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David J Schiffrin

Publications and source records attributed to David J Schiffrin.

16 recordsLinked to original sources
PubMed2006

Precision control of single-molecule electrical junctions.

There is much discussion of molecules as components for future electronic devices. However, the contacts, the local environment and the temperature can all affect their electrical properties. This sensitivity, particularly at the single-molecule level, may limit the use of molecules as active electrical components, and therefore it is important to design and evaluate molecular junctions with a robust and stable electrical response over a wide range of junction configurations and temperatures. Here we report an approach to monitor the electrical properties of single-molecule junctions, which involves precise control of the contact spacing and tilt angle of the molecule. Comparison with ab initio transport calculations shows that the tilt-angle dependence of the electrical conductance is a sensitive spectroscopic probe, providing information about the position of the Fermi energy. It is also shown that the electrical properties of flexible molecules are dependent on temperature, whereas those of molecules designed for their rigidity are not.

Journal Article↗
PubMed2006

Quantum chemical modelling of the rate determining step for oxygen reduction on quinones.

Two inner-sphere electrocatalytic channels for quinone-mediated reduction of molecular oxygen to form hydrogen peroxide have been addressed by means of density functional theory. Each of the channels comprises an initial rate determining chemical step and a subsequent electrochemical reduction step by which peroxide is produced. The reduction mechanism was determined for 9,10-anthraquinone and 9,10-phenanthrenequinone and the quantum chemical results are compared with experimental results. Two distinctly different structures were determined for the critical chemical step depending on whether the catalytic site is present as HQ* or Q*-. While a superoxo species is formed on HQ*, a van der Waals (vdW) type compound is formed on Q*-. It is shown that the Gibbs energy of activation for the semiquinone/oxygen reaction is largely determined by the entropy term. The results explain the experimentally observed pH dependence of the O2 reduction rate on quinone functionalised electrodes.

Computer Simulation↗
PubMed2006

Synthesis of metal nanoparticles stabilized by metal-carbon bonds.

A new method for the preparation of metal nanoparticles in organic media is proposed. This is based on the formation of metal-carbon bonds after reduction of the corresponding diazonium derivative of the capping ligand. The particles are very stable due to the strong metal-ligand covalent bond, and the proposed method appears to be an alternative for the preparation of monolayer-protected metal nanoparticles when the formation of metal-sulfur or metal-nitrogen bonds needs to be avoided.

Journal Article↗
PubMed2006

Plasmon interactions between gold nanoparticles in aqueous solution with controlled spatial separation.

The effects of interparticle distance on the UV-visible absorption spectrum of gold nanocrystals aggregates in aqueous solution have been investigated. The aggregates were produced by ion-templated chelation of omega-mercaptocarboxylic acid ligands covalently attached to the nanoparticles surface. Variation of the ligand chain length provides control over the interparticle separation in the aggregates. The UV-visible spectra consist typically of a single particle band and a secondary band at higher wavelengths associated with the formation of aggregates in solution. The position of the latter depends on interparticle separation up to distances of approximately 8 nm, in accordance with existing models. Potential applications therefore include distance sensitive labels or proximity probes. Conversely, variation of the ligand length allows the preparation of nanostuctured materials with tuned optical properties.

Crystallization↗
PubMed2006

Quantum chemical modeling of the reduction of quinones.

A systematic study of the redox properties of six parent quinones has been carried out using quantum chemistry methods. The reduction of the ortho (o-) and para (p-) isomers of benzoquinone and naphthoquinone, 9,10- anthraquinone and 9,10-phenantrenequinone to the corresponding hydroquinones and semiquinone radicals was investigated at the B3LYP/6-311+G(d,p) level of theory. Thermodynamic functions in the gas-phase were calculated for all the reduction reactions. Gibbs energies of reaction and standard potentials in water for the reductions were determined using the IEF-PCM model and an empirical correction to the calculations based on the limited thermodynamic data available for the quinones. Potentials were calculated both for the direct reduction to the quinols, and for the two-step reduction via the neutral semiquinones. The calculated potentials for the 2e-, 2H+ reductions were found in good agreement with experiment and to display the same trends as gas-phase enthalpies and energies, i.e., to correlate with the number of C=C double bonds, as well as on the relative position of the C=O groups. The small deviations between experiment and theoretically predicted standard potentials were found to originate from basis set incompleteness and the shortcomings in the B3LYP exchange correlation functional rather than the models used for the thermochemical calculations or description of solvation. Accurate theoretical shifts in standard potentials for the p-/o- pairs of Q <--> HQ and HQ <--> H2Q reactions are presented and compared to experiment. Reliable standard potentials and shifts for the neutral semiquinones are predicted for the first time.

