Viruses have remarkable physical properties and complex interactions with their environment. However, their aggregation in confined spaces remains unexplored, although this phenomenon is of paramount importance for understanding viral infectivity. Using hydrodynamical driving and optical detection, we developed a method to detect the transport of single virus in real time through synthetic nanopores.
View Article and Find Full Text PDFA functionalization process has been developed and the experimental conditions optimized allowing the immobilization of first-row transition metal (M) containing polyoxometalates (POMs) with the formula [M(HO)PWO] on transparent indium-tin oxide (ITO) electrodes for electrochromic applications. Both flat ITO grafted with 4-sulfophenyl moieties and sulfonate-functionalized vertically oriented silica films on ITO have been used as electrode supports to evaluate possible confinement effects provided by the mesoporous matrix on the stability of the modified surfaces and their electrochromic properties. Functionalization involved a two-step sequential process: (i) the immobilization of hexaaqua metallic ions, such as Fe(HO), onto the sulfonate-functionalized materials achieved through hydrogen bonding interactions between the sulfonate functions and aqua ligands (water molecules) coordinated to the metallic ions facilitating and stabilizing the attachment of the metallic ions to the sulfonated surfaces; (ii) their coordination to [PWO] species to generate "" the target [Fe(HO)PWO] moieties.
View Article and Find Full Text PDFMimicking and extending the gating properties of biological pores is of paramount interest for the fabrication of membranes that could be used in filtration or drug processing. Here, we build a selective and switchable nanopore for macromolecular cargo transport. Our approach exploits polymer graftings within artificial nanopores to control the translocation of biomolecules.
View Article and Find Full Text PDFThe effect of the density of active molecules in molecular junctions (MJs) has been investigated by using a host/guest strategy. Mixed layers consisting of oligothiophene (BTB) encapsulated by β-cyclodextrin (BTB@β-CD) were generated. Cyclodextrins were then removed, and the pinholes generated were filled with BTB to obtain BTB@BTB films.
View Article and Find Full Text PDFPlasmon-induced diazonium reduction was used to graft an organic semiconductor, namely oligo(bisthienylbenzene) (BTB), onto square arrays of gold nanoparticles (NPs) of various diameters. Grafting was evidenced by scanning electron microscopy (SEM) measurements by the extinction spectra of the localized surface plasmon resonance, as well as by Raman and energy dispersive X-ray (EDX) spectroscopies. We show that BTB is selectively deposited around the NPs.
View Article and Find Full Text PDFPolymers obtained by on-surface chemistry have emerged as a class of promising materials. Here, we propose a new strategy to obtain self-assembled 1D polymers by using photochemical [2+2] cyclo-addition or by using a mild thermal annealing. All nanostructures are fully characterized by using scanning tunneling microscopy at ambient conditions on a graphite surface.
View Article and Find Full Text PDFDiarylethene is a prototypical molecular switch that can be reversibly photoisomerized between its open and closed forms. Ligands bpy-DAE-bpy, consisting of a phenyl-diarylethene-phenyl (DAE) central core and bipyridine (bpy) terminal substituents, are able to self-organize. They are investigated by scanning tunneling microscopy at the solid-liquid interface.
View Article and Find Full Text PDFPhotoactive molecular junctions, based on 4 nm thick diarylethene (DAE) and 5 nm thick bisthienylbenzene (BTB) layers, were fabricated by electrochemical deposition. Total thickness was around 9 nm, that is, above the direct tunneling limit and in the hopping regime. The DAE units were switched between their open and closed forms.
View Article and Find Full Text PDFThis paper describes a rapid bottom-up approach to selectively functionalize gold nanoparticles (AuNPs) on an indium tin oxide (ITO) substrate using the plasmon confinement effect. The plasmonic substrates based on a AuNP-free surfactant were fabricated by electrochemical deposition. Using this bottom-up technique, many sub-30 nm spatial gaps between the deposited AuNPs were randomly generated on the ITO substrate, which is difficult to obtain with a top-down approach (i.
View Article and Find Full Text PDFSingle-molecule junctions (SMJs) have been fabricated using layers generated by diazonium electroreduction. This process creates a C-Au covalent bond between the molecule and the electrode. Rigid oligomers of variable length, based on porphyrin derivatives in their free base or cobalt complex forms, have been grafted on the surface.
View Article and Find Full Text PDFThin layers of cobalt and ruthenium polypyridyl-oligomers with thicknesses between 2 and 8 nm were deposited on gold by electrochemical reduction of diazonium salts. A scanning tunneling microscope was used to create single-molecule junctions (SMJs). The charge transport properties of the Au-[Co(tpy)]-Au ( = 1-4) SMJs do not depend markedly on the oligomer length, have an extremely low attenuation factor (β ∼ 0.
View Article and Find Full Text PDFCorrection for 'Multi-functional switches of ditopic ligands with azobenzene central bridges at a molecular scale' by Imen Hnid et al., Nanoscale, 2019, 11, 23042-23048.
