Orientational correlations in two-dimensional liquid crystals studied by molecular dynamics simulation

Orientational correlations in Langmuir monolayers of nematic and smectic-C liquid crystal (LC) phases are investigated by molecular dynamics simulation. In both phases, the orientational correlation functions decay algebraically yet with the different exponents of 1.9 and 0.2 for the nematic and the smectic-C monolayers, respectively. The power law decay, i.e., the absence of long-range orientational order, means the both monolayers should be the ideal 2D system with a continuous symmetry, whereas the large difference in the exponents of power law gives rise to the crucial difference in their optical properties; the nematic monolayer is optically isotropic while the smectic-C monolayer exhibits an anisotropy on the length scale of visible light. Since the exponent is inversely proportional to the molecular exchange energy, the averaged molecular interaction in the nematic monolayer should be an order of magnitude smaller than that in the smectic-C monolayer, which is ascribed to the low molecular density and the weak molecular dipole due to the water molecule. The relation between the molecular interaction and the orientational correlation calculated for the 2D LC system offers much information not only about the 2D LCs but also on the bulk system.     

Alignment of liquid crystals using Langmuir‒Blodgett films of unsymmetrical bent-core liquid crystals

ABSTRACT

The properties of the thin films of liquid crystal (LC) molecules can be governed easily by external fields. The anisotropic structure of the LC molecules has a large impact on the electrical and optical properties of the film. The Langmuir monolayer (LM) of LC molecules at the air–water interface is known to exhibit a variety of surface phases which can be transferred onto a solid substrate using the Langmuir?Blodgett (LB) technique. Here, we have studied the LM and LB films of asymmetrically substituted bent-core LC molecules. The morphology of LB film of the molecules is found to be a controlling parameter for aligning bulk LC in the nematic phase. It was found that the LB films of the bent-core molecules possessing defects favour the planar orientation of nematic LC, whereas the LB films with fewer defects show homeotropic alignment. The defect in LB films may introduce splay or bend distortions in the nematic near the alignment layer which can govern the planar alignment of the bulk LC. The uniform layer of LB film facilitates the molecules of nematic to anchor vertically due to a strong van der Waals interaction between the aliphatic chains leading to a homeotropic alignment.     

Epitaxial growth of sexiphenyl on Al(111): from monolayer to crystalline films

A combination of in situ surface sensitive-techniques, UV photoemission and low energy electron diffraction, with ex situ bulk sensitive X-ray diffraction reveals the formation of epitaxial thin films of sexiphenyl on Al(111) starting from the first monolayer. For room temperature growth, highly ordered films are formed with a unique alignment of the sexiphenyl molecules with the long axes of all molecules aligned parallel to both the surface and the <10> azimuthal directions of Al(111). This is related to a densely packed highly commensurate first monolayer, which acts as a template for the unique (21) crystallite orientation observed.     

Structure and orientation of NH3 on clean and oxygen-precovered Al(111)

On clean Al(111) bonding of molecular NH₃ occurs via the N atom with a wide distribution of tilt angles of the molecular axis with respect to the surface normal and with random azimuthal orientation. Fractional monolayers of chemisorbed oxygen induce a high degree of local azimuthal orientation of the H atoms in adsorbed NH₃, in the absence of long-range order.     

Phase transitions in Langmuir monolayer of long chain attached fluorescein studied by second harmonic generation technique

Optical second harmonic generation (SHG) measurements coupled with Π-A isotherms have been shown to be helpful, for the following and comprehension of orientational orders and phase transitions in Langmuir monolayers. Using the SHG-(Π-A) measurements, monolayers of 5-hexadecanoylaminofluorescein on the water surface were examined by monolayer compression. The phase transitions were noticeably revealed. Dependence of the square root of the intensities polarizations quotient in the molecules surface density, allowed establishing tilting orientation alignment phases. In addition, change in the monolayer symmetry C_∞v→C_2v as it goes through the LE–LC phase transition, was clearly recognized. It was concluded that a possible change in β is taking place due to aggregate formation.     

