Probing Surface Sites of TiO2: Reactions with [HRe(CO)5] and [CH3Re(CO)5]

Two carbonyl complexes of rhenium, [HRe(CO)₅] and [CH₃Re(CO)₅], were used to probe surface sites of TiO₂ (anatase). These complexes were adsorbed from the gas phase onto anatase powder that had been treated in flowing O₂ or under vacuum to vary the density of surface OH sites. Infrared (IR) spectra demonstrate the variation in the number of sites, including Ti⁺³? OH and Ti⁺⁴? OH. IR and extended X‐ray absorption fine structure (EXAFS) spectra show that chemisorption of the rhenium complexes led to their decarbonylation, with formation of surface‐bound rhenium tricarbonyls, when [HRe(CO)₅] was adsorbed, or rhenium tetracarbonyls, when [CH₃Re(CO)₅] was adsorbed. These reactions were accompanied by the formation of water and surface carbonates and removal of terminal hydroxyl groups associated with Ti⁺³ and Ti⁺⁴ ions on the anatase. Data characterizing the samples after adsorption of [HRe(CO)₅] or [CH₃Re(CO)₅] determined a ranking of the reactivity of the surface OH sites, with the Ti⁺³? OH groups being the more reactive towards the rhenium complexes but the less likely to be dehydroxylated. The two rhenium pentacarbonyl probes provided complementary information, suggesting that the carbonate species originate from carbonyl ligands initially bonded to the rhenium and from hydroxyl groups of the titania surface, with the reaction leading to the formation of water and bridging hydroxyl groups on the titania. The results illustrate the value of using a family of organometallic complexes as probes of oxide surface sites.     

Chloroperoxidase Modified Electrode for Amperometric Determination of 2,4,6‐Trichlorophenol

A carbon paste‐poly(o‐phenylendiamine)‐modified electrode to be used as amperometric biosensor for 2,4,6‐trichlorophenol (TCP) is described. The enzyme chloroperoxidase (EC 1.11.1.10) from Caldariomyces fumago is immobilized through dispersion in a graphite paraffin oil carbon paste covered by an electrogenerated poly(o‐phenylendiamine) (PPD) layer. The main enzymatic dehalogenation product, 2,6‐dichloro‐1,4‐benzoquinone (DCQ) is characterized by liquid chromatography‐mass spectrometry and cyclic voltammetry. This product is electrochemically active and can be detected amperometrically at +150 mV vs. Ag|AgCl|KCl (3 M). The biosensor exhibits a response time of 4 min, a detection limit of 10^?7 M, and a dynamic linear range between 10^?7 and 10^?6 M. Selectivity as well as operating and storage stability were evaluated.     

Pair correlations of an expanding superfluid Fermi gas

The pair correlation function of an expanding gas is investigated with an emphasis on the BEC-BCS crossover of a superfluid Fermi gas at zero temperature. At unitarity quantum Monte Carlo simulations reveal the occurrence of a sizable bunching effect due to interactions in the spin up-down channel which, at short distances, is larger than that exhibited by thermal bosons in the Hanbury-Brown-Twiss effect. We propose a local equilibrium ansatz for the pair correlation function which we predict will remain isotropic during the expansion even if the trapping potential is anisotropic, in contrast with the behavior of the density. The isotropy of the pair correlation function is an experimentally accessible signature, which makes a clear distinction with respect to the case of noninteracting gases and can be understood as a consequence of the violation of scaling.     

Long time approximations for solutions of wave equations associated with the Steklov spectral homogenization problems

The interest in the use of quasimodes, or almost frequencies and almost eigenfunctions, to describe asymptotics for low‐frequency and high‐frequency vibrations in certain singularly perturbed spectral problems, which depend on a small parameter ε, has been recently highlighted in many papers. In this paper we deal with the low frequencies for a Steklov‐type eigenvalue homogenization problem: we consider harmonic functions in a bounded domain of ?², and strongly alternating boundary conditions of the Dirichlet and Steklov type on a part of the boundary. The spectral parameter appears in the boundary condition on small segments T^ε of size O(ε) periodically distributed along the boundary; ε also measures the periodicity of the structure. We consider associated second‐order evolution problems on spaces of traces that depend on ε, and we provide estimates for the time t in which standing waves, constructed from quasimodes, approach their solutions u^ε(t) as ε→0. Copyright © 2009 John Wiley & Sons, Ltd.     

