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Abstract Background The Nigeria Demographic and Health Survey (NDHS) of 2008 show that Ondo State had the worst maternal outcomes in the South Western region of Nigeria. To address this problem, the “Abiye” (safe motherhood) programme—which included community engagement, health system strengthening and user fee removal— was implemented by the state government. We assessed the use of maternal health care services and its determinants at 5 years after the implementation of this programme using a population-based survey. We also compared the results of our survey to the NDHS 2013 to assess improvement in maternal health care services utilisation. Methods We conducted a population-based survey in 2016 among representative sample of 409 women who had given birth between 2011 and 2015, which were selected using cluster random sampling. We compared the findings of this 2016 survey to the 2013 NDHS, which contains maternal health care services utilisation information of a total of 434 women who gave birth between 2009 and 2013 to assess progress in the use of maternal health care services. We used descriptive and inferential statistics for our data analysis. Results In the 2013 NDHS survey, about 80% of women received antenatal care compared to 98% in the 2016 survey. Our survey shows that the majority of births (85.6%) took place in health facilities compared to only 56.5% in NDHS 2013 survey, which represents a 29.1 percentage points increase. In both surveys, women with primary level of education or less had lower odds of delivering their babies in health facilities. However, while the 2013 NDHS survey shows that women who resided in urban areas were twice more likely to deliver their babies in health facilities compared to those living in rural areas, the 2016 survey shows that urban residence was no longer significantly associated with a higher odds of facility-based child delivery. Conclusion Maternal health services utilisation has improved considerably following the implementation of the “Abiye” initiative. The findings of this study suggest that with community engagement, health system strengthening and user fee removal for the most vulnerable, universal access to and utilisation of maternal health services is possible.

Abstract Background Consistent condom use is central to the prevention of transmission of human immunodeficiency virus (HIV) and other sexually transmitted diseases (STDs), especially among young adults. This study drew from a cross-sectional survey of two Nigerian universities to determine the level of consistent condom use, explored the determinants of condom use consistency and reasons for inconsistent condom use. Methods We adopted a descriptive cross-sectional design, which involves the recruitment of 800 male and female students using stratified random sampling. Adjusted and unadjusted logistic regression models were used to examine the factors associated with consistent condom use among a final sample of 498 students who engaged in sex in the last year preceding the study. Results Only 38.6% of sexually active participants (n = 498) used condoms consistently in the previous year. High condom self-efficacy score (AOR: 2.40; 95% CI: 1.58–3.64), discussion of HIV/STIs with sexual partner (AOR: 1.91; 95%CI: 1.29–2.83), knowing partner’s HIV status (AOR: 1.48; 95% CI: 1.02–2.16), being students of university located in a high HIV prevalence area (AOR: 2.86; 95% CI: 1.92–4.28) and engaging in sex with only steady partner (AOR: 1.74; 95% CI: 1.17–2.60) were associated with a higher odds of consistent condom use. Trust, unavailability of condoms, dislike of condoms and a perception that condoms reduced sexual pleasure were the main reasons for inconsistent use of condoms. Conclusion The study found a low level of consistent condom use among study participants. Counselling young adults in Nigeria on condom self-efficacy, providing condoms on campuses and encouraging the discussion of sexually transmitted infections with sexual partners are central to improving the level of consistent condom use among Nigerian university students.

Abstract Objectives There appears to be an increasing trend of condom use for pregnancy prevention among nulliparous and multiparous women in developing countries. Drawing from a cross-sectional survey involving 1227 women selected using a 3-stage cluster random sampling technique, the study examines the rates of condom use and its determinants among parous women in three states in North Central and South Western Nigeria. Results The rate of condom use among parous women was 13.8% and 23.2% among women using any form of contraceptives. After adjusting for confounding factors (religion and marital status, socioeconomic status and access to a health facility in the resident community), women aged 26–35 (AOR 2.7; CI 1.6–4.5), urban residence (AOR: 3.6; CI 2.2–5.8), no income (AOR: 2.7; CI 1.4–4.9), living in Ekiti State (AOR: 1.8; CI 1.2–2.8) and having a tertiary level of education (AOR: 4.5; CI 1.3–15.6) were the independent predictors of condom use. There is an increasing trend of condom use among parous women.

Abstract Background Health care visits during pregnancy, childbirth and after childbirth may be crucial in expanding the uptake of contraceptive care in resource-poor settings. However, little is known about how health care visits influence the uptake of modern contraception in Nigeria. The focus of this paper was to examine how health care visits influence the use of contraceptives among parous women in a medically underserved setting. Methods The study adopted a descriptive survey design. Data was collected from 411 women who gave birth between 2010 and 2015 selected through a two-stage cluster random sampling technique. Health care visits for antenatal care services, childbirth, postnatal care and modern contraceptive were dichotomised (yes, no). Descriptive analyses were performed, and percentages, frequencies and means were reported. Multiple logistic regressions were computed, and odds ratios and 95% confidence intervals were calculated. Results Knowledge of all contraceptive methods was lowest among women who reside in rural areas. Health care visits for antenatal care (UOR 4.5; 95% CI 2.0–10.5), childbirth (UOR2.1; 95% CI 1.4–3.2) and postnatal care services (UOR 2.3; 95% CI 1.5–3.5) independently predict ever use of any contraceptive methods. Likewise, health care visits for antenatal care (UOR 5.6; 95% CI 2.1–14.8), childbirth (UOR 2.3; 95% CI 1.5–3.6) and postnatal care services (UOR 2.8; 95% CI 1.8–4.5) were independent predictors of current use of modern contraceptive methods. In the adjusted model, health care visits for antenatal care services (AOR 3.2; 95% CI 1.1–8.8) were significantly associated with the use of modern contraceptive methods. Conclusion Health care visits significantly predict the use of modern contraceptive methods. Expanding access to health care services would potentially increase contraceptive use among childbearing women in the medically underserved settings.

