Chemisorption of alkyl thiols and S-alkyl thiosulfates on Pt(111) and polycrystalline platinum surfaces

The self-assembled monolayers prepared from 1-dodecanethiol (C12SH) or S-dodecylthio sulfate (Bunte salt, C12SSO3Na) have been characterised on polycrystalline gold and platinum surfaces and on Pt(111). Contact angle and impedance measurements show that the film quality decreases in the order Au/C12SH > Pt/C12SH similar to Au/C12SSO3-Na > Pt/C12S SO3Na. XPS measurements show that the S-SO3 bond of organic thiosulfates is broken on platinum surfaces and the state of the surface-bound sulfur is indistinguishable from that of thiolate. On platinum three sulfur species are formed upon SAM formation and we suggest that the catalytic activity of platinum is responsible for their existence in pristine monolayers. (c) 2005 Elsevier B.V. All rights reserved

Preparation of multilayers containing conjugated thiophene-based polyelectrolytes. Layer-by-layer assembly and viscoelastic properties

We study the layer-by-layer assembly and properties of polyelectrolyte multilayers containing anionic and cationic poly(alkoxythiophene) derivatives, poly(3-(3'-thienyloxy)propanesulfonate) (P3TOPS) and poly(3-(3'-thienyloxy)propyltriethylammonium) (P3TOPA), together with poly(diallyldimethylammonum chloride) (PDADMA) or poly(styrenesulfonate) (PSS). These polythiophenes are rigid-rod-type polyelectrolytes which tend to aggregate in aqueous medium. Three types of multilayers have been prepared: (P3TOPS/P3TOPA)(n) (all-thiophene films), (P3TOPS/PDADMA)(n), and (PSS/P3TOPA)(n). The layer-by-layer adsorption of polythiophenes was followed by UV-vis spectroscopy and surface plasmon resonance (SPR). Adsorption of P3TOPS and P3TOPA took place within 10 min from dilute aqueous solution (1 mM with respect to monomers). The adsorption of anew polyion layer on top of polythiophene was always accompanied by a partial loss of the polythiophene layer. As the result, the amount of polythiophene in the film oscillated as a function of the number of layers. This behavior was attributed to the adsorption and partial desorption of aggregated polythiophene, supported by atomic force microscope (AFM) images of dry films. Per bilayer, the amount of polythiophene remaining in the film increased linearly and corresponded approximately to the formation of a thiophene monolayer. The viscoelastic properties of the film; also exhibited a marked terminal layer effect in cases where the length and hydrophobicity of the polyions were different. This effect was studied with (PSS/PDADMA) multilayers and was attributed to the formation of loops and tails, All multilayers studied appeared very soft, comparable to protein layers. This softness was attributed mainly to the film/solution interface with a hydrogel-like outer part of the films (zone III)

Water-soluble full-length single-wall carbon nanotube polyelectrolytes: Preparation and characterization

HiPco single-wall carbon nanotubes (SWNTs) have been noncovalently modified with ionic pyrene and naphthalene derivatives to prepare water-soluble SWNT polyelectrolytes (SWNT-PEs), which are analogous to polyanions and polycations. The modified nanotubes have been characterized with UV-vis-NIR, fluorescence, Raman and X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). The nanotube-adsorbate interactions consist of π-π stacking interactions between the aromatic core of the adsorbate and the nanotube surface and specific contributions because of the substituents. The interaction between nanotubes and adsorbates also involves charge transfer from adsorbates to SWNTs, and with naphthalene sulfonates the role of a free amino group was important. The ionic surface charge density of the modified SWNTs is constant and probably controlled by electrostatic repulsion between like charges. The linear ionic charge density of the modified SWNTs is similar to that of common highly charged polyelectrolytes

Spatial Structure and Coherent Motion in Dense Planetary Rings Induced by Self-Gravitational Instability

