Mesoscale self-organization of polydisperse magnetic nanoparticles at the water surface.

In this study, we investigated the self-ordering process in Langmuir films of polydisperse iron oxide nanoparticles on a water surface, employing in situ x-ray scattering, surface pressure-area isotherm analysis, and Brewster angle microscopy. X-ray reflectometry confirmed the formation of a monolayer, while grazing incidence small-angle x-ray scattering revealed short-range lateral correlations with a characteristic length equal to the mean particle size. Remarkably, our findings indicated that at zero surface pressure, the particles organized into submicrometer clusters, merging upon compression to form a homogeneous layer. These layers were subsequently transferred to a solid substrate using the Langmuir-Schaefer technique and further characterized via scanning electron microscopy and polarized neutron reflectometry. Notably, our measurements revealed a second characteristic length in the lateral correlations, orders of magnitude longer than the mean particle diameter, with polydisperse particles forming circular clusters densely packed in a hexagonal lattice. Furthermore, our evidence suggests that the lattice constant of this mesocrystal depends on the characteristics of the particle size distribution, specifically the mean particle size and the width of the size distribution. In addition, we observed internal size separation within these clusters, where larger particles were positioned closer to the center of the cluster. Finally, polarized neutron reflectometry measurements provided valuable insights into the magnetization profile across the layer.

Closing the loop: autonomous experiments enabled by machine-learning-based online data analysis in synchrotron beamline environments.

Recently, there has been significant interest in applying machine-learning (ML) techniques to the automated analysis of X-ray scattering experiments, due to the increasing speed and size at which datasets are generated. ML-based analysis presents an important opportunity to establish a closed-loop feedback system, enabling monitoring and real-time decision-making based on online data analysis. In this study, the incorporation of a combined one-dimensional convolutional neural network (CNN) and multilayer perceptron that is trained to extract physical thin-film parameters (thickness, density, roughness) and capable of taking into account prior knowledge is described. ML-based online analysis results are processed in a closed-loop workflow for X-ray reflectometry (XRR), using the growth of organic thin films as an example. Our focus lies on the beamline integration of ML-based online data analysis and closed-loop feedback. Our data demonstrate the accuracy and robustness of ML methods for analyzing XRR curves and Bragg reflections and its autonomous control over a vacuum deposition setup.

Self-Organization of Lipid-Porphyrin Conjugates at the Air/Water Interface.

Lipid-porphyrin conjugates are versatile compounds which can self-assemble into liposome-like structures with multifunctional properties. Most of the conjugates that have been described so far, consisted in grafting pyropheophorbide-a (Pyro-a) or other porphyrin derivatives through the esterification of the hydroxyl group in the sn-2 position of a lysophosphatidylcholine. However, despite the versatility of these conjugates, less is known about the impact of the lipid backbone structure on their 2D phase behavior at the air/water interface and more precisely on their fine structures normal to the interface as well as on their in-plane organization. Herein, we synthesized a new lipid-porphyrin conjugate (PyroLSM) based on the amide coupling of Pyro-a to a lysosphingomyelin backbone (LSM) and we compared its interfacial behavior to that of Pyro-a and Pyro-a conjugated lysophosphatidylcholine (PyroLPC) using Langmuir balance combined to a variety of other physical techniques. Our results provided evidence on the significant impact of the lipid backbone on the lateral packing of the conjugates as well as on the shape and size of the formed domains. Compared to Pyro-a and PyroLPC monolayers, PyroLSM exhibited the highest lateral packing which highlights the role of the lipid backbone in controlling their 2D organization which in turn may impact the photophysical properties of their assemblies.

X-ray reflectivity from curved surfaces as illustrated by a graphene layer on molten copper.

The X-ray reflectivity technique can provide out-of-plane electron-density profiles of surfaces, interfaces, and thin films, with atomic resolution accuracy. While current methodologies require high surface flatness, this becomes challenging for naturally curved surfaces, particularly for liquid metals, due to the very high surface tension. Here, the development of X-ray reflectivity measurements with beam sizes of a few tens of micrometres on highly curved liquid surfaces using a synchrotron diffractometer equipped with a double crystal beam deflector is presented. The proposed and developed method, which uses a standard reflectivity θ-2θ scan, is successfully applied to study in situ the bare surface of molten copper and molten copper covered by a graphene layer grown in situ by chemical vapor deposition. It was found that the roughness of the bare liquid surface of copper at 1400 K is 1.25 ± 0.10 Å, while the graphene layer is separated from the liquid surface by a distance of 1.55 ± 0.08 Šand has a roughness of 1.26 ± 0.09 Å.

