Azomesogens with polar chloro,nitro and phenolic –OH substituents

Two new mesogenic homologous series containing chloro, nitro and phenolic hydroxy groups were synthesised and their molecular structures characterised by a combination of element analysis and standard spectroscopic methods. The mesomorphic behaviour of the compounds of both series was investigated by polarising optical microscopy and, in some cases, differential scanning calorimetry. All the compounds of both the series exhibit an enantiotropic nematic mesophase. In series I higher members also exhibit an enantiotropic smectic A (SmA) mesophase, whereas in series II the enantiotropic SmA mesophase commences somewhat earlier for the middle members. The mesomorphic properties of both series are compared with each other and also with the properties of other structurally related series to evaluate the effects of different polar substituents on mesomorphism.     

Spectroscopic study of liquid crystalline N-[4-(4-n-alkoxybenzoyloxy)2-hydroxybenzylidene]hydroxyanilines

New homologous series of N-[4-(4-n-alkoxybenzoyloxy)-2-hydroxybenzylidene]hydroxyanilines were synthesized. All 4-hydroxyaniline derivatives exhibited a nematic phase, while 3-hydroxyaniline and 2-hydroxyaniline derivatives exhibited only a nematic phase as the terminal alkoxy group was lengthened. Infrared spectra suggest that the 4-hydroxyaniline derivatives form intermolecular hydrogen bonding of the single bridge type, while the 3-hydroxy and 2-hydroxy derivatives form the polymer type. The Raman band at around 1360 cm^-1 exhibited large differences in intensity among these derivatives. This can be explained by the effect of intermolecular or hydrogen bonding molecular conformation.     

Ethylenedioxythiophene as a novel central unit for bent-core liquid crystals

We have discovered that ethylenedioxythiophene (EDOT) can be used as a central unit for the synthesis of bent-core liquid crystals (BC LCs). Two series of EDOT-based BC LCs are prepared via Sonogashira coupling reaction. The mesophase behaviour of all the compounds was characterised using a combination of polarising optical microscopy, differential scanning calorimetry and X-ray diffraction measurements. EDOT-based three-ring compounds were found to be nonliquid crystalline, while all the four derivatives of five-ring series, including a branched alkoxy chain derivative, display enantiotropic nematic phase over wide temperature range. The bent angle of these compounds is about 153°, which falls in between typical rod-like and banana liquid crystals. The transition temperature of branched alkoxy chain compound is lower than straight alkoxy chain compounds. The detailed XRD investigations of all the mesogens corroborate the presence of nematic phase.     

Relationship between properties of fluorinated graphite intercalates and matrix composition Part III. Intercalates with 1,2-dichloroethane

A series of PA-TD mixtures were prepared and their thermal properties were studied by DSC and thermal conductivity measurement. The phase diagram of the binary system was constructed, which showed an eutectic behavior for the solid-liquid equilibrium line. The eutectic composition of the binary system was at the mass fraction of TD near 0.7 with an eutectic temperature of about 29°C. At TD side, PA was partially miscible in the TD solid matrix and the solid phase transition of TD had an effect on the solidus line. The eutectic composition mixture could be viewed as a new phase change material with large thermal energy storage capacity.     

Constitutional bis(N-salicylideneaniline)s as new class of mesogens: synthesis and thermal properties

Twelve new constitutional bis(N-salicylideneaniline)s (BSANs) belonging to three different series have been prepared and characterised by the two-fold reaction of alkoxyanilines with 2,3-dihydroxyterephthalaldehyde, 4,6-dihydroxyisophthalaldehyde and 2,5-dihydroxyterephthalaldehyde. Their thermal behaviour and liquid crystallinity has been established with the help of polarising optical microscope, differential scanning calorimeter (DSC) and powder X-ray diffraction (XRD). Our study reveals this behaviour as determined by the nature of central core and the number of alkoxy tails. For example, the three series of compounds prepared are either non-mesomorphic or stabilised calamitic and discotic mesophases, such as nematic/smectic C and columnar (Col) phases. These materials represent the first examples of mesogenic BSANs exhibiting mesomorphism.     

