Langmuir-Blodgett Films of Arachidic and Stearic Acids as Sensitive Coatings for Chloroform HF SAW Sensors.

Properties of the Langmuir-Blodgett (LB) films of arachidic and stearic acids, versus the amount of the films' monolayers were studied and applied for chloroform vapor detection with acoustoelectric high-frequency SAW sensors, based on an AT quartz two-port Rayleigh type SAW resonator (414 MHz) and ST-X quartz SAW delay line (157.5 MHz). Using both devices, it was confirmed that the film with 17 monolayers of stearic acid deposited on the surface of the SAW delay line at a surface pressure of 30 mN/m in the solid phase has the best sensitivity towards chloroform vapors, compared with the same films with other numbers of monolayers. For the SAW resonator sensing using slightly longer arachidic acid molecules, the optimum performance was reached with 17 LB film layers due to a sharper decrease in the Q-factor with mass loading. To understand the background of the result, Atomic Force Microscopy (AFM) in intermittent contact mode was used to study the morphology of the films, depending on the number of monolayers. The presence of the advanced morphology of the film surface with a maximal average roughness (9.3 nm) and surface area (29.7 µm2) was found only for 17-monolayer film. The effects of the chloroform vapors on the amplitude and the phase of the acoustic signal for both SAW devices at 20 °C were measured and compared with those for toluene and ethanol vapors; the largest responses were detected for chloroform vapor. For the film with an optimal number of monolayers, the largest amplitude response was measured for the resonator-based device. Conversely, the largest change in the acoustic phase produced by chloroform adsorption was measured for delay-line configuration. Finally, it was established that the gas responses for both devices coated with the LB films are completely restored 60 s after chamber cleaning with dry air.

Modulated Fluorescence in LB Films Based on DADQs-A Potential Sensing Surface?

Novel fluorescent Langmuir-Blodgett (LB) films have been constructed from three different amphiphilic dicynaoquinodimethanes (DADQs). The DADQs varied in functional group structure, which had an impact on the LB film structure and the fluorescence properties. As the fluorescence of DADQs competes with non-radiative decay (conformational change), the packing and/or free volume in the LB film will influence the average fluorescence lifetime and integrated intensity. The pristine (blank) LB films were then exposed to a selection of non-fluorescent target analytes (some with environmental relevance) and the fluorescence was measured and analyzed relative to the pristine LB film. Exposure of the LB films to selected target analytes results in a modulation of the fluorescence, both with respect to average fluorescence lifetime and integrated intensity. The modulation of the fluorescence is different for different DADQ LB films and can be attributed to restricted non-radiative decays or charge transfer reactions between target analyte and DADQ LB film. The response from the DADQ LB films shows that these systems can be developed into sensing surfaces based on fluorescence measurements.

Fluorescent sensing of free bilirubin at nanomolar level using a Langmuir-Blodgett film of glucuronic acid-functionalized gold nanoclusters.

Serum bilirubin is an important indicator to assess liver function and diagnose various types of liver diseases. The level of serum bilirubin is also negatively correlated with the risk of cardiovascular disease and cancer. We had fabricated a fluorescent film sensor aiming at free bilirubin detection at the nanomolar level. Gold nanoclusters capped by human serum albumin (HSA-AuNCs) were utilized as a fluorescent platform for bilirubin biorecognition. HSA-AuNCs were functionalized with glucuronic acid to increase the binding sites for bilirubin. An ultrathin film of glucuronic acid-functionalized gold nanoclusters was obtained by the Langmuir-Blodgett (LB) technique. When exposed to bilirubin, the interaction between free bilirubin and the functionalized AuNCs resulted in fluorescent quenching of the film. Good linearity could be achieved for the quenching efficiency versus the logarithm of free bilirubin concentration over a concentration range of 1.00 nM~5.00 µM. The limit of detection (LOD) was calculated to be (2.70 ± 0.14) × 10-1 nM (S/N = 3). The film sensor presents a good anti-interference capability towards common substances coexisting with bilirubin in serum. Satisfactory results achieved in the tests of real serum samples indicate that the LB film sensor can be used for bilirubin determination in nanomolar concentration.

Easily Processable, Highly Transparent and Conducting Thiol-Functionalized Reduced Graphene Oxides Langmuir-Blodgett Films.

