Redox behaviour of thermally activated platinum electrodes with particular reference to operation at elevated temperature

The present work is a continuation of an earlier investigation of the effect of severe thermal pretreatment on the redox properties of platinum electrodes in aqueous media. The most interesting observation was that raising the solution temperature to ca. 75 °C resulted in a dramatic anodic response in the positive sweep at ca. 0.25 V (RHE). Such behaviour was noted earlier at room temperature but only when the thermally pretreated sample was further activated by cathodic polarization. This transition at 0.25 V was partially reversed on the negative sweep, but the cathodic process involved was subject to severe inhibition. There is independent evidence for similar behaviour for gold in aqueous acid solution. The relevance of the present results to the operation of fuel cell anodes is outlined. Received: 2 December 1999 / Accepted: 24 February 2000     

Spectral conditioning and pseudospectral growth

Using the language of pseudospectra, we study the behavior of matrix eigenvalues under two scales of matrix perturbation. First, we relate Lidskii’s analysis of small perturbations to a recent result of Karow on the growth rate of pseudospectra. Then, considering larger perturbations, we follow recent work of Alam and Bora in characterizing the distance from a given matrix to the set of matrices with multiple eigenvalues in terms of the number of connected components of pseudospectra. J. V. Burke’s research was supported in part by National Science Foundation Grant DMS-0505712. A. S. Lewis’s research was supported in part by National Science Foundation Grant DMS-0504032. M. L. Overton’s research was supported in part by National Science Foundation Grant DMS-0412049.     

Determination of the ratior v =d v u v of the valence quark distributions in the proton from neutrino and antineutrino reactions on hydrogen and deuterium

Zeitschrift für Physik C Particles and Fields - A set of proton longitudinal polarized distributions, worked out under the assumption of small gluon polarization, is used to evaluate several...     

Solving Examination Timetabling Problems through Adaption of Heuristic Orderings

Heuristic ordering based methods, very similar to those used for graph colouring problems, have long been applied successfully to the examination timetabling problem. Despite the success of these methods on real life problems, even with limited computing resources, the approach has the fundamental flaw that it is only as effective as the heuristic that is used. We present a method that adapts to suit a particular problem instance “on the fly.” This method provides an alternative to existing forms of ‘backtracking,’ which are often required to cope with the possible unsuitability of a heuristic. We present a range of experiments on benchmark problems to test and evaluate the approach. In comparison to other published approaches to solving this problem, the adaptive method is more general, significantly quicker and easier to implement and produces results that are at least comparable (if not better) than the current state of the art. We also demonstrate the level of generality of this approach by starting it with the inverse of a known good heuristic, a null ordering and random orderings, showing that the adaptive method can transform a bad heuristic ordering into a good one.     

An investigation of the electrochemical responses of superactivated gold electrodes in alkaline solution

It is now well established that gold, in the form of oxide-supported microparticles or even as conventional macroelectrodes, displays inexplicably high catalytic activity for some reactions. In the present work, gold surfaces were superactivated by a combination of thermal and cathodic pretreatment and such electrodes in base yielded up to five distinct, and quite marked, premonolayer oxidation responses within the double layer region, over the range 0.0–1.0 V (RHE). As outlined in earlier publications, such unusual behaviour is important from an electrocatalytic (and heterogeneous catalysis) viewpoint. A new mode of active site adsorption, involving highly localized electron transfer from active surface atoms to either the external circuit (in electrocatalysis) or an adsorbing reactant (in heterogeneous catalysis), is proposed. Such localized (active site) adsorption, which is based on surface quantum confinement effects, is virtually independent of (or only indirectly related to) the electronic properties of the bulk metal.     

