Concept: Scanning tunneling microscope
Porous silicon microcavity (PSiMc) structures were used to immobilize the photosynthetic reaction center (RC) purified from the purple bacterium Rhodobacter sphaeroides R-26. Two different binding methods were compared by specular reflectance measurements. Structural characterization of PSiMc was performed by scanning electron microscopy and atomic force microscopy. The activity of the immobilized RC was checked by measuring the visible absorption spectra of the externally added electron donor, mammalian cytochrome c. PSi/RC complex was found to oxidize the cytochrome c after every saturating Xe flash, indicating the accessibility of specific surface binding sites on the immobilized RC, for the external electron donor. This new type of bio-nanomaterial is considered as an excellent model for new generation applications of silicon-based electronics and biological redox systems.
The nanoscale electrical properties of individual self-assembled GeSi quantum rings (QRs) were studied by scanning probe microscopy-based techniques. The surface potential distributions of individual GeSi QRs are obtained by scanning Kelvin microscopy (SKM). Ring-shaped work function distributions are observed, presenting that the QRs' rim has a larger work function than the QRs' central hole. By combining the SKM results with those obtained by conductive atomic force microscopy and scanning capacitance microscopy, the correlations between the surface potential, conductance, and carrier density distributions are revealed, and a possible interpretation for the QRs' conductance distributions is suggested.
Coordinatively unsaturated (CUS) iron sites are highly active in catalytic oxidation reactions; however, maintaining the CUS structure of iron during heterogeneous catalytic reactions is a great challenge. Here, we report a strategy to stabilize single-atom CUS iron sites by embedding highly dispersed FeN4 centers in the graphene matrix. The atomic structure of FeN4 centers in graphene was revealed for the first time by combining high-resolution transmission electron microscopy/high-angle annular dark-field scanning transmission electron microscopy with low-temperature scanning tunneling microscopy. These confined single-atom iron sites exhibit high performance in the direct catalytic oxidation of benzene to phenol at room temperature, with a conversion of 23.4% and a yield of 18.7%, and can even proceed efficiently at 0°C with a phenol yield of 8.3% after 24 hours. Both experimental measurements and density functional theory calculations indicate that the formation of the Fe═O intermediate structure is a key step to promoting the conversion of benzene to phenol. These findings could pave the way toward highly efficient nonprecious catalysts for low-temperature oxidation reactions in heterogeneous catalysis and electrocatalysis.
- Proceedings of the National Academy of Sciences of the United States of America
- Published over 2 years ago
Interactions between catalytically active metal particles and reactant gases depend strongly on the particle size, particularly in the subnanometer regime where the addition of just one atom can induce substantial changes in stability, morphology, and reactivity. Here, time-lapse scanning tunneling microscopy (STM) and density functional theory (DFT)-based calculations are used to study how CO exposure affects the stability of Pt adatoms and subnano clusters at the Fe3O4(001) surface, a model CO oxidation catalyst. The results reveal that CO plays a dual role: first, it induces mobility among otherwise stable Pt adatoms through the formation of Pt carbonyls (Pt1-CO), leading to agglomeration into subnano clusters. Second, the presence of the CO stabilizes the smallest clusters against decay at room temperature, significantly modifying the growth kinetics. At elevated temperatures, CO desorption results in a partial redispersion and recovery of the Pt adatom phase.
The development of methods for imaging large contiguous volumes with the electron microscope could allow the complete mapping of a whole mouse brain at the single-axon level. We developed a method based on prolonged immersion that enables staining and embedding of the entire mouse brain with uniform myelin staining and a moderate preservation of the tissue’s ultrastructure. We tested the ability to follow myelinated axons using serial block-face electron microscopy.
