Impact of Diimine Ligand on Singlet-to-Triplet Charge Transfer Electroabsorption in Iron and Ruthenium Complexes.

The electroabsorption and absorption spectra of eight homoleptic complexes of the general form [M(LL)3]2+ where M = Ru, Fe, and LL = 1,10-phenanthroline (phen), 2,2'-bipyridine (bpy), and 4,4',-(R)2-bpy where R = -OCH3, -CF3, were quantified at 77 K in a butyronitrile glass. Intense metal-to-ligand charge transfer (MLCT) absorption bands were evident in the visible region. Electroabsorption spectra measured with applied electric fields >0.2 MV/cm were analyzed by the two-state Liptay model. Significant light-induced dipole moment changes of Δµâ‡€ = 4-13 D were found consistent with a metal-to-ligand charge transfer (MLCT) excited state comprised an electron localized on a single diimine ligand, [MIII(LL-)(LL)2]*2+, in the initially formed Franck-Condon excited state. A low energy feature evident in the electroabsorption spectra was assigned to a direct singlet-to-triplet MLCT excited state. The identity of the diimine ligand had an unexpected and large impact on these transitions. Analysis relative to the higher energy absorption provides a comparison of spin-allowed and disallowed transitions for first- and second-row transition metal complexes. With the notable exception of [Fe(CF3bpy)3]2+, the change in dipole moment for the 3MLCT excited states was less than or equal to that of the 1MLCT excited states. The charge transfer distances for the iron complexes were generally larger than those for the Ru complexes, a behavior attributed to a smaller degree of iron-diimine coupling in the ground state. A striking result was the sensitivity of the extinction coefficient and spectral profile of the low energy electroabsorption assigned to the identity of the diimine ligand; data that suggests electronic coupling with ligand localized triplet states and high spin metal centered states must be considered when modeling the Franck-Condon excited state.

Universal pictures: A lithophane codex helps teenagers with blindness visualize nanoscopic systems.

People with blindness have limited access to the high-resolution graphical data and imagery of science. Here, a lithophane codex is reported. Its pages display tactile and optical readouts for universal visualization of data by persons with or without eyesight. Prototype codices illustrated microscopy of butterfly chitin-from N-acetylglucosamine monomer to fibril, scale, and whole insect-and were given to high schoolers from the Texas School for the Blind and Visually Impaired. Lithophane graphics of Fischer-Spier esterification reactions and electron micrographs of biological cells were also 3D-printed, along with x-ray structures of proteins (as millimeter-scale 3D models). Students with blindness could visualize (describe, recall, distinguish) these systems-for the first time-at the same resolution as sighted peers (average accuracy = 88%). Tactile visualization occurred alongside laboratory training, synthesis, and mentoring by chemists with blindness, resulting in increased student interest and sense of belonging in science.

The HFSA Advanced Heart Failure and Transplant Cardiology Fellowship Consensus Conference.

There is waning interest among cardiology trainees in pursuing an Advanced Heart Failure/Transplant Cardiology (AHFTC) fellowship as evidenced by fewer applicants in the National Resident Matching Program match to this specialty. This trend has generated considerable attention across the heart failure community. In response, the Heart Failure Society of America convened the AHFTC Fellowship Task Force with a charge to develop strategies to increase the value proposition of an AHFTC fellowship. Subsequently, the HFSA sponsored the AHFTC Fellowship Consensus Conference April 26-27, 2023. Before the conference, interviews of 44 expert stakeholders diverse across geography, site of practice (traditional academic medical center or other centers), specialty/area of expertise, sex, and stage of career were conducted virtually. Based on these interviews, potential solutions to address the declining interest in AHFTC fellowship were categorized into five themes: (1) alternative training pathways, (2) regulatory and compensation, (3) educational improvements, (4) exposure and marketing for pipeline development, and (5) quality of life and mental health. These themes provided structure to the deliberations of the AHFTC Fellowship Consensus Conference. The recommendations from the Consensus Conference were subsequently presented to the HFSA Board of Directors to inform strategic plans and interventions. The HFSA Board of Directors later reviewed and approved submission of this document. The purpose of this communication is to provide the HF community with an update summarizing the processes used and concepts that emerged from the work of the HFSA AHFTC Fellowship Task Force and Consensus Conference.

