Interface-Templated Crystal Growth in Sodium Dodecyl Sulfate Solutions with NaCl.

Many ionic surfactants, such as sodium dodecyl sulfate (SDS) crystallize out of solution if the temperature falls below the crystallization boundary. The crystallization temperature is impacted by solution properties and can be decreased with the addition of salt. We studied SDS crystallization at liquid/vapor interfaces from solutions at high ionic strength (sodium chloride). We show that the surfactant crystals at the surface grow from adsorbed SDS molecules, as evidenced by the preferential orientation of the crystals identified by using grazing incidence X-ray diffraction. We find a unique time scale for the crystal growth from the evolution of structure, surface tension, and visual inspection, which can be controlled through varying the SDS or NaCl concentrations.

Opportunities and new developments for the study of surfaces and interfaces in soft condensed matter at the SIRIUS beamline of Synchrotron SOLEIL.

The SIRIUS beamline of Synchrotron SOLEIL is dedicated to X-ray scattering and spectroscopy of surfaces and interfaces, covering the tender to mid-hard X-ray range (1.1-13 keV). The beamline has hosted a wide range of experiments in the field of soft interfaces and beyond, providing various grazing-incidence techniques such as diffraction and wide-angle scattering (GIXD/GIWAXS), small-angle scattering (GISAXS) and X-ray fluorescence in total reflection (TXRF). SIRIUS also offers specific sample environments tailored for in situ complementary experiments on solid and liquid surfaces. Recently, the beamline has added compound refractive lenses associated with a transfocator, allowing for the X-ray beam to be focused down to 10 µm × 10 µm while maintaining a reasonable flux on the sample. This new feature opens up new possibilities for faster GIXD measurements at the liquid-air interface and for measurements on samples with narrow geometries.

Influence of the Surface Chemistry of Metal-Organic Polyhedra in Their Assembly into Ultrathin Films for Gas Separation.

The formation of ultrathin films of Rh-based porous metal-organic polyhedra (Rh-MOPs) by the Langmuir-Blodgett method has been explored. Homogeneous and dense monolayer films were formed at the air-water interface either using two different coordinatively alkyl-functionalized Rh-MOPs (HRhMOP(diz)12 and HRhMOP(oiz)12) or by in situ incorporation of aliphatic chains to the axial sites of dirhodium paddlewheels of another Rh-MOP (OHRhMOP) at the air-liquid interface. All these Rh-MOP monolayers were successively deposited onto different substrates in order to obtain multilayer films with controllable thicknesses. Aliphatic chains were partially removed from HRhMOP(diz)12 films post-synthetically by a simple acid treatment, resulting in a relevant modification of the film hydrophobicity. Moreover, the CO2/N2 separation performance of Rh-MOP-supported membranes was also evaluated, proving that they can be used as selective layers for efficient CO2 separation.

Unique orientation of 1D and 2D nanoparticle assemblies confined in smectic topological defects.

New collective optical properties have emerged recently from organized and oriented arrays of closely packed semiconducting and metallic nanoparticles (NPs). However, it is still challenging to obtain NP assemblies which are similar everywhere on a given sample and, most importantly, share a unique common orientation that would guarantee a unique behavior everywhere on the sample. In this context, by combining optical microscopy, fluorescence microscopy and synchrotron-based grazing incidence X-ray scattering (GISAXS) of assemblies of gold nanospheres and of fluorescent nanorods, we study the interactions between NPs and liquid crystal smectic topological defects that can ultimately lead to unique NP orientations. We demonstrate that arrays of one-dimensional - 1D (dislocations) and two-dimensional - 2D (grain boundaries) topological defects oriented along one single direction confine and organize NPs in closely packed networks but also orient both single nanorods and NP networks along the same direction. Through the comparison between smectic films associated with different kinds of topological defects, we highlight that the coupling between the NP ligands and the smectic layers below the grain boundaries may be necessary to allow for fixed NP orientation. This is in contrast with 1D defects, where the induced orientation of the NPs is intrinsically induced by the confinement independently of the ligand nature. We thus succeeded in achieving the fixed polarization of assemblies of single photon emitters in defects. For gold nanospheres confined in grain boundaries, a strict orientation of hexagonal networks has been obtained with the 〈10〉 direction strictly parallel to the defects. With such closely packed and oriented NPs, new collective properties are now foreseen.

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.

Unexpected Order-Disorder Transition in Diacetylene Alcohol Langmuir Films.

