Intercalation and reactions of CO under single layer graphene/Ni(111): the role of vacancies.

We use synchrotron radiation-induced core level photoemission spectroscopy to investigate the influence of vacancies, produced by ion bombardment, on monolayer graphene/Ni(111) exposed to CO at pressures ranging from ultra-high vacuum (10-10 mbar) up to near ambient (5.6 mbar) conditions. CO intercalates at a rate which is comparable to the one observed in absence of defects and reacts via the Boudouard reaction producing additional carbon atoms and CO2. While the former attach to the graphene layer and extend it over areas previously covered by carbide, the CO2 molecules bind to the graphene vacancies forming epoxy-like bonds across them, thus mending the defects. The so-formed complexes give rise to a peak at 533.4 eV which persists upon evacuating the vacuum chamber at room temperature and which we assign to a covalently bonded species containing C and O.

Morphological characterization and electronic properties of pristine and oxygen-exposed graphene nanoribbons on Ag(110).

Graphene nanoribbons (GNRs) are at the frontier of research on graphene materials since the 1D quantum confinement of electrons allows for the opening of an energy gap. GNRs of uniform and well-defined size and shape can be grown using the bottom-up approach, i.e. by surface assisted polymerization of aromatic hydrocarbons. Since the electronic properties of the nanostructures depend on their width and on their edge states, by careful choice of the precursor molecule it is possible to design GNRs with tailored properties. A key issue for their application in nanoelectronics is their stability under operative conditions. Here, we characterize pristine and oxygen-exposed 1.0 nm wide GNRs with a well-defined mixed edge-site sequence (two zig-zag and one armchair) synthesized on Ag(110) from 1,6-dibromo-pyrene precursors. The energy gap and the presence of quantum confined states are investigated by scanning tunneling spectroscopy. The effect of oxygen exposure under ultra-high vacuum conditions is inferred from scanning tunneling microscopy images and photoemission spectra. Our results demonstrate that oxygen exposure deeply affects the overall system by interacting both with the nanoribbons and with the substrate; this factor must be considered for supported GNRs under operative conditions.

Synthesis of corrugated C-based nanostructures by Br-corannulene oligomerization.

The structure and electronic properties of carbon-based nanostructures obtained by metal surface assisted synthesis is highly dependent on the nature of the precursor molecule. Here, we report on a combined scanning tunneling microscopy, soft X-ray spectroscopy and density functional theory investigation on the surface assisted polymerization of Br-corannulene at Ag(110) and on the possibility of building a mesh of π-conjugated polymers starting from buckyball shaped molecules. Indeed, the corannulene units form one-molecule-wide ribbons in which the natural concavity of the precursor molecule is maintained. These C-based nanostructures are corrugated and merge into a covalent network on the surface.

Adatom Extraction from Pristine Metal Terraces by Dissociative Oxygen Adsorption: Combined STM and Density Functional Theory Investigation of O/Ag(110).

The reconstruction and modification of metal surfaces upon O_{2} adsorption plays an important role in oxidation processes and in gauging their catalytic activity. Here, we show by employing scanning tunneling microscopy and the ab initio density functional theory that Ag atoms are extracted from pristine (110) terraces upon O_{2} dissociation, resulting in vacancies and in Ag-O complexes. The substrate roughening generates undercoordinated atoms and opens pathways to the Ag subsurface layer. With increasing O coverage, multiple vacancies give rise to remarkable structures. The mechanism is expected to be very general depending on the delicate interplay of energy and entropy, so that it may be active for other materials at different temperatures.

Morphology of monolayer MgO films on Ag(100): switching from corrugated islands to extended flat terraces.

The ability to engineer nearly perfect ultrathin oxide layers, up to the limit of monolayer thickness, is a key issue for nanotechnological applications. Here we face the difficult and important case of ultrathin MgO films on Ag(100), for which no extended and well-ordered layers could thus far be produced in the monolayer limit. We demonstrate that their final morphology depends not only on the usual growth parameters (crystal temperature, metal flux, and oxygen partial pressure), but also on aftergrowth treatments controlling so far neglected thermodynamics constraints. We thus succeed in tuning the shape of the oxide films from irregular, nanometer-sized, monolayer-thick islands to slightly larger, perfectly squared, bilayer islands, to extended monolayers limited apparently only by substrate steps.

Unraveling the self-assembly of the (S)-glutamic acid "flower" structure on Ag(100).