Chiral and orientationally ordered fluid mesophases formed by oxadiazole bisaniline based achiral bent mesogens

Development of new liquid crystalline materials exhibiting interesting properties and phases continues to be an enabling enterprise in the forward march of their successful display and non-display applications. The design and synthesis of a homologous series of liquid crystalline bent-core compounds derived from the oxadiazole bisaniline moiety and the phase behavior of three members of the series that exhibit nematic, smectic C, and dark conglomerate phases is reported. The liquid crystalline phases exhibited by these mesogens are characterized using polarized optical microscopy, differential scanning calorimetry and x-ray scattering techniques. All three homologs prepared exhibit the nematic phase. Interestingly, the homolog with short hexyl terminal chains exhibits only the nematic phase that is stable over a very broad, nearly 100 K wide, temperature range. The compound with terminal octyl chains shows the chiral dark conglomerate phase below the nematic phase despite the bent molecules being achiral. The homolog with dodecyl alkyl chains is found to possess the smectic-C and two additional lamellar phases besides the nematic phase. These compounds enrich the library of achiral bent-core materials capable of exhibiting chiral and nematic phases.     

Oligomeric liquid crystals: From monomers to trimers

A homologous series of linear liquid crystal trimers, the 4,4′-bis[ω-(4-methoxyazobenzene-4′-yloxy)alkoxy]azobenzenes, has been synthesized and characterized. The transitional properties of the trimers are compared with those of the corresponding series of dimers, the α,ω-bis(4-methoxyazobenzene-4′-oxy)alkanes, and monomers, the 4-methoxy-4′-alkoxyazobenzenes. Characteristically pronounced odd-even effects were seen for the transitional properties of both dimers and trimers on varying the spacer lengths. The clearing temperatures of the trimers were higher than those of the corresponding dimers, but as the length of the flexible spacers was increased this difference became rather small. The ratios of T _NI, and ΔS _NI/R for monomer:dimer and dimer:trimer are discussed. These are very similar to reported values for similar materials, suggesting that there may be a rather general relationship between the transitional properties of liquid crystal oligomers as the number of mesogenic units is increased.     

The effect of mesogenic and non-mesogenic crosslinking units on the phase behaviour of side-chain smectic and cholesteric elastomers

Chiral monomer (M₁ ), mesogenic and non-mesogenic crosslinking agents (C₁ and C₂ ), and the corresponding liquid crystalline elastomers (P₁ and P₂ series), have been synthesised. Their chemical structures have been characterised by Fourier transform infrared or ¹H nuclear magnetic resonance and their phase behaviour investigated by differential scanning calorimetry, polarising optical miscoscopy, thermo-gravimetric analysis (TGA) and X-ray diffraction. The effect of the crosslinking unit on the phase behaviour of the elastomers has been studied. M₁ showed a cholesteric oily streak and focal conic texture. C₂ exhibited a nematic enantiotropic thread-like and schlieren texture, and a monotropic fan-shaped texture in the S_A phase. Due to the introduction of the mesogenic crosslinking unit, elastomers, P_2-1 ?P_2-5 , exhibited a cholesteric phase, while elastomers, P_1-1 ?P_1-4 , derived from a non-mesogenic crosslinking unit, exhibit a S_A phase. As the content of the crosslinking unit increased, the T _g of the P₁ series initially decreased and then increased, and the T _i of the series decreased. In the P₂ series the T _g increased, but the T _i initially increased and then decreased. TGA confirmed that all the elastomers had improved thermal stability.     

Columnar liquid crystals based on amino-1,3,4-thiadiazole derivatives

Novel liquid crystal materials base on amino-thiadiazoles, specifically 5-(3,4-di-, and/or 3,4,5-tri-n-alkoxy)phenyl-2-amino-1,3,4-thiadiazoles (3a–f, n?=?10, 12, 14) and 5-(3,4-di- and/or 3,4,5-tri-n-alkoxy)phenyl-2-(4-amino)phenyl-1,3,4-thiadiazoles (6a–f, n?=?10, 12, 14) were synthesised. The mesomorphic properties of these compounds were studied by differential scanning calorimetry and polarising optical microscopy. All the compounds in series 3a–f and series 6a–f display an enantiotropic columnar phase. The mesomorphic properties were found to be dependent on the number of the side alkoxy chains, and on the length of the rigid core, and on the position of the thiadiazole ring. The best results were obtained with compounds of series 3a–f.     

Banana‐shaped mesogens: mesomorphic properties of seven‐ring esters derived from 5‐chlororesorcinol

Two new homologous series of seven‐ring bent‐core compounds derived from 5‐chlororesorcinol have been synthesized. Many of the lower homologues in both series exhibit the rectangular columnar B₁ phase. However, the three analogous compounds having long terminal alkyl chains exhibit a switchable lamellar phase, which is different from the usual B₂ phase. Although the ground state structure of the mesophase is antiferroelectric, it shows chiral conglomerates with opposite tilt and polarity. Simultaneously, racemic structures are also seen. The mesophases have been characterized using a combination of polarized light microscopy, X‐ray diffraction and electro‐optical studies.     

