Boron Cluster Anions Dissolve En Masse in Lipids Causing Membrane Expansion and Thinning.

Boron clusters are applied in medicinal chemistry because of their high stability in biological environments and intrinsic ability to capture neutrons. However, their intermolecular interactions with lipid membranes, which are critical for their cellular delivery and biocompatibility, have not been comprehensively investigated. In this study, we combine different experimental methods - Langmuir monolayer isotherms at the air-water interface, calorimetry (DSC, ITC), and scattering techniques (DLS, SAXS) - with MD simulations to evaluate the impact of closo-dodecaborate clusters on model membranes of different lipid composition.

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.

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

In the present study, we investigated the effect of permodified 2,3,6-tri--trimethylsilyl β- and γ-cyclodextrin (TMS·β-CD, TMS·γ-CD) encapsulation on the optical, electrochemical, morphological, and supramolecular arrangements of a poly[2,7'-(9,9-dioctylfluorene--2',7-fluorene)] copolymer. For this purpose, the photophysical properties and Langmuir monolayer formation of and polyrotaxanes were investigated and compared with those of the reference . 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.

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.

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.

Poly(ethylene glycol)--poly(propylene glycol)--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 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.

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.

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 Mg/Mn mixed aqueous solutions. For the pure Mg and Mn 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.

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.

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.

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.

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.

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.

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.

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.

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.

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).

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.

Spontaneous polymerization at the air-water interface: a Brewster angle microscopy study.

When a dioctadecyldimethylammonium bromide (DODA) monolayer is spread onto a styrene sulfonate (SSt) aqueous solution, this monomer undergoes a spontaneous polymerization process [Fichet, O; Teyssié, D. Macromolecules 2002, 35, 5352]. However, the polymer synthesized in this monolayer cannot be investigated by classical characterization techniques.

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.