Aggregation and fibrillization of human islet amyloid polypeptide (hIAPP) plays an important role in the development of type 2 diabetes mellitus. Understanding the interaction of hIAPP with interfaces such as cell membranes at a molecular level therefore represents an important step toward new therapies. Here, we investigate the fibrillization of hIAPP at different self-assembled alkanethiol monolayers (SAMs) by quartz crystal microbalance with dissipation monitoring (QCM-D), atomic force microscopy (AFM), and polarization-modulated infrared reflection absorption spectroscopy (PM-IRRAS). We find that hydrophobic interactions with the CH-terminated SAM tend to retard hIAPP fibrillization compared to the carboxylic acid-terminated SAM where attractive electrostatic interactions lead to the formation of a three-dimensional network of interwoven fibrils. At the hydroxyl- and amino-terminated SAMs, fibrillization appears to be governed by hydrogen bonding between the peptide and the terminating groups which may even overcome electrostatic repulsion. These results thus provide fundamental insights into the molecular mechanisms governing amyloid assembly at interfaces.

Novel core-shell quinone-rich poly(dopamine)-magnetic nanoparticles (MNPs) were prepared by using an in situ polymerization method. Catechol groups were oxidized to quinone by using a thermal treatment. MNPs were characterized by using X-ray diffraction, X-ray photoelectron spectroscopy, atomic force microscopy, magnetic force microscopy, UV/Vis, Fourier-transform infrared spectroscopy, and electrochemical techniques. The hybrid nanomaterial showed an average core diameter of 17 nm and a polymer-film thickness of 2 nm. The core-shell nanoparticles showed high reactivity and were used as solid supports for the covalent immobilization of glucose oxidase (Gox) through Schiff base formation and Michael addition. The amount of Gox immobilized onto the nanoparticle surface was almost twice that of the nonoxidized film. The resulting biofunctionalized MNPs were used to construct an amperometric biosensor for glucose. The enzyme biosensor has a sensitivity of 8.7 mA M(-1)  cm(-2) , a low limit of detection (0.02 mM), and high stability for 45 days. Finally, the biosensor was used to determine glucose in blood samples and was checked against a commercial glucometer.

The adsorption of 4-mercaptobenzoic acid (MBA) has been studied on Au(111) by scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), electrochemical techniques, and density functional theory (DFT) calculations. Results show that MBA molecules adsorb on the Au surface via a thiolate bond, arranged in a (√3×4) lattice with coverage θRS = 0.25. DFT data show the strong effect of aromatic ring interactions in stabilizing the adsorbed molecules. The total absence of vacancy islands upon thiol adsorption and the surface coverage of gold islands after desorption are difficult to conciliate with the usual gold-adatom models for thiol adsorption. This is an important issue, as the strongest evidence for the existence of gold-adatom complexes arises from MBA-capped Au nanoparticles. Our results raise an interesting point as regards the validity of making a straightforward parallel between the thiol–Au interface in single crystal surfaces and in monolayer-protected clusters.

Electrical conductance across a molecular junction is strongly determined by the anchoring group of the molecule. Here we highlight the unusual behavior of 1,4-bis(1H-pyrazol-4-ylethynyl)benzene that exhibits unconventional junction current versus junction-stretching distance curves, which are peak-shaped and feature two conducting states of 2.3 × 10 G and 3.4 × 10 G. A combination of theory and experiments is used to understand the conductance of single-molecule junctions featuring this new anchoring group, i.e., pyrazolyl. These results demonstrate that the pyrazolyl moiety changes its protonation state and contact binding during junction evolution and that it also binds in either end-on or facial geometries with gold contacts. The pyrazolyl moiety holds general interest as a contacting group, because this linkage leads to a strong double anchoring of the molecule to the gold electrode, resulting in enhanced conductance values.

The full understanding of the deformation mechanisms in nanostructured bainite requires the local characterization of its mechanical properties, which are expected to change from one phase, bainitic ferrite, to another, austenite. This study becomes a challenging process due to the bainitic nanostructured nature and high Young’s modulus. In this work, we have carried out such study by means of the combination of AFM-based techniques, such as nanoindentation and Peak Force Quantitative Nanomechanical Mapping (PF-QNM) measurements. We have addressed critically the limits and advantages of these techniques and been able to measure some elastoplastic parameters of both phases. Specifically, we have analyzed by PF-QNM two nanostructured bainitic steels, with a finer and a coarser structure, and found that both phases have a similar Young’s modulus.

