Perylene bisimide macrocycles and their self-assembly on HOPG surfaces

Acetylene-linked macrocycles incorporating multiple perylene tetracarboxylic acid bisimide (PBI) chromophores have been synthesised and separated by recycling GPC. The very first example of such macrocycles, i.e., cyclic trimer 5, containing three PBI dyes self-assembles into highly ordered donut-shaped unique hexagonal nanopatterns on HOPG surfaces as revealed by atomic force microscopy (AFM).     

MMX polymer chains on surfaces

Fibres of [Ru(2)Br(micro-O(2)CEt)4]n polymer have been isolated on different surfaces under specific conditions, and morphologically characterised by AFM and STM, showing an unexpected helical internal structure.     

Synthesis of macrocycle isomers via metathesis cyclization and their self-assembly from aqueous solutions

Novel triangular macrocycle isomers were synthesized through metathesis cyclization with high yield (77%). HPLC and MALDI-TOF showed that the purity of the macrocycles was higher than 99%, while (1)H NMR clearly showed that these macrocycles contain C2 and C3 isomers in a ratio of 1:3. AFM and TEM showed that they spontaneously formed vesicular structures in a chloroform/water system with an average diameter of 460 nm, which was corroborated by DLS results.     

Structure and Growth of Two-dimensional Ices at the Surfaces Probed by Scanning Probe Microscopy

Scanning probe microscopy(SPM) stands out as one of the most powerful tools for characterizing the solid surface and the adsorbed molecules with ?ngstr?m resolution in real space. In particular, this unique technique provides an unprecedented opportunity for directly probing the low-dimensional ices at surfaces. In this perspective, we first review the recent advances of scanning tunneling microscopy(STM) imaging of various two-dimensional(2 D) ice structures on metal[1-7], insulator[8-12], graphite[13-15] surfaces and under strong confinement[10, 16-19]. We then introduce that noncontact atomic-force microscopy(AFM) with a CO-terminated tip enables atomic imaging of a genuine 2 D ice grown on a hydrophobic Au(111) surface with minimal perturbation[20], paying particular attention to the growth processes at the edges of 2 D ice. In the end, we present an outlook on the future applications of 2 D ice as well as the relation between the 2 D and 3 D ice growth.     

Self-assembled monolayers of clamped oligo(phenylene-ethynylene-butadiynylene)s

Rigid rod oligo(phenylene-ethynylene-butadiynylene)s (oPEBs), "half-rings" of two rigid rods connected via a molecular clamp unit, and shape-persistent macrocycles (cyclic "half-ring dimers") are synthesized and their self-assembled monolayers (SAMs) are investigated by scanning tunneling microscopy (STM) at the interface of 1,2,4-trichlorobenzene (TCB)/highly oriented pyrolytic graphite (HOPG). The results are important for the design of molecular building blocks for two-dimensional nanoscale architectures on solid surfaces.     

Single-molecule chemistry and physics explored by low-temperature scanning probe microscopy

It is well known that scanning probe techniques such as scanning tunnelling microscopy (STM) and atomic force microscopy (AFM) routinely offer atomic scale information on the geometric and the electronic structure of solids. Recent developments in STM and especially in non-contact AFM have allowed imaging and spectroscopy of individual molecules on surfaces with unprecedented spatial resolution, which makes it possible to study chemistry and physics at the single molecule level. In this feature article, we first review the physical concepts underlying image contrast in STM and AFM. We then focus on the key experimental considerations and use selected examples to demonstrate the capabilities of modern day low-temperature scanning probe microscopy in providing chemical insight at the single molecule level.     

The nature of alkanethiol self-assembled monolayer adsorption on sputtered gold substrates

A detailed study of the self-assembly and coverage by 1-nonanethiol of sputtered Au surfaces using molecular resolution atomic force microscopy (AFM) and scanning tunneling microscopy (STM) is presented. The monolayer self-assembles on a smooth Au surface composed predominantly of [111] oriented grains. The domains of the alkanethiol monolayer are observed with sizes typically of 5-25 nm, and multiple molecular domains can exist within one Au grain. STM imaging shows that the (4 x 2) superlattice structure is observed as a (3 x 2) structure when imaged under noncontact AFM conditions. The 1-nonanethiol molecules reside in the threefold hollow sites of the Au[111] lattice and aligned along its [112] lattice vectors. The self-assembled monolayer (SAM) contains many nonuniformities such as pinholes, domain boundaries, and monatomic depressions which are present in the Au surface prior to SAM adsorption. The detailed observations demonstrate limitations to the application of 1-nonanethiol as a resist in atomic nanolithography experiments to feature sizes of approximately 20 nm.     

