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PurposeMethodsResultsConclusionAlthough fragility hip fractures (HF) in the South African (SA) population are among the lowest worldwide, the incidence of HF is expected to more than double over the next few decades. Little is known about the contributors to increased hip fracture risk, including low bone mineral density (BMD), in our unique population. In addition, the ability of the recently calibrated SA Fracture Risk Assessment Tool (FRAX) to identify high fracture risk in the SA population accurately has not been validated.A retrospective, descriptive, cohort study of SA postmenopausal women and men ≥ 50 years who presented with fragility HFs was conducted. The ability of clinical risk factors (CRFs) and BMD measured by dual-energy X-ray absorptiometry (DXA), as well as calculated FRAX probability scores, to identify the known high fracture risk in SA patients were evaluated. The SA FRAX tool was used, and a high fracture risk defined if the United States (US) fixed thresholds for major osteoporotic (MOF) and/or HF risk were exceeded (≥ 20% and ≥ 3% over 10 years respectively).A total of 163 patients were included. The most useful predictive CRFs were age and gender, recreational toxins in men, and a history of falls. Most were females (71%), who were older than males. DXA-BMD and FRAX-HF calculations best identified the known high fracture risk in the study cohort. FRAX-MOF calculations performed poorly.Fracture risk assessment tools did not identify the known high fracture risk in all of the elderly study cohort with HF. Clinicians must continue to appreciate the important role of a good clinical assessment to ensure optimal fracture risk prediction. [ABSTRACT FROM AUTHOR]

The structural and environmental heterogeneity within southern Africa has given rise to many morphological forms of Psammophylax rhombeatus distributed throughout the country, with previous studies neglecting the associated molecular significance of these forms. The species’ widespread, generalist ecology coupled with the substantial phylogenetic structuring previously acknowledged within the species, makes P. rhombeatus the ideal candidate for phylogeographic analyses. Using 103 samples, representing the full distribution of the species, phylogenetic analyses retrieved four well-supported clades: south-eastern South Africa, south-western South Africa, north-eastern South Africa and western South Africa. Although not variable enough to warrant taxonomic re-evaluation, the clades are phylogenetically distinguishable, with relatively high intraspecific genetic divergence values separating them, irrespective of the small geographic distances separating populations. This is likely a product of the taxon’s habitat-generalist lifestyle, enabling them to bypass vicariant barriers that might otherwise cause speciation in less versatile species. The clades are also geographically distinct, with little overlap, indicating previous vicariance, a finding that is supported by the split of P. rhombeatus from P. ocellatus in the mid-Pliocene, followed by the diversification of P. rhombeatus into four clades throughout the Pleistocene. The genetic structuring observed in P. rhombeatus may be a product of population expansion following ancient refugial isolation (potentially Last Glacial Maximum). The morphological groupings highlighted in previous studies are loosely attributable to the molecular clades identified in the phylogenetic reconstruction, highlighting the complex interplay of genetic and morphological characteristics in the process of speciation, and their representation in systematic accounts. [ABSTRACT FROM AUTHOR]

Background Methods Results Conclusion In South Africa (SA), data on the incidence of thyroid cancer is limited. Papillary thyroid carcinoma is by far the most common malignancy in developed countries; however, a preponderance of follicular thyroid cancer in developing countries, despite iodized salt, has been observed. The aim of this study was to describe the national landscape of thyroid cancer in SA with reference to pathological subtypes, surgical outcomes, and treatments offered.A multi‐institutional retrospective review of thyroid cancer patients operated on between January 2015 and December 2019 was performed. Public hospitals with associated academic institutions were included. Data were collected from theater registers, pathology, and radiology records. Statistical analysis was done to determine intergroup significance.A total of 464 thyroid cancer cases from 13 centers across five SA provinces were identified. Most patients presented with a mass (67%). Ultrasound was performed in 82% of patients, and 16.3% underwent surgery without pre‐operative cytology. Of the histologically confirmed thyroid cancers, 61.8% were papillary and 22.1% follicular thyroid cancer. There was a significant association between subtype and geographical area, and T‐stage and operation performed. Surgical complication rates included hematoma in 1.8%, post‐operative hypocalcemia in 28.7%, and recurrent laryngeal nerve injury in 3.5%.This first national review describes the landscape of thyroid cancer in SA, revealing considerable differences compared to international studies. It provides valuable insight into the unique South African experience with this disease. In addition, this study serves as an impetus towards a prospective national registry with real‐world data informing contextualized guidelines. [ABSTRACT FROM AUTHOR]

Background: Respiratory viruses significantly impact global morbidity and mortality, causing more disease in humans than any other infectious agent. Beyond pathogens, various viruses and bacteria colonize the respiratory tract without causing disease, potentially influencing respiratory diseases' pathogenesis. Nevertheless, our understanding of respiratory microbiota is limited by technical constraints, predominantly focusing on bacteria and neglecting crucial populations like viruses. Despite recent efforts to improve our understanding of viral diversity in the human body, our knowledge of viral diversity associated with the human respiratory tract remains limited. Methods: Following a comprehensive search in bibliographic and sequencing data repositories using keyword terms, we retrieved shotgun metagenomic data from public repositories (n = 85). After manual curation, sequencing data files from 43 studies were analyzed using EVEREST (pipEline for Viral assEmbly and chaRactEriSaTion). Complete and high-quality contigs were further assessed for genomic and taxonomic characterization. Results: Viral contigs were obtained from 194 out of the 868 FASTQ files processed through EVEREST. Of the 1842 contigs that were quality assessed, 8% (n = 146) were classified as complete/high-quality genomes. Most of the identified viral contigs were taxonomically classified as bacteriophages, with taxonomic resolution ranging from the superkingdom level down to the species level. Captured contigs were spread across 25 putative families and varied between RNA and DNA viruses, including previously uncharacterized viral genomes. Of note, airway samples also contained virus(es) characteristic of the human gastrointestinal tract, which have not been previously described as part of the lung virome. Additionally, by performing a meta-analysis of the integrated datasets, ecological trends within viral populations linked to human disease states and their biogeographical distribution along the respiratory tract were observed. Conclusion: By leveraging publicly available repositories of shotgun metagenomic data, the present study provides new insights into viral genomes associated with specimens from the human respiratory tract across different disease spectra. Further studies are required to validate our findings and evaluate the potential impact of these viral communities on respiratory tract physiology. [ABSTRACT FROM AUTHOR]

Malignant myopericytoma is an exceedingly rare soft tissue tumour with only 14 documented cases in the scientific literature. Myopericytomas can occur in association with HIV-AIDS and have a predilection for internal organs such as the bronchus, larynx, liver and brain. Ebstein-Barr virus encoded small RNA(EBER) was positive in three out of 14 cases. In this case report we present the second documented case of a malignant myopericytoma, with a positive EBER found intracranially – specifically in the supratentorial compartment – invading the superior sagittal sinus. Gross total excision of the tumour was achieved, and the patient responded well with no recurrence with only highly active antiretroviral therapy (HAART). No chemotherapy or radiotherapy has been necessary. [ABSTRACT FROM AUTHOR]

Many recent AI policies have been structured under labels that follow a particular trend: national or international guidelines, policies or regulations, such as the EU’s and USA’s ‘Trustworthy AI’ and China’s and India’s adoption of ‘Responsible AI’, use a label that follows the recipe of [agentially loaded notion + ‘AI’]. A result of this branding, even if implicit, is to encourage the application by laypeople of these agentially loaded notions to the AI technologies themselves. Yet, these notions are appropriate only when applied to agents, which current AI technologies are not; and the concern is that this misapplication creates an incentive to inappropriately attribute trustworthiness or responsibility to AI technologies. We endeavour to show that we have good reason to avoid any general AI policy that uses agentially loaded labelling. We suggest labelling these policies not in terms of some qualification of AI, but rather in terms of our approach to the technology and its wider development and use context – focusing on being trustworthy and responsible about AI, rather than on trustworthy or responsible AI. [ABSTRACT FROM AUTHOR]

