Electrochemical reactions of catechol, methylcatechol and dopamine at tetrahedral amorphous carbon (ta-C) thin film electrodes

The electrochemical reactions of dopamine, catechol and methylcatechol were investigated at tetrahedral amorphous carbon (ta-C) thin film electrodes. In order to better understand the reaction mechanisms of these molecules, cyclic voltammetry with varying scan rates was carried out at different pH values in H2SO4 and PBS solutions. The results were compared to the same redox reactions taking place at glassy carbon (GC) electrodes. All three catechols exhibited quasi-reversible behavior with sluggish electron transfer kinetics at the ta-C electrode. At neutral and alkaline pH, rapid coupled homogeneous reactions followed the oxidation of the catechols to the corresponding o-quinones and led to significant deterioration of the electrode response. At acidic pH, the extent of deterioration was considerably lower. All the redox reactions showed significantly faster electron transfer kinetics at the GC electrode and it was less susceptible toward surface passivation. An EC mechanism was observed for the oxidation of dopamine at both ta-C and GC electrodes and the formation of polydopamine was suspected to cause the passivation of the electrodes.

Carbon-, sulfur-, and phosphorus-based charge transfer reactions in inductively coupled plasma–atomic emission spectrometry

In this work, the influence of carbon-, sulfur-, and phosphorus-based charge transfer reactions on the emission signal of 34 elements (Ag, Al, As, Au, B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, Ga, Hg, I, In, Ir, K, Li, Mg, Mn, Na, Ni, P, Pb, Pd, Pt, S, Sb, Se, Sr, Te, and Zn) in axially viewed inductively coupled plasma–atomic emission spectrometry has been investigated. To this end, atomic and ionic emission signals for diluted glycerol, sulfuric acid, and phosphoric acid solutions were registered and results were compared to those obtained for a 1% w w− 1 nitric acid solution. Experimental results show that the emission intensities of As, Se, and Te atomic lines are enhanced by charge transfer from carbon, sulfur, and phosphorus ions. Iodine and P atomic emission is enhanced by carbon- and sulfur-based charge transfer whereas the Hg atomic emission signal is enhanced only by carbon. Though signal enhancement due to charge transfer reactions is also expected for ionic emission lines of the above-mentioned elements, no experimental evidence has been found with the exception of Hg ionic lines operating carbon solutions. The effect of carbon, sulfur, and phosphorus charge transfer reactions on atomic emission depends on (i) wavelength characteristics. In general, signal enhancement is more pronounced for electronic transitions involving the highest upper energy levels; (ii) plasma experimental conditions. The use of robust conditions (i.e. high r.f. power and lower nebulizer gas flow rates) improves carbon, sulfur, and phosphorus ionization in the plasma and, hence, signal enhancement; and (iii) the presence of other concomitants (e.g. K or Ca). Easily ionizable elements reduce ionization in the plasma and consequently reduce signal enhancement due to charge transfer reactions.

Successful functionalization of superporous zeolite templated carbon using aminobenzene acids and electrochemical methods

A novel and selective electrochemical functionalization of a highly reactive superporous zeolite templated carbon (ZTC) with two different aminobenzene acids (2-aminobenzoic and 4-aminobenzoic acid) was achieved. The functionalization was done through potentiodynamic treatment in acid media under oxidative conditions, which were optimized to preserve the unique ZTC structure. Interestingly, it was possible to avoid the electrochemical oxidation of the highly reactive ZTC structure by controlling the potential limit of the potentiodynamic experiment in presence of aminobenzene acids. The electrochemical characterization demonstrated the formation of polymer chains along with covalently bonded functionalities to the ZTC surface. The functionalized ZTCs showed several redox processes, producing a capacitance increase in both basic and acid media. The rate performance showed that the capacitance increase is retained at scan rates as high as 100 mV s−1, indicating that there is a fast charge transfer between the polymer chains formed inside the ZTC porosity or the new surface functionalities and the ZTC itself. The success of the proposed approach was also confirmed by using other characterization techniques, which confirmed the presence of different nitrogen groups in the ZTC surface. This promising method could be used to achieve highly selective functionalization of highly porous carbon materials.

