Out-of-Equilibrium Mechanical Disruption of β-Amyloid-Like Fibers using Light-Driven Molecular Motors.

Artificial molecular motors have the potential to generate mechanical work on their environment by producing autonomous unidirectional motions when supplied with a source of energy. However, the harnessing of this mechanical work to subsequently activate various endoenergetic processes that can be useful in materials science remains elusive. Here, it is shown that by integrating a light-driven rotary motor through hydrogen bonds in a β-amyloid-like structure forming supramolecular hydrogels, the mechanical work generated during the constant rotation of the molecular machine under UV irradiation is sufficient to disrupt the β-amyloid fibers and to trigger a gel-to-sol transition at macroscopic scale.

Shape-assisted self-assembly.

Self-assembly and molecular recognition are critical processes both in life and material sciences. They usually depend on strong, directional non-covalent interactions to gain specificity and to make long-range organization possible. Most supramolecular constructs are also at least partially governed by topography, whose role is hard to disentangle.

Supramolecular Polymerization of Triarylamine-Based Macrocycles into Electroactive Nanotubes.

A -symmetric triarylamine-based macrocycle (i.e., hexaaza[1]paracyclophane), decorated with six lateral amide functions, is synthesized by a convergent and modular strategy.

Interfacial Behavior of Oligo(Ethylene Glycol) Dendrons Spread Alone and in Combination with a Phospholipid as Langmuir Monolayers at the Air/Water Interface.

Dendrons consisting of two phosphonate functions and three oligo(ethylene glycol) (OEG) chains grafted on a central phenoxyethylcarbamoylphenoxy group were synthesized and investigated as Langmuir monolayers at the surface of water. The OEG chain in the position was grafted with a -Bu end-group, a hydrocarbon chain, or a partially fluorinated chain. These dendrons are models of structurally related OEG dendrons that were found to significantly improve the stability of aqueous dispersions of iron oxide nanoparticles when grafted on their surface.

Microbubbles decorated with dendronized magnetic nanoparticles for biomedical imaging: effective stabilization via fluorous interactions.

Dendrons fitted with three oligo(ethylene glycol) (OEG) chains, one of which contains a fluorinated or hydrogenated end group and bears a bisphosphonate polar head (C X OEGDen, X = F or H; = 2 or 4), were synthesized and grafted on the surface of iron oxide nanoparticles (IONPs) for microbubble-mediated imaging and therapeutic purposes. The size and stability of the dendronized IONPs (IONP@C X OEGDen) in aqueous dispersions were monitored by dynamic light scattering. The investigation of the spontaneous adsorption of IONP@C X OEGDen at the interface between air or air saturated with perfluorohexane and an aqueous phase establishes that exposure to the fluorocarbon gas markedly increases the rate of adsorption of the dendronized IONPs to the gas/water interface and decreases the equilibrium interfacial tension.

-Heterocyclic Carbene-Platinum Complexes Featuring an Anthracenyl Moiety: Anti-Cancer Activity and DNA Interaction.

A platinum (II) complex stabilized by a pyridine and an N-heterocyclic carbene ligand featuring an anthracenyl moiety was prepared. The compound was fully characterized and its molecular structure was determined by single-crystal X-ray diffraction. The compound demonstrated high in vitro antiproliferative activities against cancer cell lines with IC ranging from 10 to 80 nM.

Covalently Trapped Triarylamine-Based Supramolecular Polymers.

C -Symmetric triarylamine trisamides (TATAs), decorated with three norbornene end groups, undergo supramolecular polymerization and further gelation by π-π stacking and hydrogen bonding of their TATA cores. By using subsequent ring-opening metathesis polymerization, these physical gels are permanently crosslinked into chemical gels. Detailed comparisons of the supramolecular stacks in solution, in the physical gel, and in the chemical gel states, are performed by optical spectroscopies, electronic spectroscopies, atomic force microscopy, electronic paramagnetic resonance spectroscopy, X-ray scattering, electronic transport measurements, and rheology.

Temperature Control of Sequential Nucleation-Growth Mechanisms in Hierarchical Supramolecular Polymers.

