Cyanobiphenyls and metallomesogens–where it started and where it went

The author’s work in metallomesogens stemmed from initial preparations of κ 1-complexes of cyanobiphenyls of the Group 10 metals, palladium and platinum. In this personalised account, these initial studies are described, put in the context of where the field was at that time and contextualised for the way the author’s own contributions to the field then developed

From molecules to materials : Engineering new ionic liquid crystals through halogen bonding

Herein, we demonstrate that a bottom-up approach, based on halogen bonding (XB), can be successfully applied for the design of a new type of ionic liquid crystals (ILCs). Taking advantages of the high specificity of XB for haloperfluorocarbons and the ability of anions to act as XB-acceptors, we obtained supramolecular complexes based on 1-alkyl-3-methylimidazolium iodides and iodoperfluorocarbons, overcoming the well-known immiscibility between hydrocarbons (HCs) and perfluorocarbons (PFCs). The high directionality of the XB combined with the fluorophobic effect, allowed us to obtain enantiotropic liquid crystals where a rigid, non-aromatic, XB supramolecular anion acts as mesogenic core. X-ray structure analysis of the complex between 1-ethyl-3-methylimidazolium iodide and iodoperfluorooctane showed the presence of a layered structure, which is a manifestation of the well-known tendency to segregation of perfluoroalkyl chains. This is consistent with the observation of smectic mesophases. Moreover, all the reported complexes melt below 100 °C, and most are mesomorphic even at room temperature, despite that the starting materials were non-mesomorphic in nature. The supramolecular strategy reported here provides new design principles for mesogen design allowing a totally new class of functional materials

Novel direct synthesis of mesoporous tin dioxide network intact up to 500°C

This project is supported by PAAET project no. BE-­‐13-­‐08 in collaboration with Kuwait University and the University of York. The support of the research administration of Kuwait University to the XPS instrument (Project No. GS02/08) is acknowledged.We present a direct soft templating method to synthesise mesoporous tin dioxide network that maintains a porous structure after calcination at 400 °C and 500 °C and has a relatively high BET surface area of 220 and 100 m2 g-1, respectively. TEM, BET and XRD results confirm that both crystal and pore sizes increase as a result of increasing the temperatures during the calcination step. This method is highly reproducible.PostprintPeer reviewe

Liquid crystals based on the N-phenylpyridinium cation—mesomorphism and the effect of the anion

Families of symmetric, ionic, tetracatenar mesogens are described based on a rigid, N-phenylpyridinium core, prepared as their triflimide, octyl sulfate and dodecyl sulfate salts for a range of terminal chain lengths. The mesomorphism of the individual series is described before a comparison is drawn between the different families and then more broadly with (i) neutral tetracatenar materials and (ii) related bis(3,4-dialkoxystilbazole)silver(I) salts. For the octyl and dodecyl sulfates and the related triflates reported earlier, a SmA phase is seen at shorter chain lengths, giving way to a Colh phase as the terminal chain lengthens. For the alkyl sulfate salts, an intermediate cubic phase is also seen and the terminal chain length required to cause the change from lamellar to columnar mesophase depends on the anion. Furthermore, there is an unexpected and sometime very large mesophase stabilisation seen on entering the columnar phase. All of the triflimide salts show a rectangular columnar (ribbon) phase

A response to “Likelihood ratio as weight of evidence: a closer look” by Lund and Iyer

Recently, Lund and Iyer (L&I) raised an argument regarding the use of likelihood ratios in court. In our view, their argument is based on a lack of understanding of the paradigm. L&I argue that the decision maker should not accept the expert’s likelihood ratio without further consideration. This is agreed by all parties. In normal practice, there is often considerable and proper exploration in court of the basis for any probabilistic statement. We conclude that L&I argue against a practice that does not exist and which no one advocates. Further we conclude that the most informative summary of evidential weight is the likelihood ratio. We state that this is the summary that should be presented to a court in every scientific assessment of evidential weight with supporting information about how it was constructed and on what it was based

Sequential X-ray-Induced Single-Crystal to Single-Crystal Transformation followed by Topotactic Reduction in a Potassium Crown Ether Complex of Tetrachloroaurate(III)

During data collection, the unreported potassium crown ether salt [K(18-crown-6][AuCl4] undergoes a sequential X-ray-induced and irreversible single-crystal to single-crystal transformation from P1 to C2/c followed by a topotactic reduction to crystalline [K(18-crown-6][AuCl2] within the same C2/c space group

Highly efficient blueish-green fluorescent OLEDs based on AIE liquid crystal molecules : From ingenious molecular design to multifunction materials

