Motility powered by supramolecular springs and ratchets

Not all biological movements are caused by molecular motors sliding along filaments or tubules. Just as springs and ratchets can store or release energy and rectify motion in physical systems, their analogs can perform similar functions in biological systems. The energy of biological springs is derived from hydrolysis of a nucleotide or the binding of a ligand, whereas biological ratchets are powered by Brownian movements of polymerizing filaments. However, the viscous and fluctuating cellular environment and the mechanochemistry of soft biological systems constrain the modes of motion generated and the mechanisms for energy storage, control, and release.     

Inelastic electron tunneling spectroscopy

Inelastic electron tunneling spectroscopy is a useful technique for the study of vibrational modes of molecules adsorbed on the surface of oxide layers in a metal-insulator-metal tunnel junction. The technique involves studying the effects of adsorbed molecules on the tunneling spectrum of such junctions. The data give useful information about the structure, bonding, and orientation of adsorbed molecules. One of the major advantages of inelastic electron tunneling spectroscopy is its sensitivity. It is capable of detecting on the order of 10(10) molecules (a fraction of a monolayer) on a 1-square-millimeter junction. It has been successfully used in studies of catalysis, biology, trace impurity detection, and electronic excitations. Because of its high sensitivity, this technique shows great promise in the area of solid-state electronic chemical sensing.     

Long journey into tunneling

I am, of course, deeply aware of important contributions made by many colleagues and my friends throughout this long journey. The subject of the second section was carried out when I was in Japan and all the rest (35) has been performed in the United States of America. Since my journey into tunneling is still continuing, I do not come to any conclusions in this talk. However, I would like to point out that many high barriers exist in this world: barriers between nations, races, and creeds. Unfortunately, some barriers are thick and strong. But I hope, with determination, we will find a way to tunnel through these barriers easily and freely, to bring the world together so that everyone can share in the legacy of Alfred Nobel.     

Electron tunneling paths in proteins

One of the crucial issues in biological electron transfer is the determination of the role of spatially intermediate amino acid residues in controlling or directing the electronic tunneling interaction between redox sites. A quantum path integral Monte Carlo method is developed for the analysis of electronic tunneling pathways in a highly structured environment. This path integral method is applied to intramolecular electron transfer in a ruthenium-modified myoglobin that contains a tryptophan in the "line-of-flight." A principal result is the identification of the relevant cylindrical zone swept out by the tunneling electron.     

Hydrogen tunneling in enzyme reactions

Primary and secondary protium-to-tritium (H/T) and deuterium-to-tritium (D/T) kinetic isotope effects for the catalytic oxidation of benzyl alcohol to benzaldehyde by yeast alcohol dehydrogenase (YADH) at 25 degrees Celsius have been determined. Previous studies showed that this reaction is nearly or fully rate limited by the hydrogen-transfer step. Semiclassical mass considerations that do not include tunneling effects would predict that kH/kT = (kD/kT)3.26, where kH, kD, and kT are the rate constants for the reaction of protium, deuterium, and tritium derivatives, respectively. Significant deviations from this relation have now been observed for both primary and especially secondary effects, such that experimental H/T ratios are much greater than those calculated from the above expression. These deviations also hold in the temperature range from 0 to 40 degrees Celsius. Such deviations were previously predicted to result from a reaction coordinate containing a significant contribution from hydrogen tunneling.     

Laser-induced electron tunneling and diffraction

Molecular structure is usually determined by measuring the diffraction pattern the molecule impresses on x-rays or electrons. We used a laser field to extract electrons from the molecule itself, accelerate them, and in some cases force them to recollide with and diffract from the parent ion, all within a fraction of a laser period. Here, we show that the momentum distribution of the extracted electron carries the fingerprint of the highest occupied molecular orbital, whereas the elastically scattered electrons reveal the position of the nuclear components of the molecule. Thus, in one comprehensive technology, the photoelectrons give detailed information about the electronic orbital and the position of the nuclei.     

Rapid electron tunneling through oligophenylenevinylene bridges

We measured rate constants of thermal, interfacial electron transfer through oligophenylenevinylene bridges between a gold electrode and a tethered redox species in contact with an aqueous electrolyte using the indirect laser-induced temperature jump technique. Analysis of the distance dependence indicates that, unlike other bridges studied to date, the rate constants are not limited by electronic coupling for bridges up to 28 angstroms long. The energy levels of the bridges relative to those of the redox species rule out hopping through the bridge. We conclude that, out to 28 angstroms, the transfer is limited by structural reorganization and that electron tunneling occurs in less than 20 picoseconds, suggesting that oligophenylenevinylene bridges could be useful for wiring molecular electronic elements.     

Photon tunneling microscopy of polymeric surfaces

With photon tunneling microscopy it is possible to image polymeric and other dielectric surfaces by means of the unusual properties of photon tunneling or evanescent waves. Vertical resolution is 1 nanometer, limited by the detector, over a vertical range of half a wavelength. Lateral resolution is better than a quarter of a wavelength over a field of view up to 125 micrometers. Samples can be surveyed in real time in air, with no need for metallization, and without shadowing or the intrusive effects of electrons or scanning probes. The use of this technique to study single crystals of polyethylene and processes such as latex film formation and the evolution of polystyrene topography while dewetting above the glass transition temperature are described.     

