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The sequence and helical content of two alanine-rich peptides (AQK18 and GpAQK18, Gp: l-propargylglycine) and their conjugates with poly(ethylene glycol) (PEG) have been investigated by multidimensional mass spectrometry (MS), encompassing electrospray ionization (ESI) or matrix-assisted laser desorption ionization (MALDI) interfaced with tandem mass spectrometry (MS2) fragmentation and shape-sensitive separation via ion mobility mass spectrometry (IM-MS). The composition, sequence, and molecular weight distribution of the peptides and bioconjugates were identified by MS and MS2 experiments, which also confirmed the attachment of PEG at the C-terminus of the peptides. ESI coupled with IM-MS revealed the existence of random coil and α-helical conformers for the peptides in the gas phase. More importantly, the proportion of the helical conformation increased substantially after PEG attachment, suggesting that conjugation adds stability to this conformer. The conformational assemblies detected in the gas pha...

The adsorption mechanism for the new compound, 7-ethynyl-2,4,9-trithia-tricyclo[3.3.1.13,7]decane (7ETTD), on ultra-thin films (∼3 nm) of CdS is investigated. Multiple reflection absorption IR spectroscopy, in conjunction with inelastic electron tunneling spectroscopy, indicates that this compound forms a self-assembled monolayer adsorbed on the CdS surface via each molecule’s trithia-adamantane anchor. Conductance–voltage data are recorded for tunnel junctions of the type Al/CdS/7ETTD/Pb over a temperature range of 4 K to room temperature and they indicate that the presence of the 7ETTD layer on the CdS dramatically modifies the conductance–voltage behavior of the junctions. These measurements show that different conduction mechanisms, including tunneling and possibly hopping, are responsible for charge transfer through the junctions depending on current, temperature, and voltage. WKB fits to the data are used to determine barrier parameters (height and width) for Al/CdS/Pb junctions with and without adsorbed 7ETTD layers on the CdS. Analysis of the fits shows that tunneling occurs at low bias (less than ∼0.2 V) but, at higher bias voltages, modification of the barrier parameters alone is insufficient to account for the observed conductance changes. A frontier orbital model is invoked which does offer a plausible explanation for these conductance changes. The model assumes bias-dependent coupling between HOMO and LUMO states of the adsorbed 7ETTD and the surface states on the CdS. The present work suggests that, because of the marked effect on the conductance of CdS ultra-thin films, 7ETTD and other similar compounds may be candidates for use in molecular electronic device fabrication.

Ultrathin oxygenated amorphous CdTe (a-CdTe:O) films are prepared by rf sputtering of CdTe in a background of argon or argon/nitrogen/oxygen mixtures. Atomic force microscopy (AFM) is used to characterize the films and shows that they have an island structure typical of most sputtered thin films. However, when sufficiently low powers and deposition rates are employed during sputtering, the resulting films are remarkably smooth and sufficiently thin for use as barrier layers in inelastic electron tunneling (IET) junctions. Four terminal current–voltage data are recorded for Al/a-CdTe:O/Pb tunnel junctions and conductance–voltage curves are derived numerically. WKB fits to the conductance–voltage curves are obtained using a two-component trapezoidal plus square (TRAPSQR) model barrier potential to determine values for the tunnel barrier parameters (height, shape, and width); these parameters are consistent with AFM topological measurements and values from similar devices reported in the literature. IET spec...

We report the observation of anomalously high currents of up to 500µA during direct oxide nanolithography on the surface of n-type silicon {100}. Conventional nanolithography on silicon with an atomic force microscope (AFM) normally involves currents of the order of 10−10 –10−7 A and is associated with ionic conduction within a water meniscus surrounding the tip. The anomalous current we observe is related to an electrical breakdown resulting in conduction dominated by electrons rather than ions. We discuss the electron source during the AFM-assisted nanolithography process, and the possibility of using this breakdown current for nanoscale parallel writing.

A robust technique, based on vertical (z-lift) manipulation of a negatively biased oscillating atomic force microscope cantilever, is developed which creates raised columnar nanostructures with high aspect ratios (up to 40nm high/150nm wide) on amorphous CdS thin films. The nanostructures’ height (8–40nm) is proportional to z-lift of the tip and correlates with CdS film thickness. An in-house modified electric force microscopy is used to record the associated surface charge distribution which is found to be opposite to that of the tip.