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The first layer of atoms on an oxide catalyst provides the first sites for adsorption of reactants and the last sites before products or oxygen are desorbed. We employ a unique combination of morphological, structural, and chemical analyses of a model ceria catalyst with different surface terminations under an H2 environment to unequivocally establish the effect of the last layer of atoms on surface reduction. (111) and (100) terminated epitaxial islands of ceria are simultaneously studied in situ allowing for a direct investigation of the structure-reducibility relationship under identical conditions. Kinetic rate constants of Ce4+ to Ce3+ transformation and equilibrium concentrations are extracted for both surface terminations. Unlike the kinetic rate constants, which are practically the same for both types of islands, more pronounced oxygen release, and overall higher reducibility were observed for (100) islands compared to (111) ones. The findings are in agreement with coordination-limited oxygen vacancy formation energies calculated by density functional theory. The results point out the important aspect of surface terminations in redox processes, with particular impact on the catalytic reactions of a variety of catalysts.

We examine the real space structure and the electronic structure (particularly Ce4f electron localization) of oxygen vacancies in CeO2 (ceria) as a function of U in density functional theory studies with the rotationally invariant forms of the LDA+U and GGA+U functionals. The four nearest neighbor Ce ions always relax outwards, with those not carrying localized Ce4f charge moving furthest. Several quantification schemes show that the charge starts to become localized at U≈3 eV and that the degree of localization reaches a maximum at ∼6 eV for LDA+U or at ∼5.5 eV for GGA+U. For higher U it decreases rapidly as charge is transferred onto second neighbor O ions and beyond. The localization is never into atomic corelike states; at maximum localization about 80–90% of the Ce4f charge is located on the two nearest neighboring Ce ions. However, if we look at the total atomic charge we find that the two ions only make a net gain of (0.2–0.4)e each, so localization is actually very incomplete, with localization of Ce4f electrons coming at the expense of moving other electrons off the Ce ions. We have also revisited some properties of defect-free ceria and find that with LDA+U the crystal structure is actually best described with U=3–4 eV, while the experimental band structure is obtained with U=7–8 eV. (For GGA+U the lattice parameters worsen for U>0 eV, but the band structure is similar to LDA+U.) The best overall choice is U≈6 eV with LDA+U and ≈5.5 eV for GGA+U, since the localization is most important, but a consistent choice for both CeO2 and Ce2O3, with and without vacancies, is hard to find. [ABSTRACT FROM AUTHOR]

We propose a resolution to the puzzle presented by the surface defects observed with STM at the (111) surface facet of CeO2 single crystals. In the seminal paper of Esch et al. [Science 309, 752 (2005)1 they were identified with oxygen vacancies, but the observed behavior of these defects is inconsistent with the results of density functional theory (DFT) studies of oxygen vacancies in the literature. We resolve these inconsistencies via DFT calculations of the properties of both oxygen vacancies and fluorine impurities at CeO2 (111), the latter having recently been shown to exist in high concentrations in single crystals from a widely used commercial source of such samples. We find that the simulated filled-state STM images of surface-layer oxygen vacancies and fluorine impurities are essentially identical, which would render problematic their experimental distinction by such images alone. However, we find that our theoretical results for the most stable location, mobility, and tendency to cluster, of fluorine impurities are consistent with experimental observations, in contrast to those for oxygen vacancies. Based on these results, we propose that the surface defects observed in STM experiments on CeO2 single crystals reported heretofore were not oxygen vacancies, but fluorine impurities. Since the similarity of the simulated STM images of the two defects is due primarily to the relative energies of the 2p states of oxygen and fluorine ions, this confusion might also occur for other oxides which have been either doped or contaminated with fluorine. [ABSTRACT FROM AUTHOR]

Do you know what it costs your practice to provide an adult physical, a well-child exam or an office procedure? A 'unit cost analysis' will tell you that and more. [ABSTRACT FROM AUTHOR]

Abstract Background Recent increases in patient cost-sharing for health care have lent increasing importance to monitoring cost-related changes in health care use. Despite the widespread use of survey questions to measure changes in health care use and related behaviors, scant data exists on the reliability of such questions. Methods We administered a cross-sectional survey to a stratified random sample of families in a New England health plan's high deductible health plan (HDHP) with ≥ $500 in annualized out-of-pocket expenditures. Enrollees were asked about their knowledge of their plan, information seeking, behavior change associated with having a deductible, experience of delay in care due in part to cost, and hypothetical delay in care due in part to cost. Initial respondents were mailed a follow-up survey within two weeks of each family returning the original survey. We computed several agreement statistics to measure the test-retest reliability for select questions. We also conducted continuity adjusted chi-square, and McNemar tests in both the original and follow-up samples to measure the degree to which our results could be reproduced. Analyses were stratified by self-reported income. Results The test-retest reliability was moderate for the majority of questions (0.41 - 0.60) and the level of test-retest reliability did not differ substantially across each of the broader domains of questions. The observed proportions of respondents with delayed or foregone pediatric, adult, or any family care were similar when comparing the original and follow-up surveys. In the original survey, respondents in the lower-income group were more likely to delay or forego pediatric care, adult care, or any family care. All of the tests comparing income groups in the follow-up survey produced the same result as in the original survey. Conclusions In this population of HDHP beneficiaries, we found that survey questions concerning plan knowledge, information seeking, and delayed or foregone care were moderately reliable. Our results offer reassurance for researchers using survey information to study the effects cost sharing on health care utilization.

