Molecular p-doping in organic liquid crystalline semiconductors: influence of the charge transfer complex on the properties of mesophase and bulk charge transport.

We explore the molecular nature of doping in organic semiconductors (OSCs) by employing a liquid crystalline organic semiconductor based on phenyl naphthalene as a model. The mesophase nature of composites that include a charge transfer complex (CTC) between the OSC (8-PNP-O12) and an electron acceptor (F4TCNQ) has been investigated by means of differential scanning calorimetry, polarized optical microscopy and X-ray scattering. Optical and vibrational spectroscopies allow us to explore the characteristics and the amount of charge transfer in the CTC and expose some properties that appear only in the complexed state. We have found this system to exhibit partial charge transfer, which manifests itself in all the phase states of the host 8-PNP-O12, as well as in solution. Due to the lowering of molecular symmetry as a result of the charge transfer, one of the previously IR-only vibrational bands of the nitrile group is found to be now active in the Raman spectrum. We have also made an attempt to further investigate the influence of dopant introduction on the bulk hole mobility of 8-PNP-O12. It is found that the presence of the CTC promotes the hole transport in the Smectic B mesophase, however it seems to have a somewhat negative influence in the less ordered smectic A mesophase. This work aims to establish the link between the inevitable change of molecular geometry that occurs on charge transfer with the results obtained by spectroscopic techniques and electronic charge carrier mobility measurements.

Spontaneous liquid crystal and ferromagnetic ordering of colloidal magnetic nanoplates.

Ferrofluids are familiar as colloidal suspensions of ferromagnetic nanoparticles in aqueous or organic solvents. The dispersed particles are randomly oriented but their moments become aligned if a magnetic field is applied, producing a variety of exotic and useful magnetomechanical effects. A longstanding interest and challenge has been to make such suspensions macroscopically ferromagnetic, that is having uniform magnetic alignment in the absence of a field. Here we report a fluid suspension of magnetic nanoplates that spontaneously aligns into an equilibrium nematic liquid crystal phase that is also macroscopically ferromagnetic. Its zero-field magnetization produces distinctive magnetic self-interaction effects, including liquid crystal textures of fluid block domains arranged in closed flux loops, and makes this phase highly sensitive, with it dramatically changing shape even in the Earth's magnetic field.

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.

Two-dimensional microrheology of freely suspended liquid crystal films.

Smectic liquid crystals form freely-suspended, fluid films of highly uniform structure and thickness, making them ideal systems for studies of hydrodynamics in two dimensions. We have measured particle mobility and shear viscosity by direct observation of the gravitational drift of silica spheres and smectic islands included in these fluid membranes. In thick films, we observe a hydrodynamic regime dominated by lateral confinement effects, with the mobility of the inclusion determined predominantly by coupling of the fluid flow to the fixed boundaries of the film. In thin films, the mobility of inclusions is governed primarily by coupling of the fluid to the surrounding air, as predicted by Saffman-Delbrück theory.

Birds of the Severn Estuary and Bristol Channel: their current status and key environmental issues.

The Severn Estuary and Bristol Channel encompass a number of designated sites supporting populations of waterbirds and seabirds that are of national or international importance, including the Severn Estuary and Burry Inlet Special Protection Areas (SPAs)/Ramsar Sites and Carmarthen Bay, the UK's first marine SPA. Here, we provide an overview of the present numbers and trends of the waterbirds and seabirds using these sites, updating previous reviews undertaken prior to these designations. We further provide a summary of the main issues that have affected the status of the area's bird populations. Declines in the numbers of waders on the Severn Estuary and the southwest over the last two decades have been linked to climate change. The Sea Empress oil-spill impacted both breeding seabirds and the wintering Common Scoters in Carmarthen Bay, though numbers of the latter recovered 3years after the spill. At the Burry Inlet, Oystercatcher numbers have fallen over the last 25years and considerable research has been undertaken into the conflict with cockle and mussel fisheries. A long-term study at Cardiff Bay, at the mouth of the Severn, revealed a significant impact on the survival of Redshanks following its impoundment and has helped to further understanding of responses of waterbirds to estuarine habitat loss. The potential impacts of the construction of a tidal power scheme on the Severn Estuary are also discussed.

Modeling dipolar and quadrupolar defect structures generated by chiral islands in freely suspended liquid crystal films.