Abstract Background Contraceptive use has numerous health benefits such as preventing unplanned pregnancies, ensuring optimum spacing between births, reducing maternal and child mortality, and improving the lives of women and children in general. This study examines the level of contraceptive use, its determinants, reasons for non-use of contraception among women in the reproductive age group (18–49 years) in two southwestern Nigerian states. Methods The study adopted an interviewer-administered questionnaire to collect data from 809 participants selected using a 3-stage cluster random sampling technique. We also conducted 46 in-depth interviews. In order to investigate the association between the socio-demographic variables and use of contraceptive methods, we estimated the binary logistic regression models. Results The findings indicated that knowledge of any methods of contraception was almost universal among the participants. The rates of ever use and current use of contraception was 80 and 66.6%, respectively. However, only 43.9% of the participants had ever used any modern contraceptive methods, considered to be more reliable. The fear of side effects of modern contraceptive methods drove women to rely on less effective traditional methods (withdrawal and rhythm methods). Some women employed crude and unproven contraceptive methods to prevent pregnancies. Conclusion Our findings show that the rate of contraceptive use was high in the study setting. However, many women chose less effective traditional contraceptive methods over more effective modern contraceptive methods due to fear of side effects of the latter. Patient education on the various options of modern contraceptives, their side effects and management would be crucial towards expanding the family planning services in the study setting.

Abstract Background The reasons for low utilisation of maternal health services in settings where the user-fee removal policy has been implemented continue to generate scholarly debates. Evidence of whether user-fee removal benefits the poor women in underserved settings is scanty and inconsistent. This article examines use of maternal health care services in the context of free maternal healthcare and profiles the beneficiaries of user-fee removal. Methods The study adopted a descriptive design. A three-stage cluster sampling method was used to select a representative sample of 1227 women who gave birth between 2011 and 2015. Questionnaires were administered using a face-to-face interview approach and data generated were analysed using descriptive and inferential statistics. Results The analysis shows that the use of maternal healthcare services has improved considerably in North Central and Southwestern Nigeria. While socioeconomic and geographical inequality in the use of maternal healthcare services appear to be disappearing in Southwestern Nigeria, it appears to be widening in North Central Nigeria. The findings indicate that 33.6% of women reported to have benefitted from the free child-delivery programme; however, substantial variation exists across the two regions. The proportion of beneficiaries of user-fee removal policy was highest in urban areas (35.9%), among women belonging to the middle income category (38.3%), among women who gave birth in primary health centres (63.1%) and among women who resided in communities where there was availability of health facilities (37.2%). Conclusion The study concludes that low coverage of the free maternal health programme, especially among women of low socioeconomic status residing in underserved settings is among the reasons for persistent poor maternal health outcomes in the context of free maternal healthcare. A model towards improving maternal health in underserved settings, especially in North Central Nigeria, would entail provisioning of health facilities as well as focusing on implementing equitable maternal health policies.

Abstract Background The vulnerabilities of young women of low socio-economic status and those with little or no formal education tend to dominate the discourse on unplanned pregnancy, unsafe abortion and emergency contraception (EC) in sub-Saharan Africa. This article draws on a survey conducted among female undergraduate students to shed light on sexual behaviour and the dynamics of emergency contraceptive use among this cohort. Methods The survey involved 420 female undergraduate students drawn using a multistage sampling technique, while a self-administered questionnaire was used for data collection. Univariate and bivariate analyses were applied to examine the factors associated with the use of emergency contraception. Results Of the 176 female students who reported being sexually active in the year preceding the survey, only 38.6% reported the use of condom during the entire year. Of those who reported unplanned pregnancy anxiety n = 94, about 30.1% used EC, 20.4% used non-EC pills as EC, while others reported having used no EC. A few respondents (n = 3) had terminated a pregnancy under unsafe conditions. Awareness of EC (p

Abstract Background Emergency contraception (EC) can significantly reduce the rate of unintended pregnancies and unsafe abortions especially in sub-Saharan Africa. Despite the increasing awareness of EC among educated young women in Nigeria, the rate of utilisation remains low. This study therefore explores the main barriers to the use of EC among female university students by analysing their knowledge of emergency contraception, methods ever used, perceived efficacy, and its acceptability. Methods This paper brings together the findings from several focus groups (N = 5) and in-depth interviews (N = 20) conducted amongst unmarried female undergraduate students in two Nigerian universities. Results Participants considered the use of condom and abstinence as the most effective methods of preventing unplanned pregnancy. However, many participants were misinformed about emergency contraception. Generally, participants relied on unconventional and unproven ECs; Ampiclox, “Alabukun”, salt water solution, and lime and potash and perceived them to be effective in preventing unplanned pregnancies. Furthermore, respondents’ narratives about methods of preventing unwanted pregnancies revealed that inadequate information on emergency contraception, reliance on unproven crude contraceptive methods, and misconception about modern contraception constitute barriers to the use of emergency contraception. Conclusions The findings suggested that female university students are misinformed about emergency contraception and their reliance on unproven ECs constitutes a barrier to the use of approved EC methods. These barriers have serious implications for prevention of unplanned pregnancies in the cohort. Behavioural interventions targeting the use of unproven emergency contraceptive methods and misperceptions about ECs would be crucial for this cohort in Nigeria.

Background: The emergence of a ‘Southern’ discourse of corporate social responsibility (CSR) highlight the crucial issues of poverty reduction, infrastructure development and the broader questions of social provisioning and community development. Aim: This study builds on existing knowledge to reveal how CSR has become a drive or aid in the community development discourse and poverty reduction mechanisms. This was done through the analysis of major CSR projects by Zimplats mining company. Setting: The study was carried out in Mhondoro-Ngezi, Zimbabwe, which is in a rural setting. Method: The study employed a triangulated design, with data collected using a mini-survey, focus groups and in-depth interviews. Results: The key findings are that the fundamental roles of CSR have been to link it to addressing under-development and poverty reduction issues in developing countries. Conclusion: Through distributional CSR activities, the mining company was able to address the health, educational, employment and water needs of the local people.

