On the stability of Langmuir films of pyramidic mesogens

Abstract

Pyramidic mesogens forming thermotropic liquid crystal bulk phases were spread in an air-water interface. Pressure surface measurements and polarizing microscopy on the Langmuir films were used to characterize the various states of these pyramidic-like molecules. For two compounds bearing short lateral aliphatic chains, the surface pressure isotherms exhibit a large plateau region corresponding to a metastable monolayer in which the molecules may adopt an ‘edge-on’ arrangement. The coexistence of multilayered, anisotropic, slowly growing domains with the monolayer in the plateau region has been observed at long time scale. The film area relaxation kinetics at constant surface pressure show the existence of two nucleation mechanisms for the formation of these domains.     

Phage Langmuir monolayers and Langmuir–Blodgett films

Stable, insoluble Langmuir monolayer films composed of Staphylococcus aureus-specific lytic bacteriophage were formed at an air–water interface and characterized. The phage monolayer was very strong, withstanding a surface pressure of ～40 mN/m at 20 °C. The surface pressure–area (Π–A) isotherm possessed a shoulder at ～7 × 10⁴ nm²/phage particle, attributed to a change in phage orientation at the air–water interface from horizontal to vertical capsid-down/tail-up orientation as surface pressure was increased. The Π–A-dependence was accurately described using the Volmer equation of state, assuming horizontal orientation to an air–water interface at low surface pressures with an excluded area per phage particle of 4.6 × 10⁴ nm². At high pressures phage particles followed the space-filling densely packed disks model with a specific area of 8.5 × 10³ nm²/phage particle. Lytic phage monolayers were transferred onto gold-coated silica substrates from the air–water interface at a constant surface pressure of 18 mN/m by Langmuir–Blodgett method, then dried and analyzed by scanning electron microscopy (SEM) and ellipsometry. Phage specific adsorption (Γ) in Langmuir–Blodgett (LB) films measured by SEM was consistent with that calculated independently from Π–A isotherms at the transfer surface pressure of 18 mN/m (Γ = 23 phage particles/μm²). The 50 nm-thickness of phage monolayer measured by ellipsometer agreed well with the horizontal phage average size estimated by SEM. Surface properties of phage Langmuir monolayer compare well with other monolayers formed from nano- and micro-particles at the air–water interface and similar to that of classic amphiphiles 1,2-diphytanoyl-sn-glycero-3-phosphocholine (phospholipid) and stearic acid.     

Nonequilibrium phases of nanoparticle Langmuir films

We report on an in-situ observation of the colloidal silver nanoparticle self-assembly into a close-packed monolayer at the air/water interface followed by a 2D to 3D transition. Using the fast tracking GISAXS technique, we were able to observe the immediate response to the compression of the self-assembled nanoparticle layer at the air/water interface and to identify all relevant intermediate stages including those far from the equilibrium. In particular, a new nonequilibrium phase before the monolayer collapse via the 2D to 3D transition was found that is inaccessible by the competing direct space imaging techniques such as the scanning and transmission electron microscopies due to the high water vapor pressure and surface tension.     

On the formation of calcium carbonate thin films under Langmuir monolayers of stearic acid

In this publication, we describe the growth of thin films of calcium carbonate beneath Langmuir monolayers of stearic acid. The size and shape of the crystalline structures were systematically studied by means of different microscopic techniques including Brewster angle microscopy, atomic force microscopy and scanning electron microscopy. In a series of experiments, we explored the calcium carbonate crystallization process for different lipid monolayers and subphases. The observed phenomena support a crystallization process which is induced by a thin, film-like structure of a precursor phase. The basic processes of crystal and aggregate formation can be represented by a simple model which is based on electrostatic interactions between the surfactant film and the inorganic calcium carbonate structures.     

