Synthesis, Electrochemistry and Density Functional Theory of Osmium(II) Containing Different 2,2':6',2″-Terpyridines.

In coordination chemistry, 2,2':6',2″-terpyridine is a versatile and extensively studied tridentate ligand. Terpyridine forms stable complexes with a variety of metal ions through coordination sites provided by the three nitrogen atoms in its pyridine rings. This paper presents an electrochemical study on various bis(terpyridine)osmium(II) complexes, addressing the absence of a systematic investigation into their redox behavior.

Cu(β-diketonato) bathochromic shifts from the ultraviolet towards the visible region.

Context: The DFT-calculated ultraviolet/visible properties of 11 different Cu(β-diketonato) complexes are presented. The selected β-diketonato ligands on the Cu complex contain none, one or two aromatic rings. The experimentally measured absorbance maxima range of the ultraviolet/visible is observed at 295-390 nm, and the calculated range is 302-425 nm, for the 11 complexes in this study.

Experimental and theoretically calculated structural data of different iron(II)-terpyridine complexes - validation of theoretical method.

Experimental structural data for bis(terpyridine)iron(II) and a series of related iron(II) complexes, featuring either substituted terpyridine or tris-azinyl analogues of terpyridine, are presented and analyzed in terms of the Mean Absolute Deviation (MAD) from the average experimental data for each specific complex. The experimental structural data are then juxtaposed with density functional theory (DFT) calculated data obtained using various combinations of DFT functionals and basis sets, with and without the inclusion of Grimme D3 empirical dispersion correction. These diverse computational approaches yield optimized geometries that are subsequently compared against the available experimental structural data to assess their accuracy.

Gestational gigantomastia complicated by pseudo-angiomatous stromal hyperplasia - a multidisciplinary management approach.

Gestational gigantomastia is a rare condition typified by disproportionate bilateral breast enlargement in pregnant women, resulting in skin thinning, ulceration, and bleeding. Less than sixty cases have been documented worldwide, and only one other in South Africa. Pseudo-angiomatous stromal hyperplasia (PASH) is a rare benign proliferation of stromal tissue in a tumorous or diffuse pattern.

Clinical and magnetic resonance imaging findings in a French bulldog puppy with genetically confirmed congenital hypothyroidism.

A 7-month-old male French bulldog was referred for abnormal mentation and gait. Physical examination revealed a dome shaped calvarium and persistent bregmatic fontanelle. Neurological examination revealed proprioceptive ataxia, pelvic limb paraparesis and strabismus with moderate ventriculomegaly, thinning of the cerebral parenchyma, and widened cerebral sulci on magnetic resonance imaging.

Hyperparathyroidism Jaw Tumor Syndrome, an Unforeseen Diagnosis.

Asymptomatic primary hyperparathyroidism (PHPT) is often missed in developing nations due to limited formal healthcare exposure and biochemical screening programs. Many patients are thus only diagnosed once symptomatic. We present a 32-year-old female who developed bony protrusions in her jaw during pregnancy, resulting in a stillbirth.

Solvation energies of the ferrous ion in water and in ammonia at various temperatures.

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.

Pregnancy and diabetic ketoacidosis: fetal jeopardy and windows of opportunity.

Background: Diabetic ketoacidosis (DKA) during pregnancy poses significant risks to both the mother and fetus, with an increased risk of fetal demise. Although more prevalent in women with Type I diabetes (T1D); those with Type 2 diabetes (T2D) and gestational diabetes mellitus (GDM) can also develop DKA. A lack of information about DKA during pregnancy exists worldwide, including in South Africa.

Nutritional deficiency in South African adults scheduled for bariatric surgery.

Background: Globally, there is a rising trend in obesity, known to increase morbidity and mortality. Metabolic surgery and adequate weight loss decrease mortality but may worsen pre-existing nutrient deficiencies. Most data on pre-existing nutritional deficiencies in the population undergoing metabolic surgery is from the developed world, where an extensive micronutrient assessment is achievable.

Early postpartum HbA1c after hyperglycemia first detected in pregnancy-Imperfect but not without value.

Background: South African women of childbearing age are disproportionally affected by obesity and at significant risk of Type 2 Diabetes Mellitus (T2DM). Unless pregnant, they do not readily undergo screening for T2DM. With a local focus on improved antenatal care, hyperglycemia is often first detected in pregnancy (HFDP).

Pathology-supported genetic testing for the application of breast cancer pharmacodiagnostics: family counselling, lifestyle adjustments and change of medication.

Background: Pathology-supported genetic testing (PSGT) enables transitioning of risk stratification from the study population to the individual.

Research Design And Methods: We provide an overview of the translational research performed in postmenopausal breast cancer patients at increased risk of osteoporosis due to aromatase inhibitor therapy, as the indication for referral. Both tumor histopathology and blood biochemistry levels were assessed to identify actionable disease pathways using whole exome sequencing (WES).

Retroperitoneoscopic adrenalectomy - introducing a new surgical technique in South Africa.

