Asymmetry of electron transmission through monolayers of helical polyalanine adsorbed on gold surfaces

Polyalanine derivatives containing cysteamine linker R-(Ala)14NH-(CH2)2-SH, where R is ferrocenecarbonyl or hydrogen, were synthesized and then used to form self-assembled monolayers on gold. The tilt angles and the packing density of the molecules within monolayer assemblies were determined by FTIR spectroscopy and scanning tunneling microscopy, respectively. Electrochemical properties of monolayer-modified electrodes were studied using cyclic voltammetry and impedance spectroscopy. Measurements of electron-transfer rates using electrochemical techniques and scanning tunneling spectroscopy revealed asymmetry dependent on the applied voltage. It is suggested that the observed electron-transfer behavior is connected with the electric field generated by the molecular dipole of the polyalanine helix.     

Electron Transport Through Composite Monolayers

Well-organized thiol monolayers on electrode surfaces are prepared using the Langmuir–Blodgett and self-assembly methods. Planned modification of the molecules building the monolayer allow the electron tunneling efficiency across the monolayer to be controlled. The barrier properties of the monolayers are probed by electrochemical methods. The extent of blocking for all systems under study indicates that contribution of the electroactive molecules that find direct access to the electrode surface can be neglected. These observations permit us to use the monolayers for the determination of the kinetic parameters of Fe(CN)^3– ₆ and IrCl^2– ₆ ion reduction. Such monolayers are employed for the studies of long-range electron transport. We show that insertion of amide bonds in appropriate positions of the alkyl chains of all molecules building the monolayer makes it possible to create a lateral hydrogen-bond network linking the internal amide groups in the monolayer and contributing to the electronic coupling between the redox probe and the electrode. The relation between the location of the amide moiety in the molecule and its importance for the electron tunneling efficiency through the intervening organic medium is discussed.     

Chiral recognition in NMR spectroscopy using crown ethers and their ytterbium(III) complexes

Chiral crown ethers 1 and 5 are useful enantiomeric discriminating agents in ¹H NMR spectroscopy for neutral and protonated primary amines, amino acids, and amino alcohols. The presence of the carboxylic acid groups in 1 and 5 provide sites at which ytterbium(III) can bind. Adding ytterbium(III) nitrate to crown–substrate mixtures in methanol-d₄ causes shifts in the spectra of substrates and often enhances the chiral discrimination in the ¹H NMR spectrum. The enhancement in enantiomeric discrimination that occurs in the presence of ytterbium(III) allows lower concentrations of the crown ether to be used in chiral recognition studies. Several amide derivatives of 1 were prepared and evaluated as chiral NMR discriminating agents, although except for 1e, these were less effective than 1.     

Mechanisms of modulation gap detection

It has been postulated that the central auditory system contains an array of modulation filters, each responsive to a different range of modulation frequencies present at the outputs of the (peripheral) auditory filters. In the present experiments, we tested what we call the "dip hypothesis," that a gap in modulation is detected using the "dip" in the output of the modulation filter tuned to the modulator frequency. In experiment 1, the task was to detect a gap in the sinusoidal amplitude modulation imposed on a 4-kHz carrier. The modulator preceding the gap ended with a positive-going zero-crossing. There were three conditions, differing in the phase at which the modulator started at the end of the gap; zero-phase, at a positive-going zero-crossing; pi-phase, at a negative-going zero-crossing; and "preserved" phase, at the phase the modulator would have had if it had continued without interruption. Modulation frequencies were 5, 10, 20, and 40 Hz. Psychometric functions for detection of the gap were measured using a two-alternative forced-choice task. For the zero-phase and preserved-phase conditions, the detectability index, d', increased monotonically with increasing gap duration. For the pi-phase condition, performance was good (d' > 1) for small gap durations, and initially worsened with increasing gap duration, before improving again for longer gap durations. This is the pattern of results expected from the dip hypothesis, provided that the modulation filters have Q values of 2 or more. However, it is also possible that a rhythm cue was used to improve performance in the pi-phase condition for short gap durations; the introduction of the gap markedly disrupted the regular rhythm produced by the modulator peaks. In experiment 2, the rhythm cue was disrupted by varying the modulator period randomly around its nominal value, except for the modulator periods immediately before and after the gap. This markedly impaired performance, and resulted in psychometric functions that were very similar for the zero-phase and pi-phase conditions. This pattern of results is inconsistent with the dip hypothesis. For both experiments, modulation gap "thresholds" (d' approximately 1) were roughly constant when expressed as a proportion of the modulator period. Possible mechanisms of modulation gap detection are discussed and evaluated.     

Electrochemical wiring of alpha, omega-alkanedithiol molecules into an electrical circuit

The intrinsic electrical conductivity of alpha, omega-alkanedithiol increases if both ends of the molecule are covalently bonded to metallic contacts.     

