Article hydrogen separation performance of UiO-66-NH2_{2} membranes grown via liquid-phase epitaxy layer-by-layer deposition and one-pot synthesis

The quality assurance of hydrogen fuel for mobile applications is assessed by the guidelines and directives given in the European and international standards. However, the presence of impurities in the hydrogen fuel, in particular nitrogen, water, and oxygen, is experienced in several refueling stations. Within this work, metal-organic framework (MOF)-based membranes are investigated as a fine-purification stage of the hydrogen fuel. Three H$_{2}$2/N$_{2}$ concentrations have been used to analyze the separation factor of UiO-66-NH$_{2}$ membranes prepared using the layer-by-layer (LBL) and the one-pot (OP) synthesis methods. It is shown that the separation factor for an equimolar ratio is 14.4% higher for the LBL sample compared to the OP membrane, suggesting a higher orientation and continuity of the LBL surface-supported metal-organic framework (SURMOF). Using an equimolar ratio of H$_{2}$/N$_{2}$, it is shown that selective separation of hydrogen over nitrogen occurs with a separation factor of 3.02 and 2.64 for the SURMOF and MOF membrane, respectively. To the best of our knowledge, this is the highest reported performance for a single-phase UiO-66-NH$_{2}$ membrane. For higher hydrogen concentrations, the separation factor decreases due to reduced interactions between pore walls and N$_{2}$ molecules

Reactive block copolymers for patterned surface immobilization with sub-30 nm spacing

Phase-segregating block copolymers are powerful platforms for nanofabrication, particularly when employed as lithographic mask precursors. Surface-reactive polymeric films with distinct sub-30 nm domains are also proposed as covalent docking platforms for scalable, high-resolution molecular patterned immobilization. Here, the well-known self-assembling polystyrene-block-polyisoprene system is the starting point to produce a small library of derivatives with distinct reactive pendant groups (halide, azide, pentafluorophenylalkyl) by nitroxide-mediated radical polymerization. We find that controlling film thickness is crucial to obtain a perpendicular lamellar morphology and that the presence of the functional groups has a limited impact on self-assembly, yet may influence characteristic domain dimensions. Differential scanning calorimetry (DSC), small-angle X-ray scattering (SAXS), and atomic force microscopy (AFM) are utilized in concert to assess the phase behavior of the polymers and the surface features of the nanostructures. As a proof-of-concept for the surface reactivity, click chemistry-driven immobilization of a model water-soluble polymer is evidenced by X-ray photoelectron spectroscopy (XPS) and preservation of the underlying morphology is investigated by AFM

Direct Synthesis of ZIF-8 on Transmission Electron Microscopy Grids Allows Structure Analysis and 3D Reconstruction

The first example of layer‐by‐layer growth of a metal–organic framework (MOF) directly on transmission electron microscopy (TEM) grids is described. ZIF‐8 is deposited on thin amorphous carbon films and subjected to a structure analysis by (scanning) TEM ((S)TEM). This method serves as a two‐in‐one synthesis and TEM sample‐preparation technique and allows straightforward analysis of ZIF‐8 crystallites. Artifacts resulting from sample preparation are completely avoided by this approach. The morphological properties, crystal structure, and the chemical composition of the material are investigated with high spatial resolution by a variety of methods of (analytical) electron microscopy. Furthermore, the incorporation of metallic nanoparticles in ZIF‐8 by integrating a corresponding step into the layer‐by‐layer deposition process is examined. The formation of ZIF‐8 crystals on the film proceeds as under the absence of nanoparticle‐forming synthesis steps. However, the nanoparticles rather cover the supporting amorphous carbon film than being incorporated in the ZIF‐8 material. This information cannot be obtained from standard characterization techniques but requires the application of analytical (S)TEM techniques

Direct Synthesis of ZIF-8 on Transmission Electron Microscopy Grids Allows Insights into the Growth Process