Background: Opioids are a first-line treatment for severe cancer pain. However, clinicians may be reluctant to prescribe opioids for patients with concurrent substance use disorders (SUD) or clinical concerns about non-prescribed substance use., Measures: Patient volume, 60-day retention rate, and use of sublingual buprenorphine to treat opioid use disorder., Intervention: We created the Palliative Harm Reduction and Resiliency Clinic, a palliative care clinic founded on harm reduction principles and including formal collaboration with addiction psychiatry., Outcomes: During the first 18 months, patient volume increased steadily; 70% of patients had at least one subsequent visit within 60 days of the initial appointment; and buprenorphine was prescribed for 55% of patients with opioid use disorder., Conclusions/lessons Learned: The formal collaboration with addiction psychiatry and the integration of harm reduction principles and practices into ambulatory palliative care improved our ability to provide treatment to a previously underserved patient population with high symptom burden., (Copyright © 2024 The Authors. Published by Elsevier Inc. All rights reserved.)

Objectives: Patients with chronic conditions enrolled in high-deductible health plans (HDHPs) face cost-related access barriers and high out-of-pocket spending. Our objectives were to develop a novel behavioural intervention to help HDHP enrollees with chronic conditions use cost-conscious strategies and evaluate the intervention's preliminary effectiveness, acceptability and feasibility., Design: Prospective., Setting: Online (USA)., Participants: 36 US adults enrolled in an HDHP through their employer or an exchange with diabetes, hypertension, asthma, coronary artery disease and/or chronic obstructive pulmonary disease. 31/36 participants completed the study., Intervention: We developed a 5-week intervention consisting of a website with educational modules on discussing costs with clinicians, saving for future healthcare costs, comparing healthcare prices and quality, preparing for appointments, following up after appointments and planning for future healthcare needs; and emails encouraging participants to access each module., Outcomes: We conducted a single-arm proof-of-concept pilot study of the intervention. Baseline and postintervention surveys measured primary outcomes of health insurance literacy and confidence in using cost-conscious strategies. 10 participants completed postintervention interviews., Results: 31 (86%) participants completed a baseline and postintervention survey. Mean health insurance literacy scores (20-80 scale) improved from 56.5 to 67.1 (p < 0.001). Mean confidence scores (0-10 scale) improved for talking to a healthcare provider about cost (6.1-7.6, p=0.0094), saving for healthcare (5.8-6.6, p = 0.068), comparing prices (5.4-6.9, p=0.005) and comparing quality (6.1 to 7.6, p=0.0034). Participants found the website easy to use and helpful for learning about cost-conscious strategies on postintervention interviews., Conclusions: Our novel behavioural intervention was acceptable to HDHP enrollees with chronic conditions, feasible to deliver and associated with increased health insurance literacy and confidence in using cost-conscious strategies. This intervention should be tested in a definitive randomised controlled trial that is fully powered to evaluate its effects on cost-related access barriers, out-of-pocket spending and health outcomes in this growing patient population., Competing Interests: Competing interests: None declared., (© Author(s) (or their employer(s)) 2024. Re-use permitted under CC BY-NC. No commercial re-use. See rights and permissions. Published by BMJ.)

Xtampza ER™, an oxycodone extended-release capsule (OERC), was the first long-acting opioid to feature abuse-deterrent properties and various routes of administration without pharmacokinetic alterations. The primary objective of this study was to evaluate changes in reported pain scores after initiation of or rotation to OERC from a previous opioid.  Baseline scores were from patients' outpatient visits immediately before starting OERC and were compared to those at the next two follow-up visits. Secondary objectives identified variables that influenced pain scores. Methods included screening for cancer patients with outpatient OERC prescriptions seen in the palliative care clinic. Eighty-two charts were reviewed with 66 included. Overall mean pain scores at both follow-ups were lower than those at baseline (-0.7 ± 2.1; -1.1 ± 2.4). Results were statistically significant between first and second-reported pain scores versus baseline ( p  = 0.009; 0.012) but clinically insignificant, defined as a  ≥ 2-point change in numeric pain scores. Most patients discontinued OERC at the first or second follow-up (35; 53%), and 12.1% of patients who started OERC were prescribed OERC at the end of the study. There were no significant variables identified to influence pain scores either statistically or clinically. Further studies are needed to determine the long-term efficacy and safety in cancer palliative-care patients.

