Nanoscale manipulation of pyrochlore: new nanocomposite ionic conductors

The ionic conductivity of isometric pyrochlore, ideally A2B2O (7), is extremely sensitive to disordering of A- and B-site cations and oxygen anion vacancies. We report the first use of ion beam irradiation-induced disordering in Gd 2Ti 2O (7) to produce a strain-free, buried, disordered defect-fluorite layer approximately 12 nm thick within an ordered pyrochlore matrix. This approach provides a new means of creating nanoscale, mixed ionic-electronic conductors in pyrochlore ceramics, such as those required for solid-state electrochemical cells.     

Desorption electrospray ionization–mass spectrometric analysis of low vapor pressure chemical particulates collected from a surface

The collection of a low vapor pressure chemical simulant triethyl phosphate sorbed onto silica gel (TEP/SG) from a surface with subsequent analysis of the TEP/SG particulates using desorption electrospray ionization–mass spectrometry (DESI–MS) is described. Collection of TEP/SG particulates on a surface was accomplished using a sticky screen sampler composed of a stainless steel screen coated with partially polymerized polydimethylsiloxane (PDMS). DESI–MS analysis of TEP/SG particulates containing different percentages of TEP sorbed onto silica gel enabled the generation of response curves for the TEP ions m/z 155 and m/z 127. Using the response curves the calculation of the mass of TEP in a 25 wt% sample of TEP/SG was calculated, results show that the calculated mass of TEP was 14% different from the actual mass of TEP in the sample using the m/z 127 TEP ion response curve. Detection limits for the TEP vapor and TEP/SG particulates were calculated to be 4 μg and 6 particles, respectively.     

Simulation of multiphase flows in porous media

The ability to numerically simulate single phase and multiphase flow of fluids in porous media is extremely important in developing an understanding of the complex phenomena governing the flow. The flow is complicated by the presence of heterogeneities in the reservoir and by phenomena such as diffusion, dispersion, and viscous fingering. These effects must be modeled by terms in coupled systems of nonlinear partial differential equations which form the basis of the simulator. The simulator must be able to handle both single and multiphase flows and the transition regimes between the two. A discussion of some of the aspects of modeling dispersion and viscous fingering is presented along with directions for future work.The partial differential equation models are convection-dominated and contain important local effects. An operator-splitting technique is used to address these different effects accurately. Convection is treated by time stepping along the characteristics of the associated pure convection problem, and diffusion is modeled via a Galerkin method for single phase flow and a Petrov-Galerkin technique for multiphase regimes. ELLAM (Eulerian-Lagrangian Localized Adjoint Methods) are discussed to effectively treat the advection-dominated processes. Accurate approximations of the fluid velocities needed in the Eulerian-Lagrangian time-stepping procedure are obtained by mixed finite element methods. Adaptive local grid refinement techniques are then indicated to resolve important local phenomena around wells and large heterogeneities or to resolve the moving internal boundary layers which often govern the mass transfer between phases.     

Syntheses and structural characterizations of anionic borane-capped ammonia borane oligomers: evidence for ammonia borane H2 release via a base-promoted anionic dehydropolymerization mechanism

Studies of the activating effect of Verkade's base, 2,8,9-triisobutyl-2,5,8,9-tetraaza-1-phosphabicyclo[3.3.3]undecane (VB), on the rate and extent of H(2) release from ammonia borane (AB) have led to the syntheses and structural characterizations of three anionic aminoborane chain-growth products that provide direct support for anionic dehydropolymerization mechanistic steps in the initial stages of base-promoted AB H(2) release reactions. The salt VBH(+)[H(3)BNH(2)BH(2)NH(2)BH(3)](-) (1) containing a linear five-membered anionic aminoborane chain was produced in 74% yield via the room-temperature reaction of a 3:1 AB/VB mixture in fluorobenzene solvent, while the branched and linear-chain seven-membered anionic aminoborane oligomers VBH(+)[HB(NH(2)BH(3))(3)](-) (2a) and VBH(+)[H(3)BNH(2)BH(2)NH(2)BH(2)NH(2)BH(3)](-) (2b) were obtained from VB/AB reactions carried out at 50 °C for 5 days when the AB/VB ratio was increased to 4:1. X-ray crystal structure determinations confirmed that these compounds are the isoelectronic and isostructural analogues of the hydrocarbons n-pentane, 3-ethylpentane, and n-heptane, respectively. The structural determinations also revealed significant interionic B-H···H-N dihydrogen-bonding interactions in these anions that could enhance dehydrocoupling chain-growth reactions. Such mechanistic pathways for AB H(2) release, involving the initial formation of the previously known [H(3)BNH(2)BH(3)](-) anion followed by sequential dehydrocoupling of B-H and H-N groups of growing borane-capped aminoborane anions with AB, are supported by the fact that 1 was observed to react with an additional AB equivalent to form 2a and 2b.     

Diborabutatriene: An Electron‐Deficient Cumulene

The complexation of two equivalents of a cyclic (alkyl)(amino)carbene (CAAC) to tetrabromodiborane, followed by reduction with four equivalents of sodium naphthalide, led to the formation of the CAAC‐stabilized linear diboracumulene (CAAC)₂B₂. The capacity of the CAAC ligand to facilitate B₂→CAAC donation of π‐electron density resulted in important differences between this species and a previously reported complex featuring a B?B triple bond stabilized by cyclic di(amino)carbenes, including a longer B? B bond and shorter B? C bonds. Frontier orbital analysis indicated sharing of valence electrons across the entire linear C‐B‐B‐C unit in (CAAC)₂B₂, which is supported by natural population analysis and cyclic voltammetry.     

Multilevel numerical solutions of convection‐dominated diffusion problems by spline wavelets

In this article, we utilize spline wavelets to establish an adaptive multilevel numerical scheme for time‐dependent convection‐dominated diffusion problems within the frameworks of Galerkin formulation and Eulerian‐Lagrangian localized adjoint methods (ELLAM). In particular, we shall use linear Chui‐Quak semi‐orthogonal wavelets, which have explicit expressions and compact supports. Therefore, both the diffusion term and boundary conditions in the convection‐diffusion problems can be readily handled. Strategies for efficiently implementing the scheme are discussed and numerical results are interpreted from the viewpoint of nonlinear approximation. © 2005 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq, 2006     

An improved synthesis of [1H]-isoindolin-1-one-3-carboxylic acid

Preparation of the title compound in one operation from commercially available phthalaldehydic acid in 34% yield is described.     

Making Mathematical Connections Across the Curriculum: Activities to Help Teachers Begin

Ample evidence is available to support the contention that, for learning to be meaningful, concepts must be connected and integrated within the experiences of the learner. In mathematics, at least three kinds of connections are particularly beneficial: connections within mathematics, across the curriculum, and with real world contexts. The authors' work with preservice and inservice teachers has convinced them that teachers possess both the willingness and the capability to help students make meaningful connections, given encouragement and support. This article focuses on making mathematical connections across the curriculum; activities which help teachers learn how to design their own are shared.