Mercury determination in urine samples by gold nanostructured screen-printed carbon electrodes after vortex-assisted ionic liquid dispersive liquid–liquid microextraction

A novel approach is presented to determine mercury in urine samples, employing vortex-assisted ionic liquid dispersive liquid–liquid microextraction and microvolume back-extraction to prepare samples, and screen-printed electrodes modified with gold nanoparticles for voltammetric analysis. Mercury was extracted directly from non-digested urine samples in a water-immiscible ionic liquid, being back-extracted into an acidic aqueous solution. Subsequently, it was determined using gold nanoparticle-modified screen-printed electrodes. Under optimized microextraction conditions, standard addition calibration was applied to urine samples containing 5, 10 and 15 μg L−1 of mercury. Standard addition calibration curves using standards between 0 and 20 μg L−1 gave a high level of linearity with correlation coefficients ranging from 0.990 to 0.999 (N = 5). The limit of detection was empirical and statistically evaluated, obtaining values that ranged from 0.5 to 1.5 μg L−1, and from 1.1 to 1.3 μg L−1, respectively, which are significantly lower than the threshold level established by the World Health Organization for normal mercury content in urine (i.e., 10–20 μg L−1). A certified reference material (REC-8848/Level II) was analyzed to assess method accuracy finding 87% and 3 μg L−1 as the recovery (trueness) and standard deviation values, respectively. Finally, the method was used to analyze spiked urine samples, obtaining good agreement between spiked and found concentrations (recovery ranged from 97 to 100%).

Design of Activated Carbon/Activated Carbon Asymmetric Capacitors

Supercapacitors are energy storage devices that offer a high power density and a low energy density in comparison with batteries. Their limited energy density can be overcome by using asymmetric configuration in mass electrodes, where each electrode works within their maximum available potential window, rendering the maximum voltage output of the system. Such asymmetric capacitors are optimized using the capacitance and the potential stability limits of the electrodes, with the reliability of the design largely depending on the accuracy and the approach taken for the electrochemical characterization. Therefore, the performance could be lower than expected and even the system could break down, if a well thought out procedure is not followed. In this work, a procedure for the development of asymmetric supercapacitors based on activated carbons is detailed. Three activated carbon materials with different textural properties and surface chemistry have been systematically characterized in neutral aqueous electrolyte. The asymmetric configuration of the masses of both electrodes in the supercapacitor has allowed to cover a higher potential window, resulting in an increase of the energy density of the three devices studied when compared with the symmetric systems, and an improved cycle life.

(Table 3) Carbon isotopic composition in bottom sediments and carbonate nodules from the Gulf of California at Station DM9-666

New data on phosphorites collected by dredging and trawling at depths from 2700 to 520 m in the open Atlantic Ocean (i.e. outside of the shelf and the continental slope) are reported. Aphanitic, granular, brecciated, and conglomerate-like types are distinguished among the phosphorites. A comparison of the studied phosphorites with ones from the Atlantic shelf of Africa and from seamounts of other oceans is made.

Sampling intervals, fluxes, percentages of total flux, organic carbon and lithogen for sediment trap CB9

We combined the analysis of sediment trap data and satellite-derived sea surface chlorophyll to quantify the amount of organic carbon export to the deep sea in the upwelling induced high production area off northwest Africa. In contrast to the generally global or basin-wide adoption of export models, we used a regionally fitted empirical model. Furthermore, the application of our model was restricted to a dynamically defined region of high chlorophyll concentration in order to restrict the model application to an environment of more homogeneous export processes. We developed a correlation-based approximation to estimate the surface source area for a sediment trap deployed from 11 June 1998 to 7 November 1999 at 21.25°N latitude and 20.64°W longitude off Cape Blanc. We also developed a regression model of chlorophyll and export of organic carbon to the 1000 m depth level. Carbon export was calculated for an area of high chlorophyll concentration (>1 mg/m**3) adjacent to the coast on a daily basis. The resulting zone of high chlorophyll concentration was 20,000-800,000 km**2 large and yielded a yearly export of 1.123 to 2.620 Tg organic carbon. The average organic carbon export within the area of high chlorophyll concentration was 20.6 mg/m**2d comparable to 13.3 mg/m**2d as found in the sediment trap results if normalized to the 1000 m level. We found strong interannual variability in export. The period autumn 1998 to summer 1999 was exceeding the mean of the other three comparable periods by a factor of 2.25. We believe that this approach of using more regionally fitted models can be successfully transferred even to different oceanographic regions by selecting appropriate definition criteria like chlorophyll concentration for the definition of an area to which it is applicable.

Layer description, carbon and nitrogen content and stable isotope record of bulk sedimentary organic matter from Laguna Potrok Aike

