A modified discrete random pore model allowing for different initial surface reactivity

We investigate here a modification of the discrete random pore model [Bhatia SK, Vartak BJ, Carbon 1996;34:1383], by including an additional rate constant which takes into account the different reactivity of the initial pore surface having attached functional groups and hydrogens, relative to the subsequently exposed surface. It is observed that the relative initial reactivity has a significant effect on the conversion and structural evolution, underscoring the importance of initial surface chemistry. The model is tested against experimental data on chemically controlled char oxidation and steam gasification at various temperatures. It is seen that the variations of the reaction rate and surface area with conversion are better represented by the present approach than earlier random pore models. The results clearly indicate the improvement of model predictions in the low conversion region, where the effect of the initially attached functional groups and hydrogens is more significant, particularly for char oxidation. It is also seen that, for the data examined, the initial surface chemistry is less important for steam gasification as compared to the oxidation reaction. Further development of the approach must also incorporate the dynamics of surface complexation, which is not considered here.

Changes in neutrophil surface receptor expression, degranulation, and respiratory burst activity following moderate and high intensity exercise

Intense exercise stimulates the systemic release of a variety of factors that alter neutrophil surface receptor expression and functional activity. These alterations may influence resistance to infection after intense exercise. The aim of this study was to examine the influence of exercise intensity on neutrophil receptor expression, degranulation (measured by plasma and intracellular myeloperoxidase concentrations), and respiratory burst activity. Ten well-trained male runners ran on a treadmill for 60 min at 60% [moderate-intensity exercise (MI)] and 85% maximal oxygen consumption [high-intensity exercise (HI)]. Blood was drawn immediately before and after exercise and at 1 h postexercise. Immediately after HI, the expression of the neutrophil receptor CD16 was significantly below preexercise values (P < 0.01), whereas MI significantly reduced CD35 expression below preexercise values (P < 0.05). One hour after exercise at both intensities, there was a significant decline in CD11b expression (P < 0.05) and a further decrease in CD16 expression compared with preexercise values (P < 0.01). CD16 expression was lower 1 h after HI than 1 h after MI (P < 0.01). Immediately after HI, intracellular myeloperoxidase concentration was less than preexercise values (P < 0.01), whereas plasma myeloperoxidase concentration was greater (P < 0.01), indicating that HI stimulated neutrophil degranulation. Plasma myeloperoxidase concentration was higher immediately after HI than after MI (P < 0.01). Neutrophil respiratory burst activity increased after HI (P < 0.01). In summary, both MI and HI reduced neutrophil surface receptor expression. Although CD16 expression was reduced to a greater extent after HI, this reduction did not impair neutrophil degranulation and respiratory burst activity.

Inorganic surface passivation of PbS nanocrystals resulting in strong photoluminescent emission

Strong photoluminescent emission has been obtained from 3 nm PbS nanocrystals in aqueous colloidal solution, following treatment with CdS precursors. The observed emission can extend across the entire visible spectrum and usually includes a peak near 1.95 eV. We show that much of the visible emission results from absorption by higher-lying excited states above 3.0 eV with subsequent relaxation to and emission from states lying above the observed band-edge of the PbS nanocrystals. The fluorescent lifetimes for this emission are in the nanosecond regime, characteristic of exciton recombination.

Polarized photoluminescence from surface-passivated lead sulfide nanocrystals

Effective surface passivation of lead sulfide (PbS) nanocrystals (NCs) in an aqueous colloidal solution has been achieved following treatment with CdS precursors. The resultant photoluminescent emission displays two distinct components, one originating from the absorption band edge and the other from above the absorption band edge. We show that both of these components are strongly polarized but display distinctly different behaviours. The polarization arising from the band edge shows little dependence on the excitation energy while the polarization of the above-band-edge component is strongly dependent on the excitation energy. In addition, time-resolved polarization spectroscopy reveals that the above-band-edge polarization is restricted to the first couple of nanoseconds, while the band edge polarization is nearly constant over hundreds of nanoseconds. We recognize an incompatibility between the two different polarization behaviours, which enables us to identify two distinct types of surface-passivated PbS NC.

Investigation of the role of cadmium sulfide in the surface passivation of lead sulfide quantum dots

Surface passivation of PbS nanocrystals (NC), resulting in strong photoluminescence, can be achieved by the introduction of CdS precursors. The role of CdS in the surface passivation of PbS NCs is uncertain, as the crystalline structure of CdS and PbS are different, which should impede effective epitaxial overgrowth. Absorption spectroscopy is used to show that the CdS precursors strongly interact with the PbS NC surface. Electron microscopy reveals that the introduction of CdS precursors results in an increased particle size, consistent with overcoating. However, we also find the process to be highly non-uniform. Nevertheless, evidence for epitaxial growth is found, suggesting that effective surface passivation may be possible.

