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Luciferin is one of Nature's most widespread luminophores, and enzymes that catalyze luciferin luminescence are the basis of successful commercial “glow” assays for gene expression and metabolic ATP formation. Herein we report an electrochemical method to promote firefly's luciferin luminescence in the absence of its natural biocatalyst—luciferase. We have gained experimental and computational insights on the mechanism of the enzyme-free luciferin electrochemiluminescence, demonstrated its spectral tuning from green to red by means of electrolyte engineering, proven that the colour change does not require, as still debated, a keto/enol isomerization of the light emitter, and gained evidence of the electrostatic-assisted stabilization of the charge-transfer excited state by double layer electric fields. Luciferin's electrochemiluminescence, as well as the in situ generation of fluorescent oxyluciferin, are applied towards an optical measurement of diffusion coefficients.

The evolution of gaseous products is a feature common to several electrochemical processes, often resulting in bubbles adhering to the electrode’s surface. Adherent bubbles reduce the electrode active area, and are therefore generally treated as electrochemically inert entities. Here, we show that this general assumption does not hold for gas bubbles masking anodes operating in water. By means of imaging electrochemiluminescent systems, and by studying the anisotropy of polymer growth around bubbles, we demonstrate that gas cavities adhering to an electrode surface initiate the oxidation of water-soluble species more effectively than electrode areas free of bubbles. The corona of a bubble accumulates hydroxide anions, unbalanced by cations, a phenomenon which causes the oxidation of hydroxide ions to hydroxyl radicals to occur at potentials at least 0.7 V below redox tabled values. The downhill shift of the hydroxide oxidation at the corona of the bubble is likely to be a general mechanism involved in the initiation of heterogeneous electrochemical reactions in water, and could be harnessed in chemical synthesis.

Recent declines in Atlantic salmon Salmo salar populations are generally attributed to factors in their marine life-phase. However, it is postulated that factors affecting their freshwater life-phase might impact their marine survival, such as the influence of body size. While larger smolts are widely hypothesized to have higher marine survival rates, empirical support remains scant, in part due to inadequate data and ambiguous statistical analyses. Here, we test the influence of smolt body size on marine return rates, a proxy for marine survival, using a 12-year dataset of 3688 smolts tagged with passive integrated transponders in the River Frome, Southern England. State-space models describe the probability of smolts surviving their marine phase to return as 1 sea-winter (1SW) or multi-sea-winter adults as a function of their length, while accounting for imperfect detection and missing data. Models predicted that larger smolts had higher return rates; the most parsimonious model included the effect of length on 1SW return rate. This prediction is concerning, as freshwater juvenile salmon are decreasing in size on the River Frome, and elsewhere. Thus, to maximize adult returns, restoration efforts should focus on freshwater life-stages, and maximize both the number and the size of emigrating smolts.