The aim of this study was to investigate the prevalence of psychological morbidity in the local secondary care population of people with type 1 diabetes or type 2 diabetes (T1DM or T2DM) in order to determine appropriate treatment provision. Four hundred patients seen in diabetes outpatient clinics were sent a number of standardised and validated questionnaires designed to measure: diabetes related distress; anxiety and depression; disordered eating behaviours; and borderline personality disorder. A response rate of 52.7% was achieved, providing a total of 211 completed questionnaires (111 T1DM, 100 T2DM) for analysis. This study has demonstrated a high prevalence of psychological morbidity in the local secondary care population of people with diabetes, with as many as half of those surveyed (52%) reporting some level of psychological disturbance. After controlling for age, gender and diabetes type, few differences in levels of psychological dysfunction were identified between the T1DM and T2DM cohorts. The exception to this was disinhibited eating behaviours: 22% of people with T2DM had severe levels of disinhibited eating, twice that recorded in the T1DM population. Overall, 36% (n=76) of study participants had moderate–severe levels of depression, anxiety or both, and 9.5% (16 of 168) had scores suggestive of borderline personality disorder. Copyright © 2010 John Wiley & Sons.

Abstract This chapter describes modification of platinum and some other noble metal electrodes for enhanced catalytic oxidation of methanol and formic acid. The modification was carried out by electrochemical addition of submonolayer‐to‐monolayer quantities of noble metals to noble metal substrates, with the primary focus on the use of spontaneous deposition. In contrast to underpotential deposition (UPD), the term noble metal deposition on noble metal substrates (NM/NM) is introduced to cover high reactivity model and real electrodes for fuel cells. We begin with providing a brief description of the basic mechanistic pathways for methanol and formic acid oxidative decomposition on platinum. Subsequently, we review the modified electrodes utilized for the study of methanol oxidation, such as platinum/ruthenium, platinum/osmium (and ruthenium/platinum for enhanced CO tolerance), and palladium/platinum and gold/palladium electrodes for formic acid oxidation. The Pt/Ru electrodes are reviewed most comprehensively as the Pt/Ru mixed‐metal materials are used as an anode in the direct oxidation methanol fuel cell. Despite progress recently made in the specific catalytic categories interrogated in this chapter, research is still needed to establish a solid and comprehensive base for preparation of new catalytic materials via the rational rather than trial and error principle; the latter has exhausted its utility many years ago.

Current national guidelines recommend hospitals treating ST-elevation myocardial infarction (STEMI) patients achieve a door-to-balloon (D2B) angioplasty time of less than 90 minutes. We have in place a myocardial infarction (MI) alert process where emergency physicians activate the cardiac catheterization (CC) team based on identified STEMI patients. In an effort to reduce D2B times we initiated an out-of-hospital Myocardial Infarction Alert 3 (MI-3) process where trained Emergency Medical Service (EMS) providers interpret a 12-lead electrocardiogram (ECG) in the field and notify the emergency physician allowing for earlier activation of the existing MI Alert process.

We provide an overview of structure and reactivity of selected bimetallic single crystal electrodes obtained by the method of spontaneous deposition. The surfaces that are described and compared are the following: Au(111)/Ru, Pt(111)/Ru and Pt(111)/Os. Detailed morphological information is presented and the significance of this work in current and further study of nanoisland covered surfaces in the catalytic and spectroscopic perspective is highlighted. All surfaces were investigated by in situ STM and by electroanalytical techniques. The results confirm our previous data that nanosized Ru islands are formed with specific and distinctive structural features, and that the Ru growth pattern is different for Au(111) and Pt(111). For Au(111), Ru is preferentially deposited on steps, while a random and relatively sparse distribution of Ru islands is observed on terraces. In contrast, for Ru deposited on Pt(111), a homogeneous deposition over all the Pt(111) surface was found. Os is also deposited homogeneously, and at a much higher rate than Ru, and even within a single deposition it forms a large proportion of multilayer islands. On Au(111), the Ru islands on both steps and terraces reach the saturation coverage within a short deposition time, and the Ru islands grow to multilayer heights and assume hexagonal shapes. On Pt(111), the Ru saturation coverage is reached relatively fast, but when a single deposition is applied, Ru nanoislands of mainly monoatomic height are formed, with the Ru coverage not exceeding 0.2 ML. For Ru deposits on Pt(111), we demonstrate that larger and multilayer islands obtained in two consecutive depositions can be reduced in size––both in height and width––by oxidizing the Ru islands and then by reducing them back to a metallic state. A clear increase in the Ru island dispersion is then obtained. However, methanol oxidation chronoamperometry shows that the surface with such a higher dispersion is less active to methanol oxidation than the initial surface. A preliminary interpretation of this effect is provided. Finally, we studied CO stripping reaction on Pt(111)/Ru, Au(111)/Ru and on Pt(111)/Os. We relate CO oxidation differences observed between Pt(111)/Ru and Pt(111)/Os to the difference in the oxophilicity of the two admetals. In turn, the difference in the CO stripping reaction on Pt(111)/Ru and Au(111)/Ru with respect to the Ru islands is linked to the effect of the substrate on the bond strength and/or adlayer structure of CO and OHads species.

