Elastomer Particle Monolayers Formed by the Compression of Poly(methyl acrylate) Microparticles at an Air/Water Interface.

In the previous study (Green Chem., 2023, 25, 3418), highly stretchable and mechanically tough poly(methyl acrylate) (pMA) microparticle-based elastomers can be formed by drying a microparticle-containing aqueous dispersion. This discovery has the potential to overcome the mechanical weakness of industrially produced aqueous latex films. However, in 3D-arranged particle films, structural complexity, such as the existence of defects, makes it difficult to clearly understand the relationship between the particle film structure and its mechanical properties. In this study, 2D-ordered pMA particle monolayers at the air/water interface of a Langmuir trough are prepared. Under high compression at the air/water interface, the microparticles contact their neighboring particles, and the resulting monolayers can be successfully transferred onto a solid substrate. The compression of the monolayer films is linked to an increase in the elastic modulus of the monolayer film on the solid substrate as evident from the local Young's modulus mapping using atomic force microscopy. Thus, pMA particle films with different mechanical properties can be created using a Langmuir trough.

Advancements in Engineering Planar Model Cell Membranes: Current Techniques, Applications, and Future Perspectives.

Cell membranes are crucial elements in living organisms, serving as protective barriers and providing structural support for cells. They regulate numerous exchange and communication processes between cells and their environment, including interactions with other cells, tissues, ions, xenobiotics, and drugs. However, the complexity and heterogeneity of cell membranes-comprising two asymmetric layers with varying compositions across different cell types and states (e.g., healthy vs. diseased)-along with the challenges of manipulating real cell membranes represent significant obstacles for in vivo studies. To address these challenges, researchers have developed various methodologies to create model cell membranes or membrane fragments, including mono- or bilayers organized in planar systems. These models facilitate fundamental studies on membrane component interactions as well as the interactions of membrane components with external agents, such as drugs, nanoparticles (NPs), or biomarkers. The applications of model cell membranes have extended beyond basic research, encompassing areas such as biosensing and nanoparticle camouflage to evade immune detection. In this review, we highlight advancements in the engineering of planar model cell membranes, focusing on the nanoarchitectonic tools used for their fabrication. We also discuss approaches for incorporating challenging materials, such as proteins and enzymes, into these models. Finally, we present our view on future perspectives in the field of planar model cell membranes.

Fabrication and Self-Assembly Behavior of BPEF and BBPEF Composite Langmuir-Blodgett Films with Photovoltaic Conversion Properties.

The LB films prepared through the Langmuir-Blodgett (LB) technique are of significant importance for the fabrication of functional films such as optoelectronic materials and sensors. In this study, 9,9-bis (4-(2-hydroxy-ethoxy) phenyl) fluorene (BPEF) and 9,9-bis [3-phenyl-4-(ß-hydroxy-ethoxy) phenyl] fluorene (BBPEF) were combined with saffron T (ST), methylene blue (MB) and Rhodamine B (RhB) dyes by LB technique to prepare ordered composite films. The nanostructures and morphologies of the composite films were analyzed by transmission electron microscopy (TEM) and atomic force microscopy (AFM). It was found that the films exhibited distinct aggregation morphologies. The UV-VIS absorption spectra showed that the concentration of dye molecules had a significant effect on the spectral characteristics. The contact Angle test shows that the prepared composite films are hydrophobic. The photovoltaic conversion performance of LB composite films was studied by transient photocurrent response experiments. It was found that BPEF/dye and BBPEF/dye composite films exhibited significant responses in photocurrent. In particular, BPEF/RhB and BBPEF/RhB composite films demonstrated excellent photoresponsive performance. This study used LB technology in combination with BPEF and BBPEF to demonstrate enhanced photocurrent and stable performance of LB film, which provided ideas for expanding the application range of materials.

Triptycene-Based Tripodal Molecular Platforms.

Molecular platforms are essential components of various surface-mounted molecular devices. Here, we document the synthesis of two universal triptycene-based tripodal pedestals featuring terminal alkynes in the axial position. We showcase their versatility by incorporating them into the structures of diverse functional molecules such as unidirectional light-driven molecular motors, photoswitches, and Brownian molecular rotors using standard cross-coupling reactions. We also present their fundamental physical properties, including acidity constants, data from differential scanning calorimetry, and crystallographic analysis of two parent and five derived structures. Finally, and importantly, we demonstrate that the photochemical properties of selected photoswitch representatives remain uncompromised when fused with tripods.