Metal-organic frameworks (MOFs) have received increased attention in recent years due to their exceptional properties and versatility. MOFs consist of metal nodes connected by organic linkers. Particularly interesting are surface-anchored films (SURMOFs), which are grown on bulk substrates. Transmission electron microscopy (TEM) is a key technique for the analysis of the structural and chemical properties of SURMOFs on the nanoscale. For TEM sample preparation, however, the SURMOF film must be detached from the bulk substrate and transferred to an electron-transparent support. This detachment process is a severe source of damage for the SURMOF film. The preparation of SURMOFs for TEM studies is thus an obstacle that has not yet been solved satisfactorily

Mobility of charge carriers in self-assembled monolayers

We present a new approach to study charge transport within 2D layers of organic semi-conductors (OSCs) using atomic force microscopy (AFM)-based lithography applied to self-assembled monolayers (SAMs), fabricated from appropriate organothiols. The extent of lateral charge transport was investigated by insulating pre-defined patches within OSC-based SAMs with regions of insulating SAM made from large band gap alkanethiolates. The new method is demonstrated using a phenyl-linked anthracenethiolate (PAT), 4-(anthracene-2-ylethynyl)benzyl thiolate. I-V characteristics of differently shaped PAT-islands were measured using the AFM tip as a top electrode. We were able to determine a relationship between island size and electrical conductivity, and from this dependence, we could obtain information on the lateral charge transport and charge carrier mobility within the thin OSC layers. Our study demonstrates that AFM nanografting of appropriately functionalized OSC molecules provides a suitable method to determine intrinsic mobilities of charge carriers in OSC thin films. In particular, this method is rather insensitive with regard to influence of grain boundaries and other defects, which hamper the application of conventional methods for the determination of mobilities in macroscopic samples. © 2019 Fu et al

Novel roles for well-known players: from tobacco mosaic virus pests to enzymatically active assemblies

The rod-shaped nanoparticles of the widespread plant pathogen tobacco mosaic virus (TMV) have been a matter of intense debates and cutting-edge research for more than a hundred years. During the late 19th century, their behavior in filtration tests applied to the agent causing the \u27plant mosaic disease\u27 eventually led to the discrimination of viruses from bacteria. Thereafter, they promoted the development of biophysical cornerstone techniques such as electron microscopy and ultracentrifugation. Since the 1950s, the robust, helically arranged nucleoprotein complexes consisting of a single RNA and more than 2100 identical coat protein subunits have enabled molecular studies which have pioneered the understanding of viral replication and self-assembly, and elucidated major aspects of virus–host interplay, which can lead to agronomically relevant diseases. However, during the last decades, TMV has acquired a new reputation as a well-defined high-yield nanotemplate with multivalent protein surfaces, allowing for an ordered high-density presentation of multiple active molecules or synthetic compounds. Amino acid side chains exposed on the viral coat may be tailored genetically or biochemically to meet the demands for selective conjugation reactions, or to directly engineer novel functionality on TMV-derived nanosticks. The natural TMV size (length: 300 nm) in combination with functional ligands such as peptides, enzymes, dyes, drugs or inorganic materials is advantageous for applications ranging from biomedical imaging and therapy approaches over surface enlargement of battery electrodes to the immobilization of enzymes. TMV building blocks are also amenable to external control of in vitro assembly and re-organization into technically expedient new shapes or arrays, which bears a unique potential for the development of \u27smart\u27 functional 3D structures. Among those, materials designed for enzyme-based biodetection layouts, which are routinely applied, e.g., for monitoring blood sugar concentrations, might profit particularly from the presence of TMV rods: Their surfaces were recently shown to stabilize enzymatic activities upon repeated consecutive uses and over several weeks. This review gives the reader a ride through strikingly diverse achievements obtained with TMV-based particles, compares them to the progress with related viruses, and focuses on latest results revealing special advantages for enzyme-based biosensing formats, which might be of high interest for diagnostics employing \u27systems-on-a-chip\u27