Exciton coherence lifetimes from electronic structure

We model the coherent energy transfer of an electronic excitation within covalently linked aromatic homodimers from first-principles, to answer whether the usual models of the bath calculated via detailed electronic structure calculations can reproduce the key dynamics. For these systems the timescales of coherent transport are experimentally known from time-dependent polarization anisotropy measurements, and so we can directly assess the whether current techniques might be predictive for this phenomenon. Two choices of electronic basis states are investigated, and their relative merits discussed regarding the predictions of the perturbative model. The coupling of the electronic degrees of freedom to the nuclear degrees of freedom is calculated rather than assumed, and the fluorescence anisotropy decay is directly reproduced. Surprisingly we find that although TDDFT absolute energies are routinely in error by orders of magnitude more than the coupling energy, the coherent transport properties of these dimers can be semi-quantitatively reproduced from first-principles. The directions which must be pursued to yield predictive and reliable prediction of coherent transport are suggested.Comment: 22 pages, 7 figure

Dendrimer-Encapsulated Nanoparticle Precursors to Supported Platinum Catalysts

In this contribution, we report the successful preparation of supported metal catalysts using dendrimer-encapsulated Pt nanoparticles as metal precursors. Polyamidoamine (PAMAM) dendrimers were first used to template and stabilize Pt nanoparticles prepared in solution. These dendrimer-encapsulated nanoparticles were then deposited onto a commercial high surface area silica support and thermally activated to remove the organic dendrimer. The resulting materials are active oxidation and hydrogenation catalysts. The effects of catalyst preparation and activation on activity for toluene hydrogenation and CO oxidation catalysis are discussed

Patterning High Surface Area Silica with Lysozyme: Adsorption Kinetics, Fluorescence Quenching, and Protein Readsorption Studies To Evaluate the Templated Surface

A method was developed for using an inexpensive and widely available protein, hen egg white lysozyme, as a patterning agent for commercial high surface area silicas. The basic patterning methodology involved spontaneous adsorption of the protein from aqueous solution, alkylation of the uncovered surface with an alkylsiloxane, and protein desorption in a slightly alkaline solution of morpholine. Adsorption kinetic studies using Bradford assays assisted in determining protein deposition conditions. These studies were generally consistent with results on more planar silica surfaces and indicated that the protein quickly and strongly adsorbs along its long axis at low surface coverages. A modified fluorescence resonance energy transfer (FRET) technique was developed and employed to evaluate protein spacing. This technique showed that the proteins are well dispersed at low coverages. Readsorption experiments show that the templated regions are robust, retaining the size and shape of the original protein templates

Physiological, haematological and performance characteristics of ultra endurance cyclists competing in the inaugural race around Ireland

Ultra-endurance events are a growing area within the sport of cycling. The Race Around Ireland (RAI) is a non-stop event where cyclists must complete the 2,170km route in under 96 hours. Purpose: The purpose of this study was to investigate the physiological, haematological and performance characteristics of members of a 4 man team before, during, and after the RAI. Methods: Four trained male cyclists were tested on 2 separate occasions within a 14 day period, with the second bout of testing performed within 7 days of the start of the race, to determine baseline values. Each cyclist completed a maximal incremental test on an electromagnetically braked cycle ergometer, commencing at 100W and increasing in intensity by 50W every 3 minutes until volitional exhaustion. Heart rate, VO2, power output and blood lactate were measured during the test. Following a standardized recovery period, each cyclist then completed a 20 minute maximal performance test (MPT) designed to mimic the demands of the RAI. Baseline blood samples were taken prior to each testing session to facilitate a detailed haematological analysis. Blood samples were also taken before the start of the race, at set intervals during the race, as well as on the race completion. Subjects were also weighed and urine samples collected at the same time points in order to assess hydration status using urine specific gravity (Usg). Further testing was carried out 7 days (haematology), and 14 days (haematology and MPT) post race. Results: No significant differences were found between the MPT results pre and post race. Significant differences were found for white blood cells (WBC) and granulocyte count (p<0.01), haematocrit, haemoglobin, lymphocytes, and red blood cells (p<0.05). No significant difference was observed for changes in body mass or Usg. Conclusions: Variations in WBC and other immune function markers showed initial decrease followed by a gradual elevation during the race. However this did not seem have an impact on the post race MPT. Although there appears to be a significant change in immune function during ultra endurance cycling, this may not lead to a subsequent performance decrement. However, analysis may be complicated by the specific race tactics adopted by the team during the race and the time course of post race assessment

Unstable decay and state selection II

The decay of unstable states when several metastable states are available for occupation is investigated using path-integral techniques. Specifically, a method is described which allows the probabilities with which the metastable states are occupied to be calculated by finding optimal paths, and fluctuations about them, in the weak noise limit. The method is illustrated on a system described by two coupled Langevin equations, which are found in the study of instabilities in fluid dynamics and superconductivity. The problem involves a subtle interplay between non-linearities and noise, and a naive approximation scheme which does not take this into account is shown to be unsatisfactory. The use of optimal paths is briefly reviewed and then applied to finding the conditional probability of ending up in one of the metastable states, having begun in the unstable state. There are several aspects of the calculation which distinguish it from most others involving optimal paths: (i) the paths do not begin and end on an attractor, and moreover, the final point is to a large extent arbitrary, (ii) the interplay between the fluctuations and the leading order contribution are at the heart of the method, and (iii) the final result involves quantities which are not exponentially small in the noise strength. This final result, which gives the probability of a particular state being selected in terms of the parameters of the dynamics, is remarkably simple and agrees well with the results of numerical simulations. The method should be applicable to similar problems in a number of other areas such as state selection in lasers, activationless chemical reactions and population dynamics in fluctuating environments.Comment: 28 pages, 6 figures. Accepted for publication in Phys. Rev.

Intelligence quotient–adjusted memory impairment is associated with abnormal single photon emission computed tomography perfusion

Cognitive reserve among highly intelligent older individuals makes detection of early Alzheimer's disease (AD) difficult. We tested the hypothesis that mild memory impairment determined by IQ-adjusted norms is associated with single photon emission computed tomography (SPECT) perfusion abnormality at baseline and predictive of future decline. Twenty-three subjects with a Clinical Dementia Rating (CDR) score of 0, were reclassified after scores were adjusted for IQ into two groups, 10 as having mild memory impairments for ability (IQ-MI) and 13 as memory-normal (IQ-MN). Subjects underwent cognitive and functional assessments at baseline and annual follow-up for 3 years. Perfusion SPECT was acquired at baseline. At follow-up, the IQ-MI subjects demonstrated decline in memory, visuospatial processing, and phonemic fluency, and 6 of 10 had progressed to a CDR of 0.5, while the IQ-MN subjects did not show decline. The IQ-MI group had significantly lower perfusion than the IQ-MN group in parietal/precuneus, temporal, and opercular frontal regions. In contrast, higher perfusion was observed in IQ-MI compared with IQ-MN in the left medial frontal and rostral anterior cingulate regions. IQ-adjusted memory impairment in individuals with high cognitive reserve is associated with baseline SPECT abnormality in a pattern consistent with prodromal AD and predicts subsequent cognitive and functional decline