Preparation and characterization of protein Langmuir-Blodgett films

A protein monolayer of bovin serum albumin (BSA) was stabilized at the air- water interface using glutaraldehyde (GA). The GA-treated BSA film was transferred onto the glass surface, followed by immunochemical lamination of anti-BSA antibody. Protein A-β-galactosidase (pro A-β-gal) conjugate was then reacted with the antibody molecular layer. Biofunctional protein films can be prepared on the BSA base Langmuir-Blodgett film by intermolecular complementary affinity between the proteins concerned.     

Polyimide film containing ultra-fine particles

We have succedded in fabricating a polyimide film with a molecular alignment superior to that obtainable by the conventional rubbing treatment. This phenomenon is realized by means of the dispersion of ultra-fine particles such as carbon and titanium dioxide in the polyimide precursor prior to the fabrication of the polyimide film and the rubbing treatment. The molecular alignment was evaluated with birefringence and infrared dichroism measurements. Further experiments establishe that the adsorption of polyimide molecules on ultra-fine particles is a significant factor in achieving a large orientational anisotropy. A model of the alignment is presented in which the rubbing treatment induces the particles to traverse the surface of the film, causing polyimide molecules adsorbed on them to be elongated in the rubbing direction. A potential application of oriented polymide films is the homogeneous alignment of nematic and smectic liquid crystals.     

Quantitative methods based on twisted nematic liquid crystals for mapping surfaces patterned with bio/chemical functionality relevant to bioanalytical assays

We report methods for the acquisition and analysis of optical images formed by thin films of twisted nematic liquid crystals (LCs) placed into contact with surfaces patterned with bio/chemical functionality relevant to surface-based assays. The methods are simple to implement and are shown to provide easily interpreted maps of chemical transformations on surfaces that are widely exploited in the preparation of analytic devices. The methods involve acquisition of multiple images of the LC as a function of the orientation of a polarizer; data analysis condenses the information present in the stack of images into a spatial map of the twist angle of the LC on the analytic surface. The potential utility of the methods is illustrated by mapping (i) the displacement of a monolayer formed from one alkanethiol on a gold film by a second thiol in solution, (ii) coadsorption of mixtures of amine-terminated and ethylene glycol-terminated alkanethiols on gold films, which leads to a type of mixed monolayer that is widely exploited for immobilization of proteins on analytic surfaces, and (iii) patterns of antibodies printed onto surfaces. These results show that maps of the twist angle of the LC constructed from families of optical images can be used to reveal surface features that are not apparent in a single image of the LC film. Furthermore, the twist angles of the LC can be used to quantify the energy of interaction of the LC with the surface with a spatial resolution of <10 microm. When combined, the results described in this paper suggest nondestructive methods to monitor and validate chemical transformations on surfaces of the type that are routinely employed in the preparation of surface-based analytic technologies.     

Probing Albumin Adsorption onto Calcium Phosphates by XPS and ToF-SIMS

In this study the binding and assembly of bovine serum albumin (BSA) onto three different calcium phosphate phases (hydroxyapatite, dibasic calcium phosphate dihydrate, and β-tricalcium phosphate) was investigated using a combination of X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). XPS was used to record adsorption isotherms and to quantify the amount of BSA adsorbed onto the different CaP surfaces. On all three surfaces a monolayer of adsorbed BSA was formed. ToF-SIMS was then used to investigate how the structure of BSA changes upon surface binding. ToF-SIMS data from BSA films on the three CaP surfaces showed intensity differences of secondary ions originating from both hydrophobic and hydrophilic amino acids. For a more quantitative examination of structural changes, we developed a ratio comparing the sum of intensities of secondary ions from hydrophobic and hydrophilic residues. A small, but statistically significant, increase in the value of this ratio (7%) was observed between a BSA film on hydroxyapatite versus dibasic calcium phosphate dihydrate. From this ratio we can make some initial hypotheses about what specific changes in BSA structure relate to these differences observed in the ToF-SIMS data.     

Terahertz properties of liquid crystals with negative dielectric anisotropy

We present what is believed to be the first terahertz time-domain study of a set of liquid crystals (LCs) with negative dielectric anisotropy. From the measured data, refractive indices, and absorption coefficients for ordinary and extraordinary polarization are extracted. We find that the investigated materials exhibit a much smaller absorption than LCs with positive dielectric anisotropy. Thus, these materials are more useful for switchable terahertz devices. Moreover, the LC 1808 shows what is to our knowledge the largest terahertz birefringence reported so far.     

Effect of the shape of imprinted alignment layer on the molecular orientation of liquid crystal

The molecular alignment of liquid crystals was studied with three different imprinted patterns. The three different shapes of molds (square-, V- and U-shaped) replicated the microstructures with electroplating process was fabricated. Surfaces with three different microgrooved patterns were used as the alignment layer of the liquid crystal cell. The effect of the shape of imprinted alignment layer on the molecular orientation of LC was investigated. Among these patterns, U-shaped groove pattern resulted in a high performance of liquid crystal orientation, pretilt angle and anchoring energy, which are quite comparable to the conventionally rubbed layer. It clearly shows that the molecular orientation of liquid crystals is influenced by the shape of microgrooved patterns.     

