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Royce W Murray

Publications and source records attributed to Royce W Murray.

At least 55 records · Page 3Linked to original sources
PubMed2003

Voltammetry and electron-transfer dynamics in a molecular melt of a 1.2 nm metal quantum dot.

New molecular melts of nanoparticles have been obtained by place exchanging thiolated poly(ethyleneglycol, MW = 350) ligands into the monolayer shells of the quantum dot nanoparticle Au38(phenylethylthiolate)24. These melts are nearly monodisperse in monolayer protected Au clusters with core diameters of approximately 1.2 nm. LiClO4 electrolyte can be dissolved in the melt via the PEG component of the protecting monolayer, producing an ionically conductive nanophase and enabling voltammetry of the undiluted, semisolid nanoparticle molecular melt. The optical and electrochemical charging properties of the small nanoparticles have molecule-like characteristics (as opposed to quantized double layer charging) both in dilute fluid-solvent solutions and as undiluted melts. Potential step chronoamperometry shows that electronic charge is transported through the melt by diffusion-like core-core electron hopping reactions with a rate constant of 2 x 104 s-1.

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PubMed2003

Ion atmosphere relaxation control of electron transfer dynamics in a plasticized carbon dioxide redox polyether melt.

The sorption of CO(2) into the highly viscous, semisolid hybrid redox polyether melt, [Co(phenanthroline)(3)](MePEG-SO(3))(2), where MePEG-SO(3) is a MW 350 polyether-tailed sulfonate anion, remarkably accelerates charge transport in this molten salt material. Electrochemical measurements show that as CO(2) pressure is increased from 0 to 800 psi (54 atm) at 23 degrees C, the physical diffusion coefficient D(PHYS) of the Co(II) species, the rate constant k(EX) for Co(II/I) electron self-exchange, and the physical diffusion coefficient of the counterion D(COUNTERION) all increase, from 4.3 x 10(-10) to 6.4 x 10(-9) cm(2)/s, 4.1 x 10(6) to 1.6 x 10(7) M(-1) s(-1), and 3.3 x 10(-9) to 1.6 x 10(-8) cm(2)/s, respectively. Plots of log(k(EX)) versus log(D(PHYS)) and of log(k(EX)) versus log(D(COUNTERION)) are linear, showing that electron self-exchange rate constants are closely associated with processes that also govern D(PHYS) and D(COUNTERION). Slopes of the plots are 0.68 and 0.98, respectively, indicating a better linear correlation between k(EX) and D(COUNTERION). The evidence indicates that k(EX) can be controlled by relaxation of the counterion atmosphere about the Co complexes in the semisolid redox polyether melts. Because the counterion relaxation is in turn controlled by polyether "solvent" fluctuations, this is a new form of solvent dynamics control of electron transfer.

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PubMed2003

HPLC of monolayer-protected gold nanoclusters.

Polydisperse samples of Au nanoparticles protected with monolayers of hexanethiolate ligands (C6 MPCs) and with mixed monolayers of hexanethiolate and mercaptoundecanoic acid (C6/MUA MPCs) have been chromatographically separated using C8 120-A columns and acetone/ toluene mobile phase. The spectral details of eluted peaks and of quantized double-layer charging features in the differential pulse voltammetry of collected fractions were used to show that the elution orders of C6 MPC mixtures and of C6/MUA MPC mixtures were different. For C6 MPCs, the smallest MPCs were eluted first, whereas the smallest C6/MUA MPCs were eluted last. The reversal of order of elution was rationalized in terms of intermolecular interactions with the stationary phase, dominant for the C6 MPC, being suppressed by the heightened polarity of the monolayer surface of the C6/MUA MPCs, making a size exclusion mechanism dominant. The range of apparent core diameters of the separated nanoparticles was 1.3-2 nm.

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PubMed2002

Quantized double-layer charging of highly monodisperse metal nanoparticles.

