Isolated supramolecules on surfaces studied with scanning tunneling microscopy

To date, supramolecular chemistry is an ever growing research field owing to its crucial role in molecular catalysis, recognition, medicine, data storage and processing as well as artificial photosynthetic devices.Different isolated supramolecules were prepared by molecular self-assembly on surfaces. This review mainly focuses on supramolecular aggregations on noble metal surfaces studied by scanning tunneling microscopy, including dimers, trimers, tetramers, pentamers, wire-like assemblies and Sierpin′ ski triangular fractals. The variety of self-assembled structures reflects the subtle balance between intermolecular and molecule–substrate interactions, which to some extent may be controlled by molecules, substrates and the molecular coverage. The comparative study of different architectures helps identifying the operative mechanisms that lead to the structural motifs. The application of these mechanisms may lead to novel assemblies with tailored physicochemical properties.     

Self-assembly of L-tryptophan on Cu(111) studied by low-temperature scanning tunneling microscopy

The self-assembly of L-tryptophan on Cu(111) is investigated by an ultrahigh vacuum scanning tunneling microscope (STM) at 4.4 K. A series of novel supramolecular structures have been prepared with different annealing temperatures.     

Recent progress in probing atomic and molecular quantum coherence with scanning tunneling microscopy

Quantum coherent physics and chemistry concern the creation and manipulation of an excited-state manifold that contains the superposition and entanglement of multiple quantum levels. Electromagnetic waves such as light and microwave can be used to generate and probe different quantum coherent phenomena. The recent advances in scanning tunneling microscopy (STM) techniques including ultrafast laser coupled STM and electron spin resonance STM combine electromagnetic excitation with tunneling electron detection, bringing the investigation of quantum coherence down to the atomic and molecular level. Here, we survey the latest STM studies of different quantum coherent phenomena covering molecular vibration, electron transfer, surface plasmon resonance, phonon, spin oscillation, and electronic transition, and discuss the state and promise of characterizing and manipulating quantum coherence at the atomic or molecular scale.     

Self-assembly of l-tryptophan on Cu(111) studied by low-temperature scanning tunneling microscopy

The self-assembly of l-tryptophan on Cu(111) is investigated by an ultrahigh vacuum scanning tunneling microscope (STM) at 4.4 K. When deposited onto the substrate at around 120 K with a coverage of 0.1 monolayer, molecular trimers, tetramers, hexamers, and chains coexist on Cu(111). Then almost all molecules self-assemble into chiral hexamers after being annealed at room temperature. When increasing molecular coverage to the full layer, a new type of chain is observed on the surface. Based on the high-resolution STM images at sub-molecular level, we suggest that the l-tryptophan molecules are present in neutral, zwitterionic or anionic states in these structures.     

The effect of electrochemical surface treatments of carbon fibers using scanning tunneling microscopy

Scanning tunneling microscopy (STM) has been applied to the study of the topography of polyacrylonitrile (PAN)-based carbon fibers before and after electrochemical surface treatments. The results show that the electrical anodic oxidation only changes the surface aspects; at nanometric resolution; the nanostructure and nanotexture such as the step-like crystallite stacking are decreased with increasing electric current densities.     

Photo-regulation of 2D supramolecular self-assembly: On-surface photochemistry studied by STM

During the past few years,regulation and controlling of the two-dimension(2D)self-assembled supramolecular structure on surface have drawn increasing attention in nanoscience and technology. External stimuli have been widely used to regulate these 2D nanostructures.Among various external stimuli approaches,photo-regulation as one of the most outstanding means of regulation has been extensively studied because different wave bands can lead to molecular conformation variation and new bonds to gain new molecules.In this review,the photo-regulated self-assembled structure on solid surface as well as the photo-reactions of different molecules substituted with photo-sensitive groups are introduced to give us an insight into on-surface photochemistry,which plays an important role on the nano-devices fabrication.Notably,these photo-sensitive behaviors as well as the formed structures on surface were probed at sub-molecule level by unique scanning tunneling microscopy(STM)technique.     

Surface characterization of laser-treated poly(ethylene terephthalate) by optical profilometry and scanning tunneling microscopy

Characteristic changes in the surface topography due to UV laser treatment are of high significance for the determination of material destruction thresholds and surface structure development. E.g. irradiation of poly(ethylene terephthalate) (PET) film with pulsed UV laser light of 248 nm modifies the smoth surface of the polymer into a well oriented structured surface. The development of these structures were studied with scanning tunneling microscopy (STM) and high resolution optical profilometry. Three dimensional data of the surface were taken from the samples after each laser pulse. A change of topographic data was found in relation to fluence and number of pulses applied. © 1993 John Wilcy & Sons, Inc.     

