Cationic-Surfactant-Coated Mica Surfaces below the Critical Micellar Concentration: 1. Patchy Structures As Revealed by Peak Force Tapping AFM Mode.

The morphology and structure of the self-assembled surfactant aggregates at the solid-liquid interface remain controversial. For the well-studied system of cationic cetyltrimethylammonium bromide (C16TAB) adsorbed onto the opposite negatively charged, atomically smooth mica surface, a variety of surface aggregates have been previously reported: AFM imaging pointing to cylinders and surface micelles as opposed to mono/bilayer-like structures revealed by neutron and X-ray reflectometry, NMR, spectroscopic techniques, and numerical simulations. To reconcile with the latter results, we revisit the morphometry of the C16TAB-coated mica surfaces using the recent peak force tapping (PFT-AFM) mode that allows fragile structures to be imaged with the lowest possible applied force. The evolution of the structural organization at the mica-water interface is investigated above the Krafft boundary over a wide concentration range (from 1/1000 to 2 cmc) after long equilibration times to ensure thermodynamic equilibrium. A complex but fairly complete picture has emerged: At very low concentrations, the C16TAB surfactants adsorb as isolated molecules before forming small clusters. Above 1/140 cmc, monolayer-like stripes are formed. As the concentration is increased, a connected network of these patches progressively covers the mica substrate. Above 1/80 cmc, bilayer-like patches build on top of the underlying monolayer, and ultimately a complete bilayer (at about half the cmc) covers the entire mica substrate. Thanks to the less invasive PFT-AFM imaging mode, our observations not only agree with the theoretical predictions and numerical simulations but also reconcile, at last, the direct observations by means of the AFM imaging technique with the results obtained with other techniques.

2D Spherulites of a Semi-Fluorinated Alkane: Controlled Access to Either Radial Or Ring-Banded Morphologies.

Thin films of a semi-fluorinated alkane cast onto solid substrates consist of well-formed two-dimensional non-birefringent ring-banded and/or radial spherulites. Controlling the experimental conditions allows orientation of the crystallization toward either radial-only or ring-banded-only morphologies. Intermediate states were also captured in which both radial and ring-banded spherulites coexist. Monitoring of the formation of these intermediate states brought evidence for a first crystallization mode that sweeps radially outwards from a central nucleus until the propagating front edge experiences a second crystallization mode that proceeds through a diffusion-controlled rhythmic crystallization mechanism that leads to high (≈2 µm) concentric ridges. These 2D spherulites were investigated by optical and atomic force microscopies, interferometric profilometry, and off-specular neutron scattering.

Two-Dimensional Radial or Ring-Banded Nonbirefringent Spherulites of Semifluorinated Alkanes Coexistent with Close-Packed Self-Assembled Surface Nanodomains.

A series of semifluorinated alkanes (C nF2 n+1C mH2 m+1 diblocks, F n H m, n = 6, 8, 10; m = 16, 18, 20), when cast as films onto solid substrates, were found to form ring-banded or radial spherulites when heated above their isotropic temperature and subsequently cooled down to room temperature, demonstrating that the formation of two-dimensional (2D) spherulites is a general feature of molecular fluorocarbon-hydrocarbon diblocks. These spherulites are not birefringent, a seldom encountered feature for such structures (never, so far, for spherulites made of small molecules). They also provide examples of fluorinated 2D spherulites. Film morphology was analyzed by optical microscopy, interferometric profilometry, atomic force microscopy (AFM), and scanning electron microscopy. Increasing the length of the Fn segment favors the formation of ring-banded spherulites, whereas short Fn segments tend to favor extended radial stripes. Variation of the cooling rate provides control over the size and morphology of the spherulites: slow cooling promotes fibers and radial spherulites, whereas fast cooling fosters ring-banded spherulites. The AFM studies of F10 H16 films revealed that the latter consist of stacks of regularly spaced lamellae. We also observed that, remarkably, stacked lamellae (repeating distance ∼6 nm) can coexist with a layer of close-packed monodisperse circular self-assembled surface nanodomains of Fn Hm diblocks (∼30 nm in diameter); the latter are known to form from such diblocks at interfaces at room temperature. Substrates partially covered with F10 H16 contain incomplete ring-banded spherulites and smaller objects in which the lamellae and circular nanodomains coexist.

Interplay between structure and relaxation in polyurea networks: the point of view from a novel method of cooperativity analysis of dielectric response.

The influence of structural constraints on the relaxation dynamics of three polyurea networks with a varying degree of crosslinking, has been studied by means of a thorough analysis of broadband dielectric spectroscopy measurements. Two different relaxation processes are observed, namely, a fast process involving the soft poly(propylene oxide) chains, and a slower and much broader process associated with the immediate surroundings of the hard crosslinkers. Microphase separation in soft and hard domains characterizes the systems in the presence of hydrogen bonding. In this case, different confinement conditions are explored by varying the soft chain length; overall, so called "adsorption" effects dominate. With respect to both cooperativity and the rearrangement energy threshold in fast relaxation, it is found that the enhancement of configurational constraints is similar to cooling, but only on qualitative grounds. An upper bound of the hard domains' interface thickness, in which the slow relaxation is believed to take place, is estimated from the analysis of the fast relaxation in the system characterized by the highest degree of confinement, taking into account the results of the structural analysis. Dropping the hydrogen bonding mechanism, phase separation does not occur anymore and the configurational constraints at the ends of the soft chains are reduced, leaving just those imposed by the rigid crosslinkers. This leads to a significant increase in cooperativity on approaching the glass transition, and to a complex behavior that is thoroughly discussed in comparison with those observed in the micro-segregated systems.

