ALBERT

Description: Microbial mats collected at cold methane seeps in the Black Sea carry out anaerobic oxidation of methane (AOM) to carbon dioxide using sulfate as the electron acceptor. These mats, which predominantly consist of sulfate-reducing bacteria and archaea of the ANME-1 and ANME-2 type, contain large amounts of proteins very similar to methyl-coenzyme M reductase from methanogenic archaea. Mass spectrometry of mat samples revealed the presence of two nickel-containing cofactors in comparable amounts, one with the same mass as coenzyme F430 from methanogens (m/z = 905) and one with a mass that is 46 Da higher (m/z = 951). The two cofactors were isolated and purified, and their constitution and absolute configuration were determined. The cofactor with m/z = 905 was proven to be identical to coenzyme F430 from methanogens. For the m/z = 951 species, high resolution ICP-MS pointed to F430 + CH2S as the molecular formula, and LA-ICP-SF MS finally confirmed the presence of one sulfur atom per nickel. Esterification gave two stereoisomeric pentamethyl esters with m/z = 1021, which could be purified by reverse phase HPLC and were subjected to comprehensive NMR analysis, allowing determination of their constitution and configuration as (172S)−172-methylthio-F430 pentamethyl ester and (172R)−172-methylthio-F430 pentamethyl ester. The corresponding diastereoisomeric pentaacids could also be separated by HPLC and were correlated to the esters via mild hydrolysis of the latter. Equilibration of the pentaacids under acid catalysis showed that the (172S) isomer is the naturally occurring albeit thermodynamically less stable one. The more stable (172R) isomer (80% at equilibrium) is an isolation artifact generated under the acidic conditions necessary for the isolation of the cofactors from the calcium carbonate-encrusted mats.

Description: Marine methane hydrate in sands has huge potential as an unconventional gas resource; however, no field test of their production potential had been conducted. Here, we report the world’s first offshore methane hydrate production test conducted at the eastern Nankai Trough and show key findings toward future commercial production. Geological analysis indicates that hydrate saturation reaches 80% and permeability in the presence of hydrate ranges from 0.01 to 10 mdarcies. Permeable (1–10 mdarcies) highly hydrate-saturated layers enable depressurization-induced gas production of approximately 20,000 Sm3/D with water of 200 m3/D. Numerical analysis reveals that the dissociation zone expands laterally 25 m at the front after 6 days. Gas rate is expected to increase with time, owing to the expansion of the dissociation zone. It is found that permeable highly hydrate-saturated layers increase the gas–water ratio of the production fluid. The identification of such layers is critically important to increase the energy efficiency and the technical feasibility of depressurization-induced gas production from hydrate reservoirs.

Description: The guest-exchange method (or replacement) for methane production from gas hydrates has recently received attention because it can be used for both carbon dioxide sequestration and methane production. The structure of gas hydrates is maintained as a structure I (sI) hydrate while methane molecules are exchanged with carbon dioxide. In this study, CH4 + CO2 mixed gas hydrates were examined under terahertz light at various temperatures to simulate CH4–CO2 exchange reactions. Each gas hydrate composition examined was a representative composition at each step of the exchange reaction. The molecular composition was also accurately analyzed by gas chromatography. Refractive indices calculated by the terahertz time-domain spectroscopy (THz-TDS) of gas hydrate samples were correlated to the guest composition, and this novel method was proven to be used to quantify the extent of replacement via optical constant. Furthermore, changes in the water framework from the sI hydrate to ice using THz-TDS were investigated with an increasing temperature. Overall, this study reveals the process of guest exchange and phase transition from a gas hydrate to ice via the optical properties in the terahertz region, and it offers a powerful tool in gas hydrate production.

Description: Responses obtained in consonant perception experiments typically show a large variability across stimuli of the same phonetic identity. The present study investigated the influence of different potential sources of this response variability. It was distinguished between source-induced variability, referring to perceptual differences caused by acoustical differences in the speech tokens and/or the masking noise tokens, and receiver-related variability, referring to perceptual differences caused by within- and across-listener uncertainty. Consonant-vowel combinations consisting of 15 consonants followed by the vowel /i/ were spoken by two talkers and presented to eight normal-hearing listeners both in quiet and in white noise at six different signal-to-noise ratios. The obtained responses were analyzed with respect to the different sources of variability using a measure of the perceptual distance between responses. The speech-induced variability across and within talkers and the across-listener variability were substantial and of similar magnitude. The noise-induced variability, obtained with time-shifted realizations of the same random process, was smaller but significantly larger than the amount of within-listener variability, which represented the smallest effect. The results have implications for the design of consonant perception experiments and provide constraints for future models of consonant perception.

Description: Seafloor topography is neither spatially homogeneous, nor does it obey Gaussian statistics; deviations from both of these assumptions are important from a geological and acoustic point of view. It has been found that the distribution of topographic slopes can be used as a primary tool for understanding the sources and extent of spatial heterogeneities and patterns on the seafloor. The covariance function has been widely used to characterize seafloor topography, but requires the assumption of Gaussian joint probability statistics to be valid. For heterogeneous topography characterized by large transient signals such as steep scarps and volcanoes, the covariance becomes dominated by the transients; in contrast the family slope distributions can still be used to derive stable descriptors for regions with large transient signals, as well as regions containing asymmetric features, and regions with only limited sampling. Knowledge of slopes is useful because a direct relation exists between the covariance and the slope distributions at different spatial scales. Studies of the slope distribution provide a means of identifying the presence of the non‐Gaussian elements in the topography, and flagging their spatial locations. The methods used here are demonstrated by applying them to three small patches of topography located within 20 km of each other in the Eastern Pacific. It is found that dominant azimuthal directions and dip angles differ widely between the patches. In addition, asymmetries in the cross‐sectional shapes of faulted abyssal hills are documented. [Work supported by ONR.]

Description: Microscopy, confocal Raman spectroscopy and powder X-ray diffraction (PXRD) were used for in situ investigations of the CO2-hydrocarbon exchange process in gas hydrates and its driving forces. The study comprises the exposure of simple structure I CH4 hydrate and mixed structure II CH4–C2H6 and CH4–C3H8 hydrates to gaseous CO2 as well as the reverse reaction, i.e., the conversion of CO2-rich structure I hydrate into structure II mixed hydrate. In the case of CH4–C3H8 hydrates, a conversion in the presence of gaseous CO2 from a supposedly more stable structure II hydrate to a less stable structure I CO2-rich hydrate was observed. PXRD data show that the reverse process requires longer initiation times, and structural changes seem to be less complete. Generally, the exchange process can be described as a decomposition and reformation process, in terms of a rearrangement of molecules, and is primarily induced by the chemical potential gradient between hydrate phase and the provided gas phase. The results show furthermore the dependency of the conversion rate on the surface area of the hydrate phase, the thermodynamic stability of the original and resulting hydrate phase, as well as the mobility of guest molecules and formation kinetics of the resulting hydrate phase.

Description: In the colloidal synthesis of iron sulfides, a series of dialkyl disulfides, alkyl thiols, and dialkyl disulfides (allyl, benzyl, tert-butyl, and phenyl) were employed as sulfur sources. Their reactivity was found to tune the phase between pyrite (FeS2), greigite (Fe3S4), and pyrrhotite (Fe7S8). DFT was used to show that sulfur-rich phases were favored when the C–S bond strength was low in the organosulfurs, yet temperature dependent studies and other observations indicated the reasons for phase selectivity were more nuanced; the different precursors decomposed through different reaction mechanisms, some involving the oleylamine solvent. The formation of pyrite from diallyl disulfide was carefully studied as it was the only precursor to yield FeS2. Raman spectroscopy indicated that FeS2 forms directly without an FeS intermediate, unlike most synthetic procedures to pyrite. Diallyl disulfide releases persulfide (S–S)2– due to the lower C–S bond strength relative to the S–S bond strength, as well as facile decomposition in the presence of amines through SN2′ mechanisms at elevated temperatures.

Description: Test specimens of methane hydrate were grown under static conditions by combining cold, pressurized CH4 gas with H2O ice grains, then warming the system to promote the reaction CH4 (g) + 6H2O (s???l) ??? CH4??6H2O. Hydrate formation evidently occurs at the nascent ice/liquid water interface, and complete reaction was achieved by warming the system above 271.5 K and up to 289 K, at 25-30 MPa, for approximately 8 hours. The resulting material is pure methane hydrate with controlled grain size and random texture. Fabrication conditions placed the H2O ice well above its melting temperature before reaction completed, yet samples and run records showed no evidence for bulk melting of the ice grains. Control experiments using Ne, a non-hydrate-forming gas, verified that under otherwise identical conditions, the pressure reduction and latent heat associated with ice melting is easily detectable in our fabrication apparatus. These results suggest that under hydrate-forming conditions, H2O ice can persist metastably at temperatures well above its melting point. Methane hydrate samples were then tested in constant-strain-rate deformation experiments at T= 140-200 K, Pc= 50-100 MPa, and ????= 10-4-10-6 s-1. Measurements in both the brittle and ductile fields showed that methane hydrate has measurably different strength than H2O ice, and work hardens to a higher degree compared to other ices as well as to most metals and ceramics at high homologous temperatures. This work hardening may be related to a changing stoichiometry under pressure during plastic deformation; x-ray analyses showed that methane hydrate undergoes a process of solid-state disproportionation or exsolution during deformation at conditions well within its conventional stability field.

