ALBERT

Description: The anaerobic oxidation of methane (AOM) is one of the major sinks of this substantial greenhouse gas in marine environments. Recent investigations have shown that diverse communities of anaerobic archaea and sulfate-reducing bacteria are involved in AOM. Most of the relevant archaea are assigned to two distinct phylogenetic clusters, ANME-1 and ANME-2. A suite of specific 13C-depleted lipids demonstrating the presence of consortia mediating AOM in fossil and recent environments has been established. Here we report on substantial differences in the lipid composition of microbial consortia sampled from distinct compartments of AOM-driven carbonate reefs growing in the northwestern Black Sea. Communities in which the dominant archaea are from the ANME-1 cluster yield internally cyclized tetraether lipids typical of thermophiles. Those in which ANME-2 archaea are dominant yield sn-2-hydroxyarchaeol accompanied by crocetane and crocetenes. The bacterial lipids from these communities are also distinct even though the sulfate-reducing bacteria all belong to the Desulfosarcina/Desulfococcus group. Nonisoprenoidal glycerol diethers are predominantly associated with ANME-1-dominated communities. Communities with ANME-2 yield mainly conventional, ester-linked diglycerides. ANME-1 archaea and associated sulfate-reducing bacteria seem to be enabled to use low concentrations of methane and to grow within a broad range of temperatures. Our results offer a tool for the study of recent and especially of fossil methane environments.

Description: We determined the coordination environment of Zn2+ in aqueous Cl- brines at 25 °C and 300 °C using ab initio molecular dynamics simulations. The ZnCl+ and ZnCl2 complexes exist as pseudo-octahedral ZnClm(H2O)6-m clusters at 25 °C but occur as pseudo-tetrahedral ZnClm(H2O)4-m clusters at 300 °C. The ZnCl3- complex occurs as the pseudo-tetrahedral ZnCl3(H2O)- cluster at 25 and 300 °C. The tetrahedral ZnCl42- complex, however, is the dominant Zn−Cl complex at 25 °C, at least in highly concentrated (7.4 m) Cl- brines. The change in hydration number with temperature for the ZnCl+ and ZnCl2 complexes will complicate extrapolations of solvation energies to hydrothermal conditions using a Born-model-based equation of state.

Description: The valuable nutraceutical γ-linolenic acid (GLA, (6Z,9Z,12Z)-octadecatrienoic acid) is biosynthesized by a series of regio- and stereoselective dehydrogenation reactions that are catalyzed by a set of enzymes known as fatty acid desaturases. As part of ongoing research into the mechanism of these remarkable catalysts, we have examined the cryptoregiochemistry (site of initial oxidation) of Δ6 desaturation as it occurs in the protozoan Tetrahymena thermophila. Two complementary approaches that address this issue are described. In the first set of experiments, we measured the individual primary deuterium kinetic isotope effects associated with the C−H bond cleavages at C-6 and C-7. Competition experiments using appropriately deuterium-labeled 4-thiasubstrates revealed that a large KIE (kH/kD = 7.1 ± 0.5) was observed for the C−H bond-breaking step at C-6, whereas the C−H bond cleavage at C-7 was insensitive to deuterium substitution (kH/kD = 1.04 ± 0.05). These results point to C-6 as the site of initial oxidation in Δ6 desaturation since the first chemical step in this type of reaction is rupture of a strong, unactivated C−H bond, an energetically difficult process that typically exhibits a large KIE. This conclusion was supported by the results of our second approach, which involved locating the position of the putative diiron oxo oxidant with respect to substrate by monitoring the efficiency of oxo transfer to a series of thia fatty acid probes. Thus only a 6-thia-analogue is converted to significant amounts of the corresponding sulfoxide (9% yield). The absolute configuration of this product was determined to be S using (S)-MPAA as a chiral shift reagent. Taken together, these results point to the abstraction of the C-6 pro S hydrogen as the initial event in Δ6 desaturation as it occurs in T. thermophila.

