The synthesis and characterization of two-dimensional (2D) molecular crystals composed of long and linear phosphonic acids atop graphene is reported. Using scanning probe microscopy in combination with first-principles calculations, we show that these true 2D crystals are oriented along the graphene armchair direction only, thereby enabling an easy determination of graphene flake orientation. We have also compared the doping level of graphene flakes via Raman spectroscopy. The presence of the molecular crystal atop graphene induces a well-defined shift in the Fermi level, corresponding to hole doping, which is in agreement with our ab initio calculations.
Long-range order evolution of self-assembled phosphonic acid multilayers as a function of temperature is studied here for two molecules with different alkyl chain length. By using synchrotron conventional diffraction, distinct order configurations are retrieved on phosphonic acid multilayers and their thermodynamic behavior monitored by energy-dispersive diffraction. This later technique allows us to observe the system behavior near order-disorder temperatures, as well as to determine the most stable configurations in the range from room temperature up to 120 °C. Planar order is also addressed by wide-angle X-ray scattering (WAXS) transmission experiments. Order parameter phase diagrams are built based on the experimental results, showing the dominant configuration at each temperature. The multilayer molecular long-range order retrieved from the experiments is corroborated by first principles calculations based on the Density Functional Theory. The bulk configurations depicted in this work are produced by molecule-molecule interactions and allow for future comparisons with the behavior of ordered molecules in few-monolayers configurations, commonly used in organic devices, where the presence of surfaces and interfaces strongly affects the molecule packing.
Single-layer graphene structures and devices are commonly defined using reactive ion etching and plasma etching with O 2 or Ar as the gaseous etchants. Although optical microscopy and Raman spectroscopy are widely used to determine the appropriate duration of dry etching, additional characterization with atomic force microscopy (AFM) reveals that residual graphene and/or etching byproducts persist beyond the point where the aforementioned methods suggest complete graphene etching. Recognizing that incomplete etching may have deleterious effects on devices and/or downstream processing, AFM characterization is used here to determine optimal etching conditions that eliminate graphene dry etching residues.
The production of 2D material flakes in large quantities is a rapidly evolving field and a cornerstone for their industrial applicability. Although flake production has advanced in a fast pace, its statistical characterization is somewhat slower, with few examples in the literature which may lack either modelling uniformity and/or physical equivalence to actual flake dimensions. The present work brings a methodology for 2D material flake characterization with a threefold target: (i) propose a set of morphological shape parameters that correctly map to actual and relevant flake dimensions; (ii) find a single distribution function that efficiently describes all these parameter distributions; and (iii) suggest a representation system—topological vectors—that uniquely characterizes the statistical flake morphology within a given distribution. The applicability of such methodology is illustrated via the analysis of tens of thousands flakes of graphene/graphite and talc, which were submitted to different production protocols. The richness of information unveiled by this universal methodology may help the development of necessary standardization procedures for the imminent 2D-materials industry.
Self-assembled monolayers, bilayers, and other structures of mixed phosphonic acids were investigated using atomic force microscopy. Octadecylphosphonic acid (OPA, 18 carbon atoms in the alkyl chain) was mixed in solution, with different ratios, with octylphosphonic acid (OcPA, 8 carbon atoms in the alkyl chain) and deposited onto mica substrates. Self-assembled monolayers were formed, with no evidence of phase separation, from pure OPA up to 5:10 OPA/OcPA ratio (despite the large alkyl chain length difference). It was found that water plays a crucial role in the morphology of the self-assembled structures and their time evolution. The formation of bilayers instead of monolayers (OcPA-type behavior) is dominant for high water content (both in solution and/or the atmosphere). Mechanical and thermal resistance tests were performed on mixed and pure samples and revealed different properties that can be correlated to their composition.
Studies concerning the impact of nanomaterials, especially fullerene (C(60) ), in fresh water environments and their effects on the physiology of aquatic organisms are still scarce and conflicting. We aimed to assess in vitro effects of fullerene in brain and gill homogenates of carp Cyprinus carpio, evaluating redox parameters. A fullerene suspension was prepared by continued stirring under fluorescent light during two months. The suspension concentration was measured by total carbon content and ultraviolet-visible spectroscopy nephelometry. Characterization of C(60) aggregates was performed with an enhanced dark-field microscopy system and transmission electronic microscopy. Organ homogenates were exposed during 1, 2, and 4 h under fluorescent light. Redox parameters evaluated were reduced glutathione and oxidized glutathione, cysteine and cystine, total antioxidant capacity; activity of the antioxidant enzymes glutathione S-transferase and glutathione reductase (GR), and lipid peroxidation (TBARS assay). Fullerene induced a significant increase (p < 0.05) in lipid peroxidation after 2 h in both organs and reduced GR activity after 1 h (gills) and 4 h (brain) and antioxidant capacity after 4 h (brain). Levels of oxidized glutathione increased in the brain at 1 h and decreased at 2 h as well. Given these results, it can be concluded that C(60) can induce redox disruption via thiol/disulfide pathway, leading to oxidative damage (higher TBARS values) and loss of antioxidant competence.
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