Physico-chemical confinement of helical nanofilaments.

Helical nanofilaments (HNFs) have attracted much interest because of their unique optical properties, but there have been many hurdles to overcome in using them for the practical applications due to their structural complexity. Here we demonstrate that the molecular configuration and layer conformation of a modulated HNF (HNFs(mod)) can be studied using a physicochemical confinement system. The layer directions affected by the chemical affinity between the mesogen and surface were drastically controlled in surface-modified nanochannels. Furthermore, an in situ experiment using grazing-incidence X-ray diffraction (GIXD) was carried out to investigate in detail the structural evolution through thermal transitions. The results demonstrate that the HNF(mod) structure can be perfectly controlled for functional HNF device applications, and a combined system with chemical and physical confinement effects will be helpful to better understand the fundamentals of soft matter.

Athermal photofluidization of glasses.

Azobenzene and its derivatives are among the most important organic photonic materials, with their photo-induced trans-cis isomerization leading to applications ranging from holographic data storage and photoalignment to photoactuation and nanorobotics. A key element and enduring mystery in the photophysics of azobenzenes, central to all such applications, is athermal photofluidization: illumination that produces only a sub-Kelvin increase in average temperature can reduce, by many orders of magnitude, the viscosity of an organic glassy host at temperatures more than 100 K below its thermal glass transition. Here we analyse the relaxation dynamics of a dense monolayer glass of azobenzene-based molecules to obtain a measurement of the transient local effective temperature at which a photo-isomerizing molecule attacks its orientationally confining barriers. This high temperature (T(loc)~800 K) leads directly to photofluidization, as each absorbed photon generates an event in which a local glass transition temperature is exceeded, enabling collective confining barriers to be attacked with near 100% quantum efficiency.

Chiral isotropic liquids from achiral molecules.

A variety of simple bent-core molecules exhibit smectic liquid crystal phases of planar fluid layers that are spontaneously both polar and chiral in the absence of crystalline order. We found that because of intralayer structural mismatch, such layers are also only marginally stable against spontaneous saddle splay deformation, which is incompatible with long-range order. This results in macroscopically isotropic fluids that possess only short-range orientational and positional order, in which the only macroscopically broken symmetry is chirality--even though the phases are formed from achiral molecules. Their conglomerate domains exhibit optical rotatory powers comparable to the highest ever found for isotropic fluids of chiral molecules.

Helical nanofilament phases.

In the formation of chiral crystals, the tendency for twist in the orientation of neighboring molecules is incompatible with ordering into a lattice: Twist is expelled from planar layers at the expense of local strain. We report the ordered state of a neat material in which a local chiral structure is expressed as twisted layers, a state made possible by spatial limitation of layering to a periodic array of nanoscale filaments. Although made of achiral molecules, the layers in these filaments are twisted and rigorously homochiral--a broken symmetry. The precise structural definition achieved in filament self-assembly enables collective organization into arrays in which an additional broken symmetry--the appearance of macroscopic coherence of the filament twist--produces a liquid crystal phase of helically precessing layers.

Polarization splay as the origin of modulation in the B1 and B7 smectic phases of bent-core molecules.

We report a generalized scenario for the formation of modulated smectic phases of bent-core molecules based on locally ferroelectric layering and spontaneous splay of the polarization. Twelve phases are proposed, distinguished by neighboring splay stripes with either syn- or antiorder of the polarization and undulation slope, in addition to layer continuity versus layer discontinuity at the intervening defects. We outline the experimental techniques necessary to differentiate among the phases and interpret previous results in the present context, using high resolution x-ray scattering diffraction and block and undulation models of the layer organization to distinguish among the three 2D lattice types which emerge.

Giant-block twist grain boundary smectic phases.

Study of a diverse set of chiral smectic materials, each of which has twist grain boundary (TGB) phases over a broad temperature range and exhibits grid patterns in the Grandjean textures of the TGB helix, shows that these features arise from a common structure: "giant" smectic blocks of planar layers of thickness l(b) > 200 nm terminated by GBs that are sharp, mediating large angular jumps in layer orientation between blocks (60 degrees < Delta < 90 degrees ), and lubricating the thermal contraction of the smectic layers within the blocks. This phenomenology is well described by basic theoretical models applicable in the limit that the ratio of molecular tilt penetration length-to-layer coherence length is large, and featuring GBs in which smectic ordering is weak, approaching thin, melted (nematic-like) walls. In this limit the energy cost of change of the block size is small, leading to a wide variation of block dimension, depending on preparation conditions. The models also account for the temperature dependence of the TGB helix pitch.

Control of molecular orientation in electrostatically stabilized ferroelectric liquid crystals.

The continuously reorientable (XY-like) ferroelectric polarization density of a chiral smectic liquid crystal is shown experimentally to produce nearly complete screening of the applied electric field in an appropriate cell geometry. This screening, combined with the expulsion of polarization charge for large polarization materials, is shown to produce electrostatic control of the orientation of a uniform optic axis or polarization field.

Polarization-modulated smectic liquid crystal phases.