The H2O and H2O2 molecules resemble each other in a multitude of ways as has been noted in the literature. Here, we present density functional theory (DFT) calculations for the H2O2(s) and H2O2·2H2O(s) crystals and make selected comparisons with ice polymorphs. The performance of a number of dispersion-corrected density functionals-both self-consistent and a posteriori ones-are assessed, and we give special attention to the D3 correction and its effects. The D3 correction to the lattice energies is large: for H2O2(s) the D3 correction constitutes about 25% of the lattice energy using PBE, much more for RPBE, much less for SCAN, and it primarily arises from non-H-bonded interactions out to about 5 Å.The large D3 corrections to the lattice energies are likely a consequence of several effects: correction for missing dispersion interaction, the ability of D3 to capture and correct various other kinds of limitations built into the underlying DFT functionals, and finally some degree of cell-contraction-induced polarization enhancement. We find that the overall best-performing functionals of the twelve examined are optPBEvdW and RPBE-D3. Comparisons with DFT assessments for ices in the literature show that where the same methods have been used, the assessments largely agree., (© 2023 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).)

Introduction: High-contact structured diabetes prevention programs are effective in lowering weight and HbA1cs, yet their intensity level can create barriers to participation. Peer support programs improve clinical outcomes among adults with Type 2 diabetes, but their effectiveness in diabetes prevention is unknown. This study examined whether a low-intensity peer support program improved outcomes more than enhanced usual care in a diverse population with prediabetes., Study Design: The intervention was tested in a pragmatic 2-arm RCT., Setting/participants: Participants were adults with prediabetes at three healthcare centers., Intervention: Participants randomized to the enhanced usual care arm received educational materials. Participants in the Using Peer Support to Aid in Prevention and Treatment in Prediabetes arm were matched with a peer supporter: another patient who had made healthy lifestyle changes and was trained in autonomy-supportive action planning. Peer supporters were instructed to provide weekly telephone support to their peers on specific action steps toward behavioral goals for 6 months, then monthly support for 6 months., Main Outcome Measures: Changes in primary outcomes of weight and HbA1c and secondary outcomes of enrollment in formal diabetes prevention programs, self-reported diet, physical activity, health-specific social support, self-efficacy, motivation, and activation at 6 and 12 months were examined., Results: Data collection occurred from October 2018 to March 2022, with analyses completed in September 2022. Among 355 randomized patients, in intention-to-treat analyses, there were no between-group differences in HbA1c or weight changes at 6 and 12 months. Using Peer Support to Aid in Prevention and Treatment in Prediabetes participants were more likely to enroll in structured programs at 6 (AOR=2.45, p=0.009) and 12 (AOR=2.21, p=0.016) months and to report eating whole grains at 6 (4.49, p=0.026) and 12 (4.22, p=0.034) months. They reported greater improvements in perceived social support for diabetes prevention behaviors at 6 (6.39, p<0.001) and 12 (5.48, p<0.001) months, with no differences in other measures., Conclusions: A stand-alone, low-intensity peer support program improved social support and participation in formal diabetes prevention programs but not weight or HbA1c. It will be important to examine whether peer support could effectively complement higher-intensity, structured diabetes prevention programs., Trial Registration: This trial is registered at ClinicalTrials.gov, NCT03689530. Full protocol available at https://clinicaltrials.gov/ct2/show/NCT03689530., (Copyright © 2023. Published by Elsevier Inc.)

Theoretical and experimental vibrational signatures of H2O and OH- (dissociated water) adsorbed on stoichiometric ceria{111} surfaces are compared. The experimental ones were collected from low-coverage experiments in the literature, and the theoretical anharmonic frequencies were generated using density functional theory calculations employing the optPBE-vdW functional for coverages from 0.5 to a few monolayers. It is found that (i) the experiments and our calculations overall agree well, lending credibility to both; (ii) the calculations manage to resolve the large class of H-bonded motifs into frequency classes that can guide experimental assignments; (iii) it is possible to find a geometrical H-bond definition that also captures the OH vibrational frequency downshifts well: R(H⋯O) ≤2.5 Å and the O-H⋯O angle θ ≥ 100°; and (iv) the frequency vs electric field relations for water and hydroxides (i.e., dissociated water) follow different and well-separated curves., (© 2023 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).)

