Monolayer Langmuir-Blodgett Films Research Articles

Enhanced luminescence and electrical conductivity of polymer ultrathin films doped with TiO2 nanoparticles

The chemical polymerization method was used to prepare nanocomposite materials of polyaniline (PANi) and Titanium dioxide (TiO2) nanoparticles. Ultrathin films were deposited by using the Langmuir Blodgett (LB) Technique. Surface Pressure vs mean molecular area isotherms of nanocomposite materials showed an increase in maximum attained surface pressure with variation in nanoparticle doping concentration. Photoluminescence (PL) spectra were taken for LB multilayers deposited on a quartz substrate, an increase in the intensity of PL peaks with increasing doping concentration of TiO2 nanoparticles. The topography of LB monolayer film under atomic force microscopy (AFM) revealed that films were uniformly and densely deposited on the substrate. Phase imaging ensured the presence of nanoparticles in the polymer matrix. Conductive atomic force microscopy (C-AFM) was used to investigate the local electrical properties of nanocomposite LB films. Current-voltage characteristics showed variation in current with changing doping concentrations of TiO2 nanocomposite in PANi matrix. The work presents new insights in analyzing uniformly deposited ultrathin films of the composites which can be probed by C-AFM to reveal local electric properties by understanding topography-current correlation at the nanoscale. The conductive data analysis could be useful for understanding the current flow through the nanostructure surface.

Interaction between polyene antifungal drug and saturated phospholipid monolayer regulated by calcium ions at the air-water interface

Amphotericin B (AmB) is a polyene antifungal drug, which could directly form pores on the sterol-free phospholipid monolayers. The interaction between AmB and phospholipid can be affected by calcium ions, but the mechanism is still unclear. DPPC is a saturated phospholipid with -PC group, which is often used to simulate the outer cell membrane leaflet. And DPPC is also the main constituent of pulmonary surfactants. In this work, the DPPC monolayer was used as a model membrane to study the effect of calcium ions on the interaction between AmB and phospholipid. The influence of different concentration of calcium ions on the elastic modulus, mean molecular area increment, excess Gibbs free energy and stability of the AmB/DPPC mixed monolayer has been researched at the surface pressure of 7.5 mN/m, 12.5 mN/m and 22.5 mN/m. The AmB/DPPC monolayers at the air-water interface have been observed in real-time by Brewster angle microscope and the microstructure of the Langmuir-Blodgett monolayer films transferred onto the mica have been researched by scanning electron microscope and atomic force microscope. The results showed that calcium ions had a significant influence on the elastic modulus, mean molecular area increment, excess Gibbs free energy, stability and microstructure of the AmB/DPPC monolayer. It has been indicated that the influence of calcium ions on the interaction between AmB and DPPC molecules mainly depended on the effect of calcium ions on the orientation of AmB molecules. The calcium ions could regulate the effect of AmB to the stability of the DPPC monolayer. This regulatory role changed with the different concentrations of calcium ions and the different phase states of the monolayer. This work provides useful information to further understand the influence mechanism of calcium ions on the interaction between AmB and saturated phospholipid with -PC group, which is helpful to find out the effect mechanism of calcium ion on the interaction between AmB and the outer layer of cell membrane or pulmonary surfactants in different phase states and to understand the toxicity mechanism of AmB on the cell membrane or lungs.

Mass sensitivity of Langmuir-Blodgett monolayer film coated surface acoustic wave resonators to volatile organic solvents