The phase diagram of the Langmuir film of diacetylene alcohol-henicosa-5,7-diyn-1-ol-is investigated by means of surface pressure versus surface area isotherms, Brewster angle microscopy, X-ray reflectivity, and grazing incident X-ray diffraction. Among the usual phases described in the generic phase diagram of small head group molecules, one observes an unexpected reversible transition from an ordered condensed phase to a disordered one upon increasing the surface pressure. We postulate that the origin of this unusual, unprecedented transition results from the competition between the interactions between the diacetylene blocks in the hydrophobic chain and the hydrogen bonds between head groups and water.

Catalytically active peptides affected by self-assembly and residues order.

Amphiphilic peptides that induce catalysis are interesting alternatives to natural enzymes thanks to robustness of their synthesis and the ability to induce certain types of conformations by specific motifs of amino acid sequences. Various studies aimed at mimicking the activity of serine proteases by designed peptides. Here we demonstrate that the order by which the catalytic triad residues are positioned along amphiphilic ß-strands influences both assembly structures and catalytic activity. A set of three ß-sheet amphiphilic peptides, decorated with different orders of the catalytic triad amino acids, Glu, His and Ser along the strands were evaluated for their catalytic hydrolysis efficiency of p-nitrophenyl acetate (pNPA) substrate. Among the three peptides, Ac-Cys-Phe-Glu-Phe-Ser-Phe-His-Phe-Pro-NH2 (ESH) achieved the greatest catalytic efficiency with a value of 0.19 M-1 s-1, at peptide concentration of 250 µM. This study sheds light on an overlooked factor in designing catalytic amphiphilic assemblies whereby charged residues that make up the active sites, are in fact engaged in intermolecular stabilizing interactions that in turn may hamper their catalytic action.

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.

Enhancement of photocurrent by incorporation of Preyssler type polyoxometalate protected nanoparticles in polyporphyrin films.

The introduction of nanoparticles (MNPs) at the surface of cationic poly-porphyrin films, obtained by electrostatic interaction between the bis-porphyrin copolymer and the Preyssler type polyoxometalate P5W30@MNPs, enhances the photocurrent (up to 2.5-3 times greater as a function of the used nanoparticle).

Langmuir Films of Perfluorinated Fatty Alcohols: Evidence of Spontaneous Formation of Solid Aggregates at Zero Surface Pressure and Very Low Surface Density.

In this work, Langmuir films of two highly fluorinated fatty alcohols, CF3(CF2)12CH2OH (F14OH) and CF3(CF2)16CH2OH (F18OH), were studied. Atomic Force Microscopy (AFM) images of the films transferred at zero surface pressure and low surface density onto the surface of silicon wafers by the Langmuir-Blodgett technique revealed, for the first time, the existence of solid-like domains with well-defined mostly hexagonal (starry) shapes in the case of F18OH, and with an entangled structure of threads in the case of F14OH. A (20:80) molar mixture of the two alcohols displayed a surprising combination of the two patterns: hexagonal domains surrounded by zigzagging threads, clearly demonstrating that the two alcohols segregate during the 2D crystallization process. Grazing Incidence X-Ray Diffraction (GIXD) measurements confirmed that the molecules of both alcohols organize in 2D hexagonal lattices. Atomistic Molecular Dynamics (MD) simulations provide a visualization of the structure of the domains and allow a molecular-level interpretation of the experimental observations. The simulation results clearly showed that perfluorinated alcohols have an intrinsic tendency to aggregate, even at very low surface density. The formed domains are highly organized compared to those of hydrogenated alcohols with similar chain length. Very probably, this tendency is a consequence of the characteristic stiffness of the perfluorinated chains. The diffraction spectrum calculated from the simulation trajectories compares favorably with the experimental spectra, fully validating the simulations and the proposed interpretation. The present results highlight for the first time an inherent tendency of perfluorinated chains to aggregate, even at very low surface density, forming highly organized 2D structures. We believe these findings are important to fully understand related phenomena, such as the formation of hemi-micelles of semifluorinated alkanes at the surface of water and the 2D segregation in mixed Langmuir films of hydrogenated and fluorinated fatty acids.

Controlled Synthesis of Gold Nanoparticles in Copolymers Nanomolds by X-ray Radiolysis.