Perception of amplitude and frequency modulated signals (mixed modulation)

This article discusses the detection of mixed modulation, i.e., simultaneous amplitude and frequency modulation (MM). The investigations have incorporated both a sine wave modulating signal and an irregular modulating signal, a very narrow noise band, of a specified center frequency. The results revealed that for a sinusoidal low-frequency modulating signal, amplitude and frequency changes that were separately subthreshold could be detected by listeners in mixed modulation. This indicates summation of sensations caused by simultaneous AM and FM modulation. This effect was not observed in the case of the irregular modulating signal. A hypothesis is advanced that the perception of modulated signals is governed by two mechanisms, viz., temporal and spectral. The operation of the two mechanisms depends mainly on the modulating frequency. The type of modulation does not play any significant role in this case.     

Detection of combined frequency and amplitude modulation.

This article is concerned with the detection of mixed modulation (MM), i.e., simultaneously occurring amplitude modulation (AM) and frequency modulation (FM). In experiment 1, an adaptive two-alternative forced-choice task was used to determine thresholds for detecting AM alone. Then, thresholds for detecting FM were determined for stimuli which had a fixed amount of AM in the signal interval only. The amount of AM was always less than the threshold for detecting AM alone. The FM thresholds depended significantly on the magnitude of the coexisting AM. For low modulation rates (4, 16, and 64 Hz), the FM thresholds did not depend significantly on the relative phase of modulation for the FM and AM. For a high modulation rate (256 Hz) strong effects of modulator phase were observed. These phase effects are as predicted by the model proposed by Hartmann and Hnath [Acustica 50, 297-312 (1982)], which assumes that detection of modulation at modulation frequencies higher than the critical modulation frequency is based on detection of the lower sideband in the modulated signal's spectrum. In the second experiment, psychometric functions were measured for the detection of AM alone and FM alone, using modulation rates of 4 and 16 Hz. Results showed that, for each type of modulation, d' is approximately a linear function of the square of the modulation index. Application of this finding to the results of experiment 1 suggested that, at low modulation rates, FM and AM are not detected by completely independent mechanisms. In the third experiment, psychometric functions were again measured for the detection of AM alone and FM alone, using a 10-Hz modulation rate. Detectability was then measured for combined AM and FM, with modulation depths selected so that each type of modulation would be equally detectable if presented alone. Significant effects of relative modulator phase were found when detectability was relatively high. These effects were not correctly predicted by either a single-band excitation-pattern model or a multiple-band excitation-pattern model. However, the detectability of the combined AM and FM was better than would be predicted if the two types of modulation were coded completely independently.     

Structure and thermal properties of polyketoacids and polyquinones

New aromatic polyketoacids and polyquinones have been obtained by reaction of pyromellitic dianhydride with phenanthrene, napthalene or 2-methylnaphthalene in the presence of AlCl₃. The influences of the reaction conditions and structure of the hydrocarbons on thermal stability of the resultant polymers have been examined.     

STM studies of fusion of cholesterol suspensions and mixed 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC)/cholesterol vesicles onto a Au(111) electrode surface

Electrochemical scanning tunneling microscopy (EC-STM) has been applied to study the structure of the film formed by fusion of cholesterol suspensions and mixed dimyristoylphosphatidylcholine (DMPC)/cholesterol vesicles on a Au(111) electrode surface. It has been demonstrated that cholesterol molecules assemble at the gold support into several structures templated by the crystallography of the metal surface and involving flat or edge-on adsorbed molecules. Studies of the film formed by fusion of mixed DMPC/cholesterol vesicles revealed that ordered domains of either pure DMPC or pure cholesterol were formed. These results indicate that, at the metal surface, the molecules released by the rupture of a vesicle initially self-assemble into a well-ordered monolayer. The self-assembly is controlled by the hydrocarbon skeleton-metal surface interaction. In the case of mixed DMPC/cholesterol vesicles, the molecule-metal interactions induce segregation of the two components into single component domains. However, the molecule-metal interaction induced monolayer is a transient phenomenon. When more molecules accumulate at the surface, the molecule-molecule interactions dominate the assembly, and the monolayer is transformed into a bilayer.     

Designing a Useful Lipid Raft Model Membrane for Electrochemical and Surface Analytical Studies

A model biomimetic system for the study of protein reconstitution or drug interactions should include lipid rafts in the mixed lipid monolayer, since they are usually the domains embedding membrane proteins and peptides. Four model lipid films composed of three components: 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC), cholesterol (Chol) and sphingomyelin (SM) mixed in different molar ratios were proposed and investigated using surface pressure measurements and thermodynamic analysis of the monolayers at the air–water interface and imaged by Brewster angle microscopy. The ternary monolayers were transferred from the air–water onto the gold electrodes to form bilayer films and were studied for the first time by electrochemical methods: alternative current voltammetry and electrochemical impedance spectroscopy and imaged by atomic force microscopy. In excess of DOPC, the ternary systems remained too liquid for the raft region to be stable, while in the excess of cholesterol the layers were too solid. The layers with SM in excess lead to the formation of Chol:SM complexes but the amount of the fluid matrix was very low. The equimolar content of the three components lead to the formation of a stable and well-organized assembly with well-developed raft microdomains of larger thickness, surrounded by the more fluid part of the bilayer. The latter is proposed as a convenient raft model membrane for further physicochemical studies of interactions with drugs or pollutants or incorporation of membrane proteins.