Approach combining on-line metal exchange and tangential-flow ultrafiltration for in-situ characterization of metal species in humic hydrocolloids

This paper deals with the development and optimization of an analytical procedure using ultrafiltration and a flow-injection system, and its application in in-situ experiments to characterize the lability and availability of metal species in humic-rich hydrocolloids. The on-line system consists of a tangential flow ultrafiltration device equipped with a 3-kDa filtration membrane. The concentration of free ions in the filtrate was determined by atomic-absorption spectrometry, assuming that metals not complexed by aquatic humic substances (AHS) were separated from the complexed species (M–AHS) retained by the membrane. For optimization, exchange experiments using Cu(II) solutions and AHS solutions doped with the metal ions Ni(II), Mn(II), Fe(III), Cd(II), and Zn(II) were carried out to characterize the stability of the metal–AHS complexes. The new procedure was then applied in-situ at a tributary of the Ribeira do Iguape river (Iguape, São Paulo State, Brazil) and evaluated using the ions Fe(III) and Mn(II), which are considered to be essential constituents of aquatic systems. From the exchange between metal–natural organic matter (M–NOM) and the Cu(II) ions it was concluded that Cu(II) concentrations >485 μg L^?1 were necessary to obtain maximum exchange of the complexes Mn–NOM and Fe–NOM, corresponding to 100% Mn and 8% Fe. Moreover, the new analytical procedure is simple and opens up new perspectives for understanding the complexation, transport, stability, and lability of metal species in humic-rich aquatic environments.     

A transient stochastic simulation–optimization model for operational fuel planning in-theater

Army fuel planners are responsible for developing daily loading plans that specify which tankers to load, with what fuel, and where to send the loaded tankers. The tools used to accomplish this task are custom built spreadsheets which require large amounts of time and effort to use, update, and keep free of errors. This research presents a transient stochastic simulation–optimization model of the in-theater bulk fuel supply chain, where the simulation model is used to simulate the performance of the fuel supply chain under a particular fuel distribution policy and the optimization portion is used to update the policy so that it results in the performance desired by the Army fuel planner. The fuel distribution policy can then be used to derive the daily loading plan. Due to the multi-objective nature of the problem, the set of policies that form the efficient frontier are all candidate policies for the Army fuel planner to select from. Results of experimentation with a wide variety of supply chain scenarios indicate that, for a given supply chain scenario, the optimization portion of the model identifies a set of fuel distribution policies that address the objectives of the Army fuel planner. In addition, the simulation–optimization model comfortably solves the largest supply chain scenarios the Army fuel planner would reasonably be expected to encounter.     

Formation and structure of self-assembled silica nanoparticles in basic solutions of organic and inorganic cations

The phase behavior of silica solutions containing organic and inorganic cations was studied at room temperature using conductivity, pH, and small-angle scattering experiments. A critical aggregation concentration (cac) was observed at approximately 1:1 ratio of SiO(2)/OH(-) for all cation solutions from conductivity and pH studies. From this cac, a phase diagram of the system was developed with three distinct phase regions in pseudoequilibrium: a monomer/oligomer region (I), a monomer/oligomer/nanoparticle region (II), and a gel region (III). Small-angle X-ray and neutron scattering (SAXS and SANS) on solutions of region II formed with tetrapropylammonium hydroxide (TPAOH) revealed that the nanoparticles have a core-shell structure. Structure analysis of the SAXS and SANS data was best fit by a core-shell oblate ellipsoid model. A polydisperse set of core-shell spheres also fit the data well although with lower agreement factors. Similar nanoparticle morphologies were found in solutions of TMAOH, CsOH, and NaOH.     

Physical basis for the formation and stability of silica nanoparticles in basic solutions of monovalent cations

The colloidal stability, phase behavior, and solubility of silica nanoparticles (3-10 nm) that are formed in basic solutions of monovalent cations (primarily tetrapropylammonium) are investigated using a combination of chemical equilibria and electrostatic models. The free-energy gain associated with the formation of an electric double layer surrounding the nanoparticle was obtained by solving the Poisson-Boltzmann equation. This free energy is an important contribution to the total free energy of the particle and is second only to the formation of Si-O-Si bonds. The free energy of formation of the nanoparticles becomes increasingly negative with an increase in particle size and density, which explains the lower solubility of nanoparticles compared to that of amorphous silica. There is a minimum in the free energy of condensation as a function of size that qualitatively explains why the formation of small particles with a uniform size (<5 nm) is energetically favorable. The electrostatic models provide an estimate for the nanoparticle surface potential, which is significantly higher (-120 to -170 mV) than that of zeolite silicalite-1 (-60 to -80 mV) prepared in similar solutions. This result explains the stability of such small particles in solution. It is also shown that a condensation model that is based on silica solubility can describe the phase diagram for nanoparticle formation reported by Fedeyko et al. (J. Phys. Chem. B 2004, 108, 12271) over a wide range of pH and, in conjunction with a complexation model, provides an approximate equilibrium constant (pKa = 8.4) for the dissociation of nanoparticle silanol groups.