Unusual long-term stability of enzymatic bioelectrocatalysis in organic solvents

Organic solvent tolerant enzymes are of tremendous importance for the pharmaceutical industry in search of high added-value chemicals. However, enzymes exhibit usually weak long-term activity and stability in various media. Here, we report a general strategy allowing stabilizing and keeping enzymes active in mixed-solvent systems upon immobilization on an electrode surface. It consists in the combination of an engineered solventtolerant enzyme, combined with fine-tuned osmium-based redox polymers where the concentration of osmium complex has been specifically tuned to minimize its deswelling, associated with the use of porous gold electrodes. This approach is validated with bilirubin oxidase as a model system. This copper enzyme is able to oxidize a wide range of substrates, combined with the reduction of O-2 to water. While all other enzymatic systems irreversibly lose their activity and stability in the presence of 7.5 M methanol or below, this optimized enzymatic system stays functional in 12.5 M methanol with no loss in current density. It exhibits a half-life of more than 8 days, which is unprecedented in the literature. We show that this electrode can also operate in DMSO, dioxane, acetonitrile and acetone, thus opening up a very wide variety of applications in the field of bioelectrocatalysis and bioelectrosynthesis

Spatiotemporal changes in surface sediment characteristics and benthic macrofauna composition off the Rhône River in relation to its hydrological regime

International audienceThe consequences of changes in the water flow of the Rhône River on surface sediment characteristics and benthic macrofauna composition were assessed within 3 distinct areas: (1) the delta front, (2) the prodelta, and (3) the distal zone. Five stations were sampled during or closely after: (1) an oceanic flood (April 2007), (2) a generalized flood (May 2008), (3) a Cevenol flood (December 2008), and (4) a dry period (July 2011). Measurements of sediment characteristics included granulometry (D0.5), bulk descriptors of sedimentary organics (OC, TN and THAA), descriptors of labile components of sedimentary organics (chloropigments, EHAA), and both descriptors of origin (Chl-b/Chl-a, C/N) and lability (Chl-a/(Chl-a+Phaeo-a), EHAA/THAA) of sedimentary organics. Sediment Profile Images were collected during April 2007, May 2008 and July 2011. Temporal changes in both sedimentary organics and benthic macrofauna were more important in the delta front and the prodelta than in the distal zone. Bulk characteristics of sedimentary organics presented decreasing inshore/offshore gradients during both April 2007 and July 2011 but not during May and December 2008. There were significant temporal changes in EHAA/THAA at all stations. Changes in benthic macrofauna composition differed between: (1) the delta front and the prodelta, and (2) the distal zone. In the former area, the dry period was associated with establishing a mature community characterized by high abundances and species richness. The best description of spatiotemporal changes in benthic macrofauna composition by surface sediment characteristics was obtained using D0.5, Chl-b/Chl-a, Chl-a/(Chl-a+Phaeo-a) and EHAA, which supports the role of the quality of sedimentary organics in controlling benthic macrofauna composition

Deltaic and Coastal Sediments as Recorders of Mediterranean Regional Climate and Human Impact Over the Past Three Millennia

International audienc

Unexpected biotic resilience on the Japanese seafloor caused by the 2011 Tōhoku-Oki tsunami

On March 11th, 2011 the Mw 9.0 2011 Tōhoku-Oki earthquake resulted in a tsunami which caused major devastation in coastal areas. Along the Japanese NE coast, tsunami waves reached maximum run-ups of 40 m, and travelled kilometers inland. Whereas devastation was clearly visible on land, underwater impact is much more difficult to assess. Here, we report unexpected results obtained during a research cruise targeting the seafloor off Shimokita (NE Japan), shortly (five months) after the disaster. The geography of the studied area is characterized by smooth coastline and a gradually descending shelf slope. Although high-energy tsunami waves caused major sediment reworking in shallow-water environments, investigated shelf ecosystems were characterized by surprisingly high benthic diversity and showed no evidence of mass mortality. Conversely, just beyond the shelf break, the benthic ecosystem was dominated by a low-diversity, opportunistic fauna indicating ongoing colonization of massive sand-bed deposits.Peer reviewe