Selective Activation of C=C Bond in Sustainable Phenolic Compounds from Lignin via Photooxidation: Experiment and Density Functional Theory Calculations

Lignocellulosic biomass can be converted to high‐value phenolic compounds, such as food additives, antioxidants, fragrances and fine chemicals. We investigated photochemical and heterogeneous photocatalytic oxidation of two isomeric phenolic compounds from lignin, isoeugenol and eugenol, in several nonprotic solvents, for the first time by experiment and the density functional theory (DFT) calculations. Photooxidation was conducted under ambient conditions using air, near‐UV light and commercial P25 TiO₂ photocatalyst, and the products were determined by TLC, UV–Vis absorption spectroscopy, HPLC‐UV and HPLC‐MS. Photochemical and photocatalytic oxidation of isoeugenol proceeds via the mild oxidative “dimerization” to produce the lignan dehydrodiisoeugenol (DHDIE), while photooxidation of eugenol does not proceed. The DFT calculations suggest a radical stepwise mechanism for the oxidative “dimerization” of isoeugenol to DHDIE as was calculated for the first time.     

Epi-convergence Properties of Smoothing by Infimal Convolution

This paper concerns smoothing by infimal convolution for two large classes of functions: convex, proper and lower semicontinous as well as for (the nonconvex class of) convex-composite functions. The smooth approximations are constructed so that they epi-converge (to the underlying nonsmooth function) and fulfill a desirable property with respect to graph convergence of the gradient mappings to the subdifferential of the original function under reasonable assumptions. The close connection between epi-convergence of the smoothing functions and coercivity properties of the smoothing kernel is established.     

Familial aggregation of early-onset myocardial infarction

Although ischemic heart disease tends to cluster in families, previous studies have reported a modest (2-fold increased risk) to strong (10-fold increased risk) contribution of family history to the explanation of disease occurrence. The authors assessed the familial aggregation of early-onset myocardial infarction in 11,307 adults aged <65 years who participated in the Third National Health and Nutrition Examination Survey. Logistic regression was used to obtain odds ratios (ORs) and 95% confidence intervals (CIs). A parental history was more common in those with (n = 237) than in those without (n = 11,070) a myocardial infarction (19.8 vs. 7.9%, p < or = 0.01). Adults with a parental history were also more likely to have multiple risk factors for cardiovascular disease (OR for four or five risk factors compared with none: 2.9, 95% CI: 1.4, 6.3). After multivariate adjustment, the likelihood of myocardial infarction was more than three times greater among adults with a parental history than among those without (95% CI: 1.7, 6.7). A maternal history of myocardial infarction was strongly associated (OR = 6.1, 95% CI: 2.1, 17.4) with an increased likelihood of myocardial infarction, and a paternal history was associated with a 3-fold (95% CI: 1.5, 6.3) increased likelihood of myocardial infarction after adjustment for cardiovascular disease risk factors. These results suggest a familial aggregation of early-onset myocardial infarction and show that family history is strongly associated with cardiovascular disease risk factors.     

Genetics in primary care: a USA faculty development initiative

The Genetics in Primary Care (GPC) project is a USA national faculty development initiative with the goal of enhancing the training of medical students and primary care residents by developing primary care faculty expertise in genetics. Educational strategies were developed for the project by an executive committee with input from an advisory committee, comprising individuals with primary care, medical education and genetics expertise. These committees identified the key issues in genetics education for primary care as (1) considering inherited disease in the differential diagnosis of common disorders; (2) using appropriate counseling strategies for genetic testing and diagnosis, and (3) understanding the implications of a genetic diagnosis for family members. The group emphasized the importance of a primary care perspective, which suggests that the clinical utility of genetic information is greatest when it has the potential to improve health outcomes. The group also noted that clinical practice already incorporates the use of family history information, providing a basis for discussing the application of genetic concepts in primary care. Genetics and primary care experts agreed that educational efforts will be most successful if they are integrated into existing primary care teaching programs, and use a case-based teaching format that incorporates both clinical and social dimensions of genetic disorders. Three core clinical skills were identified: (1) interpreting family history; (2) recognizing the variable clinical utility of genetic information, and (3) acquiring cultural competency. Three areas of potential controversy were identified as well: (1) the role of nondirective counseling versus shared decision-making in discussions of genetic testing; (2) the intrinsic value of genetic information when it does not influence health outcomes, and (3) indications for a genetics referral. The project provides an opportunity for ongoing discussion about these important issues.