Increasing the isomerisation kinetics of azo dyes by chemical bonding to liquid-crystalline polymers

It is well known that the proper substitution of the azobenzene core allows tuning the thermal cis-to-trans isomerisation kinetics of azo dyes. The thermal isomerisation process of nitro-substituted azobenzenes is accelerated up to 13 times with respect to that in the common isotropic solvents when they are doped in nematic low molar mass liquid crystals. This kinetic acceleration is even stronger when these azo dyes are covalently linked to a nematic siloxane polymer. In this environment, the isomerisation process is accelerated more than 10(3) times. This effect is presented herein for the first time. The possible application of the networks obtained as possible photo-actuators has been also considered.     

Field dependence of liquid-crystalline phase in liquid-crystal and carbon nanotubes composite

Due to their exceptional properties, liquid crystals are useful for a wide range of applications. As reported in the literature, a slight dispersion of liquid crystals with carbon nanotubes has a detectable effect on the liquid-crystal properties making them appropriate for various applications. The present work reports a new application of these composites disclosing a process of transformation of commercially available high-temperature liquid crystals into low-temperature liquid crystals. This is accomplished by using high concentration of carbon nanotubes in liquid-crystal materials wherein the carbon nanotubes form cluster inside the liquid-crystal cells. The application of bias on these heavily doped samples resulted in the appearance of liquid-crystal phases at room temperature which, in the case of pure liquid crystals, were observable only at high temperature. The process is reversible and hence phase change can be controlled by external field.     

Synthesis and characterisation of reactive liquid crystals containing an azo group

A new series of liquid crystal (LC) monomers – not only contain a double bond but also contain an azo group – were designed and synthesised. The length of side groups in the LC monomers containing azobenzene ester varied from 1 to 2 methylene units, and the length of the substituted groups in the main chain varied from 1 to 3 methylene units. The molecular structures of the intermediates and target compounds were confirmed by Fourier transform infrared, ultraviolet and visible spectrum and nuclear magnetic resonance (NMR) spectroscopy. The thermal phase behaviour of the LC monomers was investigated by polar optical microscopy coupled with hot stage and differential scanning calorimetry (DSC). In this paper, the effect on the LC zone with the substituents were investigated, and with the increased methylene of main chain, the melting point and the phase transition temperature of the substance will be lowered and LC regions will be narrower.     

High-throughput mass spectrometry: the mechanism of sudan azo dye fragmentation by ESI tandem mass spectrometry and extensive deuterium labeling experiments

The investigation of the gas-phase chemistry of azo compounds by mass spectrometry dates back to the introduction of this peculiar research field into the armory of physical organic chemistry tools. The mechanism of the fragmentation of the azo double bond from the protonated precursor is discussed with reference to the behavior of deuterium-labeled reference compounds. The investigated molecules belong to the sudan family and the results can be used for the detection of these potential carcinogenic compounds in different matrices by means of the isotope dilution method.     

Oxidative dimerization of aromatic amines using tBuOI: entry to unsymmetric aromatic azo compounds

It's all the hype: An oxidative dimerization reaction of aromatic amines utilizing tert-butyl hypoiodite (tBuOI) under mild reaction conditions leads to aromatic azo compounds. The method allows access to unsymmetric aromatic azo compounds, which are difficult to prepare by conventional synthetic methods, in a selective manner.     

Photochromic properties of thienylpyrrole azo dyes in solution

The photochromic behaviour of thienylpyrrole azo dyes in THF solutions was studied for the first time. The photochromic properties are strongly dependent on the substitution pattern on the dyes. Nitro-substituted thienylpyrrole azo dyes are particularly interesting since they exhibit very fast colouration/decolouration processes. The activation energies of these compounds are among the lowest values reported for heterocyclic azo dyes. These compounds show aggregation phenomena in freshly prepared solutions of THF, which lead to variable photochromic behaviours. Only after 1-5 h the solutions reach equilibrium and then reproducible photochromic behaviour can be observed.     

Antiferroelectric phase in liquid crystalline compounds containing an azo group in their molecular core

Novel lactic acid derivatives containing an azo group in their molecular core have been synthesised and their mesomorphic properties established. Compounds with a short aliphatic non-chiral chain exhibited the SmA* phase and ferroelectric (FE) SmC* phase. The monotropic antiferroelectric (AF) phase was found in the homologues with a longer terminal chain. Spontaneous polarisation and tilt angle were measured for the FE and AF phases. Dielectric spectroscopy in the frequency range 1 Hz–10 MHz was carried out and dielectric properties established within the temperature range of the smectic phases. Two high frequency modes were detected in the AF phase. Small-angle X-ray measurements were conducted, and the temperature dependence of layer spacing values is established and discussed.     

