BackgroundCoral bleaching (i.e., the release of coral symbiotic zooxanthellae) has negative impacts on biodiversity and functioning of reef ecosystems and their production of goods and services. This increasing world-wide phenomenon is associated with temperature anomalies, high irradiance, pollution, and bacterial diseases. Recently, it has been demonstrated that personal care products, including sunscreens, have an impact on aquatic organisms similar to that of other contaminants.ObjectivesOur goal was to evaluate the potential impact of sunscreen ingredients on hard corals and their symbiotic algae.MethodsIn situ and laboratory experiments were conducted in several tropical regions (the Atlantic, Indian, and Pacific Oceans, and the Red Sea) by supplementing coral branches with aliquots of sunscreens and common ultraviolet filters contained in sunscreen formula. Zooxanthellae were checked for viral infection by epifluorescence and transmission electron microscopy analyses.ResultsSunscreens cause the rapid and complete bleaching of hard corals, even at extremely low concentrations. The effect of sunscreens is due to organic ultraviolet filters, which are able to induce the lytic viral cycle in symbiotic zooxanthellae with latent infections.ConclusionsWe conclude that sunscreens, by promoting viral infection, potentially play an important role in coral bleaching in areas prone to high levels of recreational use by humans.

Bond dissociation enthalpies (BDE) of hydroxylamines containing alkyl, aryl, vinyl, and carbonyl substituents at the nitrogen atom have been determined by using the EPR radical equilibration technique in order to study the effect of the substituents on the O-H bond strength of these compounds. It has been found that substitution of an alkyl group directly bonded to the nitrogen atom with vinyl or aryl groups has a small effect, while substitution with acyl groups induces a large increase of the O-H BDE value. Thus, dialkyl hydroxylamines have O-H bond strengths of only ca. 70 kcal/mol, while acylhydroxylamines and N-hydroxyphthalimide (NHPI), containing two acyl substituents at nitrogen, are characterized by BDE values of ca. 80 and 88 kcal/mol, respectively. Since the phthalimide N-oxyl radical (PINO) has been recently proposed as an efficient oxidation catalyst of hydrocarbons or other substrates, the large BDE value found for the parent hydroxylamine (NHPI) justifies this proposal. Kinetic studies, carried out in order to better understand the mechanism of the NHPI-catalyzed aerobic oxidation of cumene, are consistent with a simple kinetic model where the rate-determining step is the hydrogen atom abstraction from the hydroxylamine by cumylperoxyl radicals.

Bulk methyl methacrylate (MMA) controlled radical polymerization was carried out using two 2,2-diphenyl-3-phenylimino-2,3-dihydroindol-1-yloxyl nitroxide (DPAIO) based alkoxyamines. Whatever the alkoxyamine used, polymerization presents a controlled character, and high conversion can be reached. Polymerization up to 60% conversion, initiated with the nitro para-substituted alkoxyamine 2, showed a linear increase of number-average molecular weight (M n) vs conversion even at the beginning of the polymerization with the final polydispersity index (PDI) close to 1.4. A reinitiation test onto n-butyl acrylate has shown that even if this nitroxide is not suited for acrylate monomers, the shift of the size exclusion chromatography (SEC)trace proved the poly(methyl methacrylate)−DPAIO macroinitiator (PMMA−DPAIO) obtained had a living character. These results showed that the range of monomers that could be polymerized by nitroxide mediated polymerization (NMP) can still be extended.

New mediators of laccase have been comparatively evaluated and ranked towards the benchmark aerobic oxidation of p-MeO-benzyl alcohol. The mechanism of oxidation of this non-phenolic substrate by each mediator, which is initially oxidised by laccase to the Medox form, has been assessed among three alternatives. The latter make the phenoloxidise laccase competent for the indirect oxidation of non-phenolic (and thus ‘unnatural’) substrates. Experimental characterisation of the mediators, by means of spectrophotometric, electrochemical and thermochemical survey, is reported. Clear-cut evidence for the formation of a benzyl radical intermediate in the oxidation of a particular benzyl alcohol with laccase and a {N–OH mediator is attained by means of a trapping experiment. The selectivity of the laccase-catalysed oxidation of two competing lignin and polysaccharide model compounds has been assessed by using the highly proficient 4-MeO-HPI mediator, and found very high in favour of the former model. This evidence is in keeping with the operation of a radical hydrogen-abstraction process that efficiently cleaves the benzylic rather than the aliphatic C–H bond of the two models. Significant is the finding that catechol, i.e., a model of recurring phenolic structures in lignin, once oxidised to aryloxyl radical by laccase is capable to mediate a radical oxidation of non-phenolic compounds. This supports a fully-fledged role of laccase as a delignifying enzyme in nature by way of no other mediators than the very phenolic groups of lignin. Finally, an evaluation of the dissociation energy of the NO–H bond of HBT, which is not accessible experimentally, is provided by the use of a thermochemical cycle and theoretical calculations

No abstract