Per- and polyfluoroalkyl substances (PFAS) are a group of environmental pollutants that have been linked to a variety of health problems in humans, including the disruption of thyroid functions. Herein, for the first time, the impact of PFAS on thyroid hormone synthesis is shown. Mid- to long-chain PFAS impact thyroid hormone synthesis by changing the local hydrogen bond network as well as the required orientation of hormonogenic residues, stopping the production of thyroxine (T4). Furthermore, the toxic effects of sulfonic PFAS are more prominent than those of carboxylic PFAS, highlighting that the exposure to these specific compounds can pose greater problems for thyroid homeostasis., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Fresh water sources, including lakes, such as the Great Lakes, are some of the most important ecosystems in the world. Despite the importance of these lakes, there is increasing concern about the presence of per- and polyfluoroalkyl substances (PFAS)─among the most prevalent contaminants of our time─due to the ability of PFAS to bioaccumulate and persist in the environment, as well as to its linkages to detrimental human and animal health effects. In this study, PFAS exposure on rainbow trout ( Oncorhynchus mykiss ) is examined at the molecular level, focusing on the impact of PFAS binding on the alpha (α) and beta (β) estrogen receptors (ERs) using molecular dynamics simulations, binding free energy calculations, and structural analysis. ERs are involved in fundamental physiological processes, including reproductive system development, muscle regeneration, and immunity. This study shows that PFAS binds to both the estrogen α and estrogen β receptors, albeit via different binding modes, due to a modification of an amino acid in the binding site as a result of a reorientation of residues in the binding pocket. As ER overactivation can occur through environmental toxins and pollutants, this study provides insights into the influence of different types of PFAS on protein function.

Proteoglycans (PGs), consisting of glycosaminoglycans (GAGs) linked with the core protein through a tetrasaccharide linkage region, play roles in many important biological events. The chemical synthesis of PG glycopeptides is extremely challenging. In this work, the enzymes required for synthesis of chondroitin sulfate (CS) PG (CSPG) have been expressed and the suitable sequence of enzymatic reactions has been established. To expedite CSPG synthesis, the peptide acceptor was immobilized on solid phase and the glycan units were directly installed enzymatically onto the peptide. Subsequent enzymatic chain elongation and sulfation led to the successful synthesis of CSPG glycopeptides. The CS dodecasaccharide glycopeptide was the longest homogeneous CS glycopeptide synthesized to date. The enzymatic synthesis was much more efficient than the chemical synthesis of the corresponding CS glycopeptides, which could reduce the total number of synthetic steps by 80 %. The structures of the CS glycopeptides were confirmed by mass spectrometry analysis and NMR studies. In addition, the interactions between the CS glycopeptides and cathepsin G were studied. The sulfation of glycan chain was found to be important for binding with cathepsin G. This efficient chemoenzymatic strategy opens new avenues to investigate the structures and functions of PGs., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Bosonic quantum devices offer a novel approach to realize quantum computations, where the quantum two-level system ( qubit ) is replaced with the quantum (an)harmonic oscillator ( qumode ) as the fundamental building block of the quantum simulator. The simulation of chemical structure and dynamics can then be achieved by representing or mapping the system Hamiltonians in terms of bosonic operators. In this Perspective, we review recent progress and future potential of using bosonic quantum devices for addressing a wide range of challenging chemical problems, including the calculation of molecular vibronic spectra, the simulation of gas-phase and solution-phase adiabatic and nonadiabatic chemical dynamics, the efficient solution of molecular graph theory problems, and the calculations of electronic structure.

Vibrational spectroscopy enables critical insight into the structural and dynamic properties of molecules. Presently, the majority of theoretical approaches to spectroscopy employ wavefunction-based ab initio or density functional methods that rely on the harmonic approximation. This approximation breaks down for large molecules with strongly anharmonic bonds or for molecules with large internuclear separations. An alternative to these methods involves generating molecular anharmonic potential energy surfaces (potentials) and using them to extrapolate the vibrational frequencies. This study examines the efficacy of density functional theory (DFT) and the correlation consistent Composite Approach (ccCA) in generating anharmonic frequencies from potentials of small main group molecules. Vibrational self-consistent field Theory (VSCF) and post-VSCF methods were used to calculate the fundamental frequencies of these molecules from their potentials. Functional choice, basis set selection, and mode-coupling are also examined as factors in influencing accuracy. The absolute deviations for the calculated frequencies using potentials at the ccCA level of theory were lower than the potentials at the DFT level. With DFT resulting in bending modes that are better described than those of ccCA, a multilevel DFT:ccCA approach where DFT potentials are used for single vibrational mode potentials and ccCA is used for vibrational mode-mode couplings can be utilized for larger polyatomic systems. The frequencies obtained with this multilevel approach using VCIPSI-PT2 were closer to experimental frequencies than the scaled harmonic frequencies, indicating the success of utilizing post-VSCF methods to generate more accurate representations of computed infrared spectra., (© 2024 The Authors. Journal of Computational Chemistry published by Wiley Periodicals LLC.)

