New chiral liquid crystal monomers and cholesteric polyacrylates: synthesis and characterisation

The synthesis of new chiral monomers (M₁ ?M₃ ) based on menthol and the corresponding polyacrylates (P₁ ?P₃ ) is described. The chemical structures, formula and phase behaviour of the obtained monomers and polymers were characterised with FT-IR, ¹H-NMR, elemental analyses, differential scanning calorimetry (DSC), polarising optical microscopy (POM) and X-ray diffraction (XRD). The effect of the mesogenic core rigidity, spacer length and menthyl steric effect on the phase behaviour of M₁ ?M₃ and P₁ ?P₃ is discussed. The expected mesophase of the compounds based on menthol can be obtained by inserting a flexible spacer between the mesogenic core and the terminal groups. For the chiral monomers and polyacrylates, their corresponding melting temperature (T _m), glass transition temperature (T _g) and clearing temperature (T _i) increased with an increase of the mesogenic core rigidity; while the T _m, T _g and T _i decreased with increasing the spacer length. M₁ and P₁ showed no mesophase, while M₂ and M₃ all revealed a SmC* and cholesteric phases. P₂ and P₃ only showed a cholesteric phase.     

Effect of chiral isosorbide groups on mesomorphic properties of side-chain liquid-crystalline polysiloxanes

Chiral side-chain liquid-crystalline (LC) polysiloxanes containing isosorbide groups were graft copolymerised with poly(methylhydrogeno)siloxane, a chiral LC monomer 6-(4-methoxy-benzoyloxy)-hexahydro-furo[3,2-b]furan-3-yl 4'-(4-undec-10-enoyloxy-benzoyloxy)-biphenyl-4-yl adipate and a nematic LC monomer 4'-(4-methoxy-benzoyloxy)-biphenyl-4-yl 4-(2-undec-10-enoyloxy-ethoxy)-benzoate. The chemical structures and LC properties of the monomers and polymers were characterised by use of various experimental techniques including Fourier transform infrared spectroscopy (FTIR), ¹H-nuclear magnetic resonance (NMR), element analyses (EA), differential scanning calorimetry (DSC), polarised optical microscopy (POM) and X-ray diffraction (XRD). All the chiral LC polymers showed LC properties with very wide mesophase temperature ranges and the chiral component in the LC polymer systems lead to the appearance of a cholesteric phase. The polymers bearing most chiral LC monomer component showed smectic phases by reason of regular structures in the polymer systems. With the increase of another nematic LC monomer in the polymers, the regular polymer structures were destroyed because of different chemical structures between the two kinds of LC monomers, leading to the disappearance of the smectic arrangement.     

Mesophase behaviour of laterally di-fluoro-substituted four-ring compounds

Four new groups of the di-fluoro-substituted 4-(2′-(or 3′)-fluoro phenylazo)-2-(or 3-) fluoro phenyl-4″-alkoxyphenylazo benzoates (In–IVn) were prepared and investigated for their mesophase behaviour. An alkoxy group of variable chain length (n = 6, 10 and 14 carbons) is attached to the terminal phenylazo benzoate moiety, and two lateral fluoro substituents are attached individually with different orientations to the other two adjacent rings. The molecular structures of the prepared compounds were confirmed by Fourier transform infrared spectroscopy and ¹H NMR spectroscopy. The study aims to investigate the steric effect of the spatial orientation and relative positions of the two lateral fluorine atoms on the mesomorphic properties in their pure states. The mesophase behaviour was investigated via differential scanning calorimetry and mesophases were identified by polarised light microscopy. The investigation shows that these compounds exhibit high enantiotropic mesophases (SmC and N) and broad mesophase temperature range. The type and stability of the mesophase depends on the length of the terminal alkoxy chain and the position the two fluoro substituents. A comparison between these investigated compounds with their corresponding three-ring analogues was discussed.     