Crystallization and Organic Field-Effect Transistor Performance of a Hydrogen-Bonded Quaterthiophene.

Crystalline thin films of π-conjugated molecules are relevant as the active layers in organic electronic devices. Therefore, materials with enhanced control over the supramolecular arrangement, crystallinity, and thin-film morphology are desirable. Herein, it is reported that hydrogen-bonded substituents serve as additional structure-directing elements that positively affect crystallization, thin-film morphology, and device performance of p-type organic semiconductors. It is observed that a quaterthiophene diacetamide exhibits a denser packing than that of other quaterthiophenes in the single-crystal structure and, as a result, displays enhanced intermolecular electronic interactions. This feature was preserved in crystalline thin films that exhibited a layer-by-layer morphology, with large domain sizes and high internal order. As a result, organic field-effect transistors of these polycrystalline thin films showed mobilities in the range of the best mobility values reported for single-crystalline quaterthiophenes. The use of hydrogen-bonded groups may, thus, provide an avenue for organic semiconducting materials with improved morphology and performance.

Reorientation of π-conjugated molecules on few-layer MoS2 films.

Small π-conjugated organic molecules have attracted substantial attention in the past decade as they are considered as candidates for future organic-based (opto-)electronic applications. The molecular arrangement in the organic layer is one of the crucial parameters that determine the efficiency of a given device. The desired orientation of the molecules is achieved by a proper choice of the underlying substrate and growth conditions. Typically, one underlying material supports only one inherent molecular orientation at its interface. Here, we report on two different orientations of diindenoperylene (DIP) molecules on the same underlayer, i.e. on a few-layer MoS2 substrate. We show that DIP molecules adopt a lying-down orientation when deposited on few-layer MoS2 with horizontally oriented layers. In contrast, for vertically aligned MoS2 layers, DIP molecules are arranged in a standing-up manner. Employing in situ and real-time grazing-incidence wide-angle X-ray scattering (GIWAXS), we monitored the stress evolution within the thin DIP layer from the early stages of the growth, revealing different substrate-induced phases for the two molecular orientations. Our study opens up new possibilities for the next-generation of flexible electronics, which might benefit from the combination of MoS2 layers with unique optical and electronic properties and an extensive reservoir of small organic molecules.

Influence of Perfluorohexane-Enriched Atmosphere on Viscoelasticity and Structural Order of Self-Assembled Semifluorinated Alkanes at the Air-Water Interface.

Semifluorinated alkanes FnHm self-assemble into nanometer-sized surface micelles at the air-water interface. In this study, we investigated how an atmosphere enriched with perfluorohexane (PFH) influences the interfacial viscoelasticity and structural order of a monolayer of FnHm by the combination of dilational rheology and grazing-incidence small-angle X-ray scattering (GISAXS). The monolayers behaved predominantly elastic which can be attributed to the strong dipole repulsions of the surface domains. Enrichment of the atmosphere with PFH lead to an increase of the compressibility and a decrease of the elastic modulus without altering the structural ordering of the FnHm molecules into highly correlated nanodomains, suggesting the adsorption of PFH molecules to the free spaces between the domains. The capability of FnHm domains to retain the structural integrity in the presence of PFH gas is promising for the fabrication of stable microbubbles for sonographic imaging.

Long-Range Lateral Correlation between Self-Assembled Domains of Fluorocarbon-Hydrocarbon Tetrablocks by Quantitative GISAXS.

The structure and lateral correlation of fluorocarbon-hydrocarbon tetrablock di(F10Hm) domains at the air/water interface have been determined by quantitative analysis of grazing incidence small-angle X-ray scattering (GISAXS) data. The measured GISAXS signals can be well represented by the full calculation of the form and structure factors. The form factor suggests that di(F10Hm) domains take a hemiellipsoid shape. Both major and minor axes of the hemiellipsoids monotonically increased in response to the elongation of the hydrocarbon blocks, which can be explained by the concominant increase in van der Waals interaction. The structure factor calculated from the GISAXS signals suggests that the domains take an orthorhombic lattice. Remarkably, the lateral correlation can reach over a distance that is more than 14 times longer than the distance to the nearest neighbors. Our data suggest that quantitative GISAXS enables the optimal design of mesoscopic self-assemblies at the air/water interface by fine-tuning of the structures of molecular building blocks.