We describe unprecedented resolution of electrochemically observed quantized double layer (QDL) charging, attained with use of reduced solution temperatures and with an annealing procedure that produces hexanethiolate monolayer protected gold clusters (C6 MPCs) with a high level of monodispersity in charging capacitance, C(CLU). The spacing DeltaV = e/C(CLU) on the electrochemical potential axis between one electron changes in the electronic charge of nanoscopic metal particles is determined by their effective capacitance C(CLU). The high monodispersity of the C6 MPCs with Au(140) cores facilitates (a) detailed rotated disk and cyclic voltammetric measurements, (b) simulation of QDL waveshapes based on assumed reversible, multivalent redox-like behavior, (c) determination of nanoparticle diffusion rates, and (d) observation of as many as 13 changes in the MPC charge state, from MPC(6-) to MPC(7+). The single electron QDL charging peaks are quite evenly spaced (DeltaV constant) at potentials near the MPC potential of zero charge, but are irregularly spaced at more positive and negative potentials. The irregular spacing is difficult to rationalize with classical double layer capacitance ideas and is proposed to arise from a correspondingly structured (e.g., not smooth) density of electronic states of the nanoparticle core, resulting from its small HOMO/LUMO gap and incipiently molecule-like behavior.

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PubMed2002

DNA binding of an ethidium intercalator attached to a monolayer-protected gold cluster.

Ethidium intercalation has been investigated as a means of inducing binding of Au nanoparticles to DNA. The ethidium sites are attached to the nanoparticles as thiolate ligands, using 3,8-diamino-5-mercaptododecyl-6-phenylphenanthridinium (ethidium thiolate). Each nanoparticle bears only one or two ethidium thiolate ligands. The rest of the thiolate monolayer ligands on the monolayer-protected Au clusters (MPCs) were either N-(2-mercaptopropionyl)glycine (tiopronin/ethidium MPC) or trimethyl(mercaptoundecyl)ammonium (TMA/ethidium MPC). In solution mixtures of DNA and MPCs, the energy-transfer quenching of the ethidium ligands by the metal-like MPC core is partially released by ethidium binding to DNA, as observed by an increase in the intensity of ethidium fluorescence. Binding of the cationic TMA/ethidium MPC to DNA was efficient and rapid. The negatively charged tiopronin/ethidium MPC, in contrast, exhibits slow intercalation kinetics, relative to ethidium cation not attached to an MPC. The slow kinetics were analyzed as two competing binding interactions. The tiopronin/ethidium MPC binding to DNA was imaged by AFM.

DNA↗
PubMed2002

Electron and mass transport in hybrid redox polyether melts contacted with carbon dioxide.

Films of neat metal salts with covalently attached oligoether side chains ([Co(bpy(CO(2)MePEG-350)(2))(3)](ClO(4))(2); bpy is 2,2'-bipyridine, and MePEG-350 is methyl-terminated oligomeric ethylene oxide with an average molecular weight of 350 Da) undergo marked changes in physical and electrochemical properties upon contact with CO(2). Electrochemical measurements indicate that the physical diffusion coefficient (D(PHYS)) of the Co(II) species, the observed rate constant for Co(II/I) self-exchange (k(EX)), and the physical diffusion coefficient of the perchlorate counterion (D(ClO4)) increase from 2.4 x 10(-11) to 7.0 x 10(-10) cm(2)/s, 6.8 x 10(5) to 4.5 x 10(6) M(-1) s(-1), and 3.4 x 10(-10) to 4.3 x 10(-9) cm(2)/s, respectively, as CO(2) pressure is increased from 0 to 2000 psi at 23 degrees C. A reduction in activation energy accompanies the enhancement of each of these properties over this pressure range. Increasing CO(2) pressure from ambient to 1000 psi causes the films to swell 13%, and free-volume theory explains the enhanced mass transport properties of the films. The origin of increases in electron-transfer kinetics is considered. Plots of log(k(EX)) versus log(D(PHYS)) and log(k(EX)) versus log(D(ClO4)) are both linear. This suggests that electron self-exchange is controlled by factors that also affect log(D(PHYS)) or log(D(ClO4)). One explanation is based on plasticization of the oligoether side-chain motions by CO(2) that affect ether dipole repolarization and Co complex diffusion rates. A second explanation for the changes in k(EX) is based on control of electron transfer by relaxation of counterions neighbor to the Co complexes, which is measured by D(ClO4). Both explanations represent a kind of solvent dynamics control of k(EX).

