Unraveling the origin of the high photocatalytic properties of earth-abundant TiO2/FeS2 heterojunctions: insights from first-principles density functional theory.

Herein, first-principles density functional theory calculations have been employed to unravel the interfacial geometries (composition and stability), electronic properties (density of states and differential charge densities), and charge carrier transfers (work function and energy band alignment) of a TiO2(001)/FeS2(100) heterojunction. Analyses of the structure and electronic properties reveal the formation of strong interfacial Fe-O and Ti-S ionic bonds, which stabilize the interface with an adhesion energy of -0.26 eV Å-2. The work function of the TiO2(001)/FeS2(100) heterojunction is predicted to be much smaller than those of the isolated FeS2(100) and TiO2(001) layers, indicating that less energy will be needed for electrons to transfer from the ground state to the surface to promote photochemical reactions. The difference in the work function between the FeS2(100) and TiO2(001) heterojunction components caused an electron density rearrangement at the heterojunction interface, which induces an electric field that separates the photo-generated electrons and holes. Consistently, a staggered band alignment is predicted at the interface with the conduction band edge and the valence-band edge of FeS2 lying 0.37 and 2.62 eV above those of anatase. These results point to efficient charge carrier separation in the TiO2(001)/FeS2(100) heterojunction, wherein photoinduced electrons would transfer from the FeS2 to the TiO2 layer. The atomistic insights into the mechanism of enhanced charge separation and transfer across the interface rationalize the observed high photocatalytic activity of the mixed TiO2(001)/FeS2(100) heterojunction over the individual components.

Emergency care visits at a South African hospital: Implications for healthcare services and policy.

BACKGROUND:  A robust knowledge on the pattern of use of emergency care resources not only serves as an indicator of universal access to care but also provides a basis for quality improvement within the health system. This study was undertaken to describe the pattern of emergency room visits at Brits District Hospital (BDH) in North West province, South Africa. The objectives of this study were to determine the sociodemographic characteristics of emergency department (ED) users and other patterns of ED use. METHODS:  This was a cross-sectional descriptive study that was conducted at a district hospital. All patients who reported for emergency care in the ED in 2016 were eligible for the study. Data were extracted and analysed from a systematic sample of 355 clinical notes and hospital administrative records. RESULTS:  The age group that visited the ED most frequently (25.3%) was 25-34 years old. A high proportion of the ED users (60%) were self-referred, and only 38% were transported by the emergency medical response services (EMRS). Few (5.6%) presentations were of a non-urgent nature. Trauma-related conditions accounted for the most frequent presentation at the ED (36.5%). CONCLUSION:  Although most ED users were self-referred, their clinical presentations were appropriate and underscore the need for policy strategies to reduce the burden of trauma in the catchment populationContribution: The study findings may have an impact on future health policies by providing decision-makers with baseline information on the pattern of use of ED resources, ensuring better resource deployment and greater access to care.

Umbilical vein catheterisation for the family physician working in primary health care.

This is part of a series of articles on vascular access in emergencies. The other two articles were on intra osseous lines and central venous lines. These are critical lifesaving emergency skills for the primary care professional. In this article, we will provide an overview of umbilical vein catheterisation highlighting its importance, the indications, contraindications, techniques, complications and nursing considerations. By familiarising healthcare providers with this procedure, we hope to enhance their knowledge and skills, ultimately leading to improved outcomes in the neonatal population.

Revolutionizing Cardiac Care: A Comprehensive Narrative Review of Cardiac Rehabilitation and the Evolution of Cardiovascular Medicine.

Cardiovascular disease (CVD) stands as a global health crisis, with its complex web of conditions, including coronary artery disease, heart failure, hypertension, and stroke, continuing to exact a heavy toll on individuals and healthcare systems worldwide. Despite substantial advances in medical technology and pharmaceutical interventions, CVD remains a formidable adversary, necessitating innovative prevention, management, and rehabilitation approaches. In tracing the historical trajectory of CVD, the narrative reveals the antiquated practices of early 20th-century medicine, marked by extended bed rest as the primary modality for heart-related conditions. It underscores the critical juncture when exercise was first recognized as a therapeutic tool for cardiac health, setting the stage for the evolution of cardiac rehabilitation (CR). CR programs have transcended their initial focus on exercise, expanding to encompass dietary guidance, psychosocial support, and comprehensive risk factor modification. These holistic interventions enhance physical recovery and address the psychosocial and lifestyle aspects of CVD management, ultimately improving patients' overall well-being. CR programs increasingly leverage advanced technologies and personalized strategies to tailor interventions to individual patient needs, ultimately enhancing outcomes and reducing the burden of CVD. In conclusion, this narrative review illuminates the transformative journey of cardiac care, with a particular spotlight on the indispensable role of CR in reshaping the landscape of cardiovascular medicine. By evolving from historical practices to comprehensive, patient-centered interventions, CR has made significant strides in improving the prognosis, quality of life, and holistic well-being of individuals grappling with the complexities of CVD. Understanding this historical context and the contemporary advancements is paramount for healthcare professionals and policymakers as they navigate the intricate terrain of cardiovascular medicine and endeavor to mitigate the impact of this pervasive disease.

