Structural factors controlling the transition between columnar hexagonal and helical mesophase in triphenylene liquid crystals.

A series of novel triphenylenes has been synthesised by a combination of palladium catalysed coupling, oxidative cyclisation, bromination and nucleophilic aromatic substitution. The new derivatives are designed to have structures which are intermediate between the known symmetrical materials hexakis(hexyloxy)triphenylene and hexakis(hexylthio)triphenylene. The compounds having four hexyloxy and two hexylthio substituents form only Colh mesophases. Triphenylenes having four hexylthio and two hexyloxy substituents also give Colh mesophases but 3,6-bis(hexyloxy)-2,7,10,11-tetrakis(hexylthio)triphenylene 5 is unique in that it cools into a stable, more ordered phase. The low temperature phase, which appears to be indefinitely stable at ambient temperature, is assumed to be helical based on transition enthalpy data

First examples of functionalisation of meso-aryl tetrabenzotriazaporphyrins (TBTAPs) through cross-coupling reactions

Recent synthetic advances have given convenient access to tetrabenzotriazaporphyrins (TBTAPs) functionalised with meso-aryl substituents. In this paper we report the first examples of further functionalization of the meso-sites through Suzuki-Miyaura and copper-free Sonagashira cross-coupling reactions of the meso-(bromophenyl)TBTAPs, demonstrating the breadth of new materials design now possible in the hybrid macrocycles

The design of a digital photogrammetric metrology system for the semi-automated surveying and recording of pipe dimensions in industrial plants

Bibliography: pages 51-53.This thesis reports on the design, development and testing of a semi-automated system to aid in the mapping of the interior of industrial plants. The system makes use of digital photogrammetry to assist an operator in locating and identifying components of the plants. All of the important photogrammetric theory is discussed in the text, and explained in detail in the appendices. Specifically, this system implements various algorithms used for camera calibration, object point intersection, and a method combining the two techniques. Considerable use is made of the iterative least squares method, which is the basis of many of the algorithms employed in this work. Image processing algorithms are implemented to enhance the digital images, and to ease the identification of objects in the images, and these are fully explained in the text. Adaptive least squares image matching is a method of matching corresponding points in different images and is used to ensure correspondence between points identified by the system operator. A weighted centre of gravity method is used to find the centre of target areas, and an algorithm is implemented to determine the radius, centre and direction of a pipe passing through a number of points. Various aspects of the system design are discussed and explained. In particular the requirements in terms of hardware and software are presented. In addition, the choices of the operating system and of the compiler are justified. Potential problems with the system, and possible enhancements of it are also described. Tests were performed to verify the correct operation of all of the algorithms used in the calibration of the cameras. Together with the point intersection routines, these tests calculated the position of various control points, the correct coordinates of which were previously known. The calculated point positions are compared to the known coordinates of the points to determine the accuracy of the various algorithms. Further tests were conducted to demonstrate and verify the ability of the system to measure distance in three dimensions. These tests illustrate that the accuracy achievable is approximately 0.053 of the total distance measured for an object occupying 803 of the width of the image. The system improves considerably on the method presently used in South Africa and in many industries worldwide which rely on analytical photogrammetry for the determination of object point locations. While the system suffers from reduced accuracy as a result of the use of digital cameras, this problem will become less important as technology and digital camera resolution improve. Possible enhancements include the use of more numerically efficient algorithms, and the introduction of techniques that would partially automate the identification of control points and pipes

A tetrabenzotriazaporphyrin based organic thin film transistor: Comparison with a device of the phthalocyanine analogue

The characteristics of bottom-gate bottom-contact organic thin film field-effect transistors (OTFTs) with 70 nm thick films of solution processed non-peripherally octahexyl-substituted nickel tetrabenzo triazaporphyrin (6NiTBTAP) molecules as active layers on silicon substrates are experimentally studied and the results are compared with the similary configured transistors using the corresponding nickel phthalocyanine (6NiPc) compound. 6NiTBTAP transistors are found to exhibit improved performance over 6NiPc transistors in terms of greater saturation hole mobility, two orders of magnitude higher on/off ratio and lower threshold voltage. This enhanced performance of 6NiTBTAP OTFTs over 6NiPc devices is attributed to improved surface morphology and large grain size of the active 6NiTBTAP film

Liquid crystalline properties of unsymmetrically substituted phthalocyanines: structural features leading to nematic mesophase materials

