Hydroxyl Transfer to Carbon Radicals by Mn(OH) vs Fe(OH) Corrole Complexes.

The transfer of •OH from metal-hydroxo species to carbon radicals (R•) to give hydroxylated products (ROH) is a fundamental process in metal-mediated heme and nonheme C-H bond oxidations. This step, often referred to as the hydroxyl "rebound" step, is typically very fast, making direct study of this process challenging if not impossible. In this report, we describe the reactions of the synthetic models M(OH)(ttppc) (M = Fe (1), Mn (3); ttppc = 5,10,15-tris(2,4,6-triphenyl)phenyl corrolato3-) with a series of triphenylmethyl carbon radical (R•) derivatives ((4-X-C6H4)3C•; X = OMe, tBu, Ph, Cl, CN) to give the one-electron reduced MIII(ttppc) complexes and ROH products. Rate constants for 3 for the different radicals ranged from 11.4(1) to 58.4(2) M-1 s-1, as compared to those for 1, which fall between 0.74(2) and 357(4) M-1 s-1. Linear correlations for Hammett and Marcus plots for both Mn and Fe were observed, and the small magnitudes of the slopes for both correlations imply a concerted •OH transfer reaction for both metals. Eyring analyses of reactions for 1 and 3 with (4-X-C6H4)3C• (X = tBu, CN) also give good linear correlations, and a comparison of the resulting activation parameters highlight the importance of entropy in these •OH transfer reactions. Density functional theory calculations of the reaction profiles show a concerted process with one transition state for all radicals investigated and help to explain the electronic features of the OH rebound process.

Community scientist program provides bi-directional communication and co-learning between researchers and community members.

Community involvement in research is key to translating science into practice, and new approaches to engaging community members in research design and implementation are needed. The Community Scientist Program, established at the MD Anderson Cancer Center in Houston in 2018 and expanded to two other Texas institutions in 2021, provides researchers with rapid feedback from community members on study feasibility and design, cultural appropriateness, participant recruitment, and research implementation. This paper aims to describe the Community Scientist Program and assess Community Scientists' and researchers' satisfaction with the program. We present the analysis of the data collected from 116 Community Scientists and 64 researchers who attended 100 feedback sessions, across three regions of Texas including Northeast Texas, Houston, and Rio Grande Valley between June 2018 and December 2022. Community Scientists stated that the feedback sessions increased their knowledge and changed their perception of research. All researchers (100%) were satisfied with the feedback and reported that it influenced their current and future research methods. Our evaluation demonstrates that the key features of the Community Scientist Program such as follow-up evaluations, effective bi-directional communication, and fair compensation transform how research is conducted and contribute to reducing health disparities.

The Selective Monobromination of a Highly Sterically Encumbered Corrole: Structural and Spectroscopic Properties of Fe(Cl)(2-Bromo-5,10,15-tris(triphenyl)phenyl corrole).

The corrole ligand serves as a versatile tri-anionic, macrocyclic platform on which to model biological catalytic systems, as well as to effect mechanistically challenging chemical transformations. Here in we describe the synthesis, structure, and characterization of an isomerically pure corrole ligand, selectively mono-brominated at the ß-carbon position adjacent to the corrole C-C bond (2-C) and produced in relatively high yields, as well as its iron chloride complex. Analysis of the iron metalated complex by cyclic voltammetry shows that the bromine being present on the ligand resulted in anodic shifts of +93 and +63 mV for first oxidation and first reduction of the complex respectively. The Mossbauer spectrum of the iron metalated complex shows negligible change relative to the non-brominated analog, indicating the presence of the halide substituent predominantly effects the orbitals of the ligand rather than the metal.

Prevalencia de fracturas periprotésicas de fémur en una serie determinada de pacientes con reemplazo de cadera / Prevalence of periprosthetic femoral fractures in a selected series of hip replacement patients

Objetivo Determinar la prevalencia de fracturas periprotésicas en pacientes con antecedente de reemplazo de cadera que ingresaron a un servicio de ortopedia entre el 2010 al 2018. Materiales y métodos 709 pacientes fueron atendidos, pero solo 15 pacientes presentaron fracturas periprotésicas. Resultados La prevalencia de fracturas periprotésicas fue del 2.1% (IC 95%: 1.05; 3.17). La mayor parte de los casos se presentaron en el sexo femenino con un porcentaje de 53,3%, con edad promedio de 74.2 año. Las principales causas de fractura periprotésica fueron el trauma en la cadera por caída desde su propia altura. Solo el 12.12% presentaron alguna complicación local o sistémica. Conclusiones La prevalencia de fracturas periprotésicas fue menor del 3%; esta patología depende de distintos factores que se deben tener en cuenta al momento de realizar los procedimientos quirúrgicos.

Objective To determine the prevalence of periprosthetic fractures in patients with a history of hip replacement admitted to an orthopedic service between 2010 and 2018. Materials and methods 709 patients were seen, but only 15 patients had periprosthetic fractures. Results The prevalence of periprotic fractures was 2.1% (95% CI: 1.05; 3.17). The majority of cases occurred in females with a percentage of 53.3%, with an average age of 74.2 years. The main causes of periprotic fracture were hip trauma from falling from its own height. Only 12.12% presented some local or systemic complication. Conclusions The prevalence of periprosthetic fractures was less than 3%; this pathology depends on different factors that must be taken into account when performing surgical procedures.

Optimizing tuberculosis testing for basic laboratories.

Optimal tuberculosis testing usually involves sputum centrifugation followed by broth culture. However, centrifuges are biohazardous and scarce in the resource-limited settings where most tuberculosis occurs. To optimize tuberculosis testing for these settings, centrifugation of 111 decontaminated sputum samples was compared with syringe-aspiration through polycarbonate membrane-filters that were then cultured in broth. To reduce the workload of repeated microscopic screening of broth cultures for tuberculosis growth, the colorimetric redox indicator 2,3-diphenyl-5-(2-thienyl) tetrazolium chloride was added to the broth, which enabled naked-eye detection of culture positivity. This combination of filtration and colorimetric growth-detection gave similar results to sputum centrifugation followed by culture microscopy regarding mean colony counts (43 versus 48; P = 0.6), contamination rates (0.9% versus 1.8%; P = 0.3), and sensitivity (94% versus 95%; P = 0.7), suggesting equivalency of the two methods. By obviating centrifugation and repeated microscopic screening of cultures, this approach may constitute a more appropriate technology for rapid and sensitive tuberculosis diagnosis in basic laboratories.