In order to seek the balance point between liquid crystallinity and high efficiency emission, two novel aggregation-induced emission-based (AIE) liquid crystal materials of TPE-PBN and TPE-2PBN, which contain a tetraphenylethene derivative as the emission core and a 4-cynobiphenyl moiety as the mesogenic unit, were designed and prepared. Both simple molecules showed a mesophase at high temperature as evidenced by polarised optical microscopy (POM), differential scanning calorimetry (DSC) and temperature-dependent X-ray diffraction (XRD). Simultaneously, TPE-PBN and TPE-2PBN presented clear AIE characteristics in the blueish-green region and achieved a high emission quantum efficiency of 71% and 83% in the solid state, respectively. Due to the self-assembly properties of thermotropic liquid crystals, both compounds showed higher hole mobilities in the annealed films than in pristine films. Employing TPE-PBN and TPE-2PBN as the emitting materials, both non-doped devices and doped devices were fabricated. The TPE-PBN-based doped OLEDs showed a better device performance with an external quantum efficiency (EQE) of 4.1% which is among the highest EQEs of blue AIE fluorescent OLEDs

Selective oxidation of allylic alcohols over highly ordered Pd/meso-Al2 O3 catalysts

Highly ordered mesoporous alumina was prepared via evaporation induced self assembly and was impregnated to afford a family of Pd/meso-Al2O3 catalysts for the aerobic selective oxidation (selox) of allylic alcohols under mild reaction conditions. CO chemisorption and XPS identify the presence of highly dispersed (0.9–2 nm) nanoparticles comprising heavily oxidised PdO surfaces, evidencing a strong palladium-alumina interaction. Surface PdO is confirmed as the catalytically active phase responsible for allylic alcohol selox, with initial rates for Pd/meso-Al2O3 far exceeding those achievable for palladium over either amorphous alumina or mesoporous silica supports. Pd/meso-Al2O3 is exceptionally active for the atom efficient selox of diverse allylic alcohols, with activity inversely proportional to alcohol mass

Pathway Analyses Implicate Glial Cells in Schizophrenia

Background: The quest to understand the neurobiology of schizophrenia and bipolar disorder is ongoing with multiple lines of evidence indicating abnormalities of glia, mitochondria, and glutamate in both disorders. Despite high heritability estimates of 81% for schizophrenia and 75% for bipolar disorder, compelling links between findings from neurobiological studies, and findings from large-scale genetic analyses, are only beginning to emerge. Method Ten publically available gene sets (pathways) related to glia, mitochondria, and glutamate were tested for association to schizophrenia and bipolar disorder using MAGENTA as the primary analysis method. To determine the robustness of associations, secondary analyses were performed with: ALIGATOR, INRICH, and Set Screen. Data from the Psychiatric Genomics Consortium (PGC) were used for all analyses. There were 1,068,286 SNP-level p-values for schizophrenia (9,394 cases/12,462 controls), and 2,088,878 SNP-level p-values for bipolar disorder (7,481 cases/9,250 controls). Results: The Glia-Oligodendrocyte pathway was associated with schizophrenia, after correction for multiple tests, according to primary analysis (MAGENTA p = 0.0005, 75% requirement for individual gene significance) and also achieved nominal levels of significance with INRICH (p = 0.0057) and ALIGATOR (p = 0.022). For bipolar disorder, Set Screen yielded nominally and method-wide significant associations to all three glial pathways, with strongest association to the Glia-Astrocyte pathway (p = 0.002). Conclusions: Consistent with findings of white matter abnormalities in schizophrenia by other methods of study, the Glia-Oligodendrocyte pathway was associated with schizophrenia in our genomic study. These findings suggest that the abnormalities of myelination observed in schizophrenia are at least in part due to inherited factors, contrasted with the alternative of purely environmental causes (e.g. medication effects or lifestyle). While not the primary purpose of our study, our results also highlight the consequential nature of alternative choices regarding pathway analysis, in that results varied somewhat across methods, despite application to identical datasets and pathways

An overview of phosphorescent metallomesogens based on platinum and iridium

Metal atoms with excellent magnetic, electrical and optical properties that are integrated into liquid crystal molecules-metallomesogens-have attracted much attention from chemists, physicists and engineers and many materials based on e.g. Ag, Pt, Pd, Ir, Ni, Cu and lanthanide ions have been reported. Though several reviews and books have been published on metallomesogens, few refer to their photophysical properties. Additionally, metallomesogens with good emission properties in solution or in neat film are still scarce. Owing to the 100% theoretical internal quantum efficiency, phosphorescent liquid-crystalline materials were developed recently. Here, a brief overview of recent research on such materials based on platinum and iridium complexes including their molecular design and structure-property relationships is reported. It is hoped that this review will stimulate further development of luminescent metallomesogens