On-resin generation and reactions of orthogonal glycosyl donors

An orthogonal series of glycosyl donors has been generated in situ from thiophenylglycosides appended to a hydroxymethylpolystyrene resin through a succinate linker. The conditions used to generate these donors and their subsequent reactions with sugar acceptors will be described.     

Preorganised effects of a tetramesogenic supermolecule on supramolecular assembly in the liquid crystalline phases

After preparing a homologous series of tetrameric mesogenic compounds in which two U-shaped molecules were connected via a rigid benzene derivative or a flexible alkyl chain, we investigated their phase transition behaviour using optical microscopy, differential scanning calorimetry and X-ray diffraction analysis. The compounds possessing an alkyl spacer as the central group exhibited nematic and smectic A phases just as the corresponding U-shaped molecule did. The compound possessing a 1,2-benzene unit as the connecting group showed nematic and smectic A phases, although the compound possessing a 1,3-benzene unit exhibited only an anticlinic smectic C phase. Structure–property relations of the liquid crystalline tetramers are interpreted in terms of preorganised effects of the four mesogenic units.     

Self-assembly of azo molecules to mesogenic phasmid-like materials through inter-molecular hydrogen bonding

A series of acid-functionalised new azo compounds was synthesised and characterised. The constituent molecules self-organise to form dimers through inter-molecular hydrogen bonding, resulting in phasmid-like compounds. This was once considered to be a promising molecular architecture to form biaxial nematic phases. The mesomorphic properties of these new azo compounds were studied using polarising optical microscopy, differential scanning calorimetry and X-ray diffraction. Investigations revealed that these compounds form nematic and columnar mesophases. A few more compounds were synthesised by replacing the??N=N- linkage in these compounds with??CH=N- and??COO- to study the effect of different linkages on the mesomorphic properties in such molecular systems. All were found to be liquid crystalline. The compounds with a??N=N- linkage are more conducive to mesomorphism and are thermally very stable. The effect of number of alkoxy chains on the mesomorphic properties of this system was also studied. To the best of our knowledge, at present, only a handful of phasmid-like mesogenic compounds, formed by the intermolecular hydrogen bonding, are known.     

氢键缔合主链超分子液晶聚合物:间隔基及扩展介晶元长度的影响研究

采用慢挥发溶剂组装方法制备了一系列羧酸/吡啶氢键缔合的主链型超分子复合物,并采用FTIR,DSC以及偏光显微镜等对其相转变与热致液晶相行为进行了比较研究.研究表明,分别具有较短的6或10个亚甲基的烷烃间隔基的双苯甲酸衍生物4',4'-二羧酸-1,6-二酚氧基己烷(C6-2COOH)和4',4'-二羧酸-1,10-二酚氧基癸烷(C10-2COOH)的系列复合物具有较高的熔点和清亮点,一般都只出现结晶近晶相和多晶型转变现象.而具有柔顺性较好的四甘醇醚链间隔基的4,4'-二羧酸-α,ω-二酚氧基四甘醇醚(C8O4-2COOH)得到的系列复合物均在降温过程生成单致的流体近晶SA和/或向列N液晶相.可见,间隔基增长,相转变温度降低,最终导致真正的流体液晶相的产生.另一方面,对于从同一种二元羧酸得到的组装体系,从4,4'-联吡啶(4,4'-BPy)、4,4'-联吡啶乙烯撑(4,4'-BPyE)到对苯二酚二异烟酸酯(p-PhBPy),由于双键或酯基的引入,可变形性和极性增大,刚性依次减弱,尽管中心核部分持续长度增大,所得复合物的各向同性化温度降低,形成流体液晶相的趋势增强,液晶有序性降低,流动性增加.指出了早期文献报道的一些不一致甚至矛盾的结果.通过不同系列的对比研究,得出的一些规律性对氢键组装尤其对羧基/吡啶氢键缔合超分子体系设计与构筑具有一定指导意义.     

New developments in microextraction techniques in bioanalysis. A review

In recent years, the interest in new extraction methods with lower sample volume requirements, simpler equipment and handling, and lower reagent consumption, has led to the development of a series of microextraction methods based on extraction phases in the microliter order. Nowadays, many references can be found for several of these methods, which imply a wide range of applications referred to both the analyte and the sample nature. In this paper, recent developments in both well-established microextraction techniques (solid phase microextraction, hollow-fiber liquid phase microextraction, dispersive liquid–liquid microextraction, etc.) and recently appeared microextraction procedures (nanoextraction systems, microchip devices, etc.) for the clinical analysis of biological samples will be reviewed and discussed.     