Reflectometry Reveals Accumulation of Surfactant Impurities at Bare Oil/Water Interfaces.

Bare interfaces between water and hydrophobic media like air or oil are of fundamental scientific interest and of great relevance for numerous applications. A number of observations involving water/hydrophobic interfaces have, however, eluded a consensus mechanistic interpretation so far. Recent theoretical studies ascribe these phenomena to an interfacial accumulation of charged surfactant impurities in water. In the present work, we show that identifying surfactant accumulation with X-ray reflectometry (XRR) or neutron reflectometry (NR) is challenging under conventional contrast configurations because interfacial surfactant layers are then hardly visible. On the other hand, both XRR and NR become more sensitive to surfactant accumulation when a suitable scattering length contrast is generated by using fluorinated oil. With this approach, significant interfacial accumulation of surfactant impurities at the bare oil/water interface is observed in experiments involving standard cleaning procedures. These results suggest that surfactant impurities may be a limiting factor for the investigation of fundamental phenomena involving water/hydrophobic interfaces.

Newly Synthesized Lipid-Porphyrin Conjugates: Evaluation of Their Self-Assembling Properties, Their Miscibility with Phospholipids and Their Photodynamic Activity In Vitro.

Lipid-porphyrin conjugates are considered nowadays as promising building blocks for the conception of supramolecular structures with multifunctional properties, required for efficient cancer therapy by photodynamic therapy (PDT). The synthesis of two new lipid-porphyrin conjugates coupling pheophorbide-a (Pheo-a), a photosensitizer derived from chlorophyll-a, to either chemically modified lyso-phosphatidylcholine (PhLPC) or egg lyso-sphingomyelin (PhLSM) is reported. The impact of the lipid backbone of these conjugates on their self-assembling properties, as well as on their physicochemical properties, including interfacial behavior at the air/buffer interface, fluorescence and absorption properties, thermotropic behavior, and incorporation rate in the membrane of liposomes were studied. Finally, their photodynamic activity was evaluated on esophageal squamous cell carcinoma (ESCC) and normal esophageal squamous epithelium cell lines. The liposome-like vesicles resulting from self-assembly of the pure conjugates were unstable and turned into aggregates with undefined structure within few days. However, both lipid-porphyrin conjugates could be efficiently incorporated in lipid vesicles, with higher loading rates than unconjugated Pheo-a. Interestingly, phototoxicity tests of free and liposome-incorporated lipid-porphyrin conjugates demonstrated a better selectivity in vitro to esophageal squamous cell carcinoma relative to normal cells.

Correction: Surface induced smectic order in ionic liquids - an X-ray reflectivity study of [C22C1im]+[NTf2].

Correction for 'Surface induced smectic order in ionic liquids - an X-ray reflectivity study of [C22C1im]+[NTf2]-' by Julian Mars et al., Phys. Chem. Chem. Phys., 2017, 19, 26651-26661.

Evidence for Anisotropic Electronic Coupling of Charge Transfer States in Weakly Interacting Organic Semiconductor Mixtures.

We present a comprehensive investigation of the charge-transfer (CT) effect in weakly interacting organic semiconductor mixtures. The donor-acceptor pair diindenoperylene (DIP) and N,N'-bis(2-ethylhexyl)-1,7-dicyanoperylene-3,4/9,10-bis(dicarboxyimide) (PDIR-CN2) has been chosen as a model system. A wide range of experimental methods was used in order to characterize the structural, optical, electronic, and device properties of the intermolecular interactions. By detailed analysis, we demonstrate that the partial CT in this weakly interacting mixture does not have a strong effect on the ground state and does not generate a hybrid orbital. We also find a strong CT transition in light absorption as well as in photo- and electroluminescence. By using different layer sequences and compositions, we are able to distinguish electronic coupling in-plane vs out-of-plane and, thus, characterize the anisotropy of the CT state. Finally, we discuss the impact of CT exciton generation on charge-carrier transport and on the efficiency of photovoltaic devices.

In situ study of the formation mechanism of two-dimensional superlattices from PbSe nanocrystals.