We investigate the formation of spatial structure in dense, self-gravitating particle systems such as Saturn's B-ring through local $N$-body simulations to clarify the intrinsic physics based on individual particle motion. In such a system, Salo (1995) showed that the formation of spatial structure such as wake-like structure and particle grouping (clump) arises spontaneously due to gravitational instability and the radial velocity dispersion increases as the formation of the wake structure. However, intrinsic physics of the phenomena has not been clarified. We performed local $N$-body simulations including mutual gravitational forces between ring particles as well as direct (inelastic) collisions with identical (up to $N\sim40000$) particles. In the wake structure particles no longer move randomly but coherently. We found that particle motion was similar to Keplerian motion even in the wake structure and that the coherent motion was produced since the particles in a clump had similar eccentricity and longitude of perihelion. This coherent motion causes the increase and oscillation in the radial velocity dispersion. The mean velocity dispersion is rather larger in a more dissipative case with a smaller restitution coefficient and/or a larger surface density since the coherence is stronger in the more dissipative case. Our simulations showed that the wavelength of the wake structure was approximately given by the longest wavelength \hs{\lambda}{cr} = 4\pi^2 G\Sigma/\kappa^2 in the linear theory of axisymmetric gravitational instability in a thin disk, where $G$, $\Sigma$, and $\kappa$ are the gravitational constant, surface density, and a epicyclic frequency.Comment: Accepted by Earth, Planets, and Space. 39 pages, 20 figures. PostScript files also available from http://www.geo.titech.ac.jp/nakazawalab/hdaisaka/works

Avoidance, biomass and survival response of soil dwelling (endogeic) earthworms to OECD artificial soil: potential implications for earthworm ecotoxicology

Soil dwelling earthworms are now adopted more widely in ecotoxicology, so it is vital to establish if standardised test parameters remain applicable. The main aim of this study was to determine the influence of OECD artificial soil on selected soil-dwelling, endogeic earthworm species. In an initial experiment, biomass change in mature Allolobophora chlorotica was recorded in Standard OECD Artificial Soil (AS) and also in Kettering Loam (KL). In a second experiment, avoidance behaviour was recorded in a linear gradient with varying proportions of AS and KL (100% AS, 75% AS + 25% KL, 50% KS + 50% KL, 25% AS + 75% KL, 100% KL) with either A. chlorotica or Octolasion cyaneum. Results showed a significant decrease in A. chlorotica biomass in AS relative to KL, and in the linear gradient, both earthworm species preferentially occupied sections containing higher proportions of KL over AS. Soil texture and specifically % composition and particle size of sand are proposed as key factors that influenced observed results. This research suggests that more suitable substrates are required for ecotoxicology tests with soil dwelling earthworms

Institutional maintenance work and power preservation in business exchanges: Insights from industrial supplier workshops

This paper aims to offer new theoretical and empirical insights into power dynamics in an industrial supplier workshop setting. Theoretically, it advances an institutional perspective on supplier workshops as an important venue in managing, preserving and instituting industrial market power. Based on a detailed ethnographic analysis of an industrial workshop setting, this article investigates the institutional maintenance work of Retail Co. in preserving the power dynamics of market dominance in business exchanges and market structures. Our findings revealed three previously unreported insights into the subtle, but nonetheless pervasive power from institutional maintenance work in an industrial workshop setting. First, the institutional workshop work comprised a cultural performance; constituting socialization practice through a performance game, the power of numbers in field comprehension and an award ceremony. Second, the institutional workshop work mobilized projective agency, stipulating, directing and appealing for the instituting of distinct market rules and collective identities. Finally, the institutional workshop work increases supplier docility and utility via the regulative technologies-of-the-self to enhance business planning, operations and market decision-making practice, without necessarily being seen to be disciplinarian. (C) 2015 Elsevier Inc. All rights reserved

Theoretical study on the electronic, structural, properties and reactivity of a series of mono-, di-, tri- and tetrachlorothiophenes as well as corresponding radical cation forms as monomers for conducting polymers

In this paper, electrical and structural properties of mono-, di-, tri- and tetrachlorothiophenes and their radical cations have been studied using the density functional theory and B3LYP method with 6-311++G** basis set. The effects of the number and position of the substituent of chlorine atoms on the properties of the thiophene ring for all chlorothiophenes and their radical cations have been studied. Vibrational frequencies, nuclear chemical shielding constants, spin-density distribution, size and direction of dipole moment vector, ionization potential, electric polarizabilities and NICS values of these compounds have been calculated as well. The analysis of these data showed that double bonds in 3-chlorothiophene are more delocalized and it is the best possible candidate monomer among all chlorothiophenes for the synthesis of corresponding conducting polymers with modified characteristics

Biodiversity and structure of spider communities along a metal pollution gradient

