Novel Insight into the Photophysical Properties and 2D Supramolecular Organization of Poly(3,4-ethylenedioxythiophene)/Permodified Cyclodextrins Polyrotaxanes at the Air-Water Interface.

Two poly(3,4-ethylenedioxythiophene) polyrotaxanes (PEDOT∙TMe-ßCD and PEDOT∙TMe-γCD) end-capped by pyrene (Py) were synthesized by oxidative polymerization of EDOT encapsulated into TMe-ßCD or TMe-γCD cavities with iron (III) chloride (FeCl3) in water and chemically characterized. The effect of TMe-ßCD or TMe-γCD encapsulation of PEDOT backbones on the molecular weight, thermal stability, and solubility were investigated in depth. UV-vis absorption, fluorescence (FL), phosphorescence (PH), quantum efficiencies, and lifetimes in water and acetonitrile were also explored, together with their surface morphology and electrical properties. Furthermore, dynamic light scattering was used to study the hydrodynamic diameter (DH) and z-potential (ZP-ζ) of the water soluble fractions of PEDOT∙TMe-ßCD and PEDOT∙TMe-γCD. PEDOT∙TMe-ßCD and PEDOT∙TMe-γCD exhibited a sharp monodisperse peak with a DH of 55 ± 15 nm and 122 ± 32 nm, respectively. The ZP-ζ value decreased from -31.23 mV for PEDOT∙TMe-ßCD to -20.38 mV for PEDOT∙TMe-γCD, indicating that a negatively charged layer covers their surfaces. Surface pressure-area isotherms and Brewster angle microscopy (BAM) studies revealed the capability of the investigated compounds to organize into sizeable and homogeneous 2D supramolecular assemblies at the air-water interface. The control of the 2D monolayer organization through the thermodynamic parameters of PEDOT∙TMe-ßCD and PEDOT∙TMe-γCD suggests potential for a wide range of optoelectronic applications.

Vertically Heterogeneous 2D Semi-Interpenetrating Networks Based on Cellulose Acetate and Cross-Linked Polybutadiene.

This work reports the feasibility of polybutadiene (PB) cross-linking under UV irradiation in the presence of a linear polymer, cellulose acetate (CA), to form semi-interpenetrating polymer networks at the air-water interface. The thermodynamic properties and the morphology of two-dimensional (2D) CA/PB blends are investigated after UV irradiation and for a wide range of CA volume fractions. A contraction of the mixed Langmuir films is observed independent of the composition, in agreement with that recorded for the individual PB monolayer after cross-linking. The PB network formation is demonstrated by in situ sum-frequency generation spectroscopy on the equivolumic CA/PB mixed film. From Brewster angle microscopy observations, the PB network synthesis does not induce any morphology change at the mesoscopic scale, and all of the mixed films remain homogeneous laterally. In situ neutron reflectometry is used to probe the effect of PB cross-linking on the vertical structure of CA/PB mixed films. For all studied compositions, significant thickening of the films is evidenced, consistent with their contraction ratio. This thickening is accompanied by a partial expulsion of the PB toward the film-air interface, which is attributed to the hydrophobic character of the PB. This phenomenon is stronger for films rich in PB. In particular, the structure of the PB-rich film undergoes a transition from vertically homogeneous to inhomogeneous along the depth. 2D semi-interpenetrating polymer networks can thus be synthesized at the air-water interface with a morphology that is strongly influenced by the polymer-polymer and polymer-environment interactions.

Synthesis, Photophysics, and Langmuir Films of Polyfluorene/Permodified Cyclodextrin Polyrotaxanes.

In the present study, we investigated the effect of permodified 2,3,6-tri-O-trimethylsilyl ß- and γ-cyclodextrin (TMS·ß-CD, TMS·Î³-CD) encapsulation on the optical, electrochemical, morphological, and supramolecular arrangements of a poly[2,7'-(9,9-dioctylfluorene-alt-2',7-fluorene)] PF copolymer. For this purpose, the photophysical properties and Langmuir monolayer formation of PF·TMS·ß-CD and PF·TMS·Î³-CD polyrotaxanes were investigated and compared with those of the reference PF. Surface pressure-area isotherms and Brewster angle microscopy studies indicated the capability of both polyrotaxanes to organize into larger and homogeneous 2D supramolecular assemblies at the air-water interface. The obtained results suggest that the presence of the surrounding TMS·ß-CD and TMS·Î³-CD macrocycles on the PF backbones leads to changes in the conformation and hydrophobicity of the film surfaces. Our investigation offers a method to assess the impact of TMS-CD encapsulation on the control of 2D monolayer formation, with particular attention on the generation of stable PF monolayers for organic electronic devices.