Spin-dependent tunneling in self-assembled cobalt-nanocrystal superlattices

Self-assembled devices composed of periodic arrays of 10-nanometer-diameter cobalt nanocrystals display spin-dependent electron transport. Current-voltage characteristics are well described by single-electron tunneling in a uniform array. At temperatures below 20 kelvin, device magnetoresistance ratios are on the order of 10%, approaching the maximum predicted for ensembles of cobalt islands with randomly oriented preferred magnetic axes. Low-energy spin-flip scattering suppresses magnetoresistance with increasing temperature and bias-voltage.     

Picosecond resolution in scanning tunneling microscopy

A method has been developed for performing fast time-resolved experiments with a scanning tunneling microscope. The method uses the intrinsic nonlinearity in the microscope's current versus voltage characteristics to resolve optically generated transient signals on picosecond time scales. The ability to combine the spatial resolution of tunneling microscopy with the time resolution of ultrafast optics yields a powerful tool for the investigation of dynamic phenomena on the atomic scale.     

Scanning tunneling microscopy of nucleic acids

The scanning tunneling microscope (STM) has been used to measure properties of poly(rA).poly(rU) and DNA, such as helical pitch, half-period oscillations that were interpreted as the alternation between the major and minor grooves, and interhelical spacing. Average pitches were measured by two-dimensional Fourier transforms and by topographic profiles along the fiber axes. Values were typically 7 percent less than standard dimensions of A-form RNA and B-form DNA fibers. This result is compatible with the mild dehydration that occurred under air-drying conditions. More extensive dehydration typically led to 19 percent shrinkage. Analysis of specific regions allowed local variations in helical pitch as small as 1 angstrom to be detected, thus demonstrating that the STM can visualize functionally significant modulations of nucleic acid structure.     

Coupling quantum tunneling with cavity photons

Tunneling of electrons through a potential barrier is fundamental to chemical reactions, electronic transport in semiconductors and superconductors, magnetism, and devices such as terahertz oscillators. Whereas tunneling is typically controlled by electric fields, a completely different approach is to bind electrons into bosonic quasiparticles with a photonic component. Quasiparticles made of such light-matter microcavity polaritons have recently been demonstrated to Bose-condense into superfluids, whereas spatially separated Coulomb-bound electrons and holes possess strong dipole interactions. We use tunneling polaritons to connect these two realms, producing bosonic quasiparticles with static dipole moments. Our resulting three-state system yields dark polaritons analogous to those in atomic systems or optical waveguides, thereby offering new possibilities for electromagnetically induced transparency, room-temperature condensation, and adiabatic photon-to-electron transfer.     

Intermolecular electron transfer by quantum mechanical tunneling

The transfer of electrons from one molecule to another by quantum mechanical tunneling has recently been implicated in biological electron transport. This report describes observations of electron transfer between aromatic molecules in a rigid matrix, in which electrons apparently tunnel through tens of angstroms of inert solvent. The kinetics tend to confirm the tunneling process, which is likely to be an important means of electron transfer when diffusion is blocked by steric factors or immobilization of the reactants.     

The magnetic stability of spin-dependent tunneling devices

The tunneling resistance between two ferromagnetic metal layers that are separated by a thin insulator depends on the relative orientation of the magnetization M of each layer. In a memory device, independent switching of the magnetically soft layer is achieved by making the other layer either exchange-biased or magnetically hard. The repeated reversal of M of the soft layer by field cycling can demagnetize the other magnetically hard layer and thus erase the tunnel junction's memory. The M of exchange-biased structures was stable at least to 10(7) cycles, whereas in hard structures, M generally decayed logarithmically with the number of field cycles. The decay was very sensitive to the thickness of the hard layer and the composition of the soft layer. However, no decay was observed when the moment reversal was accomplished by coherent rotation, establishing that demagnetization results from the formation and motion of domain walls in the soft layer during field cycling.     

Spin-polarized resonant tunneling in magnetic tunnel junctions

Insertion of a thin nonmagnetic copper Cu(001) layer between the tunnel barrier and the ferromagnetic electrode of a magnetic tunnel junction is shown to result in the oscillation of the tunnel magnetoresistance as a function of the Cu layer thickness. The effect is interpreted in terms of the formation of spin-polarized resonant tunneling. The amplitude of the oscillation is so large that even the sign of the tunnel magnetoresistance alternates. The oscillation period depends on the applied bias voltage, reflecting the energy band structure of Cu. The results are encouraging for the development of spin-dependent resonant tunneling devices.     

Scanning tunneling microscopy of electrodeposited ceramic superlattices

Cleaved cross sections of nanometer-scale ceramic superlattices fabricated from materials of the lead-thallium-oxygen system were imaged in the scanning tunneling microscope (STM). The apparent height differences between the layers were attributed to composition-dependent variations in local electrical properties. For a typical superlattice, the measured modulation wavelength was 10.6 nanometers by STM and 10.8 nanometers by x-ray diffraction. The apparent height profile for potentiostatically deposited superlattices was more square than that for galvanostatically deposited samples. These results suggest that the composition follows the applied potential more closely than it follows the applied current. The x-ray diffraction pattern of a superlattice produced under potential control had satellites out to the fourth order around the (420) Bragg reflection.