Benzoquinones↗
PubMed2006

Thermal gating of the single molecule conductance of alkanedithiols.

The temperature dependence of the single molecule conductance (SMC) of alpha,omega-alkanedithiols has been investigated using a scanning tunnelling microscopy (STM) method. This is based on trapping molecules between a gold STM tip and a gold substrate and measuring directly the current across the molecule under different applied potentials. A pronounced temperature dependence of the conductance, which scales logarithmically with T(1), is observed in the temperature range between 293 and 353 K. It is proposed the origin of this dependence is the change in distribution between molecular conformers rather than changes in either the conduction mechanism or the electronic structure of molecule. For alkanedithiols the time averaged conformer distribution shifts to less elongated conformers at higher temperatures thus giving rise to higher conductance across the molecular bridges. This is analysed by first calculating energy differences between different conformers and then calculating their partition distribution. A simple tunnelling model is then used to calculate the temperature dependent conductance based on the conformer distribution. These findings demonstrate that charge transport through single organic molecules at ambient temperatures is a subtle and highly dynamic process that cannot be described by analysing only one molecular conformation corresponding to the lowest energy geometry of the molecule.

Journal Article↗
PubMed2005

Functionalization of thioctic acid-capped gold nanoparticles for specific immobilization of histidine-tagged proteins.

This paper presents an efficient strategy for the specific immobilization of fully functional proteins onto the surface of nanoparticles. Thioctic acid-derivatized gold clusters are used as a scaffold for further stepwise modification, leading to a cobalt(II)-terminated ligand shell. A histidine tag introduced by genetic engineering into a protein is coordinated to this transition metal ion. The specific immobilization has been demonstrated for the cases of a genetically engineered horseradish peroxidase and ferredoxin-NADP(+) reductase, confirming the attachment of the fully functional proteins to the Co(II)-terminated nanointerface. The absence of nonspecific protein adsorption and the specificity of the binding site have been verified using several analogues of the enzymes without the histidine tag.

Binding Sites↗
PubMed2004

Molecular wire formation from viologen assemblies.

The adsorption behavior of viologen alpha,omega-dithiols (viologen dithiols) on gold has been investigated. At short exposures, a low-coverage phase consisting of flat-lying molecules has been determined by STM and IR spectroscopy. In contrast, multilayer films are formed after long adsorption times. Single molecular wires could be formed between a gold STM tip and a surface with a low coverage of the adsorbed dithiols, and their electrical behavior was investigated. Molecular conductivity was determined either by the repeated measurement of I(s) curves or by recording I-V curves for different tip-sample separations. These methods concurred in producing a value of (0.5 +/- 0.1) nS for the single-molecule conductivity of the alpha,omega-viologen dithiol molecule HS-6V6-SH. The high conductivity of HS-6V6-SH, as compared to that of HS-C12-SH, may be related to the low-lying LUMO, which provides a barrier indentation for electron transport in a two-step electron-transfer mechanism.

Journal Article↗
PubMed2004

Rational and combinatorial design of peptide capping ligands for gold nanoparticles.