Description: Concentrations of biodiversity, or hotspots, represent conservation priorities in terrestrial ecosystems but remain largely unexplored in marine habitats. In the open ocean, many large predators such as tunas, sharks, billfishes, and sea turtles are of current conservation concern because of their vulnerability to overfishing and ecosystem role. Here we use scientific-observer records from pelagic longline fisheries in the Atlantic and Pacific Oceans to show that oceanic predators concentrate in distinct diversity hotspots. Predator diversity consistently peaks at intermediate latitudes (20–30° N and S), where tropical and temperate species ranges overlap. Individual hotspots are found close to prominent habitat features such as reefs, shelf breaks, or seamounts and often coincide with zooplankton and coral reef hotspots. Closed-area models in the northwest Atlantic predict that protection of hotspots outperforms other area closures in safeguarding threatened pelagic predators from ecological extinction. We conclude that the seemingly monotonous landscape of the open ocean shows rich structure in species diversity and that these features should be used to focus future conservation efforts.

Description: High-performance liquid chromatography-electrospray ionization mass spectrometry was applied to the detection of the iron(III) complexes of the hydroxamate siderophores rhodotoluric acid, deferrioxamine B, and deferrichrome. Separation of the iron(III) complexes was obtained using a polystyrene-divinylbenzene stationary phase. The retention and responses of ferrioxamine and ferrichrome were optimal when a gradient elution program with methanol and 0.1% (v/v) formic acid as the mobile phases was used. These conditions were also suitable for the retention and separation of the uncomplexed ligands. Retention of iron(III) rhodotoluate was improved when formic acid was replaced by the ion-pairing reagent heptafluorobutyric acid (0.1%). Detection limits for the ferric complexes, defined as 3 SD of the lowest determined standard, were 26 nM for iron(III) rhodotoluate, 0.23 nM for ferrioxamine, and 0.40 nM for ferrichrome. A protocol for the solid-phase extraction of these hydroxamate siderophores from seawater was developed and applied to the extraction of siderophores from enriched incubated seawater samples.

Description: High-performance liquid chromatography-electrospray ionization mass spectrometry was applied to the detection of the iron(III) complexes of the hydroxamate siderophores rhodotoluric acid, deferrioxamine B, and deferrichrome. Separation of the iron(III) complexes was obtained using a polystyrene-divinylbenzene stationary phase. The retention and responses of ferrioxamine and ferrichrome were optimal when a gradient elution program with methanol and 0.1% (v/v) formic acid as the mobile phases was used. These conditions were also suitable for the retention and separation of the uncomplexed ligands. Retention of iron(III) rhodotoluate was improved when formic acid was replaced by the ion-pairing reagent heptafluorobutyric acid (0.1%). Detection limits for the ferric complexes, defined as 3 SD of the lowest determined standard, were 26 nM for iron(III) rhodotoluate, 0.23 nM for ferrioxamine, and 0.40 nM for ferrichrome. A protocol for the solid-phase extraction of these hydroxamate siderophores from seawater was developed and applied to the extraction of siderophores from enriched incubated seawater samples.

Description: The climate of the Atlantic sector exhibits considerable variability on a wide range of time scales. A substantial portion is associated with the North Atlantic Oscillation (NAO), a hemispheric meridional oscillation in atmospheric mass with centers of action near Iceland and over the subtropical Atlantic. NAO-related impacts on winter climate extend from Florida to Greenland and from northwestern Africa over Europe far into northern Asia. Over the last 3 decades, the phase of the NAO has been shifting from mostly negative to mostly positive index values. Much remains to be learned about the mechanisms that produce such low frequency changes in the North Atlantic climate, but it seems increasingly likely that human activities are playing a significant role. When the North Atlantic Oscillation (NAO) is in its positive phase, low-pressure anomalies over the Icelandic region and throughout the Arctic combine with high-pressure anomalies across the subtropical Atlantic to produce stronger-than-average westerlies across the midlatitudes. During a positive NAO, conditions are colder and drier than average over the northwestern Atlantic and Mediterranean regions, whereas conditions are warmer and wetter than average in northern Europe, the eastern United States, and parts of Scandinavia (Fig. 1 top). Walker and Bliss (1) were among the first to recognize and study this pattern of climate anomalies, which is most pronounced during boreal winter (December through March).

