Island Wakes

8 páginas, 5 figuras.Peer reviewe

The Canary Islands coastal transition zone – upwelling, eddies and filaments [Editorial]

3 pages.-- Printed version published in issue Aug-Sep 2004.-- Issue title: "The Canary Islands Coastal Transition Zone - Upwelling, Eddies and Filaments".Full-text version available Open Access at: http://www.iim.csic.es/~barton/html/pdfs.htmlThe marine science and technology (MAST) III program of the European Union funded the Canary Islands Azores Gibraltar Observations (CANIGO) project from 1996 to 1999 with the overarching objective of a better understanding of the physics, biogeochemistry and paleoceanography of the eastern subtropical North Atlantic. Parrilla et al., 2002 G. Parrilla, S. Neuer, P.Y. Le Traon and E. Fernandez-Suarez, Topical studies in oceanography: Canary Islands Azores Gibraltar Observations (CANIGO) Volume 1: Studies in the northern Canary Islands basin, Deep-Sea Research Part II-Topical Studies In Oceanography 49 (2002) (17), pp. 3409–3413. Article | PDF (73 K) | View Record in Scopus | Cited By in Scopus (12)Parrilla, Neuer, Le Traon, and Fernandez-Suarez (2002) edited two volumes of papers detailing many results of the project. The present compilation of papers complements those volumes by reporting observational work carried out in the last months of the project, too late for inclusion there. The component of CANIGO reported here, which focussed on the transition zone of the NW African coastal upwelling downstream of the Canary Islands, was an interdisciplinary effort involving researchers from ten institutes and universities in Spain, UK and France.This work was supported by the European Union (Project CANIGO, MAS3.CT96-0060).Peer reviewe

Sensitivity of Ru(bpy)_2dppz^(2+) Luminescence to DNA Defects

The luminescent characteristics of Ru(bpy)_2dppz^(2+) (dppz = dipyrido[3,2-a:2′,3′-c]phenazine), a DNA light switch, were investigated in the presence of oligonucleotides containing single base mismatches or an abasic site. In water, the ruthenium luminescence is quenched, but, bound to well matched duplex DNA, the Ru complex luminesces. Here we show that with DNAs containing a defect, rac-, Δ-, and Λ-Ru(bpy)_2dppz^(2+) exhibit significant luminescent enhancements above that with well matched DNA. In the presence of a single base mismatch, large luminescent enhancements are evident for the Δ-Ru isomer; the Λ-isomer shows particularly high luminescence bound to an oligonucleotide containing an abasic site. Similar increases are not evident with two common DNA-binding organic fluorophores, ethidium bromide and TO-PRO-3. Titrations with hairpin oligonucleotides containing a variable mismatch site show correlation between the level of luminescent enhancement and the thermodynamic destabilization associated with the mismatch. This correlation is reminiscent of that found earlier for a bulky rhodium complex that binds mismatched DNA sites through metalloinsertion, where the complex binds the DNA from the minor groove side, ejecting the mismatched bases into the major groove. Differential quenching studies with minor and major groove quenchers and time-resolved emission studies support this metalloinsertion mode for the dppz complex at the defect site. Certainly these data underscore the utility of Ru(bpy)_2dppz^(2+) as a sensitive luminescent reporter of DNA and its defects

Metal complexes for DNA-mediated charge transport

In all organisms, oxidation threatens the integrity of the genome. DNA-mediated charge transport (CT) may play an important role in the generation and repair of this oxidative damage. In studies involving long-range CT from intercalating Ru and Rh complexes to 5′-GG-3′ sites, we have examined the efficiency of CT as a function of distance, temperature, and the electronic coupling of metal oxidants bound to the base stack. Most striking is the shallow distance dependence and the sensitivity of DNA CT to how the metal complexes are stacked in the helix. Experiments with cyclopropylamine-modified bases have revealed that charge occupation occurs at all sites along the bridge. Using Ir complexes, we have seen that the process of DNA-mediated reduction is very similar to that of DNA-mediated oxidation. Studies involving metalloproteins have, furthermore, shown that their redox activity is DNA-dependent and can be DNA-mediated. Long range DNA-mediated CT can facilitate the oxidation of DNA-bound base excision repair proteins to initiate a redox-active search for DNA lesions. DNA CT can also activate the transcription factor SoxR, triggering a cellular response to oxidative stress. Indeed, these studies show that within the cell, redox-active proteins may utilize the same chemistry as that of synthetic metal complexes in vitro, and these proteins may harness DNA-mediated CT to reduce damage to the genome and regulate cellular processes

