What Stick Figures Tell Us about Irish Politics

This paper forms part of an ongoing research project using the technique of freehand drawing to study how students entering university in Ireland perceive the state of Irish politics and the wider society. By sidestepping the cognitive verbal processing routes through the use of freehand drawing, we find that students tend to present a more holistic, integrated and clearer understanding of the pertinent issues from their perspective

UK political elite networks are formed early in life and inspecific fee-paying schools

What accounts for political elite formation in the UK? And what are the implications for democracy? Here, Brendan O’Rourke, John Hogan, and Paul F. Donnelly use a new ‘Institutional Influence Index’ to demonstrate the validity of the widely-held view that elite formation takes place early in life, and in specific fee-paying private schools such as Eton and Harrow

Electrochemically tuneable multi-colour electrochemiluminescence using a single emitter

A single starting component electrochemiluminescence system from which red, green, blue or white emission can be obtained, depending on the applied potential or the mode of the ECL experiment, is described. The convoluted ECL spectral responses observed at different potentials are readily explained using a 3D-ECL technique, where the ECL spectral profile is continuously monitored as a function of potential during voltammetric scanning. The 3D plots obtained using this technique implicate cross-annihilation ECL reactions involving the complex itself and stable products resulting from its electrolysis. Combining this information with knowledge of the energetic requirements of the various reactions involved, suggests a mechanism involving traces of two emissive products, related to the loss of a methyl group from the triazole moiety. These products, while barely detectable electrochemically, are sufficiently emissive to influence and even dominate the ECL emission under some conditions

Geographic Variation in Antidiabetic Agent Adherence and Glycemic Control Among Patients with Type 2 Diabetes

BACKGROUND: Medication nonadherence is an imperative public health concern. Among patients with type 2 diabetes mellitus (T2DM), poor adherence to antidiabetic agents is strongly associated with suboptimal glycemic control. Poor adherence and hyperglycemia greatly increase diabetes-related morbidity and mortality. At a national level, diabetes drug adherence using average proportion of days covered (PDC) is estimated to range between 36% and 81%, with an estimated range for diabetes control between 38% and 47%. At a state level no such studies exist. OBJECTIVE: To estimate the level of medication adherence to antidiabetic agents and of diabetes control, and their association among patients with T2DM receiving medication treatment at the state and the Metropolitan Statistical Area (MSA) levels among the populations covered by commercial insurance, Medicare, or Medicaid. METHODS: The study population included adults with T2DM aged ≥ 18 years who were identified using ICD-9-CM code 250.xx, who received diabetes medication, and who were covered by private insurance, Medicare, or Medicaid in each state, the District of Columbia, and the top 50 MSAs. Medication adherence was measured by average PDC and the percentage of population that had a PDC ≥ 80%. Diabetes control was identified using ICD-9-CM diagnosis codes. Patients who were not diagnosed with uncontrolled diabetes (250.x2 and 250.x3) were identified as being under control. The administrative claims databases used for this study included the 2012 medical and pharmacy claims from a large U.S. health plan, the complete 2011 Medicare Standard Analytical File linked with Part D claims, and the 2008 Mini-Medicaid Analytic eXtract (Mini-Max). Medication adherence and diabetes control were adjusted for age and sex to allow comparison across insurance coverage, states, and MSAs. RESULTS: For an insured patient population with T2DM that received diabetic drug treatment, average PDC was 79%. However, 35% of patients did not achieve an adherence of at least 80% of PDC. In addition, at least 40% of patients did not have their diabetes under control. Across insurance types, we found that patients insured with Medicare had relatively high average PDC and adherence levels (83% and 71%) in comparison with the commercially insured population (77% and 60%) and Medicaid patients (75% and 57%). In contrast, commercially insured patients had relatively better diabetes control (69%) than those insured with Medicare and Medicaid (54% and 53%, respectively). At a state level, we found that commercially insured and Medicare populations have relatively smaller geographic variation in drug adherence than the Medicaid population. CONCLUSIONS: This study identified gaps in T2DM drug adherence and pinpointed geographic areas that lag in terms of diabetes drug adherence or diabetes control and would benefit from implementing strategies to increase drug adherence

Chemiluminescence from reactions with bis-cyclometalated iridium complexes in acidic aqueous solution

