Janus mesophases of matter

In ancient Roman religion and myth, Janus is the god of beginnings, gates, transitions, time, duality, doorways, passages, frames, and endings. He is usually depicted as having two faces looking in opposite directions, one towards the past and the other towards the future. This article is dedicated to Professor BK Sadashiva for his contributions to the science of liquid crystals, and new beginnings in the design and creation of mesomorphic materials. In the studies of metallomesogens based on copper(II) complexes of β-diketones, Ohta and his colleagues reported the first-established discotic-lamellar phase, in which the board-like complexes are able to form lamellar packing arrangements, and at the same time stacking into columns. Casagrande et al. later prepared synthetically modified beads with one hemisphere being hydrophobic and the other hydrophilic. These particles were considered to be amphiphilic solids, and called Janus Beads. Synthetic Janus Mesogens with supermolecular architectures having one chiral nematic hemisphere and the other with smectic tendencies were made in 2003. These complexes, particles, and supermolecules, were termed Janus to describe the structure of the material. In this article we use Janus liquid crystals to describe a material that combines two different packing motifs in a single uniform phase structure

Photoswitching of Dihydroazulene Derivatives in Liquid-Crystalline Host Systems

Photoswitches and dyes in the liquid-crystalline nematic phase have the potential for use in a wide range of applications. A large order parameter is desirable to maximize the change in properties induced by an external stimulus. A set of photochromic and nonphotochromic dyes were investigated for these applications. It was found that a bent-shaped 7-substituted dihydroazulene (DHA) photoswitch exhibited liquid-crystalline properties. Further investigation demonstrated that this material actually followed two distinct reaction pathways on heating, to a deactivated form by a 1,5-sigmatropic shift and to a linear 6-substituted DHA. In addition, elimination of hydrogen cyanide from the photoactive DHA gave both bent and linear azulene dyes. In a nematic host that has no absorbance around 350 nm, it was found that only the linear DHA derivative has nematic properties; however, both 6- and 7-substituted DHAs were found to have large order parameters. In the nematic host, ring opening of either DHA to the corresponding vinylheptafulvene resulted in a decrease in dichroic order parameter and an unusually fast back-reaction to a mixture of both DHAs. Likewise, only the linear azulene derivative showed mesomorphic properties. In the same nematic host, large order parameters were also observed for these dyes

Blue and Green Phosphorescent Liquid-Crystalline Iridium Complexes with High Hole Mobility

Blue- and green-emitting cyclometalated liquid-crystalline iridium complexes are realized by using a modular strategy based on strongly mesogenic groups attached to an acetylacetonate ancillary ligand. The cyclometalated ligand dictates the photophysical properties of the materials, which are identical to those of the parent complexes. High hole mobilities, up to 0.004 cm2 V-1 s-1, were achieved after thermal annealing, while amorphous materials show hole mobilities of only approximately 10-7-10-6 cm2 V-1 s-1, similar to simple iridium complexes. The design strategy allows the facile preparation of phosphorescent liquid-crystalline complexes with fine-tuned photophysical properties

Narrative Bytes : Data-Driven Content Production in Esports

Esports - video games played competitively that are broadcast to large audiences - are a rapidly growing new form of mainstream entertainment. Esports borrow from traditional TV, but are a qualitatively different genre, due to the high flexibility of content capture and availability of detailed gameplay data. Indeed, in esports, there is access to both real-time and historical data about any action taken in the virtual world. This aspect motivates the research presented here, the question asked being: can the information buried deep in such data, unavailable to the human eye, be unlocked and used to improve the live broadcast compilations of the events? In this paper, we present a large-scale case study of a production tool called Echo, which we developed in close collaboration with leading industry stakeholders. Echo uses live and historic match data to detect extraordinary player performances in the popular esport Dota 2, and dynamically translates interesting data points into audience-facing graphics. Echo was deployed at one of the largest yearly Dota 2 tournaments, which was watched by 25 million people. An analysis of 40 hours of video, over 46,000 live chat messages, and feedback of 98 audience members showed that Echo measurably affected the range and quality of storytelling, increased audience engagement, and invoked rich emotional response among viewers