Langmuir-Blodgett (LB) monolayer films deposited from a Dipalmytoyl Phosphatidyl Ethanolamine head labelled with Nitrbenzoxadiazole (DPPE-NBD), have been studied for their ability to be used as sensing layer for chemical gas sensors. DPPE-NBD molecules are known for their similarity to bio membrane molecules. Therefore, it is expected that they can serve as a matrix for immobilization of proteins, enzymes, aptamers, while preserving their function for selective reaction with organic analytes. In this study, LB monolayers of DPPE-NBD were deposited on Rayleigh Surface Acoustic Wave (RSAW) resonant devices working at 411 MHz and simultaneously on ultra-flat Si wafer substrates for Atomic Force Microscopy (AFM) inspection. Depositions were carried out both at a low surface pressure where the liquid-expanded phase dominates, and at a high surface pressure, where the liquid-condensed (solid) phase dominates. AFM topography reveals the liquid and solid phase coexistence as well as the formation of 3D pyramids of 3 to 30 nm height and 50 to 1000 nm in diameter. In a vapour sensing experiment, the RSAW devices were exposed subsequently to vapours of 6 volatile organic compounds (VOCs) and water. The most significant resonant frequency shift of 225 kHz which corresponds to 11.42 ng mass change was observed with chloroform vapours when the substrate with the solid phase LB monolayer was used as a sensing layer. Adsorption and desorption of the vapours was very fast (a few seconds) and completely reversible. The higher-pressure deposited LB film demonstrates higher sensitivity to all gases. Mechanisms of this behaviour are discussed.

Sustained and improved enzymatic activity of trypsin immobilized in the Langmuir Blodgett film of DPPC: A rapid enzyme sensor for the detection of Azocasein

Immobilizing enzymes on biomimicking monolayer ultrathin films of phospholipids exhibit enhanced enzymatic activities (EAs) useful for biosensing applications. Preparation of such substrates with enzyme Trypsin (TRYP) immobilized in dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) matrix with enhanced and sustained enzymatic activity is a real challenge, as the isoelectric point of TRYP is reported to exist at pH ~ 10.5. This paper reports for the first time a facile procedure to fabricate smart substrates of TRYP entrapped in the DPPC monolayer using Langmuir–Blodgett (LB) technique. The incorporation of TRYP into DPPC monolayer at the air–water interface has been demonstrated from adsorption kinetics (π – t), room temperature surface pressure–area (π – A) isotherm plot and compressibility (β – π) studies. Circular dichroism (CD) and Grazing angle IR (GAIR) spectra signify changes in the secondary structure of incubated TRYP when immobilized in DPPC monolayer. Improved and sustained EA of TRYP upon its incubation on the organized monolayer LB films of DPPC has been observed. The reason behind such improvement in the EA of immobilized TRYP has also been suggested. The as fabricated substrates of immobilized TRYP can be used to sense soy milk, soy yoghurt, mayonnaise, meringue etc. using Azocasein as the protease substrate.

Methanol and Humidity Capacitive Sensors Based on Thin Films of MOF Nanoparticles.

The successful development of modern gas sensing technologies requires high sensitivity and selectivity coupled to cost effectiveness, which implies the necessity to miniaturize devices while reducing the amount of sensing material. The appealing alternative of integrating nanoparticles of a porous metal-organic framework (MOF) onto capacitive sensors based on interdigitated electrode (IDE) chips is presented. We report the deposition of MIL-96(Al) MOF thin films via the Langmuir-Blodgett (LB) method on the IDE chips, which allowed the study of their gas/vapor sensing properties. First, sorption studies of several organic vapors like methanol, toluene, chloroform, etc. were conducted on bulk MOF. The sorption data revealed that MIL-96(Al) presents high affinity toward water and methanol. Later on, ordered LB monolayer films of MIL-96(Al) particles of ∼200 nm were successfully deposited onto IDE chips with homogeneous coverage of the surface in comparison to conventional thin film fabrication techniques such as drop-casting. The sensing tests showed that MOF LB films were selective for water and methanol, and short response/recovery times were achieved. Finally, chemical vapor deposition (CVD) of a porous thin film of Parylene C (thickness ∼250-300 nm) was performed on top of the MOF LB films to fabricate a thin selective layer. The sensing results showed an increase in the water selectivity and sensitivity, while those of methanol showed a huge decrease. These results prove the feasibility of the LB technique for the fabrication of ordered MOF thin films onto IDE chips using very small MOF quantities.

Structural and optical properties of two-dimensional gadolinium stearate Langmuir monolayer

Langmuir-Blodgett (LB) films having large stack of amphiphilic-fatty-acids bearing rare-earth-ions are ideal two-dimensional magnetic systems to study spin-vortex ordering as the distances of the magnetic-ions along the out-of-plane and in-plane directions differ by an order of magnitude. Here we present results of in-situ X-ray scattering measurements on Langmuir monolayer of the amphiphilic stearic acid on the water surface containing Gadolinium ions to understand the formation process of monolayer and multilayer LB films on the substrates. Infrared spectroscopy and microscopy measurements were also carried out to understand the growth and transfer mechanism of the LB films.

