In-situ FT-IR spectroscopic studies of fuel cell electro-catalysis: From single-crystal to nanoparticle surfaces

The work presented in this article shows the power of the variable temperature, in-situ FT-IR spectroscopy system developed in Newcastle with respect to the investigation of fuel cell electro-catalysis. On the Ru(0001) electrode surface, CO co-adsorbs with the oxygen-containing adlayers to form mixed [CO+(2x2)-O(H)] domains. The electro-oxidation of the Ru(0001) surface leads to the formation of active (1x1)-O(H) domains, and the oxidation of adsorbed CO then takes place at the perimeter of these domains. At 20 degrees C, the adsorbed CO is present as rather compact islands. In contrast, at 60 degrees C, the COads is present as a relatively looser and weaker adlayer. Higher temperature was also found to facilitate the surface diffusion and oxidation of COads. No dissociation or electro-oxidation of methanol was observed at potentials below approximately 950mV; however, the Ru(0001) surface at high anodic potentials was observed to be very active. On both Pt and PtRu nanoparticle surfaces, only one linear bond CO adsorbate was formed from methanol adsorption, and the PtRu surface significantly promoted both methanol dissociative adsorption to CO and its further oxidation to CO2. Increasing temperature from 20 to 60 degrees C significantly facilitates the methanol turnover to CO2.

Susceptibility to stress corrosion cracking of NiTi laser weldment in Hanks’ solution

In this study, the susceptibility to stress corrosion cracking (SCC) of laser-welded NiTi wires in Hanks’ solution at 37.5 °C was studied by the slow strain-rate test (SSRT) at open-circuit potential and at different applied anodic potentials. The weldment shows high susceptibility to SCC when the applied potential is near to the pitting potential of the heat-affected zone (HAZ). The pits formed in the HAZ become sites of crack initiation when stress is applied, and cracks propagate in an intergranular mode under the combined effect of corrosion and stress. In contrast, the base-metal is immune to SCC under similar conditions. The increase in susceptibility to SCC in the weldment could be attributed to the poor corrosion resistance in the coarse-grained HAZ.

Determining the electronic structure and chemical potentials of molecules in solution

A simulation scheme is proposed for determining the excess chemical potential of a substance in solution. First, a Monte Carlo simulation is performed with classical models for solute and solvent molecules. A representative sample of these configurations is then used in a hybrid quantum/classical (QM/MM) calculation, where the solute is treated quantum-mechanically, and the average electronic structure is used to construct an improved classical model. This procedure is iterated to self-consistency in the classical model, which in practice is attained in one or two steps, depending on the quality of the initial guess. The excess free energy of the molecule within the QM/MM approach is determined relative to the classical model using thermodynamic perturbation theory with a cumulant expansion. The procedure provides a method of constructing classical point charge models appropriate for the solution and gives a measure of the importance of solvent fluctuations.

Electrochemical oxidation of nitrite and the oxidation and reduction of NO2 in the room temperature ionic liquid [C(2)mim][NTf2]

The electrochemical oxidation of potassium nitrite has been studied in the room temperature ionic liquid (RTIL) [C(2)mim][NTf2] by cyclic voltammetry at platinum electrodes. A chemically irreversible oxidation peak was observed, and a solubility of 7.5(+/- 0.5) mM and diffusion coefficient of 2.0(+/- 0.2) x 10(-11) m(2) s(-1) were calculated from potential step chronoamperometry on the microdisk electrode. A second, and sometimes third, oxidation peak was also observed when the anodic limit was extended, and these were provisionally assigned to the oxidation of nitrogen dioxide (NO2) and nitrate (NO3-), respectively. The electrochemical oxidation of nitrogen dioxide gas (NO2) was also studied by cyclic voltammetry in [C(2)mim][NTf2] on Pt electrodes of various size, giving a solubility of ca. 51(+/- 0.2) mM and diffusion coefficient of 1.6(+/- 0.05) x 10(-10) m(2) s(-1) (at 25 degrees C). It is likely that NO2 exists predominantly as its dimer, N2O4, at room temperature. The oxidation mechanism follows a CE process, which involves the initial dissociation of the dimer to the monomer, followed by a one-electron oxidation. A second, larger oxidation peak was observed at more positive potentials and is thought to be the direct oxidation of N2O4. In addition to understanding the mechanisms of NO2- and NO2 oxidations, this work has implications in the electrochemical detection of nitrite ions and of NO2 gas in RTIL media, the latter which may be of particular use in gas sensing.

