A novel photoalignment film for ferroelectric liquid crystal based on self-assembled monolayer method

A novel strategy based on self-assembly technology was devised for design of photosensitive material as a ferroelectric liquid crystal (FLC) alignment layer. This development offers new tools for the study and control at the molecular level of the interaction of FLCs with solid surfaces. The photoreactive material was self-assembled to the substrate by covalent bond linkage due to a special chemical adsorption reaction. Through ester bond linkage, a cyano group with strong polarity was introduced to be terminus of the film. Under irradiation of linearly polarised ultraviolet light, an optically anisotropic self-assembled film was easily obtained. The irradiated film was demonstrated to result in homogenous alignment of FLC by optical transmittance measurements and polarising optical microscopy images of a FLC cell at different rotation angles. The alignment quality of the FLC on this self-assembled monolayer film is comparable to that of commercial rubbed polyimide film. Furthermore, it was also found that the fine alignment of the FLC may be related to the smoothness of the self-assembled film surface owing to its polar end.     

Photoinduced anchoring transitions in a nematic doped with azo dyes

Recently, we reported on a light-induced anchoring transition of an azobenzene nematic from planar to homeotropic alignment. In the proposed model of the transition, the changes in shape of the liquid crystal molecules and of their net dipole moment, due to the photoisomerization, were considered to play a vital role in the occurrence of the transition. In order to assess the validity of this model, a study of the anchoring behaviour of nematic guest-host liquid crystal mixtures containing two photochromic dyes, 3,3'- and 4,4'-substituted azobenzenes, was carried out. The dyes have very similar molecular structures to that of the azobenzene nematic previously studied, and their molecules, having a linear shape in the trans-form, maintained this shape after photoisomerization in the case of the 3,3'-azo dye, and changed it to bent in the case of the 4,4'-azo dye. The dyes possessed similar net dipole moments that increased substantially after photoisomerization, resulting in a preferential adsorption of their cis-isomers on the solid substrate. However, only the mixture containing the 4,4'-azo dye exhibited an anchoring transition from planar to homeotropic alignment upon illumination with unpolarized UV light, a behaviour in excellent agreement with the prediction of the model for the light-induced anchoring transition. An anchoring transition from random planar to uniform planar alignment was found to take place in the mixtures when linearly polarized UV light was used, requiring, however, a different exposure time for the two dyes.     

Static and dynamic dielectric effects in the vicinity of the isotropic to nematic phase transition in 7CB

Static and dynamic dielectric measurements were performed with very high accuracy on a mesogenic compound n‐heptylcyanobiphenyl (7CB) in the isotropic (I) and nematic (N) phases. The critical‐like temperature behaviour of the static permittivity of isotropic 7CB in the vicinity of the I–N phase transition can be described with the critical exponent close to 0.5, indicating the tricritical nature of the transition. Anomalously slow rotational diffusion (subdiffusion), characterized by a fractal value of the diffusion exponent α, is observed in the vicinity of the I–N transition with a lambda‐like profile of the exponent temperature dependence.     

Director configurations in nematic droplets with tilted surface anchoring

The polymer dispersed nematic liquid crystal (LC) with the tilted surface anchoring has been studied. The droplet orientational structures with two point surface defects – boojums and the surface ring defect – are formed within the films. The director tilt angle α = 40° ± 4° at the droplet interface and LC surface anchoring strength W_s ~ 10^–6 (J m^?2) have been estimated. The bipolar axes within the studied droplets of oblate ellipsoidal form can be randomly oriented are oriented randomly relatively to the ellipsoid axes as opposed to the droplets with homeotropic and tangential anchoring.     

XPS and AFM characterization of aminosilanes with different numbers of bonding sites on a silicon wafer

The aim of this work was the preparation and characterization of a silicon surface modified by different self‐assembled aminopropylsilanes with the purpose of using them in sensor applications. Single‐crystal silicon wafers (111) were modified with aminosilanes that have different numbers of bonding sites: 3‐aminopropyltrimethoxysilane (APTMS), 3‐aminopropyldiethoxymethylsilane (APRDMS) and 3‐aminopropylethoxydimethylsilane (APREMS). We deposited the self‐assembled layers from a solution of aminosilanes in toluene under various reaction conditions. The surface composition and the chemical bonding were determined using X‐ray photoelectron spectroscopy. Furthermore, the surface morphology was investigated using atomic force microscopy. Our results show that the reactivity with the Si‐oxide layer and the polymerization of aminosilanes depend on the number of possible bonding sites. The APTMS reacted the most intensively with the Si‐oxide layer; a less intensive reaction was observed for the APRDMS; and the least intensive reaction was observed for the APREMS. Copyright © 2013 John Wiley & Sons, Ltd.     

