Self-Assembly of Functionalized Lipophilic Guanosines into Cation-Free Stacked Guanine-Quartets.

The hierarchical self-assembly of various lipophilic guanosines exposing either a phenyl or a ferrocenyl group in the C(8) position was investigated. In a solution, all the derivatives were found to self-assemble primarily into isolated guanine (G)-quartets. In spite of the apparent similar bulkiness of the two substituents, most of the derivatives form disordered structures in the solid state, whereas a specific 8-phenyl derivative self-assembles into an unprecedented, cation-free stacked G-quartet architecture.

Chemical sensing with Au and Ag nanoparticles.

Noble metal nanoparticles (NPs) are ideal scaffolds for the fabrication of sensing devices because of their high surface-to-volume ratio combined with their unique optical and electrical properties which are extremely sensitive to changes in the environment. Such characteristics guarantee high sensitivity in sensing processes. Metal NPs can be decorated with ad hoc molecular building blocks which can act as receptors of specific analytes. By pursuing this strategy, and by taking full advantage of the specificity of supramolecular recognition events, highly selective sensing devices can be fabricated. Besides, noble metal NPs can also be a pivotal element for the fabrication of chemical nose/tongue sensors to target complex mixtures of analytes. This review highlights the most enlightening strategies developed during the last decade, towards the fabrication of chemical sensors with either optical or electrical readout combining high sensitivity and selectivity, along with fast response and full reversibility, with special attention to approaches that enable efficient environmental and health monitoring.

2D hybrid networks of gold nanoparticles: mechanoresponsive optical humidity sensors.

Plasmonic coupling is a fascinating phenomenon occurring between neighboring metal nanostructures. We report a straightforward approach to study such process macroscopically by fabricating 2D networks of gold nanoparticles, interconnected with responsive hygroscopic organic linkers. By controlling the humidity we tune the interparticle distance to reversibly trigger plasmonic coupling collectively over several millimeters.

Supramolecular Self-Assembly in a Sub-micrometer Electrodic Cavity: Fabrication of Heat-Reversible π-Gel Memristor.

The use of biomimetic approaches toward the production of nonsolid yet functional architectures holds potential for the emergence of novel device concepts. Gels, in particular those obtained via self-assembly of π-conjugated molecules, are dynamic materials possessing unique (opto)electronic properties. Their adaptive nature imparts unprecedented responsivity to various stimuli. Hitherto, a viable device platform to electrically probe in situ a sol-gel transition is still lacking. Here we describe the fabrication of a sub-micrometer electrodic cavity, which enables low-voltage electrical operation of π-gels. Thanks to the in situ supramolecular self-assembly of the π-gelator occurring within the cavity, we conceived a novel gel-based memristor whose sol-gel transition is reversible and can be controlled via heating and dc bias. This work opens perspectives toward the fabrication of a novel generation of nonsolid multiresponsive devices.

Self-organization of amino-acid-derived NDI assemblies into a nanofibrillar superstructure with humidity sensitive n-type semiconducting properties.

The hierarchical self-assembly of l-tyrosine substituted naphthalenediimide has been explored in solution by NMR spectroscopy and in the solid-state by atomic force microscopy. Spontaneous non-covalent polymerisation led to the formation of a three-dimensional fibre-like supramolecular polymer with n-type semiconducting properties.

Ultrafast Delamination of Graphite into High-Quality Graphene Using Alternating Currents.

To bridge the gap between laboratory-scale studies and commercial applications, mass production of high quality graphene is essential. A scalable exfoliation strategy towards the production of graphene sheets is presented that has excellent yield (ca. 75 %, 1-3 layers), low defect density (a C/O ratio of 21.2), great solution-processability, and outstanding electronic properties (a hole mobility of 430 cm2 V-1 s-1 ). By applying alternating currents, dual exfoliation at both graphite electrodes enables a high production rate exceeding 20 g h-1 in laboratory tests. As a cathode material for lithium storage, graphene-wrapped LiFePO4 particles deliver a high capacity of 167 mAh g-1 at 1 C rate after 500 cycles.

Periodic potentials in hybrid van der Waals heterostructures formed by supramolecular lattices on graphene.

The rise of 2D materials made it possible to form heterostructures held together by weak interplanar van der Waals interactions. Within such van der Waals heterostructures, the occurrence of 2D periodic potentials significantly modifies the electronic structure of single sheets within the stack, therefore modulating the material properties. However, these periodic potentials are determined by the mechanical alignment of adjacent 2D materials, which is cumbersome and time-consuming. Here we show that programmable 1D periodic potentials extending over areas exceeding 104 nm2 and stable at ambient conditions arise when graphene is covered by a self-assembled supramolecular lattice. The amplitude and sign of the potential can be modified without altering its periodicity by employing photoreactive molecules or their reaction products. In this regard, the supramolecular lattice/graphene bilayer represents the hybrid analogue of fully inorganic van der Waals heterostructures, highlighting the rich prospects that molecular design offers to create ad hoc materials.