Sum-frequency spectroscopic study of Langmuir monolayers of lipids having oppositely charged headgroups

Sum-frequency vibrational spectroscopy, with the help of surface pressure-area (π-A) isotherm, was used to study lipid Langmuir monolayers composed of molecules with positively and negatively charged headgroups as well as a 1:1 neutral mixture of the two. The spectral profiles of the CH(x) stretch vibrations are similar for all monolayers in the liquid-condensed (LC) phase. They suggest a monolayer structure of closely packed alkyl chains that are nearly all-trans and well oriented along the surface normal. In the liquid-expanded (LE) phase, the spectra of all monolayers appear characteristic of loosely packed chains with significant gauche defects. The OH stretch spectra of interfacial water for both positively and negatively charged monolayers are significantly enhanced in comparison with a neutral water interface, but the phase measurement of SFVS indicates that OH in the two cases points toward the bulk and the interface, respectively. The enhancement results mainly from surface-field-induced polar ordering of interfacial water molecules. For a charge-neutral monolayer composed of an equal number of positively and negatively charged lipid molecules, no such enhancement is observed. This mixed monolayer exhibits a wide range of LC/LE coexistence region extended to very low surface pressure and its CH(x) spectral profile in the coexistence region resembles that of the LC phase. This result suggests that in the LC/LE coexistence region, the mixed monolayer consists of coexisting LC and LE patches in which oppositely charged lipid molecules are homogeneously mixed and dispersed.     

Tunable self-organization in n-type liquid crystalline dibenzocoronene tetracarboxdiimides for high photoconductivity

ABSTRACT

A comprehensive study on the self-organised mesomorphism and charge-transport properties of three n-type liquid crystalline (LC) dibenzocoronene tetracarboxdiimide derivatives (Dibenzo-CDI 1, 2, 3) bearing branched alkyl chains with varied side-chain length and branching point (α or β site) has been carried out. All three Dibenzo-CDI compounds possessed high solubility in common organic solvents and low-lying lowest unoccupied molecular orbital energy levels below ?4.0 eV indicating their air-stable electron-transport capacity under ambient conditions. It is discovered that the side-chain length has a moderate influence on the molecular arrangement and thus leads to only limited variation of electron-transport properties. In contrast, the branching position plays a critical role on tuning molecular packing and orientation in the bulk mesophases, thereby resulting in dramatic differences in electron mobilities. Remarkably, Dibenzo-CDI 3 demonstrates good photoconductivity by time-of-flight method with high electron mobility up to 0.075 cm²/Vs, close to the highest value reported in certain n-type LC derivatives. All these results reveal that LC Dibenzo-CDI derivatives are potential candidates for high-performance solution-processable electronics, such as air-stable n-type organic field-effect transistors (OFETs) and solar cells.     

Insoluble mixed monolayers : II. Protolytic equilibria and the influence of the pH on the collapse pressure

A general thermodynamic treatment is given for the protolytic equilibria in an insoluble monolayer, containing surfactant molecules with n ionizable protons and able to accept m more protons, and being spread at the liquid/gas interface. The correlation between the pH of the subphase liquid and the collapse pressure of the monolayer is discussed. By using the approximation of perfect solutions and of binary surface systems (protonated and deprotonated molecular species of the surfactant) several methods are proposed for deriving apparent surface acidity constants from experimental collapse pressure vs pH curves, in the case of both miscible in monolayer miscible in collapsed bulk phase and miscible in monolayer immiscible in collapsed bulk phase, type systems. Some of these methods are based on a complete perfect solution approximation (CA) taking into account the molar fraction of the subphase liquid in the monolayer and the others use “surfactant” approximation (SA), neglecting this molar fraction. The methods proposed are tested on monolayers of carotenoid pigments spread at aqueous solution/air interfaces. Results obtained by the different methods are rather close to each other, but the approximation CA is better than SA. The apparent surface acidity constants of different carotenoids are compared with each other and discussed in terms of molecular structure and electronic effects.     