Using a simple solution growth technique, we grow crystals with phenanthroline as a ligand and various rare earth ions: thulium (Tm), ytterbium (Yb), gadolinium (Gd), lanthanum (La), neodymium (Nd), europium (Eu), and erbium (Er). We then selected the composition that forms thin plates with well-defined shapes, Er(NO 3 )Phen 2 , and explored the effects of various conditions on crystal formation and growth, including temperature regime, light illumination, and substrates where the crystals are formed and grown. The composition and local environment strongly affect the size and shape of microcrystals and substrate coverage. The use of gold substrates significantly enhances the crystal growing process. Elevated temperatures negatively affect the crystal growth., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Advances in superconductor technology have been pursued for decades, moving towards room temperature models, such as a postulated nitrogen-doped lutetium hydride network. While experimental observations have been contradictory, insight into the building blocks of potential new superconductor materials can be gained theoretically, unravelling the fascinating electronic structure of these compounds at a molecular level. Here, the fundamental building blocks of lutetium materials (LuH, LuN, and LuNH) have been examined. The structures, spectroscopic constants for the ground and excited states, and the potential energy curves have been obtained for these species using complete active self-consistent field (CASSCF) and multireference configuration interaction with Davidson's correction (MRCI+Q) methods. For LuNH, the energetic properties of its isomers are determined. The bond dissociation energies of the three building blocks are calculated with the state-of-the-art f -block ab initio correlation consistent composite approach ( f -ccCA) and the high accuracy extrapolated ab initio thermochemistry (HEAT) scheme. As well, an analysis of different formation pathways of LuNH has been provided.

Polaritonic states, which are formed by resonances between a molecular excitation and the photonic mode of a cavity, have a number of useful properties that offer new routes to control molecular photochemistry using electric fields. To provide a theoretical description of how polaritonic states affect the real-time electron dynamics in molecules, a new method is described where the effects of strong light-molecule coupling are implemented using real-time electronic structure theory. The coupling between the molecular electronic states and the cavity is described by the Pauli-Fierz Hamiltonian, and transitions between polaritonic states are induced via an external time-dependent electric field using time-dependent configuration interaction (TDCI) theory, producing quantum electrodynamics TDCI (QED-TDCI). This method is used to study laser-induced ultrafast charge transfer and dipole-switching dynamics of the LiCN molecule inside a cavity. The increase in cavity coupling strength is found to have a significant impact on the energies and transition dipole moments of the molecule-cavity system. The convergence of the polaritonic state energies as a function of the number of included electronic and photonic basis states is discussed., (© 2024 Author(s). Published under an exclusive license by AIP Publishing.)

The correlation consistent basis sets (cc-pVnZ with n = D, T, Q, 5) for the Ga-Br elements have been redesigned, tuning the sets for use for density functional approximations. Steps to redesign these basis sets for an improved correlation energy recovery and efficiency include truncation of higher angular momentum functions, recontraction of basis set coefficients, and reoptimization of basis set exponents. These redesigned basis sets are compared with conventional cc-pVnZ basis sets and other basis sets, which are, in principle, designed to achieve systematic improvement with respect to increasing basis set size. The convergence of atomic energies, bond lengths, bond dissociation energies, and enthalpies of formation to the Kohn-Sham limit is improved relative to other basis sets where convergence to the Kohn-Sham limit is typically not observed., (© 2024 Author(s). Published under an exclusive license by AIP Publishing.)

Background: Therapeutic lymphadenectomy (TLND) is still performed in most melanoma patients to treat nodal recurrences after initial negative lymph node biopsy (-SLNB), despite the lack of evidence for survival benefit. We sought to compare melanoma-specific survival (MSS) and distant metastasis-free survival (DMFS) of patients who underwent TLND versus no TLND using our institutional and MSTL-1 databases., Methods: We identified 146 patients with nodal recurrence following -SLNB: 132 underwent TLND and 14 did not. DMFS and MSS were evaluated for the cohorts followed by a matched-pair analysis between the cohorts., Results: No difference was observed in five-year DMFS (p ​= ​0.454) and five-year MSS (p ​= ​0.945) between the two groups. The matched-pair analysis showed similar results (p ​= ​0.329 and p ​= ​0.363 for DMSF and MSS, respectively)., Conclusions: From this limited retrospective study, TLND for nodal recurrence after a -SLNB does not appear to improve DMFS or MSS in melanoma patients compared to no TLND., Competing Interests: Declaration of competing interest RE serves on the advisory board for Castle Biosciences and Intramedical Imaging. AKW, TO, SS and KL have no conflict of interest., (Copyright © 2023 The Authors. Published by Elsevier Inc. All rights reserved.)

Nuclear receptors are the fundamental building blocks of gene expression regulation and the focus of many drug targets. While binding to DNA, nuclear receptors act as transcription factors, governing a multitude of functions in the human body. Peroxisome proliferator-activator receptor γ (PPARγ) and the retinoid X receptor α (RXRα) form heterodimers with unique properties and have a primordial role in insulin sensitization. This PPARγ/RXRα heterodimer has been shown to be impacted by per- and polyfluoroalkyl substances (PFAS) and linked to a variety of significant health conditions in humans. Herein, a selection of the most common PFAS (legacy and emerging) was studied utilizing molecular dynamics simulations for PPARγ/RXRα. The local and global structural effects of PFAS binding on the known ligand binding pockets of PPARγ and RXRα as well as the DNA binding domain (DBD) of RXRα were inspected. The binding free energies were predicted computationally and were compared between the different binding pockets. In addition, two electronic structure approaches were utilized to model the interaction of PFAS within the DNA binding domain, density functional theory (DFT) and domain-based pair natural orbital coupled cluster with perturbative triples (DLPNO-CCSD(T)) approaches, with implicit solvation. Residue decomposition and hydrogen-bonding analysis were also performed, detailing the role of prominent residues in molecular recognition. The role of l-carnitine is explored as a potential in vivo remediation strategy for PFAS interaction with the PPARγ/RXRα heterodimer. In this work, it was found that PFAS can bind and act as agonists for all of the investigated pockets. For the first time in the literature, PFAS are postulated to bind to the DNA binding domain in a nonspecific manner. In addition, for the PPARγ ligand binding domain, l-carnitine shows promise in replacing smaller PFAS from the pocket.