The growing interest in synthesizing electrochemically active organic ligands stems from extensive reports highlighting the applications of redox‐active organic molecules. These molecules play a crucial role in capturing and converting CO2 into valuable organic compounds, including carbonates used as solvents in lithium batteries. In this study, we present an electrochemical investigation of two chalcone derivatives, referred to as (1) and (2). We explored the influence of different solvent systems, specifically acetonitrile and dimethyl sulfoxide, on the reduction potential of these chalcones. The reported chalcone derivatives were characterized using various analytical techniques, including UV/Visible spectroscopy, Fourier Transform Infrared spectroscopy, Proton and Carbon‐13 nuclear magnetic resonance, as well as mass spectrometry. The characterization of the reported chalcones, exhibiting properties of both β‐diketones and 2‐hydroxyphenones, is underscored by a density functional theory (DFT) study of chalcones (1) and (2). This research establishes a correlation between the energies calculated through DFT and the experimental reduction potentials of chalcones (1) and (2), in comparing them with a series of β‐diketones and 2‐hydroxyphenones. [ABSTRACT FROM AUTHOR]

Biochars have received much attention as efficient adsorbents for water pollutants. Besides, the chemical treatment of biochars performed to increase the adsorption capacity usually causes secondary chemical pollution and increases the cost of the process. The biomass feedstock utilised in biochar preparation impacts significantly the surface properties and adsorption capacity. Thus, the need to prepare new biochars from new feedstock with potentially high uptake capacities. Herein, we prepared new biochar (POBC) from Platanus occidentalis waste leaves (POL), which was utilised for the ultrasonic-aided adsorption of bromophenol blue (BRB) and thiazolyl blue tetrazolium bromide (TTB). The FTIR, SEM, EDX, TGA, BET, pHpzc, and elemental characterisations of POBC revealed potent surface characteristics desirable for efficient dye adsorption. An increase in the surface area from 14.31 m2/g to 31.94 m2/g and the pore volume from 0.0214 cm3/g to 0.0326 cm3/g was obtained after the conversion of the POL to POBC. Besides, the SEM images of POBC revealed a highly porous surface structure of the adsorbent. The Freundlich and pseudo-second-order model presented the best fit to the isotherm and kinetics based on the high coefficient of determination (R2 > 0.9) and low sum square errors (SSE < 0.31). The heterogeneous surface nature of POBC was inferred from the independent-oriented site model. The monolayer adsorption capacity of 45.03 mg/g and 48.8 mg/g were obtained for BRB and TTB, respectively. Thermodynamics showed an endothermic, feasible, and random uptake, and POBC displayed efficient potentials to be reused. The obtained results revealed that novel POBC is an efficient low-cost biochar with high adsorption capacity for dyes. [ABSTRACT FROM AUTHOR]

Background: Illicit substance use is common at music festivals. One could question whether festival attendees deliberately plan to take drugs at such events or whether their illicit (poly)drug use is provoked by specific circumstances, such as the presence of peers or a general belief that others are using drugs at the festival. Objectives: The present study implemented the prototype willingness model, which is a model that assesses whether illicit drug use at music festivals is rather a rational or a more spontaneous decision-making process. Results: A three-wave panel survey was conducted, questioning festival attendees before (n = 304, 60.86% males), during, and after music festival visits. In total, 186 people (59.68% males) between 18 and 55 years (M = 27.80 years; SD = 8.19) completed all three surveys, of which 62.9% had taken one or more different illicit substances at the festival. Positive attitudes toward illicit drug consumption were most firmly related to attendees' intentions to take drugs at festivals. Additionally, the more festival visitors identified themselves with the prototype of an attendee using drugs, the more likely they were to be willing to use them. The perceived presence of illicit substances at such events was also strongly related to the actual behavior. Conclusion: The findings suggest that illicit drug use at music festivals relates to both a rational choice and an unplanned one. [ABSTRACT FROM AUTHOR]

Context: It has been reported that photoexcitation of azastilbene compounds like E-1,2-bispyrazinyl-ethylene (bpe) can undergo E → Z photoisomerization of its quaternary salts via the excited triplet state. However, experimentally it is possible to get low fluorescence and photoisomerisation quantum yields in a state with higher internal conversion than intersystem crossing. We modelled bpe and its methylated derivative (bpeMe), as well as its quaternary halogen salts (bpeMeX with X = F−, Cl−, Br− and I−) to study levels of fluorescence, phosphorescence and excited state potential energy surfaces (PES). Results support experimental observations of molecules where the anion of a salt is an efficient electron donor, that molecules with weak electron-donating anions like Cl− to give increased fluorescence and photoisomerization, as compared to molecules with stronger electron-donating anions like I−, which are dominated by competing electron transfer. The fluorescence of bpeMeF and bpeMeCl was found to be stronger than bpeMeBr and bpeMeI. A deep well in the triplet excited state of bpeMeI is considered responsible for the decreased photoisomerization, compared to what was experimentally observed for bpeMeCl. Uniquely, the bpeMeI molecule is characterised by near-zero splitting of the s1 and t1 excited states that can enhance charge transfer. The quaternary salt of bpeMe with stronger electron-donating Br− anion was observed to undergo fluorescence and phosphorescence at much lower energy compared to those with weak electron-donating F− and Cl− anions. This research shows how to control the excited state fluorescence, phosphorescence and isomerization of quaternary halogen salts of methyl derivatives of 1,2-bispyrazinyl-ethylene, which aids experimental design where excited state isomerization is considered. Methods: Geometry optimization, molecular electrostatic potential (MESP), and time dependent density functional theory (TDDFT) calculations were conducted utilizing Gaussian 16 with the B3LYP functional and the 6–31 + G(d,p) basis set. The minimum energy path (MEP) for the E to Z isomerization of the molecules was established employing the Nudged-Elastic-Band (NEB) method, implemented in Orca 4.2. Precise energies of the E → Z isomerization reaction path were determined employing CASSCF and a more accurate multireference method, NEVPT2. [ABSTRACT FROM AUTHOR]

Background: The need for rehabilitation in low-to-middle income countries (LMICs) is rapidly increasing as more people are living longer with chronic diseases. Primary health care (PHC) is ideally placed to provide the spectrum of care required to meet most of the complex and evolving population's health needs locally. This study aimed to describe the patient journeys of adults attending primary care in the Eastern Cape province of South Africa to understand the factors that affected their access to primary care rehabilitation services (or the lack thereof) and obtain suggestions on how rehabilitation may be enhanced at primary care. Methods: A maximum variation sampling approach was used to purposefully select persons with varied chronic health conditions and demographic characteristics to gain diverse perspectives regarding their rehabilitation needs and ways in which the current rehabilitation services at primary care may be enhanced. Data were collected via face-to-face semi-structured interviews between March and June 2022 which were electronically recorded. Inductive thematic analysis of transcribed data was done and coded in Atlas.ti.22®. Results: Twenty-five adult patients participated in the study. The patients had different experiences at their local PHC facilities that affected their access to rehabilitation at primary care. The study found that most patients were not able to access rehabilitation at primary care. There were several personal and contextual factors that resulted in the patients having a low perceived need to receive rehabilitation that potentially lowered patients' demand for and utilization of rehabilitation at primary care. Patients suggested increasing rehabilitation workforce at primary care, improving availability of assistive devices, increasing their knowledge regarding rehabilitation, and facilitating socio-economic integration into their communities. Conclusions: Patients attending primary care are not guaranteed access to rehabilitation by virtue of having entered the PHC system. It is important to consider the patient perspectives regarding their health needs and suggestions for enhancing care. [ABSTRACT FROM AUTHOR]