Description: The acoustic backscatter of eight well‐curated ferromanganese nodules has been measured in 1 °C seawater at frequencies from 45 to 167 kHz. The nodules have diameters from 37 to 121 mm and are thought to be representative of the Cu–Ni–Co‐rich nodules from the area around 14° 40’ N, 125° 25’ W (DOMES site C). They had been collected in box cores on the Echo 1 expedition and were kept refrigerated and water soaked in air‐tight plastic bags. Acoustic backscatter variations of over 10 dB were observed while the nodule was rotated 10° to 30° about one of its principal axes. The complicated fine structure, as well as the target strength, makes it clear that nodules cannot be modeled as simple spheres.

Description: Additional data from sonobuoys and the Deep Sea Drilling Project (DSDP) justify separating sound‐velocity‐depth functions and velocity gradients (in the first layer of soft marine sediments) into some geographic areas and sediment types. Based on sonobuoy and core measurements (where V is sound velocity in km/s, and h is depth in sediments in km), the following data are obtained: continental shelf basins off Sumatra and Java—V=1.484+0.710h−0.085h2; U. S. Atlantic continental rise—V=1.513+0.828h−0.138h2; deep‐sea terrigenous sediments—V=1.519+1.227h−0.473h2; and siliceous sediments of the Bering Sea— V=1.509+0.869h−0.267h2. Selected DSDP data (through leg 74) in similar areas yield: continental terrace silt–clays—V=1.505+0.712h; deep‐sea terrigenous sediments—V=1.510+1.019h; and deep‐sea siliceous sediments—V=1.533+0.761h. Computed velocity gradients from sonobuoy measurements are generally supported by the DSDP gradients. Only DSDP data give the following: hemipelagic sediments—V=1.501+1.151h; deep‐sea calcareous sediments—V=1.541+0.928h; and deep‐sea pelagic clay—V=1.526+1.046h. Where fast sediment accumulation occurs, there has not been enough time to reduce sediment pore spaces under overburden pressure; areas of slow accumulation may have relatively high sediment structural strength. Both cases have lower velocity gradients because higher porosities and consequent lower velocities persist to deeper depths.

Description: We describe a new and efficient technique to grow aggregates of pure methane hydrate in quantities suitable for physical and material properties testing. Test specimens were grown under static conditions by combining cold, pressurized CH4 gas with granulated H2O ice, and then warming the reactants to promote the reaction CH4(g) + 6H2O(s→l) → CH4·6H2O (methane hydrate). Hydrate formation evidently occurs at the nascent ice/liquid water interface on ice grain surfaces, and complete reaction was achieved by warming the system above the ice melting point and up to 290 K, at 25−30 MPa, for approximately 8 h. The resulting material is pure, cohesive, polycrystalline methane hydrate with controlled grain size and random orientation. Synthesis conditions placed the H2O ice well above its melting temperature while reaction progressed, yet samples and run records showed no evidence for bulk melting of the unreacted portions of ice grains. Control experiments using Ne, a non-hydrate-forming gas, showed that under otherwise identical conditions, the pressure reduction and latent heat associated with ice melting are easily detectable in our fabrication apparatus. These results suggest that under hydrate-forming conditions, H2O ice can persist metastably to temperatures well above its ordinary melting point while reacting to form hydrate. Direct observations of the hydrate growth process in a small, high-pressure optical cell verified these conclusions and revealed additional details of the hydrate growth process. Methane hydrate samples were then tested in constant-strain-rate deformation experiments at T = 140−200 K, Pc = 50−100 MPa, and ε = 10-4−10-6 s-1. Measurements in both the brittle and ductile fields showed that methane hydrate has measurably different strength than H2O ice, and work hardens to an unusually high degree compared to other ices as well as to most metals and ceramics at high homologous temperatures. This work hardening may be related to a changing stoichiometry under pressure during plastic deformation; X-ray analyses showed that methane hydrate undergoes a process of solid-state disproportionation or exsolution during deformation at conditions well within its conventional stability field.

Description: Numerical tools are essential for the prediction and evaluation of conventional hydrocarbon reservoir performance. Gas hydrates represent a vast natural resource with a significant energy potential. The numerical codes/tools describing processes involved during the dissociation (induced by several methods) for gas production from hydrates are powerful, but they need validation by comparison to empirical data to instill con fidence in their predictions. In this study, we successfully reproduce experimental data of hydrate dissociation using the TOUGH+HYDRATE (T+H) code. Methane(CH4)hydrate growth and dissociation in partially water- and gas-saturated Bentheim sandstone were spatially resolved using Magnetic Resonance Imaging (MRI), which allows the in situ monitoring of saturation and phase transitions. All the CH4 that had been initially converted to gas hydrate was recovered during depressurization. The physical system was reproduced numerically, usingboth a simplified 2D model and a 3D grid involving complex Voronoi elements. We modeled dissociation using both the equilibrium and the kinetic reaction options in T+H, and we used a range of kinetic parameters for sensitivity analysis and curve fitting. We successfully reproduced the experimental results, which confirmed the empirical data that demonstrated that heattransport was the limiting factor during dissociation. Dissociation was more sensitive to kinetic parameters than anticipated, which indicates that kinetic limitations may be important in short-term core studies and a necessity in such simulations. This is the first time T+H has been used to predict empirical nonmonotonic dissociation behavior, where hydrate dissociation and reformation occurred as parallel events.

Description: Methane hydrate, a potential future energy resource, is known to occur naturally in vast quantities beneath the ocean floor and in permafrost regions. It is important to evaluate how much methane is recoverable from these hydrate reserves. This article introduces the theoretical background of HydrateResSim, the National Energy Technology Laboratory (NETL) methane production simulator for hydrate-containing reservoirs, originally developed for NETL by Lawrence Berkeley National Laboratory (LBNL). It describes the mathematical model that governs the dissociation of methane hydrate by depressurization or thermal stimulation of the system, including the transport of multiple temperature-dependent components in multiple phases through a porous medium. The model equations are obtained by incorporating the multiphase Darcy’s law for gas and liquid into both the mass component balances and the energy conservation equations. Two submodels in HydrateResSim for hydrate dissociation are also considered: a kinetic model and a pure thermodynamic model. Contrary to more traditional reservoir simulations, the set of model unknowns or primary variables in HydrateResSim changes throughout the simulation as a result of the formation or dissociation of ice and hydrate phases during the simulation. The primary variable switch method (PVSM) is used to effectively track these phase changes. The equations are solved by utilizing the implicit time finite-difference method on the grid system, which can properly describe phase appearance or disappearance as well as the boundary conditions. The Newton-Raphson method is used to solve the linear equations after discretization and setup of the Jacobian matrix. We report here the application of HydrateResSim to a three-component, four-phase flow system in order to predict the methane produced from a laboratory-scale reservoir. The first results of HydrateResSim code in a peer-reviewed publication are presented in this article. The numerical solution was verified against the state-of-the art simulator TOUGH+Hydrate. The model was then used to compare twodissociation theories: kinetic and pure equilibrium. Generally, the kinetic model revealed a lower dissociation rate than the equilibrium model. The hydrate dissociation patterns differed significantly when the thermal boundary condition was shifted from adiabatic to constant-temperature. The surface area factor was found to have an important effect on the rate of hydrate dissociation for the kinetic model. The deviation between the kinetic and equilibrium models was found to increase with decreasing surface area factor.

Description: Two new cyclic peroxides, 2 and 3, were isolated from a sample of the Norwegian sponge Plakortis simplex. Their structures including relative stereochemistry were elucidated by interpretation of MS and NMR data. Compound 3 exhibited moderate in vitro activity against six solid human tumor cell lines with IC50 values in the range 7−15 μg/mL.

Description: High‐frequency bottom acoustic and geoacoustic data from three well‐characterized sites of different bottom composition are compared with scattering models in order to clarify the roles played by interface roughness and sediment volume inhomogeneities. Model fits to backscattering data from two silty sites lead to the conclusion that scattering from volume inhomogeneities was primarily responsible for the observed backscattering. In contrast, measured bottom roughness was sufficient to explain the backscattering seen at a sandy site. Although the sandy site had directional ripples, the model and data agree in their lack of anisotropy.

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: A simple equation is presented for the dependence of sound speed on temperature, salinity, and depth of water. The comparison with Del Grosso’s NRL II shows discrepancies of the order of tenths of m/sec for realistic values of the parameters.