Effect of orientation of extra fused benzene ring and lateral methyl substituent on the mesophase behaviour of three-ring azo/ester molecules

ABSTRACT

Two homologous series of the three-ring azo/ester compounds 2-(or1-) naphthyl 4?-(4?’-alkoxy phenylazo) benzoates (In_a and IIn_a) were synthesised. A lateral methyl group was introduced in different positions of the alkoxy phenyl moiety, in position-2 to give series In_b and IIn_b and in position-3 to give series In_c and IIn_c. Molecular structures were characterised via elemental analyses, infrared and ¹H-NMR. Their mesophase characteristics were investigated by differential scanning calorimetry (DSC) and their phases identified via polarised light microscopy (PLM). Transition temperatures were correlated with the alkoxy-chain length (n) that varies between 6, 8, 10, 12, 14, and 16 carbons. Comparative studies were first made to investigate the effect of including the extra fused benzene ring, and its orientation, into the previously investigated three-ring compounds, 4-phenyl 4?-(4′′-alkoxyphenylazo) benzoates (IIIn_a). Investigation of the mesophase behaviour was extended to cover the effect of introducing the lateral methyl group and its position. The comparison between the present six series and their corresponding phenyl analogues IIIn_a,b,c, indicated that the 2-naphthyl analogues, In_a,b,c, exhibit the highest mesophase stability. Whereas, the steric effect of the protruded naphthalene group destabilises all mesophases and appear only monotropically. The results were discussed in terms of polarisability effect.     

多孔芳香骨架吸附剂-固相萃取-高效液相色谱法同时测定辣椒粉中4种偶氮类染料

建立了固相萃取-高效液相色谱同时测定辣椒粉中对位红、酸性橙Ⅱ、苏丹红Ⅰ和苏丹红Ⅱ 4种偶氮染料的方法。以多孔芳香骨架-6（PAF-6）材料作为固相萃取吸附剂，考察并获得了影响自制固相萃取柱的萃取效率和吸附容量等主要因素。在优化条件下，4种目标分析物的检出限（LOD）为1.5~7.0 μg/L（信噪比S/N=3），定量限（LOQ）为5.0~22.1 μg/L（S/N=10），加标回收率为76.5%~89.8%，相对标准偏差（RSD）均不大于5.3%（n=6）。此外，基于量子化学计算，考察了PAF-6与目标分析物之间的相互作用机制，结果表明，目标分析物可以稳定地吸附在PAF-6分子上。该方法准确可靠，具有良好的回收率和较高的灵敏度，可用于辣椒粉中4种偶氮类染料的检测。     

Amide as Terminal Groups: Synthesis and Properties as New Tolane‐Type Liquid Crystals

A series of novel tolane‐type liquid crystals with amide group as terminal group have been prepared. The terminal amide groups were modified, and the influence of these structural parameters on liquid crystal phases was investigated by polarizing optical microscope (POM) and differential scanning calorimetry (DSC). Three of these new compounds exhibit nematic phase, good thermal stabilities. In general, these liquid crystals with amide as end groups have high melting points and phase transition temperatures, which result from the hydrogen bonds. Based on theoretical calculations, these new molecules with strong electron donating amide as end group have narrower HOMO‐LUMO energy gap and higher dipole moment than tolane.     

Dielectric properties near the isotropic-smectic-C* phase transition

The dielectric properties in the vicinity of the isotropic-smectic-C* phase transition in ferroelectric liquid crystals are discussed. The temperature and frequency dependence of the complex dielectric permittivity in both the phases of the transition are calculated. The theoretical phase diagram of the dielectric permittivity is studied.     

Dual-mode sorption of nonionic azo dyes by Nylon 6

Sorption isotherms of 2,4-dinitroaniline and three 4-amino-azobenzene derivatives (nonionic dyes with adequate solubility in water) on Nylon 6 (film and fiber) from water were determined at various temperatures. The observed isotherms were curved, not linear. They were very well described in terms of the dual-mode sorption model, Nernst-type partitioning, plus Langmuir sorption. The contribution of the Langmuir sorption to the total dye sorption decreased with increasing temperature. The saturation value for the Langmuir sorption increased with the crystallinity of Nylon 6 film, suggesting that the Langmuir sorption is associated with the crystalline phase.     

Supramolecular compounds of azo dyes derived from 1-phenylazo-2-naphthol and their nickel and copper complexes

In this study, experimental techniques including Raman, infrared and X-ray crystal diffraction, as well as quantum chemistry calculations, are used to investigate two new azo dyes supramolecular complexes: 1-phenylazo-2-naphthol (Sudan I) with nickel(II) ion and 1-(2,4-xylylazo)-2-naphthol (Sudan II) with copper(II) ion. The crystallographic structures have been solved for bis-1-(pheny-l-azo)-2-naphtholatenickel(II) and bis-1-(2,4-xylylazo)-2-naphtholatecopper(II) complexes, revealing the presence of supramolecular interactions, such as the centroid–centroid π-stacking interactions and CH…π hydrogen interactions. These weak intermolecular interactions appear to play an important role on the crystal structure stability for both compounds. Density functional theory calculations at B3LYP/6-311++G(d,p) level were performed in order to help understanding such molecular interactions and to assign the vibrational spectra. The experimental and theoretical data have allowed the analysis of the packing forces, revealing charge accumulation at key molecular regions.     