Background: Posterior retroperitoneoscopic adrenalectomy (PRA) is purported to be superior to the laparoscopic transperitoneal approach (LA) in patients with a select spectrum of benign adrenal pathologies. Advantages attributed to the technique include minimal blood loss, shortened operative times, and decreased postoperative pain, explained anatomically by the direct access to the adrenal gland. Reduced workspace is a limitation.

Hyperglycemia First Detected in Pregnancy in South Africa: Facts, Gaps, and Opportunities.

This review contextualizes hyperglycemia in pregnancy from a South-African perspective. It aims to create awareness of the importance of hyperglycemia in pregnancy in low-middle-income countries. We address unanswered questions to guide future research on sub-Saharan African women with hyperglycemia first detected in pregnancy (HFDP).

UV-Vis Spectroscopy, Electrochemical and DFT Study of Tris(β-diketonato)iron(III) Complexes with Application in DSSC: Role of Aromatic Thienyl Groups.

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.

Kinetic Study of the Oxidative Addition Reaction between Methyl Iodide and [Rh(imino-β-diketonato)(CO)(PPh)] Complexes, Utilizing UV-Vis, IR Spectrophotometry, NMR Spectroscopy and DFT Calculations.

The oxidative addition of methyl iodide to [Rh(β-diketonato)(CO)(PPh)] 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.

Access to care for low trauma hip fractures in South Africa.

Rationale: Early surgery is recommended for hip fractures.

Main Result: In this study only one-third of subjects with hip fractures were admitted within 24 h of the fracture, and surgery was delayed beyond 48 h in the majority.

Significance: These findings highlight the need to improve access to care for hip fracture subjects.

Radiographic and CT features of zygomatic arch pneumatization in a Thoroughbred with a recurrent progressive ethmoid hematoma.

A 7-year-old Thoroughbred gelding presented with a history of mild unilateral right-sided epistaxis and facial swelling over the right caudal maxillary sinus and zygomatic arch. Eleven months previously a progressive ethmoid hematoma had been surgically removed from the right caudal maxillary and conchofrontal sinus. Computed tomography identified a large expansile soft-tissue attenuating mass in the right caudal maxillary sinus, with protrusion into the conchofrontal sinus, that extended into the zygomatic arch.

DFT data to relate calculated LUMO energy with experimental reduction potentials of Cu(II)-β-diketonato complexes.

We present data on the computed lowest unoccupied molecular orbital energy ( ) of two series of Cu(II)-β-diketonato complexes, calculated via density functional theory (DFT). These are correlated to experimental reduction potential data ( ), obtained by cyclic voltammetry under different experimental conditions (solvent, working and reference electrodes). All calculations were done with the B3LYP functional in the gas phase.

Premenopausal osteoporosis.

In premenopausal women, bone mineral density measurement by dual-energy X-ray absorptiometry should not be used as the sole guide for diagnosis or treatment of osteoporosis, universal screening with bone mineral density is not advised and the World Health Organization classification of bone status should not be applied. A diagnosis of premenopausal osteoporosis is reserved for those with evidence of fragility and may also be considered in women with low bone mass and an ongoing secondary cause of osteoporosis. Idiopathic osteoporosis in young women is rare.

Density functional theory calculated data of the iodomethane oxidative addition to oligothiophene-containing rhodium complexes - Importance of dispersion correction.

Electronic and free energy data of density functional theory calculated optimized geometries of the reactants, transition state of the oxidative addition reaction and different reaction products of the [Rh(RCOCHCOCF)(CO)(PPh)] + CHI reactions (R = CHS, CHS-CHS and CHS-CHS-CHS) are presented to illustrate the influence of the amount of thiophene groups, the implicit solvent and dispersion correction on the calculated energies. All calculations were done with the B3LYP functional, in gas as well as in solvent phase, with and without dispersion correction. The data can save computational chemists time when choosing an appropriate method to calculate reaction energies of oxidative addition reactions.

FRAX-based fracture probabilities in South Africa.

Unlabelled: The hip fracture rates in South Africa were used to create ethnic-specific FRAX® models to facilitate fracture risk assessment.

Introduction: The aim of this study was to develop FRAX models to compute the 10-year probability of hip fracture and major osteoporotic fracture and assess their potential clinical application.

Methods: Age- and sex-specific incidence of hip fracture and national mortality rates were incorporated into a FRAX model for the White, Black African, Coloured and Indian population of South Africa.

Observations on Glucose Excursions With the Use of a Simple Protocol for Insulin, Following Antenatal Betamethasone Administration.

Aims: Pregnant women with diabetes often require preterm delivery. Antenatal betamethasone reduces perinatal morbidity and mortality, but induces hyperglycemia. The primary objective was to observe glucose excursions and determine the preliminary safety of a protocol for subcutaneous insulin following betamethasone administration in an antenatal ward.

Prevalence of Sarcopenia in Older South African Patients Following Surgery for Fragility Fractures of the Hip.

Introduction: Geriatric patients with a fragility fracture of the hip (FFH) are especially prone to sarcopenia with poor functional outcomes and quality of life. We assessed the prevalence of sarcopenia in older South African patients with FFH. Risk factors for sarcopenia were also investigated.