Design of liquid crystals with ‘de Vries-like’ properties: the effect of an ethynyl spacer in the core structure

We investigate the origins of ‘de Vries-like’ liquid crystalline behaviour by introducing an ethynyl spacer in the core of the tricarbosilane-terminated 5-phenylpyrimidine mesogens QL16-6 and QL17-6. The rationale for this structural change is based on the assumption that an ethynyl spacer would create more free volume in the core sub-layer and therefore decrease the orientational order parameter S₂ in the SmA phase. The tricarbosilane-terminated mesogens WL41-5 and WL42-6 with a 5-(phenylethynyl)pyrimidine core in either a normal or inverted orientation were synthesised, and their mesomorphic and ‘de Vries-like’ properties characterised using polarised optical microscopy, differential scanning calorimetry, birefringence measurements, small–angle (SAXS) and 2D X-ray scattering. Reduction factors R derived from SAXS and optical tilt angle measurements suggest that neither WL41-5 (R = 0.49) nor WL42-6 (R = 0.80) exhibit ‘de Vries-like’ properties. The S₂(T) profiles show an increase in orientational order with decreasing temperature and a sharp discontinuity at the SmA-SmC transition, which is consistent with ‘de Vries-like’ behaviour. However, the L_eff(T) profiles suggest an increase in interdigitation that reduces the positive effect of increasing S₂ in compensating for the molecular tilt.     

Specific crystal structure of poly(3-hydroxybutyrate) thin films studied by infrared reflection–absorption spectroscopy

Infrared reflection–absorption (IR-RAS) and transmission spectra were measured for poly(3-hydroxybutyrate) (PHB) thin films to explore its specific crystal structure in the surface region. As IR-RAS is sensitive to the vibration mode of perpendicular orientation of the surface, differences between IR-RAS and transmission spectra indicate an orientation of the lamella structure in the surface of PHB thin films. The relative intensity of the crystalline CO stretching band in the IR-RAS spectrum is significantly weaker than that in the transmission spectrum. It may be concluded that the transient dipole moment of the CO stretching mode of the crystalline state is not oriented perpendicular but nearly parallel to the substrate surface. On the other hand, the relative intensity of the band at 3009 cm⁻¹ due to the C–H stretching mode of the C–HOC hydrogen bonding is similar between the IR-RAS and transmission spectra, suggesting that the C–H bond is oriented neither perpendicular nor parallel to the substrate surface but in an intermediate direction. Since the CO group of the C–HOC hydrogen bonding is oriented nearly parallel to the surface and its C–H group is in the intermediate direction, it is very likely that the C–HOC hydrogen bonding has a somewhat bent structure. These results are in good agreement with our previous conclusion that the C–HOC hydrogen bonding of PHB exists along the a-axis (not the b-axis) between the CH₃ group of one helix and the CO group of another helix.     

Effect of precipitation procedure and detection technique on particle size distribution of CaCO3

The deposition of inorganic salts (“scales”) such as calcium carbonate is an important flow assurance problem during crude oil production. The knowledge of the features of the precipitated solids, mainly the particle size and morphology, is crucial to understand the nature of the solids and to avoid or reduce the effect of their deposition. For instance, the use of additives is one of the most usual procedures to mitigate this problem. Additives interact with scale-forming substances either by increasing the induction time, or by inhibiting crystal growth, changing the morphology of solids.     

A turn-on and reversible fluorescence sensor with high affinity to Zn in aqueous solution

A new simple receptor 1 based on aminosalicylimine was prepared. It exhibited an ‘off–on fluorescence type’ mode with high sensitivity in the presence of Zn²⁺. In particular, this chemosensor could clearly distinguish Zn²⁺ from Cd²⁺. Also, it could be a reusable chemosensor because the addition of EDTA quenched the fluorescence of the Zn²⁺-2·1 complex. Furthermore, receptor 1 had a sufficiently low detection limit (68 nM) in aqueous solutions, which implies that 1 could sense the nanomolar concentration of Zn²⁺. Therefore, this sensor has the ability to be a practical system for the monitoring of Zn²⁺ concentrations in aqueous samples.     

Film thickness measurements in liquid–liquid slug flow regimes

At present there is significant interest in the development of small scale medical diagnostic equipment. These devices offer faster processing times and require smaller sample volumes than equivalent macro scale systems. Although significant attention has been focused upon their outputs, little attention has been devoted to the detailed fluid mechanics that govern the flow mechanisms within these devices. Conventionally, the samples in these small scale devices are segmented into distinct discrete droplets or slugs which are suspended in an organic carrier phase. Separating these slugs from the channel wall is a very thin film of the organic carrier phase.The magnitude of this film is the focus of the present study and the effects of sample slug length and carrier phase fluidic properties on the film are examined over a range of Capillary numbers. A non-intrusive optical technique was used to capture images of the flow from which the magnitude of the film was determined.The experimental results show that the film is not constant along the length of the slug; however above a threshold value for slug length, a region of constant film thickness exists. When compared with existing correlations in the literature, the experimental data showed reasonable agreement with the Bretherton model when the Capillary number was calculated based on the mean two phase flow velocity. However, significant differences were observed when the Capillary number was redefined to account for the mean velocity at the liquid interface, i.e., the mean slug velocity.Analysis of the experimental data revealed that it fell into two distinct flow regimes; a visco-capillary regime and a visco-inertial regime. A modified Taylor expression is presented to estimate the magnitude of the film for flows in the visco-capillary regime while a new model is put forward, based on Capillary and Weber numbers, for flows in the visco-inertial regime. Overall, this study provides some novel insights into parameters, such as aqueous slug length and carrier phase fluidic properties, that affect the thickness of the film in liquid–liquid slug flow regimes.