Photophysical and Cellular Imaging Studies of Brightly Luminescent Osmium(II) Pyridyltriazole Complexes

The series of complexes [Os(bpy)3- n(pytz) n][PF6]2 (bpy = 2,2'-bipyridyl, pytz = 1-benzyl-4-(pyrid-2-yl)-1,2,3-triazole, 1 n = 0, 2 n = 1, 3 n = 2, 4 n = 3) were prepared and characterized and are rare examples of luminescent 1,2,3-triazole-based osmium(II) complexes. For 3 we present an attractive and particularly mild preparative route via an osmium(II) η6-arene precursor circumventing the harsh conditions that are usually required. Because of the high spin-orbit coupling constant associated with the Os(II) center the absorption spectra of the complexes all display absorption bands of appreciable intensity in the range of 500-700 nm corresponding to spin-forbidden ground-state-to-3MLCT transitions (MLCT = metal-to-ligand charge transfer), which occur at significantly lower energies than the corresponding spin-allowed 1MLCT transitions. The homoleptic complex 4 is a bright emitter (λmaxem = 614 nm) with a relatively high quantum yield of emission of ∼40% in deoxygenated acetonitrile solutions at room temperature. Water-soluble chloride salts of 1-4 were also prepared, all of which remain emissive in aerated aqueous solutions at room temperature. The complexes were investigated for their potential as phosphorescent cellular imaging agents, whereby efficient excitation into the 3MLCT absorption bands at the red side of the visible range circumvents autofluorescence from biological specimens, which do not absorb in this region of the spectrum. Confocal microscopy reveals 4 to be readily taken up by cancer cell lines (HeLa and EJ) with apparent lysosomal and endosomal localization, while toxicity assays reveal that the compounds have low dark and light toxicity. These complexes therefore provide an excellent platform for the development of efficient luminescent cellular imaging agents with advantageous photophysical properties that enable excitation and emission in the biologically transparent region of the optical spectrum

Evaluating Existing Ocean Glider Sampling Strategies for Submesoscale Dynamics

Mixing in the upper ocean is important for biological production and the transfer of heat and carbon between the atmosphere and deep ocean, properties commonly targeted by observational campaigns using ocean gliders. We assess the reliability of ocean gliders to obtain a robust statistical representation of submesocale variability in the ocean mixed layer of the Weddell Sea. A 1/48° regional simulation of the Southern Ocean is sampled with virtual ‘bow-tie’ glider deployments, which are then compared against the reference model output. Sampling biases of lateral buoyancy gradients associated with the arbitrary alignment between glider paths and fronts are formally quantified, and the magnitude of the biases are comparable to observational estimates, with a mean error of 52%. The sampling bias leaves errors in the retrieved distribution of buoyancy gradients largely insensitive to deployment length and the deployment of additional gliders. Notable sensitivity to these choices emerges when the biases are removed by sampling perpendicular to fronts at all times. Detecting seasonal change in the magnitude of buoyancy gradients is sensitive to the glider-orientation sampling bias but the change in variance is not. We evaluate the impact of reducing the number of dives and climbs in an observational campaign and find small reductions in the number of dive-climb pairs have a limited effect on the results. Lastly, examining the sensitivity of the sampling bias to path orientation indicates the bias is not dependent on the direction of travel, in our deep ocean study site

Southern ocean carbon and heat impact on climate

The Southern Ocean greatly contributes to the regulation of the global climate by controlling important heat and carbon exchanges between the atmosphere and the ocean. Rates of climate change on decadal timescales are therefore impacted by oceanic processes taking place in the Southern Ocean, yet too little is known about these processes. Limitations come both from the lack of observations in this extreme environment and its inherent sensitivity to intermittent processes at scales that are not well captured in current Earth system models. The Southern Ocean Carbon and Heat Impact on Climate programme was launched to address this knowledge gap, with the overall objective to understand and quantify variability of heat and carbon budgets in the Southern Ocean through an investigation of the key physical processes controlling exchanges between the atmosphere, ocean and sea ice using a combination of observational and modelling approaches. Here, we provide a brief overview of the programme, as well as a summary of some of the scientific progress achieved during its first half. Advances range from new evidence of the importance of specific processes in Southern Ocean ventilation rate (e.g. storm-induced turbulence, sea–ice meltwater fronts, wind-induced gyre circulation, dense shelf water formation and abyssal mixing) to refined descriptions of the physical changes currently ongoing in the Southern Ocean and of their link with global climate. This article is part of a discussion meeting issue ‘Heat and carbon uptake in the Southern Ocean: the state of the art and future priorities’.</jats:p&gt