We report synthesis and fabrication of highly thionated reduced graphene oxide and its Langmuir-Blodgett (LB) film without an LB trough. As the synthesized product, mercapto reduced graphene oxide (mRGO) contains high thiol content estimated from XPS, corresponding to a surface coverage of 1.3 SH/nm2. The mRGO LB film shows two electronic transport properties, following Efros-Shklovskii variable-range hopping (VRH) and Mott VRH at low and high temperature, respectively. Optical and band gap of the LB film was estimated from Tauc plot and semi-logarithmic-scale plot of sheet resistance versus temperature to be 0.6 and 0.1 eV, respectively. Additionally, the sheet resistance of the mRGO LB film depends on the quantity of the thiol functional group with the same transmittance at 550 nm (500 kΩ for mRGO, 1.3 MΩ for tRGO with 92% transmittance).

Morphological and Interaction Characteristics of Surface-Active Ionic Liquids and Palmitic Acid in Mixed Monolayers.

A series of water soluble, surface-active ionic liquids (SAILs), namely, 1-alkyl-3-methyl imidazolium chlorides ([Cn -mim]Cl) and their mixtures with palmitic acid (PA) are investigated in Langmuir monolayers and Langmuir-Blodgett films. It is inferred from the surface pressure-area isotherms that C16 -mim-IL mixes non-ideally with PA and stabilizes the binary mixed films. In addition, the residence of mim-IL at the water surface is enhanced as a function of the increasing alkyl side chain length. Generally, the compressional moduli values decrease upon increasing the content of the mim-ILs over a wide range of compositions. Furthermore, film relaxation measurements indicate that the IL component is selectively excluded from the mixed films upon achieving a certain target pressure. Brewster angle microscope images demonstrate minimal changes on the PA domains in the presence of either C4 - and C8 -mim-ILs, whereas presence of the hexadecyl counterpart results in the formation of condensed sheets. Atomic force microscopy imaging of deposited films show the formation of propeller-like aggregates when C8 - or C16 -mim-IL is present in the mixed films.

Interaction between C18 fatty acids and DOPE PEG2000 in Langmuir monolayers: effect of degree of unsaturation.

In this study, we address the effect of the cis-double bond in 1,2-dioleoyl-sn-glycero-3-phosphoethanolamide-N-[methoxy(polyethylene glycol)-2000, DOPE PEG2000 (DP), on the Langmuir monolayer of C18 fatty acids-namely, stearic acid (SA), oleic acid (L1), linoleic acid (L2), and linolenic acid (L3)-with the same head group but different degrees of saturation on their hydrocarbon chains. Negative values of Gibbs free energy of mixing (ΔG mix) were obtained throughout the investigated ranges of the unsaturated C18 fatty-acid (L1, L2 and L3) mixed systems, indicating that very strong attractions occurred between molecules in the monolayers. The bend and kink effects from the cis-double bond(s) in the hydrocarbon chain affected the membrane fluidity and molecular packing in the monolayers, which resulted in a greater interaction between unsaturated C18 fatty acids and DP. The most thermodynamically stable mole composition of unsaturated C18 fatty acids to DP was observed at 50:1; this ratio is suggested to be the best mole ratio and will be subsequently used to prepare DP-C18 fatty-acid nanoliposomes. The presence of cis-double bonds in both hydrocarbon chains of DOPE in DP also created an imperfection in the membrane structure of lipid-drug delivery systems, which is expected to enhance lipid-based systems for antibody conjugation and drug encapsulation.

Partially induced transition from horizontal to vertical orientation of helical peptides at the air-water interface and the structure of their monolayers transferred on the solid substrates.

To apply the Langmuir-Blodgett (LB) technique as a platform for investigating the fundamental properties of amphiphilic peptides (APs), we have investigated the structure of LB films using the APs. To vertically orient the helical APs like transmembrane proteins in the membrane, the primary structure of the APs was designed to have two domains: a hydrophilic domain (three amino acids) and a hydrophobic domain (ca. 20 amino acids). However, we are still far from having full control of their orientation. This study reports the contribution of the subphase temperature to the change in the orientation of helical APs. When the surface pressure-area isotherm of AP was observed at the subphase temperature at 41.5°C, the isotherm exhibited a plateau, implying that a phase transition of the monolayer at the air-water interface occurred. Circular dichroism (CD) spectra of the monolayers transferred on the solid substrates revealed that the orientation of the helices changed at the pressure, where the plateau of the isotherm was observed. This change was not observed at 21.5°C, i.e., the horizontal alignment of helixes was maintained. Atomic force microscopy (AFM) was used to systematically investigate the surface structure of the monolayers transferred at different surface pressures. A structural model of the monolayer that did not contradict with the results obtained by the three different techniques (the isotherm, CD spectroscopy, and AFM) was derived, and it was concluded that the horizontally oriented helices partially changed their orientation to vertical upon compression in the plateau region of the isotherm.