The design and synthesis of Aviram-Ratner-type molecular rectifiers, featuring an anilino-substituted extended tetracyanoquinodimethane (exTCNQ) acceptor, covalently linked by the σ-spacer bicyclo[2.2.2]octane (BCO) to a tetrathiafulvalene (TTF) donor moiety, are described. The rigid BCO spacer keeps the TTF donor and exTCNQ acceptor moieties apart, as demonstrated by X-ray analysis. The photophysical properties of the TTF-BCO-exTCNQ dyads were investigated by UV/Vis and EPR spectroscopy, electrochemical studies, and theoretical calculations. Langmuir-Blodgett films were prepared and used in the fabrication and electrical studies of junction devices. One dyad showed the asymmetric current-voltage (I-V) curve characteristic for rectification, unlike control compounds containing the TTF unit but not the exTCNQ moiety or comprising the exTCNQ acceptor moiety but lacking the donor TTF part, which both gave symmetric I-V curves. The direction of the observed rectification indicated that the preferred electron current flows from the exTCNQ acceptor to the TTF donor.

Nascent molecular electronic devices based on linear 'all-carbon' wires attached to gold electrodes through robust and reliable C-Au contacts are prepared via efficient in situ sequential cleavage of trimethylsilyl end groups from an oligoyne, MeSi-(C[triple bond, length as m-dash]C)-SiMe (1). In the first stage of the fabrication process, removal of one trimethylsilyl (TMS) group in the presence of a gold substrate, which ultimately serves as the bottom electrode, using a stoichiometric fluoride-driven process gives a highly-ordered monolayer, Au|C[triple bond, length as m-dash]CC[triple bond, length as m-dash]CC[triple bond, length as m-dash]CC[triple bond, length as m-dash]CSiMe (Au|CSiMe). In the second stage, treatment of Au|CSiMe with excess fluoride results in removal of the remaining TMS protecting group to give a modified monolayer Au|C[triple bond, length as m-dash]CC[triple bond, length as m-dash]CC[triple bond, length as m-dash]CC[triple bond, length as m-dash]CH (Au|CH). The reactive terminal C[triple bond, length as m-dash]C-H moiety in Au|CH can be modified by 'click' reactions with (azidomethyl)ferrocene (NCHFc) to introduce a redox probe, to give Au|CCNHCHFc. Alternatively, incubation of the modified gold substrate supported monolayer Au|CH in a solution of gold nanoparticles (GNPs), results in covalent attachment of GNPs on top of the film via a second alkynyl carbon-Au σ-bond, to give structures Au|C|GNP in which the monolayer of linear, 'all-carbon' C chains is sandwiched between two macroscopic gold contacts. The covalent carbon-surface bond as well as the covalent attachment of the metal particles to the monolayer by cleavage of the alkyne C-H bond is confirmed by surface-enhanced Raman scattering (SERS). The integrity of the carbon chain in both Au|CCNHCHFc systems and after formation of the gold top-contact electrode in Au|C|GNP is demonstrated through electrochemical methods. The electrical properties of these nascent metal-monolayer-metal devices Au|C|GNP featuring 'all-carbon' molecular wires were characterised by sigmoidal I-V curves, indicative of well-behaved junctions free of short circuits.

Gold nanoparticle electrodeposition on a modified HOPG surface with a monolayer organic film based on aryl diazonium chemistry has been studied. This organic monolayer is electrochemically grown with the use of 2,2-diphenyl-1-picrylhydrazyl (DPPH), a radical scavenger. The electrodeposition of gold on this modified surface is highly favored resulting in an AuNP surface density comparable to that found on glassy carbon. AuNPs grow only in the areas covered by the organic monolayer leaving free clean HOPG zones. A progressive mechanism for the nucleation and growth is followed giving hemispherical AuNPs, homogeneously distributed on the surface and their sizes can be well controlled by the applied electrodeposition potential. By using AFM, C-AFM and electrochemical measurements with the aid of two redox probes, namely Fe(CN)6(4-)/Fe(CN)6(3-) and dopamine, relevant results about the electrochemical modified surface as well as the gold nanoparticles electrodeposited on them are obtained.