We report a detailed theoretical analysis of quadrupolar interactions observed between islands, which are disklike inclusions of extra layers, floating in thin, freely suspended smectic- C liquid crystal films. Strong tangential anchoring at the island boundaries results in a strength +1 chiral defect in each island and a companion -1 defect in the film--these forming a topological dipole. While islands of the same handedness form linear chains with the topological dipoles pointing in the same direction, as reported in the literature, islands with different handedness form compact quadrupolar structures with the associated dipoles pointing in opposite directions. The interaction between such heterochiral-island-defect pairs is complex, with the defects moving to minimize the director field distortion as the distance between the islands changes. The details of the interisland potential and the trajectories of the -1 defects depend strongly on the elastic anisotropy of the liquid crystal, which can be modified in the experiments by varying the material chirality of the liquid crystal. A Landau model that describes the energetics of freely mobile defects is solved numerically to find equilibrium configurations for a wide range of parameters.

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.

V -shaped switching ferroelectric liquid crystal structure stabilized by dielectric surface layers.

The " V -shaped switching" mode in high polarization ferroelectric liquid crystals was studied with the aim of stabilizing the monostable bookshelf structure with the spontaneous polarization parallel to the glass plates. The director field in such cells was confirmed to be sensitive to both the liquid crystal properties and the cell parameters. In cells with only polyimide alignment layers, hysteresis free switching was never obtained, with bistable and asymmetric monostable structures compromising the zero-field dark state and preventing an ideal, hysteresis-free analog response. By incorporating a SiO(2) layer between the ITO electrode and the polyimide, the undesired states were suppressed and essentially hysteresis-free switching was obtained for driving frequencies in the range 0.2-200 Hz . Cells rubbed only on one side give more uniform alignment than cells rubbed on both sides but their inherent asymmetry shifts the long-term dark state away from 0 V and causes the response to gray level voltage modulation to be slightly asymmetric. The formation of different types of states as a function of the values of the surface parameters, and the observed stabilization of the V -shaped switching structure by the dielectric surface layers, are in good agreement with an earlier analysis by Copic [Phys. Rev. E 65, 021701 (2002)].

Liquid crystal alignment on a chiral surface: interfacial interaction with sheared DNA films.

We explore the alignment of various achiral liquid crystals on films of aligned double-stranded helical DNA. In all cases and both for the nematic and smectic A phases, we find a distinctly chiral interfacial structure, with the mean orientation of the liquid crystal in contact with the DNA-treated surfaces chirally rotated through a substantial angle with respect to the mean DNA orientation. This rotation originates in the chirality of double-stranded DNA and depends on the liquid crystal molecular structure. We discuss the role of dipolar and hydrophobic coupling in determining the observed orientation.

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.

Shorebird predation of horseshoe crab eggs in Delaware Bay: species contrasts and availability constraints.

1. Functional responses -- the relationship between resource intake rate and resource abundance -- are widely used in explaining predator-prey interactions yet many studies indicate that resource availability is crucial in dictating intake rates. 2. For time-stressed migrant birds refuelling at passage sites, correct decisions concerning patch use are crucial as they determine fattening rates and an individual's future survival and reproduction. Measuring availability alongside abundance is essential if spatial and temporal patterns of foraging are to be explained. 3. A suite of shorebird species stage in Delaware Bay where they consume horseshoe crab Limulus polyphemus eggs. Several factors including spawning activity and weather give rise to marked spatial and temporal variation in the abundance and availability of eggs. We undertook field experiments to determine and contrast the intake rates of shorebird species pecking for surface and probing for buried eggs. 4. Whether eggs were presented on the sand surface or buried, we demonstrate strong aggregative responses and rapid depletion (up to 80%). Depletion was greater at deeper depths when more eggs were present. No consistent give-up densities were found. Type II functional responses were found for surface eggs and buried eggs, with peck success twice as high in the former. Maximum intake rates of surface eggs were up to 83% higher than those of buried eggs. 5. Caution is needed when applying functional responses predicted on the basis of morphology. Our expectation of a positive relationship between body size and intake rate was not fully supported. The smallest species, semipalmated sandpiper, had the lowest intake rate but the largest species, red knot, achieved only the same intake rate as the mid-sized dunlin. 6. These functional responses indicate that probing is rarely more profitable than pecking. Currently, few beaches provide egg densities sufficient for efficient probing. Areas where eggs are deposited on the sand surface are critical for successful foraging and ongoing migration. This may be especially true for red knot, which have higher energetic demands owing to their larger body size yet appear to have depressed intake rates because they consume smaller prey than their body size should permit.