Oriented attachment of PbSe nanocubes can result in the formation of two-dimensional (2D) superstructures with long-range nanoscale and atomic order. This questions the applicability of classic models in which the superlattice grows by first forming a nucleus, followed by sequential irreversible attachment of nanocrystals, as one misaligned attachment would disrupt the 2D order beyond repair. Here, we demonstrate the formation mechanism of 2D PbSe superstructures with square geometry by using in situ grazing-incidence X-ray scattering (small angle and wide angle), ex situ electron microscopy, and Monte Carlo simulations. We observed nanocrystal adsorption at the liquid/gas interface, followed by the formation of a hexagonal nanocrystal monolayer. The hexagonal geometry transforms gradually through a pseudo-hexagonal phase into a phase with square order, driven by attractive interactions between the {100} planes perpendicular to the liquid substrate, which maximize facet-to-facet overlap. The nanocrystals then attach atomically via a necking process, resulting in 2D square superlattices.

Size, Shape, and Lateral Correlation of Highly Uniform, Mesoscopic, Self-Assembled Domains of Fluorocarbon-Hydrocarbon Diblocks at the Air/Water Interface: A GISAXS Study.

The shape and size of self-assembled mesoscopic surface domains of fluorocarbon-hydrocarbon (FnHm) diblocks and the lateral correlation between these domains were quantitatively determined from grazing incidence small-angle X-ray scattering (GISAXS). The full calculation of structure and form factors unravels the influence of fluorocarbon and hydrocarbon block lengths on the diameter and height of the domains, and provides the inter-domain correlation length. The diameter of the domains, as determined from the form factor analysis, exhibits a monotonic increase in response to the systematic lengthening of each block, which can be attributed to the increase in van der Waals attraction between molecules. The pair correlation function in real space calculated from the structure factor implies that the inter-domain correlation can reach a distance that is over 25 times larger than the domain's size. The full calculation of the GISAXS signals introduced here opens a potential towards the hierarchical design of mesoscale domains of self-assembled small organic molecules, covering several orders of magnitude in space.

Three-Legged 2,2'-Bipyridine Monomer at the Air/Water Interface: Monolayer Structure and Reactions with Ni(II) Ions from the Subphase.

The behavior of compound 2 [1,3,5-tri(2,2'-bipyridin-5-yl)benzene] with three bipyridine units arranged in a star geometry is investigated in the presence and absence of Ni(ClO4)2. Its properties at the air-water interface as well as after transfer onto a solid substrate are studied by several techniques including Brewster angle microscopy, X-ray reflectivity, neutron reflectivity, X-ray photoelectron spectroscopy, Rutherford backscattering spectrometry, and atomic force microscopy combined with optical microscopy. It is found that compound 2 within the monolayers formed stays almost vertical at the interface and that at high Ni2+/2 (Ni2+/2 = 4000, 20'000) ratios two of the three bipyridine units of 2 are complexed, resulting in supramolecular sheets that are likely composed of arrays of linear metal-organic complexation polymers.

Surface induced smectic order in ionic liquids - an X-ray reflectivity study of [C22C1im]+[NTf2].

Surface induced smectic order was found for the ionic liquid 1-methyl-3-docosylimidazolium bis(trifluoromethlysulfonyl)imide by X-ray reflectivity and grazing incidence scattering experiments. Near the free liquid surface, an ordered structure of alternating layers composed of polar and non-polar moieties is observed. This leads to an oscillatory interfacial profile perpendicular to the liquid surface with a periodicity of 3.7 nm. Small angle X-ray scattering and polarized light microscopy measurements suggest that the observed surface structure is related to fluctuations into a metastable liquid crystalline SmA2 phase that was found by supercooling the bulk liquid. The observed surface ordering persists up to 157 °C, i.e. more than 88 K above the bulk melting temperature of 68.1 °C. Close to the bulk melting point, we find a thickness of the ordered layer of L = 30 nm. The dependency of L(τ) = Λ ln(τ/τ1) vs. reduced temperature τ follows a logarithmic growth law. In agreement with theory, the pre-factor Λ is governed by the correlation length of the isotropic bulk phase.

Real Space Imaging of Nanoparticle Assembly at Liquid-Liquid Interfaces with Nanoscale Resolution.

