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M Hird

Publications and source records attributed to M Hird.

At least 19 recordsLinked to original sources

Extension of the resonant scattering technique to liquid crystals without resonant element.

We report X-ray resonant scattering experiments performed on the prototype liquid-crystalline compound MHPOBC doped with a chemical probe containing a resonant atom (selenium). We determined directly for the first time the microscopic 3- and 4-layer structure of the ferrielectric subphases (SmC(FI1)* and SmC(FI2)*) present in MHPOBC. Despite the low fraction of the selenium probe, the resonant signal is strong enough to allow an unambiguous determination of the basic structure of the ferrielectric subphases. These experiments demonstrate that the resonant scattering technique can be extended to liquid crystalline materials without resonant element and may stimulate new studies. A non-resonant Bragg reflection was also found in the SmC(FI1)* phase in pure MHPOBC, consistent with the 3-layer distorted model, but never detected before.

Ferric Compounds↗

Self-assembly of biaxial ordering and molecular tilt angle of chiral smectic liquid crystals in homeotropically aligned cells investigated using infrared spectroscopy.

Temperature dependences of the infrared absorbance have been measured for the four chiral liquid crystal samples in the homeotropic cell configuration. It is shown that the values of the orientational order parameter obtained using this method exhibit a remarkable similarity to the x-ray diffraction results of the smectic layer spacing and lead to accurate values of the molecular tilt angle. This has important consequences for the existing interpretation of the x-ray data. The proposed method, in many cases, may be considered as a valuable alternative to the x-ray diffraction, giving additional, important information about the orientations and the ordering of the molecular fragments. It is found that if the experimentally obtained order parameter is low, then the molecular biaxiality is exceptionally large. The average phenyl ring plane is found to lie close to the molecular tilt plane.

Journal Article↗

Self-assembled uniaxial and biaxial multilayer structures in chiral smectic liquid crystals frustrated between ferro- and antiferroelectricity.

With a view to obtain a molecular model for the subphases produced by the frustration between ferro- and antiferroelectricity in chiral smectic liquid crystals, we report results on two compounds and observe (i) the staircase character of uniaxial Sm C(*)(alpha) itself in the bulk and (ii) the multipeaked characteristic reflection bands due to the modulated helical structures just above the Sm C(*)(A) temperature range. We suggest the emergence of several uniaxial and biaxial subphases. The results show that both types of subphases can be specified by q(T) = [F] / ( [A] + [F] ) in the zero-order approximation; [A] and [F] are the numbers of antiferroelectric and ferroelectric orderings in the unit cell. We consider the basis of both types of subphases, particularly the description of the short-pitch helical structure of Sm C(*)(alpha), in terms of the molecular models so far proposed and emphasize the important role played by the discrete flexoelectric polarization.

Journal Article↗

Molecular orientation and the infrared dichroism of a chiral smectic liquid crystal in a homogeneously aligned cell at different temperature and bias fields.

The molecular orientation and the dichroic behavior of the vibrational bands of a homogeneously aligned helical cell containing chiral smectic liquid crystal (R)-(-)-1-methylheptyl 4-(4(')-dodecyloxybiphenyl-4-ylcarbonyloxy)-3-fluorobenzoate are studied at various temperatures as a function of the bias field. These temperatures correspond to the various phase states of the sample at zero field. For those bands that exhibit significant dichroism, the field dependencies of the dichroic parameters (the dichroic ratio and the polarization angle of maximum absorbance) are found to be dependent on temperature, phase state, and helical unwinding. For the SmA* and SmC(*)(alpha) phases, the phenyl band dichroic ratio and the corresponding orientational order parameter are found to be almost independent of the bias field. The temperature dependence of the orientational order for zero field is discussed by taking into account the structures of the phases and the molecular tilt angles. The field dependencies of the phenyl band dichroic parameters for the SmC(*)(A) and SmC(*)(gamma) phases yield results about the distribution of directors in the layers of their unit cells and the state of helical unwinding. The azimuthal orientational distribution function of the carbonyl transition moments with respect to the long molecular axis has been determined. It is found that the degrees of the polar and quadrupolar biasing increase with decrease in temperature and the azimuthal biasing angle for the chiral carbonyl group increases significantly with a reduction in temperature.

Journal Article↗

Optical rotatory power, biaxiality, and models of chiral tilted smectic phases.

