Direct observation by time-resolved infrared spectroscopy of the bright and the dark excited states of the [Ru(phen)2(dppz)]2+ light-switch compound in solution and when bound to DNA

The [Ru(phen)2(dppz)]2+ complex (1) is non-emissive in water but is highly luminescent in organic solvents or when bound to DNA, making it a useful probe for DNA binding. To date, a complete mechanistic explanation for this “light-switch” effect is still lacking. With this in mind we have undertaken an ultrafast time resolved infrared (TRIR) study of 1 and directly observe marker bands between 1280–1450 cm-1, which characterise both the emissive “bright” and the non-emissive “dark” excited states of the complex, in CD3CN and D2O respectively. These characteristic spectral features are present in the [Ru(dppz)3]2+ solvent light-switch complex but absent in [Ru(phen)3]2+, which is luminescent in both solvents. DFT calculations show that the vibrational modes responsible for these characteristic bands are predominantly localised on the dppz ligand. Moreover, they reveal that certain vibrational modes of the “dark” excited state couple with vibrational modes of two coordinating water molecules, and through these to the bulk solvent, thus providing a new insight into the mechanism of the light-switch effect. We also demonstrate that the marker bands for the “bright” state are observed for both L- and D enantiomers of 1 when bound to DNA and that photo-excitation of the complex induces perturbation of the guanine and cytosine carbonyl bands. This perturbation is shown to be stronger for the L enantiomer, demonstrating the different binding site properties of the two enantiomers and the ability of this technique to determine the identity and nature of the binding site of such intercalators.

Toeplitz operators on Dirichlet-Besov spaces

We study Toeplitz operators on the Besov spaces in the case of the open unit disk. We prove that a symbol satisfying a weak Lipschitz type condition induces a bounded Toeplitz operator. Such symbols do not need to be bounded functions or have continuous extensions to the boundary of the open unit disk. We discuss the problem of the existence of nontrivial compact Toeplitz operators, and also consider Fredholm properties and prove an index formula.

La Niña 2016/2017: historical impact analysis

El Niño conditions developed in the tropical Pacific during the latter half of 2015, peaking in December 2015 as one of the strongest El Niño events on record, comparable with the 1997-98 “El Niño of the century”. Conditions in the tropical Pacific are forecast to return to normal over the coming months, with the potential to transition into La Niña conditions during 2016-17. If this was to occur it would act as a further strong perturbation, or ‘kick’, to the climate system and lead to further significant socio-economic impacts affecting many sectors such as infrastructure, agriculture, health and energy. This report analyses La Niña events over the last 37 years of the satellite era (1979-present) and aims to identify regions where there is an increased likelihood of impacts occurring. It is important to note that this analysis is based on past analogous events and is not a prediction for this year. No two La Niña events will be the same – the timing and magnitude of events differs considerably. More importantly, no two La Niña events lead to the same impacts – other local physical and social factors come into play. Therefore, the exact timings, locations and magnitudes of impacts should be interpreted with caution and this should be accounted for in any preparedness measures that are taken. This report has been produced for Evidence on Demand with the assistance of the UK Department for International Development (DFID) contracted through the Climate, Environment, Infrastructure and Livelihoods Professional Evidence and Applied Knowledge Services (CEIL PEAKS) programme, jointly managed by DAI (which incorporates HTSPE Limited) and IMC Worldwide Limited.