Self-organization of gold-containing hydrogen-bonded rosette assemblies on graphite surface

The self-organization of supramolecular structures, in particular gold-containing hydrogen-bonded rosettes, on highly oriented pyrolytic graphite (HOPG) surfaces was investigated by tapping-mode atomic force microscopy (TM-AFM) and scanning tunneling microscopy (STM). TM-AFM and high-resolution STM results show that these hydrogen-bonded assemblies self-organize to form highly ordered domains on HOPG surfaces. We find that a subtle change in one of the building blocks induces two different orientations of the assembly with respect to the surface. These results provide information on the control over the construction of supramolecular nanoarchitectures in 2D with the potential for the manufacturing of functional materials based on structural manipulation of molecular components.     

The dependence of fractal dimension on measuring conditions of scanning probe microscopy

The fractal dimension of sputtered thin film surfaces was determined. Topography was measured using scanning tunneling microscopy (STM) and atomic force microscopy (AFM). It can be shown that measuring conditions have an important influence on the topographic data and the obtained fractal dimension. This influence was investigated systematically. The results of STM- and AFM-measurements have been compared. The results for surfaces imaged with AFM give lower values for the fractal dimension than with STM. Measurements were carried out with a standard cantilever and so the data have been filtered. Dynamic behavior of the measuring system is influenced by scanning speed and loop gain factor. During measurement of topographic signal high scanning speed and low loop gain factor produce a low pass behavior and the fractal dimension will be varied. If there is a disturbance in addition to the topographic signal (e.g. a noise) we found power spectra with more than one linear part. The calculated fractal dimension especially depended on the density of measuring points in the profile. The experimental results were verified by calculated Weierstrass-Mandelbrot functions.     

Electron transfer of plurimodified DNA SAMs

An STM-based current-voltage (I/V) investigation of deoxyribonucleic acid (DNA) 18 base pair (bp) oligonucleotide monolayers on gold is presented. Three bases of each of the immobilized and complementary strands were modified with either iodine or phenylethylene moieties. The oligonucleotides were immobilized on template stripped gold (tsg) surfaces and characterized by atomic force microscopy (AFM) and scanning tunneling microscopy (STM). AFM imaging showed that monolayers of the expected height were formed. A comparative study of normal, halogenated, and phenyl-modified DNA was made with the STM in tunneling spectroscopy (TS) mode. I/V spectroscopic measurements in the range +/-250 mV on both single- and double-stranded (ds) DNA monolayers (modified and unmodified) showed that for negative substrate bias (U(sub)) electron transfer is more efficient through a phenyl-modified monolayer than through normal or halogenated DNA. This effect was particularly clear below a threshold bias of -100 mV. For positive U(sub), unmodified ds DNA was found to conduct slightly better than the modified strands. This is presumably caused by greater order in the unmodified versus modified DNA monolayers. Modifications on the immobilized (thiolated) strand seem to improve electron transport through the DNA monolayer more than modifications on the complementary (not surface-bound) strand.     

Conjugated macrocycles: concepts and applications

One of the most important objectives in materials, chemical, and physical sciences is the creation of large conjugated macrocycles with well-defined shapes, since such molecules are not only theoretically and experimentally interesting but also have potential applications in nanotechnology. Fully unsaturated macrocycles are regarded as models for infinitely conjugated π systems with inner cavities, and exhibit unusual optical and magnetic behavior. Macrocycles have interior and exterior sites, and site-specific substitution at both or either site can afford attractive structures, such as 1D, 2D, and 3D supramolecular nanostructures. These nanostructures could be controlled through the use of π-extended large macrocycles by a bottom-up strategy. Numerous shape-persistent π-conjugated macrocycles have been synthesized, but only a few are on the nanoscale. This Review focuses on nanosized π-conjugated macrocycles (>1 nm diameter) and giant macrocycles (>2 nm diameter), and summarizes their syntheses and properties.     

Mixed self-assembled monolayers of semirigid tetrahydro-4H-thiopyran end-capped oligo(cyclohexylidenes)

Single-component and mixed self-assembled monolayers (SAMs) of one- and three-ring semirigid tetrahydro-4H-thiopyran end-capped oligo(cyclohexylidenes)-that is, thiopyran (1), 4-(4-cyclohexylidene-cyclohexylidene)tetrahydro-4H-thiopyran (2), and 4-(tetrahydro-4H-thiopyran-4-cyclohexylidene-4'-ylidene)tetrahydro-4H-thiopyran (3)--on Au(111) substrates have been prepared and studied by cyclic voltammetry (CV), atomic force microscopy (AFM), and scanning tunneling microscopy (STM). It was found that the shortest adsorbate 1 more readily forms a SAM than 2 or 3. Notwithstanding, the SAMs of 2 or 3 are thermodynamically more stable due to favorable intermolecular attractions. Holes were made with the AFM tip establishing tilt angles of 30-50 degrees with respect to the surface normal for all SAMs. STM imaging showed well-ordered, line-shaped packing patterns with molecular resolution for the SAM of 2. Similar patterned structures were not observed for 1 and 3. Mixed SAMs were prepared by exposing a SAM of 1 to ethanol solutions of either 2 or 3. STM imaging revealed that domains of molecules of 2 or 3 amidst a monolayer of 1 are formed in both cases. Whereas in the mixed SAM of 1 and 2 the domains are irregularly shaped, circular islands of uniform size are found in the mixed SAM of 1 and 3.     