Controlling the morphology of side chain liquid crystalline block copolymer thin films through variations in liquid crystalline content

In this paper, we describe methods for manipulating the morphology of side-chain liquid crystalline block copolymers through variations in the liquid crystalline content. By systematically controlling the covalent attachment of side chain liquid crystals to a block copolymer (BCP) backbone, the morphology of both the liquid crystalline (LC) mesophase and the phase-segregated BCP microstructures can be precisely manipulated. Increases in LC functionalization lead to stronger preferences for the anchoring of the LC mesophase relative to the substrate and the intermaterial dividing surface. By manipulating the strength of these interactions, the arrangement and ordering of the ultrathin film block copolymer nanostructures can be controlled, yielding a range of morphologies that includes perpendicular and parallel cylinders, as well as both perpendicular and parallel lamellae. Additionally, we demonstrate the utilization of selective etching to create a nanoporous liquid crystalline polymer thin film. The unique control over the orientation and order of the self-assembled morphologies with respect to the substrate will allow for the custom design of thin films for specific nanopatterning applications without manipulation of the surface chemistry or the application of external fields.     

Photoconducting liquid crystals

Major recent advances: ‘High’ mobility photoconduction in the columnar mesophases of disc-shaped (discotic) liquid crystals in which the charge carriers are holes or electrons was discovered in 1995. Prior to this photoconduction in liquid crystals was attributed to photo-generated ions and associated with ‘low’ mobilities. Over the last 7 years our understanding of the mechanism of carrier generation and transport in these novel, self-assembling systems has progressed to the point where we are able to design and manufacture organic semi-conductors with well-defined electronic and physical properties. Serious commercial devices incorporating conducting liquid crystals are finally on the horizon.     

Growth and properties of epitaxial barium hexaferrite films

Barium hexaferrite films have been grown by liquid phase epitaxy on Zr and Mg substituted Strontium hexagallate substrates. Continous films of 20 mm diameter have been obtained. The film surface exhibits terrace growth with a step height of about 10 nm. The saturation magnetization and anisotropy field as measured by static and FMR techniques are close to data of bulk crystals. An FMR linewidth of 45 Oe at 53 GHz was found for a 2.1 μm thick film.     

Observation of enhanced backscattering from a plane mirror viewed through polymer-film-dispersed liquid crystals

We report experimental results on enhanced backscattering from a plane mirror that is viewed through polymer-film-dispersed nematic liquid crystals. The distribution of the averaged intensity of the light reflected from the mirror placed behind the polymer film is investigated with an image-processing system when a Gaussian beam wave is incident. The enhanced light peak is observed in an incident beam direction, the result of which is predicted by a theory based on the circular Gaussian statistic random-phase-screen model. We pay attention to the enhancement dependence on parameters such as the distance between the polymer film and the flat mirror. The observed result is similar to a previous study by Jakeman et al. in which a random diffusive glass plate was used as a random-phase screen [J. Phys. D 21, 32 (1988)].     

Phase agile reflectarray cells based on liquid crystals

Experimental results at X-band are used to compare the electromagnetic scattering from a printed reflectarray cell, which is constructed on 500 mum thick layers of three different nematic state liquid crystals. It is shown that a small voltage can be used to vary the permittivity of the tunable substrate and thereby control the phase of the reflected signals. Numerical results using Ansoft HFSS are compared with the measured phase, resonant frequencies and signal attenuation for two orientations of the liquid crystal molecules. Data fitting is employed to quantify the loss tangent and the permittivity values of the three anisotropic specimens. The performance trade-offs that are imposed by the use of commercially available materials are discussed, and the computer model is used to specify the electrical properties of a liquid crystal mixture, which can provide a signal loss of < 1 dB and a dynamic phase range of 300deg from the patch elements at 10 GHz.     

Dielectric anisotropy and electrical properties of the copper phthalocyanine (CuPc): 4–4′-n-Heptylcyanobiphenyl (7CB) composite liquid crystals

Dielectric anisotropy and electrical properties of the copper phthalocyanine (CuPc): 4–4′-n-heptylcyanobiphenyl (7CB) composite liquid crystals have been investigated. Liquid crystals exhibit dielectrically-controlled positive dielectric anisotropy (p-type Δɛ) and the dielectric anisotropy changes from positive to negative dielectric anisotropy (n-type Δɛ) behavior with frequency of applied electrical field. The critical frequency f_c values for the 7CB and CuPc doped 7CB liquid crystals were found to be 602 kHz and 518 kHz, respectively. This indicates that CuPc doping causes a decrease in the critical frequency. The splay elastic coefficients of the 7CB and CuPc doped 7CB liquid crystals were determined and CuPc doping increases the splay elastic coefficient of 7CB liquid crystal. The 7CB liquid crystal exhibits a voltage-controlled differential negative resistance (VCNR) behavior and CuPc doping affects significantly VCNR behavior of 7CB.     

