Molecular mass calibration in size-exclusion chromatography of coal derivatives

A number of procedures have been investigated for the calibration of a size-exclusion chromatography (s.e.c.) column in the determination of molecular mass (MM) distributions of coal derivatives. The behaviour of narrow fractions of coal extracts in the MM range 200–3000 was compared with a variety of the more generally available calibration standards. Calibration with preparative s.e.c. subfractions of materials similar to those under study has been recommended. Polystyrene standards are satisfactory, however, for MM < 1000, but above this range other polymer standards should be sought. Universal and molar volume calibration do not apply to coal-derived materials.     

Accumulation and depuration of polychlorinated biphenyls from field-collected sediment in three freshwater organisms

As laboratory-based bioaccumulation methods are standardized and expanded to include other test species, kinetic studies assessing the major classes of contaminants with these species are needed to adequately select the standard duration for bioaccumulation tests. In the present study we measured the uptake (28-d exposure) of polychlorinated biphenyls (PCBs; total and selected congeners) from field-contaminated sediment in the oligochaete Lumbriculus variegatus, mayfly nymph Hexagenia spp., and fathead minnow Pimephales promelas. Depuration (25 d) of PCBs was measured in organisms that had been transferred to clean sediment after the 28-d exposure. Uptake and elimination of PCBs was rapid in L. variegatus and Hexagenia spp. Tissue residues reached steady-state concentrations within 28 d; elimination rates and biota-sediment accumulation factors (BSAFs) of the PCB congeners were not correlated with K(OW). Uptake and elimination rates of PCBs were slower in P. promelas, and it is not clear whether steady-state was reached in fish tissues. Elimination rates of the PCB congeners significantly decreased with increasing K(OW) in fish. The appropriateness of a 28-d exposure for measuring steady-state concentrations in tissue of the invertebrates was confirmed, but further study is required for fish.     

The labile pool of manganese in soil: Comparison of E and L value measurements with extraction methods

The size of the manganese labile pools of three sandy soils from south east Scotland with a history of Mn deficiency was investigated by four methods: extraction with CaCl₂; extraction with DTPA; E-value determination by exchange with ⁵⁴Mn; and L-value determination using barley as the test crop. There was little agreement between the methods. The L-values varied with the period of plant growth and with soil bulk density but greatly exceeded the E-values, which in turn were about twice the quantities obtained by prolonged extraction with CaCl₂ and an order of magnitude greater than the quantities extracted after 1 h with CaCl₂-DTPA extraction gave values three to six times those obtained with CaCl₂. Extractable Mn increased dramatically after prolonged air drying, indicating the need for standardisation of both pre-extraction conditions and extraction times when comparing the Mn availability of different soils.     

Chirality of synergistic sex pheromone components of the western hemlock looperLambdina fiscellaria lugubrosa (HULST) (Lepidoptera: Geometridae)

Bakers' yeast reduction of (2E)-3-(2-furanyl)-2-methyl-2-propenal yielded the synthetic intermediate, (2S)-3-(2-furanyl)-2-methylpropanol, of high chiral purity (>97% ee) for the synthesis of the enantiomers of 2,5-dimethylheptadecane and 7-methylheptadecane, two synergistic sex pheromone components of the western hemlock looper (WHL),Lambdina fiscellaria lugubrosa Hulst. In electrophysiological bioassays, (7S)- but not (7R)-7-methylheptadecane elicited strong antennal responses by male WHL antennae. In field trapping experiments, addition of (7S)- but not (7R)-7-methylheptadecane to (5R,11S)-5,11-dimethylheptadecane, the major sex pheromone component of WHL, increased attraction. Attraction to (5R,11S)-5,11-dimethylheptadecane in combination with (7S)-7-methyiheptadecane was further enhanced by the addition of (5S)- but not (5R)-2,5-dimethylheptadecane. Similarly, attraction to (5R,11S)-5,11-dimethylheptadecane combined with (5S)-2,5-dimethylheptadecane increased when 7S- but not (7R)-7-methylheptadecane was added as a third component. We conclude that (7S)-7-methylheptadecane and (5S)-2,5-dimethylheptadecane are the synergistic sex pheromone components of WHL. The synthetic methodology described is applicable to the synthesis of chiral methyl-branched pheromones in other orders of the Insecta, particularly Coleoptera, Diptera and Orthoptera.     