Effect of nano clay Laponite on stability of SHG active J-aggregate of a thiacyanine dye onto LB films

We have investigated the stability of Second Harmonic Generation (SHG) active J-aggregate of a thiacyanine dye N, N′-dioctadecylthiacyanine perchlorate (TC18) in Langmuir-Blodgett (LB) films in presence and absence of a synthetic clay mineral Laponite. Surface pressure vs area per molecule isotherm was taken to observe the monolayer stability and UV–vis absorption, deconvolution of the absorption spectra, Atomic Force Microscopy (AFM), X-Ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR) etc. have been employed to investigate the stability. It has been observed that pure TC18 J-aggregates degrades with irradiation of light, passage of time as well as post heat treatment of the TC18 J-aggregated LB films. However, in case of TC18 – Laponite hybrid films the decrease in J-aggregate is minimal. Interestingly, it was observed that the relative humidity plays a major role in the reconstruction of the J-aggregate in the treated film and thereby stabilizes the J-aggregate. Both pure TC18 and TC18 – Laponite hybrid LB monolayer films are found to be SHG active. In case of TC18 – Laponite hybrid film SHG signal shows better stability.

Reversible Monolayer-Bilayer Transition in Supported Phospholipid LB Films under the Presence of Water: Morphological and Nanomechanical Behavior.

Mixed monolayer Langmuir-Blodgett (LB) films of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) and cholesterol (Chol) in the 1:1 ratio have been prepared onto solid mica substrates. Upon immersion in water or in an aqueous HEPES solution (pH 7.4) the monolayer LB films were spontaneously converted into well-organized bilayers leaving free mica areas. The process has been demonstrated to be reversible upon removal of the aqueous solution, resulting in remarkably free of defects monolayers that are homogeneously distributed onto the mica. In addition, the nanomechanical properties exhibited by the as-formed bilayers have been determined by means of AFM breakthrough force studies. The bilayers formed by immersion of the monolayer in an aqueous media exhibit nanomechanical properties and stability under compression analogous to those of DPPC:Chol supported bilayers obtained by other methods previously described in the literature. Consequently, the hydration of a monolayer LB film has been revealed as an easy method to produce well-ordered bilayers that mimic the cell membrane and that could be used as model cell membranes.

Nanocomposite biomimetic vesicles based on interfacial complexes of polyelectrolytes and colloid magnetic nanoparticles

Development and study of novel biomimetic and biocompatible functional nanofilm structures, surfaces and colloid membranous vesicles are currently important from fundamental and applied viewpoints. They can serve as model systems for insight into the basic structural-functional interconnections and physicochemical mechanisms at the nano-scale in biomembranous systems, and are useful for development of engineering solutions efficient for bio-medical applications including controlled drug delivery. We present here the results of a study of novel nanofilm composite structures (Langmuir monolayers, Langmuir-Blodgett films and liposomes) based on the interfacial complexes formed by biogenic lipid phosphatidylcholine, synthetic amphiphilic water-insoluble polyamine stearoylspermine (a derivative of biogenic polyamine spermine and stearic acid), colloid cationic ligand-free magnetite nanoparticles and polyanions (DNA, Poly(styrenesulfonate)). It was found that stearoylspermine molecules formed stable Langmuir monolayer on an aqueous subphase surface and that monolayer compression isotherm changed as a result of interactions of the stearoylspermine monolayer with aqueous subphase components (colloid cationic magnetite nanoparticles and polyanions). Monolayer Langmuir-Blodgett films of interfacial polycomplexes formed by stearoylspermine and magnetite nanoparticles or DNA molecules were deposited onto the mica substrate surface and the structure of polycomplex films was investigated using AFM. The data obtained using Langmuir monolayer technique were further used in formation of new composite nanofilm magnetic colloidal membranous vesicles based on the interfacial polycomplexes of phosphatidylcholine, stearoylspermine, magnetite nanoparticles and polyanions. The nanocomposite membranous vesicles were prepared successfully by sequential adsorption of colloid cationic ligand-free magnetite nanoparticles and polyanions onto the cationic surface of mixed phosphatidylcholine/stearoylspermine liposomes preliminarily formed using conventional ultrasound method. The formed vesicles were characterized by transmission electron microscopy, AFM, electron magnetic resonance technique, laser light scattering and electrophoresis techniques. The synthesized stable biocompatible nanocomposite magnetic liposomal vesicles can be useful in development of novel efficient systems for capsulation, targeted transport, controlled spatial localization and physical stimuli-addressed drug and DNA delivery.