Objectives: COVID-19 has strained the household finances of many Americans who are already experiencing increasing health care expenses. Concerns about the cost of care may deter patients from seeking even urgent care from the emergency department (ED). This study examines predictors of older Americans’ concerns about ED visit costs and how cost concerns may have influenced their ED use in the early stages of the pandemic. Study Design: This was a cross-sectional survey study using a nationally representative sample of US adults aged 50 to 80 years (N = 2074) in June 2020. Methods: Multivariate logistic regressions assessed the relationships of sociodemographic, insurance, and health factors with cost concerns for ED care. Results: Of the respondents, 80% were concerned (45% very, 35% somewhat) about costs of an ED visit and 18% were not confident in their ability to afford an ED visit. Of the entire sample, 7% had avoided ED care because of cost concerns in the past 2 years. Of those who may have needed ED care, 22% had avoided care. Predictors of cost-related ED avoidance included being aged 50 to 54 years (adjusted odds ratio [AOR], 4.57; 95% CI, 1.44-14.54), being uninsured (AOR, 2.93; 95% CI, 1.35-6.52), having poor or fair mental health (AOR, 2.82; 95% CI, 1.62-4.89), and having an annual household income of less than $30,000 (AOR, 2.30; 95% CI, 1.19-4.46). Conclusions: During the early COVID-19 pandemic, most older US adults expressed concerns about the financial impact of ED use. Further research should examine how insurance design could alleviate the perceived financial burden of ED use and prevent cost-related care avoidance, especially for those at higher risk in future pandemic surges.

A computational protocol is developed for efficient studies of partially reduced redox-active oxides using the self-consistent charge density functional tight-binding method. The protocol is demonstrated for ceria, which is a prototypical reducible oxide material. The underlying idea is to achieve a consistent (and harmonized) set of Slater-Koster (SK) tables with connected repulsive potentials that enable switching on and off the in-valence description of the Ce 4f states without serious loss of accuracy in structure and energetics. The implicit treatment of the Ce 4f states, with the use of f-in-core SK-tables, is found to lead to a significant decrease in computational time. More importantly, it allows for explicit control of the oxidation states of individual Ce atoms. This makes it possible to "freeze" the electronic configuration, thereby allowing the exploration of the energetics for various meta-stable configurations. We anticipate that the outlined strategy can help to shed light on the interplay between the size, shape, and redox activity for nanoceria and other related materials.

Robust correlation curves are essential to decipher structural information from IR-vibrational spectra. However, for surface-adsorbed water and hydroxides, few such correlations have been presented in the literature. In this paper, OH vibrational frequencies are correlated against 12 structural descriptors representing the quantum mechanical or geometrical environment, focusing on those external to the vibrating molecule. A nonbiased fitting procedure based on Gaussian process regression (GPR) was used alongside simple analytical functional forms. The training data consist of 217 structurally unique OH groups from 38 water/metal oxide interface systems for MgO, CaO and CeO 2 , all optimized at the DFT level, and the fully anharmonic and uncoupled OH vibrational signatures were calculated. Among our results, we find the following: (i) The intermolecular R (H···O) hydrogen bond distance is particularly strong, indicating the primary cause of the frequency shift. (ii) Similarly, the electric field along the H-bond vector is also a good descriptor. (iii) Highly detailed machine learning descriptors (ACSF, SOAP) are less intuitive but were found to be more capable descriptors. (iv) Combinations of geometric and QM descriptors give the best predictions, supplying complementary information.

Neuropathic pain (NP) is a chronic condition that affects ~ 1% of the general population globally. Several conditions such as chronic diabetes, herpes zoster (HZ), cancer, HIV, stroke, multiple sclerosis, physical compression or damage of nerves and certain surgical procedures can lead to neuropathy and related pain. The condition is difficult to treat with traditional analgesic drugs. Typically, non-traditional analgesics are used in treating pain in this condition such as antidepressants and antiepileptic drugs. Opioids are useful in some patients, but the risk of addiction and the risk of both short-term and long-term adverse effects make it a low priority drug class in the treatment of NP. In the current review we discuss the pharmacology and pharmaceutical care aspects of various classes of drugs used in the treatment of NP, counselling points for these drug classes, and future prospects in the treatment of NP., (© 2022. The Author(s), under exclusive licence to Springer Nature Switzerland AG.)

Opioid tapering is an essential clinical tool to utilize for a variety of reasons, including safety and analgesic optimization. The need for individualized regimens reveals a corresponding need for healthcare providers who can actively manage patients throughout the process. Pharmacists have taken on an integral role for achieving success in opioid tapering. This survey was conducted to describe the current opioid tapering practices of pain and palliative care pharmacists. A Qualtrics survey was offered to the Society of Pain and Palliative Care Pharmacist members. The majority (87%) indicated they specialized in pain management. Almost all respondents (98%) reported providing tapering recommendations and 82% reported being involved with patient monitoring throughout the taper. The majority (multiple responses could be chosen) noted that the indication for initiating an opioid taper was due to abuse/misuse (91%), reduced overall efficacy (89%), and adverse drug reactions (78%). The most common follow-up intervals during tapering were weekly (15%), every 2 weeks (22%), and every 4 weeks (44%). This practice-based survey, though small, showed that pharmacists in pain management and palliative care are actively involved in opioid tapering. This survey will hopefully serve as a foundation for continuing research into opioid tapering and the pharmacist's role therein.