A new liquid surface neutron reflectometer and its application to the study of DPPC in a monolayer at the air/water interface

A constant wavelength neutron reflectometer is described. Using this reflectometer, the neutron reflectivities from phosphatidylcholine monolayers in the highly condensed LC phase on ultra pure H₂O and D₂O have been measured on a Wilhelmy film balance. The neutron reflectivities have been carefully compared with those obtained by the X-ray method applied to the same monolayer under similar conditions. A new approach to analyzing a combined set of data composed of X-ray and neutron reflectivities has been used. From the analysis it is concluded that despite their limited q_z range neutron reflectivities are as essential as X-ray reflectivities for the unique determination of the monolayer structure.     

Photo-reversible liquid crystal alignment using azobenzene-based self-assembled monolayers: comparison of the bare monolayer and liquid crystal reorientation dynamics

Photosensitive surfaces treated to have in-plane structural anisotropy by illumination with polarized light can be used to orient liquid crystals (LCs). Here we report a detailed study of the dynamic behavior of this process at both short and long times, comparing the ordering induced in the bare active surface with that of the LC in contact with the surface using a high-sensitivity polarimeter that enables detailed characterization of the anisotropy of the active surface. The experiments were carried out using self-assembled monolayers (SAMs) made from dimethylaminoazobenzene covalently bonded to a glass surface through a triethoxysilane terminus. This surface gives planar alignment of the liquid crystal director with an azimuthal orientation that can be controlled by the polarization of actinic light. We find a remarkable long-term collective interaction between the orientationally ordered SAM and the director field of the LC: while an azobenzene based SAM in contact with an isotropic gas or liquid relaxes to an azimuthally isotropic state in the absence of light due to thermal fluctuations, an orientationally written SAM in contact with LC in the absence of light can maintain the LC director twist permanently, that is, the SAM is capable of providing azimuthal anchoring to the LC even in the presence of a torque about the surface normal. We find that the short-time, transient LC reorientation is limited by the weak azimuthal anchoring strength of the SAM and by the LC viscosity.     

Calorimetric Investigation of the Monolayers Formed At Solid-liquid Interface

Heat capacity measurements have been made to investigate the formation of two solid monolayers each of n-pentane, n-heptane and n-dodecane adsorbed on graphite, one at submonolayer coverages and the other coexisting with the liquid. At submonolayer coverages the monolayers are found to melt respectively at 99.8, 151.6, and 217.3 K, well below the bulk melting points. The monolayers coexisting with the liquid melted at 205.6 for heptane and at 287.8 K for dodecane, whereas no evidence was obtained for pentane on the formation of such solid monolayer above the bulk melting point. The order persisting in the liquid near the interface depends upon the length of the molecules. The dodecane monolayers showed another transitions below the melting points both at submonolayer and multilayer coverages.This revised version was published online in November 2005 with corrections to the Cover Date.     

Use of electrochemical impedance spectroscopy to characterise the physical properties of ex situ reconstructed sea surface microlayer

The objective of this work was to develop electrochemical impedance spectroscopy (EIS) to characterise the physical properties of the sea surface microlayer ( ssm ). Samples from Lake Rogoznica in Croatia were extracted by n-hexane and dichloromethane (dcm) respectively and transferred to mercury electrodes. The EIS results were compared with those of a model phospholipid, dioleoyl phosphatidylcholine (DOPC) which forms near defect-free monolayers on a mercury surface. The ssm extracts formed inhomogeneous monolayers on the mercury surface and the dcm ssm extract monolayer showed greater surface roughness than the hexane ssm extract. The hexane ssm extract introduced defects and a greater surface roughness into mixed DOPC- ssm extract monolayers than the dcm ssm extract due to the lower compatibility of the non-polar hexane extract with the DOPC than that of the polar ssm extract. In addition, the dcm ssm component in the mixed DOPC- ssm monolayer showed an association with pyrene added to the solution.     