We show by X-ray and neutron small-angle scattering that gold nanoparticles with controlled sizes and morphologies can be obtained by the metallic reduction of AuCl4- ions trapped in 3D organic molds by X-ray radiolysis. The molds are spherical frozen micelles of polystyrene-b-poly(dimethylaminoethyl methacrylate) (PS-b-PDMAEMA) block copolymer in acidic aqueous solution with a PS spherical core surrounded by a corona of PDMAEMA chains in good solvent. The behavior of micelles is controlled by the [AuCl4-]/[DMAEMA] ratio RAuCl4-/DMAEMA. At low gold concentration, AuCl4- ions condense on the positively charged DMAEMA moieties without changing the behavior of the PDMAEMA chains. At intermediate gold concentration, the ions induce a progressive contraction of the corona's chains and dehydration of micelles. At large gold concentration, the corona becomes a fully dry phase loaded with gold ions, which induces micelle aggregation. Radiolysis of the solution by an intense X-ray beam produces different types of gold nanoparticles with respect to RAuCl4-/DMAEMA and irradiation time. At RAuCl4-/DMAEMA = 0.033, irradiation produces in the first step gold clusters in the micelle corona which in the second step merge to form nanoparticles of a similar size to that of the micelle. Conversely, at RAuCl4-/DMAEMA = 0.33, micelles do not operate as templates but only as nucleation zones and large nanoparticles grow outside the micelles.

From Chains to Monolayers: Nanoparticle Assembly Driven by Smectic Topological Defects.

In this Letter, we show how advanced hierarchical structures of topological defects in the so-called smectic oily streaks can be used to sequentially transfer their geometrical features to gold nanospheres. We use two kinds of topological defects, 1D dislocations and 2D ribbon-like topological defects. The large trapping efficiency of the smectic dislocation cores not only surpasses that of the elastically distorted zones around the cores but also surpasses the one of the 2D ribbon-like topological defect. This enables the formation of a large number of aligned NP chains within the dislocation cores that can be quasi-fully filled without any significant aggregation outside of the cores. When the NP concentration is large enough to entirely fill the dislocation cores, the LC confinement varies from 1D to 2D. We demonstrate that the 2D topological defect cores induce a confinement that leads to planar hexagonal networks of NPs. We then draw the phase diagram driven by NP concentration, associated with the sequential confinements induced by these two kinds of topological defects. Owing to the excellent large-scale order of these defect cores, not only the NP chains but also the NP hexagonal networks can be oriented along the desired direction, suggesting a possible new route for the creation of either 1D or 2D highly anisotropic NP networks. In addition, these results open rich perspectives based on the possible creation of coexisting NP assemblies of different kinds, localized in different confining areas of a same smectic film that would thus interact thanks to their proximity but also would interact via the surrounding soft matter matrix.

Structure of Langmuir Monolayers of Perfluorinated Fatty Acids: Evidence of a New 2D Smectic C Phase.

Due to the characteristic chain rigidity and weak intermolecular interactions of perfluorinated substances, the phase diagram of Langmuir monolayer formed by perfluorinated molecules has been interpreted so far as displaying only two phases, a 2D gas (G) and a liquid condensed (LC). However, in this work, we presented Grazing Incidence X-ray Diffraction measurements, which exhibit two diffraction peaks on the transition plateau: One is the signature of the hexagonal structure of the LC phase, the second one is associated to the low-density fluid phase and is thus more ordered than expected for a 2D gas or a typical fluid phase. Atomistic molecular dynamics simulations, performed on the transition plateau, revealed the existence of clusters in which domains of vertical molecules organized in a hexagonal lattice coexist with domains of parallel lines formed by tilted molecules, a new structure that could be described as a "2D smectic C" phase. Moreover, the diffraction spectrum calculated from the simulation trajectories compared favorably with the experimental spectra, fully validating the simulations and the proposed interpretation. The results were also in agreement with the thermodynamic analysis of the fluid phase and X-ray Reflectivity experiments performed before and after the transition between these two phases.

Spontaneous self-assembly and structure of perfluoroalkylalkane surfactant hemimicelles by molecular dynamics simulations.

Fully atomistic molecular-dynamics (MD) simulations of perfluoroalkylalkane molecules at the surface of water show the spontaneous formation of aggregates whose size and topography closely resemble the experimentally observed hemimicelles for this system. Furthermore, the grazing incidence X-ray diffraction (GIXD) pattern calculated from the simulation trajectories reproduces the experimental GIXD spectra previously obtained, fully validating the MD simulation results. The detailed analysis of the internal structure of the aggregates obtained by the MD simulations supports a definite rational explanation for the spontaneous formation, stability, size, and shape of perfluoroalkylalkane hemimicelles at the surface of water.

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.

Evidence of lying molecules in the structure of the most condensed phase of semi-fluorinated alkane monolayers.