Any polar-ordered material with a spatially uniform polarization field is internally frustrated: The symmetry-required local preference for polarization is to be nonuniform, i.e., to be locally bouquet-like or "splayed." However, it is impossible to achieve splay of a preferred sign everywhere in space unless appropriate defects are introduced into the field. Typically, in materials like ferroelectric crystals or liquid crystals, such defects are not thermally stable, so that the local preference is globally frustrated and the polarization field remains uniform. Here, we report a class of fluid polar smectic liquid crystals in which local splay prevails in the form of periodic supermolecular-scale polarization modulation stripes coupled to layer undulation waves. The polar domains are locally chiral, and organized into patterns of alternating handedness and polarity. The fluid-layer undulations enable an extraordinary menagerie of filament and planar structures that identify such phases.

Second-harmonic generation from rubbed ferroelectric liquid crystal mesogenic monolayer surfaces.

We have designed self-assembled monolayers of molecules containing a ferroelectric liquid crystal mesogen attached to a glass surface through an alkane chain. After mechanical rubbing these layers induce a single domain in a cell containing a high-polarization achiral liquid crystal in the smectic-C phase. We have used optical second-harmonic generation to demonstrate that this behavior is explained by rubbing-induced in-plane anisotropy of the angular distribution function that describes the ensemble of mesogenic units. The surface order parameter is 0.094, a substantial fraction of what has been observed for rubbed polymeric alignment layers.

Biaxial model of the surface anchoring of bent-core smectic liquid crystals.

In synclinically tilted smectic phases, bent-core liquid crystal molecules aligned with the director in the plane of a cell boundary will, in general, have their molecular (bow) planes parallel to the boundary, normal to it, or at a well-defined intermediate orientation. A model describing the interaction of such bent-core (banana-shaped) molecules with planar surfaces that distinguishes energetically between molecules lying flat on the surface and those oriented edge on is given by a biaxial modification of the uniaxial surface anchoring expression used for chiral smectics of rod-shaped molecules. When combined with a field-induced straightening of the smectic layers, the model provides a mechanism for the transition from an analog to a bistable director response observed electro-optically in the ferroelectric banana-shaped material (R,S)-MHOBOW.

Patterning of functional antibodies and other proteins by photolithography of silane monolayers.

We have demonstrated the assembly of two-dimensional patterns of functional antibodies on a surface. In particular, we have selectively adsorbed micrometer-scale regions of biotinylated immunoglobulin that exhibit specific antigen binding after adsorption. The advantage of this technique is its potential adaptability to adsorbing arbitrary proteins in tightly packed monolayers while retaining functionality. The procedure begins with the formation of a self-assembled monolayer of n-octadecyltrimethoxysilane (OTMS) on a silicon dioxide surface. This monolayer can then be selectively removed by UV photolithography. Under appropriate solution conditions, the OTMS regions will adsorb a monolayer of bovine serum albumin (BSA), while the silicon dioxide regions where the OTMS has been removed by UV light will adsorb less than 2% of a monolayer, thus creating high contrast patterned adsorption of BSA. The attachment of the molecule biotin to the BSA allows the pattern to be replicated in a layer of streptavidin, which bonds to the biotinylated BSA and in turn will bond an additional layer of an arbitrary biotinylated protein. In our test case, functionality of the biotinylated goat antibodies raised against mouse immunoglobulin was demonstrated by the specific binding of fluorescently labeled mouse IgG.

Near--Atomic Resolution Imaging of Ferroelectric Liquid Crystal Molecules on Graphite by STM.

Near-atomic resolution images of a two-dimensional heteroepitaxial crystal composed of the relatively "functionally rich" chiral liquid crystal mesogen MDW 74 on graphite have been obtained by scanning tunneling microscopy (STM). This work is aimed at developing an improved understanding of the commercially crucial phenomenon of liquid crystal alignment by studying well-characterized surfaces. Herein is reported molecular-level characterization of the surface underlying a ferroelectric liquid crystal in situ, a requisite starting point for understanding the liquid crystal-solid interface at the molecular level. The results are also important in the context of developing a model for the molecular. origins of the contrast observed in STM images of organic monolayers on conductor surfaces. The data and analysis provide strong evidence that neither frontier orbital alone (highest occupied or lowest unoccupied molecular orbital) is sufficient to describe the observed tunneling efficiency.

Quantized complex ferroelectric liquid crystal spatial light modulators.

A spatial light modulator design consisting of cascaded or sandwiched layers of ferroelectric liquid crystals (FLC's) is investigated. The interrelation between the FLC material, the polarization of the incident illumination, and the achievable modulation states is characterized. Magnitude modulation is accomplished by standard methods by addressing the FLC layer with linearly polarized light and following it with a properly oriented analyzer. When the FLC is addressed with circularly polarized light, lossless phase modulation results with the phase states separated by twice the angle of rotation of the optical axes. A continuum of elliptical polarization states ties together the lossless phase states achievable by using circular polarization with the more well-known 0 degrees -180 degrees phase states obtainable with linearly polarized light. Layers of various bistable FLC materials can be cascaded, possibly with polarization control layers between some of the layers, to yield a spatial light modulator that produces multip e quantized bits of complex-valued modulation and with independent control of magnitude and phase states. Four-state phase modulation, ternary amplitude-phase modulation, and four-state magnitude modulation are demonstrated experimentally by using two layers of FLC.