Molybdenum Dioxide in Carbon Nanoreactors as a Catalytic Nanosponge for the Efficient Desulfurization of Liquid Fuels

The principle of a “catalytic nanosponge” that combines the catalysis of organosulfur oxidation and sequestration of the products from reaction mixtures is demonstrated. Group VI metal oxide nanoparticles (CrO_x, MoO_x, WO_x) are embedded within hollow graphitized carbon nanofibers (GNFs), which act as nanoscale reaction vessels for oxidation reactions used in the decontamination of fuel. When immersed in a model liquid alkane fuel contaminated with organosulfur compounds (benzothiophene, dibenzothiophene, dimethyldibenzothiophene), it is found that MoO₂@GNF nanoreactors, comprising 30 nm molybdenum dioxide nanoparticles grown within the channel of GNFs, show superior abilities toward oxidative desulfurization (ODS), affording over 98% sulfur removal at only 5.9 mol% catalyst loading. The role of the carbon nanoreactor in MoO₂@GNF is to enhance the activity and stability of catalytic centers over at least 5 cycles. Surprisingly, the nanotube cavity can selectively absorb and remove the ODS products (sulfoxides and sulfones) from several model fuel systems. This effect is related to an adsorptive desulfurization (ADS) mechanism, which in combination with ODS within the same material, yields a “catalytic nanosponge” MoO₂@GNF. This innovative ODS and ADS synergistic functionality negates the need for a solvent extraction step in fuel desulfurization and produces ultralow sulfur fuel.     

Extrusion of highly filled flexible polymer sheet

Highly-filled polymer systems include color masterbatches, feedstocks for powder injection molding, and rigid sheets with high levels of flame retardants, but they have not been explored for flexible sheet. This work investigated the (a) selecting a polymer matrix with enough melt strength and flexibility to form a stable sheet with high filler loading, (b) the maximum achievable filler loading for the sheet, and (c) optimizing the process of extruding a highly-filled flexible polymer system. Extrusion grade low-density polyethylene (LDPE) provided sufficient flexibility and permitted a maximum filler loading of 36 vol% (~78 wt%). Good dispersion of the nanoparticle filler, however, required two passes through multiple screw extruders and a small reduction in the viscosity of the LDPE. Sheet with thickness of 415 μm, surface roughness of <1 μm, and sufficient flexibility was extruded continuously at a rate of 10 m/min., but it required a more traditional coat hanger manifold to prevent filler hang up in the sheet die. The filler particles were distributed uniformly through the core and skin of the sheet, giving the sheet good mechanical properties.     

Chemical-Shift Perturbations Reflect Bile Acid Binding to Norovirus Coat Protein: Recognition Comes in Different Flavors

Bile acids have been reported as important cofactors promoting human and murine norovirus (NoV) infections in cell culture. The underlying mechanisms are not resolved. Through the use of chemical shift perturbation (CSP) NMR experiments, we identified a low-affinity bile acid binding site of a human GII.4 NoV strain. Long-timescale MD simulations reveal the formation of a ligand-accessible binding pocket of flexible shape, allowing the formation of stable viral coat protein–bile acid complexes in agreement with experimental CSP data. CSP NMR experiments also show that this mode of bile acid binding has a minor influence on the binding of histo-blood group antigens and vice versa. STD NMR experiments probing the binding of bile acids to virus-like particles of seven different strains suggest that low-affinity bile acid binding is a common feature of human NoV and should therefore be important for understanding the role of bile acids as cofactors in NoV infection.     

Implementing commercial information exchange: a construction supply chain case study

The concept of electronic trading (e-trading) has transformed supply chain interactions in many industries, yet little research explored its implementation by Architecture, Engineering and Construction (AEC) supply chain firms. E-trading relies on commercial information exchange by supply chain partners which is generally adopted through intermediary technology partners (Hub Providers) to facilitate the accurate and timely communication of transactional data between buyers and supplier. A case study was conducted to explore the challenges and barriers to implementation of cross-firm commercial information exchange. The study primarily involved investigation of the interfaces between software development and organizational functions assisting with the electronic exchange of commercial information (eCIX) implementation. Findings from the case study show that implementation of commercial information exchange is not an easy task with several themes of factors to be considered during delivery of such projects, namely technical, coordination, integration and organizational. The study contributes to the knowledge and deployment of e-trading solutions within the context of AEC firms, and should be of interest to the practitioners contemplating similar projects.     

