions regarding the safety and efficacy of the most commonly used medications have led to wide variance in practice patterns and continuous reassessment through research that yields sometimes conflicting results. This review summarizes the current state of the literature and presents a management approach which attempts to maximize pain control while minimizing potential harm with combinations of medications and modification based on patient-specific factors.

Test-Retest Reliability of the 25-item version of Wender Utah Rating Scale. Impact of Current ADHD Severity on Retrospectively Assessed Childhood Symptoms.

Objective: To investigate test-retest reliability of the 25-item version of Wender Utah Rating Scale (WURS-25) and factors influencing retrospective reports of childhood behavior in adults with ADHD. Method: Eighty-five adults with ADHD and 189 controls completed the WURS-25 and the adult ADHD Self-Rating Scale (ASRS) at two time points (mean interval = 7 years) and provided information about dyslexia, somatic, and psychiatric disorders. Results: The correlation between WURS-25 scores at the two time points was strong, and reports from 60% of the adults with ADHD showed no change in severity level. Reports on the WURS-25 were positively associated with current ADHD symptoms at both time points and the presence of dyslexia and mood disorders, with the strongest association found among adults reporting the most severe WURS-25 score. Conclusion: Although our study showed an acceptable test-retest reliability of WURS-25, the substantial contribution from current ADHD symptoms to the WURS scores emphasizes the importance of collateral information from family members and others who knew the adult in childhood.

An Exploratory Investigation of Goal Management Training in Adults With ADHD: Improvements in Inhibition and Everyday Functioning.

Background: Adults with attention deficit/hyperactivity disorder (ADHD) are predominantly treated with medication. However, there is also a need for effective, psychologically based interventions. As ADHD is strongly associated with reduced inhibitory control, cognitive remediation approaches should be efficient. Goal management training (GMT) aims at enhancing inhibitory control and has shown positive effects on inhibitory control in non-ADHD patient groups. The aim of the current study was to explore whether GMT would specifically enhance inhibitory control in adults with ADHD, and if such an enhancement would lead to secondary improvements in self-reported everyday functioning. Methods: Twenty-one participants with ADHD (mean age: 39.05 years [SD 11.93]) completed the intervention and assessments pre-, post- and 6 months after the intervention. Measures included neuropsychological tests and self-report questionnaires pertaining to cognitive- and executive functioning, emotion regulation, quality of life, and ADHD symptoms. Results: Compared to baseline, the participants showed enhanced inhibitory control on performance-based measures at post-assessment and 6-month follow-up. The participants also reported increased productivity and reduced cognitive difficulties in everyday life at both assessments post-treatment, as well as improvements in aspects of emotion regulation and a reduction in the severity of core ADHD-symptoms at 6-month follow-up. Conclusion: Our exploratory study showed that GMT seems to specifically improve one of the core executive dysfunctions in ADHD, namely inhibitory control, with a positive effect lasting at least 6 months post-treatment. The adults with ADHD also reported improved self-regulation in their everyday life after completing GMT, providing strong arguments for further investigations of GMT as a treatment option for this group of adults. Clinical Trial Registration: The study is registered under ISRCTN.com (ISRCTN91988877; https://doi.org/10.1186/ISRCTN91988877).