Surface Pressure-Induced Interdiffused Structure Evidenced by Neutron Reflectometry in Cellulose Acetate/Polybutadiene Langmuir Films.

Binary blends of water-insoluble polymers are a versatile strategy to obtain nanostructured films at the air-water interface. However, there are few reported structural studies of such systems in the literature. Depending on the compatibility of the polymers and the role of the air-water interface, one can expect various morphologies. In that context, we probed Langmuir monolayers of cellulose acetate (CA), of deuterated and postoxidized polybutadiene (PBd) and three mixtures of CA/PBd at various concentrations by coupling surface pressure-area isotherms, Brewster angle microscopy (BAM), and neutron reflectometry at the air-water interface to determine their thermodynamic and structural properties. The homogeneity of the films in the vertical direction, averaged laterally over the spatial coherence length of the neutron beam (∼5 µm), was assessed by neutron reflectometry measurements using D2O/H2O subphases contrast-matched to the mixed films. At 5 mN/m, the whole mixed films can be described by a single slightly hydrated thin layer. However, at 15 mN/m, the fit of the reflectivity curves requires a two-layer model consisting of a CA/PBd blend layer in contact with the water, interdiffused with a PBd layer at the interface with air. At intermediate surface pressure (10 mN/m), the determined structure was between those obtained at 5 and 15 mN/m depending on film composition. This PBd enrichment at the air-film interface at high surface pressure, which leads to the PBd depletion in the blend monolayer at the water surface, is attributed to the hydrophobic character of this polymer compared with the predominantly hydrophilic CA.

Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) Copolymer 2D Single Network at the Air-Water Interface.

In this work, Langmuir monolayers based on poly(ethylene glycol)-poly(propylene glycol)-poly(ethylene glycol) (PEG-PPG-PEG) triblock copolymer were in situ stabilized at the air-water interface in the presence of a cross-linking agent, benzene-1,3,5-tricarboxaldehyde (BTC), in the aqueous subphase. The reaction takes place through acid-catalyzed acetalization between the terminal hydroxyl groups of the copolymer and aldehyde functions of the BTC molecules. Mean area per repeat unit measurements as a function of the reaction time show a significant monolayer contraction associated with an increase in its compressibility modulus. In addition, Brewster angle microscopy observations indicate the appearance of higher-density two-dimensional domains, irreversibly formed at constant surface pressure. This is also confirmed on a smaller scale by atomic force microscopy (AFM). These arguments, consistent with copolymer monolayer cross-linking in acidic medium, are supported in situ at the air-water interface by sum-frequency generation (SFG) spectroscopy. Furthermore, PEG-PPG-PEG monolayer cross-linking is not evidenced in alkaline medium, in coherence with the interfacial acid-catalyzed acetalization.

Confinement and Cross-Linking of 1,2-Polybutadiene in Two Dimensions at the Air-Water Interface.

Langmuir monolayers of 1,2-polybutadiene (PB) were investigated by means of surface pressure-area isotherms, Brewster angle microscopy (BAM) observations, and sum-frequency generation (SFG) spectroscopy. A homogeneous and stable monolayer is formed 1.5 h after PB spreading provided that both light and oxygen are present. This was attributed to a slight oxidation of the PB at the air-water interface. The cross-linking of PB under UV photoirradiation was then studied. SFG spectroscopy demonstrates the in situ formation of a two-dimensional network. From surface pressure-area characterizations and BAM experiments, the cross-linked PB monolayer appears significantly denser and more rigid than the non-irradiated monolayer. Atomic force microscopy images reveal an increase by a factor of three in the root-mean-square roughness of the irradiated monolayers compared with the non-irradiated ones.

An autonomous untethered fast soft robotic insect driven by low-voltage dielectric elastomer actuators.

Insects are a constant source of inspiration for roboticists. Their compliant bodies allow them to squeeze through small openings and be highly resilient to impacts. However, making subgram autonomous soft robots untethered and capable of responding intelligently to the environment is a long-standing challenge. One obstacle is the low power density of soft actuators, leading to small robots unable to carry their sense and control electronics and a power supply. Dielectric elastomer actuators (DEAs), a class of electrostatic electroactive polymers, allow for kilohertz operation with high power density but require typically several kilovolts to reach full strain. The mass of kilovolt supplies has limited DEA robot speed and performance. In this work, we report low-voltage stacked DEAs (LVSDEAs) with an operating voltage below 450 volts and used them to propel an insect-sized (40 millimeters long) soft untethered and autonomous legged robot. The DEAnsect body, with three LVSDEAs to drive its three legs, weighs 190 milligrams and can carry a 950-milligram payload (five times its body weight). The unloaded DEAnsect moves at 30 millimeters/second and is very robust by virtue of its compliance. The sub-500-volt operation voltage enabled us to develop 780-milligram drive electronics, including optical sensors, a microcontroller, and a battery, for two channels to output 450 volts with frequencies up to 1 kilohertz. By integrating this flexible printed circuit board with the DEAnsect, we developed a subgram robot capable of autonomous navigation, independently following printed paths. This work paves the way for new generations of resilient soft and fast untethered robots.

