Macroscopic transport by synthetic molecular machines

Nature uses molecular motors and machines in virtually every significant biological process, but demonstrating that simpler artificial structures operating through the same gross mechanisms can be interfaced with—and perform physical tasks in—the macroscopic world represents a significant hurdle for molecular nanotechnology. Here we describe a wholly synthetic molecular system that converts an external energy source (light) into biased brownian motion to transport a macroscopic cargo and do measurable work. The millimetre-scale directional transport of a liquid on a surface is achieved by using the biased brownian motion of stimuli-responsive rotaxanes (‘molecular shuttles’) to expose or conceal fluoroalkane residues and thereby modify surface tension. The collective operation of a monolayer of the molecular shuttles is sufficient to power the movement of a microlitre droplet of diiodomethane up a twelve-degree incline.

Interacting Preformed Cooper Pairs in Resonant Fermi Gases

We consider the normal phase of a strongly interacting Fermi gas, which can have either an equal or an unequal number of atoms in its two accessible spin states. Due to the unitarity-limited attractive interaction between particles with different spin, noncondensed Cooper pairs are formed. The starting point in treating preformed pairs is the Nozi\`{e}res-Schmitt-Rink (NSR) theory, which approximates the pairs as being noninteracting. Here, we consider the effects of the interactions between the Cooper pairs in a Wilsonian renormalization-group scheme. Starting from the exact bosonic action for the pairs, we calculate the Cooper-pair self-energy by combining the NSR formalism with the Wilsonian approach. We compare our findings with the recent experiments by Harikoshi {\it et al.} [Science {\bf 327}, 442 (2010)] and Nascimb\`{e}ne {\it et al.} [Nature {\bf 463}, 1057 (2010)], and find very good agreement. We also make predictions for the population-imbalanced case, that can be tested in experiments.Comment: 10 pages, 6 figures, accepted version for PRA, discussion of the imbalanced Fermi gas added, new figure and references adde

Phthalocyanine-nanocarbon ensembles: From discrete molecular and supramolecular systems to hybrid nanomaterials

This document is the Accepted Manuscript version of a Published Work that appeared in final form in Accounts of Chemical Research, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://dx.doi.org/10.1021/ar5004384Conspectus Phthalocyanines (Pcs) are macrocyclic and aromatic compounds that present unique electronic features such as high molar absorption coefficients, rich redox chemistry, and photoinduced energy/electron transfer abilities that can be modulated as a function of the electronic character of their counterparts in donor-acceptor (D-A) ensembles. In this context, carbon nanostructures such as fullerenes, carbon nanotubes (CNTs), and, more recently, graphene are among the most suitable Pc companions. Pc-C60 ensembles have been for a long time the main actors in this field, due to the commercial availability of C60 and the ell-established synthetic methods for its functionalization. As a result, many Pc-C60 architectures have been prepared, featuring different connectivities (covalent or supramolecular), intermolecular interactions (self-organized or molecularly dispersed species), and Pc HOMO/LUMO levels. All these elements provide a versatile toolbox for tuning the photophysical properties in terms of the type of process (photoinduced energy/electron transfer), the nature of the interactions beteen the electroactive units (through bond or space), and the kinetics of the formation/decay of the photogenerated species. Some recent trends in this field include the preparation of stimuli-responsive multicomponent systems ith tunable photophysical properties and highly ordered nanoarchitectures and surface-supported systems shoing high charge mobilities. A breakthrough in the Pc-nanocarbon field as the appearance of CNTs and graphene, hich opened a ne avenue for the preparation of intriguing photoresponsive hybrid ensembles shoing light-stimulated charge separation. The scarce solubility of these 1-D and 2-D nanocarbons, together ith their loer reactivity ith respect to C60 stemming from their less strained sp2 carbon netorks, has not meant an unsurmountable limitation for the preparation of variety of Pc-based hybrids. These systems, hich sho improved solubility and dispersibility features, bring together the unique electronic transport properties of CNTs and graphene ith the excellent light-harvesting and tunable redox properties of Pcs. A singular and distinctive feature of these Pc-CNT/graphene (single- or fe-layers) hybrid materials is the control of the direction of the photoinduced charge transfer as a result of the band-like electronic structure of these carbon nanoforms and the adjustable electronic levels of Pcs. Moreover, these conjugates present intensified light-harvesting capabilities resulting from the grafting of several chromophores on the same nanocarbon platform.In this Account, recent progress in the construction of covalent and supramolecular Pc-nanocarbon ensembles is summarized, ith a particular emphasis on their photoinduced behavior. e believe that the high degree of control achieved in the preparation of Pc-carbon nanostructures, together ith the increasing knoledge of the factors governing their photophysics, ill allo for the design of next-generation light-fueled electroactive systems. Possible implementation of these Pc-nanocarbons in high performance devices is envisioned, finally turning into reality much of the expectations generated by these materialsFinancial support from the Spanish MICINN (CTQ2011-24187/BQU), the Comunidad de Madrid (S2013/MIT-2841 FOTOCARBON) and the EU (“SO2S” FP7-PEOPLE-2012-ITN, no.: 316975) is acknowledge