Computational Exploration of Potential CFTR Binding Sites for Type I Corrector Drugs.

Cystic fibrosis (CF) is a recessive genetic disease that is caused by mutations in the cystic fibrosis transmembrane conductance regulator (CFTR) protein. The recent development of a class of drugs called "correctors", which repair the structure and function of mutant CFTR, has greatly enhanced the life expectancy of CF patients. These correctors target the most common disease causing CFTR mutant F508del and are exemplified by the FDA-approved VX-809. While one binding site of VX-809 to CFTR was recently elucidated by cryo-electron microscopy, four additional binding sites have been proposed in the literature and it has been theorized that VX-809 and structurally similar correctors may engage multiple CFTR binding sites. To explore these five binding sites, ensemble docking was performed on wild-type CFTR and the F508del mutant using a large library of structurally similar corrector drugs, including VX-809 (lumacaftor), VX-661 (tezacaftor), ABBV-2222 (galicaftor), and a host of other structurally related molecules. For wild-type CFTR, we find that only one site, located in membrane spanning domain 1 (MSD1), binds favorably to our ligand library. While this MSD1 site also binds our ligand library for F508del-CFTR, the F508del mutation also opens a binding site in nucleotide binding domain 1 (NBD1), which enables strong binding of our ligand library to this site. This NBD1 site in F508del-CFTR exhibits the strongest overall binding affinity for our library of corrector drugs. This data may serve to better understand the structural changes induced by mutation of CFTR and how correctors bind to the protein. Additionally, it may aid in the design of new, more effective CFTR corrector drugs.

Analysis of Physician Compensation Studies by Gender, Race, and Ethnicity.

Purpose: This report investigated physician compensation studies by gender, race, and ethnicity. Methods: Published U.S. physician compensation studies were assessed. Results: Of the 47 data sets within 46 studies, 36 analyzed compensation by gender and 32 (88.9%) found disparities. Thirteen and eight analyzed for race and ethnicity, with disparities found in four (30.8%) and none, respectively. The sample sizes of the four data sets with differences by race were among the largest in the subset. Conclusion: Most studies demonstrate pay disparities for women, but not for people who identify with underrepresented race/ethnic groups; however, small sample sizes may affect results.

Removing systemic barriers to equity, diversity, and inclusion: Report of the 2019 Plant Science Research Network workshop "Inclusivity in the Plant Sciences".

A future in which scientific discoveries are valued and trusted by the general public cannot be achieved without greater inclusion and participation of diverse communities. To envision a path towards this future, in January 2019 a diverse group of researchers, educators, students, and administrators gathered to hear and share personal perspectives on equity, diversity, and inclusion (EDI) in the plant sciences. From these broad perspectives, the group developed strategies and identified tactics to facilitate and support EDI within and beyond the plant science community. The workshop leveraged scenario planning and the richness of its participants to develop recommendations aimed at promoting systemic change at the institutional level through the actions of scientific societies, universities, and individuals and through new funding models to support research and training. While these initiatives were formulated specifically for the plant science community, they can also serve as a model to advance EDI in other disciplines. The proposed actions are thematically broad, integrating into discovery, applied and translational science, requiring and embracing multidisciplinarity, and giving voice to previously unheard perspectives. We offer a vision of barrier-free access to participation in science, and a plant science community that reflects the diversity of our rapidly changing nation, and supports and invests in the training and well-being of all its members. The relevance and robustness of our recommendations has been tested by dramatic and global events since the workshop. The time to act upon them is now.

Long-term treatment retention of an emergency department initiated medication for opioid use disorder program.

