Bio-Inspired Artificial Light-Harvesting Arrays Based on Boron(III)-Chelates

Many diverse natural systems use sunlight to drive critical chemical reactions. To harvest sufficient photon densities, natural organisms have developed highly sophisticated light absorbing antennae rather than rely on direct illumination of a single chromophore. Attempts to develop artificial analogues have resulted in the synthesis and spectroscopic characterisation of elaborate molecular assemblies and here we consider the case for using boron(III) chelates as the primary light absorbers. Such entities make attractive modules for the creation of multi-component arrays with individual units sited in a logical sequence for long-range electronic energy transfer. Alternatively, certain boron(III) chelates can be synthesised in high yield by simple strategies that avoid time-consuming purification. These latter materials are appealing as components for large-scale light harvesters. The use of photonic crystals avoids the need to position individual molecules at the catalyst but presents severe design challenges. Interrupting, or redirecting, the flow of excitons within the array requires the introduction of novel switches that can be activated by selective illumination. Protecting the array against adventitious photofading is a major objective that has yet to be achieved

Ultrafast electronic energy transfer beyond the weak coupling limit in a proximal but orthogonal molecular dyad

Electronic energy transfer (EET) from a donor to an acceptor is an important mechanism that controls the light harvesting efficiency in a wide variety of systems, including artificial and natural photosynthesis and contemporary photovoltaic technologies. The detailed mechanism of BET at short distances or large angles between the donor and acceptor is poorly understood. Here the influence of the orientation between the donor and acceptor on EET is explored using a molecule with two nearly perpendicular chromophores. Very fast EET with a time constant of 120 fs is observed, which is at least 40 times faster than the time predicted by Coulombic coupling calculations. Depolarization of the emission signal indicates that the transition dipole rotates through ca. 64 degrees, indicating the near orthogonal nature of the EET event. The rate of EET is found to be similar to structural relaxation rates in the photoexcited oligothiophene donor alone, which suggests that this initial relaxation brings the dyad to a conical intersection where the excitation jumps to the acceptor.PostprintPeer reviewe

The host immune response to gastrointestinal nematode infection in sheep

non peer reviewedGastrointestinal nematode infection represents a major threat to the health, welfare and productivity of sheep populations worldwide. Infected lambs have a reduced ability to absorb nutrients from the gastrointestinal tract, resulting in morbidity and occasional mortality. The current chemo-dominant approach to nematode control is considered unsustainable due to the increasing incidence of anthelmintic resistance. In addition there is growing consumer demand for food products from animals not subjected to chemical treatment. Future mechanisms of nematode control must rely on alternative, sustainable strategies such as vaccination or selective breeding of resistant animals. Such strategies take advantage of the host's natural immune response to nematodes. The ability to resist gastrointestinal nematode infection is considered to be dependent on the development of a protective acquired immune response; although the precise immune mechanisms involved in initiating this process remain to be fully elucidated. In this paper current knowledge on the innate and acquired host immune response to gastrointestinal nematode infection in sheep and the development of immunity is reviewed.We gratefully acknowledge funding support for the research in our laboratories from the Teagasc Walsh Fellowship Programme, the Allan and Grace Kay Overseas Scholarship and the EC-funded FP7 Programme. We also thank the BBSRC Animal Health Research Club for funding part of this research (grant BB/l004070/1

DRELL-YAN PROCESSES AS A PROBE OF CHARGE SYMMETRY VIOLATION IN THE PION AND NUCLEON

We extend earlier investigations of charge symmetry violation in the valence quark distributions of the nucleon, and make similar estimates for the pion. The sensitivity of pion-induced Drell-Yan measurements to such effects is then examined. It is shown that combinations of $\pi^+$ and $\pi^-$ data on deuterium and hydrogen are sensitive to these violations, and that the pion and nucleon charge symmetry violating terms separate as a function of $x_\pi$ and $x_N$ respectively. We estimate the background terms which must be evaluated to extract charge symmetry violation.Comment: 11 pages + uuencoded postscript file of 4 figure

