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We present a method for a bottom-up synthesis of atomically thin graphene sheets with tunable crystallinity and porosity using aromatic self-assembled monolayers (SAMs) as molecular precursors. To this end, we employ SAMs with pyridine and pyrrole constituents on polycrystalline copper foils and convert them initially into molecular nanosheets-carbon nanomembranes (CNMs)- via low-energy electron irradiation induced cross-linking and then into graphene monolayers via pyrolysis. As the nitrogen atoms are leaving the nanosheets during pyrolysis, nanopores are generated in the formed single-layer graphene. We elucidate the structural changes upon the cross-linking and pyrolysis down to the atomic scale by complementary spectroscopy and microscopy techniques including X-ray photoelectron and Raman spectroscopy, low energy electron diffraction, atomic force, helium ion, and high-resolution transmission electron microscopy, and electrical transport measurements. We demonstrate that the crystallinity and porosity of the formed graphene can be adjusted via the choice of molecular precursors and pyrolysis temperature, and we present a kinetic growth model quantitatively describing the conversion of molecular CNMs into graphene. The synthesized nanoporous graphene monolayers resemble a percolated network of graphene nanoribbons with a high charge carrier mobility (∼600 cm 2 /(V s)), making them attractive for implementations in electronic field-effect devices.

A method has been developed to stabilize and transfer nanofilms of functional organic semiconductors. The method is based on crosslinking of their topmost layers by low energy electron irradiation. The films can then be detached from their original substrates and subsequently deposited onto new solid or holey substrates retaining their structural integrity. Grazing incidence X-ray diffraction, X-ray specular reflectivity, and UV-Vis spectroscopy measurements reveal that the electron irradiation of ≈50 nm thick pentacene films results in crosslinking of their only topmost ≈5 nm (3-4 monolayers), whereas the deeper pentacene layers preserve their pristine crystallinity. The electronic performance of the transferred pentacene nanosheets in bottom contact field-effect devices is studied and it is found that they are fully functional and demonstrate superior charge injection properties in comparison to the pentacene films directly grown on the contact structures by vapor deposition. The new approach paves the way to integration of the organic semiconductor nanofilms on substrates unfavorable for their direct growth as well as to their implementation in hybrid devices with unusual geometries, e.g., in devices incorporating free-standing sheets., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

High-quality graphene oxide (GO) with high crystallinity and electrical conductivity as well as in situ doped with nitrogen and sulfur is obtained via the electrochemical exfoliation of graphite. Furthermore, iron incorporated GO sheets show promising catalytic activity and stable methanol tolerance durability when used as electrocatalysts for the oxygen reduction reaction.

The direct growth of single-layer graphene patterns via electron irradiation of aromatic self-assembled monolayers and subsequent annealing is demonstrated. In this way, a reduction in the number of necessary manufacturing steps is achieved. The formed micro- and nanostructures can be arbitrarily shaped and eventually implemented in a manifold of applications., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The realization of graphene-based, next-generation electronic applications essentially depends on a reproducible, large-scale production of graphene films via chemical vapor deposition (CVD). We demonstrate how key challenges such as uniformity and homogeneity of the copper metal substrate as well as the growth chemistry can be improved by the use of carbon dioxide and carbon dioxide enriched gas atmospheres. Our approach enables graphene film production protocols free of elemental hydrogen and provides graphene layers of superior quality compared to samples produced by conventional hydrogen/methane based CVD processes. The substrates and resulting graphene films were characterized by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX) and Raman microscopy, sheet resistance and transport measurements. The superior quality of the as-grown graphene films on copper is indicated by Raman maps revealing average G band widths as low as 18 ± 8 cm(-1) at 514.5 nm excitation. In addition, high charge carrier mobilities of up to 1975 cm(2)/(V s) were observed for electrons in transferred films obtained from a carbon dioxide based growth protocol. The enhanced graphene film quality can be explained by the mild oxidation properties of carbon dioxide, which at high temperatures enables an uniform conditioning of the substrates by an efficient removal of pre-existing and emerging carbon impurities and a continuous suppression and in situ etching of carbon of lesser quality being co-deposited during the CVD growth.

Free-standing nanomembranes with molecular or atomic thickness are currently explored for separation technologies, electronics, and sensing. Their engineering with well-defined structural and functional properties is a challenge for materials research. Here we present a broadly applicable scheme to create mechanically stable carbon nanomembranes (CNMs) with a thickness of ~0.5 to ~3 nm. Monolayers of polyaromatic molecules (oligophenyls, hexaphenylbenzene, and polycyclic aromatic hydrocarbons) were assembled and exposed to electrons that cross-link them into CNMs; subsequent pyrolysis converts the CNMs into graphene sheets. In this transformation the thickness, porosity, and surface functionality of the nanomembranes are determined by the monolayers, and structural and functional features are passed on from the molecules through their monolayers to the CNMs and finally on to the graphene. Our procedure is scalable to large areas and allows the engineering of ultrathin nanomembranes by controlling the composition and structure of precursor molecules and their monolayers.