Advances in the study of the host-guest interaction by using coronene as the guest molecule

This review supplied direct insight of host-guest molecule system by using COR as the guest molecule.     

Construction of two-dimensional (2D) H-bonded supramolecular nanostructures studied by STM

In this review,a group of two-dimensional（2D） hydrogen-bonded supramolecular networks developed in our laboratory are discussed.Our attention is mainly focused on:（1） recognition of Fe³⁺ through twocomponent molecular networks;（2） site-selective fabrication of 2D fullerene arrays;and（3） fabrication of the nanoporous structure regulated by photoisomerization reaction process.It is envisioned that special supramolecular nanostructures,through H-bonding interactions,can be constructed or reconstructed to be further investigated toward the research of multi-component systems,molecule recognition,single molecular switches,and host-guest supramolecular chemistry.     

Effect ofn-octyl acetate on the microstructure of corn starch sols studied by scanning tunneling microscopy

The microstructure of a corn starch sol was studied by scanning tunneling microscopy. The influence ofn-octyl acetate on the microstructure was found. The original starch sol contains compact anisodiametric particles 500–800 nm in size. The addition ofn-octyl acetate produces friable oval associates consisting of fine spherical particles 50–20 nm in size. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1478–1480, August, 2000.     

Observation of nanoparticles and film formation by scanning tunneling microscopy: methyl methacrylate/butyl methacrylate nanoparticles prepared by microemulsion polymerization

 Latexes as dispersions of poly(methyl methacrylate-co-butyl methacrylate) copolymeric nanoparticles within water were produced by microemulsion polymerization of the respective comonomers. Polymer yield, number-average and weight-average molecular weights, polydispersity index, and the glass-transition temperature of the copolymer produced were 50%, 8.8 × 10⁴, 2.54 × 10⁵, 2.87, and 45 °C. Scanning tunneling microscopy (STM) images of the latex nanoparticles and film formation on highly oriented pyrolitic graphite (HOPG) were obtained with a 2 V sample bias and a tunneling current of 20 pA. The STM pictures revealed that the particle size was 18 ± 3 nm. There was no film formation in the case of dehydration at room temperature. There was some coalesence of particles when the HOPG surface was preheated at 55 °C, while complete film formation was achieved when the latexes were annealed at 55 °C in an oven for about 10 min. Received: 23 August 1999 Accepted: 17 January 2000     

Investigation of structures of micelles of a fullerene derivative of alanine in aqueous solutions by tunneling scanning microscopy

Structures of micelles ofN-(monohydrofullerenyl)-l-alanine and their associates were studied by tunneling scanning microscopy in the regime of a profilometer with a 10-nm resolution along the vertical line. The data obtained show that the micelles of the compound studied are anisodiametric particles 0.5–10 m in size containing negligible amounts of water. The thickness of the micelles depends on their lengths.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 876–878, April, 1996.     

Electric properties of self-assembled monolayers of helical peptides by scanning tunneling spectroscopy

Helical peptides having a disulfide group at one terminal, Lipo-(Leu-Aib)₁₂-OBzl (Lipo and OBzl represent lipoic acid and benzyl ester, respectively, SSL24B), and Boc-NHCH₂CH₂NHCO-Fc-CO-Ala-(Leu-Aib)₈-lipoamide (Boc, Fc, and lipoamide represent t-butyloxycarbonyl, ferrocene, and lipoamine, respectively, FcL16SS), were synthesized, and self-assembled monolayers (SAMs) of the helical peptides were prepared on gold. When the SSL24B SAM was observed at high-bias voltage by scanning tunneling microscopy (STM) under ultrahigh vacuum, bright spots with higher conductivity appeared in the STM image. The image was restored again to a homogeneous surface with lower bias voltage, suggesting that Au–S linkage should be reversibly changed to a conductive state. The current/voltage (I-V) curve by scanning tunneling spectroscopy (STS) at the bright domains demonstrated a rectification behavior where current increases drastically at a positive bias voltage above 3.0 V. However, the I-V curve of the FcL16SS SAM showed a current increase at negative bias voltage below −1.5 V. The redox group is, thus, a determining factor for the direction of this flow. However, STS at low-bias voltage and with the tip being inserted in the peptide SAM revealed a zero-conductance region in the I-V curve. The peptide layer may act as a molecular capacitor because of a large dielectric constant of the helical peptide. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3493–3500, 2003     