Variability in the Canary Islands area of filament-eddy exchanges

24 pages, 17 figures, 1 table.-- Printed version published in issue Aug-Sep 2004.-- Issue title: "The Canary Islands Coastal Transition Zone - Upwelling, Eddies and Filaments".Full-text version available Open Access at: http://www.iim.csic.es/~barton/html/pdfs.htmlThe physical background to a suite of biological studies carried out in the Canary Islands upwelling region is presented. The area is unique in that the coastal transition zone is spanned by an archipelago of islands that shed mesoscale eddies of diameter 50–100 km into the alongshore flow. A recurrent filament and eddy system was sampled intensively to study the changing properties of waters as they are advected towards the open ocean in the filament and to investigate the exchanges between filament and eddies. The system was more complex than previously revealed. In early August, a single filament extended offshore from near Cape Juby. Two weeks later, a second filament had developed slightly farther north and extended offshore to merge with the first at 100 km offshore. The merged filament was entrained around a recurrent, topographically trapped cyclonic eddy and interacted with transient cyclonic and anticyclonic eddies shed from the island of Gran Canaria. Between the two filaments and the coast, a pair of counter-rotating eddies re-circulated water parcels for several weeks. Surface layer drifters cycled around this near-shore re-circulation several times before following convoluted paths that demonstrate significant exchange between continental shelf and open ocean waters.This work has been supported by the European Union (Project CANIGO, MAS3.CT96-0060). We thank the officers and crew of the BIO Hespérides, as well as the staff of the UTM (CSIC, Spain) for their invaluable help at sea. Analysis and writing up was supported by Catedra Patrimonial EX-010009 (Conacyt) while E.D.B. was on sabbatical leave at CICESE, Mexico.Peer reviewe

Charge Photoinjection in Intercalated and Covalently Bound [Re(CO)_(3)(dppz)(py)]^(+)–DNA Constructs Monitored by Time-Resolved Visible and Infrared Spectroscopy

The complex [Re(CO)_(3)(dppz)(py′-OR)]+ (dppz = dipyrido[3,2-a:2′,3′-c]phenazine; py′-OR = 4-functionalized pyridine) offers IR sensitivity and can oxidize DNA directly from the excited state, making it a promising probe for the study of DNA-mediated charge transport (CT). The behavior of several covalent and noncovalent Re–DNA constructs was monitored by time-resolved IR (TRIR) and UV/visible spectroscopies, as well as biochemical methods, confirming the long-range oxidation of DNA by the excited complex. Optical excitation of the complex leads to population of MLCT and at least two distinct intraligand states. Experimental observations that are consistent with charge injection from these excited states include similarity between long-time TRIR spectra and the reduced state spectrum observed by spectroelectrochemistry, the appearance of a guanine radical signal in TRIR spectra, and the eventual formation of permanent guanine oxidation products. The majority of reactivity occurs on the ultrafast time scale, although processes dependent on slower conformational motions of DNA, such as the accumulation of oxidative damage at guanine, are also observed. The ability to measure events on such disparate time scales, its superior selectivity in comparison to other spectroscopic techniques, and the ability to simultaneously monitor carbonyl ligand and DNA IR absorption bands make TRIR a valuable tool for the study of CT in DNA

Distribución horizontal de las larvas de invertebrados alrededor de la isla oceánica de Gran Canaria: Efecto de la variabilidad de mesoescala

11 pages, 7 figures, 1 table.-- Published online 21 April 2009.[EN] In October 1991, the horizontal distribution of invertebrate larvae was studied in the waters surrounding the island of Gran Canaria (Canary Islands). The cruise was typified by the presence of three recurrent mesoscale hydrographic structures: a cyclonic eddy southwest of the island, a warm lee region downstream of the island and the offshore boundary of an upwelling filament from the African coast reaching the southeast of the island. Decapod larvae were the most abundant group. In general, a rather high spatial variability was found. The horizontal distribution of the invertebrate larvae groups showed that the highest values of abundance occurred in an elongated zone around the island oriented in the overall direction of flow, leeward and windward of the island, while the lowest values occurred off the eastern and western flanks of the islands. On the other hand, Stomatopoda and Mollusca larvae showed a distribution associated with the boundary of the upwelling filament and decapod larvae of pelagic species were distributed around the eddy structure. Our results suggest specific retention mechanisms for the larvae of neritic invertebrate populations that are related to the particular physical oceanography around Gran Canaria.[ES] Se estudió la distribución horizontal de las larvas de invertebrados alrededor de la isla de Gran Canaria (Islas Canarias) en octubre de 1991. La campaña se caracterizó por la presencia de tres fenómenos oceanográficos de mesoescala recurrentes: un remolino ciclónico al suroeste de la isla, la estela cálida a sotavento de la misma y el borde de un filamento proveniente del afloramiento africano situado al sureste de Gran Canaria. Las larvas de crustáceos decápodos fueron las más abundantes. En general, las larvas de los diferentes taxa estudiados mostraron una gran variabilidad en cuanto a su distribución espacial. La distribución horizontal de las larvas de los diferentes grupos de invertebrados mostró que las densidades más altas se registraban alrededor de la isla en la banda cercana y orientada hacia el suroeste, en la dirección del flujo, mientras que los valores más bajos se encontraron en el norte y en los flancos este y oeste de la isla. Por otro lado, las larvas de estomatópodos y moluscos presentaron una distribución asociada al frente del filamento, mientras que las larvas de decápodos pelágicos se distribuyeron en torno al remolino ciclónico. Los resultados obtenidos sugieren la existencia de mecanismos de retención específicos para el mantenimiento de las poblaciones insulares, relacionados con los procesos físicos de mesoescala predominantes.This work was funded by the MAST 0031 project of the European Union and the ConAfrica project (CICYT, CTM2004-02319) of the Ministerio de Educación y Ciencia. JML was supported by a postgraduate grant (BES-2005-10960) from the European Social Fund.Peer reviewe