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: The ratio of compressional wavevelocityV p to shear wavevelocityV s , and Poisson’s ratio in marine sediments and rocks are important in modeling the sea floor for underwater acoustics,geophysics, and foundation engineering. V p and V s versus depth information was linked at common depths in terrigenous sediments (to 1000 m) and in sands (to 20 m) to yield data on V p vs V s , and V p /V s and Poisson’s ratios versus depth. Soft, terrigenous sediments usually grade with depth into mudstones and shales; V p /V s ratios vary from about 13 or more at the sea floor to about 2.6 at 1000 m. Poisson’s ratios vary from above 0.49 at the sea floor to about 0.41 at 1000 m. In sands, V p , V s , and V p /V s have very high gradients in the first few meters; below about 5 m, V p /V s ratios decrease from about 9 to about 6 at 20 m; Poisson’s ratios vary from above 0.49 at the surface to above 0.48 at 20 m. The mean value of V p /V s in 30 laboratory samples of chalk and limestone is 1.90 (standard error: 0.03); mean Poisson’s ratio is 0.31. Literature data on basalts from the sea floor are reviewed. Equations relating V p to V s are given for terrigenous sediments, sands, and basalts.

Description: Gas-hydrate accumulations located onshore in Arctic permafrost regions are seen as a potential source of natural gas. Surprisingly, most of the gas hydrate found in the Mackenzie Delta and Beaufort Sea areas was indirectly discovered or inferred from conventional hydrocarbon exploration programs. One of these occurrences, the Mallik gas-hydrate field (Figure 1), has received particular attention over the last 10 years. Two internationally partnered research well programs have intersected three intervals of gas hydrates and have allowed successful extraction of subpermafrost core samples with significant gas hydrates. The gas-hydrate intervals are up to 40 m thick and have high gas-hydrate saturation, sometimes exceeding 80% of pore volume of unconsolidated clastic sediments with average porosities from 25–40%. At Mallik, the gas-hydrate intervals are located at depths of 900–1100 m and are localized on the crest of an anticline.

Description: Calculations of the size and density of atmospheric aerosols are complicated by the fact that they can exist at concentrations highly supersaturated with respect to dissolved salts and supercooled with respect to ice. Densities and apparent molar volumes of solutes in aqueous solutions containing the solutes H2SO4, HNO3, HCl, Na2SO4, NaNO3, NaCl, (NH4)2SO4, NH4NO3, and NH4Cl have been critically evaluated and represented using fitted equations from 0 to 50 °C or greater and from infinite dilution to concentrations saturated or supersaturated with respect to the dissolved salts. Using extrapolated densities of high-temperature solutions and melts, the relationship between density and concentration is extended to the hypothetical pure liquid solutes. Above a given reference concentration of a few mol kg−1, it is observed that density increases almost linearly with decreasing temperature, and comparisons with available data below 0 °C suggest that the fitted equations for density can be extrapolated to very low temperatures. As concentration is decreased below the reference concentration, the variation of density with temperature tends to that of water (which decreases as temperature is reduced below 3.98 °C). In this region below the reference concentration, and below 0 °C, densities are calculated using extrapolated apparent molar volumes which are constrained to agree at the reference concentrations with an equation for the directly fitted density. Calculated volume properties agree well with available data at low temperatures, for both concentrated and dilute solutions. Comparisons are made with literature data for temperatures of maximum density. Apparent molar volumes at infinite dilution are consistent, on a single ion basis, to better than ±0.1 cm3 mol−1 from 0 to 50 °C. Volume properties of aqueous NaHSO4, NaOH, and NH3 have also been evaluated, at 25 °C only. In part 2 of this work (ref 1) an ion interaction (Pitzer) model has been used to calculate apparent molar volumes of H2SO4 in 0−3 mol kg−1 aqueous solutions of the pure acid and to represent directly the effect of the HSO4− ↔ H+ + SO42− reaction. The results are incorporated into the treatment of aqueous H2SO4 density described here. Densities and apparent molar volumes from −20 to 50 °C, and from 0 to 100 wt % of solute, are tabulated for the electrolytes listed in the title and have also been incorporated into the extended aerosol inorganics model (E-AIM, http://www.aim.env.uea.ac.uk/aim/aim.php) together with densities of the solid salts and hydrates.

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: A total of 19 naturally occurring bromophenols, with six new and 13 known structures, were isolated and identified from the methanolic extract of the marine red alga Rhodomela confervoides. The new compounds were identified by spectroscopic methods as 3,4-dibromo-5-((methylsulfonyl)methyl)benzene-1,2-diol (1), 3,4-dibromo-5-((2,3-dihydroxypropoxy)methyl)benzene-1,2-diol (2), 5-(aminomethyl)-3,4-dibromobenzene-1,2-diol (3), 2-(2,3-dibromo-4,5-dihydroxyphenyl)acetic acid (4), 2-methoxy-3-bromo-5-hydroxymethylphenol (5), and (E)-4-(2-bromo-4,5-dihydroxyphenyl)but-3-en-2-one (6). Each compound was evaluated for free radical scavenging activity against DPPH (α,α-diphenyl-β-dipicrylhydrazyl) and ABTS [2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonic acid)diammonium salt] radicals. Most of them exhibited potent activities stronger than or comparable to the positive controls butylated hydroxytoluene (BHT) and ascorbic acid. The results from this study suggest that R. confervoides is an excellent source of natural antioxidants, and inclusion of these antioxidant-rich algal components would likely help prevent the oxidative deterioration of food.

Description: Implantable endovascular devices such as bare metal, drug eluting, and bioresorbable stents have transformed interventional care by providing continuous structural and mechanical support to many peripheral, neural, and coronary arteries affected by blockage. Although effective in achieving immediate restoration of blood flow, the long-term re-endothelialization and inflammation induced by mechanical stents are difficult to diagnose or treat. Here we present nanomaterial designs and integration strategies for the bioresorbable electronic stent with drug-infused functionalized nanoparticles to enable flow sensing, temperature monitoring, data storage, wireless power/data transmission, inflammation suppression, localized drug delivery, and hyperthermia therapy. In vivo and ex vivo animal experiments as well as in vitro cell studies demonstrate the previously unrecognized potential for bioresorbable electronic implants coupled with bioinert therapeutic nanoparticles in the endovascular system.

Description: The current difficulty in visualizing the true extent of malignant brain tumors during surgical resection represents one of the major reasons for the poor prognosis of brain tumor patients. Here, we evaluated the ability of a hand-held Raman scanner, guided by surface-enhanced Raman scattering (SERS) nanoparticles, to identify the microscopic tumor extent in a genetically engineered RCAS/tv-a glioblastoma mouse model. In a simulated intraoperative scenario, we tested both a static Raman imaging device and a mobile, hand-held Raman scanner. We show that SERS image-guided resection is more accurate than resection using white light visualization alone. Both methods complemented each other, and correlation with histology showed that SERS nanoparticles accurately outlined the extent of the tumors. Importantly, the hand-held Raman probe not only allowed near real-time scanning, but also detected additional microscopic foci of cancer in the resection bed that were not seen on static SERS images and would otherwise have been missed. This technology has a strong potential for clinical translation because it uses inert gold-silica SERS nanoparticles and a hand-held Raman scanner that can guide brain tumor resection in the operating room.

Description: The definition of noise and signal in seismic data will vary widely with the viewer's perspective and methods to process and visualize the data. Thus we begin with our definition from the perspective of presenting structural subsurface information.

Description: The shrinking-core model of the formation of gas hydrates from ice spheres with well-defined geometry gives experimental access to the gas permeation in bulk hydrates which is relevant to their use as energy storage materials, their exploitation from natural resources, as well as to their role in flow assurance. Here we report on a new approach to model CO2 clathration experiments in the temperature range from 230 to 272 K. We develop a comprehensive description of the gas permeation based on the diffusion along the network of polyhedral cages, some of them being empty. Following earlier molecular dynamics simulation results, the jump from a cage to one of its empty neighbors is assumed to proceed via a “hole-in-cage-wall” mechanism involving water vacancies in cage walls. The rate-limiting process in the investigated temperature range can be explained by the creation of water-vacancy-interstitial pairs. The gas diffusion leads to a time-dependent cage filling which decreases across the hydrate layer with the distance from the particle surface. The model allows a prediction of the time needed for a complete conversion of ice spheres into clathrate as well as the time needed for a full equilibration of the cage fillings. The findings essentially support our earlier results obtained in the framework of a purely phenomenological permeation model in terms of the overall transformation kinetics, yet it provides for the first time insight into the cage equilibration processes. The diffusion of CO2 molecules through bulk hydrate is found to be about three to four times faster in comparison with the CH4 case.