INTRODUCTION: Medication for Opioid Use Disorder (MOUD) has been shown to decrease mortality, reduce overdoses, and increase treatment retention for patients with opioid use disorder (OUD) and has become the state-of-the-art treatment strategy in the emergency department (ED). There is little evidence on long-term (6 and 12 month) treatment retention outcomes for patients enrolled in MOUD from the ED. METHODS: A prospective observational study used a convenience sample of patients seen at one community hospital ED over 12 months. Patients >18 years with OUD were eligible for MOUD enrollment. After medical screening, patients were evaluated by the addiction care coordinator (ACC) who evaluated and counselled the patient and if eligible, directly connected them with an addiction medicine appointment. Once enrolled, the patient received treatment with buprenorphine in the ED. A chart review was completed for all enrollments during the first year of the program. Treatment retention was determined by review of the prescription drug monitoring program and defined as patients receiving regular suboxone prescriptions at 6 and 12 months after index ED visit date. RESULTS: From June 2018 - May 2019 the ACCs evaluated patients during 691 visits, screening 571 unique patients. Of the 571 unique patients screened, 279 (48.9%) were enrolled into the MOUD program. 210 (75.3%) attended their first addiction medicine appointment, 151 (54.1%) were engaged in treatment at 1 month, 120 (43.0%) at 3 months, 105 (37.6%) at 6 months, and 97 (34.8%) at 12 months post index ED visit. Self-pay insurance status was associated with a significantly decrease in the odds of long-term treatment retention. CONCLUSION: Our ED-initiated MOUD program, in partnership with local addiction medicine services, produced high rates of long-term treatment retention.

Association Between Neighborhood-Level Poverty and Incident Atrial Fibrillation: a Retrospective Cohort Study.

BACKGROUND: Atrial fibrillation (AF) is a leading cause of cardiovascular morbidity and mortality. While neighborhood-level factors, such as poverty, have been related to prevalence of AF risk factors, the association between neighborhood poverty and incident AF has been limited. OBJECTIVE: Using a large cohort from a health system serving the greater Chicago area, we sought to determine the association between neighborhood-level poverty and incident AF. DESIGN: Retrospective cohort study. PARTICIPANTS: Adults, aged 30 to 80 years, without baseline cardiovascular disease from January 1, 2005, to December 31, 2018. MAIN MEASURES: We geocoded and matched residential addresses of all eligible patients to census-level poverty estimates from the American Community Survey. Neighborhood-level poverty (low, intermediate, and high) was defined as the proportion of residents in the census tract living below the federal poverty threshold. We used generalized linear mixed effects models with a logit link function to examine the association between neighborhood poverty and incident AF, adjusting for patient demographic and clinical AF risk factors. KEY RESULTS: Among 28,858 in the cohort, patients in the high poverty group were more often non-Hispanic Black or Hispanic and had higher rates of AF risk factors. Over 5 years of follow-up, 971 (3.4%) patients developed incident AF. Of these, 502 (51.7%) were in the low poverty, 327 (33.7%) in the intermediate poverty, and 142 (14.6%) in the high poverty group. The adjusted odds ratio (aOR) of AF was higher for the intermediate poverty compared with that for the low poverty group (aOR 1.23 [95% CI 1.01-1.48]). The point estimate for the aOR of AF incidence was similar, but not statistically significant, for the high poverty compared with the low poverty group (aOR 1.25 [95% CI 0.98-1.59]). CONCLUSION: In adults without baseline cardiovascular disease managed in a large, integrated health system, intermediate neighborhood poverty was significantly associated with incident AF. Understanding neighborhood-level drivers of AF disparities will help achieve equitable care.

Mobile health and neurocognitive domains evaluation through smartphones: A meta-analysis.

BACKGROUND: Mobile health (mHealth) have significantly advanced evaluating neurocognitive functions; but, few reports have documented whether they validate neurocognitive impairments as well as paper-and-pencil neuropsychological tests. OBJECTIVE: To meta-analyze the correlation between mobile applications for neuropsychological tests and validated paper-and-pencil neuropsychological tests for evaluating neurocognitive impairments. METHOD: We used PubMed, Embase, Cochrane, Web of Science, and IEEE Explorer through January 2020 to identify studies that compared mobile applications for neuropsychological tests vs. paper-and-pencil neurophysiological tests. We used random-effects models via the DerSimonian and Laird method to extract pooled Pearson's correlation coefficients and we stratified by study design. RESULT: Nine out of 4639 screened articles (one RCT and eight prospective longitudinal case series) were included. For the observational studies, there was a statistically significant strong and direct correlation between mobile applications for neuropsychological test scores and validated paper-and-pencil neuropsychological assessment scores (r = 0.70; 95% CI 0.59, 0.79; I2 = 74.5%; p- heterogeneity <0.001). Stronger results were seen for the RCT (r = 0.92; 95% CI 0.77, 0.97). CONCLUSION: This meta-analysis showed a statistically significant correlation between mobile applications and the validated paper-and-pencil neuropsychological assessments analyzed for the evaluation of neurocognitive impairments.