Polarization characteristics of phase retardation defect mode lasing in polymeric cholesteric liquid crystals

We have studied the lasing characteristics of a dye-doped nematic layer sandwiched by two polymeric cholesteric liquid crystal (CLC) films as photonic band gap (PBG) materials. The nematic layer acts as a defect layer, the anisotropy of which brings about the following remarkable optical characteristics: (1) reflectance in the PBG region exceeds 50% due to the retardation effect, being unpredictable from a single CLC film; (2) efficient lasing occurs either at the defect mode wavelength or at the photonic band edge; and (3) the lasing emission due to both the defect mode and the photonic band edge mode contains both right- and left-circular polarizations, while the lasing emission from a dye-doped single CLC layer with a left-handed helix is left-circularly polarized.     

Polarization-independent optical fiber modulator by use of polymer-dispersed liquid crystals

Ultrasmall light modulators have been made by sandwiching a polymer-dispersed liquid crystal (PDLC) between two ferrules with optical fibers. The device can modulate light independent of the state of polarization, because the PDLC becomes transparent or opaque when either sufficient or no voltage is applied to the film. The PDLC was prepared by mixing and annealing a prepolymer and nematic liquid crystal with large anisotropy. An optical fiber modulator with a 30-mum thick PDLC film had an extinction ratio of 8:1-33:1, an insertion loss of 1.3 dB, and rise and decay times of 4 ms at a wavelength of 1.3 mum.     

Synthesis and characterization of liquid crystals and their thermoset films

We prepared a series of aromatic liquid crystals (LCs) based on aromatic ester units with the reactive end groups methyl-maleimide and nadimide, and the resulting LCs were thermally cross-linked to produce liquid crystalline thermoset (LCT) films by means of solution-casting and heat treatment. The synthesized LCs and LCTs were characterized with Fourier transform infrared (FT-IR) spectroscopy, ¹H nuclear magnetic resonance (NMR), differential scanning calorimetry (DSC), thermomechanical analysis (TMA), and polarizing optical microscopy with a hot stage. We found that all these LCs form nematic phases. The coefficients of thermal expansion (CTEs) of the LCT films are strongly affected by the reactive end group and the mesogen units in their main-chain structures. The methyl-maleimide-terminated biphenyl LCT was found to have the lowest CTE.     

Spectral narrowing phenomena in the emission from a conjugated polymer

We report a study of the morphology dependent emission properties of a liquid crystalline polyfluorene in solid thin films. Spectral narrowing (SN) is observed in spin coated films, but after thermal treatment of the same films the SN is no longer observed. For films which are spin coated on a rubbed polyimide alignment layer, the situation is different. There is then no influence of thermal treatment on the observation of SN. However, specific combinations of the pump polarization direction, film alignment direction and the long axis of the rectangular excitation area now play an important role. The spectral location of SN peaks also varies with film morphology and for different regions of the same sample. The occurrence of SN is strongly dependent on film morphology and the excitation configuration.     

Photoluminescence and photoconductivity studies of oriented polyfluorene thin films

Photoluminescence and photoconductive properties of poly(9,9-dioctylfluorene) (F8) on rubbed polyimide (PI) alignment layers have been studied. The F8 thin films are highly oriented, which is manifested from polarized absorption, fluorescence, and photoconductivity spectra (the order parameter of F8 is 0.86). The ratio of photocurrent parallel to perpendicular directions to the rubbing direction (photoconductivity anisotropy) is 18 at 2.9 eV for F8. Effects of C₆₀ addition to F8 on the optical properties are also studied. C₆₀ addition to F8 significantly increases photoconductivity but decreases the order parameter (0.67) and the photoconductivity anisotropy (7 at 2.9 eV). Both F8 and C₆₀ doped F8 thin films exhibit similar photoconductive response and similar photoconductivity anisotropy (3-4) above 3.8 eV.     

Magnetic-field-assisted formation of alignment polymer coatings in liquid crystal cells

We describe a new method for obtaining liquid crystal (LC) layers with planar orientation in plane-parallel cells, which is based on the technology of LC-polymer interface formation in solution under the action of an applied magnetic field. The azimuthal anchoring energy of LC at the polymer surface has been determined by measuring the angle of orientation of the nematic LC director on the substrate surface as a function of the magnetic field. The LC orientation provided by the proposed method is stable, and the anisotropy of LC anchoring is comparable with that achieved using well-known methods of alignment polymer film preparation by rubbing.     

Effects of backbone conformation and surface texture of polyimide alignment film on the pretilt angle of liquid crystals

Polyimides (PIs) with different inclination angle of polymer backbones, together with polar hydroxyl group and/or nonpolar trifluoromethyl group at various sites of the backbone were synthesized and used as liquid crystal alignment layers. The molecular conformation, surface chemistry, surface energy, surface morphology, and pretilt angle of the PI film were investigated. The distributions of fluorinated group and hydroxyl group at different depths of the PI surfaces were analyzed by X-ray photoelectron spectroscopy. Effects of the conformation of the PI molecular backbone on the surface morphology of the rubbed PI layer, the pretilt angle and surface energy of the alignment film were studied. The PI which contains both nonpolar fluorinated groups sticking out of the surface and the polar hydroxyl groups on the surface exhibits high pretilt angle.