Among the chiral tilted smectics, the stable existence has been confirmed in numerous investigations of SmC(*)(A), (antiferroelectric smectic-C(A)) SmC(*)(F11) (SmC(*)(gamma)), SmC(*)(F12) (antiferroelectric, AF) and SmC* phases. The structures of the ferrielectric SmC(*)(F11) and SmC(*)(F12) phases suggested by different models are essentially different although all the models use the three-layer and four-layer periodicity for them. The structures of the phases were investigated using the optical rotatory power (ORP) measurements technique. The ORP was simulated using Berreman's 4 x 4-matrix method. The compound under investigation (S)-1-methylheptyl 4-(4(')-n-undecyloxy-biphenyl-4-yl-carbonyloxy) [acronym (S)-11OF1M7] clearly provides SmC(*)(F11) and SmC(*)(F12) phases, the temperature range for the existence of these phases is about 5 degrees C each. This had not been achieved for the earlier investigated antiferroelectric liquid crystal (AFLC) samples. The results obtained confirm that the unit cell of the molecular structure of these subphases is highly biaxial. Due to the biaxiality the texture of the homeotropic cell under a polarizing microscope appears nonuniform. This requires a special approach to the measurements and a simulation of the ORP, which is discussed in detail. A technique has been designed where the transmitted intensity through a polarizing microscope is measured as a function of the angle of polarization of the incident light. From the observed output, which is a biased sine wave, the ORP is being determined. In the same scan, the wavelength of light is also being automatically altered. Comparing the simulated and measured data, we can conclude that in the SmC(*)(F12) phase the distortion angle of the directors in the Ising model is lower than 10 degrees. Using the Ising model, the pitch in SmC(*)(F11) has been determined and this is found to have a strong temperature dependence.

Journal Article↗

Interlayer structures of the chiral smectic liquid crystal phases revealed by resonant X-ray scattering.

The structures of the liquid crystalline chiral subphases exhibited by several materials containing either a selenium or sulphur atom have been investigated using a resonant x-ray scattering technique. This technique provides a unique structural probe for the ferroelectric, ferrielectric, antiferroelectric, and SmC(*)(alpha) phases. An analysis of the scattering features allows the structural models of the different subphases to be distinguished, in addition to providing a measurement of the helical pitch. This paper reports resonant scattering features in the antiferroelectric hexatic phase, the three- and four-layer intermediate phases, the antiferroelectric and ferroelectric phases and the SmC(*)(alpha) phase. The helicoidal pitch has been measured from the scattering peaks in the four-layer intermediate phase as well as in the antiferroelectric and ferroelectric phases. In the SmC(*)(alpha) phase, an investigation into the helical structure has revealed a pitch ranging from 5 to 54 layers in different materials. Further, a strong resonant scattering signal has been observed in mixtures of a selenium containing material with as much as 90% nonresonant material.

Journal Article↗

Congenital rubella syndrome: a risk in immigrant populations.

An infant with congenital rubella syndrome was born to a young mother who had recently arrived in the UK. The infection was not detected before birth, and transmission to another infant was documented. This case highlights the emerging importance of rubella as an imported infection in the developed world and the need to maintain a high index of suspicion for this disorder in recent immigrants from countries with no immunisation programme. Targeted immunisation for such groups is recommended.

Adult↗

Influence of electric fields on the smectic layer structure of ferroelectric and antiferroelectric liquid crystal devices.

The electric-field-induced structural rearrangement of smectic layers in the antiferroelectric and ferroelectric phases of three different materials is reported. The materials all have high optical tilt angles (around 30 degrees ), compared with the steric tilt angles deduced from layer spacing measurements (around 18 degrees ). The chevron angles observed in devices agree well with values found for the steric tilt angle across the tilted mesophase range. Electric fields were applied to liquid crystal devices while the smectic layer structures, in both the depth and in the plane of the device, were probed using small angle x-ray scattering. Two separate aspects of the influence of the field on the layer structure were studied. First, the organization of the smectic layers in the antiferroelectric phase is described before, during, and after the application of an electric field of sufficient magnitude to induce a chevron to bookshelf transition. Second, the evolution of the field-induced layer structure change has been investigated as the field was incrementally increased in both the antiferroelectric and ferroelectric phases. It was found that the chevron to bookshelf transition has a distinct threshold in the antiferroelectric phase, but shows low or zero threshold behavior in the ferroelectric phase for all the materials studied.

Journal Article↗

Orientational ordering in the chiral smectic-C*FI2 liquid crystal phase determined by resonant polarized x-ray diffraction.

High-resolution resonant polarized x-ray diffraction experiments near the sulfur K edge have been performed on free-standing liquid crystal films exhibiting the chiral smectic-C*FI2 phase. It is widely accepted that this phase has a four-layer repeat unit, but the internal structure of the repeat unit remains controversial. We report different resolved features of the resonant x-ray diffraction peaks associated with the smectic-C*FI2 phase that unambiguously demonstrate that the four-layer repeat unit is locally biaxial about the layer normal and that the measured angle, describing the biaxiality, is in good agreement with optical measurements.

Journal Article↗

Resonant x-ray scattering study of the antiferroelectric and ferrielectric phases in liquid crystal devices.