Inorganic mixed phase templated by a fatty acid monolayer at the air-water interface: the Mn and Mg case.

We studied by means of Grazing Incidence X-ray Diffraction (GIXD) coupled with X-ray fluorescence spectroscopy the structure of a behenic acid monolayer spread at the surface of Mg2+/Mn2+ mixed aqueous solutions. For the pure Mg2+ and Mn2+ aqueous solutions, the cations induce at the surface different 2D lattice superstructures of the organic monolayer. These superstructures correspond to an inorganic organized monolayer anchored to the hydrophilic group of the ordered behenic acid monolayer. Among the various diffraction peaks, we focused on those characteristics of the behenic acid oblique cell. As the Mg2+ mole fraction x increases in the Mg2+/Mn2+ mixed subphase, a continuous evolution of the oblique cell parameters is observed indicating the insertion of Mg2+ cations in the Mn2+ ordered monolayer. Then, a further increase leads to the appearance of a coexistence between two oblique surface phases. The cell parameters of both phases evolve continuously along the x range of the transition until a single Mg-rich ordered phase is detected. However, although the intensities of the peaks in the coexistence region are in agreement with a first-order phase transition, the cell parameters evolve simultaneously. Considering a thermodynamics analysis, this evidences that, apart from the concentration, another unidentified intensive parameter is varying. We suggest that it is the ionic strength, which appears to be strongly related to the concentrations.

From Homogeneous to Segregated Structure of Poly(dimethylsiloxane)/Cellulose Derivative Mixed Langmuir Films Depending on Composition: An in Situ Neutron Reflectivity Study.

The mixing behavior of deuterated polydimethylsiloxane (PDMSd) and cellulose acetate butyrate (CAB) spread as Langmuir films at the air-water interface was studied by means of surface pressure-area isotherms, Brewster angle microscopy (BAM) observations, and in situ neutron reflectivity. The contrast variation method was used with different D2O/H2O mixtures as subphase, allowing contrast matching to either CAB, PDMSd, or PDMSd/CAB mixed film if homogeneous. At PDMSd volume fractions Φ lower than 0.6, the mixed film is a homogeneous monolayer throughout the film compression, in agreement with the monophasic film observed by BAM and the attractive interactions between PDMSd and CAB evidenced from the isotherm measurements. In contrast, at PDMSd volume fractions Φ higher than 0.6, a vertically segregated structure of the mixed film is highlighted. Indeed, whatever the surface pressure, a bilayer structure is observed with a PDMSd layer in contact with the air over a thin CAB layer in contact with the subphase. These results show that the structure of the film is mainly driven by the PDMSd volume fraction which allows obtaining either a homogeneous membrane which composition can be tuned or a vertically segregated system. In contrast, only the thickness of the layers varies with the surface pressure while the structure of the film is not affected.

Synthesis at the air-water interface of a two-dimensional semi-interpenetrating network based on poly(dimethylsiloxane) and cellulose acetate butyrate.

The UV-induced cross-linking of methacryloxypropyl-terminated poly(dimethylsiloxane) oligomers was studied at the air-water interface either in pure PDMS Langmuir monolayers or in mixed films containing cellulose acetate butyrate. Surface pressure-area isotherms, area measurement at constant surface pressure, Brewster angle microscopy observations, and infrared-visible sum frequency generation (SFG) spectroscopy were combined to follow the evolution of the monolayers upon in situ UV photoirradiation. For both systems, the mean area per repeat unit decreases with irradiation time reflecting the monolayer contraction. In addition, SFG measurements evidence the conversion of the methacrylate groups into unconjugated poly(methacrylate) ones. These results demonstrate PDMS cross-linking, leading to the formation of either a single PDMS network or a PDMS network entrapped in a CAB matrix. The network formation is accompanied by morphology changes as shown by atomic force microscopy on the transferred monolayer. Indeed, filamentous structures appear on both pure and mixed preirradiated monolayers.

Structure and kinetics of fatty acid Langmuir monolayers on zinc salt solutions.

