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Pharmaceutical and veterinary products are a class of contaminants of emerging concern, and their presence in the environment is due to continuous and incorrect disposal. Environmental scientists have been accumulating data on their adverse effects on animal populations since toxicological effects on wildlife were first published. Therefore, recycling strategies are needed. Valuable active ingredients can be extracted from expired pharmaceuticals and recycled according to various strategies. In an effort to reveal the potential of the chemical upcycling of expired pharmaceuticals, the active ingredients gabapentin and pregabalin were extracted and used as starting materials to prepare a small collection of promising substrates endowed with functionalities and structural three-dimensionality. Gabapentin 1 was transformed into aminoalcohol 3, spiroamine 4, and the bioactive azaspirolactam 5. The lactam analog 6 was synthesized from pregabalin 2. Due to the biological profile of 5 and the structural similarity of the N-alkylated derivatives 5l and 6b with the drug piracetam, a collection of potentially bioactive structural analogs 5a-l and 6a-b were also prepared. Simple extraction, synthesis, and purification procedures were used as a means of chemical and economic revaluation, resulting in moderate to good yields at a low cost. [ABSTRACT FROM AUTHOR]

Advanced hybrid closed-loop (AHCL) therapy with the Medtronic MiniMed™ 780G system improves glycemia; however, the clinical outcomes in younger children remain less established. This pilot study aimed to explore the continuous glucose monitoring (CGM) metrics in very young children on AHCL. Children between 2 and 7 years of age and on insulin pump therapy were recruited. A 2-week phase in manual mode was followed by a 6-week AHCL phase. CGM metrics were analyzed to review glycemic outcomes. Out of 11 participants enrolled [mean (standard deviation [SD]) age 5.3 (0.8) years], 10 completed the study. Time in closed loop was 96.7 (3.9)%. In AHCL, participants had a mean (SD) time in range of 72.6 (7.4)% and spent 3.0 (1.74)% and 0.63 (0.46)% in time <70 and <54 mg/dL, respectively. AHCL is a feasible option for management of young children with type 1 diabetes. [ABSTRACT FROM AUTHOR]

In most of his plays, Shakespeare's central plots rely heavily on a primary source plot. For each play, he usually modified the action of a source plot, often renamed characters, and added new characters. Thus, his use of names from source plots compared to new names, the subject of my research, is at least one measure of his creativity, his relative reliance on source plots, and his presumption of their fictive status. In The Winter's Tale, for example, Shakespeare follows the plot of Greene's Pandosto very closely but changes all the names and radically transforms the tragic ending into a positive tale of remorse, faith, and redemption. Cymbeline, written very near in time, draws not on one but on at least four different source plots. From them Shakespeare interweaves four distinctive lines of action - 1) a Banishment story, 2) a Wager story, 3) a Tribute story, and 4) a story of Rustic Nobility. Two of these plot lines follow sources in Renaissance literature, and two follow historical sources. This paper will show that Shakespeare retains far more of the names used in his historical sources than those in his literary sources and thereby treats them as less fictive. [ABSTRACT FROM AUTHOR]

Shakespeare's central plots usually rely heavily on primary source plots. At the same time, he often renamed characters and added characters to modify the themes and actions of his source plots, especially in his comedies. However, he usually added far fewer names in his histories and tragedies. Thus, his relative use of names from source plots compared to his addition of new names, the subject of my research, is a useful indicator of his partial reliance on plot sources and of his apparent presumption of their non-fictive status. In Julius Caesar, Shakespeare closely follows the action described in Plutarch's chapters on Marcus Brutus and Julius Caesar in his Lives of the Noble Grecians and Romanes (North's 1579 translation). He adds a few names from other sources and coins a few of his own. Thus, Julius Caesar typifies Shakespeare's use of names in his histories and tragedies and reflects his apparent presumption of Plutarch's non-fictive status. At the same time, Shakespeare uses far more names from Plutarch's life of Brutus than from his lives of Julius Caesar or Mark Antony. Thus, his thematic emphasis is on Brutus and on his sense of 'honour' as a tragic strength. It is Shakespeare's first great tragedy, typified by the irony of the protagonist's virtue. [ABSTRACT FROM AUTHOR]

Despite the expansion of palliative care (PC) services, the public has little knowledge and holds misperceptions about PC, creating barriers to accessing timely specialty PC. To systematically review the evidence regarding the efficacy of educational interventions to improve knowledge and attitudes about PC among nonhealthcare workers. We searched five databases (PubMed/MEDLINE, Embase, CIANHL, Web of Science, and Scopus) for studies investigating educational interventions about specialty PC in adults who identified as patients, caregivers, or members of the public. We included studies that were available in English and had a comparator group. We excluded studies that only sampled health professionals or children. We used the Mixed Methods Appraisal Tool to assess quality and risk of bias. Of 12,420 records identified, we screened 5948 abstracts and assessed 526 full texts for eligibility. Twenty-one articles were extracted for analysis, representing 20 unique educational interventions. Common methodologies included quasi-experimental (9, 45%), randomized controlled trial (4, 20%), and nonrandomized trial (2, 10%). Common components of the educational interventions included video presentations (9, 45%), written materials (8, 40%), and lectures (4, 20%). Content included definition (14, 70%) and philosophy (14, 70%) of PC, distinctions between PC and hospice (11, 55%), and eligibility for PC (11, 55%). Fourteen (70%) interventions showed statistically significant positive differences in either knowledge or attitudes about PC. While educational interventions can positively impact knowledge and attitudes about PC among nonhealthcare workers, more research is needed to inform the design, delivery, and evaluation of interventions to increase knowledge and attitudes about PC. [ABSTRACT FROM AUTHOR]