Movement-related potentials in high-functioning autism and Asperger's disorder

Autism and Asperger's disorder (AD) are neurodevelopmental conditions that affect cognitive and social-communicative function. Using a movement-related potential (MRP) paradigm, we investigated the clinical and neurobiological issue of 'disorder separateness' versus 'disorder variance' in autism and AD. This paradigm has been used to assess basal ganglia/supplementary motor functioning in Parkinson's disease. Three groups (high functioning autism [HFA]: 16 males, 1 female; mean age 12y 5mo [SD 4y 4mo]; AD: 11 males, 2 females; mean age 13y 5mo [SD 3y 8mo]; comparison group: 13 males, 8 females; mean age 13y 10mo, [SD 3y 11 mo]) completed a cued motor task during electroencephalogram recording of MRPs. The HFA group showed reduced peak amplitude at Cz, indicating less activity over the supplementary motor area during movement preparation. Although an overall significant between-group effect was found for early slope and peak amplitude, subanalysis revealed that the group with AD did not differ significantly from either group. However, it is suggested that autism and AD may be dissociated on the basis of brain-behaviour correlations of IQ with specific neurobiological measures. The overlap between MRP traces for autism and Parkinson's disease suggests that the neurobiological wiring of motor functioning in autism may bypass the supplementary motor area/primary motor cortex pathway.

Effect of an attentional strategy on movement-related potentials recorded from subjects with Huntington's disease

Huntington's disease patients perform automatic movements in a bradykinetic manner, somewhat similar to patients with Parkinson's disease. Cortical activity relating to the preparation of movement in Parkinson's disease is significantly improved when a cognitive strategy is used. It is unknown whether patients with Huntington's disease can utilise an attentional strategy, and what effect this strategy would have on the premovement cortical activity. Movement-related potentials were recorded from 12 Huntington's disease patients and controls performing externally cued finger tapping movement, allowing an examination of cortical activity related to movement performance and bradykinesia in this disease. All subjects were tested in two conditions, which differed only by the presence or absence of the cognitive strategy. The Huntington's disease group, unlike controls, did not produce a rising premovement potential in the absence of the strategy. The Huntington's disease group did produce a rising premovement potential for the strategy condition, but the early slope of the potential was significantly reduced compared with the control group's early slope. These results are similar to those found previously with Parkinson's disease patients. The strategy may have put the task, which previously might have been under deficient automatic control, under attentional control. (C) 2002 Movement Disorder Society.

Movement-related potentials in Huntington's disease: movement preparation and execution

Movement-related potentials (MRPs) reflect increasing cortical activity related to the preparation and execution of voluntary movement. Execution and preparatory components may be separated by comparing MRPs recorded from actual and imagined movement. Imagined movement initiates preparatory processes, but not motor execution activity. MRPs are maximal over the supplementary motor area (SMA), an area of the cortex involved in the planning and preparation of movement. The SMA receives input from the basal ganglia, which are affected in Huntington's disease (HD), a hyperkinetic movement disorder. In order to further elucidate the effects of the disorder upon the cortical activity relating to movement, MRPs were recorded from ten HD patients, and ten age-matched controls, whilst they performed and imagined performing a sequential button-pressing task. HD patients produced MRPs of significantly reduced size both for performed and imagined movement. The component relating to movement execution was obtained by subtracting the MRP for imagined movement from the MRP for performed movement, and was found to be normal in HD. The movement preparation component was found by subtracting the MRP found for a control condition of watching the visual cues from the MRP for imagined movement. This preparation component in HD was reduced in early slope, peak amplitude, and post-peak slope. This study therefore reported abnormal MRPs in HD. particularly in terms of the components relating to movement preparation, and this finding may further explain the movement deficits reported in the disease.