Description: We propose an equivalence class of nonstationary Gaussian stochastic processes defined in the wavelet domain. These processes are characterized by means of wavelet multipliers and exhibit well-defined time-dependent spectral properties. They allow one to generate realizations of any wavelet spectrum. Based on this framework, we study the estimation of continuous wavelet spectra, i.e., we calculate variance and bias of arbitrary estimated continuous wavelet spectra. Finally, we develop an areawise significance test for continuous wavelet spectra to overcome the difficulties of multiple testing; it uses basic properties of continuous wavelet transform to decide whether a pointwise significant result is a real feature of the process or indistinguishable from typical stochastic fluctuations. This test is compared to the conventional one in terms of sensitivity and specificity. A software package for continuous wavelet spectral analysis and synthesis is presented.

Description: Shallow gas occurs between 0 and 1000 m below the sea floor. It consists mainly of microbial-formed or thermogenic methane or a combination of both, sometimes with a limited admixture of higher hydrocarbons (propane, butane, etc.).

Description: Consumer preference for natural food ingredients has increased in recent decades, and the natural food colorant market has grown to over one billion dollars annually. A variety of red, orange, and yellow natural colorants are approved and in use, but there still exists a lack of available blue and purple natural colorant options. The occurrence of blue colored compounds in the natural world is relatively rare. The isolation, identification, and characterization of natural blue and purple pigments obtained from underexplored natural sources such as from obscure terrestrial organisms and marine microorganisms will be discussed.

Description: A new equation for the speed of sound in sea water has been developed with validity not only for realistic combinations of the parameters salinity, temperature, and pressure, but with extension to pure water as well. This new equation, referred to as NRL II, has a standard deviation of 0.05 m/sec. Tables are presented comparing calculations using this new model to each of eight earlier equations. Graphs are also included indicating approximate corrections that could be applied to existing sound speed profiles, but it is recommended that such profiles be recalculated and new ones obtained according to NRL II.

Description: Tables for the speed of sound in sea water are presented. These tables have been prepared from an empirical formula which was derived to fit measured sound‐speed data obtained over the temperature range −3°C to 30°C, the pressure range 1.033 kg/cm2 to 1000 kg/cm2, and the salinity range 33‰ to 37‰. The discrepancy of −3.0 m/sec found by Del Grosso at 1 atm., as compared to the tables of Kuwahara, is substantiated. In addition, the pressure coefficient of sound speed observed in the present work differs from that predicted by Kuwahara.

Description: A new equation is proposed for the calculation of sound speed in seawater as a function of temperature, salinity, depth, and latitude in all oceans and open seas, including the Baltic and the Black Sea. The proposed equation agrees to better than ±0.2m∕s with two reference complex equations, each fitting the best available data corresponding to existing waters of different salinities. The only exceptions are isolated hot brine spots that may be found at the bottom of some seas. The equation is of polynomial form, with 14 terms and coefficients of between one and three significant figures. This is a substantial reduction in complexity compared to the more complex equations using pressure that need to be calculated according to depth and location. The equation uses the 1990 universal temperature scale (an elementary transformation is given for data based on the 1968 temperature scale). It is hoped that the equation will be useful to those who need to calculate sound speed in applications of marine acoustics.

Description: The first detailed quantitative observations of the two-dimensional collapse of a granular column along a horizontal channel are presented for a variety of materials. Together with the complementary study for the axisymmetric situation, we conclude that for granular collapses the generally accepted approaches, that are highly dependent on frictional parameters, do not describe the main flow phenomena. The motion divides in two main flow regimes at a∼1.8, where the aspect ratio a=hi∕di and hi and di are the initial height and width of the column. We describe the details of collapse by emphasizing the sequential occurrence of a main spreading followed by a final avalanching phase. For the low a regime, a〈1.8, we derive descriptions of the final geometry by direct physical arguments. For the large a regime, a〉1.8, we determine that nearly all details of the collapse, including the position of the flow front as a function of time, the emplacement time, the self-similar final profiles, and especially their maximum vertical and horizontal extension, are established during the spreading phase and can be expressed in terms of the initial geometrical parameters but are independent of basal and internal friction parameters.

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: Titanium (Ti) is present as a trace element in seawater at extremely low concentrations (5-350 pM, where 1 pM = 10(-12) mol L(-1)) throughout the water column. Presently, little is known about the marine biogeochemistry of Ti and there is a distinct lack of oceanic measurements of Ti, because of the combined difficulties of trace-metal clean sampling for an element at such low levels and the lack of a suitable shipboard method of analysis. Here, a new cathodic stripping voltammetry procedure is presented for the rapid determination of Ti at pM concentrations in seawater that is capable of being used directly at sea. This method utilizes the catalytic enhancement of the reduction of the complex formed between Cupferron (N-nitrosophenylhydroxylamine) and Ti(IV). While Cupferron itself acts as both a complexing agent and an oxidizing agent, it was found that the optimal sensitivity was with bromate as an auxiliary oxidant. An advantage of this method is that it is useable over the pH range of 5.5-8. Under the conditions employed in this work, detection limits ranged from 5 pM to 12 pM. This new catalytic method is significantly more sensitive than existing methods and has been extensively tested at sea in the Atlantic and Southern Oceans.

Description: Electrolytes can thermodynamically inhibit clathrate hydrate formation by lowering the activity of water in the surrounding liquid phase, causing the hydrates to form at lower temperatures and higher pressures compared to their formation in pure water. However, it has been reported that some thermodynamic hydrate inhibitors (THIs), when doped at low concentrations, could enhance the rate of gas hydrate formation. We here report a systematic study of model natural gas (a mixture of 90% methane and 10% propane) hydrate formation in strong monovalent salt solutions in a broad range of concentrations, using a high pressure automated lag time apparatus (HP-ALTA). HP-ALTA can apply a large number (〉100) of cooling ramps to a sample and construct probability distributions of gas hydrate formation for each sample. The probabilistic interpretation of data enables us to mitigate the stochastic variation inherent in the nucleation probability distributions and facilitates meaningful comparison among different samples. The electrolytes used in this work are lithium chloride (LiCl), lithium bromide (LiBr), lithium iodide (LiI), sodium chloride (NaCl), sodium bromide (NaBr), sodium iodide (NaI), potassium chloride (KCl), potassium bromide (KBr), and potassium iodide (KI). We found that (1) some salts may act as kinetic hydrate promoters at low concentrations; (2) the width of the probability distributions (stochasticity) of natural gas hydrate formation in these salt solutions was significantly narrower than that in pure water. To gain further insight, we extended the study of the solutions of the same nine salts to the formation of ice and model tetrahydrofuran (THF) hydrate for comparison.

Description: In studies in underwater acoustics,geophysics, and geology, the relations between soundvelocity and density allow assignment of approximate values of density to sediment and rock layers of the earth’s crust and mantle, given a seismicmeasurement of velocity. In the past, single curves of velocity versus density represented all sediment and rock types. A large amount of recent data from the Deep Sea Drilling Project (DSDP), and reflection and refraction measurements of soundvelocity, allow construction of separate velocity–density curves for the principal marine sediment and rock types. The paper uses carefully selected data from laboratory and i n s i t umeasurements to present empirical sound velocity–density relations (in the form of regression curves and equations) in terrigenous silt clays, turbidites, and shale, in calcareous materials (sediments, chalk, and limestone), and in siliceous materials (sediments, porcelanite, and chert); a published curve for DSDP basalts is included. Speculative curves are presented for composite sections of basalt and sediments. These velocity–density relations, with seismicmeasurements of velocity, should be useful in assigning approximate densities to sea‐floor sediment and rock layers for studies in marine geophysics, and in forming geoacoustic models of the sea floor for underwater acoustic studies.

Description: Two new natural products, 3 and 4, and their predecessor 7-isocyanoisoneoamphilecta-1(14),15-diene (2), of the rare isoneoamphilectane class of marine diterpenes, along with the known amphilectane diterpenes 6–8, were isolated from the n-hexane extract of the marine sponge Svenzea flava collected at Great Inagua Island, Bahamas. The molecular structures of compounds 3 and 4 were established by spectroscopic (1D/2D NMR, IR, UV, HRMS) methods and confirmed by a series of chemical correlation studies. In a first ever case study of the assignment of the absolute configuration of a molecule based on the isoneoamphilectane carbon skeleton, the absolute configuration of compound 5 was established as 3S,4R,7S,8S,11R,12S,13R by application of vibrational circular dichroism (VCD). In vitro anti-TB screenings revealed that metabolites 2–4 and, in particular, semisynthetic analogue 5, are strong growth inhibitors of Mycobacterium tuberculosis H37Rv.

Description: Seismic data are usually acquired and processed for imaging reflections. This paper describes a method of processing seismic data for imaging discontinuities (e.g., faults and stratigraphic features). One application of this nontraditional process is a 3-D volume, or cube, of coherence coefficients within which faults are revealed as numerically separated surfaces. Figure 1 compares a traditional 3-D reflection amplitude time slice with the results of the new method. To our knowledge, this is the first published method of revealing fault surfaces within a 3-D volume for which no fault reflections have been recorded.