Quasi-static uniaxial tension and compression, three-point bending, and Hopkinson bar measurements have been carried out on low-porosity Al/Ni compacts (pressed powders) as well as compacts of the constituent Al and Ni. Concurrently, mesoscale material point method (MPM) simulations of fully resolved Al, Ni, and Al/Ni compact microstructures and engineering scale MPM simulations of homogenized Al/Ni compacts have been conducted. These simulations, in conjunction with the experimental measurements, have allowed us to parameterize mesoscale particle/particle contact models and engineering scale anisotropic damage mechanics models for the materials. The goal of this coordinated experimental and simulation study of Al/Ni and its constituent materials was to better understand their mechanical properties and gain insight into the nature of Al–Ni and Al–Al interfaces in Al/Ni compacts and their impact on mechanical properties of the compacts. We found that brittle tensile failure of Al/Ni compacts was dominated by the strength of the Al–Al interface while ductile compressive behavior of Al/Ni compacts was largely determined by the behavior of the Al phase. The properties of both Al–Al interface and Al phase appear to be altered by the presence of Ni. Finally, it was found that softening resulting from shear damage offset underlying strain hardening of the Al and Ni phases during compressive loading of the Al/Ni compacts. [ABSTRACT FROM AUTHOR]

Continuous glucose monitoring (CGM) systems are used in therapeutic decisions for diabetes management, however, the impact of body composition on CGM accuracy is not known. Body composition variables (body mass index [BMI], midarm circumference, percentage fat, and impedance) were collected in an observational study designed to determine the accuracy of an investigational Medtronic Guardian™ sensor 3. Seven days of sensor glucose data were analyzed from 112 participants >7 years of age with mean BMI Z score 0.48 (<18 years) and BMI 26.7 kg/m2 (≥18 years). The outcome was the absolute relative difference between the sensor and blood glucose readings. Data were analyzed using generalized estimating equations to account for correlation between repeated measures. No statistically significant associations between measures of body composition and device accuracy were found. Body composition does not have a meaningful impact on the accuracy of CGM systems. [ABSTRACT FROM AUTHOR]

Objective: To explore the impact of missing data on the accuracy of continuous glucose monitoring (CGM) metrics collected for a 2-week period in a clinical trial. Research Design and Methods: Simulations were conducted to examine the effect of various patterns of missingness on the accuracy of CGM metrics as compared with a "complete" data set. The proportion of missing data, the "block size" in which the data were missing, and the missing mechanism were modified for each "scenario." The degree of agreement between simulated and "true" glycemic measures under each scenario was presented as R2. Results: Under all missing patterns, R2 declined as the proportion of missing data increased, however, as the "block size" of missing data increased, the percentage of missing data had a more pronounced effect on the agreement between measures. For a 14-day CGM data set to be considered representative for percentage time in range (%TIR), at least 70% of CGM data should be available over at least 10 days (R2 > 0.9). Skewed outcome measures, such as percentage time below range and coefficient of variation, were more affected by missing data than the less skewed measures (%TIR, percentage time above range, mean glucose). Conclusions: Both the degree and pattern of missing data impact upon the accuracy of recommended CGM-derived glycemic measures. In planning research, an understanding of patterns of missing data in the study population is required to gauge the likely effects of missing data on outcome accuracy. Trial registration number: Australian New Zealand Clinic Trials Registry ACTRN12616000753459. [ABSTRACT FROM AUTHOR]

The article discusses the Reveil project, a 24-hour live broadcast that captures the sounds of daybreak from around the world. The project aims to create connections between humans and non-human entities through the act of listening. It includes contributions from various locations, allowing listeners to experience the dawn chorus from different perspectives. The text also explores the concept of time and the role of the audience in the project, with the goal of fostering transformative encounters and blurring boundaries between different groups and environments. [Extracted from the article]

Molecular dynamics simulations of reactions in Al/Ni layered systems have been carried out under isothermal conditions for a wide range of temperatures and several system sizes. An embedded atom method potential, known to reasonably reproduce the phase behavior of Al/Ni, was employed. Simulations revealed reaction mechanisms involving an initial fast process and much slower more complex longer-time reactions. The initial reaction process consists of diffusion of Ni from the pure solid Ni phase into the molten Al phase, resulting in the formation of an Al-rich Al/Ni liquid. The initial reaction ends when the Al/Ni liquid becomes saturated in Ni and solid Al/Ni phases begin to form at the interfaces between the pure solid Ni phase and the Al/Ni liquid. The growth of these solid phases is intrinsically slow compared to the formation of the liquid and is further slowed by the need for Ni to diffuse through the growing interfacial Al/Ni solid phases. Analysis of the initial Al/Ni liquid forming process indicates Fickian behavior with the Ni diffusion coefficient exhibiting Arrhenius temperature dependence. The longer-time slow reaction process(es) resulting in the growth of Al/Ni solid phases do not lend themselves to detailed numerical analysis because of the complex dependence of the Ni transport on the detailed nature of the interfacial layers. [ABSTRACT FROM AUTHOR]

In his comedies Shakespeare changed most or all the names found in his plot sources, substituting instead names borrowed as analogs from other literature, names taken from common usage, and/or names he coined to describe appearances, actions, or attitudes of his characters. In his histories and tragedies, by contrast, Shakespeare most often relied heavily on the names he found in his plot sources. Romeo & Juliet illustrates the usual pattern of Shakespeare's tragedies insofar as he used all the names included in his plot source, a narrative poem by Arthur Brooke entitled The Tragicall Historye of Romeus and Juliet (1562), which was one of many versions. Thus, his use of names in Romeo & Juliet confirms his heavy reliance on his principal source plot. However, Shakespeare also added many names in his distinctive version of the story. He also varied the actions of the characters named and even the forms of a few names. Thus, a complete analysis of Romeo & Juliet names helps to illustrate Shakespeare's linguistic creativity, his relative independence from his plot source, and why we generally consider his version of this popular story to be the definitive version. [ABSTRACT FROM AUTHOR]

Continuum level Material Point Method (MPM) simulations have been carried out on low porosity (around 90% or greater of theoretical maximum density) microstructures of Al/Ni granular composites (Al/Ni). The Al/Ni microstructures were subjected to uniaxial (strain) compressive loading and shock compression up to 25 GPa. The MPM model accounted for frictional heating between grains in addition to plastic work and compressional heating effects. The distributions of stresses and temperature in the composite materials were found to be highly heterogeneous due to the heterogeneous nature of the composite microstructure. The manner in which interfaces between grains were treated (sliding vs. non-sliding) was found to influence both mechanical and thermal responses to loading. Plastic deformation, mechanical work, and grain/grain frictional effects led to modest increases of mean temperature and local hotspots with maximum temperature not higher than 800–850 K for loadings investigated. For all scenarios investigated, heat generation was insufficient to cause local Al melting believed to be a precursor for shock initiation. [ABSTRACT FROM AUTHOR]