The bacterium Geobacter sulfurreducens requires the expression of conductive protein filaments or pili to respire extracellular electron acceptors such as iron oxides and uranium and to wire electroactive biofilms, but the contribution of the protein fiber to charge transport has remained elusive. Here we demonstrate efficient long-range charge transport along individual pili purified free of metal and redox organic cofactors at rates high enough to satisfy the respiratory rates of the cell. Carrier characteristics were within the orders reported for organic semiconductors (mobility) and inorganic nanowires (concentration), and resistivity was within the lower ranges reported for moderately doped silicon nanowires. However, the pilus conductance and the carrier mobility decreased when one of the tyrosines of the predicted axial multistep hopping path was replaced with an alanine. Furthermore, low temperature scanning tunneling microscopy demonstrated the thermal dependence of the differential conductance at the low voltages that operate in biological systems. The results thus provide evidence for thermally activated multistep hopping as the mechanism that allows Geobacter pili to function as protein nanowires between the cell and extracellular electron acceptors.
Scaffolded DNA origami has proven to be a powerful and efficient technique to fabricate functional nanomachines by programming the folding of a single-stranded DNA template strand into three-dimensional (3D) nanostructures, designed to be precisely motion-controlled. Although two-dimensional (2D) imaging of DNA nanomachines using transmission electron microscopy and atomic force microscopy suggested these nanomachines are dynamic in 3D, geometric analysis based on 2D imaging was insufficient to uncover the exact motion in 3D. Here we use the individual-particle electron tomography method and reconstruct 129 density maps from 129 individual DNA origami Bennett linkage mechanisms at ~ 6-14 nm resolution. The statistical analyses of these conformations lead to understanding the 3D structural dynamics of Bennett linkage mechanisms. Moreover, our effort provides experimental verification of a theoretical kinematics model of DNA origami, which can be used as feedback to improve the design and control of motion via optimized DNA sequences and routing.
We report the growth of vertically aligned high crystalinity silicon nanotube (SiNT) arrays on silicon substrate by means of a Ni-Au bilayer catalyst engineering technique. Nanotubes were synthesized through solid-liquid-solid (SLS) method as well as vapor-liquid-solid (VLS). A precise evaluation utilizing atomic force microscopy (AFM) and lateral force microscopy (LFM) describes that the gold profile in Ni regions leads to the construction of multiwall SiNTs (MW-SiNT). The agreement of the structural geometry and stiffness of the obtained SiNTs with previous theoretical predictions suggest sp3 hybridization as the mechanism of tube formation. Apart from scanning electron and transmission electron microscopy (SEM, TEM) techniques, photoluminescence spectroscopy (PL) has been conducted to investigate the formation of nanostructures. PL spectroscopy confirms the evolution of ultra-fine walls of the silicon nanotubes, responsible for the observed photoemission properties.
The copolymers of N-isopropylacrylamide and sodium vinylsulphonate were synthesised by free radical polymerisation. The layer-by-layer self-assembly of the copolymers with poly(allylamine) hydrochloride was performed through assembling onto silicon wafer to form multilayer films and onto CaCO(3) microparticles doped with poly(styrene sulphonate) as well as deltamethrin microcrystals to form microcapsules. The multilayer films and microcapsules were characterised by atomic force microscopy, transmission electron microscopy and scanning electron microscopy. The release behaviour of deltamethrin in the microcapsules under different conditions was also investigated by high performance liquid chromatography. Results show that these deltamethrin microcapsules have good thermo-sensitive properties and deltamethrin release can be controlled via changing temperature or self-assembly layers.
To dissect the astonishing complexity of the biomolecular machinery functioning within a cell, imaging has been an integral tool in biology, allowing researches to “view” the detailed molecular biology responsible for coordinating cellular life. To visualize the molecular components of cellular structures requires, in particular, imaging techniques capable of reaching nanoscale spatial resolutions. Such nanoimaging techniques are the focus of this volume. Chapters in the current volume are divided into four parts and include specialized techniques in the areas of light, electron, and scanning probe microscopy, as well as methodologies employing combinatorial and complementary imaging approaches.