Cloning and characterization of a gene encoding the major surface protein of the bacterial endosymbiont Wolbachia pipientis

The maternally inherited intracellular symbiont Wolbachia pipientis is well known for inducing a variety of reproductive abnormalities in the diverse arthropod hosts it infects. It has been implicated in causing cytoplasmic incompatibility, parthenogenesis, and the feminization of genetic males in different hosts. The molecular mechanisms by which this fastidious intracellular bacterium causes these reproductive and developmental abnormalities have not yet been determined. In this paper, we report on (i) the purification of one of the most abundantly expressed Wolbachia proteins from infected Drosophila eggs and (ii) the subsequent cloning and characterization of the gene (wsp) that encodes it. The functionality of the wsp promoter region was also successfully tested in Escherichia coli. Comparison of sequences of this gene from different strains of Wolbachia revealed a high level of variability. This sequence variation correlated with the ability of certain Wolbachia strains to induce or rescue the cytoplasmic incompatibility phenotype in infected insects. As such, this gene will be a very useful tool for Wolbachia strain typing and phylogenetic analysis, as well as understanding the molecular basis of the interaction of Wolbachia with its host.

Analysis of Wolbachia protein synthesis in Drosophila in vivo

Intracellular Wolbachia infections are extremely common in arthropods and exert profound control over the reproductive biology of the host. However, very little is known about the underlying molecular mechanisms which mediate these interactions with the host. We examined protein synthesis by Wolbachia in a Drosophila host in vivo by selective metabolic labelling of prokaryotic proteins and subsequent analysis by 1D and 2D gel electrophoresis. Using this method we could identify the major proteins synthesized by Wolbachia in ovaries and testes of flies. Of these proteins the most abundant was of low molecular weight and showed size variation between Wolbachia strains which correlated with the reproductive phenotype they generated in flies. Using the gel systems we employed it was not possible to identify any proteins of Wolbachia origin in the mature sperm cells of infected flies.

Effect of multiple transverse modes in self-mixing sensors based on vertical-cavity surface-emitting lasers

We investigate the effect of coexisting transverse modes on the operation of self-mixing sensors based on vertical-cavity surface-emitting lasers (VCSELs). The effect of multiple transverse modes on the measurement of displacement and distance were examined by simulation and in laboratory experiment. The simulation model shows that the periodic change in the shape and magnitude of the self-mixing signal with modulation current can be properly explained by the different frequency-modulation coefficients of the respective transverse modes in VCSELs. The simulation results are in excellent agreement with measurements performed on single-mode and multimode VCSELs and on self-mixing sensors based on these VCSELs.

Surface Waves and Roughness in Self-Aerated Supercritical Flow

In high-velocity open channel flows, free-surface aeration is commonly observed. The effects of surface waves on the air-water flow properties are tested herein. The study simulates the air-water flow past a fixed-location phase-detection probe by introducing random fluctuations of the flow depth. The present model yields results that are close to experimental observations in terms of void fraction, bubble count rate and bubble/droplet chord size distributions. The results show that the surface waves have relatively little impact on the void fraction profiles, but that the bubble count rate profiles and the distributions of bubble and chord sizes are affected by the presence of surface waves.

Acquisition of the English article system in SLA and the Missing Surface Inflection Hypothesis

This paper examines the article system in interlanguage grammar focusing on Japanese learners of English, whose native language lacks articles. It will be demonstrated that for the acquisition of the English article system, count/mass distinctions and definiteness are the crucial factors. Although Japanese does not employ the article system to encode these aspects, it will be argued that they are nevertheless syntactically encoded through its classifier system. Hence, the problem for these learners must be to map these features onto the appropriate surface forms as the Missing Surface Inflection Hypothesis predicts (Prévost & White 2000). This suggestion will further be supported empirically by a fill-in-the article task. It will be concluded that these Japanese learners understand the English article system fairly well, possibly due to their native language, yet have problems with realizing the relevant features (i.e. count/mass distinctions and definiteness) in the target language.

Turbulence Characterisation of High-Velocity Free-Surface Flows

In high-velocity free-surface flows, air is continuously being trapped and released through the free-surface. Such high-velocity highly-aerated flows cannot be studied numerically because of the large number of relevant equations and parameters. Herein an advanced signal processing of traditional single- and dual-tip conductivity probes provides some new information on the air-water turbulent time and length scales. The technique is applied to turbulent open channel flows in a large-size facility. The auto- and cross-correlation analyses yield some characterisation of the large eddies advecting the bubbles. The transverse integral turbulent length and time scales are related to the step height: i.e., Lxy/h ~ 0.02 to 0.2, and T.sqrt(g/h) ~ 0.004 to 0.04. The results are irrespective of the Reynolds numbers. The present findings emphasise that turbulent dissipation by large-scale vortices is a significant process in the intermediate zone between the spray and bubbly flow regions (0.3 < C < 0.7). Some self-similar relationships were observed systematically at both macroscopic and microscopic levels. The results are significant because they provide a picture general enough to be used to characterise the air-water flow field in prototype spillways.