Context: Bis(terpyridine)manganese(III) exhibits Jahn–Teller distortion due to the inequivalent occupation of the degenerate eg orbitals of this high-spin d4 pseudo octahedral complex. Due to the spatially constrained nature of the terpyridine ligand, the central Mn-N bonds will always be shorter than the Mn-N terminal bonds, making it more difficult to distinguish between compression and elongation Jahn–Teller structures for bis(terpyridine)manganese(III). Density functional theory (DFT) calculations were utilized as a tool to evaluate the type of Jahn–Teller distortion in the high-spin d4 bis(terpyridine)manganese(III). The nature of the Jahn–Teller distortion calculated does depend upon the choice of density functional approximation (DFA) with the B3LYP, M06, and OLYP-D3 DFAs giving compression and the PW6B95D3, MN15, and MN15-D3 DFAs giving elongation in gas-phase calculations. All solvent-phase calculations yield an elongated structure for the bis(terpyridine)manganese(III) compound, which is yet to be structurally characterized experimentally. However, both gas and solvent OLYP-D3 calculations result in a compressed structure for the only experimentally isolated and characterized bis(terpyridine)manganese(III) complex, specifically the complex with terpyridine = 4′-(4-methylphenyl)-2,2′:6′,2′′-terpyridine. This alignment with the experimentally observed compression Jahn–Teller structure enhances the credibility of OLYP-D3 calculations in reproducing the observed geometries. The compressed Jahn–Teller geometries were near D2d symmetry with the z-axis for compression defined along the Mn-N central bonds. Elongation Jahn–Teller distortion is not possible along the Mn-N central bonds, due to their spatially constrained nature. Thus, elongation occur along one pair of opposite Mn-N terminal bonds that are longer than the other pair of opposite terminal bonds, with shorter central bonds. The highest symmetry of the elongation Jahn–Teller distortion geometry of bis(terpyridine)manganese(III) is C2v. Criteria to distinguish between a compression and elongation Jahn–Teller geometry for bis(terpyridine)manganese(III) are identified. The nature of the singly occupied eg molecular orbital, exhibiting anti-bonding interaction with the nitrogen-p MOs involved, dictates the type of Jahn–Teller distortion that occurs. The low-energy occupied bonding t2g molecular orbitals establish bonds with and undergo mixing with the ligand molecular orbitals. The OLYP-D3 functional is recommended for calculating bis(terpyridine)manganese(III) and related compounds due to its consistent generation of metal–ligand bonds slightly longer than observed in experiments, in line with the required behavior. Additionally, OLYP-D3 offers a realistic electronic structure for Jahn–Teller distorted bis(terpyridine)manganese(III), correctly identifying alpha eg molecular orbitals as the highest occupied molecular orbital and lowest unoccupied molecular orbital in agreement with experimental electrochemical studies. Furthermore, OLYP-D3 accurately reproduces the experimental compression geometry for the only structurally known bis(terpyridine)manganese(III) compound, instilling confidence in its reliability for such calculations. Methods: DFT geometry optimization and frequency calculations were done on the two different modes of Jahn–Teller distortion of bis(terpyridine)manganese(III), using the OLYP, B3LYP, M06, PW6B95D3, and MN15 functionals, with and without the Grimme's D3 dispersion correction, and the 6-311G(d,p) or def2TZVPP basis set, as implemented in Gaussian 16. All optimizations were in the gas phase and also in the solvent phase with CH3CN as implicit solvent using IEFPCM. DFT calculations were utilized to determine the Jahn–Teller effect on the geometry of high-spin d4 bis(terpyridine)manganese(III) complex containing two structurally constrained tridentate ligands. [ABSTRACT FROM AUTHOR]

In a bid to develop efficient biochars, we prepared new biochar by the pyrolysis of Ipomoea batatas feedstock for the ultrasonic-aided adsorption of eriochrome black T (EBT) and celestine blue (CB) dyes. The characterisation of the Ipomoea batatas-derived biochar (IBBC) showed potent functional groups, good thermal stability, porous structure and a point of zero charge of 6.41. The pH of 2.0 and 7.0 was found to be optimum for the uptake of anionic EBT and cationic CB onto IBBC, respectively. A decrease in the surface area of IBBC from 96.35 m2/g to 48.43 m2/g and 32.11 m2/g was obtained after the adsorption of EBT and CB, respectively. Thermogravimetric analysis revealed high thermal stability of IBBC up to 350°C. The Energy dispersive X-ray (EDX) spectrum revealed carbon (52.6%), oxygen (24.5%) and potassium (7.1%) as the major component of the biochar. The elemental analysis showed carbon, hydrogen and nitrogen compositions of 55.4%. 2.6% and 1.2%, respectively. Moreover, a biochar yield of 36.2% was obtained. The adsorption of both dye molecules was well correlated by the Freundlich isotherm, supported by the Scatchard model analysis. Kinetics was well fitted to the film diffusion and pseudo-second-order models, while thermodynamics showed an endothermic and spontaneous dye uptake on IBBC. The adsorption capacity of the biochar for EBT and CB was 59.24 mg/g and 63.69 mg/g respectively. Percentage desorption of 87.5% for EBT and 82.3% for CB was achieved during regeneration of the dye-loaded biochar. Moreover, IBBC showed good potentials to be reused for adsorption. The results revealed the potentials of the novel biochar for efficient adsorption of both cationic and anionic dye species. [ABSTRACT FROM AUTHOR]

Despite its potential importance, the computational chemistry of adsorption processes for wastewater treatment has received negligible attention. Exploring the literature shows several limitations in applying quantum chemistry to study adsorption processes in wastewater treatment. The choice of suitable functionals of density functional theory (DFT) is one of the critical limits of the current application of quantum chemistry in wastewater treatment. Therefore, in this work, we performed a benchmark study of sixteen DFT functionals (including dispersions) to select the most suitable one. The def2-TZVP basis set has been used with the sixteen DFT functionals. The sixteen DFT functionals are benchmarked to the CCSD(T)/CBS level of theory. We used four different pollutants (p-aminobenzoic acid, aniline, p-chloro phenol, and phenol) adsorbed on coronene to perform this benchmarking. In addition to the coronene and the pollutant, four explicit water molecules are used to consider the environmental effects. The results show that the functional MN15 and PW6B95-D3 have the lowest mean absolute deviation relative to the CCSD(T)/CBS adsorption energies. Overall, the functionals MN15, PW6B95-D3, ωB97X-V, M05-2X-D3, M05-D3, and M06-2X-D3 are recommended for studying the adsorption processes. [ABSTRACT FROM AUTHOR]

Interactions between humans and smart products (i.e. digital components integrated in physical Internet of Things devices) are becoming more complex and less visible. Yet designers lack tools to capture these interactions and incorporate them into their design. In this paper we present the Human-Computer-Context Interaction (HCCI) tool that helps the designer to consider the different interactions of the user early in the conceptualisation phase, in order to eventually improve the user experience for smart products. This tool introduces 5 relevant interaction levels to be considered, when defining the context-of-use. In this paper we assess the use of the tool by means of a design challenge with a total of 34 industrial design students, given the task to design a smart kitchen concept. The tool was evaluated by a mixed method approach. Results show that the tool was evaluated as useful and usable during the early concept phase of the design of smart products. Unsupported concepts typically envisioned a single user interacting with one object through explicit interactions. Hence, tool-supported designs were more holistic and better captured interactions with other objects, users, content and services. From this we conclude that the tool can help to detect possible pitfalls of design selections. The tool is aimed to be used in a new product development process by HCI researchers, designers, and developers and is technology independent. Based on observations and participant feedback, we reflect on the strengths and limitations of this tool. [ABSTRACT FROM AUTHOR]

Background. Varied assessment strategies are required in the process of deciding whether a surgeon is competent to graduate. Despite doubts about the reliability of the oral examination and the challenges of standardising examiner practices, the oral examination remains an important assessment method in surgical exit examinations. Structured oral examinations may facilitate the measurement of course outcomes. Objectives. To explore the experiences of surgical trainees and examiners using a video-assisted, mock, structured oral examination (SOE) as an assessment tool. Methods. This descriptive study incorporated procedural videos in a case-based SOE format. One group of trainees had face-to-face contact with the examiner, and the other was assessed on an online platform, e.g. Microsoft Teams, with a remote examiner. After the SOE, a focus group interview was conducted with surgical trainees and individual interviews with examiners. Results. Themes were developed from the interview transcripts. These themes centred around the use of videos in this examination format and technical issues during the SOE. Further themes highlighted the standardisation of questions and preparation of examiners. Conclusion. Overall, procedural videos as part of the mock SOE were experienced as valuable. Adding video recordings to the online platform posed administrative and technical challenges. However, the trainees and the examiners could log in from peripheral clinical training sites, which was experienced as an advantage. This study provides a glimpse into the application of procedural videos during SOEs as an assessment tool from the perspective of surgical trainees and examiners. Efforts should focus on standardisation of the examination format, optimising technical issues and improving examiner preparation. [ABSTRACT FROM AUTHOR]