Seasonal autoregressive integrated moving average (SARIMA) time-series model for milk production forecasting in pasture-based dairy cows in the Andean highlands.

Milk production in the Andean highlands is variable over space and time. This variability is related to fluctuating environmental factors such as rainfall season which directly influence the availability of livestock feeding resources. The main aim of this study was to develop a time-series model to forecast milk production in a mountainous geographical area by analysing the dynamics of milk records thorough the year. The study was carried out in the Andean highlands, using time-series models of monthly milk records collected routinely from dairy cows maintained in a controlled experimental farm over a 9-year period (2008-2016). Several statistical forecasting models were compared. The Mean Absolute Error (MAE), Root Mean Square Error (RMSE), and Mean Absolute Percent Error (MAPE) were used as selection criteria to compare models. A relation between monthly milk records and the season of the year was modelled using seasonal autoregressive integrated moving average (SARIMA) methods to explore temporal redundancy (trends and periodicity). According to white noise residual test (Q = 13.951 and p = 0.052), Akaike Information Criterion and MAE, MAPE, and RMSE values, the SARIMA (1, 0, 0) x (2, 0, 0)12 time-series model resulted slightly better forecasting model compared to others. In conclusion, time-series models were promising, simple and useful tools for producing reasonably reliable forecasts of milk production thorough the year in the Andean highlands. The forecasting potential of the different models were similar and they could be used indistinctly to forecast the milk production seasonal fluctuations. However, the SARIMA model performed the best good predictive capacity minimizing the prediction interval error. Thus, a useful effective strategy has been developed by using time-series models to monitor milk production and alleviate production drops due to seasonal factors in the Andean highlands.

Central venous pressure line insertion for the primary health care physician.

Central venous access is an important procedure to understand and perform not only in the emergency unit but also for prolonged reliable venous access. All clinicians must be familiar and confident with this procedure. This paper will focus on applied anatomy in respect of common anatomical sites for venous access, the indications, the contraindications, the technique and complications that may arise following the procedure. This article is part of a series on vascular access. We have previously written on the intra osseous procedure and an article on umbilical vein catheterisation will follow.

Intraosseous line insertion for the primary health care physician.

Early rapid access to the vascular system is essential in emergencies and is lifesaving. In this article, we will provide information on the common sites used, the equipment that is required, the indications and contraindications for intraosseous line insertion, how to correctly and safely do the procedure, medication that can be administered, post insertion line management and possible complications. This is a lifesaving procedure and primary healthcare physicians should acquire this skill.

Ovarian Follicular Dynamics and Its Functional Significance in Relation with Follicle Deviation, Vaginal Cytology, and Hormone Profiles in Llamas (Lama glama).

The reproductive physiology in camelid species has its particularities. The present study aimed to characterize the ovarian follicular dynamics and its functional significance in relation to follicular deviation, vaginal cytological characteristics, and sexual hormone profiles in llamas as the first report in South American camelids. Non-pregnant, multiparous llamas (Lama glama; n = 10; age: 48−72 mo.; BCS: 2.5−3.0) were enrolled in the study. The ultrasonographic assessment was carried out transvaginally and follicular ablation was performed (day 0) when follicles were larger than 7 mm. The follicle number and diameter were scored daily throughout the process for a proper evaluation of the deviated follicles and to monitor the presence of new follicle pools (1.5 to 2.5 mm diameter). Vaginal cytological evaluation (parabasal, intermediate, and superficial cells) was performed every other day until day 6. Endocrine profiles (17ß estradiol, anti-Mullerian hormone, testosterone, and progesterone) during pre- and post-follicular deviation were determined by using the ELISA assay. Differential follicular dynamics both in the presence of a single dominant follicle (DF) and in codominance during the follicular deviation process were detected in llamas (p < 0.05). The percentage of superficial cells was the most related to the follicular wave phase. However, the percentage of parabasal, intermediate, and superficial cells was not related to the phases of follicular growth, dominance, and regression (p > 0.05). Differential patterns among the different hormone concentration levels regarding the 17ß estradiol, anti-Mullerian hormone, progesterone, and testosterone during follicular deviation were observed, with the latter being significantly different along the deviation process (p < 0.05). In conclusion, the use of vaginal cytology assessment would not be sufficient to determine the follicular phases in llamas. Therefore, complementary analyses, such as ultrasonography and endocrine assessment, are strongly recommended to determine follicular dynamics during the follicular deviation.

