Formation, electrochemical and radical scavenging properties of novel ruthenium compounds with N, X-donor (X = O, N) heterocyclic chelators

Herein, we communicate the formation of novel ruthenium compounds with N, X-donor (X = O, N) heterocyclic- derived ligands. A paramagnetic ruthenium(IV) complex, [RuCl(pho)(bzca)(PPh3)](1) (pho = 2- aminophenolate; bzca = 2-carboxylate-1H-benzimidazole) was isolated from the reaction of the ruthenium(II) precursor, trans-[RuCl2(PPh3)3] and 2-((1H-benzimidazole)methylamino)phenol (Hbzap). The 1:1 molar reaction between the same metal precursor and N-(benzoxazole)-2-hydroxybenzamide (H2bhb) led to the formation of cis-Cl, trans-P-[RuIII(Hbhb)Cl2(PPh3)2](2). The dinuclear ruthenium compounds, (l-Htba,Cl)2[RuIICl(PPh3)]2(3) (Htba = N-(thiophene)methyl-benzoxazole-2-amine) and (l-Cl)2[RuIIICl(Hchpr)(PPh3)]2(4) (H2chpr = 2-amino-3-((tetrahydro-2H-pyran-4-ylimino)methyl)-4Hchromen- 4-one) were formed from the equimolar ratio coordination reactions between trans- [RuCl2(PPh3)3] and the respective free-ligands, Htba and H2chpr. These metal complexes were characterized via IR-, NMR- and UV–Vis spectroscopy, molar conductivity measurements and structural elucidations were confirmed by single crystal X-ray analysis. The X-ray studies revealed that all the metallic compounds exhibited octahedral geometries and that the Hbzap free ligand has undergone a unique molecular transformation to afford the pho and bzca bidentate chelators in 1. The electrochemical properties of the respective metal complexes were investigated by voltammetric analysis. The cyclic voltammograms (CVs) of 1–3 showed one redox couple while within the CV of the dinuclear compound 4, two redox couples were observed. The ligands and their metal complexes were also subjected to DPPH radical scavenging studies. The IC50 values showed that all the metallic compounds have higher radical scavenging activities than their corresponding free-ligands and the natural antioxidant, Vitamin C

The knowledge, attitudes and perceptions of healthcare students and professionals regarding the interdisciplinary health worker team at Stellenbosch University and Tygerberg Academic Hospital

Objective: To determine the knowledge, attitudes and perceptions of healthcare students and qualified health professionals regarding theinterdisciplinary health worker team.Design: A cross-sectional descriptive study.Setting: Stellenbosch University (Tygerberg Campus) and Tygerberg Academic Hospital, Western Cape.Subjects: The sample (n = 529) consisted of first-year students, final-year students and working professionals in the fields of medicine,dietetics, physiotherapy, occupational therapy and speech-language and hearing therapy.Outcome measures: Self-administered, face-validated questionnaire.Results: There was an increase in knowledge in the final-year students when compared to the first-year students of their understanding ofeach profession. However, this improvement was not apparent when the working professionals’ understanding was compared to the finalyearstudents. The results indicated an increase in understanding of the scope of practice of allied health sciences (p-value = 0.001), andagreement that the patient would always benefit from an interdisciplinary approach. It was found that better patient prognosis was stronglyassociated with the care provided by an interdisciplinary team. This association increased from first-year students to final-year students(p-value = 0.019). Doctors were considered to be most valuable in the interdisciplinary team. The allied health sciences received comparablevalue ratings. The more advanced the years of experience, the less comfortable participants were to assume some of the roles of anotherdiscipline. Knowledge of the role of the dietitian increased from first-year students to final-year students (p-value = 0.001), but it remainedthe same for the professionals.Conclusion: There was an increase in knowledge and a positive change in the attitudes and perceptions of healthcare students and professionals in accordance with years of experience

Customized reconstruction of an extensive mandibular defect: A clinical report.

Published ArticleMyoepithelial carcinomas are rare malignant tumors arising from salivary glands. They most commonly involve the parotid and minor salivary glands but may also occur in the submandibular glands. These tumors can become extensive, causing bony expansion and destruction. A 31-year-old man with a large swelling on the left side of the face is presented. Histologic examination of an incisional biopsy confirmed a diagnosis of a myoepithelial carcinoma arising from the left submandibular salivary gland. After tumor resection, the patient's mandible was reconstructed with a customized mandibular framework produced by means of 3-dimensional (3D) laser sintering. This approach significantly reduced cost, advanced surgical procedures, and operating room time, which is of great benefit in a developing country like South Africa

Ruthenium complexes with lumazine derivatives: structural, electrochemical, computational and radical scavenging studies