Graphene Oxide Surface Modification of Reverse Osmosis (RO) Membrane via Langmuir-Blodgett Technique: Balancing Performance and Antifouling Properties.

The reverse osmosis water treatment process is prone to fouling issues, prompting the exploration of various membrane modification techniques to address this challenge. The primary objective of this study was to develop a precise method for modifying the surface of reverse osmosis membranes to enhance their antifouling properties. The Langmuir-Blodgett technique was employed to transfer aminated graphene oxide films assembled at the air-liquid interface, under specific surface pressure conditions, to the polyamide surface with pre-activated carboxylic groups. The microstructure and distribution of graphene oxide along the modified membrane were characterized using SEM, AFM, and Raman mapping techniques. Modification carried out at the optimal surface pressure value improved the membrane hydrophilicity and reduced the surface roughness, thereby enhancing the antifouling properties against colloidal fouling. The flux recovery ratio after modification increased from 65% to 87%, maintaining high permeability. The modified membranes exhibited superior performance compared to the unmodified membranes during long-term fouling tests. This membrane modification technique can be easily scaled using the roll-to-roll approach and requires minimal consumption of the modifier used.

Langmuir-Blodgett Transfer of Nanocrystal Monolayers: Layer Compaction, Layer Compression, and Lattice Stretching of the Transferred Layer.

Grazing incidence small angle X-ray scattering (GISAXS) was used to study the structure and interparticle spacing of monolayers of organic ligand-stabilized iron oxide nanocrystals floating at the air-water interface on a Langmuir trough, and after transfer to a solid support via the Langmuir-Blodgett technique. GISAXS measurements of the nanocrystal arrangement at the air-water interface showed that lateral compression decreased the interparticle spacing of continuous films. GISAXS also revealed that Langmuir-Blodgett transfer of the nanocrystal layers to a silicon substrate led to a stretching of the film, with a significant increase in interparticle spacing.

Continuous protein-density gradients: A new approach to correlate physical cues with cell response.

To assess cellular behavior within heterogeneous tissues, such as bone, skin, and nerves, scaffolds with biophysical gradients are required to adequately replicate the in vivo interaction between cells and their native microenvironment. In this study, we introduce a strategy for depositing ultrathin films comprised of laminin-111 with precisely controlled biophysical gradients onto planar substrates using the Langmuir-Blodgett (LB) technique. The gradient is created by controlled desynchronization of the barrier compression and substrate withdrawal speed during the LB deposition process. Characterization of the films was performed using techniques such as atomic force microscopy and confocal fluorescence microscopy, enabling the comprehensive analysis of biophysical parameters along the gradient direction. Furthermore, human adipose-derived stem cells were seeded onto the gradient films to investigate the influence of protein density on cell attachment, showing that the distribution of the cells can be modulated by the arrangement of the laminin at the air-water interface. The presented approach not only allowed us to gain insights into the intricate interplay between biophysical cues and cell behavior within complex tissue environments, but it is also suited as a screening approach to determine optimal protein concentrations to achieve a target cellular output.

Equipment-Free Fabrication of Thiolated Reduced Graphene Oxide Langmuir-Blodgett Films: A Novel Approach for Versatile Surface Engineering.

This research presents a novel method for the fabrication of mercapto reduced graphene oxide (m-RGO) Langmuir-Blodgett (LB) films without the need for specialized equipment. The conventional LB technique offers precise control over the deposition of thin films onto solid substrates, but its reliance on sophisticated instrumentation limits its accessibility. In this study, we demonstrate a simplified approach that circumvents the necessity for such equipment, thereby democratizing the production of m-RGO LB films. Thiolation of reduced graphene oxide (rGO) imparts enhanced stability and functionality to the resulting films, rendering them suitable for a wide range of applications in surface engineering, sensing, and catalysis. The fabricated m-RGO LB films exhibit favorable morphological, structural, and surface properties, as characterized by various analytical techniques including scanning electron microscopy (SEM), X-ray diffraction (XRD), and Fourier-transform infrared spectroscopy (FTIR). Furthermore, the performance of the m-RGO LB films is evaluated in terms of their surface wettability, electrochemical behavior, and chemical reactivity. The equipment-free fabrication approach presented herein offers a cost-effective and scalable route for the production of functionalized graphene-based thin films, thus broadening the scope for their utilization in diverse technological applications.

Harnessing Quantum Capacitance in 2D Material/Molecular Layer Junctions for Novel Electronic Device Functionality.

