energy related; nanomaterials
nanotechnologies; nanomaterials; sensors
Transformations of molecular structures formed by perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) molecules on a rutile TiO2(110) surface are studied with low-temperature scanning tunnelling microscopy. We demonstrate that metastable molecular assemblies transform into differently ordered structures either due to additional energy provided by thermal annealing or when the influence of intermolecular forces is increased by the enlarged amount of deposited molecules. Proper adjustment of molecular coverage and substrate temperature during deposition allows for fabrication of desired assemblies. Differences between PTCDA/TiO2(110) and PTCDA/TiO2(011) systems obtained through identical experimental procedures are discussed.
PTCDA, TiO2, rutile, self-assembly, STM
Thermal energy storage (TES) is capable to reduce the demand of conventional energy sources for two reasons: First, they prevent the mismatch between the energy supply and the power demand when generating electricity from renewable energy sources. Second, utilization of waste heat in industrial processes by thermal energy storage reduces the final energy consumption. This review focuses mainly on material aspects of alkali nitrate salts. They include thermal properties, thermal decomposition processes as well as a new method to develop optimized salt systems.
eutectic mixture; molten salt; nitrate; phase change material; thermal decomposition
After a general introduction into the Shockley theory of current voltage (J–V) characteristics of inorganic and organic semiconductor junctions of different bandwidth, we apply the Shockley theory-based, one diode model to a new type of perovskite junctions with polaronic charge carriers. In particular, we studied manganite–titanate p–n heterojunctions made of n-doped SrTi1−
yNbyO3, y = 0.002 and p-doped Pr1−
xCaxMnO3, x = 0.34 having a strongly correlated electron system. The diffusion length of the polaron carriers was analyzed by electron beam-induced current (EBIC) in a thin cross plane lamella of the junction. In the J–V characteristics, the polaronic nature of the charge carriers is exhibited mainly by the temperature dependence of the microscopic parameters, such as the hopping mobility of the series resistance and a colossal electro-resistance (CER) effect in the parallel resistance. We conclude that a modification of the Shockley equation incorporating voltage-dependent microscopic polaron parameters is required. Specifically, the voltage dependence of the reverse saturation current density is analyzed and interpreted as a voltage-dependent electron–polaron hole–polaron pair generation and separation at the interface.
current–voltage characteristics; perovskites; photovoltaics; polarons
The small intestine is a complex system that carries out various functions. The main function of enterocytes is absorption of nutrients, whereas membranous cells (M cells) are responsible for delivering antigens/foreign substances to the mucosal lymphoid tissues. However, to get a fundamental understanding of how cellular structures contribute to physiological processes, precise knowledge about surface morphologies, cytoskeleton organizations and biomechanical properties is necessary. Atomic force microscopy (AFM) was used here as a powerful tool to study surface topographies of Caco-2 cells and M cells. Furthermore, cell elasticity (i.e., the mechanical response of a cell on a tip indentation), was elucidated by force curve measurements. Besides elasticity, adhesion was evaluated by recording the attraction and repulsion forces between the tip and the cell surface. Organization of F-actin networks were investigated via phalloidin labeling and visualization was performed with confocal laser scanning fluorescence microscopy (CLSM) and scanning electron microscopy (SEM). The results of these various experimental techniques revealed significant differences in the cytoskeleton/microvilli arrangements and F-actin organization. Caco-2 cells displayed densely packed F-actin bundles covering the entire cell surface, indicating the formation of a well-differentiated brush border. In contrast, in M cells actins were arranged as short and/or truncated thin villi, only available at the cell edge. The elasticity of M cells was 1.7-fold higher compared to Caco-2 cells and increased significantly from the cell periphery to the nuclear region. Since elasticity can be directly linked to cell adhesion, M cells showed higher adhesion forces than Caco-2 cells. The combination of distinct experimental techniques shows that morphological differences between Caco-2 cells and M cells correlate with mechanical cell properties and provide useful information to understand physiological processes/mechanisms in the small intestine.