We have examined the ruthenium island growth on Pt(111), Pt(100), and Pt(110) surfaces resulting from repeated spontaneous depositions of ruthenium from a 1 mM RuCl3 in 0.1 M HClO4 solution. Scanning tunneling microscopy and cyclic voltammetry were used to characterize the multiple depositions. We found that the details of the island growth were strongly single-crystal substrate dependent. On Pt(111), after four depositions, approximately 30–35% of the surface is covered with large (2–12 nm) ruthenium islands of varying heights. About 65% of the islands surface is a monolayer high, while 25% consists of two ruthenium layers and 10% consists of three monolayers or higher. However, it was revealed via STM imaging, that on Pt(100) and Pt(110), the two and three dimensional growth of the islands is much lower. It was possible to obtain 40% coverage of ruthenium on Pt(100) with 92% of the island area a monolayer high, while the island size ranged from 0.5–4 nm. On Pt(110), the tendency to grow in three dimensions is even less, as 98% of the islands peppering the surface are a monolayer high. These results are discussed as they pertain to possible use of additive island-covered nanoparticles in methanol oxidation fuel cell catalysis.

Spontaneous deposition of ruthenium on Au(111) surfaces from 1.0 mM RuCl3+0.5 M H2SO4 (or 0.1 M HClO4) solutions was investigated by in situ STM and cyclic voltammetry, focusing on the morphology of the resulting submonolayer Ru modified surfaces. STM results show a pronounced step decoration, indicating that the steps are active sites for the nucleation of Ru monolayer islands, while a random distribution of Ru nuclei is observed on terraces. During deposition, the open circuit potential rapidly increases from 0.38 to above 0.72 V vs. (Ag/AgCl). Experiments with different deposition times show that deposition from sulfuric acid solution saturates after 3 min deposition, the island size reaches its saturation value of 2.8 nm after 1 min. Significantly higher deposition activities and saturation coverages are found for deposition from perchlorate solution and for deposition on highly stepped surfaces/surface areas, indicative of a pronounced anion effect and reflecting the higher activity of steps for Ru deposition, respectively. In both cases, in particular for deposition in perchlorate solution, islands grow to multilayer heights and assume hexagonal shapes. Finally it is shown that multiple deposition can be utilized to reach higher coverages, attaining step saturation also in sulfuric acid solution. The Ru modified Au(111) electrode was found to be inert for hydrogen adsorption, and the electrochemical results indicate that the ruthenium islands inhibit long-range ordering of the sulfate adlayer on the substrate.

Ruthenium and osmium were deposited in submonolayer amounts on Pt(111) single crystal surfaces using the previously reported ‘spontaneous deposition’ procedure [Chrzanowski et al., Langmuir, 13 (1997) 5974]. Such surfaces were first explored using ex situ scanning tunneling microscopy (STM) to image the deposition characteristics of ruthenium and osmium islands on Pt(111). It was found that, using the spontaneous deposition procedure, a maximum coverage of 0.20ML ruthenium is formed on the surface after 120s of exposure to a RuCl3 solution in 0.1M HClO4. A homogeneous deposition on the Pt(111) surface was found, with no observed preferential deposition on step edges or surface defect sites. In contrast, in the spontaneous deposition of osmium, osmium clusters form preferentially at, though not limited to, surface defect sites and step edges. Osmium island deposition occurs at a greater rate than ruthenium on Pt(111), and possible explanations are presented. Methanol activity on the Pt(111)/Ru and Pt(111)/Os surfaces is also studied, using the coverage values determined to yield the highest activity for methanol electro-oxidation (0.20ML coverage for Ru and 0.15ML for Os). At potentials more negative than 0.40V vs. RHE, the Pt(111)/Ru surface yields a higher surface activity than Pt(111)/Os. However, at potentials more positive than 0.04V, Pt(111)/Os exhibits demonstrably higher surface activity. The relevance of this data is discussed and future avenues of interest are indicated.