The adsorption of zinc cations under behenic acid Langmuir monolayers was investigated by means of isotherm measurements, grazing incidence X-ray diffraction and Brewster angle microscopy. The structure of the films was characterized as a function of Zn(2+) concentration, for three different counterions (chloride, iodide, bromide) and at two subphase pHs (5.5 and 7.5). At pH 5.5 and in the studied concentration range, Zn(2+) adsorption leads to a condensation of the fatty acid monolayer with the same phase transitions as over pure water. In contrast, at higher pH the organic X-phase is evidenced immediately above a concentration threshold without any ion organization. Even though Cu(2+) and Zn(2+)cations induce both the fatty acid X-phase, the kinetics of its formation appears strongly different. Indeed, as for Mg(2+) and Cd(2+), the intermediate new I-structure is evidenced in the course of Zn(2+) adsorption although superstructures are observed only for Mg(2+) and Cd(2+). However, for Zn(2+), the I-phase evolves to the final state through a new structure called X' and a continuous X'-X transition. Finally, any effect of the counterion is evidenced neither during the kinetic process nor in the final state.

Limited propagation of lattice distortion in trilayer Langmuir-Blodgett films: correlation with mesoscopic structure.

The structure of trilayer Langmuir-Blodgett (LB) films on oxidized silicon wafers has been investigated using grazing incidence X-ray diffraction at various incidence angles and atomic force microscopy (AFM). These films are formed by two behenic acid (BA) layers and a third monolayer of amphiphilic molecules having different architectures. These molecules have the same polar head and differ from each other by the chain, either saturated or unsaturated hydrogenated or semi-fluorinated. The structure of the first BA monolayer appears as unchanged in all cases, whereas a condensation of the second BA monolayer is evidenced when the third layer is not formed with the saturated hydrogenated chain. We interpret this condensation as resulting from the mismatch between the lattices of the second BA layer and the external monolayer, possibly associated with the formation of a new monolayer-air interface creating line tension effects. Line tension estimation has also been made from the size of the holes observed in the different LB films.

Poly(azobenzene acrylate-co-fluorinated acrylate) spin-coated films: influence of the composition on the photo-controlled wettability.

The wetting properties of spin-coated films of copolymers based on azobenzene and fluorinated units have been investigated. The copolymers, denoted as poly(Azo-co-AcRf6), have been synthesized by free-radical polymerization of different proportions of acrylate monomers bearing either an azobenzene group or a semifluorinated side chain. The UV-visible spectroscopy analysis of the different spin-coating films through a cycle of UV and visible light irradiation indicates the reversible trans-cis isomerization of azobenzene groups. Simultaneously, atomic force microscopy shows that surface roughness does not exceed 1 nm. Advancing and receding contact angles of water and diiodomethane have been measured before and after UV photoirradiation of the different surfaces. In particular, a decrease in the advancing contact angles has been observed upon trans-cis isomerization of azobenzene groups. Switching variations up to 50° have been evidenced without any introduction of surface nanoroughness. Surface free-energy evaluations have been deduced from these measurements, including dispersive and polar components. The results show that, through surface composition and UV photoirradiation, a large range of surface free-energies can be obtained, from 7 to 46 mN·m(-1).

Sum-frequency generation spectroscopy of cinnamate modified cellulosic polymer at the air-water interface.

Monolayers of a cellulosic polymer bearing cinnamate groups were characterized at the air-water interface by combining isotherm measurements, Brewster angle microscopy, and infrared-visible sum-frequency generation (SFG) spectroscopy. This spectroscopic technique was used to detect the photochemical behavior of the cinnamate groups upon UV photoirradiation of the monolayers. From the disappearance of the C═C mode and the absence of a change in the C═O mode, it could be concluded that isomerization is the dominant photoreaction for a monolayer of this polymer. This conclusion was corroborated by a comparison of the spectra of the monolayer after irradiation with spectra measured for monolayers spread from preirradiated solutions, for which it is known that isomerization is the main process.

Laser-heating-induced displacement of surfactants on the water surface.