Water and solute mass balance of five small, relatively undisturbed watersheds in the U.S

Geochemical mass balances were computed for water years 1992-1997 (October 1991 through September 1997) for the five watersheds of the U.S. Geological Survey Water, Energy, and Biogeochemical Budgets (WEBB) Program to determine the primary regional controls on yields of the major dissolved inorganic solutes. The sites, which vary markedly with respect to climate, geology, physiography, and ecology, are: Allequash Creek, Wisconsin (low-relief, humid continental forest); Andrews Creek, Colorado (cold alpine, taiga/tundra, and subalpine boreal forest); Río Icacos, Puerto Rico (lower montane, wet tropical forest); Panola Mountain, Georgia (humid subtropical piedmont forest); and Sleepers River, Vermont (humid northern hardwood forest). Streamwater output fluxes were determined by constructing empirical multivariate concentration models including discharge and seasonal components. Input fluxes were computed from weekly wet-only or bulk precipitation sampling. Despite uncertainties in input fluxes arising from poorly defined elevation gradients, lack of dry-deposition and occult-deposition measurements, and uncertain sea-salt contributions, the following was concluded: (1) for solutes derived primarily from rock weathering (Ca, Mg, Na, K, and H(4)SiO(4)), net fluxes (outputs in streamflow minus inputs in deposition) varied by two orders of magnitude, which is attributed to a large gradient in rock weathering rates controlled by climate and geologic parent material; (2) the net flux of atmospherically derived solutes (NH(4), NO(3), SO(4), and Cl) was similar among sites, with SO(4) being the most variable and NH(4) and NO(3) generally retained (except for NO(3) at Andrews); and (3) relations among monthly solute fluxes and differences among solute concentration model parameters yielded additional insights into comparative biogeochemical processes at the sites.     

Sub-micrometer particulate air pollution and cardiovascular mortality in Beijing, China

Background

While the link between particulate matter and cardiovascular mortality is well established, it is not fully investigated and understood which properties of the aerosol might be responsible for the health effects, especially in polluted mega-city areas.

Objectives

Our goal was to explore the association between daily cardiovascular mortality and different particle metrics in the sub-micrometer range in Beijing, China.

Methods

We obtained daily counts of cause-specific cardiovascular deaths in the Beijing urban area for the period March 2004 to August 2005. Concurrently, continuous measurements of particle number size distributions were performed. Particle number concentrations (NC) between 0.003 μm and 0.8 μm were converted to particle mass and surface area concentrations assuming spherical particles. Semi-parametric Poisson regression models adjusting for trend, seasonality, day of the week, and meteorology were used to estimate immediate, delayed and cumulative particle effects. Additionally, effect modification by air mass origin was investigated.

Results

We observed associations between daily cardiovascular mortality and particle NC for a 2-days delay. Moreover, nearly all particle metrics showed 2-days delayed associations with ischemic heart disease mortality. The strongest association was found for particle NC in the size range 0.03-0.1 μm (7.1% increase in daily mortality with a 95%-confidence interval of 2.9%-11.5%, per an increase of 6250 particles/cm³). Results for surface and mass concentrations with a lag of two days indicated effect modification by air mass origin, whereas effects of particle NC were not modified.

Conclusions

Results show an elevated risk of cardiovascular mortality in Beijing from short-term exposure to particulate air pollution in the sub-micrometer range. Results also indicate that locally produced smaller particles and regionally transported particles may exhibit different effects in Beijing.     

Large-scale parallel lattice Boltzmann–cellular automaton model of two-dimensional dendritic growth

An extremely scalable lattice Boltzmann (LB)–cellular automaton (CA) model for simulations of two-dimensional (2D) dendritic solidification under forced convection is presented. The model incorporates effects of phase change, solute diffusion, melt convection, and heat transport. The LB model represents the diffusion, convection, and heat transfer phenomena. The dendrite growth is driven by a difference between actual and equilibrium liquid composition at the solid–liquid interface. The CA technique is deployed to track the new interface cells. The computer program was parallelized using the Message Passing Interface (MPI) technique. Parallel scaling of the algorithm was studied and major scalability bottlenecks were identified. Efficiency loss attributable to the high memory bandwidth requirement of the algorithm was observed when using multiple cores per processor. Parallel writing of the output variables of interest was implemented in the binary Hierarchical Data Format 5 (HDF5) to improve the output performance, and to simplify visualization. Calculations were carried out in single precision arithmetic without significant loss in accuracy, resulting in 50% reduction of memory and computational time requirements. The presented solidification model shows a very good scalability up to centimeter size domains, including more than ten million of dendrites.