Novel polyaromatic-terminated transition metal complexes for the functionalization of carbon surfaces.

In order to investigate the process of noncovalent adsorption on glassy carbon surfaces, two terpyridine ligands 4-pyren-1-yl-N-[5-([2,2';6',2'']terpyridin-4'-yloxy)-pentyl]-butyramide (tpy~py) and N-[5-([2,2';6',2'']terpyridin-4'-yloxy)-pentyl]-2-naphthamide (tpy~nap) as well as the homoleptic cobalt(II) complexes of these ligands (Co(tpy~py)(2)(PF(6))(2) and Co(tpy~nap)(2)(PF(6))(2)) were synthesized. Electrochemical measurements in solution were used to characterize the transport behavior of these complexes and to verify that the polyaromatic portion of each ligand did not dramatically influence the electronic properties of the transition metal complex. The adsorption of the cobalt complexes above on glassy carbon electrode surfaces was then examined using cyclic voltammetry and was found to be well described by Langmuir or Frumkin isotherms. The free energy of adsorption for Co(tpy~py)(2)(PF(6))(2) was considerably larger than that for Co(tpy~nap)(2)(PF(6))(2): -41 versus -30 kJ/mol.

Hyponatremia Is Associated With Increased Osteoporosis and Bone Fractures in Patients With Diabetes With Matched Glycemic Control.

CONTEXT: Patients with diabetes mellitus are at increased risk for bone fragility fracture secondary to multiple mechanisms. Hyperglycemia can induce true dilutional hyponatremia. Hyponatremia is associated with gait instability, osteoporosis, and increased falls and bone fractures, and studies suggest that compromised bone quality with hyponatremia may be independent of plasma osmolality. We performed a case-control study of patients with diabetes mellitus matched by median glycated hemoglobin (HbA1c) to assess whether hyponatremia was associated with increased risk of osteoporosis and/or fragility fracture. DESIGN: Osteoporosis (n = 823) and fragility fracture (n = 840) cases from the MedStar Health database were matched on age of first HbA1c ≥6.5%, sex, race, median HbA1c over an interval from first HbA1c ≥6.5% to the end of the encounter window, diabetic encounter window length, and type 1 vs type 2 diabetes mellitus with controls without osteoporosis (n = 823) and without fragility fractures (n = 840), respectively. Clinical variables, including coefficient of glucose variation and hyponatremia (defined as serum [Na+] <135 mmol/dL within 30 days of the end of the diabetic window), were included in a multivariate analysis. RESULTS: Multivariate conditional logistic regression models demonstrated that hyponatremia within 30 days of the outcome measure was independently associated with osteoporosis and fragility fractures (osteoporosis OR 3.09; 95% CI, 1.37 to 6.98; fracture OR, 6.41; 95% CI, 2.44 to 16.82). CONCLUSIONS: Our analyses support the hypothesis that hyponatremia is an additional risk factor for osteoporosis and fragility fracture among patients with diabetes mellitus.

Radiation Metabolomics: Current Status and Future Directions.

Human exposure to ionizing radiation (IR) disrupts normal metabolic processes in cells and organs by inducing complex biological responses that interfere with gene and protein expression. Conventional dosimetry, monitoring of prodromal symptoms, and peripheral lymphocyte counts are of limited value as organ- and tissue-specific biomarkers for personnel exposed to radiation, particularly, weeks or months after exposure. Analysis of metabolites generated in known stress-responsive pathways by molecular profiling helps to predict the physiological status of an individual in response to environmental or genetic perturbations. Thus, a multi-metabolite profile obtained from a high-resolution mass spectrometry-based metabolomics platform offers potential for identification of robust biomarkers to predict radiation toxicity of organs and tissues resulting from exposures to therapeutic or non-therapeutic IR. Here, we review the status of radiation metabolomics and explore applications as a standalone technology, as well as its integration in systems biology, to facilitate a better understanding of the molecular basis of radiation response. Finally, we draw attention to the identification of specific pathways that can be targeted for the development of therapeutics to alleviate or mitigate harmful effects of radiation exposure.

Hyponatremia Is Associated With Increased Osteoporosis and Bone Fractures in a Large US Health System Population.

CONTEXT: The significance of studies suggesting an increased risk of bone fragility fractures with hyponatremia through mechanisms of induced bone loss and increased falls has not been demonstrated in large patient populations with different types of hyponatremia. OBJECTIVE: This matched case-control study evaluated the effect of hyponatremia on osteoporosis and fragility fractures in a patient population of more than 2.9 million. DESIGN, SETTING, AND PARTICIPANTS: Osteoporosis (n = 30 517) and fragility fracture (n = 46 256) cases from the MedStar Health database were matched on age, sex, race, and patient record length with controls without osteoporosis (n = 30 517) and without fragility fractures (n = 46 256), respectively. Cases without matched controls or serum sodium (Na(+)) data or with Na(+) with a same-day blood glucose greater than 200 mg/dL were excluded. MAIN OUTCOME MEASURES: Incidence of diagnosis of osteoporosis and fragility fractures of the upper or lower extremity, pelvis, and vertebrae were the outcome measures. RESULTS: Multivariate conditional logistic regression models demonstrated that hyponatremia was associated with osteoporosis and/or fragility fractures, including chronic [osteoporosis: odds ratio (OR) 3.97, 95% confidence interval (CI) 3.59-4.39; fracture: OR 4.61, 95% CI 4.15-5.11], recent (osteoporosis: OR 3.06, 95% CI 2.81-3.33; fracture: OR 3.05, 95% CI 2.83-3.29), and combined chronic and recent hyponatremia (osteoporosis: OR 12.09, 95% CI 9.34-15.66; fracture: OR 11.21, 95% CI 8.81-14.26). Odds of osteoporosis or fragility fracture increased incrementally with categorical decrease in median serum Na(+). CONCLUSIONS: These analyses support the hypothesis that hyponatremia is a risk factor for osteoporosis and fracture. Additional studies are required to evaluate whether correction of hyponatremia will improve patient outcomes.