The effect of ethanol on the phase behaviour and micro-rheology of liquid crystals

The effect of ethanol on the phase behaviour and micro-rheology of lyotropic liquid crystals (LC) has been studied using a binary mixture of monoglyceride (MG) and aqueous ethanol. The phase behaviour study reveals the structural modulation of surfactant aggregates with increasing ethanol concentration, namely a bicontinuous cubic phase (Ia3d) transitions to the lamellar phase (L_α), at a fixed MG concentration. This behaviour is explained by considering the critical packing parameter (CPP) of the surfactant molecule. Because ethanol dehydrates the surfactant head group (a _s), the CPP values increase (decreasing a _s) and thus the formation of larger CPP aggregates is favoured (i.e., the Ia3d–L_α transition occurs). Cross-polarised images and X-ray scattering data support this conclusion. The structural modulation of the LC has further been investigated using a diffusing wave spectroscopy technique. The correlation and relaxation times, determined from the intersection point at short and long time scales of the mean square displacement (MSD), decrease with increasing concentrations of ethanol, indicating structural modulation of the LC. The micro-viscoelastic moduli (G′ and G′′) derived from the Laplace transformation of the MSD decrease with increasing ethanol concentrations, due to the LC modulation. The thermal effects on the micro-rheology of the LC have also been studied.     

Performance analysis of an opportunistic multi‐user cognitive network with multiple primary users

Consider a multi‐user underlay cognitive network where multiple cognitive users concurrently share the spectrum with a primary network with multiple users. The channel between the secondary network is assumed to have independent but not identical Nakagami‐m fading. The interference channel between the secondary users (SUs) and the primary users is assumed to have Rayleigh fading. A power allocation based on the instantaneous channel state information is derived when a peak interference power constraint is imposed on the secondary network in addition to the limited peak transmit power of each SU. The uplink scenario is considered where a single SU is selected for transmission. This opportunistic selection depends on the transmission channel power gain and the interference channel power gain as well as the power allocation policy adopted at the users. Exact closed form expressions for the moment‐generating function, outage performance, symbol error rate performance, and the ergodic capacity are derived. Numerical results corroborate the derived analytical results. The performance is also studied in the asymptotic regimes, and the generalized diversity gain of this scheduling scheme is derived. It is shown that when the interference channel is deeply faded and the peak transmit power constraint is relaxed, the scheduling scheme achieves full diversity and that increasing the number of primary users does not impact the diversity order. Copyright © 2014 John Wiley & Sons, Ltd.     

Impact of Gd3+ and Nd3+ ions substitution on structural and magnetic properties of Co0.5Ni0.5Fe2O4 ferrite system

Co_0.5Ni_0.5(Gd/Nd)_xFe_2-xO₄ (x ?= ?0.0 and 0.06) ferrites were prepared by the solid-state reaction method. These materials were characterized by XRD, FT-IR spectroscopy, and VSM techniques. The XRD analysis revealed the phase formation of all samples and their cubic spinel structure with the Fd-3m space group. Lattice constant was found to increase due to Gd and Nd ions substitution. However, the crystallite size was observed to decrease by the substitution effect. The FT-IR spectra showed the two vibrational frequency bands of the tetrahedral and octahedral sites. From the magnetic properties study, it was identified that the pure and Gd substituted Co_0.5Ni_0.5Fe₂O₄ ferrite showed a ferromagnetic behaviour. While the Nd substituted Co_0.5Ni_0.5Fe₂O₄ ferrite delivered a superparamagnetic behaviour. The substitution of Gd and Nd changed the values of the magnetic parameters of Co_0.5Ni_0.5Fe₂O₄ ferrite. An increase in the saturation magnetization (M_s) value was observed due to substitution of Gd and Nd in Co_0.5Ni_0.5Fe₂O₄ ferrite, indicating that Gd and Nd substitution strengthen the supermagnetic interactions in Co_0.5Ni_0.5Fe₂O₄ ferrite. The highest value of M_s was observed in Gd doped sample.     

Synthesis,Crystal Structure and Characterization of a Ni(Ⅱ) Complex of Constructed 2,6-Bis(benzimidazol-2-yl) pyridine

A fluorescent Ni(II) complex 1, [Ni(OH-H2Bdc)(Bibimp)]n·nH2O, constructed with 5-hydroxyisophthalic acid(OH-H2Bdc) and 2,6-bis(2-benzimidazolyl)pyridine)(Bibimp) has been synthesized by hydrothermal methods and structurally characterized by elemental analysis, IR spectroscopy, TG/DTG, fluorescence spectrum and single-crystal X-ray diffraction. The title complex crystallizes in triclinic system, space group P1 with a = 10.187(2), b = 10.273(2), c = 13.401(3), α = 69.65(3), β = 69.66(3), γ = 70.61(3)o, V = 1196.8(4) 3, and Z = 2. The adjacent chains of complex 1 are stacked offset with respect to each other in an ABAB fashion by van der Waals interactions, and only a weak interlayer nonclassical C–H···O hydrogen bond has been observed. Complex 1 displays strong blue fluorescent emissions at 483 nm in the solid state upon photo-excitation at 365 nm at room temperature.     