atomic force microscopy; Caco-2 cells; elasticity; M cells; mechanical properties
Optical beam deflection systems are widely used in cantilever based atomic force microscopy (AFM). Most commercial cantilevers have a reflective metal coating on the detector side to increase the reflectivity in order to achieve a high signal on the photodiode. Although the reflective coating is usually much thinner than the cantilever, it can still significantly contribute to the damping of the cantilever, leading to a lower mechanical quality factor (Q-factor). In dynamic mode operation in high vacuum, a cantilever with a high Q-factor is desired in order to achieve a lower minimal detectable force. The reflective coating can also increase the low-frequency force noise. In contact mode and force spectroscopy, a cantilever with minimal low-frequency force noise is desirable. We present a study on cantilevers with a partial reflective coating on the detector side. For this study, soft (≈0.01 N/m) and stiff (≈28 N/m) rectangular cantilevers were used with a custom partial coating at the tip end of the cantilever. The Q-factor, the detection and the force noise of fully coated, partially coated and uncoated cantilevers are compared and force distance curves are shown. Our results show an improvement in low-frequency force noise and increased Q-factor for the partially coated cantilevers compared to fully coated ones while maintaining the same reflectivity, therefore making it possible to combine the best of both worlds.
cantilever; force noise; partial coating; Q-factor
Literature in the field of nanotechnology is exponentially increasing with more and more engineered nanomaterials being created, characterized, and tested for performance and safety. With the deluge of published data, there is a need for natural language processing approaches to semi-automate the cataloguing of engineered nanomaterials and their associated physico-chemical properties, performance, exposure scenarios, and biological effects. In this paper, we review the different informatics methods that have been applied to patent mining, nanomaterial/device characterization, nanomedicine, and environmental risk assessment. Nine natural language processing (NLP)-based tools were identified: NanoPort, NanoMapper, TechPerceptor, a Text Mining Framework, a Nanodevice Analyzer, a Clinical Trial Document Classifier, Nanotoxicity Searcher, NanoSifter, and NEIMiner. We conclude with recommendations for sharing NLP-related tools through online repositories to broaden participation in nanoinformatics.
data mining; informatics; name entity recognition; nano-informatics; nanoparticles; nanotechnology; nanotoxicity; natural language processing; text mining
Single-stranded DNA–melamine hybrid molecular building blocks were synthesized using a phosphoramidation cross-coupling reaction with a zero linker approach. The self-assembly of the DNA–organic hybrid molecules was achieved by DNA hybridization. Following self-assembly, two distinct types of nanostructures in the form of linear chains and network arrays were observed. The morphology of the self-assembled nanostructures was found to depend on the number of DNA strands that were attached to a single melamine molecule.
DNA–organic hybrid; melamine; nanostructures; phosphoramidation; self-assembly
Disordered and uniform (2√3 × 2√3)R30° superstructures of fullerenes on the Au(111) surface have been studied using scanning tunneling microscopy and spectroscopy. It is shown that the deposition and growth process of a fullerene monolayer on the Au(111) surface determine the resulting superstructure. The supply of thermal energy is of importance for the activation of a Au vacancy forming process and thus, one criterion for the selection of the respective superstructure. However, here it is depicted that a vacancy–adatom pair can be formed even at room temperature. This latter process results in C60 molecules that appear slightly more bright in scanning tunnelling microscopy images and are identified in disordered (2√3 x 2√3)R30° superstructures based on a detailed structure analysis. In addition, these slightly more bright C60 molecules form uniform (2√3 x 2√3)R30° superstructures, which exhibit intermolecular interactions, likely mediated by Au adatoms. Thus, vacancy–adatom pairs forming at room temperature directly affect the resulting C60 superstructure. Differential conductivity spectra reveal a lifting of the degeneracy of the LUMO and LUMO+1 orbitals in the uniform (2√3 x 2√3)R30° superstructure and in addition, hybrid fullerene–Au(111) surface states suggest partly covalent interactions.