Orientational instability of nematic liquid crystal in a homeotropic cell with boundary conditions controlled by an electric field

We study the orientational instability of the director in a homeotropic nematic liquid crystal (NLC) cell in a DC electric field. The electric field is applied along or perpendicular to a cell surface depending on whether anisotropy of dielectric permittivity of NLC is positive or negative. The easy axis on one of the cell polymer substrates is allowed to deviate in perpendicular to the substrate plane due to the influence of the NLC and the electric field. It was established that the orientational instability of the director can have a threshold as well as be thresholdless which depends on the character of the coupling of the easy axis with the electric field. The temporal behaviour of a director and the easy axis during transition to the stationary state after turning on electric field and returning to the initial homogeneous state after turning off the field was investigated. In the case of the negative anisotropy of the static permittivity, the comparison of experimental and calculated time dependences of the easy axis reorientation angle let us to estimate values of the mobile easy axis viscosity coefficient and coupling parameter describing the coupling between the easy axis and the electric field.     

Ionic liquid self‐assembled monolayer and ion exchange for surface force control

Adhesion and lateral force were controlled by the formation of a self‐assembled monolayer combined with the surface ion exchange of ionic liquids on a silicon surface. In this study, the functionalized imidazolium ionic liquids were designed and synthesized with the aim of controlling surface force. N‐[3‐(Trimethoxylsilyl)propyl] ethylenediamine molecules were first self‐assembled onto a surface as an anchor layer and then 1‐propionic acid‐3‐methylimidazolium chloride were successfully grafted onto the amino‐modified surface. The surface force was changed by surface ion exchange in various anionic solutions. The self‐assembly and ion exchange processes were detected by means of attenuated total reflectance‐Fourier transform infrared spectrometry and further confirmed by X‐ray photoelectron spectra. Adhesion and friction behaviors were systematically investigated by atomic force/friction force microscope. The results indicated that anions played a great role in determining surface properties. Furthermore, surface adhesion and friction can be possibly quantitatively determined by the counter‐anions on the surface. Copyright © 2011 John Wiley & Sons, Ltd.     

Electro-optical properties of photo-aligned photonic ferroelectric liquid crystal fibres

Electro-optical and spectral studies of isotropic photonic crystal fibre (PCF) infiltrated with photo-aligned ferroelectric liquid crystal (FLC) under influence of external electric field are described. Desired alignment of FLC molecules is provided by generation of photo-aligning surface on the inner side of PCF structure. Propagation of light spectrum, as well as light attenuation have been investigated in details. Moreover, the electro-optical response times were measured and analysed.     

Electro-disclinic effect in tilted smectic phases of banana-shaped liquid crystal materials

We give the first evidence that the director tilt angle can be reduced by electric fields in the tilted smectic phase of banana-shaped molecules. In these phases the value of polarization is determined by the molecular packing and no electro-clinic effect is expected. Our studies show that high electric fields eventually induce a meta-stable phase with zero director tilt. The tilted phase slowly recovers at low fields. We propose that the field-induced quenching of the layer fluctuations is responsible for the observed effects.     

Effect of carbon nanotubes on phase transitions of nematic liquid crystals

Phase diagrams of multi‐wall carbon nanotube (MWNT)/nematic liquid crystal (E7) and buckminsterfullerene (C₆₀‐I _h)/nematic liquid crystal (E7) binary systems have been investigated by means of polarizing optical microscopy and differential scanning calorimetry. It was found that the isotropic–nematic phase transition temperature (T _NI) of the liquid crystal component was enhanced by the incorporation of MWNT within a small composition gap. A chimney‐type phase diagram can be identified in the MWNT/E7 mixture over a narrow range of ～0.1–0.2% MWNT concentration. Upon substituting the nanotubes with isotropic fillers such as fullerene, the (C₆₀‐I _h)/E7 blend showed no discernible change of T _NI in the same concentration range of the chimney of the MWNT/E7 mixture, suggesting a significant contribution of anisotropy (or the aspect ratio) of the nanotubes to the entropy of the system containing liquid crystal molecules. This enhanced T _NI phenomenon may be attributed to anisotropic alignment of liquid crystal molecules along the carbon nanotube bundles.     