Preparation of phthalocyanine-bound myristoyl celluloses for photocurrent generation system

The influences of two structural modifications on the photocurrent generation performance of the Langmuir–Blodgett (LB) film of the 6-O-phthalocyaninyl cellulose derivative were investigated. These structural modifications were the substituent groups at the O-2 and O-3 positions, and the central metal of the phthalocyanine moiety. Specifically, 6-O-Zn/phthalocyaninyl- (8a) and Pd/phthalocyaninyl (8b) -2,3-di-O-myristoylcelluloses were prepared instead of 6-O-Zn/phthalocyaninyl-2,3-di-O-myristylcellulose (2). The LB monolayer film of compound 8a on an indium thin oxide electrode showed higher photocurrent generation performance than that of compound 2. This suggested that myristoyl groups (C-14 acyl groups) were more beneficial to photocurrent generation than myristyl groups (C-14 alkyl groups), as the substituent at the O-2 and O-3 positions. The LB monolayer film of compound 8b showed photocurrent generation from 500 to 700 nm, although a blue-shift in the Q-band maximum was observed. The photocurrent generation performance of compound 8b was significantly higher than that of compound 8a. This indicated that Pd was more beneficial to photocurrent generation than Zn. The film of compound 8b prepared by the horizontal lifting method showed better photocurrent generation performance than that prepared by the vertical dipping method. Consequently, compound 8b is a complementary material to the porphyrin-appended cellulose derivative (1) for photocurrent generation system.

Study of Langmuir-Blodgett films of chiral nematic liquid crystals prepared by a templating method

The ordered alignment of liquid crystal molecules plays a critical role in the applications of their optical properties. Langmuir-Blodgett (LB) monolayer films of chiral nematic liquid crystal, 4-cyano-4′-pentylbiphenyl(5CB), doped with a proprietary left-handed chiral additive were prepared using stearic acid (SA) as template. The Langmuir isotherms of the chiral nematic liquid crystal at the CdCl2 interface with SA were studied. In the surface pressure curves, there was one sharp peak at the transition from gas phase to liquid phase. The phenomenon is considered to be the phase-separation of liquid crystals from SA. The chiral nematic liquid crystal multilayers LB films were characterized by ultraviolet-visible spectroscopy, X-ray diffraction, and atomic force microscopy. The results show that the chiral nematic liquid crystals were homogeneously and regularly dispersed in the SA template.

Langmuir monolayers and Langmuir-Blodgett films of pH-sensitive lipid

Colloidal membranous vesicles based on the functionalized liposomes are promising for development of novel efficient systems of controlled and stimuli-triggered drug delivery. In particular, the specific metabolism of cancer cells results in significant acidification in tumors, and thus the corresponding pH value changes can be used as a stimulus for drug release specifically in the tumor areas. pH-sensitive liposomes can be formed via incorporation of special pH-sensitive amphiphilic compounds into the liposomal membrane. Molecules of such compounds undergo a conformational transition caused by certain changes in the pH value of aqueous environment and resulting in corresponding membrane perturbations with rapid leakage of drug content from those liposomes into the areas with corresponding acidity. In the present work the pH-induced changes of Langmuir monolayer compression isotherm and of the structure of corresponding Langmuir-Blodgett films of pH-sensitive synthetic lipid trans-4,5,didodecyloxycarbonyl-trans-2-morpholinocyclohexanol have been observed and studied. The substantial expansion of Langmuir monolayer of that lipid caused by change of the aqueous subphase pH value from 7 to 5 was observed. Corresponding monolayer Langmuir-Blodgett films were deposited on mica substrate surface and studied using AFM technique. The substantial differences in the structure of Langmuir-Blodgett films deposited at pH values 7 and 5 were found. The observed effects directly demonstrate the pH-induced structural transformations in organized condensed planar molecular systems formed by pH-sensitive lipid molecules which underlie the pH-sensitivity of corresponding liposomal bilayer membranes containing such lipids.

