Free Radical Chemistry. Part 9.1 Approaches to Fluorinated Polyethers—Model Compound Studies

Using peroxide, γ-, and UV-irradiation, free radical addition reactions of hexafluoropropene to diethers and to 18-crown-6 have been investigated and mono-, di-, and poly-adducts have been obtained. Factors influencing these additions, especially polar characteristics of intermediate radicals, have been elucidated. Adducts of 18-crown-6 retain a capacity to complex to alkali-metal ions.     

High Speed Particle Beam Generation: A Dynamic Focusing Mechanism for Selecting Ultrafine Particles

RSMS-II is a unique characterization technique for analyzing the chemical content of individual airborne ultrafine particles in real time. Although based on earlier versions, the newest implementation offers crucial enhancements including a smart data acquisition system and a completely redesigned particle inlet. The particle inlet is based on a dynamic focusing mechanism that selectively transmits a narrow particle size range in the form of a high speed particle beam. The mean particle size that is optimally transmitted is dynamically altered by changing the nozzle source pressure, thus particles over a wide size range may be selected. Inherent in the design of dynamic focusing mechanisms is the ability to size-select particles based on their aerodynamic characteristics, thus obviating the need for additional sizing components. The principle, design, and calibration of a variable pressure inlet is presented in the current work. Characteristics are estimated employing a theoretical approach based on the Stokes number definition and supported with numerical simulations using CFD tools. Results from a preliminary effort in calibrating the inlet using monodisperse aerosol are presented. Results indicate that the size resolving capability of the inlet may be enhanced at the expense of lowered transmission rates. Finally, the capability of RSMS-II as a characterization technique is demonstrated by analyzing ultrafine atmospheric particles from a moderately polluted episode.     

Cycle stability of birnessite manganese dioxide for electrochemical capacitors

A combination of step potential electrochemical spectroscopy (SPECS) and electrochemical impedance spectroscopy (EIS) has been used to examine the electrochemical cycling behaviour of a well-characterized birnessite-phase manganese dioxide sample for use in electrochemical capacitors. The resistance and interfacial properties of the macroscopic electrode were found to be irreversible with cycling. However, the corresponding properties for the individual particles were more reversible, although they did show substantial hysteresis in their behaviour during cycling. This behaviour was discussed in terms of the structural, conductivity and morphological characteristics of the birnessite at different depths of discharge.     

Metabolomic Evidence for Peroxisomal Dysfunction in Myalgic Encephalomyelitis/Chronic Fatigue Syndrome

Myalgic encephalomyelitis/chronic fatigue syndrome (ME/CFS) is a chronic and debilitating disease characterized by unexplained physical fatigue, cognitive and sensory dysfunction, sleeping disturbances, orthostatic intolerance, and gastrointestinal problems. People with ME/CFS often report a prodrome consistent with infections. Using regression, Bayesian and enrichment analyses, we conducted targeted and untargeted metabolomic analysis of plasma from 106 ME/CFS cases and 91 frequency-matched healthy controls. Subjects in the ME/CFS group had significantly decreased levels of plasmalogens and phospholipid ethers (p < 0.001), phosphatidylcholines (p < 0.001) and sphingomyelins (p < 0.001), and elevated levels of dicarboxylic acids (p = 0.013). Using machine learning algorithms, we were able to differentiate ME/CFS or subgroups of ME/CFS from controls with area under the receiver operating characteristic curve (AUC) values up to 0.873. Our findings provide the first metabolomic evidence of peroxisomal dysfunction, and are consistent with dysregulation of lipid remodeling and the tricarboxylic acid cycle. These findings, if validated in other cohorts, could provide new insights into the pathogenesis of ME/CFS and highlight the potential use of the plasma metabolome as a source of biomarkers for the disease.