We report a combined vibrational sum-frequency generation (SFG) spectroscopy, Brewster angle microscopy (BAM), and ellipsometry study of different surfactants on water as a function of surfactant density. Vibrational SFG spectra of surfactants on the water surface in a Langmuir trough have been measured in both the surfactant CH and the water OH stretch regions. At low densities, the SFG signal generated at the surface in the presence of the surfactant is indistinguishable from the SFG signal generated at the clean water-air interface. When the surfactant density increases, i.e., upon compressing the monolayer, a very sudden increase in the SFG signal in both the CH and OH spectral regions is observed. For higher laser fluences, this stepwise increase occurs at increasingly higher surfactant densities. Since BAM shows that surfactant molecules are clearly present at these low densities, we conclude that at low surfactant density the laser beam displaces relatively high-density domains with surfactants in the liquid expanded phase out of the region of the laser focus. This is a consequence of the thermal gradient induced by local heating of the water phase with the monolayer on top due to repetitive laser excitation at 1 kHz. It can be circumvented by using a rotating trough. In this manner, the sampled surface area can be refreshed, allowing artifact-free vibrational SFG spectra to be measured down to the very lowest surfactant densities. In ellipsometry experiments, a similar step can be noticed, which, however, is of a different nature; i.e., it is not related to heating (the laser fluence is very low and the light nonresonant) but to a molecular transition. The occurrence of the step in ellipsometry as a function of area per molecule depends critically on the preparation of the monolayer. By giving the molecules time and space to relax during the preparation of the monolayer, this step could also be eliminated.

Contribution toward comprehension of contact angle values on single polydimethylsiloxane and poly(ethylene oxide) polymer networks.

The large application ranges of polydimethylsiloxane (PDMS) and poly(ethylene oxide) (PEO) based materials justify the importance of controlling polymer surface properties including morphology and wettability behavior. However, it appears that the reported contact angle values of PDMS surfaces show significant scattering which cannot always be interpreted in terms of sole chemical data. In addition, few values are reported concerning pure PEO surfaces, since the polymer generally swells in the presence of water. Thus, in order to correlate surface properties with sample preparation, several single PDMS and PEO polymer networks were synthesized with varying cross-linkers and different cross-linking densities. First, the sample surface topography was systematically analyzed by atomic force microscopy (AFM). It was proven that the removal process of the polymer film from the mold plays a significant role in surface topography according to the vitreous or rubbery state of the given polymer network at room temperature irrespective of mold surface treatment. AFM-scale smooth surfaces can be obtained for all the samples by removing them systematically from the mold at a temperature below the α-relaxation temperature. Dynamic water contact angles were then measured and the values analyzed as a function of cross-linker nature and cross-linking density.

Evolution toward the X phase of fatty acid Langmuir monolayers on a divalent cation solution.

The structure of docosanoic acid monolayers spread over chloride salt solutions of copper was investigated by means of isotherm measurements, grazing incidence X-ray diffraction, and Brewster angle microscopy, as a function of the ion concentration and at two subphase pHs (5.5 and 7.5). The X phase is evidenced immediately above a concentration threshold which depends on the pH. The sequence of phases leading to this rigid phase involves two different processes depending on the pH. The initial L(2h) phase evolves toward an X-like phase through a phase transition which is first order at pH 7.5 while it is second order at pH 5.5. The transition is then followed by a continuous evolution toward the X phase.

Sliding behavior of liquid droplets on tilted Langmuir-Blodgett surfaces.

The sliding behavior of liquid droplets on inclined Langmuir-Blodgett surfaces was investigated. The critical sliding angle defined as the tilt angle of the surface at which the drop slides down as well as the advancing and receding contact angles was measured for five different liquids on five surfaces. In addition, the contact line geometry was analyzed at critical sliding angle. The experimental relationship between the surface tension forces resulting from contact angle hysteresis and the weight of the drop was compared to theoretical predictions. Even though the shape of the drop bases was found as skewed ellipses, a model assuming parallel-sided elongated drops is shown to describe reasonably the experimental values. This result probably indicates the main influence of the capillary forces at the rear and front edges of the drop with respect to that exerted on the lateral sides.

Molecular recognition controls the organization of mixed self-organized bis-urea-based mineralization templates for CaCO(3).

To investigate the role and importance of nondirectional electrostatic interactions in mineralization, we explored the use of Langmuir monolayers in which the charge density can be tuned using supramolecular interactions. It is demonstrated that, in mixed Langmuir monolayers of bis-ureido surfactants containing oligo(ethylene oxide) and ammonium head groups associated with matching or nonmatching spacers between the two urea groups, the organization is controlled by molecular recognition. These different organizations of the molecules lead to different nucleation behavior in the mineralization of calcium carbonate. The formation of modified calcite and vaterite crystals was induced selectively by different phases of mixed monolayers, and they were characterized by SEM, TEM, and SAED. To understand the influence of the mixed Langmuir monolayers on the crystallization process, we studied the mixtures by means of (pi-A) isotherms and Brewster angle microscopy observations. Infrared reflection-absorption spectroscopy experiments were also performed on Langmuir-Schaefer films. From these results, we conclude that the local organization of the two systems discussed here gives rise to differences in both charge density and flexibility that together determine not only polymorph selection and the nucleation face but also the morphology of the resulting crystals.