BACKGROUND: Since the inception of the Youth Risk Behavior Surveillance System in 1991, all surveys have been conducted in schools, using paper and pencil instruments (PAPI). For the 2019 YRBSS, sites were offered the opportunity to conduct their surveys using electronic data collection. This study aimed to determine whether differences in select metrics existed between students who completed the survey electronically versus using PAPI. METHODS: Thirty risk behaviors were examined in this study. Data completeness, response rates and bivariate comparisons of risk behavior prevalence between administration modes were examined. RESULTS: Twenty‐nine of 30 questions examined had more complete responses among students using electronic surveys. Small differences were found for student and school response rates between modes. Twenty‐five of 30 adolescent risk behaviors showed no mode effect. CONCLUSIONS: Seven of 44 states and DC participated electronically. Because survey data were more complete; school and student response rates were consistent; and minor differences existed in risk behaviors between modes, the acceptability of collecting data electronically was demonstrated. [ABSTRACT FROM AUTHOR]

Objective: To investigate in a population‐based pediatric cohort: prevalence of moderate–severe diabetic ketoacidosis (DKA) at type 1 diabetes (T1D) diagnosis over two decades and its association with long‐term glycemic control. Research Design and Methods: Children <16 years diagnosed with T1D in Western Australia 2000–2019 were included and followed up for ≤14 years. Moderate–severe DKA at diagnosis was defined as serum pH < 7.2 or bicarbonate<10 mmol/L with hyperglycemia and ketosis. HbA1c was measured ~3‐monthly. Trend in prevalence of moderate–severe DKA at diagnosis was investigated using a logistic regression model adjusting for sex, age, socioeconomic status, and area of residence. Long‐term glycemic control associated with DKA at diagnosis was investigated using linear mixed models adjusting for the same variables and also for visit frequency, CGM and pump use. Results: Moderate–severe DKA occurred in 534 of 2111 (25.3%) participants. Odds of presenting with moderate–severe DKA increased by 4.1% (95% CI: 2.3, 5.9; p < 0.001) per year. Patients with moderate–severe DKA at diagnosis had higher HbA1c levels than other patients initially; the groups were similar between 2 and 6 years duration; from 7 years HbA1c levels tracked higher in the group with moderate–severe DKA at diagnosis with significant differences at 8 and 12 years (p < 0.05). Conclusion: The increasing prevalence of DKA at diagnosis of pediatric T1D is concerning and highlights the need for early detection programs. Unlike a similar US study, this study did not find a consistent, clinically significant relationship between DKA at diagnosis and long‐term HbA1c, raising important questions about the influence of other factors on long‐term glycemic outcomes. [ABSTRACT FROM AUTHOR]

Youth experiencing homelessness experience violence victimization, substance use, suicide risk, and sexual risk disproportionately, compared with their stably housed peers. Yet few large-scale assessments of these differences among high school students exist. The youth risk behavior survey (YRBS) is conducted biennially among local, state, and nationally representative samples of U.S. high school students in grades 9–12. In 2019, 23 states and 11 local school districts included a measure for housing status on their YRBS questionnaire. The prevalence of homelessness was assessed among states and local sites, and relationships between housing status and violence victimization, substance use, suicide risk, and sexual risk behaviors were evaluated using logistic regression. Compared with stably housed students, students experiencing homelessness were twice as likely to report misuse of prescription pain medicine, three times as likely to be threatened or injured with a weapon at school, and three times as likely to report attempting suicide. These findings indicate a need for intervention efforts to increase support, resources, and services for homeless youth. [ABSTRACT FROM AUTHOR]

The article supports the increasing utility of school health data to guide evidence-based interventions. Focus is given on the use of the Youth Risk Behavior Surveillance System (YRBSS) and the School Health Profiles for evaluating health programs and inform professional development to protect youth across the U.S. It identifies challenges facing data collection such as ban of select questions from health surveys administered to students and parent refusals for student YRBSS participation.

Context: Communities of Practice (CoP) can help geographically separated individuals who share a joint enterprise, mutual engagement, and a repertoire of tools to gain, maintain, and implement new skills, including serious illness communication.Objectives: To investigate the health system uptake, implementation and outcomes of the Serious Illness Community of Practice (SICoP).Methods: Participants included members of the online SICoP, including participants from all 50 states in the United States and 44 countries, interested in implementation of the Serious Illness Care Program. Yearly surveys asked members about their program's composition, completed trainings, number of serious illness conversations, and utilization of the online SICoP tools and resources.Results: Over four years, membership in the SICoP increased from 429 to 1,912, with an estimated 17,785 clinicians trained and 38,945 serious illness conversations conducted. Members have continued to utilize and modify the SICoP resources.Conclusions: Utilizing a CoP has contributed to improving the health care system implementation and process outcomes of serious illness communication training.Key Message: This article describes the implementation and health system outcomes of a Community of Practice developed to support serious illness communication. The results indicate that the membership of the community grew and that the community supported growth in the number of trained clinicians and the number of serious illness conversations conducted. [ABSTRACT FROM AUTHOR]

The names in As You Like It illustrate the vital importance of names in Shakespeare's development of both themes and characters. Major themes of AYLI are prominently expressed by the characters' personifications, and his character names show a mixed use of associations and the coinage of lexical equivalents (redende Namen). His associations are either borrowings from previous literature or references to topical phenomena. His lexical equivalents are sometimes phonological in other plays, but in ALYI they are etymological. This paper will describe the most salient examples in this play. A complete analysis of all names and of the semiotic basis of name meaning may be found in my recent book, Names as Metaphors in Shakespeare's Comedies (Vernon Press). [ABSTRACT FROM AUTHOR]

