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1.
J Am Chem Soc ; 146(15): 10687-10698, 2024 Apr 17.
Artigo em Inglês | MEDLINE | ID: mdl-38578843

RESUMO

Perfluorooctanoic acid (PFOA) is an artificial chemical of global concern due to its high environmental persistence and potential human health risk. Electrochemical methods are promising technologies for water treatment because they are efficient, cheap, and scalable. The electrochemical reduction of PFOA is one of the current methodologies. This process leads to defluorination of the carbon chain to hydrogenated products. Here, we describe a mechanistic study of the electrochemical reduction of PFOA in gold electrodes. By using linear sweep voltammetry (LSV), an E0' of -1.80 V vs Ag/AgCl was estimated. Using a scan rate diagnosis, we determined an electron-transfer coefficient (αexp) of 0.37, corresponding to a concerted mechanism. The strong adsorption of PFOA into the gold surface is confirmed by the Langmuir-like isotherm in the absence (KA = 1.89 × 1012 cm3 mol-1) and presence of a negative potential (KA = 3.94 × 107 cm3 mol-1, at -1.40 V vs Ag/AgCl). Based on Marcus-Hush's theory, calculations show a solvent reorganization energy (λ0) of 0.9 eV, suggesting a large electrostatic repulsion between the perfluorinated chain and water. The estimated free energy of the transition state of the electron transfer (ΔG‡ = 2.42 eV) suggests that it is thermodynamically the reaction-limiting step. 19F - 1H NMR, UV-vis, and mass spectrometry studies confirm the displacement of fluorine atoms by hydrogen. Density functional theory (DFT) calculations also support the concerted mechanism for the reductive defluorination of PFOA, in agreement with the experimental values.

2.
Am J Health Syst Pharm ; 80(21): 1542-1549, 2023 10 25.
Artigo em Inglês | MEDLINE | ID: mdl-37471466

RESUMO

PURPOSE: Post-transplantation anemia (PTA) is common in kidney transplant recipients, with patients frequently treated with erythropoietin-stimulating agents such as darbepoetin alfa. The optimal dosing for darbepoetin alfa remains controversial. METHODS: This retrospective cohort study involved kidney transplant recipients who received darbepoetin alfa at 2 clinics. Patients were stratified into 2 groups: those who received a fixed dose of 200 µg and those who received a weight-based dose of 0.45 µg/kg. The dosing interval varied depending on clinical response, clinic visit timing, and frequency allowed by insurance. The primary outcome was achieving a hemoglobin concentration of at least 10 g/dL without blood transfusion by 12 weeks after darbepoetin alfa initiation. RESULTS: Of the 110 patients in the study, 45% received weight-based dosing and 55% received fixed dosing. Darbepoetin alfa was initiated significantly earlier after transplantation in the fixed-dose group (median of 14 vs 20 days; P = 0.003). The weight-based group received more doses of darbepoetin alfa (median of 4 vs 2 doses; P = 0.002) and had a significantly lower cumulative exposure to darbepoetin alfa (125 vs 590 µg; P < 0.001). The median time between doses was 9 days (interquartile range, 7-14 days) in the weight-based group and 12 days (7-32 days) in the fixed-dose group (P = 0.04). Patients in the weight-based group more frequently achieved the primary outcome (67.3% vs 47.5%; P = 0.059). There was no significant difference in secondary or safety outcomes between the groups. CONCLUSION: Weight-based and fixed dosing approaches for darbepoetin alfa were not different in the achievement of a hemoglobin concentration of at least 10 g/dL without blood transfusion at 12 weeks after darbepoetin alfa initiation, with significantly lower cumulative darbepoetin alfa utilization in the weight-based group. Weight-based dosing of darbepoetin alfa in PTA appears to be safe and effective, with the potential for significant patient and health-system cost savings.


Assuntos
Anemia , Hematínicos , Transplante de Rim , Humanos , Darbepoetina alfa/efeitos adversos , Transplante de Rim/efeitos adversos , Estudos Retrospectivos , Anemia/diagnóstico , Anemia/tratamento farmacológico , Anemia/etiologia , Hemoglobinas/análise , Hemoglobinas/uso terapêutico , Hematínicos/efeitos adversos , Resultado do Tratamento
3.
Genome Announc ; 3(5)2015 Oct 08.
Artigo em Inglês | MEDLINE | ID: mdl-26450722

RESUMO

Silence is a newly isolated siphophage that infects Bacillus megaterium, a soil bacterium that is used readily in research and commercial applications. A study of B. megaterium phage Silence will enhance our knowledge of the diversity of Bacillus phages. Here, we describe the complete genome sequence and annotated features of Silence.

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