Cancer related pain is prevalent among patients with a cancer diagnosis, occurring from the tumor itself or as a result of treatment. Many patients require opioid therapy to manage pain and providers must balance efficacy with side effects. Transdermal buprenorphine (TDB) has shown promise for pain management, however, the maximum dose available in the US is considered low, resulting in doubts of efficacy. This study set out to assess if the patch strengths available in the US (5-20 mcg/hour) are able to provide analgesia for patients with cancer in a palliative medicine clinic. This retrospective chart review analyzed patient charts for outpatient TDB use within a palliative medicine clinic in the United States. Patients had to have a follow up visit with the clinic in order to be included. Sixty-eight patients were included for analysis with 54 (79%) continuing at least 28 days and 37 (54%) continuing for at least 84 days. The median change in pain score was 0, though 25 (46%) of patients reported a decrease of 1 or more points at the first follow up. TDB is a viable option for cancer related pain for select patients, demonstrated by duration of use and stable reporting of pain.

Opinion Statement: Buprenorphine has unique and favorable pharmacological properties that make it useful in a variety of clinical scenarios. It has been recommended to consider buprenorphine first-line opioid for chronic pain, especially in the elderly as it may be associated with less cognitive impairment, falls, sexual dysfunction, and sarcopenia when compared with schedule II opioids. It may be useful in patients with comorbid substance use disorder or non-medical opioid use, as there is less risk of misuse, euphoria and it may improve mood. When used to treat opioid use disorder, the training and waiver was recently waived for licensed practitioners with a DEA and any provider may prescribe buprenorphine. For many reasons outlined in this article, the popularity of using buprenorphine for analgesia continues to grow and a practitioner should consider this as an excellent and safe option for chronic pain., (© 2021. The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.)

Objectives: Emergency preparedness becomes more important with increased age, as older adults are at heightened risk for harm from disasters. In this study, predictors of preparedness actions and confidence in preparedness among older adults in the United States were assessed., Methods: This nationally representative survey polled community-dwelling older adults ages 50-80 y (n = 2256) about emergency preparedness and confidence in addressing different types of emergencies. Logistic regression was used to identify predictors of reported emergency preparedness actions and confidence in addressing emergencies., Results: Participants' mean age was 62.4 y (SD = 8); 52% were female, and 71% were non-Hispanic white. Living alone was associated with lower odds of having a 7-d supply of food and water (adjusted odds ratio [aOR] = 0.74; 95% confidence interval [CI]: 0.56-0.96), a stocked emergency kit (aOR = 0.64; 95% CI: 0.47-0.86), and having had conversations with family or friends about evacuation plans (aOR = 0.59; 95% CI: 0.44-0.78). Use of equipment requiring electricity was associated with less confidence in addressing a power outage lasting more than 24 h (aOR = 0.66; 95% CI: 0.47-0.94), as was use of mobility aids (OR = 0.65; 95% CI: 0.45-0.93)., Conclusions: These results point to the need for tailored interventions to support emergency preparedness for older adults, particularly among those who live alone and use medical equipment requiring electricity.

Band alignment effects of anatase and rutile nanocrystals in TiO 2 powders lead to electron-hole separation, increasing the photocatalytic efficiency of these powders. While size effects and types of possible alignments have been extensively studied, the effect of interface geometries of bonded nanocrystal structures on the alignment is poorly understood. To allow conclusive studies of a vast variety of bonded systems in different orientations, we have developed a new density functional tight-binding parameter set to properly describe quantum confinement in nanocrystals. By applying this set, we found a quantitative influence of the interface structure on the band alignment.

Context: Treatment-induced mucositis commonly affects cancer patients, and ketamine oral rinse solution has shown efficacy for refractory pain. Although intranasal ketamine as systemic therapy has previously been studied, there are no reports on intranasal ketamine spray for topical pain treatment. Objective: To present the novel use of atomized intravenous ketamine solution for topical treatment of sinonasal mucositis pain. Patient case: A patient with sinonasal undifferentiated carcinoma presented with refractory treatment-related intranasal mucositis pain. Following initiation of atomized ketamine solution delivered topically into the nostrils, pain improved, and opioid use decreased. After dose adjustment for confusion, the patient continued ketamine therapy for several weeks with good effect. Conclusion: Atomized ketamine solution delivered intranasally may be a safe and effective topical treatment for mucositis pain of the sinuses. Interpretation of safety of the initial dosing used was affected by several confounding factors. However, a reduced dose appeared efficacious and was well tolerated.

