Examining the self-assembly of patchy alkane-grafted silica nanoparticles using molecular simulation.

In this work, molecular dynamics simulations are used to examine the self-assembly of anisotropically coated "patchy" nanoparticles. Specifically, we use a coarse-grained model to examine silica nanoparticles coated with alkane chains, where the poles of the grafted nanoparticle are bare, resulting in strongly attractive patches. Through a systematic screening process, the patchy nanoparticles are found to form dispersed, string-like, and aggregated phases, dependent on the combination of alkane chain length, coating chain density, and the fractional coated surface area. Correlation analysis is used to identify the ability of various particle descriptors to predict bulk phase behavior from more computationally efficient single grafted nanoparticle simulations and demonstrates that the solvent-accessible surface area of the nanoparticle core is a key predictor of bulk phase behavior. The results of this work enhance our knowledge of the phase space of patchy nanoparticles and provide a powerful approach for future screening of these materials.

The Emotional Resources Group: Provisional outcome data for a pilot six-session emotion regulation programme for secondary care.

OBJECTIVE: To examine the effectiveness of a new, six-session emotion regulation group intervention designed for the secondary care setting: The Emotional Resources Group (ERG). METHOD: In this pilot study, participants were recruited by referral from secondary care mental health services. Forty-seven individuals participated in the study. Participants who attended the ERG were compared on measures of emotion regulation, well-being, and self-efficacy, pre- and post-intervention. RESULTS: Intent-to-treat analyses indicated highly statistically significant improvements in measures of emotion regulation, well-being, and self-efficacy, accompanied by large effect sizes. In addition, improvements in emotion regulation produced good rates of both reliable and clinically significant change. CONCLUSIONS: The ERG may be an effective, brief intervention to improve emotion regulation in the secondary care setting, worthy of further evaluation. PRACTITIONER POINTS: Clinical implications Emotion regulation may be an appropriate treatment target to improve well-being and self-efficacy in a transdiagnostic population. The ERG may be effective as a brief emotion regulation intervention for secondary care mental health settings. Outcomes of the ERG appear to be equivalent to other more intensive group-based emotion regulation interventions. The ERG's tailored design may be responsible for positive outcomes. Limitations There was a small sample size. There was no control group. There was no follow-up data.

Investigating Alkylsilane Monolayer Tribology at a Single-Asperity Contact with Molecular Dynamics Simulation.

Chemisorbed monolayer films are known to possess favorable characteristics for nanoscale lubrication of micro- and nanoelectromechanical systems (MEMS/NEMS). Prior studies have shown that the friction observed for monolayer-coated surfaces features a strong dependence on the geometry of contact. Specifically, tip-like geometries have been shown to penetrate into monolayer films, inducing defects in the monolayer chains and leading to plowing mechanisms during shear, which result in higher coefficients of friction (COF) than those observed for planar geometries. In this work, we use molecular dynamics simulations to examine the tribology of model silica single-asperity contacts under shear with monolayer-coated substrates featuring various film densities. It is observed that lower monolayer densities lead to reduced COFs, in contrast to results for planar systems where COF is found to be nearly independent of monolayer density. This is attributed to a liquid-like response to shear, whereby fewer defects are imparted in monolayer chains from the asperity, and chains are easily displaced by the tip as a result of the higher free volume. This transition in the mechanism of molecular plowing suggests that liquid-like films should provide favorable lubrication at single-asperity contacts.

Influence of Surface Morphology on the Shear-Induced Wear of Alkylsilane Monolayers: Molecular Dynamics Study.

Chemisorbed alkylsilane monolayer coatings have been shown to possess favorable lubrication properties; however, film degradation prevents the widespread use of these materials as lubricants in micro- and nanoelectromechanical systems (MEMS/NEMS). In this work, molecular dynamics (MD) simulations are used to provide insight into the conditions that promote the degradation and wear of these materials. This is achieved through removal of interfacial chain-substrate bonds during shear and the examination of the mobility of the resulting free, unbound chains. Specific focus is given to the effects of surface morphology, which has been shown previously to strongly influence frictional forces in monolayer systems. In-plane order of chain attachments is shown to lead to pressure-induced orientational ordering of monolayers, promoting film stability. This behavior is lost as nonideality is introduced into the substrate and chain patterning on the surface becomes disordered. The presence of surface roughness is found to reduce film stability, with localization of wear observed for chain attachment sites nearest the interface of contact. The influence of substrate nonideality on monolayer degradation is shown to diminish as chain length is increased.