Self-assembled monolayers of aromatic molecules on copper substrates can be converted into high-quality single-layer graphene using low-energy electron irradiation and subsequent annealing. This two-dimensional solid state transformation is characterized on the atomic scale and the physical and chemical properties of the formed graphene sheets are studied by complementary microscopic and spectroscopic techniques and by electrical transport measurements. As substrates, Cu(111) single crystals and the technologically relevant polycrystalline copper foils are successfully used., (Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Ultrathin carbon nanomembranes (CNM) comprising crosslinked biphenyl precursors have been tested as support films for energy-filtered transmission electron microscopy (EFTEM) of biological specimens. Due to their high transparency CNM are ideal substrates for electron energy loss spectroscopy (EELS) and electron spectroscopic imaging (ESI) of stained and unstained biological samples. Virtually background-free elemental maps of tobacco mosaic virus (TMV) and ferritin have been obtained from samples supported by ∼1nm thin CNM. Furthermore, we have tested conductive carbon nanomembranes (cCNM) comprising nanocrystalline graphene, obtained by thermal treatment of CNM, as supports for cryoEM of ice-embedded biological samples. We imaged ice-embedded TMV on cCNM and compared the results with images of ice-embedded TMV on conventional carbon film (CC), thus analyzing the gain in contrast for TMV on cCNM in a quantitative manner. In addition we have developed a method for the preparation of vitrified specimens, suspended over the holes of a conventional holey carbon film, while backed by ultrathin cCNM., (Copyright © 2011 Elsevier B.V. All rights reserved.)

Due to the use of radiolabeled drugs and feed additives in residue evaluation of preclearance approval of new animal drug applications (NADAs), metabolites including those which are covalently bound are detected in the edible tissues of target food animals. Isolation and characterization of these residues is often a difficult task. The approach taken is to couple safety assessment with development of the required residue information. An outline of data development is made in the context of toxicity assessment. Unless otherwise adjusted, the sponsor's method of residue analysis and drug withdrawal time reflect responsibility of all drug residues of toxicological concern found in edible tissues. The use of bioavailability studies and how they interact with safety evaluation is developed. Focus is brought to the specific problem of covalently bound residues and a framework for their assessment is presented.

The use of radiolabeled drugs and feed additives in experiments designed for preclearance approval of new animal drug applications (NADAs) demonstrates the presence of metabolites, including those which are covalently bound to macromolecules and which often persist in the edible tissues of target food animals. Isolation and characterization of these residues is often a difficult task. An outline of data development is explored in the context of toxicity assessment. Unless otherwise adjusted, the sponsor's method of residue analysis and drug withdrawal time reflect the influence of all related drug residues found in edible tissues. The use of bioavailability studies and their interaction with safety evaluation is discussed.

"Criteria and Procedures for Evaluating Assays for Carcinogenic Residues," popularly known as the "Sensitivity of the Method (SOM)" proposal for the regulation of animal drugs and feed additives, employs an initial analysis to determine whether a compound must meet the requirements as a suspect carcinogen or the requirements for general food safety (GFS). Metabolism and kinetics of drug depletion play an important role in the six-step procedure that is used for either set of regulatory criteria. The only significant difference that exists between the two sets of criteria is the degree of testing required. However, the difference will usually not be manifest until positive findings of carcinogenicity in the chronic studies in laboratory animals trigger a further evaluation of the metabolism of the drug or feed additive. For both SOM and GFS, metabolic information will be used to determine the appropriateness of the test species as well as to help select a compound for residue analysis. Residue depletion kinetics in the food animals also play an integral role in the selection of species-strains for toxicity testing selection as well as in the selection of the compound for residue analysis in food. Furthermore, depletion kinetics are used to set a safe withdrawal period. The development of guidelines is discussed.

The relationships between membranes and intramembrane compartments of isolated heart mitochondria are inadequately defined to express the induced morphological changes associated with the structural organization. The inner membrane and matrix are the major structural entities which undergo transformation upon alteration of metabolism or incubation conditions. To better express these morphological changes within a mitochondrion, two inner membranes plus enclosed matrix are defined as an inmerix (plural inmerices). Three general morphological forms of mitochondria can be distinguished by the size and shape of inmerices. These are distended, condensed, and coalesced inmerixal configurations. Hypotonic conditions and P(i) in isotonic sucrose generate distended configurations. This P(i) distention is apparently dependent on utilization of energy. It does not occur under anaerobic conditions. Oxidizable substrates generate condensed configurations. ADP and dADP generate coalesced configurations and stop formation of condensed and distended inmerixal configurations in the absence of inhibitors. ADP coalescence is apparently not dependent on an energy input. It occurs under aerobic and anaerobic conditions, and in isotonic and hypotonic media. Atractyloside completely inhibits the effects of ADP on inmerixal membranes whereas oligomycin does not. Distention by P(i) is unaffected by the two inhibitors. Distended inmerices, without added P(i) (12 mM and 62 mM sucrose), are coalesced by ADP. These studies indicate that coalescence of inmerixal membranes probably reflects the consequences of specific stoichiometric binding or translocation of adenine nucleotides.