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Michael C Leopold

Publications and source records attributed to Michael C Leopold.

4 recordsLinked to original sources

Covalently networked monolayer-protected nanoparticle films.

Covalently networked films of nanoparticles can be assembled on various substrates from functionalized monolayer-protected clusters (MPCs) via ester coupling reactions. Exposure of a specifically modified substrate to alternating solutions of 11-mercaptoundecanoic acid exchanged and 11-mercaptoundecanol exchanged MPCs, in the presence of ester coupling reagents, 1,3-dicyclohexylcarbodiimide and 4-(dimethylamino)pyridine, results in the formation of a multilayer film with ester bridges between individual nanoparticles. These films can be grown in a controlled manner to various thicknesses and exhibit certain properties that are consistent with films having other types of interparticle connectivity, including chemical vapor response behavior and quantized double layer charging. Ester coupling of MPCs into assembled films is a straightforward and highly versatile approach that results in robust films that can endure harsher chemical environments than other types of films. The stability of these covalent films is assessed and compared to other more traditional MPC film assemblies.

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Growth, conductivity, and vapor response properties of metal ion-carboxylate linked nanoparticle films.

Nanoparticles of metals (Au, Ag, Pd, alloys) in the size range 1-3 nm diameter can be stabilized against aggregation of the metal particles by coating the metal surface with a dense monolayer of ligands (thiolates). The stabilization makes it possible to analytically define the nanoparticle composition (for example, Au140(hexanethiolate)53, I) and to elaborate the chemical functionality of the protecting monolayer (for example, Au140(C6)35(MUA)18, II, where C6 = hexanethiolate and MUA = mercaptoundecanoic acid). Network polymer films (IIfilm) on interdigitated array electrodes can be prepared from II, based on cation coordination (i.e., Cu2+, Zn2+, Ag+, methyl viologen) by the carboxylates of MUA. The electronic conductivity of the IIfilm network polymer films occurs by electron hopping between the Au140 nanoparticle cores, and offers an avenue for investigation of metal-to-metal nanoparticle electron transfer chemistry. The report begins with a brief summary of what is known about metal nanoparticle electron transfer chemistry. The investigation goes on to assess factors that influence the dynamics of film formation as well as film conductivity, in the interest of better understanding the parameters affecting electron hopping rates in IIfilm network polymer films. Finally, sorption of organic vapors into IIfilm causes a decreased electronic conductivity and increased mass that can be assessed using quartz crystal microbalance measurements. The change in electronic conductivity can be exploited for the sensing of organic vapors.

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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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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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