Given the potential impact of climate change on amphibians, there is a need to establish baseline phenological data for vulnerable species and to investigate their responses to changing climatic conditions. We recorded vocalisations of Hewitt's ghost frog Heleophryne hewitti in the Baviaanskloof World Heritage Site, South Africa, to investigate its breeding phenology and vocalisation behaviour. Our objectives were to: 1) characterise seasonal and diel vocalisation patterns, 2) examine relationships between environmental variables and calling behaviour and 3) evaluate the effectiveness of acoustic recording as a monitoring technique. We employed automatic vocalisation recognition software to detect calls and used hurdle regression to model the relationships between environmental variables and the number of calls produced. Our study confirmed that H. hewitti is a seasonal prolonged breeder, with reproductive activity occurring from early to late spring. We found that while relative humidity seemed to influence the probability of calling, none of the weather variables appeared to have a strong influence on the number of calls produced. Acoustic monitoring combined with automatic vocalisation recognition has proven to be a viable technique for monitoring this species. Further investigation of cues for breeding initiation is required to understand the impacts of climate change on this species. [ABSTRACT FROM AUTHOR]

Rigorously accounting for mutual coupling effects in antenna array synthesis, generally requires that embedded element patterns (EEPs) be determined. The method of moments (MoM) is typically used. Multiple linear system solutions are required, corresponding to every excitation vector associated with an EEP. This paper presents the direct coupling technique (DCT) to obtain the MoM solution for arrays with disjoint elements, by iteratively solving a series of localized subproblems, one associated with each array element. It utilizes a physics‐based, direct‐coupling approximation to incorporate global coupling into the local problems. Local matrices do not change between iterations or with excitation vectors, hence they can be inverted as a preprocessing step, allowing for efficient solution of multiple excitation configurations. Numerical results demonstrate rapid convergence. The convergence rate can be controlled via local problem domain sizing. Since the DCT is ideally suited to parallelization, it is applicable to very large arrays. [ABSTRACT FROM AUTHOR]

Superficial CD34 positive fibroblastic tumor is a rare low-grade neoplasm of the skin and subcutis with indolent behavior. This entity has been included in the current World Health Organisation (WHO) classification of soft tissue tumors. Pathological diagnosis can be challenging due to significant morphological overlap with other entities and the large spectrum of CD34 positive tumors. We report a case in a twenty-five male which showed characteristic diagnostic features, but in addition showed myxoid stroma. The presence of myxoid stroma has not been previously emphasized in this entity and broadens the histologic differential diagnosis significantly to include myxoid soft tissue tumors. A subset of these tumors harbor PRDM10 -rearrangements, but a defining molecular feature has not yet been described, highlighting the need for further molecular characterization of this potentially genetically heterogenous tumor. Awareness of this entity among surgeons and pathologists is important to prevent misclassification as an aggressive sarcoma and avoid over-treatment. [ABSTRACT FROM AUTHOR]

Bis(terpyridine)nickel(II) complexes in their reduced form feature a Ni(II) center, whereas the oxidized compound contains Ni(III). [Display omitted] A series of bis(terpyridine)nickel(II) complexes were synthesized and subjected to electrochemical (cyclic voltammetry) and theoretical (using density function theory, DFT) studies. DFT calculations have confirmed, consistent with existing literature, that the oxidation and reduction reactions of bis(terpyridine)nickel(II) complexes are centered on nickel and the terpyridine ligand, respectively. Upon oxidation of the pseudo-octahedral Ni(II) complex, large changes in Ni-N bonds occur since a Jahn-Teller distorted Ni(III) complex is formed, leading to a quasi-reversible Ni(II/III) oxidation process. Conversely, small geometric changes observed during the reduction of bis(terpyridine)nickel(II) suggest a reversible process, as experimentally observed. The second reduction is quasi-reversible and is attributed to the instability of the neutral bis(terpyridine)nickel complex containing two tpy ligand radicals. The nature of the substituents on the terpyridine ligand, characterized by Hammett constants, influences the redox potentials. These shifts result in linear relationships between the experimental redox potentials and Hammett constants, as well as DFT-calculated potentials, energies and charges associated with the specific redox process. [ABSTRACT FROM AUTHOR]

Nuclear magnetic resonance measurements confirm that, as expected, the mer isomer of tris(β-diketonato) cobalt(III) complexes is more stable (mer isomers are more stable because they are less affected by steric hindrance and they have lower dipoles). An excess of the mer isomer or only the mer isomer is experimentally observed. The existence of both fac and mer isomers is predicted by density functional theory calculations. At room temperature, the nuclear magnetic resonance peaks of phenyl-containing mer complexes are broad due to the intermediate rotation of bulky phenyl groups resulting in only the average orientation of the non-equivalent protons in the mer complexes. However, upon heating to 55°C (thus speeding up the rotation) or cooling to −50°C (slowing down the rotation), this broad peak is resolved into three sets of carbon peaks appearing in the 13C NMR spectrum, as well as splitting of the ¹H NMR peaks for the non-equivalent protons in the mer isomer. In solid-state 13C NMR the aromatic rings do not rotate, resulting in the splitting of all the 13C NMR peaks. Two sets of well-defined peaks are observed for the fluorine-containing compound [Co(CF3COCHCOCPh)3] in both the 13C and 19F NMR spectra, indicating that both the fac and mer isomers are present with a ratio of fac:mer = 0.1:1. The X-ray photoelectron spectroscopy measured binding energy of the Co 2p3/2 photoelectron lines are influenced by the subtle electronic (electron-donating or electron-withdrawing) properties of the R groups on the β-diketonato ligands. Various relationships are established between the binding energy of Co 2p3/2 and several physical and density functional theory–calculated properties, confirming good electronic communication (the measurable electronic effect that a molecular fragment has on the physical properties of another molecular fragment in the molecule) of the substituent groups through the pseudo aromatic system of the β-diketonato backbones to the metal. [ABSTRACT FROM AUTHOR]

The travesty of the Life Esidimeni project in South Africa, which claimed the lives of 144 mental health users at psychiatric facilities in Gauteng between 2016 and 2017, is multifaceted. One facet involves strategies of blame avoidance designed to escape liability for the deaths that were expressed by the former Member of the Executive Council for Health and other public health officials during the Life Esidimeni Arbitration Hearings. These hearings were broadcast on state television between October 2017 and 2018, and eight samples from the hearings were analysed for specific blame avoidance strategies. Following the principles of qualitative discourse analysis, this paper extends research on blame avoidance behaviour in the public administration and policy domain, exploring three key officials' micro- and macro-level choices of blame avoidance in the context of the arbitration hearings to develop a more comprehensive account of these strategies. A public hearing is a discourse setting that is reactionary in nature, and our findings on the micro-level, a neglected dimension of research on blame avoidance behaviour, extend our understanding of these behaviours. We propose that at least two continua for blame avoidance are relevant in this setting. [ABSTRACT FROM AUTHOR]

This article explores the loss of biodiversity and species extinction from the perspective of Christian eschatology and, more specifically, the hope for eternal life. A thought experiment on the coexistence of various hominid and hominin species is entertained in order to gain some clarity on the nature of the problems posed by extinction. The question is then raised whether any of the traditional eschatological symbols of the reign of God, a final judgment, the resurrection of the dead, or eternal life can be retrieved to address the problems posed by extinction. It is argued that each of these symbols poses serious difficulties in this regard while there is an apparent contradiction embedded in the notion of eternal life. This is not resolved through notions of 'objective immortality,' as this by itself eternalizes the injustices of history. With Joseph Sittler, it is argued that only some notion of cosmic redemption can suffice, but how this is to be imagined remains elusive. [ABSTRACT FROM AUTHOR]

The most representative interval temporal logic, called HS, was introduced by Halpern and Shoham in the nineties. Recently, HS has been proposed as a suitable formalism for modern artificial intelligence applications; however, when dealing with real-life data one is not always able to express temporal relations and propositional labels in a definite, crisp way. In this paper, following the seminal ideas of Fitting and Zadeh, we present a fuzzy generalization of HS, called FHS, that partially solves such problems of expressive power. We study FHS from both a theoretical and an application standpoint: first, we discuss its syntax, semantics, expressive power, and satisfiability problem; then, we define and solve the time series FHS finite model checking problem, to serve as the basis of future applications. [ABSTRACT FROM AUTHOR]