adatom–vacancy mechanism; differential conductance; fullerene; Ising model; scanning tunnelling microscopy
We have studied the charge and thermal transport properties of a porphyrin-based single-molecule transistor with electro-burnt graphene electrodes (EBG) using the nonequilibrium Green’s function method and density functional theory. The porphyrin-based molecule is bound to the EBG electrodes by planar aromatic anchor groups. Due to the efficient π–π overlap between the anchor groups and graphene and the location of frontier orbitals relative to the EBG Fermi energy, we predict HOMO-dominated transport. An on–off ratio as high as 150 is predicted for the device, which could be utilized with small gate voltages in the range of ±0.1 V. A positive thermopower of +280 μV/K is predicted for the device at the theoretical Fermi energy. The sign of the thermopower could be changed by tuning the Fermi energy. By gating the junction and changing the Fermi energy by +10 meV, this can be further enhanced to +475 μV/K. Although the electrodes and molecule are symmetric, the junction itself can be asymmetric due to different binding configurations at the electrodes. This can lead to rectification in the current–voltage characteristic of the junction.
electro-burnt graphene electrodes; nanoelectronics; porphyrin; single-molecule transistor
The coating of regular-shaped, readily available nanorod biotemplates with inorganic compounds has attracted increasing interest during recent years. The goal is an effective, bioinspired fabrication of fiber-reinforced composites and robust, miniaturized technical devices. Major challenges in the synthesis of applicable mineralized nanorods lie in selectivity and adjustability of the inorganic material deposited on the biological, rod-shaped backbones, with respect to thickness and surface profile of the resulting coating, as well as the avoidance of aggregation into extended superstructures. Nanotubular tobacco mosaic virus (TMV) templates have proved particularly suitable towards this goal: Their multivalent protein coating can be modified by high-surface-density conjugation of peptides, inducing and governing silica deposition from precursor solutions in vitro. In this study, TMV has been equipped with mineralization-directing peptides designed to yield silica coatings in a reliable and predictable manner via precipitation from tetraethoxysilane (TEOS) precursors. Three peptide groups were compared regarding their influence on silica polymerization: (i) two peptide variants with alternating basic and acidic residues, i.e. lysine–aspartic acid (KD)x motifs expected to act as charge-relay systems promoting TEOS hydrolysis and silica polymerization; (ii) a tetrahistidine-exposing polypeptide (CA4H4) known to induce silicification due to the positive charge of its clustered imidazole side chains; and (iii) two peptides with high ZnO binding affinity. Differential effects on the mineralization of the TMV surface were demonstrated, where a (KD)x charge-relay peptide (designed in this study) led to the most reproducible and selective silica deposition. A homogenous coating of the biotemplate and tight control of shell thickness were achieved.
biomineralization; charge-relay system; peptide; silica; tobacco mosaic virus (TMV)
nanomaterials; nanostructures; self-assembly phenomena
This paper presents the results of a thermal treatment process for magnetite nanoparticles in the temperature range of 50–500 °C. The tested magnetite nanoparticles were synthesized using three different methods that resulted in nanoparticles with different surface characteristics and crystallinity, which in turn, was reflected in their thermal durability. The particles were obtained by coprecipitation from Fe chlorides and decomposition of an Fe(acac)3 complex with and without a core–shell structure. Three types of ferrite nanoparticles were produced and their thermal stability properties were compared. In this study, two sets of unmodified magnetite nanoparticles were used where crystallinity was as determinant of the series. For the third type of particles, a Ag shell was added. By comparing the coated and uncoated particles, the influence of the metallic layer on the thermal stability of the nanoparticles was tested. Before and after heat treatment, the nanoparticles were examined using transmission electron microscopy, IR spectroscopy, differential scanning calorimetry, X-ray diffraction and Mössbauer spectroscopy. Based on the obtained results, it was observed that the fabrication methods determine, to some extent, the sensitivity of the nanoparticles to external factors.