OBJECTIVE: Continuous glucose monitoring (CGM) can detect early dysglycemia in older children and adults with presymptomatic type 1 diabetes (T1D) and predict risk of progression to clinical onset. However, CGM data for very young children at greatest risk of disease progression are lacking. This study aimed to investigate the use of CGM data measured in children being longitudinally observed in the Australian Environmental Determinants of Islet Autoimmunity (ENDIA) study from birth to age 10 years. RESEARCH DESIGN AND METHODS: Between January 2021 and June 2023, 31 ENDIA children with persistent multiple islet autoimmunity (PM Ab+) and 24 age-matched control children underwent CGM assessment alongside standard clinical monitoring. The CGM metrics of glucose SD (SDSGL), coefficient of variation (CEV), mean sensor glucose (SGL), and percentage of time >7.8 mmol/L (>140 mg/dL) were determined and examined for between-group differences. RESULTS: The mean (SD) ages of PM Ab+ and Ab− children were 4.4 (1.8) and 4.7 (1.9) years, respectively. Eighty-six percent of eligible PM Ab+ children consented to CGM wear, achieving a median (quartile 1 [Q1], Q3) sensor wear period of 12.5 (9.0, 15.0) days. PM Ab+ children had higher median (Q1, Q3) SDSGL (1.1 [0.9, 1.3] vs. 0.9 [0.8, 1.0] mmol/L; P < 0.001) and CEV (17.3% [16.0, 20.9] vs. 14.7% [12.9, 16.6]; P < 0.001). Percentage of time >7.8 mmol/L was greater in PM Ab+ children (median [Q1, Q3] 8.0% [4.4, 13.0] compared with 3.3% [1.4, 5.3] in Ab− children; P = 0.005). Mean SGL did not differ significantly between groups (P = 0.10). CONCLUSIONS: CGM is feasible and well tolerated in very young children at risk of T1D. Very young PM Ab+ children have increased SDSGL, CEV, and percentage of time >7.8 mmol/L, consistent with prior studies involving older participants. [ABSTRACT FROM AUTHOR]

It is recommended that people with type 1 diabetes should generally aim to achieve glycated hemoglobin (HbA1c) <53 mmol/mol.[1],[2] Likewise, as defined by continuous glucose monitoring (CGM) metrics, the proposed general aims are to spend >70% time-in-range (TIR, 70-180 mg/dL), <4% below 70 mg/dL, <1% below 54 mg/dL, <25% above 180 mg/dL, and <5% above 250 mg/dL.[3] However, the proportion of individuals achieving the goals of CGM metrics among cohorts meeting target HbA1c is not much known. Percentage TIR was higher in participants who met target HbA1c, with less time in hyperglycemia but more time in hypoglycemia than individuals not meeting target HbA1c (Table 1). [Extracted from the article]

Context: Understanding the unique needs of patients seen in clinic versus at home can help palliative care (PC) teams choose how to maximize available resources.Objectives: To compare the characteristics and PC needs of patients seen by PC teams in clinic versus at home.Methods: We analyzed data from the Palliative Care Quality Network between August 2016 and September 2019 and compared demographics, diagnosis, reason for referral, PC needs, functional status, self-reported symptoms, and patient-reported quality of life.Results: Compared to patients receiving PC in clinic, patients receiving PC at home were more likely to be of age 80 years or older (odds ratio [OR] 7.5, 95% CI 5.0, 10.9, P < 0.0001), have lower functional status (mean Palliative Performance Scale score 53% vs. 68%, P < 0.0001), and were less likely to screen positive for needing pain management (OR 0.31, 95% CI 0.22, 0.42, P < 0.0001) or other symptom management (OR 0.61, 95% CI 0.41, 0.90, P = 0.01). Patients receiving care at home were more likely to be referred for care planning (goals of care discussions or advance care planning) (OR 11.5, 95% CI 8.3, 16.0 P < 0.0001) and patient/family support (OR 5.9, 95% CI 4.2, 8.3, P < 0.0001).Conclusion: Patients seen by PC teams at home had worse function and were more likely to be referred for care planning, while patients seen in clinic had more PC needs related to pain and symptom management. Despite these differences, both populations have significant PC needs that support routine assessment and require appropriately staffed interdisciplinary teams to address these needs. [ABSTRACT FROM AUTHOR]

Wind‐wave hindcast data have many applications including climatology assessments for renewable energy projects, maritime engineering design, event‐based impact assessments, generating boundary conditions for further downscaling, amongst others. Here, we present a global wave hindcast with nested high‐resolution grids for the Exclusive Economic Zones of Australia and south west Pacific Island Countries, that is extended in time monthly. The model employs strategic methods to incorporate the effects of subgrid sized features such as small islands and islets. Various bulk wave parameters are available hourly from January 1979 to present, along with the full wave spectra at a set of 3,683 predetermined points distributed globally. [ABSTRACT FROM AUTHOR]

The names in Shakespeare's Love's Labour's Lost present a delightful linguistic mix. The names of major characters are Anglicized names of actual French nobles, which emphasizes the thematic parallelism of historical and fictive events. Other names broaden the international landscape, including Nathaniel, a biblical association, Forester (which is French as well as English), and Armado, a Spanish tag. The length of this paper does not allow room to describe many names in detail. However, the cross-cultural puns make this play especially interesting; e.g., Moth has at least two meanings in English, but pronounced mot in French means 'word,' 'remark,' 'cue,' or 'answer to a riddle' – which points most clearly to a thematic meaning. A full analysis of this play will appear soon in my book Names as Metaphors in Shakespeare's Comedies (Vernon Press). [ABSTRACT FROM AUTHOR]

Molecular dynamics (MD) simulations of mixtures of the room temperature ionic liquids (ILs) 1-butyl-4-methyl imidazolium [BMIM]/dicyanoamide [DCA] and [BMIM][NO3-] with HNO3 have been performed utilizing the polarizable, quantum chemistry based APPLE&P® potential. Experimentally it has been observed that [BMIM][DCA] exhibits hypergolic behavior when mixed with HNO3 while [BMIM][NO3-] does not. The structural, thermodynamic, and transport properties of the IL/HNO3 mixtures have been determined from equilibrium MD simulations over the entire composition range (pure IL to pure HNO3) based on bulk simulations. Additional (non-equilibrium) simulations of the composition profile for IL/HNO3 interfaces as a function of time have been utilized to estimate the composition dependent mutual diffusion coefficients for the mixtures. The latter have been employed in continuum-level simulations in order to examine the nature (composition and width) of the IL/HNO3 interfaces on the millisecond time scale. [ABSTRACT FROM AUTHOR]