This study compared four South African sheep producing districts relative to each other and a common metafrontier to analyse within and between group efficiency and explored what could be learnt from this technique compared to simple frontiers. A sample was compiled from sources that were previously successfully used in local benchmarking exercises, and despite very modest sample sizes at the group level and minimal information on how groups differ, the group models performed adequately while the meta-model performed very well. The results revealed that while within group performances were comparable across districts, there were huge differences in between group performance. These differences are partly attributable to natural resource endowments, but institutional arrangements also contribute significantly to local success. This suggests that to achieve rural regeneration public–private partnerships are necessary to address this issue. State support is insufficient and producer organisations have a major role in promoting institutional innovation. [ABSTRACT FROM AUTHOR]

The capacity to comprehend experiences in a coherent way and attribute meaning to existence is unique to human beings. Through Dasein, being consciously concerned with the ontophenomenological experience, thus interpreting what it means to exist amid that which is and is still becoming, human beings strive to connect with their Lebenswelt (a lived world). Only when individuals are consciously receptive to and involved in their own ontological being and becoming can they empathise with the very nature of another. Woven into this larger disposition characterised by continuous onto-phenomenological self-making-in-a-situation (Bildung) -- the Nietzschean call -- is the empathic attitude. In the context of psychology, in particular psychotherapy, the empathic attitude -- that is, being sensitively aware of how we understand ourselves, others and the world we share -- is undeniably part of the repertoire of qualities that a therapist ought to possess. Often, however, the attitude of novice therapists towards what is happening between them and their clients here and now involves inflated self-awareness that is devoid of ontological considerations. Frequently, this results in a clichéd form of empathy based primarily on sentimental emotionality. It seems to be true that, in a ubiquitous cyberculture characterised by self-absorption and the mere accumulation of simplistic explanations, the ability to be ontologically receptive -- as the sine qua non of an empathetic attitude -- is gradually becoming undervalued. Art, in particular literary theatre, has the capacity to push psychotherapy students (as spectators) to the edge of what it means to be human beings; by implication, therefore, it constitutes an appeal for existential phenomenological involvement. Suddenly the spectators cannot escape the incantatory circle of what is affectively transcendent and become participants in their own self-developmental needs and psychological yearnings. This article seeks to illustrate how the existential phenomenological elements of literary theatre, including physicality (language, movement, actions and sound), time and spatiality, can be used to comprehend an embodied involvement (being with the client, here, now) and encourage ontological reflection in psychotherapy students. In this regard, literary theatre displays certain existential phenomenological characteristics that can be understood and applied as part of a pedagogical enterprise in psychotherapy teaching and training. Some core characteristics include inner stillness, a sensitive-receptive attitude, and an awareness of Jungian or depth-psychology archetypes. Of importance is therefore the existential phenomenological attitude of the psychotherapy student towards a child's being (ontoinvolvement) in the therapy room or clinical evaluation situation. By way of a conceptual explication, we attempt to provide an understanding of the relationship between the psychological function of literary theatre and the existential phenomenological attitude of the educational psychology student. This attitude embodies a certain artistry or aesthetic disposition, characterised by qualities such as honed intuition, sensitive awareness and the formation of nuanced connections. Such artistry allows the psychotherapy student to explore the developmentally and contextually layered client, and to articulate den Zachen Zelbst meaningfully by way of contemplative, nuanced thought and language. Den Zachen Zelbst, ingrained in the Husserlian and Heideggerian vernacular of philosophy of phenomenology, refers to existence as intentional; to be consciously concerned with the meaning of being, therefore life-world experience, as opposed to merely registering and measuring impressions from the outside world. An existential phenomenological disposition cannot be assumed, however, nor can it be simply taught as part of a postgraduate module on psychotherapy skills. Instead, the existential phenomenological disposition ought to be fostered and developed through carefully crafted embodiment activities of an intersectional nature (the intersection of philosophy, psychology, literature and drama, for example) as part of the teaching and training of psychotherapy students. This article attempts to cast light on the existential phenomenological disposition as an essential attitude of the psychotherapy student, especially in the context of an often unmindful, mechanistic and utilitarian society. At its core, the existential-phenomenological attitude presupposes a more embodied (as opposed to essentialist) psychotherapy, characterised by ontological awareness, deepening insight and symbolic language. These intellectual qualities need to be protected at all costs from the technocratic materialism of mass psychology. [ABSTRACT FROM AUTHOR]

This study conducts a critical race theoretic (CRT) reading of interviews with contractually-employed teaching assistants (facilitators). Facilitators are tasked with actively engaging small groups of first-year students in analyses of post-colonial literature. During the interviews, facilitators described the frustrations and discomfort they encounter while discussing racism and while assessing students' essays on the subject. Using CRT, this study examines how facilitators respond to what they construe as: (1) resistance from some students racialised as white, and (2) a perceived eagerness from students racialised as black to set experiential knowledge of racialised inequalities in conversation with the literature under study. [ABSTRACT FROM AUTHOR]

In this work, we have studied the microsolvation of phenol in water. We started by identifying initial configurations of phenol-water clusters using classical molecular dynamics. The configurations are optimised at the ωB97XD/aug-cc-pVDZ level of theory. To understand the interaction between phenol and the solvating water molecules, we performed a quantum theory of atoms in molecules (QTAIM) analysis. The results show that the structures of phenol-water clusters are similar to those of neutral water clusters. The QTAIM analysis shows that the structures of phenol-water clusters are stabilised by strong OH··· O hydrogen bondings, weak CH··· O hydrogen bondings, and OH ⋯ π bonding interactions. The located structures of phenol-water clusters have been used to calculate the absolute hydration free energy and enthalpy of phenol for temperatures between 20 and 400 K. The hydration energies are calculated using the cluster continuum solvation model. It has been found that the explicit solvation has negligible effects on the hydration free energy and enthalpy of phenol. Furthermore, the hydration free energy of phenol is found to be linearly varying with increasing temperature, while the hydration enthalpy is found to be temperature independent. The estimated hydration free energy of phenol is slightly underestimated as compared to a previously reported experimental estimate. [ABSTRACT FROM AUTHOR]

The oxidative addition of methyl iodide to [Rh(β-diketonato)(CO)(PPh)3] complexes, as modal catalysts of the first step during the Monsanto process, are well-studied. The β-diketonato ligand is a bidentate (BID) ligand that bonds, through two O donor atoms (O,O-BID ligand), to rhodium. Imino-β-diketones are similar to β-diketones, though the donor atoms are N and O, referred to as an N,O-BID ligand. In this study, the oxidative addition of methyl iodide to [Rh(imino-β-diketonato)(CO)(PPh)3] complexes, as observed on UV–Vis spectrophotometry, IR spectrophotometry and NMR spectrometry, are presented. Experimentally, one isomer of [Rh(CH3COCHCNPhCH3)(CO)(PPh3)] and two isomers of [Rh(CH3COCHCNHCH3)(CO)(PPh3)] are observed—in agreement with density functional theory (DFT) calculations. Experimentally the [Rh(CH3COCHCNPhCH3)(CO)(PPh3)] + CH3I reaction proceeds through one reaction step, with a rhodium(III)-alkyl as the final reaction product. However, the [Rh(CH3COCHCNHCH3)(CO)(PPh3)] + CH3I reaction proceeds through two reaction steps, with a rhodium(III)-acyl as the final reaction product. DFT calculations of all the possible reaction products and transition states agree with experimental findings. Due to the smaller electronegativity of N, compared to O, the oxidative addition reaction rate of CH3I to the two [Rh(imino-β-diketonato)(CO)(PPh)3] complexes of this study was 7–11 times faster than the oxidative addition reaction rate of CH3I to [Rh(CH3COCHCOCH3)(CO)(PPh3)]. [ABSTRACT FROM AUTHOR]