Upon cooling in solution, chiral triarylamine tris-amide unimers produce organogels by stacking into helical supramolecular polymers, which subsequently bundle into larger fibers. Interestingly, circular dichroism, vibrational circular dichroism, and AFM imaging of the chiral self-assemblies revealed that monocolumnar P-helical fibrils formed upon fast cooling, whereas bundled M-superhelical fibers formed upon slow cooling. The mechanistic study of this structural bifurcation reveals the presence of a strong memory effect, reminiscent of a complex stepwise combination of primary and secondary nucleation-growth processes.

Supramolecular Electropolymerization.

Gaining control over supramolecular polymerization mechanisms is of high fundamental interest to understand self-assembly and self-organization processes at the nanoscale. It is also expected to significantly impact the design and improve the efficiency of advanced materials and devices. Up to now, supramolecular polymerization has been shown to take place from unimers in solution, mainly by variations of temperature or of concentration.

3D supramolecular self-assembly of [60]fullerene hexaadducts decorated with triarylamine molecules.

A clickable fullerene hexa-adduct scaffold has been functionalized with twelve triarylamine subunits. The light-triggered self-assembly of this molecular unit leads to 3D honeycomb-like structures with inner pores of around 10 nm diameter. Multiple grafting of triarylamine subunits onto a hard-core C unit increases the dimensionality of the self-assembly process by reticulating the 1D nanowires typically obtained from the supramolecular polymerization of triarylamine monomers.

Anisotropic Self-Assembly of Supramolecular Polymers and Plasmonic Nanoparticles at the Liquid-Liquid Interface.

The study of supramolecular polymers in the bulk, in diluted solution, and at the solid-liquid interface has recently become a major topic of interest, going from fundamental aspects to applications in materials science. However, examples of supramolecular polymers at the liquid-liquid interface are mostly unexplored. Here, we describe the supramolecular polymerization of triarylamine molecules and their light-triggered organization at a chloroform-water interface.

Self-assembly of supramolecular triarylamine nanowires in mesoporous silica and biocompatible electrodes thereof.

Biocompatible silica-based mesoporous materials, which present high surface areas combined with uniform distribution of nanopores, can be organized in functional nanopatterns for a number of applications. However, silica is by essence an electrically insulating material which precludes applications for electro-chemical devices. The formation of hybrid electroactive silica nanostructures is thus expected to be of great interest for the design of biocompatible conducting materials such as bioelectrodes.

Supramolecular Organic Nanowires as Plasmonic Interconnects.

Metallic nanostructures are able to interact with an incident electromagnetic field at subwavelength scales by plasmon resonance which involves the collective oscillation of conduction electrons localized at their surfaces. Among several possible applications of this phenomenon, the theoretical prediction is that optical circuits connecting multiple plasmonic elements will surpass classical electronic circuits at nanoscale because of their much faster light-based information processing. However, the placement and coupling of metallic elements smaller than optical wavelengths currently remain a formidable challenge by top-down manipulations.

Hierarchical Self-Assembly of Supramolecular Muscle-Like Fibers.

An acid-base switchable [c2]daisy chain rotaxane terminated with two 2,6-diacetylamino pyridine units has been self-assembled with a bis(uracil) linker. The complementary hydrogen-bond recognition patterns, together with lateral van der Waals aggregations, result in the hierarchical formation of unidimensional supramolecular polymers associated in bundles of muscle-like fibers. Microscopic and scattering techniques reveal that the mesoscopic structure of these bundles depends on the extended or contracted states that the rotaxanes show within individual polymer chains.

Hydrogen-Bonded Multifunctional Supramolecular Copolymers in Water.

We have investigated the self-assembly in water of molecules having a single hydrophobic bis-urea domain linked to different hydrophilic functional side chains, i.e., bioactive peptidic residues and fluorescent cyanine dyes.

Light-controlled morphologies of self-assembled triarylamine-fullerene conjugates.

A family of triarylamine-fullerene conjugates has been synthesized and shown to self-assemble upon light stimulation in chlorinated solvents. This light-induced process primarily involves excitation of triarylamine derivatives, which then oxidize and stack with their neutral counterparts to form charge transfer complexes in the form of p-conducting channels, while fullerenes are consequently enforced in coaxial n-conducting columnar arrangements. These supramolecular heterojunctions can be organized over very long distances in micrometric fibers when a controlled amount of photons is provided from a white light source to initiate the process.

