Natural convection in porous media—dual reciprocity boundary element method solution of the Darcy model

This paper describes the solution of a steady state natural convection problem in porous media by the dual reciprocity boundary element method (DRBEM). The boundary element method (BEM) for the coupled set of mass, momentum, and energy equations in two dimensions is structured by the fundamental solution of the Laplace equation. The dual reciprocity method is based on augmented scaled thin plate splines. Numerical examples include convergence studies with different mesh size, uniform and non‐uniform mesh arrangement, and constant and linear boundary field discretizations for differentially heated rectangular cavity problems at filtration with Rayleigh numbers of Ra*=25, 50, and 100 and aspect ratios of A=1/2, 1, and 2. The solution is assessed by comparison with reference results of the fine mesh finite volume method (FVM). Copyright © 2000 John Wiley & Sons, Ltd.     

Algorithm for recognizing Cartesian graph bundles

Graph bundles generalize the notion of covering graphs and graph products. In [8], authors constructed an algorithm that finds a presentation as a nontrivial Cartesian graph bundle for all graphs that are Cartesian graph bundles over triangle-free simple base. In [21], the unique square property is defined and it is shown that any equivalence relation possessing the unique square property determines the fundamental factorization of a graph as a nontrivial Cartesian graph bundle over arbitrary base graph. In this paper we define a relation Δ having a unique square property on Cartesian graph bundles over K₄e-free simple base. We also give a polynomial algorithm for recognizing Cartesian graph bundles over K₄e-free simple base.     

An efficient methyltrioxorhenium(VII)-catalyzed transformation of hydrotrioxides (ROOOH) into dihydrogen trioxide (HOOOH)

Dihydrogen trioxide (HOOOH) is formed nearly quantitatively in the low-temperature (-70 degrees C) methyltrioxorhenium(VII) (MTO)-catalyzed transformation of silyl hydrotrioxides (R3SiOOOH), and some acetal hydrotrioxides, in various solvents, as confirmed by 1H, and 17O NMR spectroscopy. The calculated energetics (B3LYP) for the catalytic cycle, using H3SiOOOH as a model system, is consistent with the experimentally observed activation energy (9.5 +/- 2.0 kcal/mol) and a small kinetic solvent isotope effect (kH2O/kD2O = 1.1 +/- 0.1), indicating an initial concerted reaction between the silyl hydrotrioxide and MTO in the rate-determining step. With the addition of water in the next step, the intermediate undergoes a sigma-bond metathesis reaction to break the Re-OOOH bond and form HOOOH, together with the second dihydroxy intermediate. The final step in the catalytic cycle involves a second, catalytic water that lowers the barrier to form H3SiOH and MTO.     

Synthesis and characterization of dicyclopalladated complexes of azobenzene derivatives by experimental and computational methods

A series of doubly cyclopalladated complexes of azobenzene and its unsymmetrical substituted derivatives, namely, {LPdCl(mu-AZB)LPdCl}, where AZB is azobenzene, 4-methylazobenzene, 4-aminoazobenzene, or 4-(dimethylamino)-4'-nitroazobenzene, while L is N,N-dimethylformamide, dimethylsulfoxide, or pyridine, have been prepared. Their structural and spectroscopic properties were determined by X-ray diffraction analysis as well as by (1)H NMR, IR, UV-vis, and fluorimetric studies. Experimental results were rationalized by quantum chemical calculations. Crystal structures of several complexes have been resolved, and for the first time, it was demonstrated that the cyclopalladation may take place at the azobenzene aromatic ring having the strong electron-withdrawing substituent at the para position. In all cases, the metalated carbon and N,N-dimethylformamide or dimethylsulfoxide ligands are mutually trans, whereas the pyridine ligands are in the cis arrangement. cis/trans isomerism in the isolated compounds is explained by comparing the calculated energies of isomeric structures. All of the complexes absorb strongly in the visible region, and according to time-dependent density functional theory calculations, most of the absorptions can be attributed to intraligand pi --> pi* or metal-to-ligand charge-transfer transitions. The fluorescence emission was observed for the complexes with 4-aminoazobenzene or 4-(dimethylamino)-4'-nitroazobenzene. The aromaticity of palladacycles is evaluated by several aromaticity indices and related to relevant experimental findings.     