Direct Patterning of Organic Functional Polymers through Conventional Photolithography and Noninvasive Cross-Link Agents.

A new technique for direct patterning of functional organic polymers using commercial photolithography setups with a minimal loss of the materials' performances is reported. This result is achieved through novel cross-link agents made by boron- and fluorine-containing heterocycles that can react between themselves upon UV- and white-light exposure.

Enhancing the Liquid-Phase Exfoliation of Graphene in Organic Solvents upon Addition of n-Octylbenzene.

Due to a unique combination of electrical and thermal conductivity, mechanical stiffness, strength and elasticity, graphene became a rising star on the horizon of materials science. This two-dimensional material has found applications in many areas of science ranging from electronics to composites. Making use of different approaches, unfunctionalized and non-oxidized graphene sheets can be produced; among them an inexpensive and scalable method based on liquid-phase exfoliation of graphite (LPE) holds potential for applications in opto-electronics and nanocomposites. Here we have used n-octylbenzene molecules as graphene dispersion-stabilizing agents during the graphite LPE process. We have demonstrated that by tuning the ratio between organic solvents such as N-methyl-2-pyrrolidinone or ortho-dichlorobenzene, and n-octylbenzene molecules, the concentration of exfoliated graphene can be enhanced by 230% as a result of the high affinity of the latter molecules for the basal plane of graphene. The LPE processed graphene dispersions were further deposited onto solid substrates by exploiting a new deposition technique called spin-controlled drop casting, which was shown to produce uniform highly conductive and transparent graphene films.

Self-assembly of diphenylalanine backbone homologues and their combination with functionalized carbon nanotubes.

The integration of carbon nanotubes (CNTs) into organized nanostructures is of great interest for applications in materials science and biomedicine. In this work we studied the self-assembly of ß and γ homologues of diphenylalanine peptides under different solvent and pH conditions. We aimed to investigate the role of peptide backbone in tuning the formation of different types of nanostructures alone or in combination with carbon nanotubes. In spite of having the same side chain, ß and γ peptides formed distinctively different nanofibers, a clear indication of the role played by the backbone homologation on the self-assembly. The variation of the pH allowed to transform the nanofibers into spherical structures. Moreover, the co-assembly of ß and γ peptides with carbon nanotubes covalently functionalized with the same peptide generated unique dendritic assemblies. This comparative study on self-assembly using diphenylalanine backbone homologues and of the co-assembly with CNT covalent conjugates is the first example exploring the capacity of ß and γ peptides to adopt precise nanostructures, particularly in combination with carbon nanotubes. The dendritic organization obtained by mixing carbon nanotubes and peptides might find interesting applications in tissue engineering and neuronal interfacing.

Dispersibility-Dependent Biodegradation of Graphene Oxide by Myeloperoxidase.

Understanding human health risk associated with the rapidly emerging graphene-based nanomaterials represents a great challenge because of the diversity of applications and the wide range of possible ways of exposure to this type of materials. Herein, the biodegradation of graphene oxide (GO) sheets is reported by using myeloperoxidase (hMPO) derived from human neutrophils in the presence of a low concentration of hydrogen peroxide. The degradation capability of the enzyme on three different GO samples containing different degree of oxidation on their graphenic lattice, leading to a variable dispersibility in aqueous media is compared. hMPO fails in degrading the most aggregated GO, but succeeds to completely metabolize highly dispersed GO samples. The spectroscopy and microscopy analyses provide unambiguous evidence for the key roles played by hydrophilicity, negative surface charge, and colloidal stability of the aqueous GO in their biodegradation by hMPO catalysis.

Self-Assembly of an Amphiphilic π-Conjugated Dyad into Fibers: Ultrafast and Ultrasensitive Humidity Sensor.

The self-assembly of an amphiphilic monomolecular electron acceptor-donor dyad into electroactive π-π stacked fibrillar structures can be triggered by irradiation with visible light. These fibers, exposing hydrophilic ethylene glycol in their external shell, show unique characteristics as resistive humidity sensors that exhibit high sensitivity and ultrafast response.

The dramatic effect of the annealing temperature and dielectric functionalization on the electron mobility of indene-C60 bis-adduct thin films.

Herein we report on the charge transport properties of spin-coated thin films of an n-type fullerene derivative, i.e. the indene-C60 bis-adduct (ICBA). In particular, the effects of annealing temperature and duration as well as surface functionalization are explored. Electron mobilities approaching 0.1 cm(2) V(-1) s(-1) are reported.