Description: This paper proposes improved guidelines for dissolved organic matter (DOM) isolation by solid phase extraction (SPE) with a styrene-divinylbenzene copolymer (PPL) sorbent, which has become an established method for the isolation of DOM from natural waters, because of its ease of application and appreciable carbon recovery. Suwannee River water was selected to systematically study the effects of critical SPE variables such as loading mass, concentration, flow rate, and up-scaling on the extraction selectivity of the PPL sorbent. High-field Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS) and proton nuclear magnetic resonance (H-1 NMR) spectroscopy were performed to interpret the DOM chemical space of eluates, as well as permeates and-wash liquids with molecular resolution. Up to 89% dissolved organic carbon (DOC) recovery was obtained with a DOC/PPL mass ratio of 1:800 at a DOC concentration of 20 mg/L. With the 0 application of larger loading volumes, low proportions of highly oxygenated compounds were retained on the PPL sorbent. The effects of the flow rate on the extraction selectivity of the sorbent were marginal. Up-scaling had a limited effect on the extraction selectivity with the exception of increased self-esterification with a methanol solvent, resulting in methyl ester groups. Furthermore, the SPE/PPL extract exhibited highly authentic characteristics in comparison with original water and reverse osmosis samples. These findings will be useful for reproducibly isolating DOM with representative molecular compositions from various sources and concentrations and minimizing potential inconsistencies among interlaboratory comparative studies.

Description: Metabolomics offers great potential for understanding the metabolic consequences of exposure to chemicals and other stressors in the environment. Biological systems encompass humans exposed to chemicals in the environment as well as the diverse organisms inhabiting an ecosystem and exposed to environmental contaminants. An overall goal of environmental metabolomics is to understand what is metabolomically “normal” or adaptive and what constitutes a threat to human health and the environment.

Description: Two sets of equations, covering all world oceans and seas, are presented to calculate pressure from depth for the computation of sound speed, and depth from pressure for use in ocean engineering. They are based on the algorithm of UNESCO 1983 [N. P. Fofonoff and R. C. Millard, Jr., Unesco Tech. Papers in Mar. Sci. No. 44 (1983)], and on calculations from temperature and salinity profiles. The pressure to depth conversion is presented first. The equations can be used in those cases where the desired accuracy is reduced to ±0.8 m. The equations to convert depth to pressure provide an overall accuracy between ±8000 Pa and ±1000 Pa. This leads to errors in sound speed consistently smaller than ±0.02 m/s. The discussion, and comparisons with results and other formulas, suggest that the new equations are a substantial improvement on the previous simplified ones, which should now be abandoned.

Description: An overview is provided of time-independent physical/chemical properties as related to crystal structures. The following two points are illustrated in this review:  (1) Physical and chemical properties of structure I (sI) and structure II (sII) hydrates are well-defined; measurements have begun on sH. Properties of sI and sII are determined by the molecular structures, described by three heuristics:  (i) Mechanical properties approximate those of ice, perhaps because hydrates are 85 mol % water. Yet each volume of hydrate may contain as much as 180 volumes (STP) of the hydrate-forming species. (ii) Phase equilibrium is set by the size ratio of guest molecules within host cages, and three-phase (Lw−H−V) equilibrium pressure depends exponentially upon temperature. (iii) Heats of formation are set by the hydrogen-bonded crystals and are reasonably constant within a range of guest sizes. (2) Fundamental research challenges are (a) to routinely measure the hydrate phase (via diffraction, NMR, Raman, etc.), and (b) to formulate an acceptable model for hydrate formation kinetics. The reader may wish to investigate details of this review further, via references contained in several recent monographs.

Description: Attributes have proliferated recently with different selections available on different workstations. What do they all mean? When do we use one and when another? The answers to these questions are not easy but the first step is to understand what our options are, and herein lies the purpose of this article.

Description: As offshore petroleum exploration and development move into deeper water, industry must contend increasingly with gas hydrate, a solid compound that binds water and a low-molecular-weight gas (usually methane). Gas hydrate has been long studied in industry from an engineering viewpoint, due to its tendency to clog gas pipelines. However, hydrate also occurs naturally wherever there are high pressures, low temperatures, and sufficient concentrations of gas and water. These conditions prevail in two natural environments, both of which are sites of active exploration: permafrost regions and marine sediments on continental slopes. In this article we discuss seismic detection of gas hydrate in marine sediments. Gas hydrate in deepwater sediments poses both new opportunities and new hazards. An enormous quantity of natural gas, likely far exceeding the global inventory of conventional fossil fuels, is locked up worldwide in hydrates. Ex-traction of this unconventional resource presents unique exploration, engineering, and economic challenges, and several countries, including the United States, Japan, Canada, India, and Korea, have initiated joint industry-academic-governmental programs to begin studying those challenges. Hydrates also constitute a potential drilling hazard. Because hydrates are only stable in a restricted range of pressure and temperature, any activity that sufficiently raises temperature or lowers pressure could destabilize them, releasing potentially large volumes of gas and decreasing the shear strength of the host sediments. Assessment of the opportunities and hazards associated with hydrates requires reliable methods of detecting hydrate and accurate maps of their distribution and concentration. Hydrate may occur only within the upper few hundred meters of deepwater sediment, at any depth between the seafloor and the base of the stability zone, which is controlled by local pressure and temperature. Hydrate is occasionally exposed at the seafloor, where it can be detected either visually or acoustically by strong seismic reflection amplitudes or high backscatter …

Description: The conversion of alkylboranes to the corresponding alkanes is classically per-formed via protonolysis of alkylboranes. This simple reaction requires the use of severe reaction conditions, that is, treatment with a carboxylic acid at high temperature (〉150 °C). We report here a mild radical procedure for the transformation of organoboranes to alkanes. 4-tert-Butylcatechol, a well-established radical inhibitor and antioxidant, is acting as a source of hydrogen atoms. An efficient chain reaction is observed due to the exceptional reactivity of phenoxyl radicals toward alkylboranes. The reaction has been applied to a wide range of organoboron derivatives such as B-alkylcatecholboranes, trialkylboranes, pinacolboronates, and alkylboronic acids. Furthermore, the so far elusive rate constants for the hydrogen transfer between secondary alkyl radical and catechol derivatives have been experimentally determined. Interestingly, they are less than 1 order of magnitude slower than that of tin hydride at 80 °C, making catechols particularly attractive for a wide range of transformations involving C−C bond formation.

Description: The Green's function (GF) for the scalar wave equation is numerically constructed by an advanced geometric ray-tracing method based on the eikonal approximation related to the semiclassical propagator. The underlying theory is first briefly introduced, and then it is applied to acoustics and implemented in a ray-tracing-type numerical simulation. The so constructed numerical method is systematically used to calculate the sound field in a rectangular (cuboid) room, yielding also the acoustic modes of the room. The simulated GF is rigorously compared to its analytic approximation. Good agreement is found, which proves the devised numerical approach potentially useful also for low frequency acoustic modeling, which is in practice not covered by geometrical methods.

Description: Chemicals targeting the liver stage (LS) of the malaria parasite are useful for causal prophylaxis of malaria. In this study, four lichen metabolites, evernic acid (1); vulpic acid (2), psoromic acid (3), and, (+)-usnic acid (4), were evaluated against LS parasites of Plasmodium berghei. Inhibition Of P. falciparum blood Stage (BS) parasites was also assessed to determine stage specificity. Compound 4 displayed the highest LS activity and stage specificity (LS IC50 value 2.3 mu M, BS IC50 value 47.3 mu M). The compounds 1 - 3 inhibited one Or more enzymes (Pf FabI, PfFabG, and pfFabZ), from the Plasmodial fatty acid biosynthesis (FAS-II) pathway, a potential drug. target for LS activity. To determine species specificity and to clarify the mechanism of reported antibacterial effects, 1-4 were also evaluated against FabI homologues and Whole cells of various pathogens -(S. aureus, E. coli M. tuberculosis). Molecular modeling studies suggest that lichen acids act indirectly via binding to allosteric sites on the protein surface of the FAS-II enzymes. Potential. toxicity, of compounds was assessed in human hepatocyte and cancer cells (in vitro) as well as in a zebrafish model (in vivo):. This study indicates the therapeutic and prophylactic potential of lichen metabolites as antibacterial and antiplasmodial agents.

Description: Macroalgae have for centuries been consumed whole among the East Asian populations of China, Korea, and Japan. Due to the environment in which they grow, macroalgae produce unique and interesting biologically active compounds. Protein can account for up to 47% of the dry weight of macroalgae depending on species and time of cultivation and harvest. Peptides derived from marcoalgae are proven to have hypotensive effects in the human circulatory system. Hypertension is one of the major, yet controllable, risk factors in cardiovascular disease (CVD). CVD is the main cause of death in Europe, accounting for over 4.3 million deaths each year. In the United States it affects one in three individuals. Hypotensive peptides derived from marine and other sources have already been incorporated into functional foods such as beverages and soups. The purpose of this review is to highlight the potential of heart health peptides from macroalgae and to discuss the feasibility of expanding the variety of foods these peptides may be used in.