Not all G-quadruplexes exhibit ion-channel-like properties: NMR study of ammonium ion (non)movement within the d(G(3)T(4)G(4))(2) quadruplex

A solution-state NMR study on 15NH4(+) ion movement within d(G(3)T(4)G(4))(2), a dimeric G-quadruplex consisting of three G-quartets and two T(4) loops, rather unexpectedly demonstrated the absence of 15NH4(+) ion movement between the binding sites U and L along the central axis of the G-quadruplex. Distinct temperature dependences of autocorrelation signals for U and L binding sites have been observed in 15N-1H NzExHSQC spectra which correlate with the local stiffness of the G-quadruplex. The volumes of the cross-peaks, which are the result of 15NH4(+) ion movement, have been interpreted in terms of rate constants, T(1) relaxation, and proton exchange. 15NH4(+) ion movements from the binding sites U and L into the bulk solution are characterized by lifetimes of 139 ms and 1.7 s at 298 K, respectively. The 12 times faster movement from the binding site U demonstrates that 15NH4(+) ion movement is controlled by the structure of T4 loop residues, which through diagonal- vs edge-type orientations impose distinct steric restraints for cations to leave or enter the G-quadruplex. Arrhenius-type analysis has afforded an activation energy of 66 kJ mol(-)1 for the UB process, while it could not be determined for the LB process due to slow rates at temperatures below 298 K. We further the use of the 15NH4(+) ion as an NMR probe to gain insight into the occupancy of binding sites by cations and kinetics of ion movement which are intrinsically correlated with the structural details, dynamic fluctuations, and local flexibility of the DNA structure.     

Wiring of glucose oxidase with graphene nanoribbons: an electrochemical third generation glucose biosensor

A reagentless third generation electrochemical glucose biosensor was fabricated based on wiring the template enzyme glucose oxidase (GOx) with graphene nanoribbons (GN) in order to create direct electron transfer between the co-factor (flavin adenine dinucleotide, FAD) and the electrode. The strategy involved: (i) isolation of the apo-enzyme by separating it from its co-enzyme; (ii) preparation of graphene nanoribbons (GN) by oxidative unzipping of multi-walled carbon nanotubes; (iii) adsorptive immobilization of GNs on the surface of a screen printed carbon electrode (SPCE); (iv) covalent attachment of FAD to the nanoribbons; (v) recombination of the apo-enzyme with the covalently bound FAD to the holoenzyme; and (vi) stabilization of the bio-layer with a thin membrane of Nafion. The biosensor (referred to as GN/FAD/apo-GOx/Nafion/SPCE) is operated at a potential of +0.475 V vs Ag/AgCl/{3 M KCl} in flow-injection mode with an oxygen-free phosphate buffer (pH 7.5) acting as a carrier. The signals are linearly proportional to the concentration of glucose in the range from 50 to 2000 mg?L^?1 with a detection limit of 20 mg?L^?1. The repeatability (10 measurements, at 1000 mg?L^?1 glucose) is ±1.4% and the reproducibility (5 sensors, 1000 mg?L^?1 glucose) is ±1.8%. The biosensor was applied to the determination of glucose in human serum.

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Graphical abstract Wiring of the apo-enzyme of glucose oxidase (apo-GOx) with graphene nanoribbons (GN) bound to FAD at a screen-printed carbon electrode (SPCE). Cyclic voltammetric and amperometric responses to various glucose concentrations.

     

On duality between étale groupoids and Hopf algebroids

For any étale Lie groupoid G over a smooth manifold M, the groupoid convolution algebra of smooth functions with compact support on G has a natural coalgebra structure over the commutative algebra which makes it into a Hopf algebroid. Conversely, for any Hopf algebroid A over we construct the associated spectral étale Lie groupoid over M such that is naturally isomorphic to G. Both these constructions are functorial, and is fully faithful left adjoint to . We give explicit conditions under which a Hopf algebroid is isomorphic to the Hopf algebroid of an étale Lie groupoid G.     

A Simple and Efficient Preparation of High‐Purity Hydrogen Trioxide (HOOOH)

A simple and efficient method allows the synthesis of solutions of high‐purity hydrogen trioxide (HOOOH), released in the low‐temperature methytrioxorhenium(VII) (MTO)‐catalyzed transformation of the ozonized polystyrene‐supported dimethylphenylsilane. High‐purity hydrogen trioxide solutions in diethyl ether, separated from the polymer and free of any reactants and by‐products, can be stored at ?20 °C for weeks. By removing the solvent in vacuo, HOOOH could be isolated in highly pure form or transferred to other solvents, thus significantly extending the research perspectives of HOOOH for novel applications.