(S)-Glutamic acid adsorbed on Ag(100) organizes in different self-assembled structures depending on surface temperature [Smerieri, M.; Vattuone, L.; Kravchuk, T.; Costa, D.; Savio, L. (S)-Glutamic Acid on Ag(100): Self-Assembly in the Nonzwitterionic Form. Langmuir2011, 27, 2393-2404]. In particular, two of these structures, referred to as "square" and "flower" geometries, are found to coexist on the surface upon deposition at T = 350 K. The former assembly was fully resolved at the atomic level in the work of Smerieri et al. [Smerieri, M.; Vattuone, L.; Costa, D.; Tielens, F.; Savio, L. Self-Assembly of (S)-Glutamic Acid on Ag(100): A Combined LT-STM and Ab Initio Investigation. Langmuir2010, 26, 7208-7215], in which we proved that the driving force for adsorption is the van der Waals interactions between the molecules and the Ag surface, that is, that molecules are in a physisorbed state. In this paper, we complete our work by presenting the characterization of the "flower" structure. In contrast to the case of the "square" assembly, a strong chemical bond between glutamic acid radicals and the surface is at the basis of the "flowers" geometry. Whereas the chemisorbed central GLU tetramer interacts strongly with the surface, the physisorbed surrounding GLU molecules conserve some degree of freedom in the layer which counterbalances the weak adsorption energy. The "flower" and the "square" assemblies have similar dispersion energy and H-bond interaction energy; as a consequence of the different chemical state of the GLU molecules, however, such contributions have a very different relative weight in the stabilization of the two structures.

Adsorption of glutamic acid on clean and hydroxylated rutile TiO2(110): an XPS and NEXAFS investigation.

Due to its biocompatibility, TiO2is a relevant material for the study of bio-interfaces. Its electronic and chemical properties are influenced by defects, which mainly consist of oxygen vacancies or adsorbed OH groups and which affect, consequently, also the interaction with biological molecules. Here we report on an x-ray photoemission spectroscopy and near edge adsorption fine structure study of glutamic acid (Glu) adsorption on the rutile TiO2(110) surface, either clean or partially hydroxylated. We show that Glu anchors to the surface through a carboxylate group and that the final adsorption state is influenced by the presence of hydroxyl groups on the surface prior to Glu deposition. Indeed, molecules adsorb both in the anionic and in the zwitterionic form, the former species being favored on the hydroxylated substrate.

Ecotoxicity of Polyvinylidene Difluoride (PVDF) and Polylactic Acid (PLA) Microplastics in Marine Zooplankton.

The aim of this study was to investigate the ecotoxicity of polyvinylidene difluoride (PVDF) and polylactic acid (PLA) microplastics (MPs) in two marine zooplankton: the crustacean Artemia franciscana and the cnidarian Aurelia sp. (common jellyfish). To achieve this goal, (i) MP uptake, (ii) immobility, and (iii) behavior (swimming speed, pulsation mode) of crustacean larval stages and jellyfish ephyrae exposed to MPs concentrations (1, 10, 100 mg/L) were assessed for 24 h. Using traditional and novel techniques, i.e., epifluorescence microscopy and 3D holotomography (HT), PVDF and PLA MPs were found in the digestive systems of the crustaceans and in the gelatinous tissue of jellyfish. Immobility was not affected in either organism, while a significant behavioral alteration in terms of pulsation mode was found in jellyfish after exposure to both PVDF and PLA MPs. Moreover, PLA MPs exposure in jellyfish induced a toxic effect (EC50: 77.43 mg/L) on the behavioral response. This study provides new insights into PLA and PVDF toxicity with the potential for a large impact on the marine ecosystem, since jellyfish play a key role in the marine food chain. However, further investigations incorporating additional species belonging to other trophic levels are paramount to better understand and clarify the impact of such polymers at micro scale in the marine environment. These findings suggest that although PVDF and PLA have been recently proposed as innovative and, in the case of PLA, biodegradable polymers, their effects on marine biota should not be underestimated.

Synthesis of graphene nanoribbons with a defined mixed edge-site sequence by surface assisted polymerization of (1,6)-dibromopyrene on Ag(110).

By a combination of scanning tunneling microscopy, X-ray spectroscopic techniques and density functional theory calculations, we prove the formation of extended patterns of parallel, graphene nanoribbons with alternate zig-zag and armchair edges and selected width by surface-assisted Ullmann coupling polymerization and dehydrogenation of 1,6-dibromopyrene (C16H8Br2). Besides the relevance of these nanostructures for their possible application in nanodevices, we demonstrate the peculiarity of halogenated pyrene derivatives for the formation of nanoribbons, in particular on Ag(110). These results open the possibility of tuning the shape and dimension of nanoribbons (and hence the correlated electronic properties) by choosing suitably tailored or on-purpose designed molecular precursors.

Accretion disc origin of the Earth's water.

Earth's water is conventionally believed to be delivered by comets or wet asteroids after the Earth formed. However, their elemental and isotopic properties are inconsistent with those of the Earth. It was thus proposed that water was introduced by adsorption onto grains in the accretion disc prior to planetary growth, with bonding energies so high as to be stable under high-temperature conditions. Here, we show both by laboratory experiments and numerical simulations that water adsorbs dissociatively on the olivine {100} surface at the temperature (approx. 500-1500 K) and water pressure (approx. 10⁻8 bar) expected for the accretion disc, leaving an OH adlayer that is stable at least up to 900 K. This may result in the formation of many Earth oceans, provided that a viable mechanism to produce water from hydroxyl exists. This adsorption process must occur in all disc environments around young stars. The inevitable conclusion is that water should be prevalent on terrestrial planets in the habitable zone around other stars.