Surface interactions of molecular C60 and impact on Ni(100) and Co(0001) film growth: A scanning tunneling microscopy study

Here, the interactions of C₆₀ at the surface of pseudomorphic Ni/Cu(100) and Co/Ru(0001) thin films and its effect on film growth and morphology were determined using in-situ scanning tunneling microscopy (STM) and Auger electron spectroscopy (AES). The novel development of C₆₀-metallic based nanosystems, such as C₆₀ molecular junction transistors, hinges on our ability to understand the factors governing structural stability in these nanosystems and the nature of the bond interactions at the C₆₀–metal interface. In this study, C₆₀ deposited onto the Ni(100) film surface is observed to be fairly immobile and uniformly distributed across the Ni surface. On the Co(0001) film surface however, C₆₀ mobility is observed to be severely limited in some regions and highly mobile in others dependent upon Co film surface reconstruction, resulting in a non-uniform distribution of C₆₀ across the Co film surface. Despite the presence of C₆₀ on the Ni surface, there is no obvious influence of the C₆₀ on further Ni film growth. In contrast, during Co film growth, islands only nucleate and grow from step edges or locally around C₆₀ molecules. The strength of the Co–C₆₀ bond interaction appears stronger than the Co–Co bond on Co film terrace. Generally, the Ni and Co films both continue epitaxial film growth in the presence of molecular C₆₀. AES results indicate the C₆₀ molecules maintain their chemical integrity during growth.     

Determination of reactivity ratios for ethylene/α-olefin copolymerization catalysed by the C2H4[Ind]2ZrCl2/methylaluminoxane system

The present study reports values of reactivity ratios for ethylene/1-hexene, ethylene/1-octene and ethylene/1-decene copolymerizations promoted by C₂H₄[Ind]₂ZrCl₂/MAO. The comonomer reactivities are markedly influenced by the number of carbon atoms of the α-olefin. The ethylene/1-decene copolymerization depends on the concentration of α-olefin in the feed.     

Development of Abraham model correlations for describing the transfer of molecular solutes into propanenitrile and butanenitrile from water and from the gas phase

Experimental solubilities were measured for 20 crystalline organic solutes dissolved in propanenitrile and for 13 crystalline organic solutes dissolved in butanenitrile at 298.15 K. Infinite dilution activity coefficient data for solutes dissolved in propanenitrile and butanenitrile have been compiled from the published chemical and engineering literature and converted into gas-to-liquid partition coefficients and water-to-organic solvent partition coefficients through standard thermodynamic relationships. Abraham model correlations were developed for describing solute transfer into both propanenitrile and butanenitrile by combining our measured solubility data with the partition coefficients that we calculated from the published activity coefficient data. The derived Abraham model correlations were found to back-calculate the observed partition coefficients and molar solubility data to within 0.14 log units.     

Linearization of a class of non-linear systems modelled by multibond graphs

Based on non-linear systems described by multibond graphs, a procedure designed to present symbolic linearization of these multibond graphs, is presented in this paper. Firstly, a junction structure of a multibond graph with multiport gyrators that represent Eulerian junction structures is proposed. In addition, non-linear multiport resistors are considered. By knowing the non-linear causal paths and loops of the non-linear multibond graph, the linearization is obtained by two steps: (1) The original multibond graph on the nominal operating point is evaluated; (2) New and additional paths based on the non-linear causal paths and loops are included. The state space representation of the linearized multibond graph using the corresponding junction structure is presented. An advantage of this methodology is its ability to allow the user to define a nominal operating point in which the linearization will be carried out.

In order to apply the proposed methodology, two physical systems are modelled and linearized by multibond graphs: a synchronous generator and a two degrees of freedom PUMA. Simulation results of these non-linear and linearized systems are shown.     

13Carbon nuclear magnetic resonance of ethylene–propylene–1‐hexene terpolymers

We report the complete ¹³C NMR characterization of a series of ethylene–propylene–1‐hexene terpolymers obtained with the metallocenic system rac‐ethylene bis‐indenyl zirconium dichloride, with different comonomer ratios. A detailed study of ¹³C NMR chemical shifts, triad sequence distributions, monomer‐average sequence lengths, and reactivity ratios for these terpolymers is presented. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2474–2482, 2004     

Metallocene supported on a polyhedral oligomeric silsesquioxane‐modified silica with high catalytic activity for ethylene polymerization

A polyhedral oligomeric silsesquioxane (POSS) consisting of a mixture of perfect and imperfect polyhedra with 8–10 Si atoms bonded to bulky and branched organic groups functionalized with (β‐hydroxy)‐tertiary amines, was adsorbed on an activated silica from a toluene solution. POSS fixation was confirmed by measuring its concentration in the solutions resulting from filtering and repeatedly washing with toluene. Diffuse reflectance infrared Fourier‐transformed (DRIFTS) spectra of the modified silica showed a decrease in the absorption of isolated SiOH groups. A POSS previously marked by reaction with an isocyanate was also used, and the presence of the carbonyl in the urethane group was recorded in the DRIFTS spectra of the modified silica, confirming the presence of adsorbed POSS. X‐ray photoelectron spectroscopy (XPS) was used to measure the amount of Si (2p) of POSS adsorbed on the SiO₂ surface as a function of the POSS concentration in the toluene solution. A linear increase of adsorbed POSS as a function of its concentration in toluene was found, even after successive washings with toluene. A metallocene, (nBuCp)₂ZrCl₂, was then adsorbed on the POSS‐modified silica from a toluene solution, and the fixed Zr amount was measured by Rutherford backscattering spectrometry (RBS). The activity of the resulting catalyst for ethylene polymerization in toluene, using methylaluminoxane (MAO) as a cocatalyst, was determined in two different devices operating in the range of 1.6–7.0 bar. Under every experimental condition, POSS‐modification of the silica support led to an increase of about 50% in the activity of the resulting catalyst when compared to the use of the unmodified support. Reasons for the observed increase in activity are discussed. The molar mass distribution and crystallinity of the resulting polyethylenes was not affected by the POSS modification of the silica support. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5465–5476, 2005     

Sample treatment selection for routine mercury speciation in seafood by gas chromatography–atomic fluorescence spectroscopy

A general analytical strategy for mercury speciation in seafood samples has been proposed to increase sample throughput. This consists of the initial determination of total mercury content, and then mercury speciation using gas chromatography coupled to atomic fluorescence spectroscopy. The appropriate sample treatment for mercury speciation is selected between a method based on aqueous ethylation with sodium tetraethylborate (Approach A: a rapid methodology for samples with methylmercury concentrations between 150 and 2000 ng g^?1) and another one based on the determination of organomercury chlorides (Approach B: a much more time‐consuming methodology, applicable to samples with methylmercury at 1.2–200 ng g^?1). Both procedures have been used together for the analysis of bivalves and fish samples. Copyright © 2005 John Wiley & Sons, Ltd.     

Transition metal complexes with 1-methyl-4,4-dimercaptopiperidine

The syntheses of Co(AH₂)₂X₂ (AH₂ = 1-methyl-4, 4-dimercaptopiperidine, X = Cl Br, I, acetate, propanate, perchlorate, nitrate and sulphate), M(AH₂) Cl₂ (M = Cd, Zn) are described. According to IR and UV-visible data it seems most probable that the aminogem-dithiol (AH₂) coordinates Co via both sulphur atoms, but Zn and Cd via one sulphur. A square pyramidal geometry about Co and a tetrahedral geometry about Zn and Cd are proposed. In no case has coordination via nitrogen been found. Strong X-H…N hydrogen bonds have been observed in most of these complexes.