Achiral bent-core azo compounds: observation of photoinduced effects in an antiferroelectric tilted smectic mesophase

We report the synthesis and physical properties of four novel bent-core compounds, containing an azo linkage and alkyl terminal chains. It is found that, except for the lowest homologue, all the materials are liquid crystalline, exhibiting columnar or tilted polar smectic phases. In one of the compounds a reversible photoinduced variation of the spontaneous polarization of the antiferroelectric state was observed.     

Characterisation of azo dye and carbon nanoparticle-doped guest–host liquid crystalline matrix

During the recent years, liquid crystals (LCs) have much attention owing to their wide range of possible application and structural properties in electronics and optics. In this study, two different azo structured dyes (Disperse Yellow 3 and 7) and their mixture were separately doped to each of two different nematic LCs (E8 and E63). Their solubilities (except dye mixture), order parameters, textures and phase transition temperatures were determined. Single-walled nanotubes and fullerene C60 in a small amount were separately added to each of these solutions, and the experiments were repeated at the final stage analogously except solubilities. The solubilities of dyes in the LC E63 were lower than those of E8. The highest order parameter value was attained with Yellow 7 dye in E63 nematic host.     

Preparation and photochemical study of soluble optically active block copolymethacrylates and azo-containing random copolymethacrylates

A series of soluble optically active block copolymers of trityl methacrylate (TrMA) and cyclohexyldiphenylmethyl methacrylate (CHDPMA) with methyl methacrylate (MMA) and n-butyl methacrylate (n-BuMA) were synthesized using the complex of 9-fluorenyllithium and (S,S)-(+)-2,3-dimethoxy-1,4-bis(dimethylamino)butane as an initiator in toluene at −78°C. Soluble optically active random copolymers derived from TrMA and azo methacrylates, 6-(4-phenylazophenoxy)hexyl methacrylate (PAHM) and 2-(4-phenylazophenoxy)ethyl methacrylate (PAEM), were obtained under similar anionic polymerization conditions. Optical activities of the copolymers largely depended on the weight percentage of TrMA or CHDPMA component in the polymer chains. Solubility and film formability were significantly improved for the copolymers. Irradiation of optically active TrMA–MMA and CHDPMA–MMA block copolymer films containing photoacid, diphenyl-p-tolylsulfonium triflate, causes the partial hydrolysis of bulky esters and results in the conformational randomization of helical chains, which in turn leads to a significant change in optical rotation of the films. Photoisomerization studies of azo-containing random copolymers indicate that the trans to cis isomerization induces the helical conformation racemization in solution. © 1997 John Wiley & Sons, Inc.     

Transient holographic grating in azo-dye-doped liquid crystals with off-resonant light

Holographic gratings in nematic liquid crystals doped with Disperse Red 1 (DR1) were investigated using a linearly polarised He–Ne laser. Although the electric transitions of the samples were almost off-resonant, the diffraction of the transient holographic grating was found to exhibit a sinusoidal feature with changing the polarisation of recording beams, and the diffraction intensities and response time of the gratings were strongly dependent on DR1 concentration. The results revealed that the diffraction of holographic grating depends on the rate of trans–cis isomerisation of DR1 molecules. Moreover, the temperature dependence of diffraction indicated that the grating formation mechanism was attributed to photoinduced reorientation of photoisomerisation effect.     

Self-assembly and liquid-crystalline properties of 5-fluoroalkylporphyrins

We report three crystal structures of a synthetic 5-fluoroalkylporphyrin molecule that was programmed for self-assembly. All the X-ray structures of zincated and free-base porphyrins Zn2 b, Zn5 a, and 2 b revealed rigorous pi-pi stacking and extremely hydrophobic interactions. Other the other hand, the strong aggregation of 5-fluoroalkylporphyrins in solution was also found. Interestingly, the regular nanopore formation of the 5-fluoroalkylporphyrin was visualized by atomic force microscopy (AFM). Importantly, the 5-fluoroalkylporphyrins possess liquid-crystalline properties that were confirmed by using a combination of differential scanning calorimetry (DSC) and polarizing optical microscopy (POM) techniques. By comparison, the self-assembly of non-fluorine-containing porphyrins with similar structure showed much lower aggregation ability, as investigated by NMR techniques. Additionally, no birefringent mesophase was observed for the non-fluorine-containing porphyrin.