Separating Ability of Some Polar Mobile Phases in Reverse Phase High Performance Liquid Chromatography

Abstract

Homologous series of n-alkanes, n-alcohols, ethers, esters, amides and ketones were studied as solutes. Methanol, acetonitrile, ethanol, dioxane, 2-propanol and tetrahydrofuran were mobile phases. Spherisorb ODS columns with light and heavy octadecyl coatings were used. Methanol and acetonitrile were found to be the most selective solvents for reverse phase separation. The polar amides, alcohols, and ketones behaved differently from nonpolar solutes in acetonitrile mobile phases. Results were interpreted with the solvophobic theory.     

Separation of chiral phosphorus compounds on the substituted β‐cyclodextrin stationary phase in normal‐phase liquid chromatography

The separation of enantiomers of a series of eighteen novel nitrogen mustard linked phosphoryl diamide derivatives was investigated on the prepared phenyl carbamate derivative β‐cyclodextrin bonded phase in normal‐phase HPLC. Some of the enantiomers could be separated in baseline. The chiral recognition mechanism was also suggested for the separation of chiral phosphorus organic compounds.     

T-型氢键液晶复合物的制备与液晶行为

以不具有液晶行为的2,6-二[N,N′-二-(4-烷基苯甲酰基)]氨基吡啶(A系列)和4-正烷氧基苯甲酸(D系列)作为氢键液晶复合物的单体,组装成T-型氢键液晶系列复合物(AmDn)。用红外光谱对其结构进行了表征,用DSC及偏光显微方法对其液晶行为进行了研究。结果表明:所合成的21种复合物分子间存在氢键且都具有向列相。通过调整2,6-二[N,N′-二-(4-烷基苯甲酰基)]氨基吡啶分子上柔性烷基的长度和极性,可以有效地调节它与4-烷氧基苯甲酸形成的氢键复合物的液晶相变温度以及液晶态的稳定性;增加2,6-二[N,N′-二-(4-烷基苯甲酰基)]氨基吡啶分子上柔性烷基的长度,其复合物AmDn的液晶相温度范围趋于变窄,清亮点逐渐下降,其液晶态稳定性也逐渐下降;以2,6-二[N,N′-二-(4-烷基苯甲酰基)]氨基吡啶分子替代2,6-二[N,N′-二-(4-烷氧基苯甲酰基)]氨基吡啶分子,可以降低分子的极性,使其单体的熔点及其氢键复合物AmDn的相变温度下降。     

Synthesis and properties of fluorine tail-terminated cyanobiphenyls and terphenyls for chemoresponsive liquid crystals

ABSTRACT

A series of fluorine tail-terminated alkoxy and alkyl cyanobiphenyl compounds and some cyano-p-terphenyl derivatives were synthesised and mesogenic properties described. Comparison with the non-fluorinated K series and M series indicates that the terminal fluorine atom generally decreases the transition temperatures and, more interestingly, depresses the formation of a smectic phase. Several binary LC mixtures formed by the fluorine tail-terminated compounds were found exhibiting promising room temperature nematic phases with wide ranges. The mixture F7OCB and F8OCB shows homeotropic ordering at the metal salts-decorated surfaces and planar ordering at the free surface, which may have potential application in designing a more sensitive and faster LC system to targeted analytes.     

Amphiphilic taper-shaped oligomer exhibiting a monolayer smectic A to columnar phase transition

We prepared two series of liquid-crystalline oligomers composed of phenylpyrimidine based mesogenic cores, alkyl spacers and semiperfluorinated alkyl chains in one series and only alkyl chains in the second series. Their physical properties were investigated using optical microscopy, differential scanning calorimetry and X-ray diffraction measurements. The oligomers possessing a semiperfluorinated alkyl chain show a phase sequence of SmC–SmA–Col when the number of phenylpyrimidine moieties was increased. The compound possessing three phenylpyrimidine cores was found to exhibit monolayer SmA and Col phases. On the other hand, the oligomer composed of an alkyl chain and three phenylpyrimidine cores showed only a nematic phase. We discuss effects of the shape amphiphilicity and the hydrocarbon–fluorocarbon amphiphilicity on phase transition behaviour of the amphiphilic oligomers.