An investigation of stable isotope (d13C TOC and d15N TN) and elemental parameters (TOC, TN contents and TOC/TN ratios) of bulk organic matter (<200 µm) from sediment cores recovered from the Patagonian lake Laguna Potrok Aike (Argentina) in the framework of the ICDP deep drilling project PASADO provided insights into past changes in lake primary productivity and environmental conditions in South Patagonia throughout the last Glacial-Interglacial transition. Stratigraphically constrained cluster analyses of all proxy parameters suggest four main phases. From ca 26,100 to 17,300 cal. years BP, lacustrine phytoplankton was presumably the predominant organic matter source in an aquatic environment with low primary productivity rates. At around 17,300 cal. years BP, abrupt and distinct shifts of isotopic and elemental values indicate that the lacustrine system underwent a rapid reorganization. Lake primary productivity (phytoplankton and aquatic macrophytes) shows higher levels albeit with large variations during most of the deglaciation until 13,000 cal. years BP. The main causes for this development can be seen in improved growing conditions for primary producers because of deglacial warming in combination with expedient availability of nutrients and likely calm wind conditions. After 13,000 cal. years BP, decreased d13C TOC values, TOC, TN contents and TOC/TN ratios indicate that the lake approached a new state with reduced primary productivity probably induced by unfavourable growing conditions for primary producers like strengthened winds and reduced nutrient availability. The steady increase in d15N TN values presumably suggests limitation of nitrate supply for growth of primary producers resulting from a nutrient shortage after the preceding phase with high productivity. Nitrate limitation and consequent decreased lacustrine primary productivity continued into the early Holocene (10,970-8400 cal. years BP) as reflected by isotopic and elemental values.

The role of large woody debris and riparian forest in channel avulsion in the Carbon River, Mount Rainier National Park, Washington

A specific type of natural log jam in the upper alluvial reach of the Carbon River was found to influence secondary channel avulsion, causing flooding hazards to the adjacent Carbon River Road in the northwest quadrant of Mount Rainier National Park, Washington. The fence-like natural log jam was characterized by large woody debris buttressed horizontally against standing riparian trees (i.e. ìfence railsî and ìfence postî). The objectives of this report are two-fold. First, physical characteristics and spatial distribution were documented to determine the geomorphic controls on the fence-like log jams. Second, the function and timing of the natural log jam in relation to channel avulsion was determined to provide insight into flooding hazards along the Carbon River Road. The fence-like log jams are most abundant in the upper reaches of the Carbon River between 3.0 and 5.5 kilometers from the Carbon Glacier terminus, where longitudinal gradient significantly decreases from about 0.06 to 0.03. Sediment impoundment can occur directly upstream of the fence-like log jam, creating vertical bed elevation difference as high as 1.32 meters, and can form during low magnitude, high frequency flood event (3.5-year recurrence interval). In some locations, headcuts and widening of secondary channel were observed directly to the side of the log jams, suggesting its role in facilitating secondary channel avulsions. Areas along the Carbon River Road more prone to damages from avulsion hazards were identified by coupling locations of the log jams and Relative Water Surface Elevation map created using the 1-meter 2012 Light Detection and Ranging Digital Elevation Map. Ultimately, the results of this report may provide insight to flooding hazards along the Carbon River Road from log jam-facilitated channel avulsion.

Non-additivity of attractive potentials in modeling of N-2 and Ar adsorption isotherms on graphitized carbon black and porous carbon by means of density functional theory

We present a new approach accounting for the nonadditivity of attractive parts of solid-fluid and fluidfluid potentials to improve the quality of the description of nitrogen and argon adsorption isotherms on graphitized carbon black in the framework of non-local density functional theory. We show that the strong solid-fluid interaction in the first monolayer decreases the fluid-fluid interaction, which prevents the twodimensional phase transition to occur. This results in smoother isotherm, which agrees much better with experimental data. In the region of multi-layer coverage the conventional non-local density functional theory and grand canonical Monte Carlo simulations are known to over-predict the amount adsorbed against experimental isotherms. Accounting for the non-additivity factor decreases the solid-fluid interaction with the increase of intermolecular interactions in the dense adsorbed fluid, preventing the over-prediction of loading in the region of multi-layer adsorption. Such an improvement of the non-local density functional theory allows us to describe experimental nitrogen and argon isotherms on carbon black quite accurately with mean error of 2.5 to 5.8% instead of 17 to 26% in the conventional technique. With this approach, the local isotherms of model pores can be derived, and consequently a more reliab * le pore size distribution can be obtained. We illustrate this by applying our theory against nitrogen and argon isotherms on a number of activated carbons. The fitting between our model and the data is much better than the conventional NLDFT, suggesting the more reliable PSD obtained with our approach.

