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T E Mallouk

Publications and source records attributed to T E Mallouk.

7 recordsLinked to original sources

Autonomously moving nanorods at a viscous interface.

We study the autonomous motion of catalytic nanorods in Gibbs monolayers. The catalytic activity of the rods on a hydrogen peroxide aqueous subphase gives rise to anomalous translational and rotational diffusion. The rods perform a Levy-walk superdiffusive motion that can be decomposed into thermal orientation fluctuations and an active motion of the rods with a constant velocity along their long axis. Since interfacial dissipation increases relative to bulk phase dissipation when miniaturizing the size of objects moving in the interface, the autonomous nanorods allow for precise measurements of surface shear viscosities as low as a few nN s/m. The cross over from active motion toward passive diffusion when increasing the surfactant concentration is explained by a loss of friction asymmetry of the rods.

Journal Article↗

Combined experimental and theoretical DFT study of molecular nanowires negative differential resistance and interaction with gold clusters.

Electric-field-assisted assembly has been used to place rod-shaped metal nanowires containing 4-[[2-nitro-4-(phenylethynyl) phenyl] ethynyl] benzenthiol molecules onto lithographically defined metal pads. These junctions exhibited negative differential resistance. The quantum chemical approach was used to compare the properties of Au-bonded 4-[[2-nitro-4-(phenylethynyl) phenyl] ethynyl] benzenthiol molecule and a molecule that does not exhibit the negative differential resistance, Au-bonded 4-[[4-(phenylethynyl) phenyl] ethynyl] benzenthiol. The influence of the static electric field and charge variation were modelled for both systems.

Journal Article↗

Modular synthesis of pi-acceptor cyclophanes derived from 1,4,5,8-naphthalenetetracarboxylic diimide and 1,5-dinitronaphthalene.

Three neutral cyclophanes were synthesized, and their association with indole, an aromatic pi-donor, was studied. The cyclophanes were designed to contain a rigid, hydrophobic binding cavity with 1,4,5,8-naphthalenetetracarboxylic diimide or 1,5-dinitronaphthalene as the pi-acceptor. Two of the cyclophanes also contain a (S)-(valine-leucine-alanine) tripeptide unit to provide chiral hydrogen bonding interactions with guest molecules. Despite the fact that these cyclophanes contain a hydrophobic binding cavity of appropriate dimensions, their association with indole is very weak. In the case of cyclophanes derived from 1,5-dinitronaphthalene, steric interactions force the nitro groups out of the plane of the naphthalene ring, diminishing their effectiveness as pi-acceptors. A simple UV--visible titrimetric method, using N,N,N',N'-tetramethyl-1,4-phenylenediamine (TMPD) as a pi-donor, was used to rank the pi-acceptor strength of these and other aromatic units. These titrations show that 1,4,5,8-naphthalenetetracarboxylic diimide and 1,5-dinitronaphthalene derivatives are weaker pi-acceptors than viologens, which make good pi-acceptor cyclophanes. Methyl viologen is in turn a weaker pi-acceptor than anthaquinone disulfonate, suggesting that the latter may serve as a useful building block for pi-accepting cyclophane hosts.

Ethers, Cyclic↗

Combinatorial discovery of alloy electrocatalysts for amperometric glucose sensors.

Combinatorial methods were used to search for active alloy electrocatalysts for use in enzyme-free amperometric glucose sensors. Electrode arrays (715-member) containing combinations of Pt, Pb, Au, Pd, and Rh were prepared and screened by converting anodic current to visible fluorescence. The most active compositions contained both Pt and Pb. Bulk quantities of catalysts with compositions corresponding to those identified in the screening experiments were prepared and characterized. The best alloy electrocatalysts catalyzed glucose oxidation at substantially more negative potentials than pure platinum in enzyme-free voltammetric measurements. They were also insensitive to potential interfering agents (ascorbic and uric acids, and 4-acetamidophenol), which are oxidized at slightly more positive potentials. Rotating disk electrode (RDE) experiments were carried out to study the catalytic mechanism. The improvement in catalytic performance was attributed to the inhibition of adsorption of oxidation products, which poison Pt electrodes.

Alloys↗

Ordered mesoporous polymers of tunable pore size from colloidal silica templates.

Ordered mesoporous polymers have been prepared by replication of colloidal crystals made from silica spheres 35 nanometers in diameter. The pores in the colloidal crystals were filled with divinylbenzene (DVB), ethyleneglycol dimethacrylate (EDMA), or a mixture of the two. Polymerization and subsequent dissolution of the silica template leaves a polycrystalline network of interconnected pores. When mixtures of DVB and EDMA are used, the pore size of the polymer replicas can be varied continuously between 35 and 15 nanometers because the polymer shrinks when the silica template is removed.

Colloids↗

Structure of [Mg(HO3PCH(C6H5)2)2].8H2O, a layered phosphonate salt.

Bis(hydrogen diphenylmethylphosphonato)-magnesium octahydrate, [Mg(C13H12O3P)2].8H2O. Mr = 662.85, triclinic, P1, a = 6.1051 (15), b = 8.8308(14), c = 15.312(3) A, alpha = 78.514(13), beta = 83.993(11), gamma = 75.772(15) degrees, V = 782.8(3) A3, Z = 1, Dx = 1.41 g cm-3 (163 K), Mo K alpha, lambda = 0.71069 A, mu = 2.171 cm-1, F(000) = 350, T = 163 K, R = 0.0351 for 3749 reflections [F0 greater than or equal to 4 sigma(F0)]. The structure consists of alternating polar and nonpolar layers stacked along the crystallographic c axis. The polar layers contain Mg(H2O)26+ ions, water of hydration and the phosphonate O atoms, and the nonpolar layers contain the benzhydryl groups. Two-dimensional hydrogen-bonding networks link Mg(H2O)26+ and the water of hydration to the phosphonate O atoms. The shortest hydrogen bonds in the structure, 1.68(2) A, connect the P-OH H atom and the water of hydration. Slightly longer contacts [1.79(2), 1.85(2), 1.91(2), 1.92(2) A] connect the phosphonate O atoms (O1 and O3) to the H atoms of the Mg(H2O)26+ group. The coordination environment of the Mg atom is a very nearly regular octahedron of water O atoms.

Chemical Phenomena↗