Long-term (1998 vs. 2010) large-scale comparison of soft-bottom benthic macrofauna composition in the Gulf of Lions, NW Mediterranean Sea

We achieved a long term (i.e.,1998 vs. 2010) large scale (i.e., whole Gulf of Lions) study of benthic macrofauna composition in the Gulf of Lions based on the resampling of 91 stations located along 21 inshore-offshore transects. Results show that the 3 main benthic communities identified in 1998 were still present in 2010 although their composition changed. Using only year and station of sampling we found a significant space-time interaction explaining changes in macrofaunal community composition, and, in this study, stations differ primarily in terms of depth and distance to the Rhone river mouth. Temporal changes in benthic macrofauna composition were clearly most important at shallow stations (i.e., in the Littoral Fine Sand community) than at deep ones (i.e., Terrigenous Coastal Mud community). These results are in good agreement with the current paradigm according to which climatic oscillations such as NAO (North Atlantic Oscillation) and WeMO (Western Mediterranean Oscillation) are indirectly (i.e., through changes in the frequency of occurrence and the intensity of storms) controlling benthic macrofauna composition in the Gulf of Lions. This hypothesis is further supported by a meta-analysis of changes in the average and maximal yearly abundances of the polychaete Ditrupa arietina. At last, the spatial modelling of 1998 and 2010 benthic macrofauna compositions both suggested a significant effect of Rhone River inputs on the spatial distribution of benthic macrofauna in the Gulf of Lions

Influence of the mud shrimp Upogebia pusilla (Decapoda: Gebiidea) on solute and porewater exchanges in an intertidal seagrass (Zostera noltei) meadow of Arcachon Bay: An experimental assessment

The aim of the present study was to investigate the influence of the mud shrimp Upogebia pusilla on porewater and solute exchanges in an intertidal Zostera noltei meadow of Arcachon Bay. Laboratory experiments carried out during three seasons showed that U. pusilla strongly enhanced sediment porewater exchange rates (averaging 26, 45 and 71 L m− 2 d− 1 in winter, spring and summer, respectively) in comparison to uninhabited sediments for which these rates were moderate (averaging 9, 9 and 16 L m− 2 d− 1 in winter, spring and summer, respectively). Total Oxygen Uptakes (TOUs) were increased by factors around 2.5 during the three studied seasons whilst oxygen consumption by the shrimp accounted for 64, 28 and 21% of TOU in winter, spring and summer, respectively. U. pusilla also significantly enhanced the uptake of nitrate (up to 13.8-fold in summer) and the release of ammonium (up to 3.0-fold in summer) and silicate (up to 3.8-fold in spring) by the sediment. Overall, our results highlight the key role of U. pusilla in controlling oxygen and nutrient fluxes in Arcachon Bay. Because U. pusilla populations are predominantly found in the sediments of Z. noltei meadows, the full assessment of the functional effects resulting from the decline of this meadow should include the effects associated to the disappearance of U. pusilla as well

High-Content Screening of Plankton Alkaline Phosphatase Activity in Microfluidics

One way for phytoplankton to survive orthophosphate depletion is to utilize dissolved organic phosphorus by expressing alkaline phosphatase. The actual methods to assay alkaline phosphate activity—either in bulk or as a presence/absence of enzyme activity—fail to provide information on individual living cells. In this context, we develop a new microfluidic method to compartmentalize cells in 0.5 nL water-in-oil droplets and measure alkaline phosphatase activity at the single-cell level. We use enzyme-labeled fluorescence (ELF), which is based on the hydrolysis of ELF-P substrate, to monitor in real time and at the single-cell level both qualitative and quantitative information on cell physiology (i.e., localization and number of active enzyme sites and alkaline phosphatase kinetics). We assay the alkaline phosphatase activity of Tetraselmis sp. as a function of the dissolved inorganic phosphorus concentration and show that the time scale of the kinetics spans 1 order of magnitude. The advantages of subnanoliter-scale compartmentalization in droplet-based microfluidics provide a precise characterization of a population with single-cell resolution. Our results highlight the key role of cell physiology to efficiently access dissolved organic phosphorus.Initiative d'excellence de l'Université de Bordeau