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PubMed2002

Electron hopping conductivity and vapor sensing properties of flexible network polymer films of metal nanoparticles.

Films of monolayer protected Au clusters (MPCs) with mixed alkanethiolate and omega-carboxylate alkanethiolate monolayers, linked together in a network polymer by carboxylate-Cu2+-carboxylate bridges, exhibit electronic conductivities (sigma(EL)) that vary with both the numbers of methylene segments in the ligands and the bathing medium (N2, liquid or vapor). A chainlength-dependent swelling/contraction of the film's internal structure is shown to account for changes in sigma(EL). The linker chains appear to have sufficient flexibility to collapse and fold with varied degrees of film swelling or dryness. Conductivity is most influenced (exponentially dependent) by the chainlength of the nonlinker (alkanethiolate) ligands, a result consistent with electron tunneling through the alkanethiolate chains and nonbonded contacts between those chains on individual, adjacent MPCs. The sigma(EL) results concur with the behavior of UV-vis surface plasmon adsorption bands, which are enhanced for short nonlinker ligands and when the films are dry. The film conductivities respond to exposure to organic vapors, decreasing in electronic conductivity and increasing in mass (quartz crystal microgravimetry, QCM). In the presence of organic vapor, the flexible network of linked nanoparticles allows for a swelling-induced alteration in either length or chemical nature of electron tunneling pathways or both.

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PubMed2002

Dynamics and extent of ligand exchange depend on electronic charge of metal nanoparticles.

Both the rate and extent of ligand place exchange reactions between the hexanethiolate monolayer of Au(140) monolayer protected clusters (C6 MPCs) and dissolved 6-mercapto-1-hexanol thiol (HOC6SH) increase with increasing positive electronic charge on the Au cluster core. The rate constant of the ligand place exchange, taken at the early stage of the exchange, is increased by ca. 2-fold for reaction of +3 charged Au(140) cores as compared to neutral ones. The initially exchanged ligands are thought to reside mainly on edge and vertex sites of the Au(140) core, where the lability of the slightly more ionic Au[bond]S bonds there becomes further enhanced by removing electrons from the core. The reactions slow markedly after 35-50% of the original ligands have been replaced, continuing at a much slower pace for some time to reach an apparent reaction equilibrium. On +2 charged Au(140) cores, 85% of the C6 ligands have been exchanged with HOC(6)H(12)SH after 20 h. The slower phase of the reaction includes exchange of thiolate ligands on terrace lattice sites most of which--owing to the small sizes of the nanoparticle's Au(111) faces--are no more than one Au atom row removed from the nanoparticle edge sites. This slower exchange, the extent of which is also enhanced by positively charging the core, occurs either by intramolecular place exchange with edge sites that subsequently place-exchange with solution thiol or by direct place-exchange with solution thiol. Acid-base studies show that thiolate is more reactive in place exchange reactions than the corresponding thiol.

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PubMed2002

Electrical characterization of gel collected from shark electrosensors.

To investigate the physical mechanism of the electric sense, we present an initial electrical characterization of the glycoprotein gel that fills the electrosensitive organs of marine elasmobranchs (sharks, skates, and rays). We have collected samples of this gel, postmortem, from three shark species, and removed the majority of dissolved salts in one sample via dialysis. Here we present the results of dc conductivity measurements, low-frequency impedance spectroscopy, and electrophoresis. Electrophoresis shows a range of large protein-based molecules fitting the expectations of glycoproteins, but the gels of different species exhibit little similarity. The electrophoresis signature is unaffected by thermal cycling and measurement currents. The dc data were collected at various temperatures, and at various electric and magnetic fields, showing consistency with the properties of seawater. The impedance data collected from a dialyzed sample, however, show large values of static permittivity and a loss peak corresponding to an unusually long relaxation time, about 1 ms. The exact role of the gel is still unknown, but our results suggest its bulk properties are well matched to the sensing mechanism, as the minimum response time of an entire electric organ is on the order of 5 ms.

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