The coronavirus disease 2019 has brought public attention to questions regarding the type of care individuals would want to receive in the event of becoming suddenly critically ill. Advance care planning (ACP) is one way to help individuals and families address these questions. However, social distancing, stay-at-home orders, and hospital visitor restrictions have raised new barriers to facilitating these conversations. Here, we describe the implementation and evaluation of a novel, public-facing, and two-part virtual ACP workshop. Participants were recruited through electronic communication, and evaluations were collected through surveys administered after each part of the workshop. We found that using a virtual format allowed us to reach a large and geographically diverse audience. Participants were likely to recommend the workshop to friends and family. There was no change in ACP engagement between the postsession surveys between the first and second parts of the workshop. [ABSTRACT FROM AUTHOR]

We have carried out molecular dynamics simulation studies of binary mixtures of spherical nanoparticles (NPs) in a matrix of dense isotropic rod-shaped nematogens, with the size of the nematogen length being similar to that of the NP diameter. NPs at even low concentrations were found to shift the isotropic-nematic (I-N) transition significantly to higher pressure at a given temperature, indicative of long-range perturbation of the nematogenic matrix by the NPs. The NPs were found to be dispersed in the dense isotropic nematogenic matrix over a wide range of NP concentrations due to long-range (compared with the molecular size of the nematogens) repulsion caused by NP-induced local order fluctuations and reduced local orientational correlation in the isotropic nematogenic matrix, in contrast to the phase separation predicted and observed in other studies where the particles were much larger or smaller than the nematogens. Furthermore, since the repulsion observed in the NP-nematogen mixtures is only microscopically long range (on the order of about ten molecular lengths of the nematogens), globally ordered clustering observed in mixtures of colloidal particles in nematic matrices resulting from macroscopically long-range interaction is not observed in our simulations. [ABSTRACT FROM AUTHOR]

We report results of molecular dynamics simulation studies of the behavior of spherical nanoparticles (NPs) in a dense isotropic nematogen matrix comprised of soft spherocylinders (SSCs). The SSCs exhibit a tendency for frustrated planar anchoring at the NP surface that results in a long-range (compared to the size of the NPs and SSCs) reduction in local orientational ordering and increased fluctuations in local orientational ordering compared to the pure isotropic phase of the SSCs. The potential of mean force between two nanoparticles exhibits a novel long-range repulsive tail separated from short-range molecular packing peaks by a shallow local minimum in free energy. The long-range repulsion is caused by NP-induced ordering fluctuations while the shallow minimum results from increased local ordering within the confinement region in between two NPs. The influence of the NPs on local orientational order in the nematogen matrix and the nematogen-induced interaction between NPs are found to depend strongly on the size of the NPs. [ABSTRACT FROM AUTHOR]

The dynamic coherent structure factor Scoh(q,t) for a 1,4-polybutadiene (PBD) melt has been investigated using atomistic molecular dynamics simulations. The relaxation of Scoh(q,t) at q=1.44 Å-1 and q=2.72 Å-1, corresponding to the first and second peaks in the static structure factor for PBD, was studied in detail over a wide range of temperature. It was found that time-temperature superposition holds for the α-relaxation for both q values over a wide temperature range and that the α-relaxation can be well described by a stretched (Kohlrauch-William-Watts) exponential with temperature independent but q dependent amplitude and stretching exponent. The α-relaxation times for both q values were found to exhibit the same non-Arrhenius temperature dependence, indicating that the same physical processes are responsible for relaxation on both length scales. The α-relaxation time was found to depend strongly upon the dynamical range of data utilized in determining the relaxation time, accounting for qualitative discrepancies between α-relaxation times reported here and those extracted for PBD from experimentally measured Scoh(q,t). © 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

We carried out Brownian dynamics simulation studies of the translocation of single polymer chains across a nanosized pore under the driving of an applied field (chemical potential gradient). The translocation process can be either dominated by the entropic barrier resulted from restricted motion of flexible polymer chains or by applied forces (or chemical gradient across the wall), we focused on the latter case in our studies. Calculation of radius of gyrations at the two opposite sides of the wall shows that the polymer chains are not in equilibrium during the translocation process. Despite this fact, our results show that the one-dimensional diffusion and the nucleation model provide an excellent description of the dependence of average translocation time on the chemical potential gradients, the polymer chain length and the solvent viscosity. In good agreement with experimental results and theoretical predictions, the translocation time distribution of our simple model shows strong non-Gaussian characteristics. It is observed that even for this simple tubelike pore geometry, more than one peak of translocation time distribution can be generated for proper pore diameter and applied field strengths. Both repulsive Weeks–Chandler–Anderson and attractive Lennard-Jones polymer–nanopore interaction were studied, attraction facilitates the translocation process by shortening the total translocation time and dramatically improve the capturing of polymer chain. The width of the translocation time distribution was found to decrease with increasing temperature, increasing field strength, and decreasing pore diameter. © 2003 American Institute of Physics. [ABSTRACT FROM AUTHOR]

A molecular dynamics simulation study of the influence of a polymer melt matrix consisting of bead-necklace polymers on the effective interaction between two spherical nanoparticles was performed. The potential of mean force (POMF) between the two nanoparticles as well as entropy and energy contributions to the POMF was determined as a function of nanoparticle separation. The role of energy on the POMF was investigated by varying the strength of the polymer–nanoparticle interaction and comparing structure and POMF with those obtained for an athermal model. All features of the POMF as a function of nanoparticle separation were found to be strongly correlated with the polymer matrix density, the structure of the polymer at the nanoparticle interface, and the structure of the polymer in the interparticle region. The POMF was not found to correlate with polymer chain dimensions (e.g., radius of gyration) in contrast to colloidal suspensions in dilute and semidilute solutions. Both energy and entropy effects were found to make important contributions to the POMF. For the athermal system, where all matrix-induced interactions are entropic in nature, the nanoparticle POMF was found to exhibit qualitatively different behavior from that of the energetic systems. © 2003 American Institute of Physics. [ABSTRACT FROM AUTHOR]