Bottom up self-assembly of functional materials at liquid-liquid interfaces has recently emerged as method to design and produce novel two-dimensional (2D) nanostructured membranes and devices with tailored properties. Liquid-liquid interfaces can be seen as a "factory floor" for nanoparticle (NP) self-assembly, because NPs are driven there by a reduction of interfacial energy. Such 2D assembly can be characterized by reciprocal space techniques, namely X-ray and neutron scattering or reflectivity. These techniques have drawbacks, however, as the structural information is averaged over the finite size of the radiation beam and nonperiodic isolated assemblies in 3D or defects may not be easily detected. Real-space in situ imaging methods are more appropriate in this context, but they often suffer from limited resolution and underperform or fail when applied to challenging liquid-liquid interfaces. Here, we study the surfactant-induced assembly of SiO2 nanoparticle monolayers at a water-oil interface using in situ atomic force microscopy (AFM) achieving nanoscale resolved imaging capabilities. Hitherto, AFM imaging has been restricted to solid-liquid interfaces because applications to liquid interfaces have been hindered by their softness and intrinsic dynamics, requiring accurate sample preparation methods and nonconventional AFM operational schemes. Comparing both AFM and grazing incidence X-ray small angle scattering data, we unambiguously demonstrate correlation between real and reciprocal space structure determination showing that the average interfacial NP density is found to vary with surfactant concentration. Additionally, the interaction between the tip and the interface can be exploited to locally determine the acting interfacial interactions. This work opens up the way to studying complex nanostructure formation and phase behavior in a range of liquid-liquid and complex liquid interfaces.

Self-Organization of Polystyrene-b-polyacrylic Acid (PS-b-PAA) Monolayer at the Air/Water Interface: A Process Driven by the Release of the Solvent Spreading.

We present an in situ structural study of the surface behavior of PS-b-PAA monolayers at the air/water interface at pH 2, for which the PAA blocks are neutral and using N,N-dimethyformamide (DMF) as spreading solvent. The surface pressure versus molecular area isotherm shows a perfectly reversible pseudoplateau over several cycles of compression/decompression. The width of such plateau enlarges when increasing temperature, conversely to what is classically observed in the case of an in-plane first order transition. We combined specular neutron reflectivity (SNR) experiments with contrast variation to solve the profile of each block perpendicular to the surface with grazing-incidence small-angle scattering (GISAXS) measurements to determine the in-plane structure of the layer. SNR experiments showed that both PS and PAA blocks remain adsorbed on the surface for all surface pressure probed. A correlation peak at Q(xy)* = 0.021 Å(-1) is evidenced by GISAXS at very low surface pressure which intensity first increases on the plateau. When compressing further, its intensity decays while Q(xy)* is shifted toward low Q(xy). The peak fully disappears at the end of the plateau. These results are interpreted by the formation of surface aggregates induced by DMF molecules at the surface. These DMF molecules remain adsorbed within the PS core of the aggregates. Upon compression, they are progressively expelled from the monolayer, which gives rise to the pseudoplateau on the isotherm. The intensity of the GISAXS correlation peak is set by the amount of DMF within the monolayer as it vanishes when all DMF molecules are expelled. This result emphizes the role of the solvent in Langmuir monolayer formed by amphiphilic copolymers which hydrophobic and hydrophilic parts are composed by long polymer chains.

Solvent Extraction: Structure of the Liquid-Liquid Interface Containing a Diamide Ligand.

Knowledge of the (supra)molecular structure of an interface that contains amphiphilic ligand molecules is necessary for a full understanding of ion transfer during solvent extraction. Even if molecular dynamics already yield some insight in the molecular configurations in solution, hardly any experimental data giving access to distributions of both extractant molecules and ions at the liquid-liquid interface exist. Here, the combined application of X-ray and neutron reflectivity measurements represents a key milestone in the deduction of the interfacial structure and potential with respect to two different lipophilic ligands. Indeed, we show for the first time that hard trivalent cations can be repelled or attracted by the extractant-enriched interface according to the nature of the ligand.

The Link Between Self-Assembly and Molecular Conformation of Amphiphilic Block Copolymers Monolayers at the Air/Water Interface: The Spreading Parameter.

Two amphiphilic block copolymers, namely polystyrene-b-poly(methyl-methacrylate) (PS-b-PMMA), at the air/water interface were studied combining the in situ structural characterization, by means of X-ray reflectivity (XRR) and grazing incidence small-angle X-ray scattering (GISAXS), and the ex situ morphological one, by atomic force microscopy (AFM). We observed that the conformation of the hydrophilic block spread on the water surface is dramatically influenced by the morphology of the monolayer. Our results showed that the hydrophilic PMMA block adopts an expanded conformation when thermodynamically stable nanodots are formed, whereas a coiled conformation is observed when the block copolymer formed kinetically frozen nanostrands. This effect is interpreted in terms of the spreading parameter, which changes with the relative length ratio between the two blocks. Finally, we proved that, even for block copolymer monolayer with fixed block length ratio, it is possible to change the morphology, and in turn the conformation of the hydrophilic block, by changing the spreading parameter value.