Protein-DNA charge transport: Redox activation of a DNA repair protein by guanine radical

DNA charge transport (CT) chemistry provides a route to carry out oxidative DNA damage from a distance in a reaction that is sensitive to DNA mismatches and lesions. Here, DNA-mediated CT also leads to oxidation of a DNA-bound base excision repair enzyme, MutY. DNA-bound Ru(III), generated through a flash/quench technique, is found to promote oxidation of the [4Fe-4S](2+) cluster of MutY to [4Fe-4S](3+) and its decomposition product [3Fe-4S](1+). Flash/quench experiments monitored by EPR spectroscopy reveal spectra with g = 2.08, 2.06, and 2.02, characteristic of the oxidized clusters. Transient absorption spectra of poly(dGC) and [Ru(phen)(2)dppz](3+) (dppz = dipyridophenazine), generated in situ, show an absorption characteristic of the guanine radical that is depleted in the presence of MutY with formation instead of a long-lived species with an absorption at 405 nm; we attribute this absorption also to formation of the oxidized [4Fe-4S](3+) and [3Fe4S](1+) clusters. In ruthenium-tethered DNA assemblies, oxidative damage to the 5'-G of a 5'-GG-3' doublet is generated from a distance but this irreversible damage is inhibited by MutY and instead EPR experiments reveal cluster oxidation. With ruthenium-tethered assemblies containing duplex versus single-stranded regions, MutY oxidation is found to be mediated by the DNA duplex, with guanine radical as an intermediate oxidant; guanine radical formation facilitates MutY oxidation. A model is proposed for the redox activation of DNA repair proteins through DNA CT, with guanine radicals, the first product under oxidative stress, in oxidizing the DNA-bound repair proteins, providing the signal to stimulate DNA repair

Oceanographic processes shape genetic signatures of planktonic cephalopod paralarvae in two upwelling regions

The planktonic paralarval stage of cephalopods (octopus, squids and cuttlefishes) is an important dispersal phase, particularly of benthic species, that lasts from days to months. Cephalopod paralarvae modify their vertical position in the water in upwelling ecosystems and such behaviour influences their spatial distribution and genetic structure, but to what extent? In this work specific water masses were sampled with Lagrangian buoys in two contrasting upwelling systems (Iberian Peninsula and Morocco) of the Iberian-Canary current eastern boundary upwelling (ICC) in order to: (i) identify the cephalopod assemblage in the different upwelling systems (ii) define their planktonic dispersal patterns and (iii) analyse the effect of different dispersal patterns on genetic structure and connectivity. Cephalopod paralarvae were identified using the cytochrome c oxidase subunit I gene (COI), revealing 21 different species and F-st values showed no population structure between both upwelling systems. Cephalopod species richness was two times higher in the Moroccan upwelling than in the Iberian Peninsula, with an undescribed Ancistrocheiridae species identified in Moroccan waters. Three common planktonic dispersal patterns were identified in the ICC: coastal, coastal-oceanic and oceanic. Coastal and oceanic dispersal patterns favoured spatio-temporal paralarval retention or "schooling" of different cohorts over the continental shelf and continental slope in 9 and 11 species, respectively. Such spatio-temporal retention was reflected in the complex haplotype networks and high nucleotide/haplotype diversity recorded for these two groups. The only cephalopod species displaying a coastal-oceanic dispersal pattern was Octopus vulgaris, where low nucleotide and haplotype diversity was observed. The observed decline in genetic structure resulted from the dispersal of similar cohorts within upwelling currents and upwelling filaments to the oceanic realm. Seascape analysis revealed that cephalopod paralarvae from two coastal upwelling ecosystems of the ICC display three planktonic dispersal patterns with contrasting distributions and signatures at the genetic level