We have conducted molecular dynamics simulations of the stretching of a poly(ethylene oxide) (PEO) chain in water and n-tridecane in order to elucidate the mechanisms of elastic response of the amphiphilic PEO chain in hydrophilic and hydrophobic environments. Quantitative agreement was found for the restoring force as a function of the degree of chain extension between simulation and recent atomic force microscopy measurements in the highly and severely stretched regimes. In these regimes the free energy of the PEO chain and the restoring force are determined by changes in local conformational populations and geometries. In the highly stretched regime stretching of the PEO chain results in an increased trans population of C-C and C-O dihedrals as well as the deformation of dihedral geometries. Here the restoring force is greater in water than in n-tridecane due to the greater free energy (mostly enthalpic) penalties for C-C trans dihedrals and the deformation of C-C gauche dihedrals in the polar solvent. In both solvents the conversion of gauche C-C and C-O dihedrals to trans in the highly stretched regime makes a significantly entropic contribution to the chain free energy and restoring force. No tendency toward extended gauche helical conformations of the PEO chain in water, as has been previously speculated, was observed in this regime. An estimation of the PEO free energy as a function of the degree of chain extension based upon conformational populations relative to equilibrium (unstretched) chains was found to lead to an overestimation of the free energy cost of chain extension in the highly stretched regime in n-tridecane due to neglect of the influence of deformation of dihedral geometries on chain dimensions. In water, the influence of the deformation of dihedral geometries was largely offset by an increase in their free energy due to decreased polar interactions of the distorted dihedrals with water. In the severely stretched regime, the PEO chain... [ABSTRACT FROM AUTHOR]

We have carried out atomistic molecular dynamics simulations of a melt of 1,4-poly(butadiene) from temperatures well above the experimentally observed merging of the primary α process and secondary β process down to temperatures approaching the experimentally observed bifurcation temperature. The relaxation strength and maximum loss frequency and its temperature dependence for the combined α-β dielectric relaxation process from simulations were in good agreement with experiment. The maximum loss frequency, melt viscosity, chain normal-mode relaxation times and torsional autocorrelation times were found to exhibit nearly identical non-Arrhenius temperature dependencies well represented by a Vogel-Fulcher fit with parameters in good agreement with experimental values obtained from dielectric and viscosity measurements. The dielectric susceptibility showed increasing intensity at high frequency for the lower temperatures investigated, indicative of a breakdown in time-temperature superposition due to an emerging β process. Comparison of time scales for the chain normal-mode dynamics and dielectric relaxation revealed that the latter is associated with motions on the segmental length scale. The correspondence of time scales and temperature dependence for the dielectric relaxation and the torsional autocorrelation function further confirmed the localized nature of the dielectric relaxation and indicated that the combined α-β dielectric process is fundamentally tied to microscopic conformational dynamics of individual dihedrals. However, the mean conformational transition rates were found to exhibit Arrhenius temperature dependence, leading to a divergence of time scales between the torsional, dielectric, chain and mechanical relaxation processes and the rates of conformational transitions with decreasing temperature. This divergence was associated with the increasingly heterogeneous character of conformational dynamics in the... [ABSTRACT FROM AUTHOR]

We have carried out molecular dynamics simulations of model polymer-nanoparticle composites (PNCs) consisting of coarse-grained bead-necklace polymer chains and roughly spherical nanoparticles comprised of like beads for the purpose of gaining understanding of the influence of the nanoparticle-polymer interface on the viscoelastic properties of PNCs. The dynamic shear modulus G[SUBc](t) and viscosity n[SUBc] of the PNCs were determined as a function of nanoparticle volume fraction, specific nanoparticle-polymer interfacial area, and the nature of the nanoparticle-polymer interaction. The viscoelastic properties of the PNCs were well described as a product of a polymer matrix dynamic shear modulus or viscosity and a particle volume fraction dependent effect independent of particle size, analogous to treatments of conventional particle composites. In contrast to many conventional composites, however, the viscoelastic properties of the polymer matrix were strongly perturbed by the nanoparticles and depended upon the nature of the nanoparticle-polymer interactions. [ABSTRACT FROM AUTHOR]

We have performed a molecular-dynamics simulation study of the influence of attractive dispersion interactions on the phase behavior of an ensemble of rigid bead-necklace molecules by gradually scaling the bead-bead interaction from a purely repulsive potential to a full Lennard-Jones potential. The system consisted of 600 bead-necklace molecules each composed of 11 interaction centers (beads). For all values of the attractive potential investigated the system manifested a nematic phase and a smectic A phase and both the isotropic-nematic and nematic-smectic A transitions were found to be weakly first order. The Gibbs-Duhem integration method was employed to trace the isotropic-nematic and nematic-smectic A (P, T) coexistence curves over the range of attractive interactions. With increasing attraction, the temperature-pressure range over which each phase was stable deceased to the advantage of the more ordered coexisting phase with a consequent narrowing of (P,T) space for the mesophases. Systems with weak attractions manifested transition strengths (entropy of transition) for the isotropic-nematic and nematicsmectic A transitions that were only weakly dependent upon temperature-pressure, while systems with stronger attractions exhibited transition strengths that decreased with increasing temperature. The phase behavior and thermodynamics of the isotropic-nematic and nematic-smectic A phase transitions for the systems with relatively strong dispersion interactions were found to be more representative of the behavior of real liquid crystalline materials than systems dominated by repulsive interactions. [ABSTRACT FROM AUTHOR]

Lattice Monte Carlo and off-lattice molecular dynamics simulations of h[sub 1]t[sub 4] and h[sub 4]t[sub 1] (head/tail) amphiphile solutions have been performed as a function of surfactant concentration and temperature. The lattice and off-lattice systems exhibit quite different self-assembly behavior at equivalent thermodynamic conditions. We found that in the weakly aggregating regime (no preferred-size micelles), all models yield similar micelle size distributions at the same average aggregation number, albeit at different thermodynamic conditions (temperatures). In the strongly aggregating regime, this mapping between models (through temperature adjustment) fails, and the models exhibit qualitatively different micellization behavior. [ABSTRACT FROM AUTHOR]