Description: The chemical composition of the Caribbean sponge Pandaros acanthifolium was reinvestigated and led to the isolation of 12 new steroidal glycosides, namely, pandarosides E-J (1-6) and their methyl esters (7-12). Their structures were determined on the basis of extensive spectroscopic analyses, including two-dimensional NMR and HRESIMS data. Like the previously isolated pandarosides A-D (13-16), the new compounds 1-12 share an unusual oxidized D-ring and a cis C/D ring junction. The absolute configurations of the aglycones were assigned by interpretation of CD spectra, whereas the absolute configurations of the monosaccharide units were determined by chiral GC analyses of the acid methanolysates. The majority of the metabolites showed in vitro activity against three or four parasitic protozoa. Particularly active were the compounds 3 (pandaroside G) and its methyl ester (9), which potently inhibited the growth of Trypanosoma brucei rhodesiense (IC(50) values 0.78 and 0.038 mu M, respectively) and Leishmania donovani (IC(50)'s 1.3 and 0.051 mu M, respectively).

Description: Anthecularin (1), a minor sesquiterpene lactone with a novel ring system was isolated from Greek Anthemis auriculata (Asteraceae). Its structure was elucidated by means of NMR, HRMS, and X-ray crystallography. Anthecularin showed antitrypanosomal (IC50 = 10.1 μg/mL) and antiplasmodial activity (IC50 = 23.3 μg/mL) and inhibited two key enzymes of the plasmodial type II fatty acid biosynthesis pathway, PfFabI and PfFabG (IC50 values = 14 and 28.3 μg/mL, respectively). A probable biogenesis of 1 is also proposed and discussed.

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: The water-soluble part of the methanolic extract from the aerial parts of Scrophularia crypthophila, through chromatographic methods, yielded three new resin glycosides, crypthophilic acids A−C (1−3). Compounds 1−3 are tetraglycosides of (+)-3S,12S-dihydroxypalmitic acid. The structures of these and 10 known compounds were elucidated by spectroscopic and chemical means. All natural resin glycosides known so far have been obtained from Convolvulaceae plants; this is the first report of such glycosides from another, taxonomically unrelated family (Scrophulariaceae).

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: Two new iridoid glucosides, 6-O-acetylajugol (1) and 7,8-epoxy-8-epi-loganic acid (2), together with five known iridoid glucosides, galiridoside (3), ajugoside (4), 10-deoxygeniposidic acid (5), 7-deoxy-8-epi-loganic acid (6), and 8-O-acetylharpagide (7), have been isolated from the aerial parts of Leonurus persicus. Leucosceptoside A (8), eugenyl β-rutinoside (9), and kaempferol 3-O-glucoside (10) were also isolated. The structures of 1 and 2 were elucidated by extensive 1D- and 2D-NMR spectroscopy and molecular modeling. The structure of 3 was confirmed by single-crystal X-ray diffraction. Antimicrobial activity of compounds (1−10) was also evaluated against a panel of Gram-positive and Gram-negative bacteria and two strains of fungi.

Description: Six new labdane diterpenoids, leopersin C (1), 15-epi-leopersin C (2), leopersin D (3), leopersin E (4), leopersin F (5), and 7-epi-leopersin F (6) were isolated from the aerial parts of Leonurus persicus. Their structures were elucidated by extensive use of 1D and 2D homonuclear and heteronuclear shift-correlated 1H−13C-NMR spectroscopic methods. Leopersin C (1) and 15-epi-leopersin C (2) were obtained as a C-15 epimeric mixture, and their structures were elucidated on this basis.

Description: Seven new labdane diterpenoids, leopersin G−L (1−4, 6−7) and 15-epi-leopersin J (5), and two known ones, 13-hydroxyballonigrinolide (8) and ballotenol (9), were isolated from the aerial parts of Leonurus persicus along with β-sitosterol and stigmasterol. The structure determinations were mainly based on 1D and 2D NMR spectra. The stereochemical configuration of ballotenol (9) was reestablished by 2D ROESY spectroscopy and by single-crystal X-ray diffraction analysis.

Description: The effects of dissolved organic compounds on the determination of nanomolar concentrations of Fe(II) have been compared using two luminol-based flow injection chemiluminescence (FI-CL) methods. One used the direct injection of sample into the luminol reagent stream, and the other incorporated on-line solid-phase extraction of the analyte on an 8-hydroxyquinoline microcolumn. The CL signals from analyses of dissolved iron species (Fe(II) and Fe(III)) with model ligands and organic compounds were examined in high-purity water and seawater. The organic compounds included natural reducing agents (e.g., ascorbic acid), nitrogen σ-donor/π-acceptor compounds (e.g., 1,4-dipyridine, protoporphyrin IX), aromatic compounds (e.g., 1,4-dihydroxybenzene), synthetic iron chelators (e.g., EDTA), and natural iron binding compounds (e.g., desferrioxamine B, ferrichrome A). Fe(II) determinations for both luminol FI-CL methods were affected by submicromolar concentrations of redox-active compounds, strong iron binding ligands (i.e., log KFeL > 6), and compounds with electron-donating functional groups in both high-purity water and seawater. This was due to reactions between organic molecules and iron species before and during analysis, rather than chemiluminescence caused by the individual organic compounds. In addition, the effects of strong ligands and size speciation on Fe(II) recoveries from seawater following acidification (pH 2) and reduction (100 μM sodium sulfite) were investigated. © 2005 American Chemical Society.

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: An automated method for on-site monitoring of uranium(VI) in raffinate streams originating from nuclear fuel reprocessing plants is described. An in-line stripping procedure (based on liquid/liquid extraction) was developed to extract U(VI) from this stream, a solvent mixture of 20% tributyl phosphate and nitric acid in kerosene, into an aqueous sodium sulfate solution, Degradation products in the solvent mixture, especially dibutyl phosphate, give rise to very strong complexes and are responsible for moderate but constant U(VI) recoveries (similar to 50%), Optimal conditions for in-line stripping comprise a mixing ratio of extractant (0.5 M sodium sulfate in water)/solvent mixture of similar to 3 and a pumping rate of similar to 0.4 mL min(-1) of the solvent mixture. The determination of U(VI) was by on-line cathodic stripping voltammmetry (CSV), preceded by adsorptive collection of the U(VL) as an oxine complex onto a hanging mercury drop electrode, Quantities of 1-2 mL of the aqueous extract were pumped into the voltammmetric cell and diluted (1/5 to 1/10) with a background electrolyte containing 0.1 M PIPES buffer, 2 x 10(-4) M oxine, 10(-4) M EDTA, and 0.2 M hydrazine hydrate (pH 9.0), The CSV peak for U(VI) was obtained at -0.68 V with a detection limit of 20 nM in the raffinate stream using an adsorption time of 120 s, Both the inline stripping procedure and the on-line measurement were fully automated, with a relative standard deviation in the measurements of 〈 5%.

Description: New indicators for optical CO2 sensors are synthesized in two steps from the commercially available diketo-pyrrolo-pyrrole (DPP) pigments Irgazin Ruby and Irgazin Scarlet. After introduction of bis(2-ethylhexyl) sulfonamide groups via a simple two-step synthesis, the pigments are rendered highly soluble in organic solvents and in polymers and show pH-dependent absorption and emission spectra. The new indicators have molar absorption coefficients in a 20 000–50 000 M–1 cm–1 range, possess quantum yields close to unity, and feature good photostability. The indicators along with a quaternary ammonium base are embedded into ethyl cellulose to give optical carbon dioxide sensors. The absorption and emission spectra of the deprotonated form are bathochromically shifted by more than 100 nm compared to the neutral form (λmax absorption 496–550 nm; λmax emission 564–587 nm). This enables colorimetric read-out and self-referenced ratiometric fluorescence intensity measurements. Importantly, the dynamic range of the sensors based on the new indicators is significantly different (0–10 kPa and 1–100 kPa CO2) that enables a broad variety of applications. New DPP dyes are conveniently prepared from commercially available pigments and represent a new class of colorimetric and fluorescent pH indicators for optical carbon dioxide sensors.

Description: The seismic trace is a complex aggregate of reflected and scattered signals from subsurface formation interfaces and heterogeneities. Although many varieties of random noise may also be present in the trace, we know from reacquiring the same seismic survey that seismic data are highly repeatable, indicating that significant information about the subsurface is contained in the trace but not yet used by our standard analysis methods. Seismic scattering is a type of signal contained in the data that is generally not utilized.

Description: Three monoterpenoid indole alkaloids (MIAs), tabernabovines A–C (1–3), were isolated from Tabernaemontana bovina. They were elucidated by spectroscopic data and computational calculations. Unlike precursors of MIAs, strictosidine and alstrostine A, alkaloid 1 consists of tryptamine and secologanin in a 2:1 ratio. Alkaloid 2 is a cage compound, and 3 possesses a bridged ring. Tabernabovine A exhibited inhibitory activity against NO production with IC50 44.1 μM compared to l-NMMA with IC50 of 48.6 μM.