Alkyl-thiol Langmuir films on the surface of liquid mercury

The coverage dependent phase behavior of monolayers of alkyl thiols (CH3(CH2)(n-1)SH, denoted as CnSH) on mercury was studied for chain lengths 9 相似文献   

Langmuir and langmuir-blodgett films of metallosupramolecular polyelectrolyte-amphiphile complexes

A detailed analysis of a metallosupramolecular polyelectrolyte-amphiphile complex (PAC) at the air-water interface is presented. Langmuir isotherms, Brewster angle microscopy, and X-ray reflectance and diffraction methods are employed to investigate the structure of the Langmuir monolayers. The PAC is self-assembled from 1,3-bis[4'-oxa-(2,2':6',2' '-terpyridinyl)]propane, iron acetate, and dihexadecyl phosphate (DHP). Spreading the PAC at the air-water interface results in a monolayer that consists of two strata. DHP forms a monolayer at the top of the interface, while the metallosupramolecular polyelectrolyte is immersed in the aqueous subphase. Both strata are coupled to each other through electrostatic interactions. The monolayers can be transferred onto solid substrates, resulting in well-ordered multilayers. Such multilayers are model systems for well-ordered metal ions in two dimensions.     

Effect of metal cations on polydiacetylene Langmuir films

Polydiacetylene (PDA) Langmuir films (LFs) are a unique class of materials that couple a highly aligned conjugated backbone with tailorable pendant side groups and terminal functionalities. The films exhibit chromatic transitions from monomer to blue polymer and finally to a red phase that can be activated optically, thermally, chemically, and mechanically. The properties of PDA LFs are strongly affected by the presence of metal cations in the aqueous subphase of the film due to their interaction with the carboxylic head groups of the polymer. In the present study the influence of divalent cadmium, barium, copper, and lead cations on the structural, morphological, and optical properties of PDA LFs was investigated by means of surface pressure-molecular area (π-A) isotherms, atomic force microscopy, optical absorbance, and Raman spectroscopy. The threshold concentrations for the influence of metal cations on the film structure, stability, and phase transformation were determined by π-A analyses. It was found that each of the investigated cations has a unique influence on the properties of PDA LFs. Cadmium cations induce moderate phase transition kinetics with reduced domain size and fragmented morphology. Barium cations contribute to stabilization of the PDA blue phase and enhanced linear strand morphology. On the other hand, copper cations enhance rapid formation of the PDA red phase and cause fragmented morphology of the film, while the presence of lead cations results in severe perturbation of the film with only a small area of the film able to be effectively polymerized. The influence of the metal cations is correlated with the solubility product (K(sp)), association strength, and ionic-covalent bond nature between the metal cations and the PDA carboxylic head groups.     

Dynamic surface tensiometry of tissues using Langmuir films

Langmuir monolayers are useful models of biomembranes as they allow simulation of biological conditions and rigorous thermodynamic analysis. This technique was used to characterize tissues at body temperature for the first time in our study. The organs studied include liver, kidney, stomach, testis, heart and brain from goat and certain human cancerous as well as their corresponding normal biopsies to reveal the potential of the tissue monolayer technique. Monolayers were formed on the surface of deionized water by spreading monolayer amounts of the tissue homogenates. The parameters calculated were minimum surface tension, relative lift off area, relative limiting area, compressibility and hysteresis area. Our results reveal that the parameters can differentiate between tissues obtained from different organs and were statistically significant using one-way ANOVA and Newman Keul's test (P<0.05). For example goat's stomach tissue had the lowest hysteresis area (DeltaG) value (27.6 microJ) whereas brain DeltaG value was nine folds higher than stomach value. Brain had the lowest minimum surface tension of 30.3+/-1.0 mN/m whereas stomach had a value of 40.5+/-0. 2 mN/m. Interestingly, the DeltaG values of human normal neck and esophageal tissues were 3.4 and 3.2 folds greater than that of their respective cancer tissues whereas the DeltaG values of vulval and breast cancer tissues were 4.6 and 4 folds greater than that of their respective normal tissues. While the gammamin values of neck cancer tissue showed 95% increase from normal tissue values, those of vulval and breast cancer tissues were 46 and 50% less compared to their respective normal tissue values. Though all the surface tensiometric parameters showed significant changes, minimum surface tension and hysteresis area were the most sensitive indicators of tissue types and diseased states. Further, the effects of therapeutics could also be monitored by this technique. This is evidenced by the post-radiotherapy tissue isotherms of neck and vulval cancers, where clinical radio-sensitivity was associated with a shift in the tensiometry towards their respective normal isotherms. The small sample amounts required, precision of the technique, very low within group variability, organ specificity and sensitivity to detect changes in diseased states make it a promising tool for prognostic evaluation of diseased states and monitoring effects of therapeutics. Further research is warranted in this promising and hitherto unexplored field of tissue tensiometry.     