Real-time in situ monitoring of manufacturing process and CFRP quality by relative resistance change measurement

In situ monitoring of resin flow, impregnation of carbon fiber fabrics, and curing during composite manufacturing are very important for determining the quality of composite parts. In conventional methods, sensors, such as optical fibers and strain gages, are bonded to or embedded in the composites for measuring the changes in mechanical and chemical properties. Although they can detect resin curing behavior and impregnation of carbon fibers, they may adversely affect the manufacturing process or structural integrity of the composites. In this study, carbon fiber itself was used as a sensor that minimizes the degradation of mechanical properties and increases the efficiency of monitoring the manufacturing process. The change in the electrical resistance of carbon fiber fabrics was monitored during the various manufacturing processes when the resin flowed through the carbon fiber fabric and curing progressed. The effectiveness of this monitoring method was confirmed, and it is expected to be applicable in monitoring the quality of the finished composite parts.     

Electrochemical Oxidative Determination and Electrochemical Behavior of 4‐Nitrophenol Based on an Au Electrode Modified with Electro‐polymerized 3,5‐Diamino‐1,2,4‐triazole Film

A simple and fast electrochemical method was described and evaluated to determine the hazardous compound, 4‐nitrophenol (4NP). In this work, concentration of 4NP was determined by differential wave voltammetry (DPV). A gold electrode (Au) was modified with 3,5‐diamino‐1,2,4‐triazole (35DT). The modified electrode (35DT‐Au) was characterized by using electrochemical impedance spectroscopy (EIS), fouirer transform infrared spektrofotometre (FTIR), cyclic voltammetry (CV) and DPV. The modified electrode showed more sensitivity towards 4NP compared to unmodified one. A wide linear concentration range from 0.24 to 130.6 μM was obtained for 4NP with a detection limit of 0.09 μM. In the reproducibility and repeatability studies, the relative standard deviation (RSD%) values of the method were obtained as 3.72 % and 2.56 %, respectively, which are acceptable values. This proposed method was successfully used for the analysis of 4NP in lake and tap water samples. Simplicity, sensitivity, selectivity and high efficiency of the proposed method can be used in routine analysis of trace amounts of 4NP in polluted waters.     

Multivalent ions and biomolecules: Attempting a comprehensive perspective

Ions are ubiquitous in nature. They play a key role for many biological processes on the molecular scale, from molecular interactions, to mechanical properties, to folding, to self-organisation and assembly, to reaction equilibria, to signalling, to energy and material transport, to recognition etc. Going beyond monovalent ions to multivalent ions, the effects of the ions are frequently not only stronger (due to the obviously higher charge), but qualitatively different. A typical example is the process of binding of multivalent ions, such as Ca²⁺, to a macromolecule and the consequences of this ion binding such as compaction, collapse, potential charge inversion and precipitation of the macromolecule. Here we review these effects and phenomena induced by multivalent ions for biological (macro)molecules, from the “atomistic/molecular” local picture of (potentially specific) interactions to the more global picture of phase behaviour including, e. g., crystallisation, phase separation, oligomerisation etc. Rather than attempting an encyclopedic list of systems, we rather aim for an embracing discussion using typical case studies. We try to cover predominantly three main classes: proteins, nucleic acids, and amphiphilic molecules including interface effects. We do not cover in detail, but make some comparisons to, ion channels, colloidal systems, and synthetic polymers. While there are obvious differences in the behaviour of, and the relevance of multivalent ions for, the three main classes of systems, we also point out analogies. Our attempt of a comprehensive discussion is guided by the idea that there are not only important differences and specific phenomena with regard to the effects of multivalent ions on the main systems, but also important similarities. We hope to bridge physico-chemical mechanisms, concepts of soft matter, and biological observations and connect the different communities further.