Simultaneous Determination of Dopamine and Ascorbic Acid at an In‐Site Functionalized Self‐Assembled Monolayer on Gold Electrode

The in‐site functionalization of 4‐aminothiophenol (4‐ATP) self‐assembled monolayer on gold electrode at physiological pH yields a redox active monolayer of 4′‐mercapto‐N‐phenylquinone diimine (MNPD). The functionalized electrode exhibits excellent electrocatalytic responses towards dopamine (DA) and ascorbic acid (AA), reducing the overpotentials by about 0.22 V and 0.34 V, respectively, with greatly enhanced current responses. Due to its different catalytic activities toward DA and AA, the modified electrode resolves the overlapping voltammetric responses of DA and AA into two well‐defined voltammetric peaks by differential pulse voltammetry (DPV), which can be used for the simultaneous determination of these species in a mixture. The catalytic peak current obtained from DPV was linearly related to DA and AA concentration in the ranges of 5.0×10^?6?1.25×10^?4 M and 8.0×10^?6?1.3×10^?4 M with correlation coefficient of 0.999 and 0.998, respectively. The detective limits (3σ) for DA and AA were found to be 1.2×10^?6 M and 2.4×10^?6 M, respectively. The modified electrode shows good sensitivity, selectivity and stability, and has been applied to the determination of DA and AA simultaneously in samples with satisfactory results.     

Spectroscopic quantification of covalently immobilized oligonucleotides

Quantitative determination of surface coverage, film thickness and molecular orientation of DNA oligomers covalently attached to aminosilane self‐assembled monolayers has been obtained using complementary infrared and photoelectron studies. Spectral variations between surface immobilized oligomers of the different nucleic acids are reported for the first time. Carbodiimide condensation was used for covalent attachment of phosphorylated oligonucleotides to silanized aluminum substrates. Fourier transform infrared (FTIR) spectroscopy and x‐ray photoelectron spectroscopy (XPS) were used to characterize the surfaces after each modification step. Infrared reflection–absorption spectroscopy of covalently bound DNA provides orientational information. Surface density and layer thickness are extracted from XPS data. The surface density of immobilized DNA, 2–3 (×10¹³) molecules cm^?2, was found to depend on base composition. Comparison of antisymmetric to symmetric phosphate stretching band intensities in reflection–absorption spectra of immobilized DNA and transmission FTIR spectra of DNA in KBr pellet indicates that the sugar–phosphate backbone is predominantly oriented with the sugar–phosphate backbone lying parallel to the surface, in agreement with the 10–20 Å DNA film thickness derived from XPS intensities. Copyright © 2004 John Wiley & Sons, Ltd.     

Electrochemical and Photoelectrochemical Study of Self‐assembled Monolayer of Phytic Acid on Brass

Phytic acid is an environment-friendly reagent for processing metals. The anticorrosion and inhibiting mechanism for phytic acid monolayers self-assembled on a brass (HSn70-1) electrode has been investigated by using electrochemical and photocurrent response methods. The electrochemical measurements indicate that phytic acid is liable to form surface complexes on the brass electrode, and the self-assembled monolayers (SAM) change the structure of the electric double-layer and shift the potential of zero charge positively. The photochemical measurement indicates that the brass electrode shows a p-type photoresponse owing to the formation of a Cu2O layer on its surface, and the presence of SAM weakens significantly the photoresponse, suggesting an excellent effect on anticorrosion, which is consistent with the EIS and polarization curve measurements. Adsorption of phytic acid was found to be typical of chemisorption, which can be reasonably described on the basis of the Langmuir isotherm.     

Enhancement of flexoelectric ratio of nematic liquid crystal by doping calamitic ferroelectric liquid crystal

We measured the flexoelectric ratio e* of a nematic liquid crystal (NLC) doped with a calamitic ferroelectric liquid crystal (FLC). We doped two kinds of commercial FLC into the pure NLC at a weight concentration of 5 wt%. The absolute value of the flexoelectric ratio was increased up to 49% compared to the pure NLC. The greater transverse dipole moment and the elastic constant of FLC are thought to be related to the increase of the flexoelectric ratio.     