Synthesis, characterization, and reversible hydrogen sorption study of sodium-doped fullerene.

Herein is presented a novel, straightforward route to the synthesis of an alkali metal-doped fullerene as well as a detailed account of its reversible and enhanced hydrogen sorption properties in comparison to pure C60. This work demonstrates that a reaction of sodium hydride with fullerene (C60) results in the formation of a sodium-doped fullerene capable of reversible hydrogen sorption via a chemisorption mechanism. This material not only demonstrated reversible hydrogen storage over several cycles, it also showed the ability to reabsorb over three times the amount of hydrogen (relative to the hydrogen content of NaH) under optimized conditions. The sodium-doped fullerene was hydrogenated on a pressure composition temperature (PCT) instrument at 275 °C while under 100 bar of hydrogen pressure. The hydrogen desorption behavior of this sodium-doped fullerene hydride was observed over a temperature range up to 375 °C on the PCT and up to 550 °C on the thermogravimetric analysis (TGA). Powder x-ray diffraction verifies the identity of this material as being Na6C60. Characterization of this material by thermal decomposition analysis (e.g. PCT and TGA methods), as well as FT-IR and mass spectrometry, indicates that the hydrogen sorption activity of this material is due to the reversible formation of a hydrogenated fullerene (fullerane). However, the reversible formation of fullerane was found to be greatly enhanced by the presence of sodium. It was also demonstrated that the addition of a catalytic amount of titanium (via TiO2 or Ti(OBu)4) further enhances the hydrogen sorption process of the sodium-doped fullerene material.

Trans-seasonal activation of the neuroendocrine reproductive axis: Low-temperature winter dormancy modulates gonadotropin-releasing hormone neurons in garter snakes.

All animals use external cues from the environment to accurately time life-history events. How the brain decodes environmental stimuli to effect changes in physiology and behavior, however, is poorly understood, particularly with regard to supplementary environmental cues such as temperature. We asked if low-temperature dormancy alters the synthesis and/or release of gonadotropin-releasing hormone (GnRH). We used the well-studied red-sided garter snake (Thamnophis sirtalis) for this study, as low-temperature exposure is both necessary and sufficient to induce reproduction in northern populations of this species. Snakes were collected from the field and hibernated at 4°C or 10°C in complete darkness for up to 16 weeks. In males, increasing duration of low-temperature dormancy significantly increased GnRH-immunoreactive cell number and GnRH soma size (a proxy for relative cell activity) in the forebrain. These changes mirrored those in male reproductive behavior (reported previously) and plasma androgen concentrations. The changes in GnRH cell area observed in males were specific to the neuroendocrine population of cells in the medial preoptic area; soma size in the rostral GnRH cells did not change. Finally, temperature-induced changes in GnRH were sexually dimorphic: neither hibernation temperature nor the duration of winter dormancy significantly modulated GnRH cell number or soma size in females, despite the fact that plasma estradiol and corticosterone increased significantly in response to both. These data demonstrate that the neuroendocrine GnRH system is sensitive to environmental temperature and suggest that GnRH neurons play a conserved but trans-seasonal role in mediating changes in reproductive physiology and behavior in dissociated breeders.

Epidemiology of Pediatric Nonballistic Firearm Injuries to the Upper Extremity in the United States From 2000 to 2017.

Background: This study aimed to describe the epidemiology of pediatric upper extremity injury secondary to nonballistic firearms in the United States. Methods: The National Electronic Injury Surveillance Survey (NEISS) database was queried between 2000 and 2017 for injuries to the upper extremity from nonballistic firearms in patients aged ≤18 years. In total, 1502 unique cases were identified. Using input parameters intrinsic to the NEISS database, national weighted estimates were derived using Stata/IC 15.1 statistical software (StataCorp LLC, College Station, Texas), which yielded an estimate of 52 118 cases of nonballistic firearm trauma to the upper extremity who presented to US emergency departments over the study period. Descriptive statistics were performed using NEISS parameters. Results: An average of 2895 annual pediatric upper extremity nonballistic firearm injuries were identified between 2000 and 2017. Over 91% were sustained by men, and adolescents aged 12 to 18 were the most commonly injured (69.8%). Only 3.5% of all injuries required inpatient admission, and the most common sites of injury were the hand (41.1%), followed by fingers (35.9%). Conclusions: We conclude that nonballistic firearm injuries represent a significant burden of disease to adolescent men in the United States.

MoSDeF, a Python Framework Enabling Large-Scale Computational Screening of Soft Matter: Application to Chemistry-Property Relationships in Lubricating Monolayer Films.