Real-time (RT) electronic structure methods provide a natural framework for describing light-matter interactions in arbitrary time-dependent electromagnetic fields (EMF). Optically induced excited state transitions are of particular interest, which require tuned EMF to drive population transfer to and from the specific state(s) of interest. Intersystem crossing, or spin-flip, may be driven through shaped EMF or laser pulses. These transitions can result in long-lived "spin-trapped" excited states, which are especially useful for materials requiring charge separation or protracted excited state lifetimes. Time-dependent configuration interaction (TDCI) is unique among RT methods in that it may be implemented in a basis of eigenstates, allowing for rapid propagation of the time-dependent Schrödinger equation. The recent spin-orbit TDCI (TD-SOCI) enables a real-time description of spin-flip dynamics in an arbitrary EMF and, therefore, provides an ideal framework for rational pulse design. The present study explores the mechanism of multiple spin-flip pathways for a model transition metal complex, FeCO, using shaped pulses designed to drive controlled intersystem crossing and charge transfer. These results show that extremely tunable excited state dynamics can be achieved by considering the dipole transition matrix elements between the states of interest., (© 2023 Author(s). Published under an exclusive license by AIP Publishing.)

Background: Persons with hemophilia may encounter various traumatic experiences related to their bleeding disorder throughout their lifetime. Little is known about the clinical impact of disease-related trauma on this population., Objectives: To explore the prevalence of posttraumatic stress disorder (PTSD) and posttraumatic stress symptoms in adults with hemophilia A and B and characterize the traumatic experiences they report., Methods: An online survey tool collecting data on participant characteristics and a validated questionnaire containing the PTSD checklist for Diagnostic and Statistical Manual of Mental Disorders 5 were distributed via Research Electronic Data Capture to adults with hemophilia A and B during their annual visit to their hemophilia treatment center. Participants were asked about traumatic experiences specific to their hemophilia prior to self-administering the PTSD checklist for Diagnostic and Statistical Manual of Mental Disorders 5 questionnaire., Results: Survey responses from 178 individuals across 3 hemophilia treatment centers were included in the analysis, representing a 70% response rate. One hundred one (56.7%) participants identified a hemophilia-related traumatic event, and 21 (11.8%) participants met criteria for a provisional diagnosis of PTSD. Multivariable analysis showed higher odds of a positive PTSD screen in participants with noninfectious (odds ratio [OR], 13.89; 95% CI, 2.23-86.62) and infectious comorbidities (OR, 11.18; 95% CI, 1.34-93.45) and in participants with >1 mental health comorbidity (OR, 10.07; 95% CI, 2.39-42.52). On the contrary, age >46 years (OR, 0.6; 95% CI, 0.01-0.62) and higher education (OR, 0.25; 95% CI, 0.07-0.88) reduced odds of PTSD., Conclusion: Persons with hemophilia are at risk of developing PTSD and posttraumatic stress symptoms. These data support the need for trauma screening, psychosocial services in the bleeding disorders community, and provision of trauma-informed care by providers., (© 2023 The Authors.)

Atomic charge and its distribution across molecules provide important insight into chemical behavior. Though there are many studies on various routes for the determination of atomic charge, there are few studies that examine the broader impact of basis set and quantum method used over many types of population analysis methods across the periodic table. Largely, such a study of population analysis has focused on main-group species. In this work, atomic charges were calculated using several population analysis methods including orbital-based methods (Mulliken, Löwdin, and Natural Population Analysis), volume-based methods (Atoms-in-Molecules (AIM) and Hirshfeld), and potential derived charges (CHELP, CHELPG, and Merz-Kollman). The impact of basis set and quantum mechanical method choices upon population analysis has been considered. The basis sets utilized include Pople (6-21G**, 6-31G**, 6-311G**) and Dunning (cc-pV n Z, aug-cc-pV n Z; n = D, T, Q, 5) basis sets for main group molecules. For the transition metal and heavy element species examined, relativistic forms of the correlation consistent basis sets were used. This is the first time the cc-pV n Z-DK3 and cc-pwCV n Z-DK3 basis sets have been examined with respect to their behavior across all levels of basis sets for atomic charges for an actinide. The quantum methods chosen include two density functional (PBE0 and B3LYP), Hartree-Fock, and second-order Møller-Plesset perturbation theory (MP2) approaches., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2023 North, Jorgensen, Pricetolstoy and Wilson.)

The determination of gas phase thermochemical properties of per- and polyfluoroalkyl substances (PFAS) is central to understanding the long-range transport behavior of PFAS in the atmosphere. Prior gas-phase studies have reported the properties of perfluorinated sulfonic acid (PFOS) and perfluorinated octanoic acid (PFOA). Here, this study reports the gas phase enthalpies of formation of short- and long-chain PFAS and their precursor molecules determined using density functional theory (DFT) and ab initio approaches. Two density functionals, two ab initio methods and an empirical method were used to compute enthalpies of formation with the total atomization approach and an isogyric reaction. The performance of the computational methods employed in this work were validated against the experimental enthalpies of linear alkanoic acids and perfluoroalkanes. The gas-phase determinations will be useful for future studies of PFAS in the atmosphere, and the methodological choices will be helpful in the study of other PFAS., (© 2022 The Authors. Journal of Computational Chemistry published by Wiley Periodicals LLC.)

Complete active space self-consistent field (CASSCF) and multireference configuration interaction with Davidson correction (MRCI+Q) calculations have been carried out for lawrencium fluoride (LrF) and lawrencium oxide (LrO) molecules, detailing 19 and 20 electronic states for LrF and LrO, respectively. For LrF, two dissociation channels were considered, Lr( 2 P)+F( 2 P) and Lr( 2 D)+F( 2 P). However, due to the more complex electronic manifold of LrO, three dissociation channels were computed: Lr( 2 P)+O( 3 P), Lr( 2 D)+O( 3 P), and Lr( 2 P)+O( 1 D). In addition, equilibrium bond lengths, harmonic vibrational frequencies ω e , anharmonicity constants ω e χ e , Δ G 1/2 values, and excitation energies T e for the ground and several excited electronic states were calculated for both molecules, for the first time. Bond dissociation energies (BDEs) were calculated for LrF and LrO using several different levels of theory: unrestricted coupled-cluster with single, double, and perturbative triple excitations (UCCSD(T)), density functional theory (B3LYP, TPSS, M06-L, and PBE), and the correlation-consistent composite approach developed for f -elements ( f -ccCA).