Nucleation and growth of Ge nanoclusters on the Si(111)‐(7 × 7) surface studied by scanning tunneling microscopy

Nucleation and growth of two‐dimensional Ge nanoclusters on the Si(111)‐(7 × 7) surface at elevated substrate temperatures have been studied using scanning tunneling microscopy. The uniformity of the Ge nanoclusters is improved with the increase of substrate temperature, and ordered Ge nanoclusters are formed on the faulted and unfaulted halves of (7 × 7) unit cell at substrate temperature of 200 °C. It is proposed that the Ge nanoclusters consist of six Ge atoms with three on top of the center adatoms and others on the rest atoms within one half of a unit cell. Copyright © 2014 John Wiley & Sons, Ltd.     

The specific behavior of MxTiS2 (x=1/4, M=Fe, Ni) surfaces probed by scanning microscopy (STM and AFM)

The scanning tunneling microscopy (STM) and atomic force microscopy (AFM) images of two model systems M_1/4TiS₂ (M=Fe, Ni) were interpreted on the basis of the partial electron density ρ(r,E_F) and total electron density ρ(r) of a slab which consists of seven (0 0 1) M_1/4TiS₂ atomic layers. The geometrical structure of the slabs investigated was optimized. Electronic structure calculations were performed using the ab initio periodic LCAO-DFT method. The top sulfur plane (0 0 1) imaged gives a different answer depending both of the compounds considered and the scanning probe microscopic instrument used. Theoretical calculations have then been carried out in order to improve our knowledge of the surface electronic structure of these inserted compounds and attempts are made to rationalize the experimental data. A specific behavior of the surface electronic structure in comparison with the 3D compounds (depending on the guest specie inserted) is shown.     

ChemInform Abstract: The Electronic Structure of Trifluorophosphine Studied by Photoelectron Spectroscopy with Variable Photon Energy

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.     

Three‐dimensional structural analysis of a block copolymer by scanning electron microscopy combined with a focused ion beam

A three‐dimensional (3D) lamellar structure of a poly(styrene‐block‐isoprene) block copolymer was observed at submicrometer and micrometer levels by scanning electron microscopy combined with a focused ion beam (FIB–SEM). The 3D lamellar structure with an exceptionally large periodicity, about 0.1 μm, was successfully reconstructed, and the size of the reconstructed image by FIB–SEM was 6.0 × 6.0 × 4.0 μm³, which was greater than the transmission electron microtomography data, 3.8 × 3.9 × 0.24 μm³, by a factor of about 40. This result indicates that 3D reconstruction using FIB–SEM is quite useful for direct 3D observations, especially analyses of polymeric materials at the submicrometer and micrometer levels. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 677–683, 2007     

Phase morphology of blends of polycarbonate with poly(methyl methacrylate-co-cyclohexyl methacrylate), and of polycarbonate with poly(methyl methacrylate) by solid state nuclear magnetic resonance,differential scanning calorimetry,and transmission electron microscopy

The miscibility of polycarbonate (PC) with poly(methyl methacrylate-co-cyclohexyl methacrylate) (PMCHM) and with poly(methyl methacrylate) (PMMA) was studied by nuclear magnetic resonance (NMR) ¹H spin-lattice relaxation time in the rotating frame (¹H T_1p), differential scanning calorimetry (DSC), and transmission electron microscopy (TEM). A blend of PC/PMCHM (50/50 wt/wt) with the acrylic component PMCHM, a copolymer of PMMA and poly(cyclohexyl methacrylate) (80/20 wt/wt), shows only one T_1p value, which indicates high miscibility in this blend. A blend of PC/PMMA (50/50 wt/wt) shows two ¹H T_1p values, which are similar to those of the homopolymers PC and PMMA. These results indicate high immiscibility. The “domain size” calculated from NMR results of the miscible blend PC/PMCHM is approximately 40 Å. The results of DSC and TEM are similar to the NMR results. However, TEM results show the presence of 3% PC domains in the PC/PMCHM blend, which are not seen by NMR or DSC. Those PC domains are approximately 500 Å. A strong intramolecular repulsion in the copolymer PMCHM and specific intermolecular interactions between PC and PMMA may explain the miscibility in the PC/PMCHM system. © 1994 John Wiley & Sons, Inc.