CLATHRATE HYDRATE FORMATION ENHANCES NEAR-CRITICAL AND SUPERCRITICAL SOLVENT EXTRACTION EQUILIBRIA

Pre-concentration of dilute aqueous solutions by hydrate formation can improve the effective distribution coefficient and selectivity of solvent extraction. Many solvents can serve simultaneously to promote solution concentration by hydrate formation and also to extract non-polar solutes from the resulting concentrated solution. This concept is illustrated for systems with supercritical ethylene and with near-critical liquid carbon dioxide, and its application to conventional solvents is discussed.     

Substrate-mediated interactions and intermolecular forces between molecules adsorbed on surfaces

Adsorbate interactions and reactions on metal surfaces have been investigated using scanning tunneling microscopy. The manners in which adsorbates perturb the surface electronic structure in their vicinity are discussed. The effects these perturbations have on other molecules are shown to be important in overlayer growth. Interactions of molecules with surface steps are addressed, and each molecule's electron affinity is shown to dictate its adsorption sites at step edges. Standing waves emanating from steps are demonstrated to effect transient molecular adsorption up to 40 A away from the step edge. Halobenzene derivatives are used to demonstrate how the surface is important in aligning reactive intermediates.     

Fischer-tropsch synthesis on a precipitated iron catalyst: Influence of silica support on product selectivities

The influence of silica support on the α-olefins, internal olefins and branched hydrocarbon selectivities of the gasoline range products of a precipitated iron catalyst in the Fischer-Tropsch synthesis was investigated. Three catalysts with varying silica content and constant promoter content were studied. It was found that there is a linear relationship between the silica content of the catalysts and the internal olefin and branched hydrocarbon product selectivities. The selectivities of the aromatic and alcohol products remain relatively constant, indicating that the production of these two groups of compounds is not affected by the presence of silica support in the catalysts.     

Functionally substituted tetramethylcyclopentadienes: Synthesis of 1-(p-hydroxyphenyl)-2,3,4,5-tetramethylcyclopentadiene and its use in the synthesis of an organometallic polymer

Reaction of 2,3,4,5-tetramethylcyclopent-2-enone (1) withp-LiC₆H₄OC-Me₂OMe, followed by treatment with aqueous acid afforded 1-(p-hydroxyphenyl)-2,3,4,5-tetramethylcyclopentadiene (2). This new ligand was then used in the synthesis of the functionally substituted organomolybdenum reagent (⁵-C₅Me₄-p-C₆H₅OH)Mo(CO)₂(NO) (3). Treatment of a preformed 1/1 styrene/maleic anhydride copolymer ( ) with 5 mol% 3 led to chemical incorporation of the organometallic species into the polymer. The final product contained 3 mol% of the organometallic moiety.     

The mechanism of CO oxidation over Cu(110): Effect of CO gas energy

The effect of the temperature of gas phase CO upon the kinetics of the oxygen titration reaction: CO_g +O_a CO_2,g, has been studied. It is found that the reaction's rate is independant of CO gas temperature between 300 and 623 K. The activation energy (6.5 kcal/mole), dependence upon CO pressure (first-order), and independence upon oxygen coverage for 0.1 _o 0.4 are all independant of the CO gas phase temperature. This result rules out any Eley-Rideal type mechanism whereby CO reacts directly from the gas phase with an oxygen adatom without first being accommodated to the surface temperature in an absorbed state. The result is instead interpretable in terms of a Langmuir-Hinshelwood mechanism.Camille and Henry Dreyfus Foundation Teacher-Scholar Fellowship.     

Challenges in Liquid‐Phase Exfoliation,Processing, and Assembly of Pristine Graphene

Recent developments in the exfoliation, dispersion, and processing of pristine graphene (i.e., non‐oxidized graphene) are described. General metrics are outlined that can be used to assess the quality and processability of various “graphene” products, as well as metrics that determine the potential for industrial scale‐up. The pristine graphene production process is categorized from a chemical engineering point of view with three key steps: i) pretreatment, ii) exfoliation, and iii) separation. How pristine graphene colloidal stability is distinct from the exfoliation step and is dependent upon graphene interactions with solvents and dispersants are extensively reviewed. Finally, the challenges and opportunities of using pristine graphene as nanofillers in polymer composites, as well as as building blocks for macrostructure assemblies are summarized in the context of large‐scale production.     

Business processes in the agile organisation: a socio-technical perspective

This paper takes a cross-disciplinary view of the ontology of “business process”: how the concept is treated in the IS research literature and how related concepts (with stronger human behavioural orientation) from organisation and management sciences can potentially inform this IS perspective. In particular, is there room for socio-technical concepts such as technology affordance, derived from the constructivist tradition, in improving our understanding of operational business processes, particularly human-centric business processes? The paper presents a theoretical framework for understanding the role of business processes in organisational agility that distinguishes between the process-as-designed and the process-as-practiced. How this practice aspect of business processes also leads to the improvisation of various information technology enablers, is explored using a socio-technical lens. The posited theoretical framework is illustrated and validated with data drawn from an interpretive empirical case study of a large IT services company. The research suggests that processes within the organisation evolve both by top-down design and by the bottom-up routinisation of practice and that the tension between these is driven by the need for flexibility.     

Vehicle Teleoperation Interfaces

Despite advances in autonomy, there will always be a need for human involvement in vehicle teleoperation. In particular, tasks such as exploration, reconnaissance and surveillance will continue to require human supervision, if not guidance and direct control. Thus, it is critical that the operator interface be as efficient and as capable as possible. In this paper, we provide an overview of vehicle teleoperation and present a summary of interfaces currently in use.     

A quantum chemical study of the mechanism of action of Vitamin K epoxide reductase (VKOR) II. Transition states

A reaction path including transition states is generated for the Silverman mechanism [R.B. Silverman, Chemical model studies for the mechanism of Vitamin K epoxide reductase, J. Am. Chem. Soc. 103 (1981) 5939-5941] of action for Vitamin K epoxide reductase (VKOR) using quantum mechanical methods (B3LYP/6-311G**). VKOR, an essential enzyme in mammalian systems, acts to convert Vitamin K epoxide, formed by Vitamin K carboxylase, to its (initial) quinone form for cellular reuse. This study elaborates on a prior work that focused on the thermodynamics of VKOR [D.W. Deerfield II, C.H. Davis, T. Wymore, D.W. Stafford, L.G. Pedersen, Int. J. Quant. Chem. 106 (2006) 2944-2952]. The geometries of proposed model intermediates and transition states in the mechanism are energy optimized. We find that once a key disulfide bond is broken, the reaction proceeds largely downhill. An important step in the conversion of the epoxide back to the quinone form involves initial protonation of the epoxide oxygen. We find that the source of this proton is likely a free mercapto group rather than a water molecule. The results are consistent with the current view that the widely used drug Warfarin likely acts by blocking binding of Vitamin K at the VKOR active site and thereby effectively blocking the initiating step. These results will be useful for designing more complete QM/MM studies of the enzymatic pathway once three-dimensional structural data is determined and available for VKOR.