1. Analyze existing literature about public- and patient-facing educational interventions targeting PC awareness, knowledge, attitudes, and behaviors. 2. Design an educational intervention to influence public acceptance and willingness to utilize specialty PC using lessons learned from this review. Although efforts to improve awareness and knowledge about palliative care (PC) are ongoing, the public continues to have misperceptions about PC, creating barriers to patients' willingness to access specialty PC. We performed a systematic review to understand and describe the efficacy of public- and patient-facing educational interventions that could impact awareness, knowledge, and attitudes about PC. We searched five databases (PubMed/MEDLINE, Embase, CIANHL, Web of Science, and Scopus) for studies investigating educational interventions about PC in adults (aged 18 years or older) who identified as patients, caregivers, or were part of the general public. We only included studies that were available in English and had a comparator group (pre-/post- or control/intervention). We excluded studies that only sampled health professionals or children. We used the Mixed Methods Appraisal Tool to assess quality and risk of bias. This study is registered on PROSPERO CRD42021276433. We screened 5,948 abstracts and assessed 535 full texts for eligibility. Twenty-two articles were extracted for analysis. Common methodologies included quasi-experimental (12), RCTs (four), and qualitative (two). Intervention components were video presentations (11), written materials (seven), lecture presentations (five), interactions with healthcare workers (three), small-group education (two), structured discussions about PC (three), electronic module/app (three), live skit/play (one), and interaction with patients/caregivers (one). Content included definitions (14) or philosophy (13) of PC, distinctions between PC and hospice (11), services provided (11), appropriateness/eligibility for PC referral (11), and team-based approach (six). Fourteen interventions showed statistically positive differences in awareness, knowledge, attitudes, and/or behaviors. One intervention resulted in a statistically negative difference in attitudes towards PC. Overall, these studies were heterogeneous in methodology, type of intervention, and measured outcomes. While this review demonstrates that educational interventions can positively impact the public's awareness, knowledge, attitudes, and behaviors toward palliative care, more research is needed to inform targeted interventions to improve uptake of PC. [ABSTRACT FROM AUTHOR]

Background: The Predictive Low-Glucose Management (PLGM) system suspends basal insulin when hypoglycemia is predicted and reduces hypoglycemia. The aim of this analysis was to explore the characteristics of automated insulin suspension and sensor glucose (SG) responses following PLGM-initiated pump suspension.Research Design and Methods: Children and adolescents with type 1 diabetes used the Medtronic MiniMed™ 640G pump as part of a randomized controlled trial. Data collected on a subgroup of participants on PLGM (suspend before low enabled) from CareLink® Therapy Management Software were analyzed to explore the time and duration of PLGM-initiated pump suspension. Day and nighttime were defined as 06:00 am to 10:00 pm and 10:00 pm to 6:00 am, respectively.Results: There were 20,183 suspend before low events in 8523 days (2.37 events/day). The mean suspend duration was 55.0 ± 32.7 min (day 50.0 ± 30.1, night 71.7 ± 35.1; P < 0.001). Although a 2-h pump suspension was more frequent at night (day 5%, night 18%), a patient-initiated resumption occurred more during day (day 34%, night 12%). SG values did not reach <3.5 and <3 mmol/L in 79% and 91% of the events, respectively. The 2-h SG following pump resumption was higher following autoresumption during the day (day vs. night 9.3 mmol/L vs. 8.4 mmol/L; P < 0.001).Conclusions: Longer suspends and fewer glycemic excursions occur at night compared with day. The higher glycemic daytime excursions could be due to carbohydrate consumption to increase glucose levels and highlights the need for health care professionals to educate patients about carbohydrate intake around pump suspension. [ABSTRACT FROM AUTHOR]

Considerable evidence supports that close to two thirds of all fourth-grade students read at less than adequate levels on reading achievement tests and that the problem has persisted for decades. This study of 1,064 third-grade students at risk for reading failure uses path analytic techniques to measure a hypothesized model linking developmental spelling, sight- and pseudo-word reading, and reading fluency to achievement on an end-of-year state reading test. While all hypothesized paths were found to be significant, paths not hypothesized were also significant. These paths included direct effects for spelling development on fluency and reading achievement, as well as the direct effect of sight-word reading on state reading achievement. In total, the model predicted 41.9% of the variance in state reading achievement and found that students proficient at foundational reading skills were 7 times more likely to be proficient on the state reading achievement assessment. [ABSTRACT FROM AUTHOR]

Becoming a fluent reader has been established as important to reading comprehension. Prosody (expression) is an indicator of fluent reading that is linked to improved comprehension in students across elementary, middle, and secondary grades. Fluent reading is most often evaluated by classroom teachers through the use of a rubric, with the most common being the Multi-Dimensional Fluency Scale (MDFS) and the National Assessment of Educational Progress (NAEP) scale. This investigation uses a generalizability study (G-study) and a decision study (G-study) to determine reliability and efficiency of the two rubrics across five raters and two rating occasions in 177 first- through third-grade students. The results revealed the MDFS and NAEP to be parallel instruments with variance attributable to raters ranging from nearly 0 to 2.2%. Generalizability coefficients ranging from 0.91 to 0.94, indicating high reliability were found for both instruments. Recommendations for administration efficiency of each rubric are provided and instructional implications are discussed. [ABSTRACT FROM AUTHOR]

Background: Long‐term glycemic outcomes in people with type 1 diabetes (T1D) on insulin pump therapy (continuous subcutaneous insulin infusion [CSII]) with appropriate control data are limited. Randomized controlled studies of technology in diabetes care are generally limited in duration and likely to have a selection bias. Hence, evaluation of population‐based data provides a robust alternative evaluation of the benefits of insulin pump therapy. Aim: To investigate the outcomes of insulin pump therapy, as compared to injection therapy, in children with T1D attending a state‐wide diabetes service in Western Australia. Methods: Patients using insulin pump therapy between January 1999 and July 2016 were matched to patients on injection therapy on the basis of age, date of diagnosis, and hemoglobin A1C (HbA1c) at the start of pump therapy. Results: A total of 513 pump‐injection matches were identified. The pump cohort had a significantly lower mean HbA1c for the first 6 years of follow‐up. The difference in HbA1c between the cohorts was observed by 6 months (3 mmol/mol [0.3%], standard error of the mean (SEM) 0.05, N = 463 matched pairs, P < 0.001) and was sustained with the greatest difference in HbA1c at 6 years (4 mmol/mol [0.4%], SEM 0.21, N = 112 matched pairs, P = 0.04). Beyond 6 years of follow‐up, the HbA1c was not significantly lower in the pump cohort (N < 70 matched pairs). Conclusions: Patients using insulin pump therapy had a better long‐term glycemic control relative to the matched injection therapy cohort. Large population‐based cohort studies using real‐world data provide a valuable perspective on evaluation of new technologies in children with T1D. [ABSTRACT FROM AUTHOR]

