Microelectrode Voltammetry of Dioxygen Reduction in a Phosphonium Cation-Based Room-Temperature Ionic Liquid: Quantitative Studies

Microelectrode voltammetry is used to study the electrochemical reduction of dioxygen, O-2, in the room-temperature ionic liquid trihexyl(tetradecyl)phosphonium trifluorotris(pentafluoroethyl)phosphate [P6,6,6,14][FAP]. The nature of the unusual voltammetric waves is quantitatively modeled via digital simulation with the aim of clarifying apparent inconsistencies in the literature. The reduction is shown to proceed via a two-electron reaction and involve the likely capture of a proton from the solvent system. The oxidative voltammetric signals seen at fast scan rates are interpreted as resulting from the reoxidation of HO2 center dot. In the presence of large amounts of dissolved carbon dioxide the reductive currents decrease by a factor of ca. two, consistent with the trapping of the superoxide radical, O-2(center dot), intermediate in the two-electron reduction process.

Robust Room Temperature Hysteresis in an FeIII Spin Crossover Metallomesogen

The high temperature magnetic and structural properties of an amphiphilic iron(III) spin crossover complex are reported. Thermal cycling reveals a scan rate-dependent 20 K thermal hysteresis in the mT vs. T data close to room temperature. A fast scan rate is essential for the hysteresis but it is robust and reproducible after multiple thermal cycles. Differential scanning calorimetry and cross polarized microscopy are used to show that the magnetic switching aligns with a material state change from solid to ordered liquid phase on warming.

Extraction of electrode kinetic parameters from microdisc voltammetric data measured under transport conditions intermediate between steady-state convergent and transient linear diffusion as typically applies to room temperature ionic liquids

The extraction of electrode kinetic parameters for electrochemical couples in room-temperature ionic liquids (RTILs) is currently an area of considerable interest. Electrochemists typically measure electrode kinetics in the limits of either transient planar or steady-state convergent diffusion for which the voltammetic response is well understood. In this paper we develop a general method allowing the extraction of this kinetic data in the region where the diffusion is intermediate between the planar and convergent limits, such as is often encountered in RTILs using microelectrode voltammetry. A general working surface is derived, allowing the inference of Butler-Volmer standard electrochemical rate constants for the peak-to-peak potential separation in a cyclic voltammogram as a function of voltage scan rate. The method is applied to the case of the ferrocene/ferrocenium couple in [C(2)mim][N(Tf)(2)] and [C(4)mim][N(Tf)(2)].

Electroreduction of Chlorine Gas at Platinum Electrodes in Several Room Temperature Ionic Liquids: Evidence of Strong Adsorption on the Electrode Surface Revealed by Unusual Voltammetry in Which Currents Decrease with Increasing Voltage Scan Rates

Voltammetry is reported for chlorine, Cl-2, dissolved in various room temperature ionic liquids using platinum microdisk electrodes. A single reductive voltammetric wave is seen and attributed to the two-electron reduction of chlorine to chloride. Studies of the effect of voltage scan rate reveal uniquely unusual behavior in which the magnitude of the currents decrease with increasing scan rates. A model for this is proposed and shown to indicate the presence of strongly adsorbed species in the electrode reaction mechanism, most likely chlorine atoms, Cl*((ads)).

A genome-wide linkage scan for genes controlling variation in urinary albumin excretion in type ll diabetes

The main hallmark of diabetic nephropathy is elevation in urinary albumin excretion. We performed a genome-wide linkage scan in 63 extended families with multiple members with type II diabetes. Urinary albumin excretion, measured as the albumin-to-creatinine ratio (ACR), was determined in 426 diabetic and 431 nondiabetic relatives who were genotyped for 383 markers. The data were analyzed using variance components linkage analysis. Heritability (h2) of ACR was significant in diabetic (h2=0.23, P=0.0007), and nondiabetic (h2=0.39, P=0.0001) relatives. There was no significant difference in genetic variance of ACR between diabetic and nondiabetic relatives (P=0.16), and the genetic correlation (rG=0.64) for ACR between these two groups was not different from 1 (P=0.12). These results suggested that similar genes contribute to variation in ACR in diabetic and nondiabetic relatives. This hypothesis was supported further by the linkage results.

Fast and frugal models of clinical judgement in novice and expert physicians

Our objective was to study whether “compensatory” models provide better descriptions of clinical judgment than fast and frugal models, according to expertise and experience. Fifty practitioners appraised 60 vignettes describing a child with an exacerbation of asthma and rated their propensities to admit the child. Linear logistic (LL) models of their judgments were compared with a matching heuristic (MH) model that searched available cues in order of importance for a critical value indicating an admission decision. There was a small difference between the 2 models in the proportion of patients allocated correctly (admit or not-admit decisions), 91.2% and 87.8%, respectively. The proportion allocated correctly by the LL model was lower for consultants than juniors, whereas the MH model performed equally well for both. In this vignette study, neither model provided any better description of judgments made by consultants or by pediatricians compared to other grades and specialties.

A Fast Nonlinear Model Identification Method

The identification of nonlinear dynamic systems using linear-in-the-parameters models is studied. A fast recursive algorithm (FRA) is proposed to select both the model structure and to estimate the model parameters. Unlike orthogonal least squares (OLS) method, FRA solves the least-squares problem recursively over the model order without requiring matrix decomposition. The computational complexity of both algorithms is analyzed, along with their numerical stability. The new method is shown to require much less computational effort and is also numerically more stable than OLS.

Triply differential single ionization cross sections in coplanar and non-coplanar geometry for fast heavy ion-atom collisions

We have performed a kinematically complete experiment and calculations on single ionization in 100 MeV/amu C6+ + He collisions. For electrons ejected into the scattering plane (defined by the initial and final projectile momentum vectors) our first- and higher-order calculations are in good agreement with the data. In the plane perpendicular to the scattering plane and containing the initial projectile axis a strong forward-backward asymmetry is observed. In this plane both the first-order and the higher-order calculations do not provide good agreement neither with the data nor amongst each other.

Total cross sections for transfer ionization in fast ion-helium collisions

The effects of electron correlation and second-order terms on theoretical total cross sections of transfer ionization in collisions of the helium atom with fast H+, He2+ and Li3+ ions are studied and reported. The total cross sections are calculated using highly correlated wavefunctions with expansion of the transition amplitude in the Born series through the second order. The results of these calculations are in sensible agreement with experimental data.