All‐Carbon Electrode Molecular Electronic Devices Based on Langmuir–Blodgett Monolayers

Nascent molecular electronic devices, based on monolayer Langmuir-Blodgett films sandwiched between two carbonaceous electrodes, have been prepared. Tightly packed monolayers of 4-((4-((4-ethynylphenyl)ethynyl)phenyl)ethynyl)benzoic acid are deposited onto a highly oriented pyrolytic graphite electrode. An amorphous carbon top contact electrode is formed on top of the monolayer from a naphthalene precursor using the focused electron beam induced deposition technique. This allows the deposition of a carbon top-contact electrode with well-defined shape, thickness, and precise positioning on the film with nm resolution. These results represent a substantial step toward the realization of integrated molecular electronic devices based on monolayers and carbon electrodes.

Metal ion-induced H-aggregation of a water-soluble anionic dye Congo red (CR) in Langmuir–Blodgett (LB) film

Present communication reports the preparation of Langmuir monolayer of water-soluble anionic dye Congo red (CR) by allowing it to adsorb from the aqueous subphase onto the preformed Langmuir monolayer of anionic stearic acid using divalent metal cations Mg2+ as mediator. Isotherm and compressibility studies of SA-Mg-CR hybrid monolayer gave valuable information about the molecular organisation in the Langmuir monolayer. Absorption spectroscopic studies revealed the formation of H-aggregates in the hybrid Langmuir–Blodgett (LB) films fabricated at lower salt concentration in the subphase. Atomic Force Microscopic image gave visual evidence of distinct nanocrystalline domains in the LB monolayer film.

Factors affecting photocurrent generation performances of Langmuir–Blodgett films of tetraphenylporphyrin-bound acyl celluloses

Various Langmuir–Blodgett (LB) films of tetraphenylporphyrin (TPP)-bound acyl celluloses with different degrees of substitution of the TPP groups (DSTPP) and different acyl groups were prepared. TPP-bound acyl celluloses with DSTPP values less than 0.38 and myristoyl groups as the O-2 and O-3 substituents were suitable for obtaining LB mono-layer films with high quantum yields. The horizontal lifting method was better than the vertical dipping method for the deposition of LB films. The number of layers in LB multi-layer films of TPP-bound myristoyl cellulose with a DSTPP of 0.36 also influenced the quantum yield, and the quantum yield of the LB di-layer film was higher than those of the LB mono- and tri-layer films. This information will be useful in the improvement of the photocurrent generation performances of LB films of TPP-bound acyl celluloses.

Preparation of a squaraine-bounded cellulose derivative for photocurrent generation system

A regio-selectively squaraine (SQ)-bounded cellulose derivative (4) with a degree of substitution of SQ (DSSQ) of 0.55 was prepared from 6-O-(4-methoxytrityl) cellulose (1) by three reaction steps in 77% total yield. Lauryl SQ carboxylate (8) was also prepared as a reference sample. The photostability of SQ moieties of compound 4 in CHCl3 was not improved when compared with SQ-COOH (7), but that of SQ moiety of compound 8 was improved unexpectedly. The Langmuir–Blodgett monolayer films 4B and 8B on an indium tin oxide (ITO) electrode were successfully prepared from compounds 4 and 8 by a vertical dipping method, respectively. The films 4B and 8B showed photocurrent generation performances in the region of 550–680 nm. The quantum yield at 650 nm of film 4B was higher than that of film 8B. These results showed that the cellulose backbone of compound 4 acts as an effective scaffold for the good photocurrent generation performances and that compound 4 was a promising complementary material of the porphyrin-bounded cellulose derivatives (for photocurrent generation at 400–420 nm) for effective utilization of solar light, as well as the phthalocyanine-bounded cellulose derivatives (for photocurrent generation at 650–720 nm).