Molecular Design Parameters of Anthraquinone Dyes for Guest-Host Liquid-Crystal Applications : Experimental and Computational Studies of Spectroscopy, Structure and Stability

A set of five anthraquinone dyes with bis(4-propylphenyl) substituent groups, connected via sulfide or amine linkages at the 1,5-positions or directly at the 2,6-positions, have been studied in solution by UV-vis spectroscopy and electrochemistry, allied with density functional theory calculations of structures, electronic transitions, and redox potentials. The visible transitions and redox potentials are shown to vary with the HOMO and LUMO energies, with the variation in both color and redox stability between the dyes being attributable principally to variations in the HOMOs located mainly on the substituents and outer anthraquinone rings. The calculated molecular structures and visible transition dipole moments are shown to vary subtly with substituent, giving variations in the molecular aspect ratios, minimum moment of inertia axes, and transition dipole moment vector orientations that can rationalize the alignment trends reported in the literature for such anthraquinone dyes in liquid crystal hosts, showing why 1,5-disulfide and 2,6-diphenyl substituents give better designs than 1,5-diamine substituents. The computational approaches reported here are shown to give good matches with experimental trends, indicating that they may be used more generally to aid the rational molecular design of dyes for applications as guests in liquid crystal hosts

Condensation of free volume in structures of nematic and hexatic liquid crystals

Eight novel liquid crystalline materials were prepared containing highly branched terminal chains, either 2,4,4-trimethylpentyl or 3,5,5-trimethylhexyl. All materials exhibit nematic mesophases, with additional smectic (Sm) C, hexatic B and SmI phases for certain homologues. Analysis by small- and wide-angle X-ray scattering reveals continual build-up of the correlation length within the nematic phases, where we also observe splitting of the small angle peak into four lobes, indicating pretransitional Sm fluctuations. Connoscopy confirms the nematic phase to be uniaxial and optically positive. We observe that in the solid state, the molecules exist as staggered antiparallel pairs as a consequence of the sterically demanding bulky terminal group, and this would also appear to manifest in the hexatic B phase, where the layer spacing was found to be greater than the molecular length. If true, this is an example of pair formation driven by sterics rather than dipole–dipole interactions and suggests that reentrant systems driven purely by steric frustration may be found

Unusual mesomorphic behaviour of silyloxy-linked chiral bimesogens

In this article, we report on the synthesis of chiral bimesogens that possess silyloxy central linking groups. On first examination of the mesomorphic properties of the materials by X-ray diffraction and electrical field studies we came to the conclusion that the materials exhibit ferroelectric and antiferroelectric smectic C* phase behaviour. However, detailed investigations of the bimesogens indicated that the phases were not conventional smectics, but in addition strange phases that exhibited natural helical filaments on cooling from the isotropic liquid were formed. Indications are that these phases are possibly related to twist-bend structures or in-plane, modulated bent-core phases

Liquid-crystalline circularly polarised fluorescent emitters with a high luminescence dissymmetry factor

Chiral liquid-crystalline emitters based on 9,9-dimethyl-10-(4-(phenylsulfonyl)phenyl)-9,10-dihydroacridine and a functionalised binaphthol show smectic liquid crystal phases and circularly polarised blue fluorescence with a high luminescence dissymmetry factor |glum| of 0.13. Solution-processable organic light-emitting diodes (OLEDs) based on the enantiomers were explored

Sensitivity of Household Transmission to Household Contact Structure and Size

Study the influence of household contact structure on the spread of an influenza-like illness. Examine whether changes to in-home care giving arrangements can significantly affect the household transmission counts.We simulate two different behaviors for the symptomatic person; either s/he remains at home in contact with everyone else in the household or s/he remains at home in contact with only the primary caregiver in the household. The two different cases are referred to as full mixing and single caregiver, respectively.The results show that the household's cumulative transmission count is lower in case of a single caregiver configuration than in the full mixing case. The household transmissions vary almost linearly with the household size in both single caregiver and full mixing cases. However the difference in household transmissions due to the difference in household structure grows with the household size especially in case of moderate flu.These results suggest that details about human behavior and household structure do matter in epidemiological models. The policy of home isolation of the sick has significant effect on the household transmission count depending upon the household size