Reasons given by women for discontinuing the use of progestogen implants at Koster Hospital, North West province.

BACKGROUND: In 2014, the South African National Department of Health introduced a new addition to the long-acting reversible contraceptive (LARC) options available in the country. This was a single rod subdermal progestogen implant (Implanon®NXT) which provided 3 years of effective contraception cover. However, the new contraceptive device uptake and general acceptance amongst women quickly diminished, with a slew of requests for its removal. The aim of this study was to explore the reasons given by women for discontinuing the use of their progestogen implants at Koster Hospital, North West province, South Africa. METHODS: A qualitative study was conducted using semistructured interviews. Thirteen women were purposively selected and interviewed at Koster Hospital Family Planning Unit. The transcriptions of the audio-taped interviews were analysed thematically. RESULTS: The following themes emerged from the interviews as reasons the women discontinued their progestogen implants: side effects such as menstrual problems, arm discomfort and weight gain. Other themes were family or social factors and the desire to conceive. CONCLUSION: The reasons for discontinuation of Implanon by women at Koster Hospital were the undesirable side effects they experienced whilst using the contraceptive device. These side effects were mainly menstrual problems, arm discomfort and weight gain. Family and other social dynamics also influenced some of the participants' decision to discontinue their contraceptive implants.

Acquired Hemophilia A Post-COVID-19 Vaccination: A Case Report and Review.

Acquired hemophilia A (AHA) is an inhibitory coagulopathy that represents a rare variant of hemorrhagic syndromes. We present a case of idiopathic AHA in a 75-year-old male patient with a cutaneous hematoma that could be attributed to a recent COVID-19 vaccination. The aim of this report is to raise awareness of a possible association between AHA and COVID-19 vaccination and to review similar reported cases and management plans to prevent the development of possible morbidity and debilitating complications. This case illustrates an exceptionally rare side effect of the COVID-19 vaccination. The advantages of obtaining the COVID-19 vaccine outweigh the risks.

Total body irradiation using helical tomotherapy: Set-up experience and in-vivo dosimetric evaluation.

PURPOSE: Helical Tomotherapy (HT) appears as a valuable technique for total body irradiation (TBI) to create highly homogeneous and conformal dose distributions with more precise repositioning than conventional TBI techniques. The aim of this work is to describe the technique implementation, including treatment preparation, planning and dosimetric monitoring of TBI delivered in our institution from October 2016 to March 2019. MATERIAL AND METHOD: Prior to patient care, irradiation protocol was set up using physical phantoms. Gafchromic films were used to assess dose distribution homogeneity and evaluate imprecise patient positioning impact. Sixteen patients' irradiations with a prescribed dose of 12Gy were delivered in 6 fractions of 2Gy over 3 days. Pre-treatment quality assurance (QA) was performed for the verification of dose distributions at selected positions. In addition, in-vivo dosimetry was carried out using optically stimulated luminescence dosimeters (OSLD). RESULTS: Planning evaluation, as well as results of pre-treatment verifications, are presented. In-vivo dosimetry showed the strong consistency of OSLD measured doses. OSLD mean relative dose differences between measurement and calculation were respectively +0,96% and -2% for armpit and hands locations, suggesting better reliability for armpit OSLD positioning. Repercussion of both longitudinal and transversal positioning inaccuracies on phantoms is depicted up to 2cm shifts. CONCLUSION: The full methodology to set up TBI protocol, as well as dosimetric evaluation and pre-treatment QA, were presented. Our investigations reveal strong correspondence between planned and delivered doses shedding light on the dose reliability of OSLD for HT based TBI in-vivo dosimetry.

SAR Matrices Enable Discovery of Mixed Efficacy µ-Opioid Receptor Agonist Peptidomimetics with Simplified Structures through an Aromatic-Amine Pharmacophore.