Objectives : Sexual health is an important component of overall health and well-being for older adults. Despite this, little is known about the importance of sex to quality of life, as part of romantic relationships for older adults, and potential drivers of interactions between healthcare providers and older adults about sexual health. In this study using a nationally representative population, we describe perceptions and experiences of sex among older adults. Methods : A nationally representative, cross-sectional sample of community-dwelling U.S. adults aged 65-80 was surveyed about their sexual health and interaction with their health care providers about sexual health. Results : The survey completion rate was 75% (N = 1,002). Overall, 50.9% of men and 30.8% of women reported being sexually active. In all, 17.3% of adults aged 65-80 reported speaking to their health care provider about sexual health in the past two years and of those, 60.5% of patients initiated the conversation. Multivariable logistic regression demonstrated that sexual activity (yes/no), interest in sex, and satisfaction with sex life are major drivers of sexual health conversations between patients and healthcare providers. Conclusions : Many adults aged 65-80 are interested in and engage in sexual activity. While the majority of older adults reported a willingness to discuss their sexual health with their health care providers, few had done so, and most conversations were initiated by patients. Iterest in sex and satisfaction with sex life may be targets for intervention and offer a segue for providers as they begin the conversation to engage with older adults about their sexual health. Clinical Implications : Providers may have conversations with older adults about sexual health and may need sexual health training to have effective discussions; age nor chronic conditions should preclude this essential conversation. Clinical gerontologists may be helpful in this training and in encouraging patients to bring up sexual health concerns during their medical appointments.

The Curvature Constrained Splines (CCS) methodology has been used for fitting repulsive potentials to be used in SCC-DFTB calculations. The benefit of using CCS is that the actual fitting of the repulsive potential is performed through quadratic programming on a convex objective function. This guarantees a unique (for strictly convex) and optimum two-body repulsive potential in a single shot, thereby making the parametrization process robust, and with minimal human effort. Furthermore, the constraints in CCS give the user control to tune the shape of the repulsive potential based on prior knowledge about the system in question. Herein, we developed the method further with new constraints and the capability to handle sparse data. We used the method to generate accurate repulsive potentials for bulk Si polymorphs and demonstrate that for a given Slater-Koster table, which reproduces the experimental band structure for bulk Si in its ground state, we are unable to find one single two-body repulsive potential that can accurately describe the various bulk polymorphs of silicon in our training set. We further demonstrate that to increase transferability, the repulsive potential needs to be adjusted to account for changes in the chemical environment, here expressed in the form of a coordination number. By training a near-sighted Atomistic Neural Network potential, which includes many-body effects but still essentially within the first-neighbor shell, we can obtain full transferability for SCC-DFTB in terms of describing the energetics of different Si polymorphs.

Plasmonic materials have optical cross sections that exceed by 10-fold their geometric sizes, making them uniquely suitable to convert light into electrical charges. Harvesting plasmon-generated hot carriers is of interest for the broad fields of photovoltaics and photocatalysis; however, their direct utilization is limited by their ultrafast thermalization in metals. To prolong the lifetime of hot carriers, one can place acceptor materials, such as semiconductors, in direct contact with the plasmonic system. Herein, we report the effect of operating temperature on hot electron generation and transfer to a suitable semiconductor. We found that an increase in the operation temperature improves hot electron harvesting in a plasmonic semiconductor hybrid system, contrasting what is observed on photodriven processes in nonplasmonic systems. The effect appears to be related to an enhancement in hot carrier generation due to phonon coupling. This discovery provides a new strategy for optimization of photodriven energy production and chemical synthesis.

Adsorption of molecules is a fundamental step in all heterogeneous catalytic reactions. Nevertheless, the basic mechanism by which photon-mediated adsorption processes occur on solid surfaces is poorly understood, mainly because they involve excited catalyst states that complicate the analysis. Here we demonstrate a method by which density functional theory (DFT) can be used to quantify photoinduced adsorption processes on transition metal oxides and reveal the fundamental nature of these reactions. Specifically, the photoadsorption of SO 2 on TiO 2 (101) has been investigated by using a combination of DFT and in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The combined experimental and theoretical approach gives a detailed description of the photocatalytic desulfurization process on TiO 2 , in which sulfate forms as a stable surface product that is known to poison the catalytic surface. This work identifies surface-SO 4 2- as the sulfate species responsible for the surface poisoning and shows how this product can be obtained from a stepwise oxidation of SO 2 on TiO 2 (101). Initially, the molecule binds to a lattice O 2 - ion through a photomediated adsorption process and forms surface sulfite, which is subsequently oxidized into surface-SO 4 2- by transfer of a neutral oxygen from an adsorbed O 2 molecule. The work further explains how the infrared spectra associated with this oxidation product change during interactions with water and surface hydroxyl groups, which can be used as fingerprints for the surface reactions. The approach outlined here can be generalized to other photo- and electrocatalytic transition metal oxide systems.