In‐Plane Structures of Synthetic Oligolactose Lipid Monolayers—Impact of Saccharide Chain Length

Grazing incidence X‐ray diffraction (GIXD) was used to investigate the in‐plane structure of monolayers of synthetic glycolipids with oligolactose head groups (Lac N, with N=number of lactose units) at the air/water interface. The Lac 1 monolayer exhibits three sharp diffraction peaks. One peak can be deconvoluted into two diffraction peaks, which suggests that alkyl chains in the monolayer form an orthorhombic lattice. On the other hand, the other two peaks are related to bulk crystalline materials residing at the interface. Another weak peak from the head group correlation, either in a monolayer or in bulk crystals, can also be observed in some experiments. The scattering patterns of the Lac 2 monolayer indicate that the alkyl chains order in an orthorhombic lattice, where a shift in the hydrophilic/hydrophobic balance seems to fluidize the film. Alkyl chains in the Lac 3 monolayer also seem to assume an orthorhombic lattice; however, a weak diffraction peak from the correlation between trilactose head groups can also be observed. The estimated lattice dimensions are compared systematically to those of bulk dispersions, as well as to the viscoelastic properties of the monolayer. The obtained results strongly suggest that the in‐plane structure of synthetic glycolipid monolayers can provide a well‐defined basis to understand the impact of the chemical structure on the cooperativity and function of the glycocalix of cellular surfaces.     

Fatty-acid monolayers at the nematic/water interface: phases and liquid-crystal alignment

The two-dimensional (2D) phases of fatty-acid monolayers (hexadecanoic, octadecanoic, eicosanoic, and docosanoic acids) have been studied at the interface of a nematic liquid crystal (LC) and water. When observed between crossed polarizers, the LC responds to monolayer structure owing to mesoscopic alignment of the LC by the adsorbed molecules. Similar to Langmuir monolayers at the air/water interface, the adsorbed monolayer at the nematic/water interface displays distinct thermodynamic phases. Observed are a 2D gas, isotropic liquid, and two condensed mesophases, each with a characteristic anchoring of the LC zenithal tilt and azimuth. By varying the monolayer temperature and surface concentration we observe reversible first-order phase transitions from vapor to liquid and from liquid to condensed. A temperature-dependent transition between two condensed phases appears to be a reversible swiveling transition in the tilt azimuth of the monolayer. Similar to monolayers at the air/water interface, the temperature of the gas/liquid/condensed triple-point temperature increased by about 10 degrees C for a two methylene group increase in chain length. However, the absolute value of the triple-point temperatures are depressed by about 40 degrees C compared to those of analogous monolayers at the air/water interface. We also observe a direct influence by the LC layer on the mesoscopic and macroscopic structure of the monolayer by analyzing the shapes and internal textures of gas domains in coexistence with a 2D liquid. An effective anisotropic line tension arises from elastic forces owing to deformation of the nematic director across phase boundaries. This results in the deformation of the domain from circular to elongated, with a distinct singularity. The LC elastic energy also gives rise to transition zones displaying mesoscopic realignment of the director tilt or azimuth between adjacent regions with a sudden change in anchoring.     

Orientational changes in dipalmitoyl phosphatidyl glycerol Langmuir monolayers

Dipalmitoyl phosphatidyl glycerol (DPPG) as Langmuir monolayers at the air/water interface was investigated by means of surface pressure measurements in addition to Brewster angle microscopy (BAM) during film compression/expansion. A characteristic phase transition region appeared in the course of surface pressure-area (pi-A) isotherms for monolayers spread on alkaline water or buffer subphase, while on neutral or acidic water the plateau region was absent. This phase transition region was attributed to the ionization of DPPG monolayer. It has been postulated that the ionization of the phosphatidyl glycerol group leads to its increased solvation, which probably provokes both a change in the orientation of the polar group and its deeper penetration into bulk phase. Film compression along the transition region provokes the dehydration of polar groups and subsequent change of their conformation, thus causing the DPPG molecules to emerge up to the interface. Quantitative Brewster angle microscopy (BAM) measurements revealed that along the liquid-expanded to liquid-condensed phase transition the thickness of the ionized DPPG monolayer increases by 4.2 A as a result of the conformational changes of the ionized polar groups, which tend to emerge from the bulk subphase up to the surface.     