Semifluorinated alkanes are known to form peculiar nano-structured monolayers on the surface of water. A comprehensive analysis of in situ Grazing Incidence Small Angle X-ray Scattering (GISAXS) proves that the structure of their condensed phase consists of domains of upright molecules surrounded by lying down molecules. Such a model explains the non-coalescence of the domains and is in agreement with the high resolution AFM images of monolayers at the surfaces of solid substrates. The interaction of the lying molecule dipoles with the dipole of the water surface is proposed to explain the observed structuration.

Coupled Effects of Spreading Solvent Molecules and Electrostatic Repulsions on the Behavior of PS-b-PAA Monolayers at the Air-Water Interface.

We describe the surface behavior of PS-b-PAA monolayers at the air/water interface using N,N-dimethyformamide (DMF) as spreading solvent. At low pH, when the PAA blocks are neutral, the surface pressure versus molecular area isotherm shows a pseudoplateau associated with the presence of remaining spreading solvent molecules in the monolayer, as we described in a former study (Guennouni et al., Langmuir, 2016). We show here that the width of the plateau decreases when increasing pH up to its complete disappearance at high pH, when PAA blocks are fully charged, although two regimes of compressibilities on the isotherm still exist. A refined structural study at pH 9 combining specular neutron reflectivity (SNR), grazing-incidence small-angle X-ray scattering (GISAXS), and atomic force microscopy (AFM) in liquid measurements shows that (i) PAA blocks are stretched in solution, as expected from polyelectrolyte brushes in the osmotic regime; (ii) the system undergoes a spinodal decomposition during deposit at the air/water interface in the presence of DMF. Upon compression, the Qxy* position of the peak associated with the spinodal structure remains almost constant but its intensity evolves strongly and passes through a maximum at intermediate pressures. This reveals two operating processes in the system: strong electrostatic repulsions between chains that prevent in-plane reorganizations and force such reorganizations to occur from the surface to the volume and progressive expulsion of the DMF molecules from the monolayer. These processes have antagonist effects on the intensity of the peak: the increase of the repulsions makes it more pronounced, whereas the expulsion of solvent makes it vanish due to the loss of contrast.

Organization and structure of mixed Langmuir films composed of polydiacetylene and hemicyanine.

Mixed Langmuir monolayers of 10,12-Pentacosadiynoic acid (DA) monomer and an amphiphilic Hemicyanine dye derivative have been formed at the air/water interface. Two derivatives of docosylpyridinium have been used, with either one included in the monolayer in 1:1molar ratio. The DA monomers within the mixed monolayers have been polymerized in situ at the air/water interface. The crystalline structure of the monolayer and the kinetics of polymerization have been probed by grazing incidence X-ray diffraction (GIXD). The polymerization of DA proceeds with no phase segregation, exclusively leading to the red polydiacetylene form. The kinetics of polymerization at the air/water interface has been monitored in situ by GIXD. The experimental results have been combined with Molecular Mechanics computer simulations, revealing that DA molecules are sequentially arranged with molecules of Hemicyanine dye in alternating rows. The hydrophobic chains of the dye molecules act as spacers between the DA monomers. Surprisingly, such molecular arrangement does not hinder the in situ photopolymerization of DA. The mechanism of polymerization of DA within the mixed Langmuir monolayers has been convincingly described in molecular detail. This approach for interfacial polymerization of DA holds great potential for optically active devices and nanostructures comprising self-assembled thin films based in polydiacetylene.

How exfoliated graphene oxide nanosheets organize at the water interface: evidence for a spontaneous bilayer self-assembly.

In this study, we have characterized graphene oxide films formed at the air-water interface by X-ray reflectivity and grazing incidence X-ray diffraction using synchrotron sources. Surprisingly, the results of both measurements show that at non zero surface pressures, the film is organized as a bilayer of sheets interfaced between air and water with water molecule bridges. Such a spontaneous bilayer structure and its evolution with respect to the surface pressure has been observed for the first time. These results should allow precise control of the density of sheets deposited on the substrate when these films are transferred through the Langmuir Blodgett or Schaefer procedures. Indeed, graphene oxide keeps on attracting more and more attention, increasing the need for the production of well-controlled graphene oxide thin films due to its application in energy devices or in sensor domains.

Crystalline-like structures and multilayering in Langmuir films of ionic liquids at the air-water interface.

Langmuir films of [C18mim][NTf2] ionic liquid exhibited, for the first time, the reversible formation of crystalline-like structures at the surface of water, compatible with the formation of multilayers. Atomistic molecular dynamics simulation results support the experimental findings, unambiguously indicating the existence of a trilayer.