In this research study, the formation and characterization of new ruthenium(II) and (III) complexes encompassing multidentate ligands derived from 6-acetyl-1,3, 7-trimethyllumazine (almz) are reported. The 1:1 molar coordination reactions of trans-[RuCl2(PPh3)3] with N-1-[1,3, 7-trimethyllumazine]benzohydride (bzlmz) and 6-(N-methyloxime)- 1,3,7-trimethyllumazine (ohlmz) formed a diamagnetic ruthenium(II) complex, cis-[RuCl2(bzlmz)(PPh3)] (1), and paramagnetic complex, cis-[RuIIICl2(olmz)(PPh3)] (2) [Holmz = 6-(N-hydroxy-N0-methylamino)-1,3,7-trimethyllumazine], respectively. These ruthenium complexes were characterized via physico-chemical and spectroscopic methods. Structural elucidations of the metal complexes were confirmed using single crystal X-ray analysis. The redox properties of the metal complexes were investigated via cyclic voltammetry. Electron spin resonance spectroscopy confirmed the presence of a paramagnetic metal centre in 2. The radical scavenging activities of the metal complexes were explored towards the DPPH and NO radicals. Quantum calculations at the density functional theory level provided insight into the interpretation of the IR and UV–Vis experimental spectra of 1

Reconstruction of an Extensive Midfacial Defect Using Additive Manufacturing Techniques

Published ArticleMalignant peripheral nerve sheath tumors are extremely rare tumors arising in peripheral nerves. Only 17 cases involving the trigeminal nerve have ever been reported. These tumors have a very poor prognosis and very high rates of recurrence and metastases. Their recommended treatment involves complete tumor resection followed by radiation. This can be problematic in the head and neck region. We present a clinical case involving a 33-year-old female patient presenting with a slow-growing, exophytic mass of the anterior maxilla. Incisional biopsy and subsequent histological examination revealed a diagnosis of a malignant peripheral nerve sheath tumor. Surgical resection involved a complete maxillectomy, rhinectomy, and resection of the upper lip and aspects of the left and right cheeks. Reconstruction of the subsequent defect incorporated the placement of four zygomatic oncology implants to aid in retention of a facial prosthesis. These implants, however, were subsequently lost; and an anatomical model of the hard tissues was manufactured via 3D printing. This model was used to design and manufacture a titanium frame (customized implant) for the patient. The frame was then fixated and secured intraoperative with 21 cortical screws. A maxillary denture and silicone facial prosthesis were also made to fit onto this frame. This is the first known case where additive manufacturing, via the use of rapid prototyping and 3D printing, was employed to manufacture a facial prosthesis

Coordination of di- and triimine ligands at ruthenium(II) and ruthenium(III) centers: structural, electrochemical and radical scavenging studies

Herein, we explore the coordination of di- and triimine chelators at ruthenium(II) and ruthenium(III) centers. The reactions of 2,6-bis-((4- tetrahydropyranimino)methyl)pyridine (thppy), N1,N2-bis((3-chromone) methylene)benzene-1,2-diamine (chb), and tris-((1H-pyrrol-2-ylmethylene) ethane)amine (H3pym) with trans-[RuIICl2(PPh3)3] afforded the diamagnetic ruthenium(II) complex cis-[RuCl2(thppy)(PPh3)] (1) and the paramagnetic complexes [mer-Ru2(μ-chb)Cl6(PPh3)2] (2), and [Ru(pym)] (3), respectively. The complexes were characterized by IR, NMR, and UV–vis spectroscopy and molar conductivity measurements. The structures were confirmed by single crystal X-ray diffraction studies. The redox properties of the metal complexes were probed via cyclic- and squarewave voltammetry. Finally, the radical scavenging capabilities of the metal complexes towards the NO and 2,2-di(4-tert-octylphenyl)-1-picrylhydrazyl (DPPH) radicals were investigate

Ruthenium complexes with Schiff base ligands containing benz(othiazole/imidazole) moieties: Structural, electron spin resonance and electrochemistry studies

Novel ruthenium(II/III) complexes of Schiff bases containing benzimidazole (bz) or benzothiazole (bs) moieties were isolated: the diamagnetic ruthenium complex, cis-[RuIICl2(bzpy)(PPh3)2] (1) was formed from the 1:1 M reaction between N-((pyridine-2-yl)methylene)-1H-benzimidazole (bzpy) and metal precursor, trans-[RuCl2(PPh3)3]. The same metal precursor, when reacted with the benzimidazole-derived Schiff bases [N-(2-hydroxybenzylidene)-benzothiazole (Hbsp) and N-(2-hydroxybenzylidene)-benzimidazole (Hbzp)], afforded the paramagnetic ruthenium(III) complexes [RuCl(bsp)2(PPh3)] (2) and trans-[RuCl(bzp)(PPh3)2] (3), respectively. These metal complexes were characterized via IR, mass and UV–Vis spectroscopy, elemental analysis, single crystal XRD analysis as well as conductivity measurements. Their redox properties were probed by voltammetry and accompanying UV–Vis spectroelectrochemistry experiments. Structural features of complex 1 were further investigated by multinuclear (1H and 31P) NMR spectroscopy

Air transport liberalisation and airport dependency: developing a composite index