铜氮杂配合物修饰金电极对抗坏血酸的分析测定

本实验制备了一种新型的氮杂铜配合物修饰金电极,该电极可用于抗坏血酸的测定。采用循环伏安法和扫描电化学显微镜技术对电极进行了表征。该修饰电极可催化氧化抗坏血酸,相对于裸电极抗坏血酸在修饰电极上氧化电位移动了250mV,并且氧化电流在抗坏血酸的浓度为5.0×10−7 to 4.0×10−5 mol/L时呈线性关系,检测限为4.8×10-8 mol/L。用此方法测定抗坏血酸与文献报道的测定结果一致,这表明该电极可用作抗坏血酸测定的电化学传感器。     

Electrochemical oxidative formation of ordered monolayers of thiol molecules on Au(111) surface

Electrochemical oxidative formation of thiolate monolayers on a Au(111) surface in KOH ethanol solutions of various thiol concentrations is described. The formation process was investigated by electrochemistry, in situ scanning tunneling microscopy (STM), and surface X‐ray diffraction (SXRD). The reductive charge in the linear sweep voltammogram after keeping the potential at +0.1 V increased with holding time and reached the saturated value of 103 µC cm^?2, corresponding to the full monolayer coverage of the ( ) structure. The desorption peak shifted negatively with holding time even after the monolayer was formed, suggesting that ordering of the monolayer requires a much longer time than full coverage adsorption. The herringbone structure, corresponding to the ( × 23) structure, was observed on the Au(111) surface in KOH ethanol solution by in situ STM, which shows that a clean surface was exposed. When hexanethiol ethanol solution was added into the ethanol solution at ?450 mV so that the final thiol concentration was higher than ca. 5 µM, generation of vacancy islands (VIs) was observed, which shows the potentiostatic monolayer formation. When the potential was scanned positively from ?950 mV where a clean reconstructed Au(111) surface was exposed, generation of VIs was observed accompanied by anodic current flow. During both oxidative adsorption and reductive desorption of the monolayer, the shape of the steps of the gold surface changed drastically, which suggests that the gold atoms on the surface are extremely mobile during the monolayer formation. SXRD measurement confirmed the surface reconstruction lifting upon monolayer formation. © 2009 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 9: 199–209; 2009: Published online in Wiley InterScience ( www.interscience.wiley.com ) DOI 10.1002/tcr.200900002     

硫辛酸在金电极上自组装成膜动力学研究

自组装单层膜 (ＳＡＭ)应用广泛[1～ 3] 。但对于硫辛酸 (ＴＡ)自组装成膜动力学过程的研究尚未见报道。本研究利用石英晶体微天平 (ＱＣＭ)对ＴＡ自组装成膜过程进行在线监测 ,研究成膜动力学特征 ,并探讨浓度、温度对成膜过程的影响 ,以及在不同ｐＨ值下 ,ＳＡＭ的稳定性 ,推算了不同温度下的速率常数及成膜的活化能。1　实验部分1 1　基本原理通过监测成膜过程中石英晶体微天平 (ＱＣＭ)的振荡频率的变化 ,据Ｓａｕｅｒｂｒｅｙ方程 ,可推知在石英谐振器 (ＱＣＭ)的金电极表面 ,ＴＡ的吸附质量Γ(Γ =Δｍ Ａ ,ｇ ｃｍ2 )与ＱＣＭ的频率…     

Molecular dynamics simulation of polymer dispersed liquid crystal droplets under competing boundary conditions

This paper is devoted to the molecular dynamics simulation of structural organization inside a polydispersed liquid crystal (LC) droplet under competing boundary conditions. The droplet is assumed to be placed at the liquid crystal interface between two different regions of the solid polymer matrix, which accordingly separates the droplet into two hemispheres: the first of these is under radial boundary conditions; the second hemisphere is under bipolar boundary conditions. The droplet is considered as a jagged sphere filled with LC molecules, modelled as classical spins (unit vectors), whose centres of mass are associated with sites of a cubic lattice inside the cavity. The orienting action of the polymer matrix, and hence the resulting boundary conditions, are modelled by the interaction between the internal LC molecules (possessing only orientational degrees of freedom), and those of a delimiting surface layer (a jagged spherical shell), whose orientations are fixed, radial or bipolar, respectively. All interactions are modelled by the short range McMillan pair potential. The molecular orientation inside the LC droplet has been determined for various anchoring strengths of the interaction between internal spins and boundary layers. We have investigated the structure of the spherical defect resulting in the central region of the droplet, as well as of the boojum ‐ like defects existing near the poles of the droplet. It has been found that a change of relative radial and bipolar anchoring strengths can affect both central and boojum ‐ like defects. The effect of an external field on the molecular orientation inside the droplet has also been investigated. It has been found that a sufficiently strong external field increases the radius of the spherical defect placed in the central region of the droplet.