Biomimetic monolayer films of digalactosyldiacylglycerol incorporating plastoquinone.

The photosynthesis is the process used by plants and bacteria cells to convert inorganic matter in organic thanks to the light energy. This process consist on several steps, being one of them the electronic transport from the photosystem II to the cytochrome thanks to plastoquinone-9 (PQ). Here we prepare membranes that mimic the characteristics and composition of natural photosynthetic cell membranes and we characterize them in order to obtain the PQ molecules position in the membrane and their electrochemical behaviour. The selected galactolipid is digalactosyldiacylglycerol (DGDG) that represents the 30% of the thylakoid membrane lipid content. The results obtained are worthful for several science fields due to the relevance of galactolipids as anti-algal, anti-viral, anti-tumor and anti-inflammatory agents and the antioxidant and free radical scavenger properties of prenylquinones. Both pure components (DGDG and PQ) and the DGDG:PQ mixtures have been studied using surface pressure-area isotherms. These isotherms give information about the film stability and indicate the thermodynamic behaviour of the mixture and their physical state. The Langmuir-Blodgett (LB) film has been transferred forming a monolayer that mimics the bottom layer of the biological membranes. This monolayer on mica has been topographically characterized using AFM and both the height and the physical state that they present have been obtained. Moreover, these monolayers have been transferred onto ITO that is a hydrophilic substrate with good optical and electrical features, so that, it is suitable for studying the electrochemical behaviour of these systems and it is a good candidate for energy producing devices.

Oriented assembly of bacteriorhodopsin on ZnO nanostructured electrode for enhanced photocurrent generation.

Bacteriorhodopsin (bR) is a photoactive protein that has great potential to be used in bioelectronics applications. For the first time, a monolayer of bR created by the Langmuir-Blodgett method is immobilized on a ZnO nanoporous film. Scanning electron microscopy and atomic force microscopy analyses are used to study the morphological properties of the electrodes. In addition, an efficient biosolar cell is designed and fabricated, and the performance of produced nano-biohybrid electrode is investigated by the measurement of power conversion efficiency of biosolar cell. Under AM1.5 irradiation, a short-circuit current of 0.39 mA cm(-2) , open-circuit voltages of 0.5 V, fill factor of 0.52, and an overall energy conversion efficiency of 0.1% are achieved.

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.

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.

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.

Atomic force microscopy study of the complexation of sterols and the glycoalkaloid α-tomatine in Langmuir-Blodgett monolayers.

Glycoalkaloids are secondary metabolites produced by plants that aid in their protection from pathogens and pests. They are known to form 1:1 complexes with 3ß-hydroxysterols such as cholesterol causing membrane disruption. So far, the visual evidence showcasing the complexes formed between glycoalkaloids and sterols in monolayers has been mainly restricted to some earlier studies using Brewster angle microscopy which were of low resolution showing the formation of floating aggregates of these complexes. This study is aimed at using atomic force microscopy (AFM) for topographic and morphological analysis of the aggregates of these sterol-glycoalkaloid complexes. Langmuir-Blodgett (LB) transfer of mixed monolayers of the glycoalkaloid α-tomatine, sterols, and lipids in varying molar ratios onto mica followed by AFM examination was performed. The AFM method allowed visualization of the aggregation of sterol-glycoalkaloid complexes at nanometer resolution. While aggregation was observed in mixed monolayers of α-tomatine with cholesterol and in mixed monolayers with coprostanol, no sign of complexation was observed for the mixed monolayers of epicholesterol and α-tomatine, confirming their lack of interaction found in prior monolayer studies. Aggregates were observed in transferred monolayers of ternary mixtures of α-tomatine with cholesterol and the phospholipids 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) or egg sphingomyelin (egg SM). The formation of aggregates was found to be less prevalent for mixed monolayers of DMPC and cholesterol containing α-tomatine than it was for mixed monolayers containing egg SM and cholesterol with α-tomatine. The observed aggregates were generally elongated structures, of a width ranging from about 40-70 nm.