Air transport liberalisation in Europe has produced some major changes to the networks operated by airlines and the services available at airports. Within this context the degree of airport dependency in terms of market, spatial and temporal concentration is important to know from an economic geography and risk management perspective. A composite index called the Airport Dependency Index (ADI) is developed to measure airport dependency based on the concept of the relative Gini coefficient. Liberalisation has had varying impacts depending on the size and type of airport and so a comparison is made of the degree of dependency at a large sample of European airports using the ADI. The ADI has the potential to provide insight on the sustainability and worthiness of financing airport projects, and on whether airports should diversify further their activities by investing in the growth and expansion of their network

Who is accessing public-sector anti-retroviral treatment in the Free State, South Africa? An exploratory study of the first three years of programme implementation

<p>Abstract</p> <p>Background</p> <p>Although South Africa has the largest public-sector anti-retroviral treatment (ART) programme in the world, anti-retroviral coverage in adults was only 40.2% in 2008. However, longitudinal studies of who is accessing the South African public-sector ART programme are scarce. This study therefore had one main research question: who is accessing public-sector ART in the Free State Province, South Africa? The study aimed to extend the current literature by investigating, in a quantitative manner and using a longitudinal study design, the participants enrolled in the public-sector ART programme in the period 2004-2006 in the Free State Province of South Africa.</p> <p>Methods</p> <p>Differences in the demographic (age, sex, population group and marital status) socio-economic (education, income, neo-material indicators), geographic (travel costs, relocation for ART), and medical characteristics (CD4, viral load, time since first diagnosis, treatment status) among 912 patients enrolled in the Free State public-sector ART programme between 2004 and 2006 were assessed with one-way analysis of variance, Bonferroni post-hoc analysis, and cross tabulations with the chi square test.</p> <p>Results</p> <p>The patients accessing treatment tended to be female (71.1%) and unemployed (83.4%). However, although relatively poor, those most likely to access ART services were not the most impoverished patients. The proportion of female patients increased (<it>P </it>< 0.05) and their socio-economic situation improved between 2004 and 2006 (<it>P </it>< 0.05). The increasing mean transport cost (<it>P </it>< 0.05) to visit the facility is worrying, because this cost is an important barrier to ART uptake and adherence. Encouragingly, the study results revealed that the interval between the first HIV-positive diagnosis and ART initiation decreased steadily over time (<it>P </it>< 0.05). This was also reflected in the increasing baseline CD4 cell count at ART initiation (<it>P </it>< 0.05).</p> <p>Conclusions</p> <p>Our analysis showed significant changes in the demographic, socio-economic, geographic, and medical characteristics of the patients during the first three years of the programme. Knowledge of the characteristics of these patients can assist policy makers in developing measures to retain them in care. The information reported here can also be usefully applied to target patient groups that are currently not reached in the implementation of the ART programme.</p

Changing character and waning impact of COVID-19 at a tertiary centre in Cape Town, South Africa.

BACKGROUND: The emergence of genetic variants of SARS-CoV-2 was associated with changing epidemiological characteristics throughout coronavirus disease 2019 (COVID-19) pandemic in population-based studies. Individual-level data on the clinical characteristics of infection with different SARS-CoV-2 variants in African countries is less well documented. OBJECTIVES: To describe the evolving clinical differences observed with the various SARS-CoV-2 variants of concern and compare the Omicron-driven wave in infections to the previous Delta-driven wave. METHOD: We performed a retrospective observational cohort study among patients admitted to a South African referral hospital with COVID-19 pneumonia. Patients were stratified by epidemiological wave period, and in a subset, the variants associated with each wave were confirmed by genomic sequencing. Outcomes were analysed by Cox proportional hazard models. RESULTS: We included 1689 patients were included, representing infection waves driven predominantly by ancestral, Beta, Delta and Omicron BA1/BA2 & BA4/BA5 variants. Crude 28-day mortality was 25.8% (34/133) in the Omicron wave period versus 37.1% (138/374) in the Delta wave period (hazard ratio [HR] 0.68 [95% CI 0.47-1.00] p = 0.049); this effect persisted after adjustment for age, gender, HIV status and presence of cardiovascular disease (adjusted HR [aHR] 0.43 [95% CI 0.28-0.67] p < 0.001). Hospital-wide SARS-CoV-2 admissions and deaths were highest during the Delta wave period, with a decoupling of SARS-CoV-2 deaths and overall deaths thereafter. CONCLUSION: There was lower in-hospital mortality during Omicron-driven waves compared with the prior Delta wave, despite patients admitted during the Omicron wave being at higher risk. CONTRIBUTION: This study summarises clinical characteristics associated with SARS-CoV-2 variants during the COVID-19 pandemic at a South African tertiary hospital, demonstrating a waning impact of COVID-19 on healthcare services over time despite epidemic waves driven by new variants. Findings suggest the absence of increasing virulence from later variants and protection from population and individual-level immunity