Herein, we have investigated the CO 2 reduction paths on the (101) anatase TiO 2 surface using an approach based on the density functional tight binding (DFTB) theory. We analyzed the reaction paths for the conversion of carbon dioxide to methane by performing a large number of calculations with intermediates placed in various orientations and locations at the surface. Our results show that the least stable intermediate is CO 2 H and therefore a key bottleneck is the reduction of CO 2 to formic acid. Hydrogen adsorption is also weak and would also be a limiting factor, unless very high pressures of hydrogen are used. The results from our DFTB approach are in good agreement with the hybrid functional based density functional theory calculations presented in the literature., Competing Interests: The authors declare no competing financial interest.

Background: There is an urgent need to develop and evaluate effective and scalable interventions to prevent or delay the onset of type 2 diabetes mellitus (T2DM)., Methods: In this randomized controlled pragmatic trial, 296 adults with prediabetes will be randomized to either a peer support arm or enhanced usual care. Participants in the peer support arm meet face-to-face initially with a trained peer coach who also is a patient at the same health center to receive information on locally available wellness and diabetes prevention programs, discuss behavioral goals related to diabetes prevention, and develop an action plan for the next week to meet their goals. Over six months, peer coaches call their assigned participants weekly to provide support for weekly action steps. In the final 6 months, coaches call participants at least once monthly. Participants in the enhanced usual care arm receive information on local resources and periodic updates on available diabetes prevention programs and resources. Changes in A1c, weight, waist circumference and other patient-centered outcomes and mediators and moderators of intervention effects will be assessed., Results: At least 296 participants and approximately 75 peer supporters will be enrolled., Discussion: Despite evidence that healthy lifestyle interventions can improve health behaviors and reduce risk for T2DM, engagement in recommended behavior change is low. This is especially true among racial and ethnic minority and low-income adults. Regular outreach and ongoing support from a peer coach may help participants to initiate and sustain healthy behavior changes to reduce their risk of diabetes., Trial Registration: The ClinicalTrials.gov registration number is NCT03689530., (Copyright © 2020. Published by Elsevier Inc.)

A low-cost template-free solution chemical route to highly porous nanocrystalline sponges of ZnO-EuO 1.5 with 0-5 mol % Eu is presented. The process uses Zn- and Eu-acetate-nitrate and triethanolamine as precursors in methanol. After evaporation of the solvent and heating at 200 °C for 3 min, crystalline ZnO:Eu sponges with minor amounts of organic residues were obtained. Heating to 400 °C replaced the organics with carbonate, which in its turn was decomposed at temperatures below 600 °C, forming ZnO:Eu sponges. Samples heated to 200-1000 °C for 3 min were studied with XRD, SEM, TEM, TG, XPS, and IR spectroscopy. The ZnO:Eu crystallite sizes could be tuned from below 10 nm for sponges prepared at 200-500 °C, to over 100 nm range at 900 °C, without sintering of the overall microstructure. XRD showed the presence of hexagonal ZnO:Eu (or at 700-1000 °C, ZnO:Eu and cubic Eu 2 O 3 ) as the only phases present. The ZnO:Eu had slightly larger unit cell dimensions than the literature value of ZnO for samples obtained at 200-600 °C, while the unit cells of samples obtained at higher temperatures were quite close to the value of undoped ZnO. XPS showed that Eu was mainly in its 3+ state and well-distributed within the sponges but segregated at the ZnO sponge surface upon heating at 700-1000 °C, in accordance with XRD studies showing Eu 2 O 3 formation.

Thin film structures of water on the CeO 2 (111) surface for coverages between 0.5 and 2.0 water monolayers have been optimized and analyzed using density functional theory (optPBE-vdW functional). We present a new 1.0 ML structure that is both the lowest in energy published and features a hydrogen-bond network extending the surface in one-dimension, contrary to what has been found in the literature, and contrary to what has been expected due to the large bulk ceria cell dimension. The adsorption energies for the monolayer and multilayered water structures agree well with experimental temperature programmed desorption results from the literature, and we discuss the stability window of CeO 2 (111) surfaces covered with 0.5-2.0 ML of water.

