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Molecular resolution imaging of polyglucose by scanning tunneling microscopy.

We have obtained atomic resolution images of poly-alpha-D-glucose by scanning tunneling microscopy. The oxygen atoms near the scanning tip were imaged, but the carbon and hydrogen atoms were not visible. The measured inter-atomic distances are consistent with the molecular structure of poly-alpha-D-glucose deduced from chemical and X-ray diffraction studies. The results also demonstrate that is is feasible to image surface atomic structures of a relatively thick non-conducting specimen, suggesting that the technique may be applied to the study of other macromolecules of biological importance.

Animals↗

New methods for depositing and imaging molecules in scanning tunneling microscopy.

Methods and apparatus are described to deposit and image molecules by scanning tunneling microscopy (STM) under an inert atmosphere. Three methods of applying molecules have been evaluated: equilibrium adsorption from the vapor phase, sublimation, and electrospraying. Using these methods, a variety of organic and biopolymer molecules have been deposited and imaged on graphite and on gold (111), grown epitaxially on mica. Compared with alternatives, such as the use of high vacuum apparatus or glove boxes, these procedures offer some important advantages: they are inexpensive, convenient, and more rapid. Mercaptoethanol, ethanolamine, ethanol, acetic acid, and water produce two-dimensional crystalline adlayers on gold substrates, when they are introduced into the scanning cell as vapors. These adlayers are assumed to involve hydrogen bonding of the molecules to an oxide of gold formed on the surface. Electrospraying protein solutions on gold surfaces yielded images of individual protein molecules with lateral dimensions close to those measured by X-ray analysis, and thicknesses of 0.6-1.3 nm. In the case of metallothionein, the known internal domain structure of the molecule was reproducibly observed. No detailed internal structure could be resolved in the other examples examined.

Acetates↗

Physical adsorption of immunoglobulin G on gold studied by scanning tunnelling microscopy.

This paper describes a preliminary scanning tunnelling microscope (STM) study of the physical adsorption of a mouse monoclonal anti-hCG (human chorionic gonadotrophin) immunoglobulin G (IgG) on vacuum-evaporated gold surfaces in air. Ellipsoid-like protrusions of various geometric sizes assembled in different surface patterns were observed on scanning adsorbed IgG molecules. It is believed that both the adsorption process per se and the tip-molecule interactions are key factors which determine the topographical features of adsorbed IgG molecules.

Adsorption↗

Imaging of metal-coated biological samples by scanning tunneling microscopy.

A method for imaging biological samples by scanning tunneling microscopy (STM) is presented. There are two main difficulties in imaging biological samples by STM: (1) the low conductivity of biological material and (2) finding a method of reliably depositing the sample on a flat conducting surface. The first of these difficulties was solved by coating the samples with a thin film of platinum-carbon. The deposition problem was solved by a method similar to a procedure used to deposit biological molecules onto field ion microscope (FIM) tips. STM images of bacteriophage T7 and filamentous phage fd are shown. The substrate on which the samples were absorbed was atomically flat gold. The images do not show molecular detail due to the metal coating, but the gross dimensions and morphology are correct for each type of virus. Also, the surface density of virus particles increases and decreases in the way expected when the conditions of deposition are changed. These methods allow reliable and reproducible STM imaging of biological samples.

Bacteriophages↗

Scanning tunneling microscopy of a luttinger liquid

Explicit predictions for scanning tunneling microscopy (STM) on interacting one-dimensional electron systems are made using the Luttinger liquid formalism. The STM current changes with the distance from an impurity or boundary in a characteristic way, which reveals the spin-charge separation and the interaction strength in the system. The current exhibits Friedel-like oscillations, but also carries additional modulated behavior as a function of voltage and distance, which shows the spin-charge separation in real space. Moreover, very close to the boundary the current is strongly reduced, which is an indication of the interaction strength in the system.

Journal Article↗

Selective analysis of molecular states by functionalized scanning tunneling microscopy tips.

Selective analysis of molecular states in scanning tunneling microscopy (STM) has so far been achieved in a few cases by tuning the bias range of the STM in high-resolution measurements. Correspondingly, perylene adsorbed in a close-packed monolayer on Ag(110) is imaged mainly through the pi states of the molecule. By contrast, functionalizing the STM tip with a perylene molecule leads to a mismatch between the energy levels of the STM tip and the molecule adsorbates and, instead, images only the metal states of the underlying silver surface. The observation opens a route for better energy selectivity in electron transport measurements through organic interfaces.