Two-dimensional (2D) materials promise advances in electronic devices beyond Moore's scaling law through extended functionality, such as non-monotonic dependence of device parameters on input parameters. However, the robustness and performance of effects like negative differential resistance (NDR) and anti-ambipolar behavior have been limited in scale and robustness by relying on atomic defects and complex heterojunctions. In this paper, we introduce a novel device concept that utilizes the quantum capacitance of junctions between 2D materials and molecular layers. We realized a variable capacitance 2D molecular junction (vc2Dmj) diode through the scalable integration of graphene and single layers of stearic acid. The vc2Dmj exhibits NDR with a substantial peak-to-valley ratio even at room temperature and an active negative resistance region. The origin of this unique behavior was identified through thermoelectric measurements and ab initio calculations to be a hybridization effect between graphene and the molecular layer. The enhancement of device parameters through morphology optimization highlights the potential of our approach toward new functionalities that advance the landscape of future electronics.

Recent Progress in the Applications of Langmuir-Blodgett Film Technology.

Langmuir-Blodgett (LB) film technology is an advanced technique for the preparation of ordered molecular ultra-thin films at the molecular level, which transfers a single layer of film from the air/water interface to a solid substrate for the controlled assembly of molecules. LB technology has continually evolved over the past century, revealing its potential applications across diverse fields. In this study, the latest research progress of LB film technology is reviewed, with emphasis on its latest applications in gas sensors, electrochemical devices, and bionic films. Additionally, this review evaluates the strengths and weaknesses of LB technology in the application processes and discusses the promising prospects for future application of LB technology.

Voltage-Driven Fluorine Motion for Novel Organic Spintronic Memristor.

Integrating tunneling magnetoresistance (TMR) effect in memristors is a long-term aspiration because it allows to realize multifunctional devices, such as multi-state memory and tunable plasticity for synaptic function. However, the reported TMR in different multiferroic tunnel junctions is limited to 100%. This work demonstrates a giant TMR of -266% in La0.6Sr0.4MnO3(LSMO)/poly(vinylidene fluoride)(PVDF)/Co memristor with thin organic barrier. Different from the ferroelectricity-based memristors, this work discovers that the voltage-driven florine (F) motion in the junction generates a huge reversible resistivity change up to 106% with nanosecond (ns) timescale. Removing F from PVDF layer suppresses the dipole field in the tunneling barrier, thereby significantly enhances the TMR. Furthermore, the TMR can be tuned by different polarizing voltage due to the strong modification of spin-polarization at the LSMO/PVDF interface upon F doping. Combining of high TMR in the organic memristor paves the way to develop high-performance multifunctional devices for storage and neuromorphic applications.

Exploring the physicochemical properties of the integration of Tristearoyl uridine in Langmuir monolayers: An approach to cell membrane modeling for prodrugs.

Understanding the mechanisms by which drugs interact with cell membranes is crucial for unraveling the underlying biochemical and biophysical processes that occur on the surface of these membranes. Our research focused on studying the interaction between an ester-type derivative of tristearoyl uridine and model cell membranes composed of lipid monolayers at the air-water interface. For that, we selected a specific lipid to simulate nontumorigenic cell membranes, namely 1,2-dihexadecanoyl-sn-glycero-3-phospho-l-serine. We noted significant changes in the surface pressure-area isotherms, with a noticeable shift towards larger areas, which was lower than expected for ideal mixtures, indicating monolayer condensation. Furthermore, the viscoelastic properties of the interfacial film demonstrated an increase in both the elastic and viscous parameters for the mixed film. We also observed structural alterations using vibrational spectroscopy, which revealed an increase in the all-trans to gauche conformers ratio. This confirmed the stiffening effect of the prodrug on the lipid monolayer. In summary, this study indicates that this lipophilic prodrug significantly impacts the lipid monolayer's thermodynamic, rheological, electrical, and molecular characteristics. This information is crucial for understanding how the drug interacts with specific sites on the cellular membrane. It also has implications for drug delivery, as the drug's passage into the cytosol may involve traversing the lipid bilayer.

Eminent Antimicrobial Peptide Resistance in Zymomonas mobilis: A Novel Advantage of Intrinsically Uncoupled Energetics.