We previously described the development of potent µ-opioid receptor (MOR)-agonist/δ-opioid receptor (DOR)-antagonist peptidomimetic ligands as an approach toward effective analgesics with reduced side effects. In this series, a tetrahydroquinoline (THQ) or substituted phenyl is employed to link two key pharmacophore elements, a dimethyltyrosine amino acid and typically an aromatic pendant. Using new and previously reported analogues, we constructed a structure-activity relationship (SAR) matrix that probes the utility of previously reported amine pendants. This matrix reveals that the MOR-agonist/DOR-antagonist properties of these ligands do not change when a tetrahydroisoquinoline (THIQ) pendant is used, despite removal of substituents on the core phenyl ring. Based on this observation, we retained the THIQ pendant and replaced the phenyl core with simpler aliphatic chain structures. These simpler analogues proved to be potent MOR-agonists with high variability in their effects at the DOR and the κ-opioid receptor (KOR). These data show that the amine of the THIQ pendant may be a novel pharmacophore element that favors high MOR-efficacy, whereas the aromatic ring of the THIQ pendant may produce high MOR-potency. Combined, the two pharmacophores within the THIQ pendant may be a structurally efficient means of converting opioid peptides and peptidomimetics into potent and efficacious MOR-agonists.

Citrobacter freundii: A Cause of Cardiac Tamponade and Empyema Thoracis in a Nigerian Child.

Citrobacter infection is an uncommon but serious, difficult to treat infection associated with high mortality. Accumulation of pus or fluid in a pericardial space causes restriction of cardiac filling and consequent decrease in cardiac output. We herein report Citrobacter freundii, a rare infectious cause of this uncommon disorder. Our patient is a 10yr old male referred with complaints of cough productive of mucoid sputum and associated chest pain of two weeks duration, difficulty in breathing and orthopnoea for one week. He was acutely ill looking in respiratory distress with tachypnoea and tachycardia. Blood pressure was normal with pulsus alternans, there was increased jugular venous pressure, diffused apex beat and distant heart sounds with pericardial rub. Retroviral screening and gene Xpert for Mycobacterium tuberculosis were negative. Chest radiograph showed enlarged heart of "water bottle" appearance with cardiothoracic ratio of 0.77 and right sided pleural effusion which was drained. Transthoracic Echocardiogram confirm pyopericardium with multiples echoes in cardiac temponade. Echo-guided percutaneous pericardiocentesis yielded 600mls of purulent aspirates. Citrobacter freundii Sensitive to gentamycin, co-amoxiclav but resistant to cefuroxime and cefixime was cultured from pericardial aspirates and sputum. Patient recovered fully after pericardiocentesis and intravenous antibiotics. In this case report, we describe Citrobacter freundii causing cardiac temponade and empyema in a Nigerian immunocompetent child which to our knowledge has thus far not been reported. Pyopericardium may follow rare causes as Citrobacter freundii which require high index of suspicion.

Flawed scientific studies block progress and sow confusion.

Research in crop science in recent years has advanced at an unprecedented rate, and the intermingling of old and new crop breeding technologies has made the term "genetically modified" - and its variant, Genetically Modified Organism, or "GMO" - virtually obsolete. A kind of pseudo-category, it is primarily used pejoratively to refer to the use of the newest, most precise, most predictable, molecular genetic techniques. Prodigious amounts of time, effort and care have been expended to ensure that crops developed for commercialization using molecular techniques are safe, and that new traits are beneficial. Â Yet, despite these advances, some skepticism persists about them, partly due to the publication of fraudulent, poorly designed, and biased studies by a few "rogue scientists" whose intention is to contaminate the scientific literature and sow mistrust about molecular genetic modification among regulators and the public. We discuss how such flawed studies make it to publication and how the scientific community can combat such disinformation.

Aromatic-Amine Pendants Produce Highly Potent and Efficacious Mixed Efficacy µ-Opioid Receptor (MOR)/δ-Opioid Receptor (DOR) Peptidomimetics with Enhanced Metabolic Stability.

We previously reported a novel SAR campaign that converted a metabolically unstable series of µ-opioid receptor (MOR) agonist/δ-opioid receptor (DOR) antagonist bicyclic core peptidomimetics with promising analgesic activity and reduced abuse liabilities into a more stable series of benzylic core analogues. Herein, we expanded the SAR of that campaign and determined that the incorporation of amines into the benzylic pendant produces enhanced MOR-efficacy in this series, whereas the reincorporation of an aromatic ring into the pendant enhanced MOR-potency. Two compounds, which contain a piperidine (14) or an isoindoline (17) pendant, retained the desired opioid profile in vitro, possessed metabolic half-lives of greater than 1 h in mouse liver microsomes (MLMs), and were active antinociceptive agents in the acetic acid stretch assay (AASA) at subcutaneous doses of 1 mg/kg.