Film-pore diffusion models—analytical and numerical solutions

The sorption of acid dyes from aqueous effluents onto activated carbon has been studied. The effects of initial dye concentration and activated carbon mass on the rate of Acid Blue 80 and Acid Yellow 117 removal have been investigated. Three mass transport models based on film and pore diffusion control have been applied to model the experimental concentration decay curves. The models are compared on the basis of the solid-phase loading capacity using various assumptions since the assignment of an appropriate solid-phase loading has been the subject of several papers on this topic and no comparisons have been provided on the effectiveness of each approach. The equilibrium solid-phase concentration is assumed: (i) incorporating a time-dependent solid-phase concentration Y_e,t, (ii) equal to the intersection point of the equilibrium isotherm and the operating line and (iii) the point on the equilibrium isotherm where the liquid-phase concentration equals the initial concentration in the film-pore diffusion model.     

Characterization of protein immobilization on nanoporous gold using atomic force microscopy and scanning electron microscopy

Nanoporous gold (NPG), made by dealloying low carat gold alloys, is a relatively new nanomaterial finding application in catalysis, sensing, and as a support for biomolecules. NPG has attracted considerable interest due to its open bicontinuous structure, high surface-to-volume ratio, tunable porosity, chemical stability and biocompatibility. NPG also has the attractive feature of being able to be modified by self-assembled monolayers. Here we use scanning electron microscopy (SEM) and atomic force microscopy (AFM) to characterize a highly efficient approach for protein immobilization on NPG using N-hydroxysuccinimide (NHS) ester functionalized self-assembled monolayers on NPG with pore sizes in the range of tens of nanometres. Comparison of coupling under static versus flow conditions suggests that BSA (Bovine Serum Albumin) and IgG (Immunoglobulin G) can only be immobilized onto the interior surfaces of free standing NPG monoliths with good coverage under flow conditions. AFM is used to examine protein coverage on both the exterior and interior of protein modified NPG. Access to the interior surface of NPG for AFM imaging is achieved using a special procedure for cleaving NPG. AFM is also used to examine BSA immobilized on rough gold surfaces as a comparative study. In principle, the general approach described should be applicable to many enzymes, proteins and protein complexes since both pore sizes and functional groups present on the NPG surfaces are controllable.     

A highly sensitive ultraviolet sensor based on a facile in situ solution-grown ZnO nanorod/graphene heterostructure

The weak photon absorption and fast carrier kinetics of graphene limit its application in photodetection. This limitation can be overcome by introducing photosensitive nanostructures to graphene. Herein we report the synthesis of a ZnO nanorod/graphene heterostructure by a facile in situ solution growth method. By combining the attributes of photosensitive ZnO nanorods and highly conductive graphene, we for the first time demonstrate a highly sensitive visible-blind ultraviolet (UV) sensor based on graphene related heterostructure. The photoresponsibility of the UV sensor can reach 22.7 A W(-1), which is over 45,000 fold higher than that of single graphene sheet based photodetectors.     