Description: Modern models for the development and evolution of the geochemical heterogeneity in the Earth's mantle and the genesis of mantle magmas attach much importance to the processes of interaction between deepseated rocks and metasomatic fluids, which are able, when occurring under mantle conditions, to dissolve significant amounts of major and trace elements (see, for example, [1]). Fluorine is one of the major anions of natural fluids and also one of the principal complex-forming ligands of several metals. To evaluate the possible role of fluorine in the processes of mantle magma genesis and to identify the source of this element in natural magmas in various geodynamic environments, it is necessary to know the fluorine concentration in primitive mantle melts. These data are still relatively scarce, particularly for low alkaline magmas [2-4]. The fluorine concentrations in magmas from suprasubduction zones, whose genesis is largely controlled by the interaction between mantle rocks and fluids, remain poorly known and need further refinement. Data presented in this paper are among the first to characterize the concentrations of fluorine in primitive magmas of suprasubduction zones. These data were obtained by secondary ion mass spectrometry of chill glasses from the lava complex of the Troodos ophiolites in Cyprus. Along with information on the concentrations of major and trace elements, H2O, and Cl in the glasses, our results make it possible to utilize the example of the Troodos ophiolites to characterize the main regularities in the geochemistry of fluorine during the origin of magmas above subduction zones and to assay the contributions of various components that participated in the processes of mantle melting. These data are among the first to demonstrate that subduction-related melts became enriched in F relative to LREE.

Description: Microcionamides A (1) and B (2) have been isolated from the Philippine marine sponge Clathria (Thalysias) abietina. These new linear peptides are cyclized via a cystine moiety and have their C-terminus blocked by a 2-phenylethylenamine group. Their total structures, including absolute stereochemistry, were determined by a combination of spectral and chemical methods. Compound 1 was shown to slowly isomerize about the C-36/C-37 double bond when stored in DMSO. Microcionamides A (1) and B (2) exhibited significant cytotoxicity against the human breast tumor cells lines MCF-7 and SKBR-3 and displayed inhibitory activity against Mycobacterium tuberculosis H37Ra.

Description: Two new isomalabaricane triterpenes, stellettin H (1) and stellettin I (2), have been isolated from the marine sponge Rhabdastrella globostellata, collected from the Philippines. Stellettins A−D (3−6), (−)-stellettin E (7), and rhabdastrellic acid-A (8) were also isolated and characterized. Stellettin B (4) and (−)-stellettin E (7) showed selective cytotoxicity toward p21WAF1/Cip1-deficient human colon tumor (HCT-116) cells with IC50 values of 0.043 and 0.039 μM, respectively.

Description: Raf/MEK-1/MAPK cascade inhibitor activity-directed fractionation of the sponge Stylissa massa afforded eight known alkaloids:  aldisine (1), 2-bromoaldisine (2), 10Z-debromohymenialdisine (3), 10E-hymenialdisine (4), 10Z-hymenialdisine (5), hymenin (6), oroidin (7), and 4,5-dibromopyrrole-2-carbonamide (8). Both 4 and 5 showed significant enzyme inhibitory activity (IC50 3 and 6 nM, respectively). Secondary assays identified these compounds as potent MEK-1 inhibitors. Compounds 4 and 5 also inhibited the growth of human tumor LoVo cells.

Description: From the aerial parts of Putoria calabrica, two new flavonol triglycosides were isolated and their structures were elucidated as quercetin-3-O-[α-l-rhamnopyranosyl-(1→2)-α-l-arabinopyranoside]-7-O-β-d-glucopyranoside (1, calabricoside A) and quercetin-3-O-[4‘ ‘‘-O-caffeoyl-α-l-rhamnopyranosyl-(1→2)-α-l-arabinopyranoside]-7-O-β-d-glucopyranoside (2, calabricoside B). Additionally, seven iridoid and three lignan glycosides were isolated and characterized. Radical scavenging activities of all compounds were determined by quantifying their effects on luminol-enhanced chemiluminescence in formyl-methionyl-leucyl-phenylalanine (FMLP) stimulated human polymorphonuclear neutrophils (PMNs). Calabricoside A and B showed strong radical scavenging activity with IC50 values of 0.25 and 0.3 μM, respectively.