Effect of Water on the Electrochemical Window and Potential Limits of Room-Temperature Ionic Liquids

The effect of water content on room-temperature ionic liquids (RTILs) was studied by Karl Fischer titration and cyclic voltammetry in the following ionic liquids: tris(P-hexyl)tetradecylphosphonium trifluorotris(pentafluoroethyl)phosphate [P-14,P-6,P-6,P-6][NTf2], N-butyl-N-methyl-pyrrolidinium bis(trifluoromethylsulfonyl)imide [C(4)mpyrr][NTf2], 1-hexyl-3-methylimidazolium tris(perfluoroethyl)trifluorophosphate [C(6)mim][FAP], 1-butyl3-methylimidazolium bis(trifluoromethylsulfonyl)imide [C(4)mim][NTf2], 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [C(4)dmim][NTf2], N-hexyltriethylammonium bis(trifluoromethylsolfonyl)imide [N-6,N-2,N-2,N-2][NTf2], 1-butyl-3-methylirnidazolium hexafluorophosphate [C(4)mim][PF6], F6], 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [C(2)mim][NTf2], 1-butyl-3-methylimidazolium tetrafluoroborate [C(4)mim][BF4], 1-hexyl-3-methylimidazolium iodide [C(4)mim][I], 1-butyl-3-methylimidazolium trifluoromethylsulfonate [C(4)mim][OTf], and 1-hexyl-3-methylimidazolium chloride [C(6)mim][Cl]. In addition, electrochemically relevant properties such as viscosity, conductivity, density, and melting point of RTILs are summarized from previous literature and are discussed. Karl Fisher titrations were carried out to determine the water content of RTILs for vacuum-dried, atmospheric, and wet samples. The anion in particular was found to affect the level of water uptake. The hydrophobicity of the anions adhered to the following trend: [FAP](-) > [NTf2](-) > [PF6](-) > [BF4](-) > halides. Cyclic voltammetry shows that an increase in water content significantly narrows the electrochemical window of each ionic liquid. The electrochemical window decreases in the following order: vacuum-dried > atmospheric > wet at 298 K > 318 K > 338 K. The anodic and cathodic potentials vs ferrocene internal reference are also listed under vacuum-dried and atmospheric conditions. The data obtained may aid the selection of a RTIL for use as a solvent in electrochemical applications.

Lowest energy potentials of Li2 + F accessible at ultracold temperatures

Ab initio calculations for the strongly exoergic Li2+F harpoon reaction are presented using density-functional theory, complete active space self-consistent field, and multireference configuration interaction methods to argue that this reaction would be an ideal candidate for investigation with ultracold molecules. The lowest six states are calculated with the aug-correlation-consistent polarized valence triple-zeta basis set and at least two can be accessed by a ground rovibronic Li2 molecule with zero collision energy at all reaction geometries. The large reactive cross section (characteristic of harpoon reactions) and chemiluminescent products are additional attractive features of these reactions.

N1, P2 and T-complex of the auditory brain event-related potentials to tones with varying rise times in adults with and without dyslexia

Dyslexia is a learning difficulty affecting the acquisition of fluent reading and spelling skills due to poor phonological processing. Underlying deficits in processing sound rise time have also been found in children and adults with dyslexia. However, the neural basis for these deficits is unknown. In the present study event-related potentials were used to index neural processing and examine the effect of rise time manipulation on the obligatory N1. T-complex and P2 responses in English speaking adults with and without dyslexia. The Tb wave of the T-complex showed differences between groups, with the amplitudes for Tb becoming less negative with increased rise time for the participants with dyslexia only. Frontocentral N1 and P2 did not show group effects. Enhanced Tb amplitude that is modulated by rise time could indicate altered neural networks at the lateral surface of the superior temporal gyrus in adults with dyslexia. (C) 2011 Elsevier B.V. All rights reserved.