Structure-function studies of an engineered scaffold protein derived from Stefin A. II: Development and applications of the SQT variant

Constrained binding peptides (peptide aptamers) may serve as tools to explore protein conformations and disrupt protein-protein interactions. The quality of the protein scaffold, by which the binding peptide is constrained and presented, is of crucial importance. SQT (Stefin A Quadruple Mutant-Tracy) is our most recent development in the Stefin A-derived scaffold series. Stefin A naturally uses three surfaces to interact with its targets. SQT tolerates peptide insertions at all three positions. Peptide aptamers in the SQT scaffold can be expressed in bacterial, yeast and human cells, and displayed as a fusion to truncated pIII on phage. Peptides that bind to CDK2 can show improved binding in protein microarrays when presented by the SQT scaffold. Yeast two-hybrid libraries have been screened for binders to the POZ domain of BCL-6 and to a peptide derived from PBP2', specific to methicillin-resistant Staphylococcus aureus. Presentation of the Noxa BH3 helix by SQT allows specific interaction with Mcl-1 in human cells. Together, our results show that Stefin A-derived scaffolds, including SQT, can be used for a variety of applications in cellular and molecular biology. We will henceforth refer to Stefin A-derived engineered proteins as Scannins.     

Effects of selected water chemistry variables on copper pitting propagation in potable water

The pit propagation behavior of copper (UNS C11000) was investigated from an electrochemical perspective using the artificial pit method. Pit growth was studied systematically in a range of HCO₃⁻, SO₄²⁻ and Cl⁻ containing-waters at various concentrations. Pit propagation was mediated by the nature of the corrosion products formed both inside and over the pit mouth (i.e., cap). Certain water chemistry concentrations such as those high in sulfate were found to promote fast pitting that could be sustained over long times at a fixed applied potential but gradually stifled in all but the lowest concentration solutions. In contrast, Cl⁻ containing waters without sulfate ions resulted in slower pit growth and eventual repassivation. These observations were interpreted through understanding of the identity, amount and porosity of corrosion products formed inside and over pits. These factors controlled their resistive nature as characterized using electrochemical impedance spectroscopy. A finite element model (FEM) was developed which included copper oxidation kinetics, transport by migration and diffusion, Cu(I) and Cu(II) solid corrosion product formation and porosity governed by equilibrium thermodynamics and a saturation index, as well as pit current and depth of penetration. The findings of the modeling were in good agreement with artificial pit experiments. Malachite, bronchantite, cuprite, nantokite and atacamite corrosion products were both observed in experiment and predicted by the model. Stifling and/or repassivation occurred when the resistance of the corrosion product layer became high enough to lower the pit bottom potential and pit current density such as 10^-5 A/cm² could be attained with thick and dense layer. The ramifications of these findings towards pit propagation characteristics in potable waters will be discussed with improved insight into the roles of Cl⁻ and SO₄²⁻ ions.     

Systematic study of back pressure and anode stoichiometry effects on spatial PEMFC performance distribution

A segmented cell system was applied to investigate the effects of the anode and cathode back pressure and hydrogen stoichiometry on fuel cell performance in terms of overpotential distributions along the flow field. The segmented cell system was designed with closed loop Hall sensors and a data acquisition system allowing simultaneous spatial electrochemical impedance spectra (EIS) measurements. It was determined that an increase in back pressure for the tested serpentine flow field design results in an improvement of the cell performance and uneven improvement of individual segments’ performance. In general, the performance and the overpotentials become more uniform downstream with an increase in the back pressure due to a decrease in activation and mass transfer losses. Spatial EIS data for the PEMFC operated at different back pressures support the overpotential analysis. Hydrogen stoichiometry variations do not affect the performance of the cell or the individual segments at low current density because there is no significant hydrogen concentration gradient in the flow field. However, at high current densities a reduction in hydrogen stoichiometry produces a slight decrease in performance for inlet segments while outlet segments showed a noticeable performance loss. The decrease in performance is attributed to an increase in mass transfer losses due to nitrogen diffusion from the cathode to the anode. This effect becomes more pronounced for the outlet segments due to a downstream nitrogen accumulation. Under high current density conditions, the cell is locally fuel starved even with a high fuel stoichiometry creating conditions leading to cell degradation by carbon corrosion. More importantly, this local degradation is masked by the overall cell performance which remains largely unaffected.