We demonstrate how the recently developed Python-based Molecular Simulation and Design Framework (MoSDeF) can be used to perform molecular dynamics screening of functionalized monolayer films, focusing on tribological effectiveness. MoSDeF is an open-source package that allows for the programmatic construction and parametrization of soft matter systems and enables TRUE (transferable, reproducible, usable by others, and extensible) simulations. The MoSDeF-enabled screening identifies several film chemistries that simultaneously show low coefficients of friction and adhesion. We additionally develop a Python library that utilizes the RDKit cheminformatics library and the scikit-learn machine learning library that allows for the development of predictive models for the tribology of functionalized monolayer films and use this model to extract information on terminal group characteristics that most influence tribology, based on the screening data.

Utility of the Current Procedural Terminology Codes for Prophylactic Stabilization for Defining Metastatic Femur Disease.

INTRODUCTION: Cohorts from the electronic health record are often defined by the Current Procedural Terminology (CPT) codes. The error prevalence of CPT codes for patients receiving surgical treatment of metastatic disease of the femur has not been investigated, and the predictive value of coding ontologies to identify patients with metastatic disease of the femur has not been adequately discussed. METHODS: All surgical cases at a single academic tertiary institution from 2010 through 2015 involving prophylactic stabilization of the femur or fixation of a pathologic fracture of the femur were identified using the CPT and International Classification of Disease (ICD) codes. A detailed chart review was conducted to determine the procedure performed as documented in the surgical note and the patient diagnosis as documented in the pathology report, surgical note, and/or office visit notes. RESULTS: We identified 7 CPT code errors of 171 prophylactic operations (4.1%) and one error of 71 pathologic fracture fixation s(1.4%). Of the 164 prophylactic operations that were coded correctly, 87 (53.0%) had metastatic disease. Of the 70 pathologic operations that were coded correctly, 41 (58%) had metastatic disease. DISCUSSION: The error prevalence was low in both prophylactic stabilization and pathologic fixation groups (4.1% and 1%, respectively). The structured data (CPT and ICD-9 codes) had a positive predictive value for patients having metastatic disease of 53% for patients in the prophylactic stabilization group and 58% for patients in the pathologic fixation group. The CPT codes and ICD codes assessed in this analysis do provide a useful tool for defining a population in which a moderate proportion of individuals have metastatic disease in the femur at an academic medical center. However, verification is necessary.

Managing dyspepsia in primary care.

NICE recommends immediate referral for patients with dyspepsia and significant acute GI bleeding and urgent specialist referral for investigation if any of the following alarm symptoms are present: progressive difficulty swallowing; chronic GI bleeding; unintentional weight loss; persistent vomiting; abdominal mass; iron deficiency anaemia; suspicious findings on barium meal. Patients aged > 55 with unexplained and persistent dyspepsia, despite H. pylori testing and acid suppression therapy, should also be considered for endoscopy, as should those with previous gastric ulcer or surgery, continuing need for NSAIDs or raised risk of gastric cancer. Patients with uninvestigated dyspepsia should be managed by empirical treatment with a PPI or testing for and treating H. pylori if present. Testing by urea breath test, stool antigen test, or locally validated lab-based serology is suggested. H. pylori eradication is usually given as triple therapy, for seven days, involving a PPI, clarithromycin and either amoxicillin or metronidazole. It is important to take a thorough history and to enquire about any medication the patient is taking. Drugs that are common culprits for dyspepsia include: NSAIDs; calcium antagonists; bisphosphonates; steroids; theophyllines; nitrates. NSAIDs can also cause GI bleeding. Absence of dyspepsia in patients taking NSAIDs does not indicate a reduced risk of bleeding. Peptic ulcers fall into three categories: H. pylori associated ulcers; drug-induced ulcers (particularly NSAIDs); and ulcers in H. pylori-negative patients not taking causative medication. H. pylori is associated with both gastric and duodenal ulcer disease but it is in the duodenum where the closest relationship exists. In any 6-12 month period, 20-40% of healthy people, more commonly men, will experience symptoms of heartburn. Oesophageal reflux can progress to more serious disease such as erosive oesophagitis, stricture or Barrett's oesophagus.

A Transferable, Multi-Resolution Coarse-Grained Model for Amorphous Silica Nanoparticles.