Nanocolloids that are cumulatively referred to as nanocarbons, attracted significant attention during the last decade because of facile synthesis methods, water solubility, tunable photoluminescence, easy surface modification, and high biocompatibility. Among the latest development in this reserach area are chiral nanocarbons exemplified by chiral carbon dots (CDots). They are expected to have applications in sensing, catalysis, imaging, and nanomedicine. However, the current methods of CDots synthesis show often contradictory chemical/optical properties and structural information that required a systematic study with careful structural evaluation. Here, we investigate and optimize chiroptical activity and photoluminescence of L- and D-CDots obtained by hydrothermal carbonization of L- and D-cysteine, respectively. Nuclear magnetic resonance spectroscopy demonstrates that they are formed via gradual dehydrogenation and condensation reactions of the starting amino acid leading to particles with a wide spectrum of functional groups including aromatic cycles. We found that the chiroptical activity of CDots has an inverse correlation with the synthesis duration and temperature, whereas the photoluminescence intensity has a direct one, which is associated with degree of carbonization. Also, our studies show that the hydrothermal synthesis of cysteine in the presence of boric acid leads to the formation of CDots rather than boron nitride nanoparticles as was previously proposed in several reports. These results can be used to design chiral carbon-based nanoparticles with optimal chemical, chiroptical, and photoluminescent properties., (© 2022 The Authors. Chirality published by Wiley Periodicals LLC.)

Introduction: The social worker (SW) role in the Hemophilia Treatment Center (HTC) is complex and broad, providing direct support, spanning across micro, mezzo and macro levels of care., Aim: Research demonstrates discrepancy between actual and ideal SW roles among the HTC SW community. Soliciting perceptions from HTC staff about the SW role can provide a deeper understanding of this discrepancy and improve collaboration amongst care team members in meeting the psychosocial needs of HTC patients., Methods: Funded by the National Hemophilia Foundation (NHF), a national online survey was conducted in 2020 to determine the views and attitudes of what the SW role is by HTC staff. Separate surveys were emailed to active HTC SWs and staff to collect anonymous data. Demographics of SWs gathered included age, education, years of practice, full time equivalent (FTE) status, and caseload. All disciplines were asked questions about perceptions, barriers, and potential ways to enhance and strengthen the SW role within HTCs., Results: Results demonstrated that subcategory-oriented questions (40 in total) and qualitative responses highlighted diverse viewpoints and offered clarity about these differences., Conclusion: Findings indicated most HTC staff value the multi-faceted role of SW at their centres, and both groups identified time, limited resources, and role confusion as barriers to utilizing SW services. Outcomes will inform the development of a "standards of practice" tool that will provide education for HTC staff, patients, and families, and serve as an empowerment tool for SW to highlight their skillset and define their role., (© 2022 John Wiley & Sons Ltd.)

Perfluoroalkyl and polyfluoroalkyl substances (PFASs) are a class of chemicals widely used in industrial applications due to their exceptional properties and stability. However, they do not readily degrade in the environment and are linked to contamination and adverse health effects in humans and wildlife. To find alternatives for the most commonly used PFAS molecules that maintain their desirable chemical properties but are not adverse to biological lifeforms, a novel approach based upon machine learning is utilized. The machine learning model is trained on an existing set of PFAS molecules to generate over 260,000 novel PFAS molecules, which we dub PFAS-AI-Gen. Using molecular descriptors with known relationships to toxicity and industrial suitability followed by molecular docking and molecular dynamics simulations, this set of molecules is screened. In this manner, increasingly complex calculations are performed only for candidate molecules that are most likely to yield the desired properties of low binding affinity toward two selected protein receptors, the human pregnane x receptor (hPXR) and peroxisome proliferator-activated receptor γ (PPAR-γ), and high industrial suitability, defined by critical micelle concentration (CMC). The selection criteria of low binding affinity and high industrial suitability are relative to the popular PFAS alternative GenX. hPXR and PPAR-γ are selected as they are PFAS targets and facilitate a variety of functions, such as drug metabolism and glucose regulation, respectively. Through this approach, 22 promising new PFAS substitutes that may warrant experimental investigation are identified. This integrated approach of molecular screening and toxicity estimation may be applicable to other chemical classes.

The f-block ab initio correlation consistent composite approach was used to predict the dissociation energies of lanthanide sulfides and selenides. Geometry optimizations were carried out using density functional theory and coupled cluster singles, doubles, and perturbative triples with one- and two-component Hamiltonians. For the two-component calculations, relativistic effects were accounted for by utilizing a third-order Douglas-Kroll-Hess Hamiltonian. Spin-orbit coupling was addressed with the Breit-Pauli Hamiltonian within a multireference configuration interaction approach. The state averaged complete active space self-consistent field wavefunctions obtained for the spin-orbit coupling energies were used to assign the ground states of diatomics, and several diagnostics were used to ascertain the multireference character of the molecules.

