Synthesis and Characterization of Pyridine-Armed Reinforced Macrocycles and Their Transition Metal Complexes as Potential Oxidation Catalysts

Oxidation catalysts stable in aqueous solution under both harsh pH\u27s and at high temperature would be environmentally friendly alternatives to current technologies. Transition metal complexes of tetraazamacrocycles reinforced with additional ethylene bridges have produced such oxidation catalysts. A controlling aspect of the usefulness of any metal catalyst is its set of oxidation and reduction potentials. Reversible redox processes that bracket a potential window within which useful oxidation of substrate molecules can occur are desirable. Though quite robust, and exhibiting reversible electrochemistry, some reinforced macrocycle complexes are not useful catalysts because their redox potentials are not in a desired potential range. An established method of modifying the electrochemical properties of a transition metal complex is to modify the ligand, which subsequently modifies the properties of its complexed metal ion. We wished to determine if the addition of pyridine pendant arms to the known reinforced macrocycle ligands would result in beneficial shifts in the redox potentials of their transition metal complexes. The resulting ligands must allow at least one open coordination site on the bound metal ion for oxidant and/or substrate binding. We have synthesized and characterized both cross-bridged and side-bridged cyclen and cyclam tetraazamacrocycles with pyridine pendant arms. Cobalt, nickel, copper, and zinc complexes were made. The synthesis and characterization of the ligands and the synthesis and characterization of their complexes will be presented

Capnocytophaga canimorsus meningitis in a 38-year-old immunocompetent woman from household pet exposure.

A 38-year-old otherwise healthy woman with no history of immunocompromise, recent travel, or concerning exposures presented to the ED with several days of nonspecific cold-like symptoms with associated generalized headache. After the patient was symptomatically treated and discharged, she returned several hours later with worsening of symptoms and new vomiting, confusion, and sensorineural hearing loss. Blood and cerebrospinal fluid cultures eventually returned positive for a Capnocytophaga canimorsus infection, a bacterial pathogen found in the saliva of dogs and cats. Only after that, the patient recalled being scratched and licked by her pets, two dogs and a cat. She was treated with a course of systemic steroids, antibiotics and discharged home

Contextual behavioural coaching: An evidence-based model for supporting behaviour change

As coaching psychology finds its feet, demands for evidence-based approaches are increasing both from inside and outside of the industry. There is an opportunity in the many evidence-based interventions in other areas of applied psychology that are of direct relevance to coaching psychology. However, there may too be risks associated with unprincipled eclecticism. Existing approaches that are gaining popularity in the coaching field such as Dialectic Behavioural Therapy and Mindfulness enjoy close affiliation with Contextual Behavioral Science (CBS). In this article, we provide a brief overview of CBS as a coherent philosophical, scientific, and practice framework for empirically supported coaching work. We review its evidence base, and its direct applicability to coaching by describing CBS’s most explicitly linked intervention – Acceptance and Commitment Therapy/Training (ACT). We highlight key strengths of ACT including: its great flexibility in regard of the kinds of client change it can support; the variety of materials and exercises available; and, the varied modes of delivery through which it has been shown to work. The article lays out guiding principles and provides a brief illustrative case study of Contextual Behavioural Coaching

Diminished Antioxidant Activity of High-Density Lipoprotein–Associated Proteins in Systolic Heart Failure

Background— Diminished serum arylesterase activity, catalyzed by the high-density lipoprotein–associated paraoxonase-1, is associated with heightened systemic oxidative stress and atherosclerosis risk. In the present study, we sought to determine the prognostic role of serum arylesterase activity in subjects with systolic heart failure, particularly in relation to established cardiac biomarkers. Methods and Results— We measured serum arylesterase activity in 760 subjects with impaired left ventricular systolic function (left ventricular ejection fraction \u3c50%), and prospectively followed major adverse cardiac events (including death, nonfatal myocardial infarction, and stroke) for 3 years. In our study cohort (mean age, 64±11 years; 74% men; median left ventricular ejection fraction, 35%; median creatinine clearance, 96 mg/dL), mean serum arylesterase activity (98±25 μmol/L/min/mL) was lower compared with that in healthy control subjects (mean, 115±26 μmol/L/min/mL, P\u3c0.01) but higher compared with advanced decompensated heart failure subjects (mean, 69±22 μmol/L/min/mL, P\u3c0.01). Within our cohort, there was modest correlation between serum arylesterase activity and high-density lipoprotein cholesterol (r=0.33, P\u3c0.01) as well as B-type natriuretic peptide (r=−0.23, P\u3c0.01). Lower serum arylesterase activity was a strong predictor of poorer outcomes (hazard ratio, 2.94; 95% confidence interval, 1.54, 5.62; P\u3c0.001). After adjusting for traditional risk factors, medication use, B-type natriuretic peptide, and creatinine clearance, lower serum arylesterase still conferred an increased risk of major adverse cardiac events at 3 years (hazard ratio, 2.69; 95% confidence interval, 1.37 to 5.28; P=0.004). Conclusions— In patients with systolic heart failure, decreased serum arylesterase activity, a measure of diminished antioxidant properties of high-density lipoprotein, predicts higher risk of incident long-term adverse cardiac event independent of established clinical and biochemical risk factors

Diminished Antioxidant Activity of High-Density Lipoprotein–Associated Proteins in Systolic Heart Failure

Background— Diminished serum arylesterase activity, catalyzed by the high-density lipoprotein–associated paraoxonase-1, is associated with heightened systemic oxidative stress and atherosclerosis risk. In the present study, we sought to determine the prognostic role of serum arylesterase activity in subjects with systolic heart failure, particularly in relation to established cardiac biomarkers. Methods and Results— We measured serum arylesterase activity in 760 subjects with impaired left ventricular systolic function (left ventricular ejection fraction \u3c50%), and prospectively followed major adverse cardiac events (including death, nonfatal myocardial infarction, and stroke) for 3 years. In our study cohort (mean age, 64±11 years; 74% men; median left ventricular ejection fraction, 35%; median creatinine clearance, 96 mg/dL), mean serum arylesterase activity (98±25 μmol/L/min/mL) was lower compared with that in healthy control subjects (mean, 115±26 μmol/L/min/mL, P\u3c0.01) but higher compared with advanced decompensated heart failure subjects (mean, 69±22 μmol/L/min/mL, P\u3c0.01). Within our cohort, there was modest correlation between serum arylesterase activity and high-density lipoprotein cholesterol (r=0.33, P\u3c0.01) as well as B-type natriuretic peptide (r=−0.23, P\u3c0.01). Lower serum arylesterase activity was a strong predictor of poorer outcomes (hazard ratio, 2.94; 95% confidence interval, 1.54, 5.62; P\u3c0.001). After adjusting for traditional risk factors, medication use, B-type natriuretic peptide, and creatinine clearance, lower serum arylesterase still conferred an increased risk of major adverse cardiac events at 3 years (hazard ratio, 2.69; 95% confidence interval, 1.37 to 5.28; P=0.004). Conclusions— In patients with systolic heart failure, decreased serum arylesterase activity, a measure of diminished antioxidant properties of high-density lipoprotein, predicts higher risk of incident long-term adverse cardiac event independent of established clinical and biochemical risk factors

Colitis Induced Microvascular Leak Triggers Colonic Dysmotility

Graduate Basi