Relative to several model bacteria, the ethanologenic bacterium Zymomonas mobilis is shown here to have elevated resistance to exogenous antimicrobial peptides (AMPs)- with regard to both peptide bulk concentration in the medium and the numbers of peptide molecules per cell. By monitoring the integration of AMPs in the bacterial cell membrane and observing the resulting effect on membrane energy coupling, it is concluded that the membranotropic effects of the tested AMPs in Z. mobilis and in Escherichia coli are comparable. The advantage of Z. mobilis over E. coli apparently results from its uncoupled mode of energy metabolism that, in contrast to E. coli, does not rely on oxidative phosphorylation, and hence, is less vulnerable to the disruption of its energy-coupling membrane by AMPs. It is concluded that the high resistance to antimicrobial peptides (AMPs) observed in Z. mobilis not only proves crucial for its survival in its natural environment but also offers a promising platform for AMP production and sheds light on potential strategies for novel resistance development in clinical settings.

An Exploration of Cysteamine as a Subphase Additive for the Fabrication of Uniform Gold Nanorod Arrays using Langmuir-Blodgett Deposition.

Gold nanorods (AuNRs) have attracted significant attention over the past several decades for a variety of applications and there has been steady progress with regards to their synthesis and modification. Despite these advances, the assembly of AuNRs into well-organized hierarchical assemblies remains a formidable challenge. Specifically, there is a need for tools that can fabricate assemblies of nanorods over large length scales at low cost with the potential for high-throughput manufacturing. Langmuir-Blodgettry is a monolayer deposition technique which has been primarily applied to amphiphilic molecules, but which has recently shown promise for the ordering of functionalized nanoparticles residing at the air-water interface. In this work, Langmuir-Blodgett deposition is explored for the formation of AuNR arrays for enhanced surface-enhanced Raman spectroscopy (SERS) sensing. In particular, both surface modification of the AuNRs as well as subphase modification with cysteamine were evaluated for AuNR array fabrication.

The effect of nanobubbles on Langmuir-Blodgett films.

Nanobubbles (NBs) are classified in two distinct categories: surface and bulk. Surface NBs are readily observed using atomic force microscopy (AFM), while the existence of bulk NBs has been a subject of debate, conflicting with the diffusion theory's predictions. Current methodologies for identifying bulk NBs yield inconclusive results. In this study, Langmuir Blodgett (LB) technique and AFM, are utilized to visualize NB imprints on anionic, cationic and zwitterionic lipid films deposited on glass-slide substrates. Our analysis of Langmuir monolayers compression isotherms reveals the impact of bulk NBs on lipid monolayer development. AFM scans of the deposited lipid films consistently show NB imprints. Notably, cationic and zwitterionic film depositions exhibit NB formations from the 1st layer, whereas in anionic films, these formations are observed only after the 3rd layer. These results suggest that the origin of these imprinted formations may be attributed to bulk NBs.

Interfacing Langmuir-Blodgett and Pickering Emulsions for the Synthesis of 2D Nanostructured Films: Applications in Copper Ion Adsorption.

This research focuses on developing a 2D thin film comprising a monolayer of silica nanoparticles functionalized with polyethyleneimine (PEI), achieved through a novel integration of Langmuir-Blodgett (L-B) and Pickering emulsion techniques. The primary aim was to create a nanostructured film that exhibits dual functionality: iridescence and efficient metal ion adsorption, specifically Cu(II) ions. The methodology combined L-B and Pickering emulsion polymerization to assemble and stabilize a nanoparticle monolayer at an oil/water interface, which was then polymerized under UV radiation to form an asymmetrically structured film. The results demonstrate that the film possesses a high adsorption efficiency for Cu(II) ions, with the enhanced mechanical durability provided by a reinforcing layer of polyvinyl alcohol/glycerol. The advantage of combining L-B and Pickering emulsion technology is the ability to generate 2D films from functional nanoparticle monolayers that are sufficiently sturdy to be deployed in applications. The 2D film's practical applications in environmental remediation were confirmed through its ability to adsorb and recover Cu(II) ions from aqueous solutions effectively. We thus demonstrate the film's potential as a versatile tool in water treatment applications owing to its combined photonic and adsorptive properties. This work paves the way for future research on the use of nanoengineered films in environmental and possibly photonic applications focusing on enhancing the film's structural robustness and exploring its broader applicability to other pollutants and metal ions.

Mechanical control of molecular machines at an air-water interface: manipulation of molecular pliers, paddles.

Many artificial molecular machines have been synthesized, and various functions have been expressed by changing their molecular conformations. However, their structures are still simple compared with those of biomolecular machines, and more energy is required to control them. To design artificial molecular machines with more complex structures and higher functionality, it is necessary to combine molecular machines with simple movements such as components. This means that the motion of individual molecular machines must be precisely controlled and observed in various environments. At the air - water interface, the molecular orientation and conformation can be controlled with little energy as thermal fluctuations. We designed various molecular machines and controlled them using mechanical stimuli at the air - water interface. We also controlled the transfer of forces to the molecular machines in various lipid matrices. In this review, we describe molecular pliers with amphiphilic binaphthyl, molecular paddles with binuclear platinum complexes, and molecular rotors with julolidine and BODIPY that exhibit twisted intramolecular charge transfer.