The objective of the study was to determine whether long-term metal pollution affects communities of epigeal spiders (Aranea), studied at three taxonomic levels: species, genera, and families. Biodiversity was defined by three indices: the Hierarchical Richness Index (HRI), Margalef index (DM) and Pielou evenness index (J). In different ways the indices describe taxa richness and the distribution of individuals among taxa. The dominance pattern of the communities was described with four measures: number of dominant species at a site, percentage of dominant species at a site, average dominant species abundance at a site, and the share of the most numerous species (Alopecosa cuneata) at a site. Spiders were collected along a metal pollution gradient in southern Poland, extending ca. 33 km from zinc and lead smelter to an uncontaminated area. The zinc concentration in soil was used as the pollution index.The study revealed a significant effect of metal pollution on spider biodiversity as described by HRI for species (p = 0.039), genera (p = 0.0041) and families (p = 0.0147), and by DM for genera (p = 0.0259) and families (p = 0.0028). HRI correlated negatively with pollution level, while DM correlated positively. This means that although broadly described HRI diversity decreased with increasing pollution level, species richness increased with increasing contamination. Mesophilic meadows were generally richer. Pielou (J) did not show any significant correlations. There were a few evidences for the intermediate disturbance hypothesis: certain indices reached their highest values at moderate pollution levels rather than at the cleanest or most polluted sites

Fractionation of Li, Be, Ga, Nb, Ta, In, Sn, Sb, W and Bi in the peraluminous Early Permian Variscan granites of the Cornubian Batholith: precursor processes to magmatic-hydrothermal mineralisation

The Early Permian Variscan Cornubian Batholith is a peraluminous, composite pluton intruded into Devonian and Carboniferous metamorphosed sedimentary and volcanic rocks. Within the batholith there are: G1 (two-mica), G2 (muscovite), G3 (biotite), G4 (tourmaline) and G5 (topaz) granites. G1-G2 and G3-G4 are derived from greywacke sources and linked through fractionation of assemblages dominated by feldspars and biotite, with minor mantle involvement in G3. G5 formed though flux-induced biotite-dominate melting in the lower crust during granulite facies metamorphism. Fractionation enriched G2 granites in Li (average 315 ppm), Be (12 ppm), Ta (4.4 ppm), In (74 ppb), Sn (18 ppm) and W (12 ppm) relative to crustal abundances and G1 granites. Gallium (24 ppm), Nb (16 ppm) and Bi (0.46 ppm) are not significantly enriched during fractionation, implying they are more compatible in the fractionating assemblage. Sb (0.16 ppm) is depleted in G1-G2 relative to the average upper and lower continental crust. Muscovite, a late-stage magmatic/subsolidus mineral, is the major host of Li, Nb, In, Sn and W in G2 granites. G2 granites are spatially associated with W-Sn greisen mineralisation. Fractionation within the younger G3-G4 granite system enriched Li (average 364 ppm), Ga (28 ppm), In (80 ppb), Sn (14 ppm), Nb (27 ppm), Ta (4.6 ppm), W (6.3 ppm) and Bi (0.61 ppm) in the G4 granites with retention of Be in G3 granites due to partitioning of Be into cordierite during fractionation. The distribution of Nb and Ta is controlled by accessory phases such as rutile within the G4 granites, facilitated by high F and lowering the melt temperature, leading to disseminated Nb and Ta mineralisation. Lithium, In, Sn and W are hosted in biotite micas which may prove favourable for breakdown on ingress of hydrothermal fluids. Higher degrees of scattering on trace element plots may be attributable to fluid–rock interactions or variability within the magma chamber. The G3-G4 system is more boron-rich, evidenced by a higher modal abundance of tourmaline. In this system, there is a stronger increase of Sn compared to G1-G2 granites, implying Sn in tourmaline-dominated mineral lodes may represent exsolution from G4 granites. G1-G4 granite abundances can be accounted for by 20–30% partial melting and 10–40% fractionation of a greywacke source. G5 granites are analogues of Rare Metal Granites described in France and Germany. These granites are enriched in Li (average 1363 ppm), Ga (38 ppm), Sn (21 ppm), W (24 ppm), Nb (52 ppm) and Ta (15 ppm). Within G5 granites, the metals partition into accessory minerals such as rutile, columbite-tantalite and cassiterite, forming disseminated magmatic mineralisation. High observed concentrations of Li, In, Sn, W, Nb and Ta in G4 and G5 granites are likely facilitated by high F, Li and P, which lower melt temperature and promote retention of these elements in the melt, prior to crystallisation of disseminated magmatic mineralisation