We have performed a detailed quantum chemistry study of the gas-phase benzene dimer. Large atomic orbital basis sets with multiple polarization functions were used. The effects of basis set size, electron correlation, and basis set superposition error were investigated for the low-energy planar sandwich (D[SUB6h] and C[SUB6v]), parallel displaced (C[SUB2h]), and T-shaped (C[SUB2v]) dimer structures. Our studies indicate that the C[SUB2h]-symmetry parallel displaced geometry is the lowest-energy structure for the) benzene dimer. The T-shaped structure was found to be a low-energy saddle point for interconversion between parallel displaced structures, while the planar sandwich structure was found to be a saddle point on a higher-energy interconversion path between parallel displaced structures. Detailed analysis of the low-energy (T-shaped saddle point) path revealed the presence of a shallow minimum corresponding to a tilt angle between phenyl ring planes of about 45°. Much of the behavior of the benzene dimer observed through molecular jet spectroscopy can be explained by considering a population of the low-energy parallel displaced structure and structures along the low-energy interconversion path, including the tilt- and T-shaped structures. [ABSTRACT FROM AUTHOR]

Employing an explicit atom (EA) model of polymethylene, we have carried out molecular dynamics simulations of n-tridecane (C13H28) melts at experimental densities to compute both equilibrium and dynamic properties. The calibrated EA model reproduces quite well the experimental results of pressure, x-ray diffraction patterns, and self-diffusion constants at different temperatures. A united atom (UA) model that reproduces the experimental pressures also yields good agreement with experimental x-ray diffraction patterns and self-diffusion data, and the calculated degree of intermolecular orientational correlation is in good agreement with predictions of the EA model. However, the UA model yields significantly more extended chain dimensions than a previously investigated model, and, most importantly, significantly enhanced local chain dynamics compared to the EA model, as monitored by the chain vector reorientation and local torsional dynamics. The EA model simulations yield C–H vector orientational correlation times associated with each carbon of n-tridecane, in excellent agreement with experimental values deduced from C13-NMR T1 spin–lattice relaxation times. The C–H vector reorientation was found to be closely related to conformational jumps. These jumps, whose rates closely follow torsional correlation times, appear to occur mostly as unconcerted individual transitions for these short chains. [ABSTRACT FROM AUTHOR]

We have carried out stochastic dynamics and molecular dynamics simulations of n-tridecane (C13H28) as isolated chains, in bulk melts, and in confined melts between solid surfaces, employing both a united atom (UA) model and an explicit atom (EA) model, in order to compare chain conformations, packing, orientational correlations, and self-diffusion predicted by the UA and EA models. The EA model, which explicitly takes into account all hydrogens, exhibits nearly identical results for chain conformations to those from the UA model. However, only the EA model, which shows considerably enhanced interchain packing and orientational correlations in the melts over those for the UA model, reproduces very closely the height and the width of the interchain peak in the experimental x-ray scattering profile. Dynamically, inclusion of explicit hydrogens decreases the self-diffusion constants in the melts by a factor of 6–8, resulting in reasonably good agreement with the experimental value. Moreover, in the melts confined between solid surfaces, the presence of explicit hydrogens leads to much more pronounced layering of both the monomer segments and the entire molecules, which are strongly oriented along the solid surfaces. [ABSTRACT FROM AUTHOR]

Examines the anomalous conformational behavior of poly(ethylene oxide) oligomers in aqueous solutions. Relationship between dihedral systems and water content; Analysis of the compositional dependence of diglyme conformational populations; Correlation of diglyme anomalous conformational behavior with temperature.

Compares incoherent dynamic structure factors with results from atomistic molecular dynamics simulations. Time-of-flight (TOF) neutron scattering measurements; Molecular dynamics trajectories; Decay that occurs as a result of a combination of torsional librations and jumps.

Studies the properties of methyl capped polyoxyethylene (POE) melts. Examination of dynamic properties that depend primarily on the local conformational dynamics of the chains; C nuclear magnetic resonance spin-lattice relaxation; Dielectric relaxation.

We sought to identify distinguishing comorbid conditions, functional limitations, and social risk factors that differentiate patients, who had 5 or more hospitalizations over a 2-year period, years before they became high-utilizers. Graph: Figure 1 Change in prevalence of risk factors associated with frequent hospitalization over time. This study also adds to the literature by investigating a unique population who accrue multiple hospitalizations outside of 30-day readmissions and by investigating risk factors years upstream from high utilization. [Extracted from the article]

The simple view of reading hypothesises that reading comprehension is predicted by decoding and language abilities. In this study, 257 fifth‐grade English‐language learners (Ells) in south‐central India were assessed on reading and language measures. Using a model of the simple view, we fit the data using path analysis to determine the extent to which it predicts reading comprehension. Results show that the effect of listening vocabulary on reading comprehension is mediated by listening comprehension, while the effect of word reading fluency on reading comprehension is mediated by passage reading fluency. The final path model explains 33.8% of the variance in reading comprehension. Results are discussed in relation to previous studies. [ABSTRACT FROM AUTHOR]

A self-consistent density-functional approach has been employed to study the structure of nonuniform binary hard-core Yukawa mixtures as well as the structure of its uniform counterpart. The second-order direct correlation function and the bridge function of the corresponding uniform fluid mixture required as input in the self-consistent theory are obtained from integral equation theory using an accurate closure relation. The calculated density and concentration profiles of the nonuniform mixtures as well as the radial distribution function profiles of the uniform fluid mixtures are shown to compare well with available simulation results. [ABSTRACT FROM AUTHOR]