Background . Many employers now incentivize employees to engage in wellness programs, yet few studies have examined differences in preferences for incentivizing participation in healthy behaviors and wellness programs. Method . We surveyed 2,436 employees of a large university about their preferences for incentivizing participation in different types of healthy behaviors and then used multivariable logistic regression to estimate associations between employees' socioeconomic and demographic characteristics and their preferences for incentives for engaging in healthy behaviors. Results. Compared with nonunion members, union members had higher odds of wanting an incentive for eating healthily (adjusted odds ratio [AOR] = 1.60, 95% [CI; 1.21, 2.12]), managing weight (AOR = 1.53, 95% CI [1.14, 2.06]), avoiding drinking too much alcohol (AOR = 1.41, 95% CI [1.11, 1.78]), quitting tobacco (AOR = 1.37, 95% CI [1.06, 1.77]), managing stress (AOR = 1.37, 95% CI [1.08, 1.75]), and managing back pain (AOR = 1.64, 95% CI [1.28, 2.10]). Compared with staff, faculty employees reported higher odds for wanting an incentive for reducing alcohol intake (AOR = 1.34, 95% CI [1.00, 1.78]) and quitting tobacco (AOR = 1.43, 95% CI [1.04, 1.96]). Women had lower odds than men (AOR = 0.80, 95% CI [0.64, 0.99]) of wanting an incentive for managing back pain. Conclusions. Preferences for incentives to engage in different types of healthy behaviors differed by employees' socioeconomic and demographic characteristics. Organizations may consider using survey data on employee preferences for incentives to more effectively engage higher risk populations in wellness programs.

The electrolyte is an essential constituent of the light-emitting electrochemical cell (LEC), since its operating mechanism is dependent on the redistribution of mobile ions in the active layer. Recent developments of new ion transporters have yielded high-performance devices, but knowledge about the interactions between the ionic species and the ion transporters and the influence of these interactions on the LEC performance is lacking. We therefore present a combined computational and experimental effort that demonstrates that the selection of the end group in a star-branched oligomeric ion transporter based on trimethylolpropane ethoxylate has a paramount influence on the ionic interactions in the electrolyte and thereby also on the performance of the corresponding LECs. With hydroxyl end groups, the cation from the salt is strongly coordinated to the ion transporter, which leads to suppression of ion pairing, but the penalty is a hindered ion release and a slow turn-on for the LEC devices. With methoxy end groups, an intermediate coordination strength is seen together with the formation of contact ion pairs, but the LEC performance is very good with fast turn-on. Using a series of ion transporters with alkyl carbonate end groups, the ion transporter:cation coordination strength is lowered further, but the turn-on kinetics are slower than what is seen for devices comprising the methoxy end-capped ion transporter.

Evidence guiding inpatient management of buprenorphine is lacking-this retrospective cohort study evaluated the clinical impact of hospital continuation versus discontinuation of buprenorphine at an academic medical center. The primary outcome was inpatient oral morphine equivalents (OME). Secondary outcomes included patient pain levels, functional assessment, and hospital length of stay. One hundred thirty-one patients (74 continued buprenorphine, 57 discontinued) were included in the analysis. Median OME were significantly lower among patients continued on buprenorphine versus discontinued (11 mg vs 103 mg, p  < 0.001), as was maximum 24-hour opioid utilization (60 mg vs 240 mg, p  < 0.001) and 24-hour pre-discharge utilization (10 mg vs 128 mg, p  < 0.001). Median pain levels were similar between groups at the time of admission (8 in each group, p  = 0.48), discharge (7 in each group, p  = 0.26), and over the first 7 days of hospitalization (7 vs 8, p  = 0.08). Hospital length of stay was similar between groups (5 days in each group, p  > 0.99). Failure to reinitiate buprenorphine occurred in 31/57 patients (54.4%) in the discontinuation group. Hospital buprenorphine continuation is associated with reduced opioid requirements, while not significantly impacting pain levels, functionality, or length of admission. Failure to reinitiate buprenorphine was common and may have negative implications for addiction treatment.

Combining experimental spectroscopy and hybrid density functional theory calculations, we show that the incorporation of fluoride ions into a prototypical reducible oxide surface, namely, ceria(111), can induce a variety of nontrivial changes to the local electronic structure, beyond the expected increase in the number of Ce 3+ ions. Our resonant photoemission spectroscopy results reveal new states above, within, and below the valence band, which are unique to the presence of fluoride ions at the surface. With the help of hybrid density functional calculations, we show that the different states arise from fluoride ions in different atomic layers in the near surface region. In particular, we identify a structure in which a fluoride ion substitutes for an oxygen ion at the surface, with a second fluoride ion on top of a surface Ce 4+ ion giving rise to F 2p states which overlap the top of the O 2p band. The nature of this adsorbate F - -Ce 4+ resonant enhancement feature suggests that this bond is at least partially covalent. Our results demonstrate the versatility of anion doping as a potential means of tuning the valence band electronic structure of ceria.