Effect of spacer length on mesomorphic behaviours of chiral liquid crystal compounds containing (-)-menthyl

ABSTRACT

A homologous series of new chiral liquid crystal compounds, MnBEB (n = 4–10), was prepared by covalently linking a chiral (–)-menthyl with biphenyl-benzoate via a dicarboxylic spacer of varying length and parity. A combination of analysis methods, such as FT-IR, ¹H NMR spectra, differential scanning calorimetry (DSC), polarised optical microscopy (POM) and X-ray diffraction was carried out to systematically investigate their phase structures and phase transition behaviours. The length and parity of the flexible spacers has a profound influence on the T_m and T_c and a modest odd-even effect is observed for the chiral liquid crystal compounds MnBEB. Only compound M4BEB developed an N* phase with selectively reflection on heating and a blue phase on cooling process. In addition, increasing the length of the flexible spacers tends to narrow the temperature range of the N* phase and widen the smectic phase, moreover, the pitch becomes longer with the spacer increases.     

Storage stability studies for tributyltin determination in human urine samples using headspace solid‐phase microextraction and gas chromatography mass spectrometry

A headspace solid‐phase micro‐extraction (HS‐SPME) method was employed in order to study the effect of storage conditions of human urine samples spiked with tributyltin (TBT) using gas chromatography and mass spectrometry. To render the analyte more volatile, the derivatization (ethylation) was made in situ by sodium tetraethylborate (NaBEt₄), which was added directly to dilute unpreserved urine samples and in buffers of similar acidity. The stability of TBT in human urine matrix was compared with the stability of TBT in buffer solutions of similar pH value. Critical parameters of storage conditions such as temperature and time, which affect the stability of TBT in this kind of matrix, were examined extensively. The tests showed that the stability of TBT remains practically satisfactory for a maximum of 2 days of storage either at +4 or 20°C. Greater variations were observed in the concentration of TBT in human urine samples at +4°C and lower ones at ?20°C over a month's storage. The freeze–thaw cycles have negative effect on the stability and should be kept to a minimum. The results from spiked urine samples are also discussed in comparison to those acquired from buffer solutions of equal TBT concentration. Copyright © 2012 John Wiley & Sons, Ltd.     

TRIFLUOROMETHYLTHIOLATION OF NORBORNENE

Treatment of norbornene with trifluoromethylsulfenyl chloride at ?80°C furnishes, in addition to trifluoromethylthionortricyclane, four isomeric (chloro) (trifluoromethylthio)-norbornanes and bis-(2, 6-trifluoromethylthio)norbornane. The probable mechanism of the formation of the various compounds via free radical intermediates and their mass spectral characterization are described in this communication.     

Propagation of a pre-existing turbulent fluid fracture

The propagation of rough and smooth wall pre-existing turbulent fluid fractures is investigated. The laminar fluid fracture is included as a special case for comparison. Lubrication theory is assumed to apply in the fracture and turbulence is introduced through the wall shear stress. The Perkins–Kern–Nordgren approximation is made in which the fluid pressure is proportional to the half-width of the fracture. The fracture half-width satisfies a non-linear diffusion equation. By using a linear combination of the Lie point symmetries of the non-linear diffusion equation a group invariant solution for the fracture length, volume and half-width is derived. The evolution of the length, half-width and mean flow velocity is analysed for a range of working conditions at the fracture entry. It is found that the mean flow velocity increases approximately linearly along the fracture.     

Controlled Activity Polymers. IV. Copolymers of 2-(1-Naphthylacetyl)Ethyl Acrylate With Hydrophilic Comonomers: Synthesis and Characterization

2-(1-Naphthylacetyl)ethyl acrylate (NAEA) was synthesized by esterification of 1-naphthylacetic acid (NAA) and 2-hydroxyethyl acrylate (HEA) and then polymerized to obtain the polymer-bound auxin NAA. The resulting polymer is potentially useful as a plant growth regulator through hydrolytic release of NAA. Copolymers of NAEA with hydrophilic comonomers were prepared by solution polymerization. The copolymer compositions were determined from elemental analysis, ¹³C-NMR, and UV spectroscopy. The copolymer microstructure was predicted from the reactivity ratios in order to investigate the influence on the behavior of controlled release. These model structures will be utilized for assessment of structure/hydrolysis relationships in a subsequent paper.     