Despite the ubiquity of nanoparticles in modern materials research, computational scientists are often forced to choose between simulations featuring detailed models of only a few nanoparticles or simplified models with many nanoparticles. Herein, we present a coarse-grained model for amorphous silica nanoparticles with parameters derived via potential matching to atomistic nanoparticle data, thus enabling large-scale simulations of realistic models of silica nanoparticles. Interaction parameters are optimized to match a range of nanoparticle diameters in order to increase transferability with nanoparticle size. Analytical functions are determined such that interaction parameters can be obtained for nanoparticles with arbitrary coarse-grained fidelity. The procedure is shown to be extensible to the derivation of cross-interaction parameters between coarse-grained nanoparticles and other moieties and validated for systems of grafted nanoparticles. The optimization procedure used is available as an open-source Python package and should be readily extensible to models of non-silica nanoparticles.

Investigation of the Impact of Cross-Polymerization on the Structural and Frictional Properties of Alkylsilane Monolayers Using Molecular Simulation.

Cross-linked chemisorbed n-alkylsilane (CH3(CH2)n-1Si(OH)3) monolayers on amorphous silica surfaces have been studied and their structural properties and frictional performance were compared to those of equivalent monolayers without cross-linkages. The simulations isolated for the first time the effects of both siloxane cross-linkages and the fraction of chains chemisorbed to the surface, providing insight into a longstanding fundamental question in the literature regarding molecular-level structure. The results demonstrate that both cross-linkages and the fraction of chemisorbed chains affect monolayer structure in small but measurable ways, particularly for monolayers constructed from short chains; however, these changes do not appear to have a significant impact on frictional performance.

The role of postoperative radiation and coordination of care in patients with metastatic bone disease of the appendicular skeleton.

Metastatic bone disease affects approximately 300,000 people in the United States, and the burden is rising. These patients experience significant morbidity and decreased survival. The management of these patients requires coordinated care among a multidisciplinary team of physicians, including orthopaedic surgeons. This article reviews the role of radiation therapy after orthopaedic stabilization of impending or realized pathologic extremity fractures. Orthopaedic surgeons have an opportunity to benefit patients with metastatic bone disease by referring them for consideration of post-operative radiation therapy. Further research into rates of referral and the effect on clinical outcomes in this population is needed.

Comparison of bond strength between a conventional resin adhesive and a resin-modified glass ionomer adhesive: an in vitro and in vivo study.

The objectives of this study were (1) to compare the in vivo survival rates of orthodontic brackets bonded with a resin-modified glass ionomer adhesive (Fuji Ortho LC; GC America, Alsip, Ill) after conditioning with 10% polyacrylic acid and a conventional resin adhesive (Light Bond; Reliance Orthodontic Products, Itasca, Ill) bonded with 37% phosphoric acid, (2) to compare the in vitro bond shear/peel bond strength between the 2 adhesives, (3) to determine the mode of bracket failure in the in vivo and in vitro tests according to the adhesive remnant index (ARI), and (4) to compare the changes in surface morphology of enamel surface after etching or conditioning with 10% polyacrylic acid, with scanning electron microscopy. In the in vitro study, 50 extracted premolars were randomly divided into 4 groups: brackets bonded with Fuji Ortho LC or Light Bond adhesive that were debonded after either 30 minutes or 24 hours. Bond strengths were determined with a testing machine at a crosshead speed of 1 mm/min. Data were analyzed with analysis of variance and a paired Student t test. The in vivo study consisted of 398 teeth that were randomly bonded with Fuji Ortho LC or Light Bond adhesive in 22 subjects with the split-mouth technique. Bracket survival rates and distribution were followed for 1.3 years. Data were analyzed with Kaplan-Meier product-limit estimates of survivorship function. The in vitro study results showed significant differences (P <.05) among the adhesives and the debond times. Light Bond had significantly greater bond strengths than Fuji Ortho LC at 24 hours (18.46 +/- 2.95 MPa vs 9.56 +/- 1.85 MPa) and 30 minutes (16.19 +/- 2.04 MPa vs 6.93 +/- 1.93 MPa). Mean ARI scores showed that Fuji Ortho LC had significantly greater incidences of enamel/adhesive failure than Light Bond adhesive (4.9 vs 4.1). For the in vivo study, no significant differences in failure rate, sex, or location in dental arch or ARI ratings were found between the 2 adhesives. These results suggest that, compared with conventional resin, brackets bonded with resin-modified glass ionomer adhesive had significantly less shear bond strength in vitro. However, similar survival rates of the 2 materials studied after 1.3 years indicate that resin-reinforced glass ionomers can provide adequate bond strengths clinically. The weaker chemical bonding between the adhesive and the enamel might make it easier for clinicians to clean up adhesives on the enamel surface after debonding.