Macroscopic contraction of a gel induced by the integrated motion of light-driven molecular motors.

Making molecular machines that can be useful in the macroscopic world is a challenging long-term goal of nanoscience. Inspired by the protein machinery found in biological systems, and based on the theoretical understanding of the physics of motion at the nanoscale, organic chemists have developed a number of molecules that can produce work by contraction or rotation when triggered by various external chemical or physical stimuli. In particular, basic molecular switches that commute between at least two thermodynamic minima and more advanced molecular motors that behave as dissipative units working far from equilibrium when fuelled with external energy have been reported.

Control over nanostructures and associated mesomorphic properties of doped self-assembled triarylamine liquid crystals.

We have synthesized a series of triarylamine-cored molecules equipped with an adjacent amide moiety and dendritic peripheral tails in a variety of modes. We show by (1) H NMR and UV/Vis spectroscopy that their supramolecular self-assembly can be promoted in solution upon light stimulation and radical initiation. In addition, we have probed their molecular arrangements and mesomorphic properties in the bulk by integrated studies on their film state by using differential scanning calorimetry (DSC), variable-temperature polarizing optical microscopy (VT-POM), variable-temperature X-ray diffraction (VT-XRD), and atomic force microscopy (AFM).

Atomic force microscopy study of DNA flexibility on short length scales: smooth bending versus kinking.

The apparently anomalous flexibility of DNA on short length scales has attracted a lot of attention in recent years. We use atomic force microscopy (AFM) in solution to directly study the DNA bending statistics for small lengths down to one helical turn. The accuracy of experimental estimates could be improved due to a large data volume and a refined algorithm for image processing and measuring bend angles.

Supramolecular self-assembly and radical kinetics in conducting self-replicating nanowires.

By using a combination of experimental and theoretical tools, we elucidate unique physical characteristics of supramolecular triarylamine nanowires (STANWs), their packed structure, as well as the entire kinetics of the associated radical-controlled supramolecular polymerization process. AFM, small-angle X-ray scattering, and all-atomic computer modeling reveal the two-columnar "snowflake" internal structure of the fibers involving the π-stacking of triarylamines with alternating handedness. The polymerization process and the kinetics of triarylammonium radicals formation and decay are studied by UV-vis spectroscopy, nuclear magnetic resonance and electronic paramagnetic resonance.

Healable supramolecular polymers as organic metals.

Organic materials exhibiting metallic behavior are promising for numerous applications ranging from printed nanocircuits to large area electronics. However, the optimization of electronic conduction in organic metals such as charge-transfer salts or doped conjugated polymers requires high crystallinity, which is detrimental to their processability. To overcome this problem, the combination of the electronic properties of metal-like materials with the mechanical properties of soft self-assembled systems is attractive but necessitates the absence of structural defects in a regular lattice.

Surface charge effects on the 2D conformation of supercoiled DNA.

We have adsorbed plasmid pUc19 DNA on a supported bilayer. By varying the fraction of cationic lipids in the membrane, we have tuned the surface charge. Plasmid conformations were imaged by Atomic Force Microscopy (AFM).

DNA flexibility on short length scales probed by atomic force microscopy.

Unusually high bending flexibility has been recently reported for DNA on short length scales. We use atomic force microscopy (AFM) in solution to obtain a direct estimate of DNA bending statistics for scales down to one helical turn. It appears that DNA behaves as a Gaussian chain and is well described by the wormlike chain model at length scales beyond 3 helical turns (10.

Light-triggered self-construction of supramolecular organic nanowires as metallic interconnects.

The construction of soft and processable organic material able to display metallic conduction properties-a large density of freely moving charges-is a major challenge for electronics. Films of doped conjugated polymers are widely used as semiconductor devices, but metallic-type transport in the bulk of such materials remains extremely rare. On the other hand, single-walled carbon nanotubes can exhibit remarkably low contact resistances with related large currents, but are intrinsically very difficult to isolate and process.