Ruthenium and osmium were deposited in sub-monolayer amounts on Pt(100) and Pt(110) single crystal surfaces via spontaneous deposition and explored using scanning tunneling microscopy (STM) and cyclic voltammetry. The results were compared to previously published Pt(111) data to yield a comprehensive discussion of all low-index platinum surfaces modified by ruthenium and osmium. Ex-situ STM was utilized to image the deposition characteristics of ruthenium and osmium islands on Pt(hkl). The spontaneous deposition procedure yielded a maximum coverage of 0.22 and 0.10 monolayer of ruthenium on Pt(100) and Pt(110), respectively. Homogeneous deposition of ruthenium on the Pt(hkl) surfaces was observed without preferential deposition on step edges or surface defect sites. In contrast to the results with Pt/Ru, the spontaneous deposition of osmium yields osmium clusters preferentially (though not exclusively) at surface defect sites and step edges. Osmium island deposition occurs at a greater rate than ruthenium on all low index surfaces, and follows the same affinity as Ru; that is, deposition on Pt(100) is greater than Pt(111) which is greater than Pt(110). It was also determined that both ruthenium and osmium deposit in mainly mono-layer high islands on all three crystal faces.

We address some basic issues involved in catalytic activity for anode applications in the direct oxidation methanol fuel cell. We first report methanol oxidation data obtained with a Johnson-Matthey nanoparticle catalyst used both "as received" or processed by electrochemical reduction. Full chronoamperometric curves for the oxidation process that develop over a period of ca. 18 hours (until the current stabilizes) are presented. The steady-state currents depend on the extent of the catalyst electroreduction, are smaller than those previously obtained from the Pt(111)/Ru catalyst, but are significantly higher than from the Pt(100)/Ru surfaces. Next, polycrystalline platinum was used as a substrate onto which controlled amounts of ruthenium and osmium were deposited, and such prepared surfaces were used as the catalyst for methanol oxidation. Current densities obtained from all surfaces are critically compared. Apparently, osmium added to platinum is an enhancing element for the methanol oxidation process but at low potentials, advantageous for fuel cell use, osmium is less effective than ruthenium. The enhancing strength of osmium increases as the electrode potential increases and, at 0.6 V, nearly equals that of Pt/Ru. The significance of this observation with respect to the activity of the ternary Pt/Ru/Os catalyst for methanol oxidation is highlighted in the paper Conclusions. We also present preliminary STM data obtained on Pt single crystal surfaces deposited with various amounts of ruthenium, in order to examine the growth character of the deposits in the submonolayer regime of the deposition.

This is a comprehensive study in which a formic acid decomposition reaction is examined as a probe of catalytic properties of polycrystalline platinum and palladized platinum electrodes. The electrode potential varies in a broad range, and the reaction is carried out in perchloric acid and sulfuric acid solutions containing different concentrations of HCOOH. Analytical methods used to access the decomposition reaction are chronoamperometry and cyclic voltammetry. At very short times, we prove that only a negligible amount of surface CO is formed, and the CO unaffected decomposition reaction, leading to CO2 formation, can be interrogated. Surprisingly, the decomposition reaction displays Tafel behavior only in a very narrow potential range. This observation, made with both clean Pt and Pt/Pd electrodes, suggests that water-surface interactions, and/or (bi)sulfate-surface interactions, increase with increasing electrode potential and create a steric/electronic barrier for the decomposition of formic acid (and methanol, J. Phys. Chem. 1994, 98, 5074). We therefore offer a pessimistic view about platinum as a universal material for heterogeneous catalysis applications involving rearrangements of organic molecules. Such rearrangements may only be fulfilled with a low electrochemical driving force, at least at room temperature, but at higher potentials, the electrode becomes deactivated due to the unique attributes of the double layer structure on the platinum electrode. We have also found that the deceleration of formic acid oxidation (to CO2) is primarily due to CO chemisorption only at potentials overlapping with those from the hydrogen adsorption range, or not too positive from this range. At more positive potentials, the decay in formic acid decomposition is neither due to CO formation nor to solution mass transfer limitations. The presence of interfacial CO2 (J. Electroanal. Chem. 1994, 376, 151) or adsorption of formic acid and/or formate anion, could account for the decay. Finally, a detailed analysis of kinetic isotherms involved in the two pathways, CO2 formation and CO chemisorption, is made and the mechanism of formic acid decomposition on platinum is discussed. The electrolyte anion effects involved in formic acid oxidation in HClO4 and in H2SO4 solutions are also presented.