Copper oxide nanoparticles (CuONPs) have received tremendous attention as efficient adsorbents owing to their low cost, desirable surface area, abundant active sites, potent textural characteristics and high adsorption capacities. However, CuONPs have not been employed to decontaminate water laden with increasing environmental contaminants such as thiazolyl blue and paracetamol. Herein, the adsorption of thiazolyl blue and paracetamol onto green synthesized CuONPs prepared from the aqueous leaf extract of Platanus occidentalis was studied. The BET, SEM, FTIR, XRD, EDX and pH point of zero charge showed the successful synthesis of CuONPs having desirable surface properties with a surface area of 58.76 m2/g and an average size of 82.13 nm. The maximum monolayer adsorption capacities of 72.46 mg/g and 64.52 mg/g were obtained for thiazolyl blue and paracetamol, respectively. The Freundlich, pseudo-second-order and intraparticle diffusion models were well fitted to the adsorption of both pollutants. The pH studies suggested the predominance of electrostatic and weaker intermolecular interactions in the adsorption of the thiazolyl blue and paracetamol, respectively. Spontaneous, physical, endothermic and random adsorption of the pollutants on CuONPs was obtained from the thermodynamic consideration. The biosynthesized CuONPs were found to be highly reusable and efficient for the adsorption of thiazolyl blue and paracetamol from water. [ABSTRACT FROM AUTHOR]

Copper oxide nanoparticles (CuONPs) have received tremendous attention as efficient adsorbents owing to their low cost, desirable surface area, abundant active sites, potent textural characteristics and high adsorption capacities. However, CuONPs have not been employed to decontaminate water laden with increasing environmental contaminants such as thiazolyl blue and paracetamol. Herein, the adsorption of thiazolyl blue and paracetamol onto green synthesized CuONPs prepared from the aqueous leaf extract of Platanus occidentalis was studied. The BET, SEM, FTIR, XRD, EDX and pH point of zero charge showed the successful synthesis of CuONPs having desirable surface properties with a surface area of 58.76 m2/g and an average size of 82.13 nm. The maximum monolayer adsorption capacities of 72.46 mg/g and 64.52 mg/g were obtained for thiazolyl blue and paracetamol, respectively. The Freundlich, pseudo-second-order and intraparticle diffusion models were well fitted to the adsorption of both pollutants. The pH studies suggested the predominance of electrostatic and weaker intermolecular interactions in the adsorption of the thiazolyl blue and paracetamol, respectively. Spontaneous, physical, endothermic and random adsorption of the pollutants on CuONPs was obtained from the thermodynamic consideration. The biosynthesized CuONPs were found to be highly reusable and efficient for the adsorption of thiazolyl blue and paracetamol from water. [ABSTRACT FROM AUTHOR]

A Killian-Jamieson diverticulum potentially mimicking a thyroid nodule: A case report highlighting the cytology of a pharyngoesophageal diverticulum Fine-needle aspiration of a pharyngoesophageal diverticulum mimicking a calcified thyroid nodule on ultrasonography. Details of oesophageal content on fine needle aspiration biopsy (FNAB) of the thyroid to discern PED from thyroid nodules have been described in reports.[[1], [3], [5], [7]] Although radiological imaging is needed to differentiate diverticula from thyroid nodules, FNAB has been shown to be a useful initial test to evaluate and diagnose pretenders of thyroidal lesions. Keywords: Bethesda nondiagnostic; fine needle aspiration biopsy; oesophageal diverticulum; paraesophageal; pharyngoesophageal; thyroid nodule EN Bethesda nondiagnostic fine needle aspiration biopsy oesophageal diverticulum paraesophageal pharyngoesophageal thyroid nodule 72 76 5 12/13/22 20230101 NES 230101 The authors highlight the important contribution of rapid on-site evaluation by the cytopathologist of a pharyngoesophageal diverticulum in a mass initially interpreted clinically as thyroidal in origin. [Extracted from the article]

Background and aim: Unplanned cardiac readmissions in patients with percutaneous intervention (PCI) is very common and is seen as a quality indicator of in-hospital care. Most studies have reported on the 30-day cardiac readmission rates, with very limited information being available on 1-year readmission rates and their association with mortality. The aim of this study was to investigate the impact of biological sex at 1-year post-PCI on unplanned cardiac readmissions. Methods and results: Patients enrolled into the GenesisCare Cardiovascular Outcomes Registry (GCOR-PCI) from December 2008 to December 2020 were included in the study. A total of 13,996 patients completed 12 months of follow-up and were assessed for unplanned cardiac readmissions. All patients with unplanned cardiac readmissions in the first year of post-PCI were followed in year 2 (post-PCI) for survival status. The rate of unplanned cardiac readmissions was 10.1%. Women had a 29% higher risk of unplanned cardiac readmission (HR 1.29, 95% CI 1.11 to 1.48; p = 0.001), and female sex was identified as an independent predictor of unplanned cardiac readmissions. Any unplanned cardiac readmission in the first year was associated with a 2.5-fold higher risk of mortality (HR 2.50, 95% CI 1.67 to 3.75; p < 0.001), which was similar for men and women. Conclusion: Unplanned cardiac readmissions in the first year post-PCI was strongly associated with increased all-cause mortality. Whilst the incidence of all-cause mortality was similar between women and men, a higher incidence of unplanned cardiac readmissions was observed for women, suggesting distinct predictors of unplanned cardiac readmissions exist between women and men. [ABSTRACT FROM AUTHOR]

The World Health Organization recognizes rehabilitation as an essential component of universal health coverage (UHC). In many countries, UHC builds on a standard benefits package of services that is informed by the country's essential medicines list, standard treatment guidelines and primary health care essential laboratory list. In South Africa, primary health care is largely provided and managed by primary health-care nurses and medical officers in accordance with primary health care standard treatment guidelines. However, rehabilitation is mostly excluded from these guidelines. This paper describes the 10-year process that led to rehabilitation referral recommendations being considered for inclusion in South Africa's primary health care standard treatment guidelines. There were five key events: (i) a breakthrough moment; (ii) producing a scientific evidence synthesis and formulating recommendations; (iii) presenting recommendations to the national essential medicines list committee; (iv) mapping rehabilitation recommendations onto relevant treatment guideline sections; and (v) submitting revised recommendations to the committee for final consideration. The main lesson learnt is that, by working together, rehabilitation professionals can be of sufficient number to make a difference, improve service delivery and increase referrals to rehabilitation from primary health care. A remaining challenge is the lack of a rehabilitation representative on the national essential medicines list committee, which could hamper understanding of rehabilitation and of the complexities of the supporting evidence. [ABSTRACT FROM AUTHOR]

Processes of blame-attribution can be conceptualised as socially-situated and discursively-mediated events that feature attempts to assign meaning to harmful (or at least potentially harmful) occurrences. Part of the process involves the search for culprits and subsequent argumentation as to the blameworthiness of those singled out for blame. This study conducts a discourse analysis of blame-attribution in 33 online opinion pieces, posted on the website of the civil society organisation: ACTIVATE! Change Drivers. It concentrates on arguments that address the nexus between youth activism, active citizenship, the legacy of Apartheid and blame for the numerous problems afflicting the South African youth. The most recurring arguments hinged on constructions of the South African government as responsible to supporting the capacity of the contemporary youth to participate effectively in democracy, particularly since the youth continue to endure the repercussions of Apartheid. My analysis details the discursive repertoires through which this proposition is made, and considers its implications for research into contemporary online youth cultures and democratic argumentation. [ABSTRACT FROM AUTHOR]

We here describe a new species of feather-tailed leaf-toed gecko, Kolekanos, from southern Benguela Province, Angola, based on morphological and osteological evidence, supported by phylogenetic analysis of mitochondrial data. The new species adds to the rapidly growing and newly-recognised endemic biodiversity of Angola, doubling the number of Kolekanos species, breaking the pattern observed within other closely-related African members of a clade of circum-Indian Ocean leaf-toed geckos -- Ramigekko, Cryptactites and Afrogecko -- all of which are presently monotypic. The new species is easily distinguished from K. plumicaudus, based on spine-like (as opposed to feather-like) scales on the margins of the original tail. Phylogenetic analyses also recovered the new taxon as monophyletic, with a well-supported sister relationship to K. plumicaudus, from which it differs by a substantial 24.1% NADH-dehydrogenase subunit 2 mitochondrial gene uncorrected p-distance. [ABSTRACT FROM AUTHOR]

Critical whiteness studies (CWS) holds that challenging systemic racism in higher education must include scholarly attention to the everyday conditions under which students engage and produce knowledge about racism. This study examines the context of tutorials on postcolonial literature in a historically-white South African Department of English. Using individual interviews with contractually-employed Tutors, I map how these Tutors assign meaning to discomforting experiences and how they manage their own intersectional subjectivities while engaging undergraduates on systemic racism via postcolonial literature. Specifically, many students attempted to explore marginalization by grounding their essays in lived experiences of material deprivation. How Tutors' responses might be read within CWS is a core concern of this article. [ABSTRACT FROM AUTHOR]