Based on protein folding considerations, a pentapeptide ligand, CALNN, which converts citrate-stabilized gold nanoparticles into extremely stable, water-soluble gold nanoparticles with some chemical properties analogous to those of proteins, has been designed. These peptide-capped gold nanoparticles can be freeze-dried and stored as powders that can be subsequently redissolved to yield stable aqueous dispersions. Filtration, size-exclusion chromatography, ion-exchange chromatography, electrophoresis, and centrifugation can be applied to these particles. The effect of 58 different peptide sequences on the electrolyte-induced aggregation of the nanoparticles was studied. The stabilities conferred by these peptide ligands depended on their length, hydrophobicity, and charge and in some cases resulted in further improved stability compared with CALNN, yielding detailed design criteria for peptide capping ligands. A simple strategy for the introduction of recognition groups is proposed and demonstrated with biotin and Strep-tag II.

Amino Acid Sequence↗
PubMed2004

Silver halide colloid precursors for the synthesis of monolayer-protected clusters.

A new method for the synthesis of monolayer-protected silver clusters (MPCs) based on the two-phase reduction of a stable negatively charged silver bromide sol is described. Phase transfer of the colloid to toluene is accomplished using tetra-n-octylammonium bromide as the phase transfer reagent. The advantage of this synthesis is to uncouple the formation of the silver halide colloid from its transfer and reduction in the organic phase, thus allowing control over each reaction step. The silver colloid in toluene was reduced with aqueous borohydride in the presence of 4-bromobenzenethiol as the passivating agent. The UV-visible absorption spectra indicate the intermediate formation of Ag(core)AgBr(shell) clusters during reduction. The resulting MPCs have been characterized by optical and transmission electron microscopy, energy-dispersive X-ray analysis, thermogravimetry, and UV-vis absorption spectroscopy. The formation of spiral cracks in the nanoparticulate agglomerates on solvent evaporation was observed. The spectra of thin films obtained by solvent evaporation have been analyzed using an effective medium theory.

Journal Article↗
PubMed2004

Wiring nanoparticles with redox molecules.

Gold nanoparticles were used to make electrical contact to redox-active organic molecules. Viologen based dithiols were self-assembled from solution on Au(111) for use as tethers to attach nanoparticles to a conducting substrate. The topography and electrical properties of the resulting films were investigated by STM and STS and the orientation of these linkers was investigated by FTIR. Surface coverage increased with increasing reaction time, resulting in a change of film orientation from a flat to a more upright standing conformation. Gold nanoparticles attached to these self-assembled films were characterised by STM. It was possible to isolate a single redox-active molecule in an alkanethiol matrix and by subsequent attachment of a single gold nanoparticle the electrical properties of single wired molecules could be investigated. This method allowed the measurement of the conductivity of single molecules connecting a nanoparticle to the substrate chemically, thus forming stable electrical contacts at both ends.

Journal Article↗
PubMed2003

Redox state dependence of single molecule conductivity.

Spontaneous formation of stable molecular wires between a gold scanning tunneling microscopy (STM) tip and substrate is observed when the sample has a low coverage of alpha,omega-dithiol molecules and the tunneling resistance is made sufficiently small. Current-distance curves taken under these conditions exhibit characteristic current plateaux at large tip-substrate separations from which the conductivity of a single molecule can be obtained. The versatility of this technique is demonstrated using redox-active molecules under potential control, where substantial reversible conductivity changes from 0.5 to 2.8 nS were observed when the molecule was electrochemically switched from the oxidized to the reduced state.

Journal Article↗
PubMed2003

Purification of dodecanethiol derivatised gold nanoparticles.

Monolayer protected gold nanoparticles synthesised by a two-phase method contain a significant amount of tetraoctylammonium bromide (TOABr), the quaternary ammonium salt used as the phase transfer reagent, as a persistently retained impurity. A simple purification protocol is described.

Journal Article↗
PubMed2002

An FTIR study of the surface chemistry of the dynamic Si(100) surface during etching in alkaline solution.

In situ FTIR spectroscopy has been used in the attenuated total reflectance (ATR) mode to investigate the surface chemistry of etching Si(100) surfaces in aqueous KOH. The effect of solution concentration and electrode potential on the Si-H vibrations has been explored and the experimental results compared with density functional theory calculations. In addition. the kinetics of surface passivation of n-Si(100) has been investigated using FTIR spectroscopy.

Journal Article↗