Self-assembly of a catechol-based macrocycle at the liquid-solid interface: experiments and molecular dynamics simulations

This combined experimental (STM, XPS) and molecular dynamics simulation study highlights the complex and subtle interplay of solvent effects and surface interactions on the 2-D self-assembly pattern of a Schiff-base macrocycle containing catechol moieties at the liquid-solid interface. STM imaging reveals a hexagonal ordering of the macrocycles at the n-tetradecane/Au(111) interface, compatible with a desorption of the lateral chains of the macrocycle. Interestingly, all the triangular-shaped macrocycles are oriented in the same direction, avoiding a close-packed structure. XPS experiments indicate the presence of a strong macrocycle-surface interaction. Also, MD simulations reveal substantial solvent effects. In particular, we find that co-adsorption of solvent molecules with the macrocycles induces desorption of lateral chains, and the solvent molecules act as spacers stabilizing the open self-assembly pattern.     

Morphology of platinum electrodeposits in the three-dimensional sublayer to full layer range produced under different potential modulations on highly oriented pyrolytic graphite

The topography of platinum electrodes produced by electrodeposition (19 to 200 mC cm-2) on highly oriented pyrolytic graphite (HOPG) under different potential modulations was investigated by atomic force microscopy, scanning tunneling microscopy, and H-atom electrosorption voltammetry. To modulate electrodeposition, (i) triangular potential cycling at 0.1 V s-1, (ii) a linear cathodic potential at 0.1 V s-1 and anodic potential step cycling, and (iii) square wave potential cycling at 5000 Hz were utilized. AFM and STM imaging showed that at lower platinum loading the HOPG surface was partially covered by a 3D sublayer of platinum. Electrodes produced by procedure (i) were made of faceted platinum aggregates of about 200 nm and nanoclusters in the range of 5-20 nm; those that resulted from procedure (ii) consisted of anisotropic aggregates of nanoclusters arranged as quasi-parallel domains. These electrodes from (i) and (ii) behaved as fractal objects. The electrodes resulting from procedure (iii) exhibited a flat surface that behaved as a Euclidean object. For all WEs, as the platinum loading was increased the HOPG surface was fully covered by a thin 3D layer of platinum aggregates produced by electrodeposition and coalescence phenomena. Large platinum loading led to electrodes with fractal geometry. Statistical parameters (root-mean-square height, skewedness, kurtosis, anisotropy, Abbot curve, number of protrusions and valleys, and fractal dimension) were obtained from the analysis of AFM and STM imaging data. Platinum electrodeposition coupled to either H-adatom formation for procedures (i) and (ii) or phonon dispersion for (iii) was involved in the surface atom rearrangements related to electrofaceting. The H-adatom electrosorption voltammetry data were used to evaluate the real electrode surface area via the voltammetric charge and to advance a tentative explanation of the contribution of the different crystallographic facets to the global electrochemical process dominated by weak H-Pt adsorption interactions.     

Ordering of dipeptide chains on Cu surfaces through 2D cocrystallization

We report on the induced ordering of dispersed chiral diphenylalanine (Phe-Phe) chains grown on the anisotropic Cu(110) and isotropic Cu(100) surfaces. Scanning tunneling microscopy (STM) data reveal that 2D extended hybrid molecular motifs can be fabricated by utilizing terephthalic acid (TPA) molecules as linkers. These act as a molecular "glue" to bridge the isolated Phe-Phe chains without altering the global chirality of the final structures. Our results demonstrate the applicability and effectiveness of this 2D analogue of the 3D cocrystallization approach.     

Self-assembly of aromatic molecules over zeolite (0 1 0) surfaces: An AFM and semiempirical study

Self-assembly of pyridine base molecules, pyridine and b-picoline, were observed by atomic force microscopy (AFM) on (0 1 0) surfaces of natural zeolites, heulandite and stilbite, respectively. The molecular array structures of the self-assembled adlayers were determined from the AFM images, and they showed well-ordered, two-dimensional (quasi-) hexagonal lattice structures. Orientations of the molecules within the 2D adlayers were also estimated from the AFM images, and their energetics were calculated by means of a semiempirical molecular orbital method.     