Thermodynamics properties as well as infrared spectra of liquids can be determined using the quantum cluster equilibrium (QCE) theory. The QCE theory requires the knowledge of the structures of the clusters formed by the solvent molecules. In prelude to this determination, in this work, we studied the non-covalent bondings, the structures and the temperature-dependence of the clusters of dimethylformamide (DMF) from dimer to tetramer. To perform this study, we used classical molecular dynamics to sample initial geometries of DMF clusters. Then, optimisation of the geometries is carried out at the MP2/aug-cc-pVDZ level of theory. Besides, we carried out a quantum theory of atoms in molecule analysis. The results show that the structures of the DMF dimer exhibit a stacking configuration, and mainly stabilised by CH··· O hydrogen bondings. For the DMF trimer and DMF tetramer, the structures exhibit an amorphous behaviour. Moreover, it has been found that the CH··· O hydrogen bondings are the main non-covalent bondings in DMF clusters. CH··· C, CH··· N, N··· O, N··· C, C··· O and H··· H bonding interactions are also located in the studied DMF clusters. In addition, the temperature-dependence study shows that only isomers with relative energy within ∼ 1.0 kcal/mol have meaningful contribution to the population of DMF clusters. [ABSTRACT FROM AUTHOR]

African Shovel-snout snakes (Prosymna Gray, 1849) are small, semi-fossorial snakes with a unique compressed and beak-like snout. Prosymna occur mainly in the savanna of sub-Saharan Africa. Of the 16 currently recognised species, four occur in Angola: Prosymna ambigua Bocage, 1873, P. angolensis Boulenger, 1915, P. frontalis (Peters, 1867), and P. visseri FitzSimons, 1959. The taxonomical status and evolutionary relationships of P. angolensis have never been assessed due to the lack of genetic material. This species is known to occur from western Angola southwards to Namibia, and eastwards to Zambia, Botswana and Zimbabwe. The species shows considerable variation in dorsal colouration across its range, and with the lower ventral scales count, an ‘eastern race’ was suggested. In recent years, Prosymna material from different parts of Angola has been collected, and with phylogenetic analysis and High Resolution X-ray Computed Tomography, the taxonomic status of these populations can be reviewed. Strong phylogenetic evidence was found to include the angolensis subgroup as part of the larger sundevalli group, and the existence of three phylogenetic lineages within the angolensis subgroup were identified, which each exhibit clear morphological and colouration differences. One of these lineages is assigned to the nominotypical P. angolensis and the other two described as new species, one of which corroborates the distinct eastern population previously detected. These results reinforce that a considerable part of Angolan herpetological diversity is still to be described and the need for further studies. [ABSTRACT FROM AUTHOR]

A wide range of weathering processes contributes to the degradation of plastic litter items which leads to the formation of microplastics that may be detrimental to marine ecosystems and the organisms inhabiting them. In this study, the impact of UV exposure on the degradation of clear polypropylene (CPP), black polypropylene (BPP), and polyethylene terephthalate (PET) packaging materials was investigated over a period of 6 weeks under dry air conditions representing the terrestrial environment. The exposure was conducted using differently sized and shaped samples at irradiation intensities of 65 W/m2 and 130 W/m2. Results indicated that UV irradiation led to changes in the properties of PET, BPP, and CPP that were proportional to the intensity delivered, leading to a higher level of mass loss, carbonyl indices, crystallinities, and microhardness in all polymer types at 130 W/m2 relative to 65 W/m2. However, material shape and size did not have a significant influence on any property for any of the test materials. Increased mass loss over time was accompanied by considerable increases in carbonyl index (CI) for both PPs. Clear PP (CPP) underwent the most severe degradation, resulting in the highest mass loss, increase in crystallinity, and CI. BPP was less degraded and modified by the UV irradiation than the CPP, indicating that the colorant, carbon black, provided some degree of protection to the bulk polymer material. PET was the least degraded of the three materials, suggesting this polymer type is more resistant to UV degradation. The differences in the degradation behaviours of the three test materials under dry environmental conditions indicate that the UV exposure history of plastic litter might play an important role in its potential for further degradation once it reaches the marine environment. Furthermore, analysis of samples exposed to UV in aqueous media reveals a more irregular set of trends for most material properties measured. Overall, the degree of degradation resulting from UV irradiation in dry environments was more pronounced than in aqueous environments, although the most significant property changes were observed for materials without previous UV exposure histories. Samples with previous UV histories showed higher resistance to further crystallinity changes, which appeared to be due to crosslinking in the pretreatment exposures inhibiting chain alignment into crystalline structures. The effect of solution medium was insignificant, although the presence of water allowed hydrolytic degradation to proceed simultaneously with UV degradation for PET. The reduction of CI in pretreated materials in the aqueous exposures, combined with the mass loss, suggest that the degraded surface layer erodes or products dissolve into surrounding solution medium, leaving a fresh surface of plastic exposed. [ABSTRACT FROM AUTHOR]

Background and aim: poor quality of life (QoL) has been identified as an independent risk factor for mortality and major cardiac events (MACE) in patients with cardiovascular disease (CVD). The aim of this study was to assess health-related quality of life (HRQoL) at baseline and its association with outcome in patients with coronary artery disease presenting for percutaneous coronary intervention (PCI). The outcome was measured by mortality and MACE at 1-year, and whether there was any difference for sex and different age groups. Methods and results: all patients prospectively enrolled into the GenesisCare Outcome Registry (GCOR) over a 11-year period were included in the study. The EQ-5D-5L and VAS patient survey were used for assessment of baseline HRQoL. Of the 15,198 patients, only 6591 (43.4%) completed the self-assessment. Women had significantly more impairment of all five dimensions of the EQ-5D-5L survey, and their self-reported QoL was significantly lower than men (68.3 in women vs. 71.9 in men, p < 0.001). Poor QoL was strongly associated with increased mortality (HR 2.85; 95% CI 1.76 to 4.62, p < 0.001) and MACE (HR 1.40; 95% CI 1.10 to 1.79, p = 0.01). A similar trend was noted for women and men, but did not reach significance in women due to the smaller number of female patients. Conclusion: poor HRQoL is associated with subsequent mortality and MACE in patients undergoing PCI. By not assessing quality of life as a standard of care, an opportunity is lost to identify high-risk patients who may benefit from targeted interventions to improve health outcomes. [ABSTRACT FROM AUTHOR]

Background: The bedaquiline-pretomanid-linezolid regimen has been reported to have 90% efficacy against highly drug-resistant tuberculosis, but the incidence of adverse events with 1200 mg of linezolid daily has been high. The appropriate dose of linezolid and duration of treatment with this agent to minimize toxic effects while maintaining efficacy against highly drug-resistant tuberculosis are unclear.Methods: We enrolled participants with extensively drug-resistant (XDR) tuberculosis (i.e., resistant to rifampin, a fluoroquinolone, and an aminoglycoside), pre-XDR tuberculosis (i.e., resistant to rifampin and to either a fluoroquinolone or an aminoglycoside), or rifampin-resistant tuberculosis that was not responsive to treatment or for which a second-line regimen had been discontinued because of side effects. We randomly assigned the participants to receive bedaquiline for 26 weeks (200 mg daily for 8 weeks, then 100 mg daily for 18 weeks), pretomanid (200 mg daily for 26 weeks), and daily linezolid at a dose of 1200 mg for 26 weeks or 9 weeks or 600 mg for 26 weeks or 9 weeks. The primary end point in the modified intention-to-treat population was the incidence of an unfavorable outcome, defined as treatment failure or disease relapse (clinical or bacteriologic) at 26 weeks after completion of treatment. Safety was also evaluated.Results: A total of 181 participants were enrolled, 88% of whom had XDR or pre-XDR tuberculosis. Among participants who received bedaquiline-pretomanid-linezolid with linezolid at a dose of 1200 mg for 26 weeks or 9 weeks or 600 mg for 26 weeks or 9 weeks, 93%, 89%, 91%, and 84%, respectively, had a favorable outcome; peripheral neuropathy occurred in 38%, 24%, 24%, and 13%, respectively; myelosuppression occurred in 22%, 15%, 2%, and 7%, respectively; and the linezolid dose was modified (i.e., interrupted, reduced, or discontinued) in 51%, 30%, 13%, and 13%, respectively. Optic neuropathy developed in 4 participants (9%) who had received linezolid at a dose of 1200 mg for 26 weeks; all the cases resolved. Six of the seven unfavorable microbiologic outcomes through 78 weeks of follow-up occurred in participants assigned to the 9-week linezolid groups.Conclusions: A total of 84 to 93% of the participants across all four bedaquiline-pretomanid-linezolid treatment groups had a favorable outcome. The overall risk-benefit ratio favored the group that received the three-drug regimen with linezolid at a dose of 600 mg for 26 weeks, with a lower incidence of adverse events reported and fewer linezolid dose modifications. (Funded by the TB Alliance and others; ZeNix ClinicalTrials.gov number, NCT03086486.). [ABSTRACT FROM AUTHOR]