Chemical reactions between certain bis-cyclometalated iridium complexes, cerium(IV) and organic reducing agents in aqueous solution produce an emission of light which in some cases is more intense than that from analogous reactions with conventional ruthenium-based reagents, thus providing a new avenue for chemically-initiated luminescence detection.<br /

Simultaneous control of spectroscopic and electrochemical properties in functionalised electrochemiluminescent tris(2,2\u27-bipyridine)ruthenium(II) complexes

Using a combination of electrochemical, spectroscopic and computational techniques, we have explored the fundamental properties of a series of ruthenium diimine complexes designed for coupling with other molecules or surfaces for electrochemiluminescence (ECL) sensing applications. With appropriate choice of ligand functionality, it is possible to manipulate emission wavelengths while keeping the redox ability of the complex relatively constant. DFT calculations show that in the case of electron withdrawing substituents such as ester or amide, the excited state is located on the substituted bipyridine ligand whereas in the case of alkyl functionality it is localised on a bipyridine. The factors that dictate annihilation ECL efficiency are interrelated. For example, the same factors that determine &Delta;G for the annihilation reaction (i.e. the relative energies of the HOMO and LUMO) have a corresponding effect on the energy of the excited state product. As a result, most of the complexes populate the excited state with an efficiency (&Phi;ex) of close to 80% despite the relatively wide range of emission maxima. The quantum yield of emission (&Phi;p) and the possibility of competing side reactions are found to be the main determinants of ECL intensity

Chemiluminescence from osmium(ii) complexes with phenanthroline, diphosphine and diarsine ligands

The reaction of various [Os(L)2(L&prime;)]2+ complexes (where L and L&prime; are phenanthroline, diphosphine or diarsine ligands) and organic reducing agents after chemical or electrochemical oxidation of the reactants produces an emission of light corresponding to MLCT transitions. In certain instances, the emission was greater than that of [Ru(bipy)3]2+, but the relative signals were dependent on many factors, including reagent concentration, mode of oxidation, reducing agent and the sensitivity of the photodetector over the wavelength range

Reagentless Electrochemiluminescence from a Nanoparticulate Polymer of Intrinsic Microporosity (PIM-1) Immobilized onto Tin-Doped Indium Oxide

In contrast to most common electrochemiluminescence (ECL) techniques that require either an additional reagent or continuous pulsing between oxidative and reductive potentials, here a fluorescent polymer of intrinsic microporosity (PIM-1) is shown to exhibit intrinsic ECL without the need for a co-reactant at positive applied potentials and as a function of pH. PIM-1 is known to possess high microporosity (based on its rigid and contorted molecular structure) and excellent fluorescence properties. By depositing a nanoparticulate form of the PIM-1 material onto tin-doped indium oxide, we achieve a hierarchically porous deposit with good sustained ECL activity in aqueous media. The mechanism for this reagentless ECL is suggested to be linked to reactive oxygen species produced at positive potentials and discussed in terms of potential analytical applications.EPSRC [EP/K004956/1, EP/K008102/2]SCI(E)[email protected]

New perspectives on the annihilation electrogenerated chemiluminescence of mixed metal complexes in solution

Preliminary explorations of the annihilation electrogenerated chemiluminescence (ECL) of mixed metal complexes have revealed opportunities to enhance emission intensities and control the relative intensities from multiple luminophores through the applied potentials. However, the mechanisms of these systems are only poorly understood. Herein, we present a comprehensive characterisation of the annihilation ECL of mixtures of tris(2,2&prime;-bipyridine)ruthenium(ii) hexafluorophosphate ([Ru(bpy)3](PF6)2) and fac-tris(2-phenylpyridine)iridium(iii) ([Ir(ppy)3]). This includes a detailed investigation of the change in emission intensity from each luminophore as a function of both the applied electrochemical potentials and the relative concentrations of the two complexes, and a direct comparison with two mixed (Ru/Ir) ECL systems for which emission from only the ruthenium-complex was previously reported. Concomitant emission from both luminophores was observed in all three systems, but only when: (1) the applied potentials were sufficient to generate the intermediates required to form the electronically excited state of both complexes; and (2) the concentration of the iridium complex (relative to the ruthenium complex) was sufficient to overcome quenching processes. Both enhancement and quenching of the ECL of the ruthenium complex was observed, depending on the experimental conditions. The observations were rationalised through several complementary mechanisms, including resonance energy transfer and various energetically favourable electron-transfer pathways