Metal Ion Enhanced Charge Transfer in a Terpyridine-bis-Pyrene System

The synthesis, electrochemical and photophysical properties of a branched molecule 3,5-bis(pyrene-1-yl)-4′-phenyl-2,2′:6′,2″-terpyridine are reported. Spectroscopy in different solvents reveals that an optical electron transfer from the pyrene donor to the terpyridyl electron acceptor can occur in polar media, as the system displays both charge transfer (CT) absorption and CT emission. Furthermore, the study of the zinc complex as well as the bis-protonated form shows an enhancement of the electron transfer character of the system, by an increase of the acceptor strength. This is accompanied by a large increase of the non-radiative processes. With sub-nanosecond transient absorption spectroscopy, the CT state, consisting of the pyrene radical cation and the terpyridine radical anion, has been detected. At room temperature, the study of the nanosecond transient absorption spectra reveals the formation of a low-lying triplet excited state that we attribute to the pyrene moiety through which the CT state decays. At 77K, the absence of the terpyridine triplet emission also suggests the population of a low-lying triplet state of the pyrene unit

Micronutrient malnutrition and wasting in adults with pulmonary tuberculosis with and without HIV co-infection in Malawi

BACKGROUND: Wasting and micronutrient malnutrition have not been well characterized in adults with pulmonary tuberculosis. We hypothesized that micronutrient malnutrition is associated with wasting and higher plasma human immunodeficiency virus (HIV) load in adults with pulmonary tuberculosis. METHODS: In a cross-sectional study involving 579 HIV-positive and 222 HIV-negative adults with pulmonary tuberculosis in Zomba, Malawi, anthropometry, plasma HIV load and plasma micronutrient concentrations (retinol, α-tocopherol, carotenoids, zinc, and selenium) were measured. The risk of micronutrient deficiencies was examined at different severity levels of wasting. RESULTS: Body mass index (BMI), plasma retinol, carotenoid and selenium concentrations significantly decreased by increasing tertile of plasma HIV load. There were no significant differences in plasma micronutrient concentrations between HIV-negative individuals and HIV-positive individuals who were in the lowest tertile of plasma HIV load. Plasma vitamin A concentrations <0.70 μmol/L occurred in 61%, and zinc and selenium deficiency occurred in 85% and 87% respectively. Wasting, defined as BMI<18.5 was present in 59% of study participants and was independently associated with a higher risk of low carotenoids, and vitamin A and selenium deficiency. Severe wasting, defined as BMI<16.0 showed the strongest associations with deficiencies in vitamin A, selenium and plasma carotenoids. CONCLUSIONS: These data demonstrate that wasting and higher HIV load in pulmonary tuberculosis are associated with micronutrient malnutrition

Colorants: A New Journal Bringing Colour to Life

Colorant: A substance which is used to impart colour to another material! [...

Electronic Communication in Closely Connected BODIPY-Based Bichromophores

A small series of closely spaced, bichromophoric boron dipyrromethene (BODIPY) derivatives has been examined by optical spectroscopy and compared to the corresponding mononuclear dyes. The compounds vary according to the site of attachment and also by the nature of alkyl or aryl substituents incorporated into the dipyrrin backbone. Excitonic coupling splits the lowest-energy absorption transition in each case, but to highly variable degrees. There are also marked changes in the fluorescence quantum yields across the series but much less variation in the excited-state lifetimes. After comparing different models, it is concluded that the ideal dipole approximation gives a crude qualitative representation of the observed splitting of the absorption transition, but the extended dipole approach is not applicable to these systems. Agreement is substantially improved by employing a model that takes into account the dihedral angle between the planes of the two dipyrrin units. The large variation in radiative rate constants, and those for the accompanying nonradiative processes, is accountable in terms of electronic coupling and/or intensity borrowing between the two excitonic states. In all cases, the dihedral angle between the two BODIPY units plays a key role