Electric-field-induced chirality flipping in smectic liquid crystals: the role of anisotropic viscosity.

We demonstrate the homogeneous and permanent reversal of the chirality of a condensed phase by an applied electric field. Tilted chiral smectic layers exhibit a coupled polarization density and molecular orientation fields which reorient about the layer normal as couple of fixed handedness in response to small applied electric fields. Experiments on some bent-core smectics show that above a threshold field the induced rotation can occur instead about the molecular long axis and that, as a result, the handedness of the phase can be flipped. The effect is quantitatively described by a nonequilibrium dissipative model of chiral smectic dynamics with anisotropic rotational viscosities.

Thermoregulatory observations in soccer match play: professional and recreational level applications using an intestinal pill system to measure core temperature.

BACKGROUND: Technological limitations associated with oesophageal and rectal temperature probes have previously limited match play observations of body temperature. OBJECTIVE: To investigate the application of an intestinal pill system to measure core temperature during dynamic, field based, soccer matches. METHODS: Core temperature (T(c)) was assessed using the intestinal pill system (CorTemp 2000) and changes in plasma volume were calculated using the values for haemoglobin and packed cell volume obtained before and after recreational (n = 8) and the professional soccer (n = 7) matches. RESULTS: In the recreational match, there were significant post-match reductions in body mass (-1.6%, p<0.05) and plasma volume (-7.2%, p<0.01). Significant increases were observed in T(c) from rest to half time (p<0.01) and from half time to full time (p<0.05). In the professional match, body mass decreased by 1.9% (p<0.05) and plasma volume by 11.6% (p<0.01). T(c) increased from rest to half time (p<0.01) but was unchanged from half time to full time. Significant associations were observed between maximum oxygen consumption and match play heart rates in the second half of each match but these were not related to changes in plasma volume or T(c). CONCLUSIONS: Intestinal temperature proved a useful method of recording core temperature during soccer match play and assisted in the measurement of alterations in thermoregulatory variables in response to both professional and recreational level soccer matches; however, technological limitations still restrict the wider application of this method, especially at a competitive level.

Layer-scale optical chirality of liquid-crystalline phases.

We present a model for the optical chirality of layered liquid-crystalline phases. The model demonstrates that uniform stacking of chiral layers can lead to significant collective optical rotation, even in the absence of a superlayer helix. We predict the optical rotation of the B2 phases of bent-core liquid crystals, which can have optical rotation as large as 1000 times the molecular optical activity.

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.

Pretransitional behavior of a water in liquid crystal microemulsion close to the demixing transition: evidence for intermicellar attraction mediated by paranematic fluctuations.

We present a study of a water-in-oil microemulsion in which surfactant coated water nanodroplets are dispersed in the isotropic phase of the thermotropic liquid-crystal penthyl-cyanobiphenyl (5CB). As the temperature is lowered below the isotropic to nematic phase transition of pure 5CB, the system displays a demixing transition leading to a coexistence of a droplet-rich isotropic phase with a droplet-poor nematic. The transition is anticipated, in the high T side, by increasing pretransitional fluctuations in 5CB molecular orientation and in the nanodroplet concentration. The observed phase behavior supports the notion that the nanosized droplets, while large enough for their statistical behavior to be probed via light scattering, are also small enough to act as impurities, disturbing the local orientational ordering of the liquid crystal and thus experiencing pretransitional attractive interaction mediated by paranematic fluctuations. The pretransitional behavior, together with the topology of the phase diagram, can be understood on the basis of a diluted Lebwohl-Lasher model which describes the nanodroplets simply as holes in the liquid crystal.

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.

Fluctuation mediated interaction and phase separation of nanoparticles in a liquid crystal solvent.

Water-in-oil microemulsions of nanodroplets in the isotropic phase of a thermotropic liquid crystal exhibit, with decreasing temperature and in anticipation of a demixing transition, enhanced correlation in fluctuations of both molecular orientation and droplet concentration. Mean field modeling of this pretransition behavior, on the basis of a lattice in which the nanodroplets are introduced as holes, shows that the observed interdroplet attractive interaction is produced by the disordering effect of the droplets on the liquid crystal and mediated solely by paranematic fluctuations.