Polymer multilayer films obtained by electrochemically catalyzed click chemistry.

We report the covalent layer-by-layer construction of polyelectrolyte multilayer (PEM) films by using an efficient electrochemically triggered Sharpless click reaction. The click reaction is catalyzed by Cu(I) which is generated in situ from Cu(II) (originating from the dissolution of CuSO(4)) at the electrode constituting the substrate of the film. The film buildup can be controlled by the application of a mild potential inducing the reduction of Cu(II) to Cu(I) in the absence of any reducing agent or any ligand. The experiments were carried out in an electrochemical quartz crystal microbalance cell which allows both to apply a controlled potential on a gold electrode and to follow the mass deposited on the electrode through the quartz crystal microbalance. Poly(acrylic acid) (PAA) modified with either alkyne (PAA(Alk)) or azide (PAA(Az)) functions grafted onto the PAA backbone through ethylene glycol arms were used to build the PEM films. Construction takes place on gold electrodes whose potentials are more negative than a critical value, which lies between -70 and -150 mV vs Ag/AgCl (KCl sat.) reference electrode. The film thickness increment per bilayer appears independent of the applied voltage as long as it is more negative than the critical potential, but it depends upon Cu(II) and polyelectrolyte concentrations in solution and upon the reduction time of Cu(II) during each deposition step. An increase of any of these latter parameters leads to an increase of the mass deposited per layer. For given buildup conditions, the construction levels off after a given number of deposition steps which increases with the Cu(II) concentration and/or the Cu(II) reduction time. A model based on the diffusion of Cu(II) and Cu(I) ions through the film and the dynamics of the polyelectrolyte anchoring on the film, during the reduction period of Cu(II), is proposed to explain the major buildup features.

Experimental evidence for a surface concentration-dependent mechanism of formation of hemimicelles in Langmuir monolayers of semi-fluorinated alkanes.

We show that formation of surface hemimicelles by a series of molecular semi-fluorinated alkanes CFCH (F8Hm diblocks; = 14, 16, 18, 20) in Langmuir-Blodgett monolayers is not promoted by surface pressure, but depends on the surface area available before transfer, hence on a critical surface concentration. Evidence is provided for the presence of isolated micelles at zero surface pressure (very large molecular area) for certain FnHm diblocks. It is the molecular structure of the diblock that essentially determines the morphology of the hemimicelles, independently of compression conditions.

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. Here, we show that organic supramolecular triarylamine nanowires of ≈1 nm in diameter are able to act as plasmonic waveguides. Their self-assembly into plasmonic interconnects between arrays of gold nanoparticles leads to the bottom-up construction of basic optical nanocircuits. When the resonance modes of these metallic nanoparticles are coupled through the organic nanowires, the optical conductivity of the plasmonic layer dramatically increases from 259 to 4271 Ω(-1)·cm(-1). We explain this effect by the coupling of a hot electron/hole pair in the nanoparticle antenna with the half-filled polaronic band of the organic nanowire. We also demonstrate that the whole hybrid system can be described by using the abstraction of the lumped circuit theory, with a far field optical response which depends on the number of interconnects. Overall, our supramolecular bottom-up approach opens the possibility to implement processable, soft, and low cost organic plasmonic interconnects into a large number of applications going from sensing to metamaterials and information technologies.

Size-selective 2D ordering of gold nanoparticles using surface topography of self-assembled diamide template.

Size-selective organization of ~2 nm dodecanethiol stabilized gold nanoparticles (AuNPs) into periodic 1D arrays by using the surface topographical features of a soft template is described. The template consists of micrometer length nanotapes organized into nanosheets with periodic valleys running along their length and is generated by the hierarchical self-assembly of a diamide molecule (BHPB) in cyclohexane. The AuNP ordering achieved simply by mixing the preformed template with the readily available ~2 nm dodecanethiol stabilized AuNPs is comparable to those obtained using programmable DNA and functional block copolymers. The observed periodicity of the AuNP arrays provided valuable structural clues about the organization of nanotapes into nanosheets. Self-assembling BHPB molecules in the presence of AuNPs by heating and cooling the two components led to a comparatively disordered organization because the template structure was changed under these conditions. Moreover, the template could not order larger AuNPs (~5 nm) into a similar 1D array, owing to the steric restriction imposed by the dimension of the valleys on the template. Interestingly, this geometric constraint led to AuNP size sorting when a polydisperse sample (2.5 ± 0.9 nm) was used for organization, with AuNPs attached to the template edges being larger (≥2.2 ± 0.9 nm) than those associated to the inner valleys (1.6 ± 0.8 nm). This is a unique example of size-sorting induced by the surface topographical features of a soft template.