A novel homologous series of four 1,4,8,11,15,18-hexakis(pentyl)-22-methyl-25-hydroxyalkylphthalocyanine derivatives with the hydroxyalkyl chain varying from hydroxynonyl through to hydroxydodecyl has been synthesized to investigate the role of the hydroxyalkyl chain in promoting thermotropic liquid crystalline behavior. Polarizing optical miscoscopy reveals that the compound with the shortest hydroxyalkyl chain (hydroxynonyl) exhibits a mesophase with a texture characteristic of a columnar mesophase, common among liquid crystalline phthalocyanine derivatives. However, as the chain is lengthened along the series, there appears a second type of mesophase that shows a schlieren texture. Such a texture is characteristic of a nematic phase and rare among liquid crystalline phthalocyanine derivatives. A fifth compound, the novel 1,4,8,11,15,18-hexakis(pentyl)-22-methyl-25- dodecylphthalocyanine, exhibits only columnar mesophase behavior suggesting that the hydroxyl group at the end of the longer chains of the former compounds is important in developing the nematic phase

Synthesis of Meso‐Substituted Subphthalocyanine–Subporphyrin Hybrids: Boron Subtribenzodiazaporphyrins

The first syntheses of hybrid structures that lie between SubPhthalocyanines and SubPorphyrins are reported. The versatile, single-step synthetic protocol uses a preformed aminoisoindolene to provide the bridging methine unit and its substituent, while trialkoxyborates simultaneously act as Lewis acid/template and provider of the apical substituent. Selection of each component therefore allows controlled formation of diverse, differentially functionalised systems. The new hybrids are isolated as robust, pure materials that display intense absorption and emission in the mid-visible region. They are further characterised in solution and solid state by variable temperature NMR spectroscopy and X-ray crystallography respectivel

In situ chemichromic studies of interactions between a lutetium bis-octaalkyl-substituted phthalocyanine and selected biological cofactors

This article is available open access through the publisher’s website at the link below. Copyright @ 2011 The Royal Society.Spin-coated films, approximately 100 nm thick, of a newly synthesized bis[octakis(octyl)phthalocyaninato] lutetium(III) complex on ultrasonically cleaned glass substrates exhibit pronounced chemichromic behaviour with potential application in healthcare. In situ kinetic optical absorption spectroscopic measurements show that the phthalocyanine Q-band is red shifted by 60 nm upon oxidation arising from exposure to bromine vapour. Recovery to the original state is achieved by the treatment of the oxidized films with nicotinamide adenine dinucleotide and l-ascorbic acid (vitamin C) in an aqueous solution containing 1.5 M lithium perchlorate. The neutralization process is found to be governed by first-order kinetics. The linear increase of the reduction rate with increasing concentration of cofactors provides a basis for calibration of analyte concentrations ranging from 3.5 mM down to 0.03 mM.Air Force Office of Scientific Research, Air Force Material Command, USAF and the Leverhulme Trust

Neuropeptide VF neurons promote sleep via the serotonergic raphe

Although several sleep-regulating neuronal populations have been identified, little is known about how they interact with each other to control sleep/wake states. We previously identified neuropeptide VF (NPVF) and the hypothalamic neurons that produce it as a sleep-promoting system (Lee et al., 2017). Here we show using zebrafish that npvf-expressing neurons control sleep via the serotonergic raphe nuclei (RN), a hindbrain structure that is critical for sleep in both diurnal zebrafish and nocturnal mice. Using genetic labeling and calcium imaging, we show that npvf-expressing neurons innervate and can activate serotonergic RN neurons. We also demonstrate that chemogenetic or optogenetic stimulation of npvf-expressing neurons induces sleep in a manner that requires NPVF and serotonin in the RN. Finally, we provide genetic evidence that NPVF acts upstream of serotonin in the RN to maintain normal sleep levels. These findings reveal a novel hypothalamic-hindbrain neuronal circuit for sleep/wake control

High-mobility solution-processed copper phthalocyanine-based organic field-effect transistors

© 2011 National Institute for Materials ScienceSolution-processed films of 1,4,8,11,15,18,22,25-octakis(hexyl) copper phthalocyanine (CuPc6) were utilized as an active semiconducting layer in the fabrication of organic field-effect transistors (OFETs) in the bottom-gate configurations using chemical vapour deposited silicon dioxide (SiO2) as gate dielectrics. The surface treatment of the gate dielectric with a self-assembled monolayer of octadecyltrichlorosilane (OTS) resulted in values of 4×10−2 cm2 V−1 s−1 and 106 for saturation mobility and on/off current ratio, respectively. This improvement was accompanied by a shift in the threshold voltage from 3V for untreated devices to −2V for OTS treated devices. The trap density at the interface between the gate dielectric and semiconductor decreased by about one order of magnitude after the surface treatment. The transistors with the OTS treated gate dielectrics were more stable over a 30-day period in air than untreated ones.Technology Strategy Board, UK (Project No: TP/6/EPH/6/S/K2536J)