Description: A synthesis of the 12,12′-azo-analogue of ritterazine N from hecogenin is reported. Ring contraction of two 6/5 bicyclic ring systems, one trans-fused and another spiro, to 5/5 spiro ring systems is accomplished with excellent stereochemical control. Key transformations include an abnormal Baeyer–Villiger oxidation, a Norrish type I cleavage, an intramolecular dipolar [3 + 2] cycloaddition, and an intramolecular oxymecuration. Failing to uncover the β-OH ketone from the isoxazoline ring, we end up with a synthesis of a cyclic analogue of ritterazine N.

Description: The first total synthesis and structure revision of (−)-11β-hydroxycurvularin (1b), a macrolide possessing a β-hydroxyketone moiety, were accomplished. The β-hydroxyketone moiety in this natural product was introduced by cleavage of the N–O bond in an isoxazoline ring that was formed diastereoselectively in a 1,5-remote stereocontrolled fashion by employing intramolecular nitrile oxide cycloaddition

Description: Euphorkanlide A (1), a highly modified ingenane diterpenoid with a C24 appendage forming an additional hexahydroisobenzofuran-fused 19-membered macrocyclic bis-lactone ring system was isolated from the roots of Euphorbia kansuensis. Its structure was determined by extensive spectroscopic analysis and quantum-chemical calculations. Compound 1 showed significant cytotoxicities against a panel of cancer cell lines (IC50s 〈 5 μM). Mechanistic study revealed that 1 could induce the generation of ROS, leading to cell cycle arrest and cell apoptosis in drug-resistant cancer cell line HCT-15/5-FU.

Description: Methane is a powerful greenhouse gas and its biological conversion in marine sediments, largely controlled by anaerobic oxidation of methane (AOM), is a crucial part of the global carbon cycle. However, little is known about the role of iron oxides as an oxidant for AOM. Here we provide the first field evidence for iron-dependent AOM in brackish coastal surface sediments and show that methane produced in Bothnian Sea sediments is oxidized in distinct zones of iron- and sulfate-dependent AOM. At our study site, anthropogenic eutrophication over recent decades has led to an upward migration of the sulfate/methane transition zone in the sediment. Abundant iron oxides and high dissolved ferrous iron indicate iron reduction in the methanogenic sediments below the newly established sulfate/methane transition. Laboratory incubation studies of these sediments strongly suggest that the in situ microbial community is capable of linking methane oxidation to iron oxide reduction. Eutrophication of coastal environments may therefore create geochemical conditions favorable for iron-mediated AOM and thus increase the relevance of iron-dependent methane oxidation in the future. Besides its role in mitigating methane emissions, iron-dependent AOM strongly impacts sedimentary iron cycling and related biogeochemical processes through the reduction of large quantities of iron oxides.

Description: High-resolution 3D (HR3D) seismic data are important for hydrocarbon exploration of shallow reservoirs, site characterization, and geohazard assessments. The goal of this contribution is to identify and quantify the parameters to increase the resolution of HR3D seismic data to meter scale. The main acquisition parameters controlling the resolution of the collected data are the spectrum of the seismic source, source-receiver offset range, and trace density. An evolution to one-meter-scale resolution of 3D seismic will rely on combining a reproducible seismic source with high frequencies up to at least 600 Hz, a high uniform trace density of more than 4 million traces per square kilometer, and an offset range shorter than approximately 200 m. The resulting 3D seismic data volume will reach meter-scale resolution for water and target depths of less than 600 m. The proposed HR3D system will be suitable for 3D and 4D characterization of seabed properties and shallow stratigraphy, the identification of geohazards and hydrocarbon leakage, and monitoring the environmental impact of offshore activities. The P-Cable 3D system is an excellent starting point for achieving one-meter-scale resolution due to its flexible and tight meter-scale shot and receiver spacing.

Description: The vast amount of plastic waste emitted into the environment and the increasing concern of potential harm to wildlife has made microplastic and nanoplastic pollution a growing environmental concern. Plastic pollution has the potential to cause both physical and chemical harm to wildlife directly or via sorption, concentration, and transfer of other environmental contaminants to the wildlife that ingest plastic. Small particles of plastic pollution, termed microplastics (〉100 nm and 〈5 mm) or nanoplastics (〈100 nm), can form through fragmentation of larger pieces of plastic. These small particles are especially concerning because of their high specific surface area for sorption of contaminants as well as their potential to translocate in the bodies of organisms. These same small particles are challenging to separate and identify in environmental samples because their size makes handling and observation difficult. As a result, our understanding of the environmental prevalence of nanoplastics and microplastics is limited. Generally, the smaller the size of the plastic particle, the more difficult it is to separate from environmental samples. Currently employed passive density and size separation techniques to isolate plastics from environmental samples are not well suited to separate microplastics and nanoplastics. Passive flotation is hindered by the low buoyancy of small particles as well as the difficulty of handling small particles on the surface of flotation media. Here we suggest exploring alternative techniques borrowed from other fields of research to improve separation of the smallest plastic particles. These techniques include adapting active density separation (centrifugation) from cell biology and taking advantage of surface-interaction-based separations from analytical chemistry. Furthermore, plastic pollution is often challenging to quantify in complex matrices such as biological tissues and wastewater. Biological and wastewater samples are important matrices that represent key points in the fate and sources of plastic pollution, respectively. In both kinds of samples, protocols need to be optimized to increase throughput, reduce contamination potential, and avoid destruction of plastics during sample processing. To this end, we recommend adapting digestion protocols to match the expected composition of the nonplastic material as well as taking measures to reduce and account for contamination. Once separated, plastics in an environmental sample should ideally be characterized both visually and chemically. With existing techniques, microplastics and nanoplastics are difficult to characterize or even detect. Their low mass and small size provide limited signal for visual, vibrational spectroscopic, and mass spectrometric analyses. Each of these techniques involves trade-offs in throughput, spatial resolution, and sensitivity. To accurately identify and completely quantify microplastics and nanoplastics in environmental samples, multiple analytical techniques applied in tandem are likely to be required.

Description: Noninvasive diagnostic by imaging combined with a contrast agent (CA) is by now the most used technique to get insight into human bodies. X-ray and magnetic resonance imaging (MRI) are widely used technologies providing complementary results. Nowadays, it seems clear that bimodal CAs could be an emerging approach to increase the patient compliance, accessing different imaging modalities with a single CA injection. Owing to versatile designs, targeting properties, and high payload capacity, nanocarriers are considered as a viable solution to reach this goal. In this study, we investigated efficient superparamagnetic iron oxide nanoparticle (SPION)-loaded iodinated nano-emulsions (NEs) as dual modal injectable CAs for X-ray imaging and MRI. The strength of this new CA lies not only in its dual modal contrasting properties and biocompatibility, but also in the simplicity of the nanoparticulate assembling: iodinated oily core was synthesized by the triiodo-benzene group grafting on vitamin E (41.7% of iodine) via esterification, and SPIONs were produced by thermal decomposition during 2, 4, and 6 h to generate SPIONs with different morphologies and magnetic properties. SPIONs with most anisotropic shape and characterized by the highest r2/r1 ratio once encapsulated into iodinated NE were used for animal experimentation. The in vivo investigation showed an excellent contrast modification because of the presence of the selected NEs, for both imaging techniques explored, that is, MRI and X-ray imaging. This work provides the description and in vivo application of a simple and efficient nanoparticulate system capable of enhancing contrast for both preclinical imaging modalities, MRI, and computed tomography.

Description: Understanding mechanical interactions between hydrate and hosting sediments is critical for evaluating formation stability and associated environmental impacts of hydrate-bearing sediments during gas production. While core-scale studies of hydrate-bearing sediments are readily available and some explanations of observed results rely on pore-scale behavior of hydrate, actual pore-scale observations supporting the larger-scale phenomena are rarely available for hydrate-bearing sediments, especially with methane as guest molecules. The primary reasons for the scarcity include the challenge of developing tools for small-scale testing apparatus and pore-scale visualization capability. We present a testing assembly that combines pore-scale visualization and triaxial test capability of methane hydrate-bearing sediments. This testing assembly allows temperature regulation and independent control of four pressures: influent and effluent pore pressure, confining pressure, and axial pressure. Axial and lateral effective stresses can be applied independently to a 9.5 mm diameter and 19 mm long specimen while the pore pressure and temperature are controlled to maintain the stability of methane hydrate. The testing assembly also includes an X-ray transparent beryllium core holder so that 3D computed tomography scanning can be conducted during the triaxial loading. This testing assembly permits pore-scale exploration of hydrate-sediment interaction in addition to the traditional stress-strain relationship. Exemplary outcomes are presented to demonstrate applications of the testing assembly on geomechanical property estimations of methane-hydrate bearing sediments.