Resonant x-ray scattering has been used to investigate the interlayer ordering of the antiferroelectric and ferrielectric smectic C* subphases in a device geometry. The liquid crystalline materials studied contain a selenium atom and the experiments were carried out at the selenium K edge allowing x-ray transmission through glass. The resonant scattering peaks associated with the antiferroelectric phase were observed in two devices containing different materials. It was observed that the electric-field-induced antiferroelectric to ferroelectric transition coincides with the chevron to bookshelf transition in one of the devices. Observation of the splitting of the antiferroelectric resonant peaks as a function of applied field also confirmed that no helical unwinding occurs at fields lower than the chevron to bookshelf threshold. Resonant features associated with the four-layer ferrielectric liquid crystal phase were observed in a device geometry. Monitoring the electric field dependence of these ferrielectric resonant peaks showed that the chevron to bookshelf transition occurs at a lower applied field than the ferrielectric to ferroelectric switching transition.

Journal Article↗

Structure of the liquid-crystal ferrielectric phases as determined by ellipsometry

The unit cell structures of two ferrielectric liquid-crystal phases are determined from ellipsometric studies of freestanding films in a nondistorting rotatable electric field. A highly biaxial mode with out-of-plane distortions describes all of the data from two different compounds. Qualitative and quantitative features of the data rule out alternate models. We also present a detailed explanation for apparent inconsistencies between previous resonant x-ray and optical experiments.

Journal Article↗

The effect of EDTA and fulvic acid on Cd, Zn, and Cu toxicity to a bioluminescent construct (pUCD607) of Escherichia coli.

The hypothesis, that metal toxicity is dominated by free ion activity, was tested by comparing calculated metal activities with measured toxic responses to a genetically modified, luminescent bacterium, Escherichia coli. The toxicity of Cd, Cu, and Zn sulphate salts in the presence of EDTA and fulvic acid in well-defined solutions was measured. Good agreement between free metal activity and toxicity was found for Cu but not for Zn and Cd. The toxicity relationships were altered by glucose addition to the organism. Stable chloride complexes may have contributed to the toxicity of Cd under the test conditions. The results suggest that there is not always a simple relationship between toxicity and free-ion metal concentration and that further account should be taken of competitive interactions between living cells and ligands and the physiological status of the organism.

Benzopyrans↗

Short limbed skeletal dysplasia associated with combined immunodeficiency and congenital subglottic stenosis: a new constellation of features.

A newborn male is described with an association of short limbed dwarfism with hip dislocation, combined immunodeficiency characterized by absent B cells and CD4 lymphopaenia and congenital subglottic stenosis. This constellation of abnormalities is distinct from other described skeletal dysplasias associated with immunodeficiency such as ADA deficiency and cartilage hair hypoplasia.

CD4 Lymphocyte Count↗

Field-induced phase transitions in an antiferroelectric liquid crystal using the pyroelectric effect

The antiferroelectric liquid crystal (AFLC) under investigation possesses different helical polar phases. Measurements of pyroelectric response of these phases as a function of temperature and bias field have elucidated the ability of this method for investigating the nature of antiferroelectric phases and phase transitions under the bias field. The pyroelectric signal as a function of the bias field at fixed temperatures and as a function of temperature for fixed bias fields was measured for different phases of the investigated AFLC material. A theoretical model describing the pyroelectric response in different phases of AFLC is given, and the experimental results are interpreted. The threshold fields for field induced phase transitions are determined. The type of field induced phase transition from the AF phase in particular is found to be dependent on the temperature within its range. The properties of an unusual ferrielectric phase existing between ferrielectric chiral smectic-C (SmC*) and antiferroelectric AF phases are studied in a great detail. The results confirm that this phase is one of the incommensurate phases, predicted by the axial next-nearest neighbor Ising model and Landau model for this temperature region.

Journal Article↗

Structures of chiral smectic-C mesophases revealed by polarization-analyzed resonant x-ray scattering.

We report polarization-analyzed, resonant x-ray diffraction at the sulfur K edge performed upon free-standing liquid-crystal films. Our studies of the thiobenzoate liquid-crystal enantiomer 10OTBBB1M7 yield the polarization states of resonant satellite peaks arising from characteristic superlattices in the chiral smectic-C (SmC(*)) variant phases, including the antiferroelectric SmC(*)(A), ferrielectric SmC(*)(FI1) and SmC(*)(FI2), as well as SmC(*)(alpha). The observed polarizations agree with the clock model of chiral smectic-C variants, and rule out other proposals made to date for these structures. Data from the 10OTBBB1M7 racemate also support the clock model. Our resonant diffraction results from a thiophene liquid-crystal compound reveal the same superlattice periodicities seen in corresponding antiferroelectric and ferrielectric phases of 10OTBBB1M7.

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Congenital primitive neuroectodermal tumour presenting as obstructed labour.

Brain tumours presenting at delivery are extremely rare. A case of primitive neuroectodermal tumour (PNET) that presented intrapartum with failure to progress due to hydrocephalus is reported. Diagnosis required imaging with magnetic resonance and computed tomography in addition to open biopsy.

Brain Neoplasms↗