This review discusses the dependence of the behaviour of molecular machines around their environment through the mechanically control of simple molecular machines at the air ­ water interface.

Synthesis of silicon carbide in a matrix of graphite-like carbon prepared via carbonization of rigid-rod polyimide Langmuir-Blodgett films on silicon substrate.

Silicon carbide (SiC) is a wide-band gap semiconductor that exceeds other semiconducting materials (except diamond) in electrical, mechanical, chemical, and radiation stability. In this paper, we report a novel approach to fabrication of SiC nano films on a Si substrate, which is based on the endotaxial growth of a SiC crystalline phase in a graphite-like carbon (GLC) matrix. GLC films were formed by carbonization of rigid rod polyimide (PI) Langmuir-Blodgett (LB) films on a Si substrate at 1000 °C in vacuum. After rapid thermal annealing of GLC films at 1100 °C and 1200 °C, new types of heterostructures SiC(10 nm)/GLC(20 nm)/Si(111) and SiC(20 nm)/GLC(15 nm)/SiC(10 nm)/Si(111) were obtained. The SiC top layer was formed due to the Si-containing gas phase present above the surface of GLC film. An advantage of the proposed method of endotaxy is that the SiC crystalline phase is formed within the volume of the GLC film of a thickness predetermined by using PI LB films with different numbers of monolayers for carbonization. This approach allows growing SiC layers close to the 2D state, which is promising for optoelectronics, photovoltaics, spintronics.

Materials Nanoarchitectonics at Dynamic Interfaces: Structure Formation and Functional Manipulation.

The next step in nanotechnology is to establish a methodology to assemble new functional materials based on the knowledge of nanotechnology. This task is undertaken by nanoarchitectonics. In nanoarchitectonics, we architect functional material systems from nanounits such as atoms, molecules, and nanomaterials. In terms of the hierarchy of the structure and the harmonization of the function, the material created by nanoarchitectonics has similar characteristics to the organization of the functional structure in biosystems. Looking at actual biofunctional systems, dynamic properties and interfacial environments are key. In other words, nanoarchitectonics at dynamic interfaces is important for the production of bio-like highly functional materials systems. In this review paper, nanoarchitectonics at dynamic interfaces will be discussed, looking at recent typical examples. In particular, the basic topics of "molecular manipulation, arrangement, and assembly" and "material production" will be discussed in the first two sections. Then, in the following section, "fullerene assembly: from zero-dimensional unit to advanced materials", we will discuss how various functional structures can be created from the very basic nanounit, the fullerene. The above examples demonstrate the versatile possibilities of architectonics at dynamic interfaces. In the last section, these tendencies will be summarized, and future directions will be discussed.

Dense Monolayer Network Structures of Double Hydrophilic Hyperbranched Copolymers at the Air/Water Interface.

Influences of subphase pH and temperature on the interfacial aggregation behavior of two double hydrophilic hyperbranched copolymers of poly[oligo(ethylene glycol) methacrylate-co-(2-diisopropylamino)ethyl methacrylate] (P(OEGMA-co-DIPAEMA)) at the air/water interface are studied by the Langmuir film balance technique. Morphologies of their Langmuir-Blodgett (LB) films are characterized by atomic force microscopy (AFM). At the interface, P(OEGMA-co-DIPAEMA) copolymers tend to form a dense network structure of circular micelles composed of branching agent-connected carbon backbone cores and mixed shells of OEGMA and DIPAEMA segments (pendant groups). This network structure containing many honeycomb-like holes with diameters of 6-8 nm is identified for the first time and clearly observed in the enlarged AFM images of their LB films. Under acidic conditions, surface pressure versus molecular area isotherms of the two copolymers in the low-pressure region show larger mean molecular area than those under neutral and alkaline conditions due to the lack of impediment from DIPAEMA segments. Upon further compression, each isotherm exhibits a wide pseudo-plateau, which corresponds to OEGMA segments being pressed into the subphase. Furthermore, the isotherms under neutral and alkaline conditions exhibit the lower critical solution temperature behavior of OEGMA segments, and the critical temperature is lower when the hyperbranched copolymer contains higher OEGMA content.