Description: A new iridoid glucoside, 5β,6β-dihydroxyboschnaloside (1), was isolated from the aerial parts of Euphrasia pectinata. Five known iridoid glucosides, 6β-hydroxyboschnaloside (2), aucubin, euphroside, plantarenaloside, and geniposidic acid, and two known phenylethanoid glycosides, verbascoside (= acteoside) and leucosceptoside A, were also obtained and characterized. The structure of compound 1 was established by spectroscopic evidence.

Description: The increasing environmental pressures on estuarine and coastal waters call for improved monitoring techniques of chemical constituents to aid management decisions. Automated stripping voltammetry is a suitable technique for continuous, near real-time monitoring of trace metals in marine systems. This contribution describes the application of voltammetric monitoring techniques in estuarine and coastal waters of the UK and Spain. The high spatial and temporal resolution of the data obtained, allows a thorough interpretation of the trace metal sources and behaviour. Future trends in this field research include submersible sensors which can be remotely deployed for a period of several weeks.

Description: Coccolithophores are a group of calcifying unicellular algae that constitute a major fraction of oceanic primary productivity, play an important role in the global carbon cycle, and are key biostratigraphic marker fossils. Their taxonomy is primarily based on the morphology of the minute calcite plates, or coccoliths, covering the cell. These are diverse and include widespread fine scale variation, of which the biological/taxonomic significance is unknown. Do they represent phenotypic plasticity, genetic polymorphisms, or species-specific characters? Our research on five commonly occurring coccolithophores supports the hypothesis that such variation represents pseudocryptic speciation events, occurring between 0.3 and 12.9 million years ago from a molecular clock estimation. This finding suggests strong stabilizing selection acting on coccolithophorid phenotypes. Our results also provide strong support for the use of fine scale morphological characters of coccoliths in the fossil record to improve biostratigraphic resolution and paleoceanographic data retrieval.

Description: Penicillium expansum is known for its destructive rot and patulin production in apple juice. According to the literature, P. expansum can, among other compounds, produce citrinin, ochratoxin A, patulin, penitrem A, and rubratoxin B. In this study the qualitative production of metabolites was examined using TLC (260 isolates), HPLC (85 isolates), and MS (22 isolates). The results showed that none of the 260 isolates produced ochratoxin A, penitrem A, or rubratoxin B. However, chaetoglobosin A and communesin B were produced consistently by all 260 isolates. Patulin and roquefortine C were produced by 98% of the isolates. Expansolides A/B and citrinin were detected in 91 and 85% of the isolates, respectively. Chaetoglobosins and communesins were detected in naturally infected juices and potato pulp, whereas neither patulin nor citrinin was found. Because most P. expansum isolates produce patulin, citrinin, chaetoglobosins, communesins, roquefortine C, and expansolides A and B, foods contaminated with this fungus should ideally be examined for chaetoglobosin A as well as patulin.

Description: Results of an experimental study of a Hopf bifurcation with broken translation symmetry that organizes chaotic homoclinic dynamics from a T2 torus in a fluid flow as a direct consequence of physical boundaries are presented. It is shown that the central features of the theory of Hopf bifurcation in O(2)-symmetric systems where the translation symmetry is broken are robust and are appropriate to describe the appearance of modulated waves, homoclinic bifurcation, Takens-Bogdanov point, and chaotic dynamics in a fluid flow experiment.

Description: Experimental evidence for standing waves resulting from a supercritical Hopf bifurcation that appears as the first pattern-forming instability in counterrotating Taylor-Couette flow is presented. Depending on the aspect ratio two different types of standing waves, denoted as SW0 and SWp, could be observed. Both modes have an azimuthal wave number m51 but differ in symmetry. While for SWp , a spatiotemporal glide-reflection symmetry could be found, SW0 is purely spatial reflection symmetric. The transition between the two modes is found to be organized in a cusp bifurcation unfolded by variations of the aspect ratio. The ‘‘classical’’ spiral vortex flow appears in this control parameter regime only as a result of a secondary steady bifurcation from SW0. This transition is found to be either subcritical or supercritical. The experimentally observed bifurcation structure has been predicted by theory of Hopf bifurcation to spiral vortex flow in finite counterrotating Taylor-Couette systems.