View Article and Find Full Text PDFLigands are designed to have ditopic bipyridine terminal groups linked through photochromic azobenzene central units, which exhibit multi-switchable properties by different external stimuli. The molecule can switch between cis-and trans-conformations at their bipyridine terminal groups upon protonation and at their central azobenzene units upon irradiation of photons. As a result, the system shows four different isomeric states: cis-TRANS, trans-TRANS, cis-CIS and trans-CIS.
View Article and Find Full Text PDFIn this work, we have combined nanosphere lithography with electrochemical reduction of aryldiazonium salts to elaborate nanostructured mixed layers of organic materials. The strategy consists first in the deposition of a close-packed hexagonal monolayer of microbeads used as a mask for the electroreduction of a first aryldiazonium salt. After removing the beads, an ultrathin organic layer with holes remains.
View Article and Find Full Text PDFVarious architectures have been generated and observed by STM at a solid/liquid interface resulting from an in situ chemical reaction between the bipyridine terminal groups of a ditopic ligand and Co(II) ions. Large monodomains of one-dimensional (1D) double wires are formed by Co(II)/ligand coordination, with polymer lengths as long as 150 nm. The polymers are organized as parallel wires 8 nm apart, and the voids between wires are occupied by solvent molecules.
View Article and Find Full Text PDFThe quantum interaction between molecules and electrode materials at molecule/electrode interfaces is a major ingredient in the electron transport properties of organic junctions. Driven by the coupling strength between the two materials, it results mainly in the broadening and energy shift of the interacting molecular orbitals. Using new electrode materials, such as the recently developed semi-conducting two-dimensional nanomaterials, has become a significant advancement in the field of molecular/organic electronics that opens new possibilities for controlling the interfacial electronic properties and thus the charge injection properties.
View Article and Find Full Text PDFThin layers of viologen-based oligomers with thicknesses between 3 and 14 nm were deposited on gold electrodes by electrochemical reduction of a diazonium salt, and then a Ti/Au top contact was applied to complete a solid-state molecular junction (MJ). MJs show symmetric J- V curves and highly efficient long-range transport, with an attenuation factor as small as 0.25 nm.
View Article and Find Full Text PDFMuch of the motivation for developing molecular electronic devices is the prospect of achieving novel electronic functions by varying molecular structure. We describe a "building block" approach for molecular junctions resulting in one, two or three nanometer-thick molecular layers in a commercially proven junction design. A single layer of anthraquinone between carbon electrodes provides a tunnel device with applications in electronic music, and a second layer of a thiophene derivative yields a molecular rectifier with quite different audio characteristics.
View Article and Find Full Text PDFThe formation of copper atomic contacts has been investigated. Copper nanowires were grown by electrochemical deposition, in the scanning electrochemical microscopy (SECM) configuration, from a platinum microelectrode to an indium tin oxide (ITO) substrate. Self-termination leaves copper filaments between the two electrodes with an atomic point contact at the ITO electrode.
View Article and Find Full Text PDFAn electron donor-acceptor dyad has been designed for the creation of large-area molecular junctions (MJ). Diazonium cation electrografting was used to form well controlled monolayers. The robustness of the monolayer enabled the creation of MJs using direct top-coat evaporation with a high yield of operating devices.
View Article and Find Full Text PDFThin layers of oligomers with thickness between 7 and 9 nm were deposited on flat gold electrode surfaces by electrochemical reduction of diazonium reagents, then a Ti(2 nm)/Au top contact was applied to complete a solid-state molecular junction. The molecular layers investigated included donor molecules with relatively high energy HOMO, molecules with high HOMO-LUMO gaps and acceptor molecules with low energy LUMO and terminal alkyl chain. Using an oligo(bisthienylbenzene) based layer, a molecule whose HOMO energy level in a vacuum is close to the Fermi level of the gold bottom electrode, the devices exhibit robust and highly reproducible rectification ratios above 1000 at low voltage (2.
View Article and Find Full Text PDFA plasmonic molecular electronic device, consisting of poly(3,4-ethylenedioxythiophene) (PEDOT) nanowires bridging an ultramicroelectrode and an indium tin oxide (ITO) substrate covered by gold nanoparticles (Au NPs), has been developed. Light irradiation of this device has a dramatic impact on its conductance. Polymer strands, maintained electrochemically in their oxidized, conducting state, reversibly switch to their insulating state upon irradiation by visible-wavelength light, resulting in a sharp decrease in the conductance.
View Article and Find Full Text PDFMolecular junctions consisting of a Ru(bpy) oligomer between conducting carbon contacts exhibit an exponential dependence of junction current on molecular layer thickness (d) similar to that observed for other aromatic devices when d < 4 nm. However, when d > 4 nm, a change in transport mechanism occurs which coincides with light emission in the range of 600-900 nm. Unlike light emission from electrochemical cells or solid-state films containing Ru(bpy), emission is bipolar, occurs in vacuum, has rapid rise time (<5 ms), and persists for >10 h.
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