Monolayers Langmuir-Blodgett Films of Synthetic Artificial Mimic Molecules That Resemble the Following Tetraether Lipids on Silicon Wafers

This study investigated the behavior and molecular organization of synthetic artificial mimic molecules that resemble the following tetraether lipids: di-O-hexadecyl-glycero-3-phosphatidyl-glycerol (DHGPG) and bis-4-dodecylphenyl-12-phosphate. These molecules were analyzed using Langmuir film balance, ellipsometry and atomic force microscopy. The monolayer Langmuir-Blodgett films of DHGPG and bis-4-dodecylphenyl-12-phosphate were stable on the solid surface silicon wafers. The ellipsometry and AFM results showed that monolayers Langmuir-Blodgett films of DHGPG and bis-4-dodecylphenyl-12-phosphate were present, and the thickness of the observed films varied from 1.2 - 5.0 nm.

Single Gold Atom Containing Oligo(phenylene)ethynylene: Assembly into LB Films and Electrical Characterization

Monomolecular films of an oligo(phenylene)ethynylene, OPE, derivative [2-isocyano-1,3-dimethylbenzene][4-(4′-aminophenylethynyl)phenylethynyl]gold, 1, containing a gold atom in the molecule backbone have been prepared by the Langmuir–Blodgett (LB) method in order to study how the electrical properties can be modulated in monolayers of OPEs by incorporation of a gold center in their structures. UV–vis reflection spectra of Langmuir monolayers of 1 at the air–water interface reveal strong aurophilic interactions between neighboring molecules that increase upon compression. Monolayer Langmuir–Blodgett (LB) films were readily fabricated by the transfer of Langmuir films of 1 onto solid substrates. Quartz crystal microbalance (QCM) experiments conclusively demonstrate formation of monolayer LB films with a high surface coverage. The morphology of these films was analyzed by atomic force microscopy (AFM), revealing formation of homogeneous layers with an optimum surface pressure of transference of 6 mN·m–1. Fil...

Easily processable highly ordered Langmuir-Blodgett films of quaterthiophene disiloxane dimer for monolayer organic field-effect transistors.

Self-assembly of highly soluble water-stable tetramethyldisiloxane-based dimer of α,α'-dialkylquaterthiophene on the water-air interface was investigated by Langmuir, grazing incidence X-ray diffraction, and X-ray reflectivity techniques. The conditions for formation of very homogeneous crystalline monolayer Langmuir-Blodgett (LB) films of the oligomer were found. Monolayer organic field-effect transistors (OFETs) based on these LB films as a semiconducting layer showed hole mobilities up to 3 × 10(-3) cm(2)/(V s), on-off ratio of 10(5), small hysteresis, and high long-term stability. The electrical performance of the LB films studied is close to that for the same material in the bulk or in the monolayer OFETs prepared from water vapor sensitive chlorosilyl derivatives of quaterthiophene by self-assembling from solution. These findings show high potential of disiloxane-based LB films in monolayer OFETs for large-area organic electronics.

Photoresponsive LB Films under Light Irradiation Observed by Time-Resolved XRR

Langmuir-Blodgett (LB) films containing azobenzene undergo reversible structural change under light irradiation because of trans-to-cis or cis-to-trans transformations of azobenzene molecules. Such films are a candidate for molecular machines. Time resolved measurements of specular X-ray reflectivity (XRR) curves were carried out for polymer specimens of azobenzene-containing polyvinil alcohol (6Az10-PVA) monolayer LB films on quartz substrates during light (365 nm or 436 nm) irradiation (1 mW/cm2). Measurements were performed with a time-resolution of 10 s using an X-ray reflectometer [1, 2], which can simultaneously measure the whole XRR curves with no need to rotate the specimen, detector or monochromator crystal. Profiles of XRR curves changed as a function of the elapsed time after initiation of the light irradiation reflecting the structural change of the film. Despite of a common belief that the photo-induced structural change occurs directly between the initial and final states, we found an evidence of the existence of the intermediate third structure. We also found that the time needed for changes in XRR curves was several times longer than for optical absorption spectroscopy (OAS) spectra reported with the same irradiation power. Details of such changes of XRR curves and structures of the film will be discussed and compared with the changes of OAS spectra. An XRR curve for the intermediate state of the 6Az10-PVA monolayer LB film specimen separated from the XRR curves measured under 365 nm light irradiation is shown in the figure together with curves for the initial and final states of the same specimen.