Microwave Assisted Rupture of Furoxans to Nitrile Oxides and Intermolecular Capture by Dipolarophiles

3,4-Diaroylfuroxans 1 react with various dipolarophiles 3 under microwave activation to afford the cycloadduct 4 instead of the expected isoxazole 5 in good yields in the absence of solvent.     

Click Chemistry on Polymer Support: Synthesis of 1-Vinyl- and 1-Allyl-1,2,3-triazoles via Selenium Linker

Polystyrene-supported 2-azidoethyl phenyl selenide and 3-azidopropyl phenyl selenide reagents have been developed and applied to the traceless solid-phase organic synthesis of 1-vinyl- and 1-allyl-1,2,3-triazoles by CuI-mediated azide–alkyne cycloadditions and subsequent cleavage from the polymer support through oxidation–elimination reaction with 30% hydrogen peroxide. The advantages of this method include straightforward operation, good yield and purity of the products, and good stability and lack of odor for the reagents.     

A comparative first-principles study on electronic structures and mechanical properties of ternary intermetallic compounds Al8Cr4Y and Al8Cu4Y: Pressure and tension effects

An investigation into the bulk properties, elastic properties and Debye temperature under pressure, and deformation mode under tension of Al₈Cu₄Y and Al₈Cr₄Y compounds was investigated by using first principles calculations based on density functional theory. The calculated lattice constants for the ternary compounds (Al₈Cu₄Y and Al₈Cr₄Y) are in good agreement with the experimental data. It can be seen from interatomic distances that the bonding between Al1 atom and Cr, Y, and Al2 atoms in Al₈Cr₄Y are stronger than Al₈Cu₄Y. The results of cohesive energy show that Al₈Cr₄Y should be easier to be formed and much stronger chemical bonds than Al₈Cu₄Y. The bulk modulus B, shear modulus G, Young's modulus E and Poisson's ratio ν can be obtained by using the Voigt–Reuss–Hill averaging scheme. From the results of elastic properties, Al₈Cr₄Y has the stronger mechanical behavior than Al₈Cu₄Y. Our calculations also show that pressure has a greater effect on mechanical behavior for both compounds. The ideal tensile strength are obtained by stress-strain relationships under [001](001) uniaxial tensile deformation, which are 15.4 and 23.4 GPa for Al₈Cu₄Y and Al₈Cr₄Y, respectively. The total and partial density of states and electron charge density under uniaxial tensile deformations for Al₈Cu₄Y and Al₈Cr₄Y compounds are also calculated and discussed in this work.     

Growth characteristics of spherical titanium oxide nanoparticles during the rapid gaseous detonation reaction

The nanosize grain growth characteristics of spherical single-crystal titanium oxide (TiO₂) during the rapid gaseous detonation reaction are discussed. Based on the experimental conditions and the Chapman–Jouguet theory, the Kruis model was introduced to simulate the growth characteristics of spherical TiO₂ nanoparticles obtained under high pressure, high temperature and by rapid reaction. The results show that the numerical analysis can satisfactorily predict the growth characteristics of spherical TiO₂ nanoparticles with diameters of 15–300 nm at different affecting factors, such as concentration of particles, reaction temperature and time, which are in agreement with the obtained experimental results. We found that the increase of the gas-phase reaction temperature, time, and particle concentration affects the growth tendency of spherical nanocrystal TiO₂, which provides effective theoretical support for the controllable synthesis of multi-scale nanoparticles.