Preparation,Characterization, and Electrochemical Behaviors of Self-Assembled Monolayer on Gold Electrode Surface with Mercapto-Derivatized Cobaltous Porphyrin

Abstract

5-[4-(3-Mercaptopropyloxy)phenyl]-10,15,20-tris (2-chlorphenyl) porphyrin was utilized for fabricating a self-assembled monolayer (SAM) on a gold electrode. Then cobalt(II) was inserted into the the monolayer by refluxing the cobalt(II) solution in which the pre-assembled porphyrin-modified electrode was immersed. The monolayers were characterized by cyclic voltammetry (CV). Oxidation and catalytic mechanisms of dopamine on the modified electrode were also investigated and elucited respectively. Catalytic currents increased linearly with dopamine (DA) concentration in the range of 1.0 × 10^?9 to 2.0 × 10^?3 mol/L with the correlation coefficient of 0.9989. The modified electrode can be help develop a simple, quick, sensitive, and accurate method for the determination of the biomolecules such as dopamine.     

General description of optical dichroic orientation factors for relating optical anisotropy of bulk polymer to orientation of structural units

The relationship between the optical anisotropy of high polymeric materials in bulk and the orientation of structural units within the materials was described in general by using several types of mean values of the orientation distribution function of three Eulerian angles, i.e., the orientation factors, under some assumptions about the symmetry of the function being applicable for the most of the industrial products. A newly defined biaxial orientation factor, F_θηⁱ = 〈sin² θ_j cos 2η_j〉, where θ_j and η_j are the polar and azimuthal angles of the jth axis within the structural unit with respect to the bulk axes, may relate the biaxial orientation of the structural units to the dichroic orientation factors, which are measurable optical anisotropic indices of the bulk materials. Some applications of the results to the birefringence and infrared and dye dichroism are also discussed.     

Methylene Blue Adsorption on a DMPA Lipid Langmuir Monolayer

Adsorption of methylene blue (MB) onto a dimyristoylphosphatidic acid (DMPA) Langmuir air/water monolayer is studied by molecular dynamics (MD) simulations, UV reflection spectroscopy and surface potential measurements. The free‐energy profile associated with MB transfer from water to the lipid monolayer shows two minima of ?66 and ?60 kJ mol^?1 for its solid and gas phase, respectively, corresponding to a spontaneous thermodynamic process. From the position of the free‐energy minima, it is possible to predict the precise location of MB in the interior of the DMPA monolayer. Thus, MB is accommodated in the phosphoryl or carbonyl region of the DMPA Langmuir air/water interface, depending on the isomorphic state (solid or gas phase, respectively). Reorientation of MB, measured from the bulk solution to the interior of the lipid monolayer, passes from a random orientation in bulk solution to an orientation parallel to the surface of the lipid monolayer when MB is absorbed.     

Liquid crystal phases in confined geometries

ABSTRACT

The orientation control of liquid crystal (LC) phases is essential for fundamental studies as well as practical applications. Surface treatment and topographic confinement have emerged as two of the most effective tools to control ordering and orientation of various types of LC phases. This review is intended to give an overview of the LC phases controlled in confined geometries at micro- and nanometre scales, in which the orientation control methods and the effective analytical techniques will be covered. Finally, the review closes with the applications using such confined LC phases.     

Synthesis and characterization of partially fluorinated stearolic acid analogs: Effect of their fluorine content on the monolayer at the air-water interface

Novel stearolic acid analogs (i.e., 9-octadecynoic acid analogs: 1a-d) containing the shorter perfluoroalkyl groups, CF₃, C₂F₅, n-C₃F₇ or n-C₄F₉ group were synthesized. Equilibrium spreading pressures (π_es) of their monolayers at the air-water interface were measured in order to demonstrate how the fluorine content has an effect on the stability of the fatty acid monolayers. As the fluorine content in stearolic acid molecule increased, its melting points was lowered indicating the solid bulk phase of stearolic acid became thermally unstable, while its monolayer stability evaluated by π_e at 25 °C, dramatically increased and subsequently leveled off above a certain fluorine content. Under this condition, the replacement of at least five hydrogen atoms at the terminal hydrophobic segment in stearolic acid molecule by fluorine atoms (CF₃CF₂ group) was required to alter the bulk property of stearolic acid and exhibit the stabilization of monolayers, whereas further fluorination of stearolic acid had a minor effect on the monolayer stability. This behavior suggests the terminal fluorinated hydrophobic segment exclusively controls the interfacial stability of fatty acid monolayers.