Polyethylene multiwalled carbon nanotube composites

Polyethylene (PE) multiwalled carbon nanotubes (MWCNTs) with weight fractions ranging from 0.1 to 10 wt% were prepared by melt blending using a mini-twin screw extruder. The morphology and degree of dispersion of the MWCNTs in the PE matrix at different length scales was investigated using scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM) and wide-angle X-ray diffraction (WAXD). Both individual and agglomerations of MWCNTs were evident. An up-shift of 17 cm(-1) for the G band and the evolution of a shoulder to this peak were obtained in the Raman spectra of the nanocomposites, probably due to compressive forces exerted on the MWCNTs by PE chains and indicating intercalation of PE into the MWCNT bundles. The electrical conductivity and linear viscoelastic behaviour of these nanocomposites were investigated. A percolation threshold of about 7.5 wt% was obtained and the electrical conductivity of PE was increased significantly, by 16 orders of magnitude, from 10(-20) to 10(-4) S/cm. The storage modulus (G') versus frequency curves approached a plateau above the percolation threshold with the formation of an interconnected nanotube structure, indicative of 'pseudo-solid-like' behaviour. The ultimate tensile strength and elongation at break of the nanocomposites decreased with addition of MWCNTs. The diminution of mechanical proper-ties of the nanocomposites, though concomitant with a significant increase in electrical conductivity, implies the mechanism for mechanical reinforcement for PE/MWCNT composites is filler-matrix interfacial interactions and not filler percolation. The temperature of crystallisation (T.) and fraction of PE that was crystalline (F-c) were modified by incorporating MWCNTs. The thermal decomposition temperature of PE was enhanced by 20 K on addition of 10 wt% MWCNT. (c) 2005 Elsevier Ltd. All rights reserved.

Comparison of the particulate organic carbon and permanganate oxidation methods for estimating labile soil organic carbon

Forty-four soils from under native vegetation and a range of management practices following clearing were analysed for ‘labile’ organic carbon (OC) using both the particulate organic carbon (POC) and the 333 mm KmnO4 (MnoxC) methods. Although there was some correlation between the 2 methods, the POC method was more sensitive by about a factor of 2 to rapid loss in OC as a result of management or land-use change. Unlike the POC method, the MnoxC method was insensitive to rapid gains in TOC following establishment of pasture on degraded soil. The MnoxC method was shown to be particularly sensitive to the presence of lignin or lignin-like compounds and therefore is likely to be very sensitive to the nature of the vegetation present at or near the time of sampling and explains the insensitivity of this method to OC gain under pasture. The presence of charcoal is an issue with both techniques, but whereas the charcoal contribution to the POC fraction can be assessed, the MnoxC method cannot distinguish between charcoal and most biomolecules found in soil. Because of these limitations, the MnoxC method should not be applied indiscriminately across different soil types and management practices.

Some like it wet - biological characteristics underpinning tolerance of extreme water stress events in Antarctic bryophytes

Antarctic bryophyte communities presently tolerate physiological extremes in water availability, surviving both desiccation and submergence events. We investigated the relative ability of three Antarctic moss species to tolerate physiological extremes in water availability and identified physiological, morphological, and biochemical characteristics that assist species performance under such conditions. Tolerance of desiccation and submergence was investigated using chlorophyll fluorescence during a series of field- and laboratory-based water stress events. Turf water retention and degree of natural habitat submergence were determined from gametophyte shoot size and density, and delta C-13 signatures, respectively. Finally, compounds likely to assist membrane structure and function during desiccation events (fatty acids and soluble carbohydrates) were determined. The results of this study show significant differences in the performance of the three study species under contrasting water stress events. The results indicate that the three study species occupy distinctly different ecological niches with respect to water relations, and provide a physiological explanation for present species distributions. The poor tolerance of submergence seen in Ceratodon purpureus helps explain its restriction to drier sites and conversely, the low tolerance of desiccation and high tolerance of submergence displayed by the endemic Grimmia antarctici is consistent with its restriction to wet habitats. Finally the flexible response observed for Bryum pseudotriquetrum is consistent with its co-occurrence with the other two species across the bryophyte habitat spectrum. The likely effects of future climate change induced shifts in water availability are discussed with respect to future community dynamics.

Assembly of Human Papillomavirus Type-16 Virus-Like Particles: Multifactorial Study of Assembly and Competing Aggregation

Pentameric capsomeres of human papillomavirus capsid protein L1 expressed in Escherichia coli self-assemble into virus-like particles (VLPs) in vitro. A multifactorial experimental design was used to explore a wide range of solution conditions to optimize the assembly process. The degree of assembly was measured using an enzyme-linked immunosorbent assay, and a high-throughput turbidity assay was developed to monitor competing aggregation. The presence of zinc ions in the assembly buffer greatly increased the incidence of aggregation and had to be excluded from the experiment for meaningful analysis. Assembly of VLPs was optimal at a pH of about 6.5, calcium and sodium ions had no measurable effect, and dithiothreitol and glutathione inhibited assembly. Tryptophan fluorescence spectroscopy demonstrated that an increase in urea concentration reduced the rate of VLP formation but had no effect on the final concentration of assembled VLPs. This study demonstrates the use of the hanging-drop vapor-diffusion crystallization method to screen for conditions that promote aggregation and the use of tryptophan fluorescence spectroscopy for real-time monitoring of the assembly process.