Impact of organic matter source and quality on living benthic foraminiferal distribution on a river-dominated continental margin: A study of the Portuguese margin

International audienceLiving (rose Bengal stained) benthic foraminifera were investigated on surface sediments from 23 stations from the river-dominated northwestern Portuguese margin. Samples were collected in March 2011, following the period of the maximum rainfall over the Iberian Peninsula, between 20 and 2000 m water depth along five cross-margin transects. Four of them are located off the Douro, Mondego, Tagus, and Sado Rivers and one off the Estremadura coast. The major objectives of this study are (1) to assess the impact of organic matter of various origin and quality on the benthic foraminifera and (2) to investigate the spatial differences of faunal distribution from coastal waters to the deep sea under river influences. To do this, sedimentological and biogeochemical characteristics of the sediments were identified by measuring grain size, oxygen penetration depth, total organic carbon (TOC) content, stable carbon isotopic composition of TOC (δ13CTOC) and concentration of pigments and amino acids. Based on the principal component and cluster analyses of the environmental data, three major geographical groups are identified: (1) deep stations, (2) coastal and middle slope stations, and (3) shelf stations under river influence. At the deepest stations, species are associated with high organic matter (OM) quantity but low OM quality, where Uvigerina mediterranea, Hoeglundina elegans, and agglutinated species such as Reophax scorpiurus or Bigenerina nodosaria are dominant. All stations off the Sado River, which is the most affected area by the anthropogenic influence, are also characterized by high quantity but low quality of OM with the minimum faunal density and diversity within the study area. Middle slope stations are associated with low OM content and coarse sediments (Q50) with the predominance of N. scaphum. Shallow shelf stations close to the Douro and Tagus River mouths show a dominance of taxa (e.g., Ammonia beccarii, Bulimina aculeata, Eggerelloides scaber, Nonion scaphum, Cancris auriculus, and Quinqueloculina seminula) adapted to environments characterized by high OM quality (high fresh chlorophyll (Chl a/Phaeo)) and available amino acids (enzymatically hydrolyzable amino acid (EHAA)/total enzymatically hydrolyzable amino acid (THAA)). The Biotic and Environmental linking analysis suggests that the benthic foraminiferal distribution is mostly controlled by three environmental parameters, i.e., TOC (quantity), EHAA/THAA (quality), and δ13CTOC (source). Hence, this study clearly highlights that the quantitative and qualitative inputs of OM and its source are the most important factors controlling the living benthic foraminiferal distribution with clear influences between the different rivers. This study also suggests a good tolerance of several species for river discharges where the OM quality is high

Low-Molecular-Weight Hydrogels as New Supramolecular Materials for Bioelectrochemical Interfaces

International audienceControlling the interface between biological tissues and electrodes remains an important challenge for the developmentof implantable devices in terms of electroactivity, biocompatibility, and long-term stability. To engineer such a biocompatible interface a low molecular weight gel (LMWG) based on a glycosylated nucleoside fluorocarbon amphiphile (GNF) was employed for the first time to wrap gold electrodes via a noncovalent anchoring strategy, that is, self-assembly of GNF at the electrode surface. Scanning electron microscopy (SEM) studies indicate that the gold surface is coated with the GNF hydrogels. Electrochemical measurements using cyclic voltammetry (CV) clearly show that the electrode properties are not affected by the presence of the hydrogel. This coating layer of 1 to 2 μm does not significantly slow down the mass transport through the hydrogel. Voltammetry experiments with gel coated macroporous enzyme electrodes reveal that during continuous use their current is improved by 100% compared to the noncoated electrode...