Solution structure and proposed binding mechanism of a novel potassium channel toxin kappa-conotoxin PVIIA

Background: kappa-PVIIA is a 27-residue polypeptide isolated from the venom of Conus purpurascens and is the first member of a new class of conotoxins that block potassium channels. By comparison to other ion channels of eukaryotic cell membranes, voltage-sensitive potassium channels are relatively simple and methodology has been developed for mapping their interactions with small-peptide toxins, PVIIA, therefore, is a valuable new probe of potassium channel structure. This study of the solution structure and mode of channel binding of PVIIA forms the basis for mapping the interacting residues at the conotoxin-ion channel interface. Results: The three-dimensional structure of PVIIA resembles the triple-stranded beta sheet/cystine-knot motif formed by a number of toxic and inhibitory peptides. Subtle structural differences, predominantly in loops 2 and 4, are observed between PVIIA and other conotoxins with similar structural frameworks, however. Electrophysiological binding data suggest that PVIIA blocks channel currents by binding in a voltage-sensitive manner to the external vestibule and occluding the pore, Comparison of the electrostatic surface of PVIIA with that of the well-characterised potassium channel blocker charybdotoxin suggests a likely binding orientation for PVIIA, Conclusions: Although the structure of PVIIA is considerably different to that of the alpha K scorpion toxins, it has a similar mechanism of channel blockade. On the basis of a comparison of the structures of PVIIA and charybdotoxin, we suggest that Lys19 of PVIIA is the residue which is responsible for physically occluding the pore of the potassium channel.

Synthesis, structure and magnetism of the oxalato-bridged chromium(III) complex [NBu4n](4)[Cr-2(ox)(5)]center dot 2CHCl(3)

The binuclear complex [NBu4n](4)[Cr-2(ox)(5)]. 2CHCl(3) has been prepared by an ion-exchange procedure employing Dowex 50WX2 cation-exchange resin in the n-butylammonium form and potassium tris(oxalato)chromate(III). The dimeric complex was characterised by a crystal structure determination: monoclinic, space group C2/c, a = 29.241(7), b = 15.192(2), c = 22.026(5) Angstrom, beta = 94.07(1)degrees, Z = 4. The magnetic susceptibility (300-4.2 K) indicated that the chromium(III) sites were antiferromagnetically coupled (J = -3.1 cm(-1)).

Synthesis, NMR studies and conformational analysis of oxazolidine derivatives of the beta-adrenoreceptor antagonists metoprolol, atenolol and timolol

Formaldehyde-derived oxazolidine derivatives 4-7 of the beta-adrenoreceptor antagonists metoprolol 1, atenolol 2 and timolol 3 have been synthesised. Conformational analysis of 1-3 and the oxazolidine derivatives 4-7 has been performed using H-1 NMR spectroscopy and computational methods. The H-1 NMR studies show that for the aryloxypropanolamine beta-adrenoreceptor antagonists there is a predominance of the conformer in which the amine group is approximately antiperiplanar or trans to the aryloxymethylene group. Both H-1 NMR data and theoretical studies indicate that the oxazolidine derivatives 4-7 and the aryloxypropanolamine beta-adrenoreceptor antagonists 1-3 adopt similar conformations around the beta-amino alcohol moiety. Thus, oxazolidine ring formation does not dramatically alter the preferred conformation adopted by the beta-amino alcohol moiety of 1-3. Oxazolidine derivatives of aryloxypropanolamine beta-adrenoreceptor antagonists may therefore be appropriate as prodrugs, or semi-rigid analogues, when greater lipophilicity is required for drug delivery.

p-cresol as a reversible acylium ion scavenger in solid-phase peptide synthesis

In this work we have defined the nature of the p-cresol and p-thiocresol adducts generated from acylium ions during HF cleavage, following contemporary Boc/benzyl solid-phase peptide synthesis. Contrary to the results in previous reports, we found that both p-cresol and p-thiocresol predominantly form. aryl esters under typical cleavage conditions. Initially we investigated a number of small peptides containing either a single glutamate residue or a C-terminal long-chain amino acid which allowed us to unambiguously characterize the scavenged side products. Whereas, the p-cresol esters are stable at 0 degrees C they rearrange irreversibly at higher temperatures (5-20 degrees C) to form aryl ketones. By contrast, p-thiocresol esters do not undergo a Fries rearrangement but readily undergo further additions of p-thiocresol to form ketenebisthioacetals and trithio ortho esters, even at low temperatures. Importantly, we found by LC/MS and FT-ICR MS analysis that peptides containing p-cresol esters at glutamyl side chains are susceptible to amidation and fragmentation reactions at these sites during standard mild base workup procedures. The significance of these side reactions was further demonstrated in the synthesis of neutrophil immobilization factor, a 26-residue peptide, containing four glutamic acid residues. The side reactions were largely avoided by mild hydrogen peroxide-catalyzed hydrolysis which converted the p-cresol adducts to the free carboxylic acids in near quantitative yield. The choice of p-cresol as a reversible acylium ion scavenger when coupled with the simple workup conditions described is broadly applicable to Boc/benzyl peptide synthesis and will significantly enhance the quality of peptides produced.