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Surface-assisted cyclodehydrogenation and dehydrogenative polymerization of polycyclic (hetero)aromatic hydrocarbons (PAH) are among the most important strategies for bottom-up assembly of new nanostructures from their molecular building blocks. Although diverse compounds have been formed in recent years using this methodology, a limited knowledge on the molecular machinery operating at the nanoscale has prevented a rational control of the reaction outcome. We show that the strength of the PAH-substrate interaction rules the competitive reaction pathways (cyclodehydrogenation versus dehydrogenative polymerization). By controlling the diffusion of N-heteroaromatic precursors, the on-surface dehydrogenation can lead to monomolecular triazafullerenes and diazahexabenzocoronenes (N-doped nanographene), to N-doped oligomeric or polymeric networks, or to carbonaceous monolayers. Governing the on-surface dehydrogenation process is a step forward toward the tailored fabrication of molecular 2D nanoarchitectures distinct from graphene and exhibiting new properties of fundamental and technological interest.

Graphene oxide (GO) assists a diverse set of promising routes to build bioactive neural microenvironments by easily interacting with other biomaterials to enhance their bulk features or, alternatively, self-assembling toward the construction of biocompatible systems with specific three-dimensional (3D) geometries. Herein, we first modulate both size and available oxygen groups in GO nanosheets to adjust the physicochemical and biological properties of polycaprolactone–gelatin electrospun nanofibrous systems. The results show that the incorporation of customized GO nanosheets modulates the properties of the nanofibers and, subsequently, markedly influences the viability of neural progenitor cell cultures. Interestingly, the partially reduced GO (rGO) nanosheets with larger dimensions trigger the best cell response, while the rGO nanosheets with smaller size provoke an accentuated decrease in the cytocompatibility of the resulting electrospun meshes. Then, the most auspicious nanofibers are synergistically accommodated onto the surface of 3D-rGO heterogeneous porous networks, giving rise to fibrous-porous combinatorial architectures suitable for enhancing adhesion and differentiation of neural cells. By varying the chemical composition of the nanofibers, it is possible to adapt their performance as physical crosslinkers for the rGO sheets, leading to the modulation of both pore size and structural/mechanical integrity of the scaffold. Importantly, the biocompatibility of the resultant fibrous-porous systems is not compromised after 14 days of cell culture, including standard differentiation patterns of neural progenitor cells. Overall, in light of these in vitro results, the reported scaffolding approach presents not only an indisputable capacity to support highly viable and interconnected neural circuits but also the potential to unlock novel strategies for neural tissue engineering applications.

We report titania nanoheterostructures decorated with silver, exhibiting tuneable photochromic properties for the first time when stimulated only by visible white light (domestic indoor lamp), with no UV wavelengths. Photochromic materials show reversible color changes under light exposure. However, all inorganic photochromic nanoparticles (NPs) require UV light to operate. Conventionally, multicolor photochromism in Ag-TiO films involves a change in color to brownish-gray during UV-light irradiation (i.e., reduction of Ag to Ag) and a (re)bleaching (i.e., (re)oxidation of Ag to colorless Ag) upon visible-light exposure. In this work, on the contrary, we demonstrate visible-light-induced photochromism (ranging from yellow to violet) of 1-10 mol % Ag-modified titania NPs using both spectroscopic and colorimetric CIEL*a*b* analyses. This is not a bleaching of the UV-induced color but a change in color itself under exposure to visible light, and it is shown to be a completely different mechanism-driven by the interfacial charge transfer of an electron from the valence band of TiO to that of the AgO clusters that surround the titania-to the usual UV-triggered photochromism reported in titania-based materials. The quantity of Ag or irradiation time dictated the magnitude and degree of tuneability of the color change, from pale yellow to dark blue, with a rapid change visible only after a few seconds, and the intensity and red shift of surface plasmon resonance induced under visible light also increased. This effect was reversible after annealing in the dark at 100 °C/15 min. Photocatalytic activity under visible light was also assessed against the abatement of nitrogen oxide pollutants, for interior use, therefore showing the coexistence of photochromism and photocatalysis-both triggered by the same wavelength-in the same material, making it a multifunctional material. Moreover, we also demonstrate and explain why X-ray photoelectron spectroscopy is an unreliable technique with such materials.

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While high-quality defect-free epitaxial graphene can be efficiently grown on metal substrates, strong interaction with the supporting metal quenches its outstanding properties. Thus, protocols to transfer graphene to insulating substrates are obligatory, and these often severely impair graphene properties by the introduction of structural or chemical defects. Here we describe a simple and easily scalable general methodology to structurally and electronically decouple epitaxial graphene from Pt(111) and Ir(111) metal surfaces. A multi-technique characterization combined with calculations was employed to fully explain the different steps involved in the process. It was shown that, after a controlled electrochemical oxidation process, a single-atom thick metal-hydroxide layer intercalates below graphene, decoupling it from the metal substrate. This decoupling process occurs without disrupting the morphology and electronic properties of graphene. The results suggest that suitably optimized electrochemical treatments may provide effective alternatives to current transfer protocols for graphene and other 2D materials on diverse metal surfaces.

Pinardi, A.L.; Biddau, G.; van de Ruit, K.; Otero-Irurueta, G.; Gardonio, S.; Lizzit, S.; Schennach, R.; Flipse, C.F.J.; Lopez, M.F.; Méndez, J.; Perez, R.; Martin-Gago, J.A. Published in: Nanotechnology DOI:10.1088/0957-4484/25/38/385602Published: 01/01/2014 Document VersionPublisher's PDF, also known as Version of Record (includes final page, issue and volume numbers) Please check the document version of this publication:• A submitted manuscript is the author's version of the article upon submission and before peer-review. There can be important differences between the submitted version and the official published version of record. People interested in the research are advised to contact the author for the final version of the publication, or visit the DOI to the publisher's website.• The final author version and the galley proof are versions of the publication after peer review.• The final published version features the final layout of the paper including the volume, issue and page numbers. Link to publication Citation for published version (APA):Pinardi, A. L., Biddau, G., Ruit, van de, K., Otero-Irurueta, G., Gardonio, S., Lizzit, S., ... Martin-Gago, J. A. (2014). Vacancy formation on C60/Pt (111): unraveling the complex atomistic mechanism. Nanotechnology, 25, 385602-1/13. DOI: 10.1088/0957-4484/25/38/385602 General rightsCopyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright owners and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights.• Users may download and print one copy of any publication from the public portal for the purpose of private study or research.• You may not further distribute the material or use it for any profit-making activity or commercial gain • You may freely distribute the URL identifying the publication in the public portal ? Take down policyIf you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim. AbstractThe interaction of fullerenes with transition metal surfaces leads to the development of an atomic network of ordered vacancies on the metal. However, the structure and formation mechanism of this intricate surface reconstruction is not yet understood at an atomic level. We combine scanning tunneling microscopy, high resolution and temperature programmed-x-ray photoelectrons spectroscopy, and density functional theory calculations to show that the vacancy formation in C60/Pt(111) is a complex process in which fullerenes undergo two significant structural rearrangements upon thermal annealing. At first, the molecules are physisorbed on the surface; next, they chemisorb inducing the formation of an adatom-vacancy pair on the side of the fullerene. Finally, this metastable state relaxes when the adatom migrates away and the vacancy moves under the molecule. The evolution from a weakly-bound fullerene to a chemisorb...

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