Description: The exploration and proposed mining of sulfide massive deposits in deep-sea environments and increased use deep-sea tailings placement (DSTP) in coastal zones has highlighted the need to better understand the fate and effects of mine-derived materials in marine environments. Metal sulfide ores contain high concentrations of metal(loid)s, of which a large portion exist in highly mineralized or sulfidised forms and are predicted to exhibit low bioavailability. In this study, sediments were spiked with a range of natural sulfide minerals (including chalcopyrite, chalcocite, galena, sphalerite) to assess the bioavailability and toxicity to benthic invertebrates (bivalve survival and amphipod survival and reproduction). The metal sulfide phases were considerably less bioavailable than metal contaminants introduced to sediment in dissolved forms, or in urban estuarine sediments contaminated with mixtures of metal(loid)s. Compared to total concentrations, the dilute-acid extractable metal(loid) (AEM) concentrations, which are intended to represent the more oxidized and labile forms, were more effective for predicting the toxicity of the sulfide mineral contaminated sediments. The study indicates that sediment quality guidelines based on AEM concentrations provide a useful tool for assessing and monitoring the risk posed by sediments impacted by mine-derived materials in marine environments.

Description: Undaria pinnatifida, commonly known as wakame in Japan, is one species of brown seaweeds containing valuable bioactive organic compounds such as fucoxanthin, a carotenoid, which has numerous functional properties. However, most of the seaweeds that do not meet strict quality standards are normally discarded as wastes or returned to the sea, a situation which is becoming an environmental concern. In this research, supercritical carbon dioxide (SCCO2) extraction was investigated for the isolation of fucoxanthin. SCCO2 extraction experiments were carried out at temperature range of 25–60 °C and pressure range of 20–40 MPa, at a carbon dioxide flow rate of 1.0–4.0 mL/min. Results showed that fucoxanthin recovery closed to 80% could be obtained at 40 °C and 40 MPa in extraction time of 180 min. The recovery increased with decreasing temperature and increasing pressure. Pretreatment with microwave (MW) also enhanced the efficiency of extraction due most likely to disruption of the cell membrane. Application of SCCO2, generally regarded as safe and environmentally benign solvent, for extraction of useful bioactive compounds from unwanted or substandard seaweeds look promising in the near future. The extracts obtained using the method can be utilized as food and pharmaceutical additive, and can be used in the development of new health supplements.

Description: A bottom-simulating reflection (BSR) is a seismic reflectivity phenomenon that is widely accepted as indicating the base of the gas-hydrate stability zone. The acoustic impedance difference between sediments invaded with gas hydrate above the BSR and sediments without gas hydrate, but commonly with free gas below, are accepted as the conditions that create this reflection. The relationship between BSRs and marine gas hydrate has become so well known since the 1970s that investigators, when asked to define the most important seismic attribute of marine gas-hydrate systems, usually reply, “a BSR event.” Research conducted over the last decade has focused on calibrating seafloor seismic reflectivity across the geology of the northern Gulf of Mexico (GoM) continental slope surface to the seafloor. This research indicates that the presence and character of seafloor bright spots (SBS) can be indicators of gas hydrates in surface and near-surface sediments (Figure 1). It has become apparent that SBSs on the continental slope generally are responses to fluid and gas expulsion processes. Gas-hydrate formation is, in turn, related to these processes. As gas-hydrate research expands around the world, it will be interesting to find if SBS behavior in other deepwater settings is as useful for identifying gas-hydrate sites as in the GoM.

Description: UPLC–TOF/MS profiling, followed by the recently reported differential off-line LC–NMR (DOLC–NMR) and quantitative 1H NMR spectroscopy (qHNMR), led to the differential qualitative analysis and accurate quantitation of l-tryptophan-induced metabolome alterations of Penicillium roqueforti, which is typically used in making blue-mold cheese. Among the 24 metabolites identified, two tetrapeptides, namely, d-Phe-l-Val-d-Val-l-Tyr and d-Phe-l-Val-d-Val-l-Phe, as well as cis-bis(methylthio)silvatin, are reported for the first time as metabolites of P. roqueforti. Antimicrobial activity tests showed strong effects of the catabolic l-tryptophan metabolites 3-hydroxyanthranilic acid, anthranilic acid, and 3-indolacetic acid against Saccharomyces cerevisiae, with IC50 values between 15.6 and 24.0 μg/mL, while roquefortine C and cis-bis(methylthio)silvatin inhibited the growth of Gram-negative Escherichia coli and Gram-positive Bacillus subtilis with IC50 values between 30.0 and 62.5 μg/mL.

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: Viruses play important roles in microbial ecology and some infectious diseases, but relatively little is known about the concentrations, sources, transformation, and fate of viruses in the atmosphere. We have measured total airborne concentrations of virus-like and bacterium-like particles (VLPs between 0.02 and 0.5 μm in size and BLPs between 0.5 and 5 μm) in nine locations: a classroom, a daycare center, a dining facility, a health center, three houses, an office, and outdoors. Indoor concentrations of both VLPs and BLPs were ∼105 particles m–3, and the virus:bacteria ratio was 0.9 ± 0.1 (mean ± standard deviation across different locations). There were no significant differences in concentration between different indoor environments. VLP and BLP concentrations in outdoor air were 2.6 and 1.6 times higher, respectively, than in indoor air. At the single outdoor site, the virus:bacteria ratio was 1.4.

Description: Marine plastic debris is a global environmental problem. Surveys have shown that 〈5 mm plastic particles, known as microplastics, are significantly more abundant in surface seawater and on shorelines than larger plastic particles are. Nevertheless, quantification of microplastics in the environment is hampered by a lack of adequate high-throughput methods for distinguishing and quantifying smaller size fractions (〈1 mm), and this has probably resulted in an underestimation of actual microplastic concentrations. Here we present a protocol that allows high-throughput detection and automated quantification of small microplastic particles (20–1000 μm) using the dye Nile red, fluorescence microscopy, and image analysis software. This protocol has proven to be highly effective in the quantification of small polyethylene, polypropylene, polystyrene, and nylon-6 particles, which frequently occur in the water column. Our preliminary results from sea surface tows show a power-law increase in small microplastics (i.e., 〈1 mm) with a decreasing particle size. Hence, our data help to resolve speculation about the “apparent” loss of this fraction from surface waters. We consider that this method presents a step change in the ability to detect small microplastics by substituting the subjectivity of human visual sorting with a sensitive and semiautomated procedure.

Description: A critical examination of published data obtained primarily from recent nuclear magnetic resonance spectroscopy, X-ray absorption near-edge structure spectroscopy, electrospray ionization-mass spectrometry, and pyrolysis studies reveals an evolving new view of the molecular structure of soil humic substances. According to the new view, humic substances are collections of diverse, relatively low molecular mass components forming dynamic associations stabilized by hydrophobic interactions and hydrogen bonds. These associations are capable of organizing into micellar structures in suitable aqueous environments. Humic components display contrasting molecular motional behavior and may be spatially segregated on a scale of nanometers. Within this new structural context, these components comprise any molecules intimately associated with a humic substance, such that they cannot be separated effectively by chemical or physical methods. Thus biomolecules strongly bound within humic fractions are by definition humic components, a conclusion that necessarily calls into question key biogeochemical pathways traditionally thought to be required for the formation of humic substances. Further research is needed to elucidate the intermolecular interactions that link humic components into supramolecular associations and to establish the pathways by which these associations emerge from the degradation of organic litter.

Description: The curves of optimum frequencies versus maximum range for active sonar detection under specific sets of assumptions are presented for the more recent expressions for attenuation given by Lovett [J. Acoust. Soc. Am. 58, 620–625 (1975)] for the eastern North Pacific and Thorp [J. Acoust. Soc. Am. 42, 270 (1967)] for the western North Atlantic as corrected at low frequencies by Kibblewhite et al. [J. Acoust. Soc. Am. 60, 1040–1047 (1976)].

Description: Significant changes have occurred in the anthropogenic emissions of many compounds related to the Kyoto and Montreal Protocols within the past 20 years and many of their atmospheric abundances have responded dramatically. Additionally, there are a number of related natural compounds with underdetermined source or sink budgets. A new instrument, Medusa, was developed to make the high frequency in situ measurements required for the determination of the atmospheric lifetimes and emissions of these compounds. This automated system measures a wide range of halocarbons, hydrocarbons, and sulfur compounds involved in ozone depletion and/or climate forcing, from the very volatile perfluorocarbons (PFCs, e.g., CF4 and CF3CF3) and hydrofluorocarbons (HFCs, e.g., CH3CF3) to the higher-boiling point solvents (such as CH3CCl3 and CCl2CCl2) and CHBr3. A network of Medusa systems worldwide provides 12 in situ ambient air measurements per day of more than 38 compounds of part per trillion mole fractions and precisions up to 0.1% RSD at the five remote field stations operated by the Advanced Global Atmospheric Gases Experiment (AGAGE). This custom system couples gas chromatography/mass spectrometry (GC/MSD) with a novel scheme for cryogen-free low-temperature preconcentration (−165 °C) of analytes from 2 L samples in a two-trap process using HayeSep D adsorbent.