Context: The solvation of metal ions is crucial to understanding relevant properties in physics, chemistry, or biology. Therefore, we present solvation enthalpies and solvation free energies of the ferrous ion in water and ammonia. Our results agree well with the experimental reports for the hydration free energy and hydration enthalpy. We obtained - 1888.7 kJ mol - 1 for the hydration free energy and - 1900.7 kJ mol - 1 for the hydration enthalpy of ferrous ion in water at room temperature. At ambient temperature, we obtained - 2065.7 kJ mol - 1 as the F e 2 + ammoniation free energy and - 2124.2 kJ mol - 1 for the ammoniation enthalpy. In addition, the free energy of solvation is deeply affected when the temperature increases. This pattern can be attributed to the rise of entropy when the temperature rises. Besides, the temperature does not affect the ammoniation enthalpies and the hydration enthalpy of the F e 2 + ion. Method: All the geometry optimizations are performed at the MP2 methods associated with the 6-31++g(d,p) basis set of Pople. solvated phase structures of F e 2 + ion in water or in ammonia are performed using the PCM model. The G a u s s i a n 16 program suite was used to perform all the calculations. The program TEMPO was also used to evaluate the temperature sensitivity of the different obtained geometries. [ABSTRACT FROM AUTHOR]

Newly collected material from northern Namibia's Otjihipa Mountains and west-central Angola allowed us to revisit the Afroedura bogerti Loveridge, 1944 group. The employment of additional gene markers, including nuclear markers, allowed us to identify two new species in the group and infer species boundaries and potential speciation events in Afroedura from southwestern Africa. The new Namibian material is recovered as a sister species to A. donveae, from which it differs mostly by the colour of the iris (copper versus black) and dorsal colouration. Material from the first elevational gradient of the escarpment in Benguela Province, Angola was found to be more closely related to A. bogerti than A. wulfhaackei. The differences between these two species are more subtle, although the new species exhibits higher mid-body scale rows (79.5 versus 74.8), different dorsal colouration and supranasal scales always in contact (versus 57% in contact). [ABSTRACT FROM AUTHOR]

A series of tris(β-diketonato)iron(III) complexes, with the β-diketonato ligand bearing different substituent groups, have been synthesized and characterized by Fourier transform infrared (FT-IR), ultraviolet-visible (UV-Vis) and mass spectroscopic methods. The maximum band UV-Vis absorption wavelengths of the tris(β-diketonato)iron(III) complexes were in the range of 270–380 nm. The complexes have very good solubility in various solvents such as chloroform, dichloromethane, ethyl acetate, tetrahydrofurane, dimethylsulphoxide and dimethylformamide. After the syntheses and characterization processes, spectroscopic and electrochemical properties of these tris(β-diketonato)iron(III) complexes were investigated. A density functional theory (DFT) study related to the spectroscopic and electrochemical properties of the tris(β-diketonato)iron(III) complexes was used to investigate the possible application of these complexes as dye sensitizers or redox mediators in dye-sensitized solar cells. [ABSTRACT FROM AUTHOR]

This study presents a novel way to measure the contribution of private extension to farm productivity for club data. Club data refers to any convenience sample obtained from a study group, consulting firm, cooperative or producer organisation. The study develops a stochastic frontier production function model with the inefficiency effects of pasture-based dairy farming in the Eastern Cape, South Africa. The analysis for 2012–2018 involves 49 adopter farms, and controls for inter-calf period, nutrient use efficiency and the amount of extension contact. Results are robust to functional form specification and there is no evidence of frontier-shifting technical progress for the Cobb Douglas or translog model, but there is a clear productivity benefit to engaging with the private extension service provider working locally (adoption). Productivity rises at 0.91–1.06% p.a. over time and by 1.54–1.62% p.a. with each extra year of the extension. Large farms close to the private extension provider's base of operations benefit most from being in the group. This case study is important because it documents productivity growth in the period since 2010 and puts the effect of extension on productivity growth back on the local research agenda. [ABSTRACT FROM AUTHOR]

Background: Hormone therapy in transgender individuals may impact processes that lead to changes in biochemical analytes, and therefore reference intervals. Currently, few reference interval studies are available for the transgender population. We determined biochemical reference intervals for transgender individuals receiving hormone therapy. Methods: Our retrospective, laboratory-based, observational study included healthy transgender males (N = 24) and transgender females (N = 84) on hormone therapy. Various biochemical reference intervals were established for each cohort and compared to their cisgender counterparts. Results: We detected significant differences in reference intervals for sodium, 139–142 mmol/L vs. 136–145 mmol/L when comparing transgender males (TM) with cisgender males (CM). The following significant changes in upper reference limits (URL) for TM versus CM were detected, ALP (URL: 96 U/L vs. 128 U/L), GGT (URL: 27 U/L vs. 67 U/L) and testosterone (URL: 46.7 nmol/L vs. 29.0 nmol/L), respectively. Moreover, when comparing transgender female (TF) to cisgender female (CF), significant differences in creatinine (URL: 117 μmol/L vs. 90 μmol/L), albumin (lower reference limit: 41 g/L, vs. 35 g/L), AST (URL: 50 U/L vs. 35 U/L), ALP (URL: 118 U/L vs. 98 U/L) and oestradiol (URL: 934 pmol/L vs. 213 pmol/L) were noted, respectively. Significantly higher LDL-C was observed for TM on hormone treatment, compared to baseline (2.9 mmol/L vs. 2.2 mmol/L, p <0.01). Conclusions: Biochemical results for TM and TF receiving hormone therapy can be evaluated against our transgender-specific reference intervals for some analytes, while others can be compared to their identified gender reference intervals. [ABSTRACT FROM AUTHOR]

Increased bone resorption is a well-described consequence of primary hyperparathyroidism (PHPT). In South Africa, little is known about the impact of PHPT on skeletal health. To determine the prevalence of decreased bone mineral density (BMD), vertebral fractures and osteitis fibrosa cystica in patients with PHPT who underwent parathyroidectomy. Retrospective study of patients who underwent parathyroidectomy for PHPT at Tygerberg Hospital in Cape Town, from January 2010 to December 2019. Clinical, biochemical and BMD parameters are described. Final analysis included 56 patients (median age 63.5 years; 80.4% female). Initial calcium, parathyroid hormone (PTH) and 25-hydroxyvitamin D (25[OH]D) levels were 2.93 mmol/l, 19.4 pmol/l and 34.0 nmol/l, respectively. Of the total cohort, 71.4% had decreased BMD. The prevalence of osteoporosis and osteopenia in postmenopausal women and men ≥ 50 years was 50.0% and 39.1% respectively; low bone mass for age in premenopausal women and men < 50 years was 20.0%. Vertebral fractures were seen in 21.2% of patients on radiography. Osteitis fibrosa cystica was present in five patients (9.6%). PTH levels were significantly elevated in patients with osteoporosis compared with those with normal BMD (36.4 vs. 16.1 pmol/l; p = 0.02). Two-thirds of patients who underwent parathyroidectomy for PHPT had decreased BMD, with osteoporosis present in 50% of postmenopausal women and older men. One in five had vertebral fractures. These findings underscore the importance of skeletal assessment in the management of PHPT. [ABSTRACT FROM AUTHOR]