Background: Current guidelines recommend excisional/complete biopsy for melanoma diagnosis, owing to high rates of residual disease found at wide local excision (WLE) after partial biopsy techniques. We sought to determine any survival disadvantage associated with the presence of residual invasive melanoma in the WLE after diagnosis with a partial biopsy technique., Study Design: Data were examined from Multicenter Selective Lymphadenectomy Trials I and II (MSLT-I and -II), 2 large melanoma trials. Patients diagnosed with excisional/complete biopsy were excluded. Clinicopathologic characteristics, melanoma-specific survival (MSS), distant disease-free survival (DDFS), and disease-free survival (DFS) of those with residual invasive melanoma in the definitive WLE and those with no residual melanoma were compared. Matched pairing was used to reduce variability between groups., Results: From 1994 through 2014, 3,939 patients were enrolled in these trials and 874 (22%) were diagnosed using partial biopsy techniques. Of these, 399 (46%) had residual tumor in the WLE. Only 6 patients had residual tumor in their WLE resulting in T-upstaging of their tumor. Match-pairing formed two cohorts (1:1) of patients with and without residual invasive tumor after WLE. A total of 514 patients were paired; 288 (56%) males, 148 (28.8%) aged 60 or older, 192 (37.4%) with truncal melanomas, 214 (41.6%) had Breslow thickness 2 mm or greater, and 376 (73.2%) had positive sentinel nodes. Kaplan-Meier analysis showed no statistical difference in 10-year MSS (73.6% ± 3.3% vs 73.9% ± 3.7%, p = 0.891), DDFS (68.7% ± 3.4% vs 65.3% ± 4.0%, p = 0.548), or DFS (59.6% ± 3.7% vs 59.4% ± 3.9%, p = 0.783)., Conclusions: Survival in patients with primary melanoma does not appear to be worse in patients who undergo a partial biopsy technique and are later found to have residual invasive tumor in the WLE specimen., (Copyright © 2022 by the American College of Surgeons. Published by Wolters Kluwer Health, Inc. All rights reserved.)

The ubiquitous presence of poly- and perfluoroalkyl substances (PFAS) in different natural settings poses a serious threat to environmental and human health. Soils and sediments represent one of the important exposure pathways of PFAS for humans and animals. With increasing bioaccumulation and mobility, it is extremely important to understand the interactions of PFAS molecules with the dominant constituents of soils such as clay minerals. This study reports for the first time the fundamental molecular-level insights into the adsorption, interfacial structure, and dynamics of short- and long-chain PFAS molecules at the water-saturated mesopores of kaolinite clay using classical molecular dynamics (MD) simulations. At environmental conditions, all the PFAS molecules are exclusively adsorbed near the hydroxyl surface of the kaolinite, irrespective of the terminal functional groups and metal cations. The interfacial adsorption structures and coordination environments of PFAS are strongly dependent on the nature of the functional groups and their hydrophobic chain length. The formation of large, aggregated clusters of long-chain PFAS at the hydroxyl surface of kaolinite is responsible for their restricted dynamics in comparison to short-chain PFAS molecules. Such comprehensive knowledge of PFAS at the clay mineral interface is critical to developing novel site-specific degradation and mitigation strategies.

The first, second, and third gas-phase ionization potentials have been determined for the actinide series of elements using an ab initio composite scalar and fully relativistic approach, employing the coupled cluster with single, double, and perturbative triple excitations (CCSD(T)) and Dirac Hartree-Fock (DHF) methods, extrapolated to the complete basis set (CBS) limit. The impact of electron correlation and basis set choice within this framework are examined. Additionally, the first three ionization potentials were obtained using an ab initio heavy element correlation-consistent Composite Approach (here referred to as α-ccCA). This is the first utilization of a ccCA for actinide species.

Possible modifications in electrochemical reaction kinetics are explored in a nanostructured plasmonic environment with and without additional light illumination using a cyclic voltammetry (CV) method. In nanostructured gold, the effect of light on anodic and cathodic currents is much pronounced than that in a flat system. The electron-transfer rate shows a 3-fold increase under photoexcitation. The findings indicate a possibility of using plasmonic excitations for controlling electrochemical reactions., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

The multi-configuration electron-nuclear dynamics for open shell systems with a spin-unrestricted formalism is described. The mean fields are evaluated using second-order reduced density matrices for electronic and nuclear degrees of freedom. Applications to light-element diatomics including equilibrium geometries, electronic energies, dipole moments, and absorption spectra are presented. The von Neumann entropies for different spin states of a LiH molecule are compared.

The importance of spin-orbit effects on the predictions of energetic properties of actinide compounds has been considered for 18 different density functionals, comparing the spin-orbit and non-spin-orbit ("standard") forms of density functional theory (DFT). A set of enthalpies of formation for 66 small actinide (Th-Am) compounds-the An66 set, for which experimental data are available-have been investigated. The set includes actinide halides, oxides, and oxohalides in the general form AnO m X n , where n = 0-6, m = 0-3, and X = F, Cl, Br, or I. The impact of basis set choice was investigated, and to help account for the impact of relativity, the Stuttgart general and segmented contracted atomic natural orbital (ANO) basis sets paired with small core relativistic effective core potentials (RECP) as well as all-electron calculations utilizing the third-order Douglas-Kroll-Hess were considered.

High level multireference calculations were performed for LuF for a total of 132 states, including four dissociation channels Lu( 2 D) + F( 2 P), Lu( 2 P) + F( 2 P), and two Lu( 4 F) + F( 2 P). The 6s, 5d, and 6p orbitals of lutetium, along with the valence 2p and 3p orbitals of fluorine, were included in the active space, allowing for the accurate description of static and dynamic correlation. The Lu( 4 F) + F( 2 P) channel has intersystem spin crossings with the Lu( 2 P) + F( 2 P) and Lu( 2 D) + F( 2 P) channels, which are discussed herein. To obtain spectroscopic constants, bond lengths, and excited states, multi-reference configuration interaction (MRCI) was used at a quadruple-ζ basis set level, correlating also the 4f electrons and corresponding orbitals. Core spin-orbit (C-MRCI) calculations were performed, revealing that 1 3 Π 0- is the first excited state closely followed by 1 3 Π 0+ . In addition, the dissociation energy of LuF was determined at different levels of theory, with a range of basis sets. A balance between core correlation and a relativistic treatment of electrons is fundamental to obtain an accurate description of the dissociation energy. The best prediction was obtained with a combination of coupled-cluster single, double, and perturbative triple excitations /Douglas-Kroll-Hess third order Hamiltonian methods at a complete basis set level with a zero-point energy correction, which yields a dissociation value of 170.4 kcal mol -1 . Dissociation energies using density functional theory were calculated using a range of functionals and basis sets; M06-L and B3LYP provided the closest predictions to the best ab initio calculations.