Unexpected bilayer formation in Langmuir films of nucleolipids

Langmuir monolayers have been extensively investigated by various experimental techniques. These studies allowed an in-depth understanding of the molecular conformation in the layer, phase transitions, and the structure of the multilayer. As the monolayer is compressed and the surface pressure is increased beyond a critical value, usually occurring in the minimal closely packed molecular area, the monolayer fractures and/or folds, forming multilayers in a process referred to as collapse. Various mechanisms for monolayer collapse and the resulting reorganization of the film have been proposed, and only a few studies have demonstrated the formation of a bilayer after collapse and with the use of a Ca(2+) solution. In this work, Langmuir isotherms coupled with imaging ellipsometry and polarization modulation infrared reflection absorption spectroscopy were recorded to investigate the air-water interface properties of Langmuir films of anionic nucleolipids. We report for these new molecules the formation of a quasi-hexagonal packing of bilayer domains at a low compression rate, a singular behavior for lipids at the air-water interface that has not yet been documented.     

Langmuir and Langmuir-Blodgett films of amphiphilic bistable rotaxanes

A series of amphiphilic bistable [2]rotaxanes--in which a ring-shaped component, the tetracationic cyclophane, cyclobis(paraquat-p-phenylene), has been assembled around two recognition sites, a tetrathia-fulvalene (TTF) unit and a 1,5-dioxynaphthalene (DNP) ring system, situated apart at different strategic locations within the central polyether section of an amphiphilic dumbbell component that is terminated by a hydrophobic tetraarylmethane-based stopper (near the TTF unit) at one end and by a hydrophilic tetraarylmethane-based stopper (near the DNP ring system) at the other end--has been designed and synthesized. The effects of systematic changes in the constitutions of the three ethylene glycol tails (diethylene or tetraethylene glycol) and end groups (hydroxyl or methoxyl functions) attached to the hydrophilic stoppers on Langmuir film balance and surface rheology experiments at 20 degreesC were examined to determine the monolayer stabilities and co-conformations of the [2] rotaxanes and their free dumbbell counterparts. These experiments allow us to propose a model for the rotaxane's structures at different surface pressures. All the [2]rotaxanes form stable Langmuir films. These films typically pass from a liquid-expanded region to a liquid-condensed region. The transition between the two regions was either directly observed or ascertained using film stability experiments. Film balance and surface rheology experiments showed that the addition of the tetracationic cyclophane component and hydroxyl end groups markedly increased the stabilities and viscoelasticity of the films.     

Designing new lyotropic amphiphilic mesogens to optimize the stability of nematic phases

The factors which govern the stability of lyotropic amphiphilic nematic phases are delineated and then used to design mesogens which give rise to stable N_C and N_D phases on dissolution in water. The synthesis and phase behaviour of novel discoid amphiphiles, designed to form N_C phases, are described.     

Langmuir monolayer and Langmuir–Blodgett films of amphiphilic triblock copolymers with water-soluble middle block

Langmuir monolayers and Langmuir–Blodgett (LB) film morphology of amphiphilic triblock copolymers are studied using surface pressure-area measurements and atomic force microscopy (AFM), respectively. The triblock copolymers are composed of long water-soluble poly(ethylene oxide) (PEO) chains as middle block with very short poly(perfluorohexylethyl methacrylate) (PFMA) end blocks. The surface pressure-area isotherms show phase transitions in the brush regime. This phase transition is due to a rearrangement of PFMA block at the air–water interface. It becomes more significant with increasing PFMA content in the copolymer. LB films transferred at low surface pressures from the air–water interface to hydrophilic silicon substrates show surface micelles in the size range of 50–100 nm. A typical crystalline morphology of the corresponding PEO homopolymer is observed in LB films of copolymers with very short PFMA blocks, transferred in the brush region at high surface pressure. This crystallization is hindered with increasing PFMA content in the copolymer.     