Journal Article↗

In situ scanning tunneling microscopy of DNA-modified gold surfaces: bias and mismatch dependence.

In situ scanning tunneling microscopy has been performed on DNA-modified gold surfaces under physiological conditions. The STM images of DNA-modified gold surfaces are strongly dependent on the applied potential and percentage of DNA duplexes containing a single base mismatch. At negative surface potentials we observe reproducible features that are attributed to DNA agglomerates where the DNA duplexes are in the upright orientation; at positive potentials, when DNA molecules lie down on the surface, the film is transparent, and only the gold surface is distinguishable. These observations indicate that DNA possesses a non-negligible local density of states which can be probed when the DNA duplex is in the upright orientation. By varying the percentage of DNA duplexes containing a single base mismatch, we have observed a dramatic change in the image contrast as a result of the perturbation induced by the mismatch on the electronic pathway inside the DNA. These results emphasize the central role of the integrity of the pi-stack for DNA charge transport. Duplex DNA is a promising candidate in molecular electronics, but only in arrangements where the orbitals can efficiently overlap with the electronic states of the electrodes and the environment does not constrain the DNA in non-native, poorly stacked conformations.

DNA↗

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.

DNA↗

Resolving complex atomic-scale spin structures by spin-polarized scanning tunneling microscopy.

The spin-polarized scanning tunneling microscope (SP-STM) operated in the constant current mode is proposed as a powerful tool to investigate complex atomic-scale magnetic structures of otherwise chemically equivalent atoms. The potential of this approach is demonstrated by successfully resolving the magnetic structure of Cr/Ag(111), which is predicted on the basis of ab initio vector spin-density calculations to be a coplanar noncollinear periodic 120 degrees Néel structure. Different operating modes of the SP-STM are discussed on the basis of the model of Tersoff and Hamann.

Journal Article↗

Scanning tunneling microscopy of an ionic crystal: ferritin core.

Ferritin molecules were imaged directly in air by scanning tunneling microscopy (STM). The lateral dimensions were close to the values determined by electron microscopy, and the vertical dimension was much reduced. Several clusters of partially naked ferritin cores displayed a hexagonal structure of lattice constant 4.9 +/- 0.5 A. It is thus shown that the STM can be used to image thin ionic crystals at high resolution.

Crystallography↗

Raising flags: applications of chemical marker groups to study self-assembly, chirality, and orientation of interfacial films by scanning tunneling microscopy.

When used in conjunction with "chemical marker groups" (functionalities such as -Br and -COOH), scanning tunneling microscopy is a powerful tool for studying the properties of liquid-solid interfaces. Chemical markers serve as "flags" for the identification of interfacial structures, allowing, for example, the absolute chirality of optically active molecules self-assembling on a graphite surface to be determined. Subtle changes in the orientation of these chemical functionalities that affect the long-range order of interfacial films have also been observed and explored. Finally, alterations in self-assembly resulting from variations in adsorbate or substrate structure can be deduced by taking advantage of these STM "flags".

Chemistry↗

Distinct reaction mechanisms in the catalytic oxidation of carbon monoxide on Rh(110): scanning tunneling microscopy and density functional theory studies.

By means of scanning tunneling microscopy measurements and density functional theory calculations, we identify the reaction mechanism for the oxidation of carbon monoxide to carbon dioxide on the Rh(110) surface at 160 K, which appears to be completely different than the one active at room temperature. The reasons for these different behaviors are determined. Our results demonstrate that even for a very simple catalytic reaction, the microscopic mechanism can dramatically change with temperature, following pathways that differ for nucleation sites and surface propagation and involve different surface moieties.

Journal Article↗

Mott phase at the surface of 1T-TaSe2 observed by scanning tunneling microscopy.

In this Letter we report the observation, by scanning tunneling microscopy, of a Mott metal to insulator transition at the surface of 1T-TaSe2. Our spectroscopic data compare considerably well with previous angle-resolved photoemission spectroscopy measurements and confirm the presence of a large hysteresis related to a first order process. The local character of the tunneling spectroscopy technique allows a direct visualization of the surface symmetry and provides spectroscopic measurements on the defect-free region of the sample. It follows that the electronic localization is driven purely by the enhancement of the charge density wave amplitude which drives a bandwidth controlled metal-insulator transition.

Journal Article↗