Peroxisome proliferator receptor gamma (PPARγ), a type II nuclear receptor, fundamental in the regulation of genes, glucose metabolism, and insulin sensitization has been shown to be impacted by per- and poly-fluoroalkyl substances (PFASs). To consider the influence of PFASs upon PPARγ, the molecular interactions of 27 PFASs have been investigated. Two binding sites have been identified on the PPARγ homodimer structure: the dimer pocket and the ligand binding pocket, the former has never been studied prior. Molecular dynamics calculations were performed to gain insights about PFASs-PPARγ binding and the role of acidic and basic residues. The electrostatic interactions for acidic and basic residues far from the binding site were probed, together with their effect on PPARγ recognition. Short-range electrostatic and van der Waals interactions with nearby residues and their influence on binding energies were investigated. As the negative effects of perfluorooctane sulfonate acid were previously shown to be alleviated by one of its natural ligands, l-carnitine, here, the utility of l-carnitine as a possible inhibitor for other PFASs has been considered. A comparison of the binding patterns of l-carnitine and PFASs provides insights toward mitigation strategies for PFASs., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

Statistical Assessment of Modeling of Proteins and Ligands (SAMPL) challenges provide routes to compare chemical quantities determined using computational chemistry approaches to experimental measurements that are shared after the competition. For this effort, several computational methods have been used to calculate the binding energies of Octa Acid (OA) and exo-Octa Acid (exoOA) host-guest systems for SAMPL7. The initial poses for molecular dynamics (MD) were generated by molecular docking. Binding free energy calculations were performed using molecular mechanics combined with Poisson-Boltzmann or generalized Born surface area solvation (MMPBSA/MMGBSA) approaches. The factors that affect the utility of the MMPBSA/MMGBSA approaches including solvation, partial charge, and solute entropy models were also analyzed. In addition to MD calculations, quantum mechanics (QM) calculations were performed using several different density functional theory (DFT) approaches. From SAMPL6 results, B3PW91-D3 was found to overestimate binding energies though it was effective for geometry optimizations, so it was considered for the DFT geometry optimizations in the current study, with single-point energy calculations carried out with B2PLYP-D3 with double-, triple-, and quadruple-ζ level basis sets. Accounting for dispersion effects, and solvation models was deemed essential for the predictions. MMGBSA and MMPBSA correlated better to experiment when used in conjunction with an empirical/linear correction.

Objective: Determine if a standardized methadone and lorazepam weaning protocol that is based on dose and duration of exposure can reduce the length of opioid and benzodiazepine weaning and shorten hospital stay., Methods: Retrospective cohort study performed in a 24-bed medical/surgical PICU. A total of 177 patients on opioid and/or benzodiazepine infusions for >3 days were included; 75 patients pre protocol (June 2012- June 2013) were compared with 102 patients post implementation of a standardized weaning protocol of methadone and lorazepam (March 2014-March 2015). The recommended wean was based on duration of infusions of >3 days up to 5 days (no wean), 5 to 13 days (short wean), and ≥14 days (long wean)., Results: Median number of days on methadone for patients on opioid infusions for 5 to 13 days was reduced from 8.5 to 5.7 days (p = 0.001; n = 45 [pre], n = 68 [post]) and for patients on opioid infusions for ≥14 days, from 29.7 to 11.5 days (p = 0.003; n = 9 [pre], n = 9 [post]) after protocol implementation. The median number of days on lorazepam for patients on benzodiazepine infusions for 5 to 13 days was reduced from 8.1 to 5.2 days (p = 0.020; n = 43 [pre], n = 55 [post]) and for patients on benzodiazepine infusions for ≥14 days, from 27.4 to 9.3 days (p = 0.011; n = 9 [pre], n = 8 [post]). There was no difference in methadone or lorazepam wean length for patients on 3 to 5 days of infusions. There was no difference in adverse events or hospital length of stay., Conclusions: A methadone and lorazepam weaning protocol based on patient's exposure to opioids and benzodiazepines (dose and duration) reduces weaning length., Competing Interests: Disclosures. The authors declare no conflicts or financial interest in any product or service mentioned in the manuscript, including grants, equipment, medications, employment, gifts, and honoraria. The authors had full access to all the data in the study and take responsibility for the integrity of the data and the accuracy of the data analysis., (Copyright Pediatric Pharmacy Association. All rights reserved. For permissions, email: mhelms@pediatricpharmacy.org 2021.)

Per- and polyfluoroalkyl substances (PFASs) are a class of environmentally persistent industrial compounds that disrupt various metabolic pathways. Among the protein receptors to which PFASs bind, the human pregnane X receptor (hPXR) is found to be a host for a variety of long- and short-chain PFASs that lead to its overactivation. Overactivation of hPXR is linked to potential endocrine disruption, oxidative stress, hepatic steatosis, and adverse drug interactions. In this study, molecular dynamics (MD) is used to study the binding between hPXR and a number of PFAS compounds, including alternatives whose activity on hPXR has not been experimentally tested. This is the first-time MD is used to study the interactions between PFASs and hPXR, showing how relative binding free energies of PFASs relate to hPXR agonism. Binding free energy calculations, hydrogen bond analysis, per-residue decomposition calculations, and alanine scanning studies are done to provide further insight. Activities on hPXR for several short-chain and alternative PFAS compounds to long-chain PFASs that have yet to be reported will also be considered. These short-chain and alternative species include perfluorobutane sulfonic acid (PFBS), Gen-X (trade name for 2,3,3,3-tetrafluoro-2-heptafluoropropoxy propanoic acid), ADONA (trade name for 4,8-dioxa-3 H -perfluorononanoic acid), and 6:2 fluorotelomer carboxylic acid (6:2 FTCA). The study shows key aspects of PFAS recognition on the hPXR, the link between PFAS binding to hPXR and the hPXR activity change observed upon the PFAS exposure, and the potential effects of alternative PFASs on hPXR activity.