El Niño impact on mollusk biomineralization-implications for trace element proxy reconstructions and the paleo-archeological record.

Marine macroinvertebrates are ideal sentinel organisms to monitor rapid environmental changes associated with climatic phenomena. These organisms build up protective exoskeletons incrementally by biologically-controlled mineralization, which is deeply rooted in long-term evolutionary processes. Recent studies relating potential rapid environmental fluctuations to climate change, such as ocean acidification, suggest modifications on carbonate biominerals of marine invertebrates. However, the influence of known, and recurrent, climatic events on these biological processes during active mineralization is still insufficiently understood. Analysis of Peruvian cockles from the 1982-83 large magnitude El Niño event shows significant alterations of the chemico-structure of carbonate biominerals. Here, we show that bivalves modify the main biomineralization mechanism during the event to continue shell secretion. As a result, magnesium content increases to stabilize amorphous calcium carbonate (ACC), inducing a rise in Mg/Ca unrelated to the associated increase in sea-surface temperature. Analysis of variations in Sr/Ca also suggests that this proxy should not be used in these bivalves to detect the temperature anomaly, while Ba/Ca peaks are recorded in shells in response to an increase in productivity, or dissolved barium in seawater, after the event. Presented data contribute to a better understanding of the effects of abrupt climate change on shell biomineralization, while also offering an alternative view of bivalve elemental proxy reconstructions. Furthermore, biomineralization changes in mollusk shells can be used as a novel potential proxy to provide a more nuanced historical record of El Niño and similar rapid environmental change events.

Synthesis and characterization of CoPt nanoparticles prepared by room temperature chemical reduction with PAMAM dendrimer as template.

We describe an approach to synthesize monodisperse CoPt nanoparticles with dendrimer as template by a simple chemical reduction method in aqueous solution using NaBH4 as reducing agent at room temperature. The as-made CoPt nanoparticles buried in the dendrimer matrix have the chemically disordered fcc structure and can be transformed to the fct phase after annealing at 700 degrees C. This is the first report of dendrimer-mediated room temperature synthesis of monodisperse magnetic nanoparticles in aqueous solution.

Synthesis and electrocatalytic activity of photoreduced platinum nanoparticles in a poly(ethylenimine) matrix.

Monodisperse polymer-mediated platinum (Pt) nanoparticles (NPs) have been synthesized by photoreduction in the presence of poly(ethylenimine) (PEI), a hyperbranched polymer. The formation process of the Pt NPs is pursued by UV-vis spectroscopy, and the formation mechanism is discussed. The morphology and size of the Pt NPs were characterized by transmission electron microscopy (TEM). TEM imaging shows that the Pt NPs' average diameter is 2.88 +/- 0.53 nm. The PEI/Pt NPs were immobilized on glassy carbon electrodes, and the electrocatalytic activity of the catalysts was investigated by cyclic voltammetry. PEI/Pt NPs exhibit very high catalytic activity for a methanol oxidation reaction. PEI/Pt NPs on glassy carbon electrodes are robust, showing good tolerance to poisoning even after many cycles. The electrocatalytic activity of PEI/Pt NPs compares favorably with other polymer-mediated Pt NPs. The results indicate that PEI is an appropriate complexing reducing agent for the photochemical production of Pt NPs and a good capping agent, allowing immobilization of the NPs on the working electrode.