Does congenital deafness affect the structural and functional architecture of primary visual cortex?

Deafness results in greater reliance on the remaining senses. It is unknown whether the cortical architecture of the intact senses is optimized to compensate for lost input. Here we performed widefield population receptive field (pRF) mapping of primary visual cortex (V1) with functional magnetic resonance imaging (fMRI) in hearing and congenitally deaf participants, all of whom had learnt sign language after the age of 10 years. We found larger pRFs encoding the peripheral visual field of deaf compared to hearing participants. This was likely driven by larger facilitatory center zones of the pRF profile concentrated in the near and far periphery in the deaf group. pRF density was comparable between groups, indicating pRFs overlapped more in the deaf group. This could suggest that a coarse coding strategy underlies enhanced peripheral visual skills in deaf people. Cortical thickness was also decreased in V1 in the deaf group. These findings suggest deafness causes structural and functional plasticity at the earliest stages of visual cortex

Game accessibility for visually impaired people: a review

Playing games is an important way to promote the integration, inclusion, and socialization of participants. This is especially the case of persons with disabilities, such as visually impaired people. Unfortunately, very few games are accessible to such persons. Hopefully, in many digital games, this accessibility can be enabled in principle by assistive technologies, such as screen readers. The aim of this work consists in reviewing the recent literature on game accessibility for people with visual impairment and discussing benefits, limitations, and possible improvements of currently available accessibility solutions. After providing a definition of visual impairment and describing its relationship with gaming, the work reviews general techniques for designing more accessible games. Subsequently, it focuses on specific techniques based on replacing visual stimuli with auditory stimuli (e.g., sonification and sound-source simulation), also presenting some recently proposed sonification-mapping strategies. Then, the application of machine-learning techniques to the development of accessible interfaces for online versions of board games is illustrated by a recent case study. Finally, a discussion and some conclusions are provided, with a particular focus on policy implications of improvements in game accessibility for visually impaired people

The Calabrian Arc subduction complex in the Ionian Sea: Regional architecture, active deformation, and seismic hazard

We analyzed the structure and evolution of the external Calabrian Arc (CA) subduction complex through an integrated geophysical approach involving multichannel and single‐channel seismic data at different scales. Pre‐stack depth migrated crustal‐scale seismic profiles have been used to reconstruct the overall geometry of the subduction complex, i.e., depth of the basal detachment, geometry and structural style of different tectonic domains, and location and geometry of major faults. High‐resolution multichannel seismic (MCS) and sub‐bottom CHIRP profiles acquired in key areas during a recent cruise, as well as multibeam data, integrate deep data and constrain the fine structure of the accretionary wedge as well as the activity of individual fault strands. We identified four main morpho‐structural domains in the subduction complex: 1) the post‐Messinian accretionary wedge; 2) a slope terrace; 3) the pre‐Messinian accretionary wedge and 4) the inner plateau. Variation of structural style and seafloor morphology in these domains are related to different tectonic processes, such as frontal accretion, out‐of-sequence thrusting, underplating and complex faulting. The CA subduction complex is segmented longitudinally into two different lobes characterized by different structural style, deformation rates and basal detachment depths. They are delimited by a NW/SE deformation zone that accommodates differential movements of the Calabrian and the Peloritan portions of CA and represent a recent phase of plate re‐organization in the central Mediterranean. Although shallow thrust‐type seismicity along the CA is lacking, we identified active deformation of the shallowest sedimentary units at the wedge front and in the inner portions of the subduction complex. This implies that subduction could be active but aseismic or with a locked fault plane. On the other hand, if underthrusting of the African plate has stopped recently, active shortening may be accommodated through more distributed deformation. Our findings have consequences on seismic hazard, since we identified tectonic structures likely to have caused large earthquakes in the past and to be the source regions for future events