From Langmuir–Blodgett films to single molecules

The author recollects his time in the group of D. Möbius in 1985–1986, within the department headed by Hans Kuhn, and the influence of Kuhn's concept of molecular assembly in the gestation of the first single-molecule experiments. He then briefly surveys the recent applications of single-molecule spectroscopy to complex and heterogeneous systems. In particular the field of single-molecule microscopy in membranes and at biological interfaces is now strongly growing, closing the circle back to Langmuir films, the systems which led to the development of single-molecule optical techniques.     

Structural phase transition in Langmuir films of vanadyl phthalocyanine

The Langmuir-Blodgett films based on vanadyl phthalocyanine (NHSO₂C₁₈H₃₇)₄ were studied. By the method of piezoresonance quartz balance, the isotherms of adsorption of water, pyridine, and hexane on film surfaces were obtained. A structural phase transition in the Langmuir films of vanadyl phthalocyanine at about 313 K was revealed. The phase transition was observed in ultrathin films and disappeared as the number of layers increased.     

Studies of Athabasca asphaltene Langmuir films at air-water interface

Asphaltenes are present in heavy oils and bitumen. They are a mixture of hydrocarbons having complex structures of polyaromatic rings and short side chains. In general, the high-molecular-weight asphaltene is the most aromatic fraction with the highest number of side chains and the low-molecular-weight asphaltene contains the lowest number of side chains, while the number of side chains of the whole asphaltene fraction lies in between. In this study, asphaltenes were extracted and/or fractionated from Athabasca oil sand bitumen. Subfractions of high and low molecular weight and the whole asphaltenes were characterized using a Langmuir trough and complementary techniques such as VPO, FTIR, AFM, and contact angle measurements. At an air-water interface, amphiphilic asphaltene molecules can form a monolayer. Various fractions (high, low, and whole) of the asphaltene molecules behave similarly at the air-water interface, characterized by close resemblance of their surface pressure-area, hysteresis, and relaxation isotherms. The high-molecular-weight asphaltene is the most expanded fraction, while the low-molecular-weight asphaltene fraction is the most condensed, with the whole asphaltene lying in between. At the air-water interface a monolayer of the low-molecular-weight asphaltene relaxes at a faster rate than one of the high-molecular-weight asphaltene.     

Order in amphiphilic polyimides: Cast and Langmuir films

Amphiphilic polyimides with side methylene tails and various chemical structure of the backbones have been studied in the “bulk” state (cast films) and in the form of multilayered molecular films (Langmuir films) by means of calorimetry, X-ray scattering and pressure-area diagrams.     

Langmuir monolayers and the transferred films of fluorinated amphiphiles containing vinyl groups

The monolayer behavior of long-chain esters of acrylic and methacrylic acids containing perfluoro or partially fluorinated carbon chains at the air/water interface was studied by surface pressure-area isotherm measurements and Brewster angle microscopy. It has been found that a minor change in the chemical structures of these fluorinated amphiphiles, such as a hydrogen substituted at the omega-position of the hydrophobic fluorocarbon tails instead of a fluorine as well as hydrophilic vinyl ester groups inserted between acrylates and methacrylates, induces a drastic change in the isotherms for the monolayers, suggesting different molecular orientation and packing in the films. The monolayers were transferred by horizontal lifting, Langmuir-Blodgett, and surface-lowering methods to give the X-, Y-, and Z-type films, respectively. These films were characterized by scanning probe microscopy, to clarify the mesoscopic surface structures of the molecular films exposed with the hydrophilic or hydrophobic moieties in air, depending upon the dipping methods. The Z-type films with the outermost surface of the fluorinated substituents were examined in relation to the frictional properties that strongly depend upon the fluorine and the hydrogen atoms at the end of the hydrophobic fluorocarbon chains, which is controllable at the atomic level.