A new Phosphorylated Polysaccharide for Biomedical Applications: Generation of 3D Scaffolds with Osteogenic Activity and Coating of Titanium Oxide Surfaces

Summary: A new phosphorylated derivative of carboxymethylcellulose and amidic carboxymethylcellulose containing one phosphate group for each disaccharide unit was synthesized using sodium trimetaphospahte (STMP) as the phosphating agent. The new polysaccharide was characterized by infrared spectroscopy (FT-IR) and the amount of phosphate groups was determined by elemental analysis. These modified polysaccharides were used both to prepare 3D scaffolds and functionalize titanium oxide surfaces with the aim to improve the osseointegration with the host tissue. The presence of phosphate groups modify the physical-chemical properties of the hydrogels with respect to the native ones. The evaluation of the bioactivity of the phosphorylated carboxymethylcellulose hydrogels towards osteoblast-like cells showed a significant increase in the osteocalcin production. The modified surfaces were chemically characterized by means of X-ray photoelectron spectroscopy (XPS) and FT-IR, whereas the surface topography was analysed by Atomic Force Measurements (AFM) measurements before and after the polysaccharide coating. In vitro biological tests using osteoblast-like cells demonstrated that phosphorylated carboxymethylcellulose functionalized TiO₂ surfaces promoted better cell adhesion and significantly enhanced their proliferation. These findings suggest that the phosphate polysaccharide both as a 3D scaffold and as a surface coating promotes osteoblast growth potentially improving the biomaterial osseointegration rate.     

Hydrogen bond partner reorganization in the coadsorption of a monodendron and pyridylethynyl derivatives

Hydrogen bonds with high selectivity and directionality are significant in harnessing molecules to form 2D supramolecular nanostructures. The competition and reorganization of hydrogen bond partners determine the ultimate molecular assembly and pattern in a 2D supramolecular system. In this study, multicomponent assemblies of a monodendron (5-benzyloxy-isophthalic acid derivative, BIC) and pyridylethynyl derivatives [1,4-bis(4-pyridylethynyl)-2,3-bis-dodecyloxy-benzene (PBPC12) and 1,4-bis(4-pyridylethynyl)-2,3-bis-octadecyloxy-benzene (PBPC18)] have been studied by scanning tunneling microscopy (STM) on a graphite surface. BIC molecules are able to associate with PBPC12 and PBPC18 molecules to induce the rearrangement of hydrogen bond partners and form coassembly structures. Interestingly, BIC acts as a template molecule in the coassembly process, and these multicomponent structures exhibit similar structural features to the assembly structures of BIC itself. The structural details of the coassembled structures are revealed by high-resolution STM images, and their relationship with the original BIC assemblies is discussed. These results provide important insights into the design and fabrication of hydrogen-bond-directed multicomponent molecular nanostructures on solid surfaces.     

sp2碳连接的二维高分子：在原子分子尺度下的观察与研究

二维聚合物在光电催化、能量存储和气体存储与分离等领域具有重要的应用潜力。其中,基于sp~2杂化碳(C_(sp~2))连接的二维聚合物具有独特的电学性质与化学性质。通过扫描隧道显微镜(STM)技术可以在Au(111)、Ag(111)、Cu(111)、Ru(111)、HOPG等晶格表面上进行原子尺度的精确聚合,这为构建C_(sp~2)相连的二维聚合物提供了有效的新策略。STM技术具有高分辨率能力,可用于表面二维聚合物的结构表征以及内在的光电磁性质的研究。本文将介绍基于STM技术对C_(sp~2)-C_(sp~2)连接的二维聚合物进行观察与研究的新进展。     

Characterization and surface reactivity of ferrihydrite nanoparticles assembled in ferritin

Ferrihydrite nanoparticles with nominal sizes of 3 and 6 nm were assembled within ferritin, an iron storage protein. The crystallinity and structure of the nanoparticles (after removal of the protein shell) were evaluated by high-resolution transmission electron microscopy (HRTEM), atomic force microscopy (AFM), and scanning tunneling microscopy (STM). HRTEM showed that amorphous and crystalline nanoparticles were copresent, and the degree of crystallinity improved with increasing size of the particles. The dominant phase of the crystalline nanoparticles was ferrihydrite. Morphology and electronic structure of the nanoparticles were characterized by AFM and STM. Scanning tunneling spectroscopy (STS) measurements suggested that the band gap associated with the 6 nm particles was larger than the band gap associated with the 3 nm particles. Interaction of SO2(g) with the nanoparticles was investigated by attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, and results were interpreted with the aid of molecular orbital/density functional theory (MO/DFT) frequency calculations. Reaction of SO2(g) with the nanoparticles resulted primarily in SO(3)2- surface species. The concentration of SO3(2-) appeared to be dependent on the ferrihydrite particle size (or differences in structural properties).