Langmuir-Blodgett transfer from the oil-water interface.

HYPOTHESIS: Almost all Langmuir-Blodgett (LB) films were prepared with the classical Langmuir film balance, developed more than a century ago. To date, the success of the classical Langmuir film balance and the LB transfer technique is primarily restricted to the study of self-assembled monolayers at the air-water surface. It is challenging to study self-assembled monolayers at the oil-water interface, since the Langmuir film balance requires stacked oil and water layers. We hypothesize that a newly developed experimental method, called constrained drop surfactometry (CDS), is capable of preparing and characterizing LB films from the oil-water interface. EXPERIMENTS: We have developed a novel droplet-based LB transfer technique capable of preparing LB films from the oil-water interface. In conjunction with atomic force microscopy, we have demonstrated the capacity of the CDS in studying a natural pulmonary surfactant film self-assembled at the perfluorocarbon-water interface, and have compared to the LB films prepared from the air-water surface using the classical Langmuir film balance. FINDINGS: Our findings have demonstrated a novel paradigm for studying self-assembled monolayers and for preparing LB films from the oil-water interface. The CDS holds great promise for expanding the applicability of the traditional LB transfer technique from the air-water surface to the oil-water interface.

C-undecylcalix[4]resorcinarene Langmuir-Blodgett/Porous Reduced Graphene Oxide Composite Film as a Electrochemical Sensor for the Determination of Tryptophan.

In this study, a composite film was developed for the electrochemical sensing of tryptophan (Trp). Porous reduced graphene oxide (PrGO) was utilized as the electron transfer layer, and a C-undecylcalix[4]resorcinarene Langmuir-Blodgett (CUCR-LB) film served as the molecular recognition layer. Atomic force microscopy (AFM), transmission electron microscopy (TEM), Raman spectroscopy, scanning electron microscopy (SEM), and electrochemical experiments were employed to analyze the characteristics of the CUCR-LB/PrGO composite film. The electrochemical behavior of Trp on the CUCR-LB/PrGO composite film was investigated, revealing a Trp linear response range of 1.0 × 10-7 to 3.0 × 10-5 mol L-1 and a detection limit of 3.0 × 10-8 mol L-1. Furthermore, the developed electroanalytical method successfully determined Trp content in an amino acid injection sample. This study not only introduces a rapid and reliable electrochemical method for the determination of Trp but also presents a new strategy for constructing high-performance electrochemical sensing platforms.

Periodic stacking of two dimensional Bismuth bi-layers in Bismuth stearate thin films.

Investigations of single and bilayers of bismuth are one of the most thrusting areas of research in contemporary condensed matter physics and material sciences. This is because such ultrathin layers of bismuth host interesting exotic electronic properties, which are important from both fundamental science and future application perspectives. In the past, many inorganic processes for the synthesis of single and bi-layers of bismuth were reported using physical and chemical vapor deposition techniques. The ultrathin films deposited are found to interact electronically with the substrates due to their proximity to the substrate surface. We introduce a new and easy organic channel for the synthesis of the bismuth multi-bilayers in ambient conditions. Bismuth stearate multi-bilayer thin films are deposited on the hydrophobic silicon and hydrophilic glass substrates using the Langmuir-Blodgett technique. Optical absorption spectroscopy measurements in the infrared region provided information on various bond structures present in those bismuth stearate thin films. Specular x-ray reflectivity (XRR) experiments and their analysis of such thin films unambiguously show the highly periodic stacking of bismuth bilayers along the surface-normal directions within the multilayer film structure. Model-based microstructural analysis of the XRR data further shows that each bilayer of bismuth is well separated (3.5 nm) from other bismuth bilayers by hydrocarbon chains. At these separations,the electronic states of the bismuth bilayers are expected to be non-interacting with each other. The morphology of the surface obtained from field emission scanning electron microscopy supports the XRR analysis. A bandgap of 3.2 eV was obtained for such bismuth stearate thin films from the optical spectroscopy measurements in the UV-visible range. The large separations between the bismuth-bilayers and between the substrate and the bismuth bilayers are expected to minimize the electronic interactions between them.

Fabrication of gold nanoparticles tethered in heat-cooled calf thymus-deoxyribonucleic acid Langmuir-Blodgett film as effective surface-enhanced Raman scattering sensing platform.