high temperature corrosion; internal oxidation; IR spectroscopy; metal matrix composites; Mössbauer spectroscopy; X-ray diffraction
Here we detail high performance, enzymatic electrodes for oxygen bio-electroreduction, which can be easily and reproducibly fabricated with industry-scale throughput. Planar and nanostructured electrodes were built on biocompatible, flexible polymer sheets, while nanoimprint lithography was used for electrode nanostructuring. To the best of our knowledge, this is one of the first reports concerning the usage of nanoimprint lithography for amperometric bioelectronic devices. The enzyme (Myrothecium verrucaria bilirubin oxidase) was immobilised on planar (control) and artificially nanostructured, gold electrodes by direct physical adsorption. The detailed electrochemical investigation of bioelectrodes was performed and the following parameters were obtained: open circuit voltage of approximately 0.75 V, and maximum bio-electrocatalytic current densities of 18 µA/cm2 and 58 µA/cm2 in air-saturated buffers versus 48 µA/cm2 and 186 µA/cm2 in oxygen-saturated buffers for planar and nanostructured electrodes, respectively. The half-deactivation times of planar and nanostructured biocathodes were measured to be 2 h and 14 h, respectively. The comparison of standard heterogeneous and bio-electrocatalytic rate constants showed that the improved bio-electrocatalytic performance of the nanostructured biocathodes compared to planar biodevices is due to the increased surface area of the nanostructured electrodes, whereas their improved operational stability is attributed to stabilisation of the enzyme inside nanocavities.
bilirubin oxidase; bio-electrocatalysis; direct electron transfer; nanoimprint lithography; oxygen reduction reaction
We investigate the formation and evolution of Au–CO single-molecule break junctions. The conductance histogram exhibits two distinct molecular configurations, which are further investigated by a combined statistical analysis. According to conditional histogram and correlation analysis these molecular configurations show strong anticorrelations with each other and with pure Au monoatomic junctions and atomic chains. We identify molecular precursor configurations with somewhat higher conductance, which are formed prior to single-molecule junctions. According to detailed length analysis two distinct types of molecule-affected chain-formation processes are observed, and we compare these results to former theoretical calculations considering bridge- and atop-type molecular configurations where the latter has reduced conductance due to destructive Fano interference.
atomic chains; break junction; carbon monoxide; correlation analysis; gold
Metal nanocages have raised great interest because of their new properties and wide applications. Here, we report on the use of galvanic replacement reactions to synthesize substrate-supported Ag–Au nanocages from silver templates electrodeposited on transparent indium tin oxide (ITO) film coated glass. The residual Ag in the composition was dealloyed with 10% nitric acid. It was found that chains of Au nanocages were formed on the substrate surface during dealloying. When the concentration of HNO3 increased to 20%, the structures of nanocages were damaged and formed crescent or semi-circular shapes. The transfer process on the substrate surface was discussed.
dealloying; gold nanocage chains; nitric acid; solid substrate
Hollow nanostructures are ranked among the top materials for applications in various modern technological areas including energy storage devices, catalyst, optics and sensors. The last years have witnessed increasing interest in the Kirkendall effect as a versatile route to fabricate hollow nanostructures with different shapes, compositions and functionalities. Although the conversion chemistry of nanostructures from solid to hollow has reached a very advanced maturity, there is still much to be discovered and learned on this effect. Here, the recent progress on the use of the Kirkendall effect to synthesize hollow nanospheres and nanotubes is reviewed with a special emphasis on the fundamental mechanisms occurring during such a conversion process. The discussion includes the oxidation of metal nanostructures (i.e., nanospheres and nanowires), which is an important process involving the Kirkendall effect. For nanospheres, the symmetrical and the asymmetrical mechanisms are both reviewed and compared on the basis of recent reports in the literature. For nanotubes, in addition to a summary of the conversion processes, the unusual effects observed in some particular cases (e.g., formation of segmented or bamboo-like nanotubes) are summarized and discussed. Finally, we conclude with a summary, where the prospective future direction of this research field is discussed.
hollow nanospheres; Kirkendall effect; metals; nanotubes; oxides