SERS active substrate fabricated through self-assembly of Gold nanoparticles on the disjointed networks of Heat-cooled Calf Thymus DNA (HC-Ct DNA) Langmuir-Blodgett (LB) film has been reported. Adsorption kinetics of HC-Ct DNA molecules at the air-water interface has been studied explicitly. The UV-Vis electronic absorption spectra in conjunction with the FESEM images collectively suggest the presence of H- type aggregated domains most likely owing to plane-to-plane self-association of the HC-Ct DNA molecules aligned vertically on the surface of the LB film. Elemental composition and the morphological features of the as-prepared substrate (APS) are explored from XPS analysis and the FESEM, AFM images respectively. The SERS efficacy of the APS has been tested with trace concentrations of 4-Mercaptopyridine molecule. Finally, this SERS active substrate has also been used for the detection of malathion at ultrasensitive concentrations.

Influence of Potassium Ions on Act of Amphotericin B to the DPPC/Chol Mixed Monolayer at Different Surface Pressures.

Amphotericin B (AmB) is an antifungal drug that rarely develops resistance. It has an affinity with the cholesterol on mammalian cell membranes, disrupting the structure and function of the membranes, which are also affected by potassium ions. However, the mechanism is unclear. In this paper, the Langmuir monolayer method was used to study the effects of potassium ions on the surface pressure-mean molecular area of isotherms, elastic modulus and the surface pressure-time curves of a 1,2-dipalmitoyl-sn-glycero-3-phosphocholine/cholesterol (DPPC/Chol) monolayer and a DPPC/Chol/AmB monolayer. The morphology and thickness of the Langmuir-Blodgett films were studied via atomic force microscopy. The results showed that AmB can increase the mean molecular area of the DPPC/Chol mixed monolayer at low pressures (15 mN/m) but reduces it at high pressures (30 mN/m). The potassium ions may interfere with the effect of AmB in different ways. The potassium ions can enhance the influence of AmB on the stability of monolayer at low surface pressures, but weaken it at high surface pressures. The potassium ions showed significant interference with the interaction between AmB and the cholesterol-enriched region. The results are helpful for us to understand how the effect of amphotericin B on the phospholipid membrane is interfered with by potassium ions when amphotericin B enters mammalian cell membrane.

Influence of the porphyrin structure and linker length on the interfacial behavior of phospholipid-porphyrin conjugates.

HYPOTHESIS: Phospholipid-porphyrin (Pl-Por) conjugates consist of porphyrin derivatives grafted to a lysophosphatidylcholine backbone. Owing to their structural similarities with phospholipids, Pl-Por conjugates can self-assemble into liposome-like assemblies. However, there is a significant lack of information concerning the impact of the porphyrin type and the length of the alkyl chain bearing the porphyrin on the interfacial behavior of the Pl-Por conjugates. We hypothesized that changing the chain length and the porphyrin type could impact their two-dimensional phase behavior and modulate the alignment between the two chains. EXPERIMENTS: 6 Pl-Por conjugates with different alkyl chain lengths in the sn2 position of C16 lysophosphatidylcholine and coupled to either pheophorbide-a or pyropheophorbide-a were synthesized. Their interfacial behavior at the air/water interface was assessed using Langmuir balance combined to a variety of other physical techniques including Brewster angle microscopy, atomic force microscopy and X-ray reflectometry. FINDINGS: Our results showed that all 6 Pl-Por form stable monolayers with the porphyrin moiety at the air/water interface. We also showed that changing the porphyrin moiety controlled the packing of the monolayer and thus the formation of organized domains. The chain length dictated the structure of the formed domains with no evidence of the alignment between the two chains.

Features of the Preparation and Luminescence of Langmuir-Blodgett Films Based on the Tb(III) Complex with 3-Methyl-1-phenyl-4-stearoylpyrazol-5-one and 2,2'-Bipyridine.

In this study, we investigated the effect of terbium ions (Tb3+) on the subphases of the limiting area of the molecule for the complex compound (CC) TbL3∙bipy (where HL is 3-methyl-1-phenyl-4-stearoylpyrazol-5-one and bipy is 2,2'-bipyridine). We examined the Langmuir monolayer and the change in the luminescence properties of TbL3∙bipy-based Langmuir-Blodgett films (LBFs). The analysis of the compression isotherms, infrared, and luminescence spectra of TbL3∙bipy LBFs was performed by varying the concentration of Tb3+ in the subphases. Our results demonstrate the partial dissociation of the CC at concentrations of C(Tb3+) < 5 × 10-4 M.