Hot-stage Polarizing Optical Microscopy Research Articles

Designed new mesogens via Vilsmeier–Haack reagent: synthesis and phase transition study

ABSTRACT A new four series of 2,2′-([1,1′- phenyl or biphenyl]-4,4′-diylbis(azanediyl)) bis(N′-((E)-1-(4-alkoxyphenyl) ethylidene) acetohydrazide) [V-XI]a,b and 1,1′-(2,2′-([1,1′- phenyl or biphenyl]-4,4′-diyl bis(azanediyl)) bis- (acetyl)) bis(3-(4-ethoxyphenyl)-1H-pyrazole-4-carbalde hyde) [XII-XVIII]a,b have been synthesized by varying terminal lateral alkoxy chain length (n = 1–3, 5–8), central linkage group (phenyl or biphenyl) and induced pyrazole heterocyclic ring in the main chain. The last two series were synthesized by the cyclization of substituted acetophenone hydrazones with Vilsmeier–Haack reagent (DMF/POCl3) to produce 4-formylpyrazole derivatives. The chemical structures of the synthesized compounds were examined by elemental analysis, FTIR and 1H-NMR. The results are in agreement with the considered molecular structure. The liquid crystalline behaviors were studied by using hot-stage optical polarizing microscopy (OPM) and differential scanning calorimetry (DSC). The correlation between the molecular structures and mesomorphic behavior and transition temperatures was discussed.

Experimental study on thermotropic side-chain liquid crystalline photo-sensitive polymers

When the chalcone moiety and methylene spacers are bonded to polymer backbone, they are expected to incorporate photosensitive and liquid crystalline properties, respectively. The thermotropic side-chain liquid crystalline photosensitive polymers were synthesized using 4-phenyl styryl carbonyl (phenyl-4-oxy-4-hexyl) methacrylate (PSCPOHMA) and 4-phenyl styryl carbonyl (phenyl-4-oxy-4-decyl) methacrylate (PSCPODMA) monomers by free-radical polymerization using benzoyl peroxide (BPO) as an initiator. The structures of the synthesized monomers and polymers were confirmed by FT-IR, 1H NMR and 13C NMR techniques. The thermal stability and glass transition temperature of the poly (PSCPOHMA) were higher than that of the poly (PSCPODMA). The photocrosslinking of the polymers on irradiation with UV light established that the polymers followed 2π + 2π cyclo addition. The rate of crosslinking increased with increase in the length of the methylene chain. The mesophase of the polymers was also characterized using x-ray diffraction analysis. The liquid crystalline behavior of the polymers was confirmed by DSC and Hot stage optical polarized microscopy (HOPM).The polymers exhibited nematic phase in HOPM. So the polymers have high potential for application in photo resists and electro optic technology.

Synthesis and characterization of symmetrical liquid crystalline compounds based on oxazole and thaizole rings

Twelve compounds containing a sulphur- or oxygen-based heterocyclic core, 1,3- oxazole or 1,3-thiazole ring with hydroxy, methoxy and methyl terminal substituent, were synthesized and characterized. The molecular structures of these compounds were performed by elemental analysis and different spectroscopic tequniques. The liquid crystalline behaviors were studied by using hot-stage optical polarizing microscopy and differential scanning calorimetry. All compounds of 1,4- disubstituted benzene core with oxazole ring display liquid crystalline smectic A (SmA) mesophase. The compounds of 1,3- and 1,4-disubstituted benzene core with thiazole ring exhibit exclusively enantiotropic nematic liquid crystal phases.

Molecular Order of Topologically Variant Flexible Mesogens by 13C Nuclear Magnetic Resonance.

13C nuclear magnetic resonance investigations in the nematic phase of mesogens comprising a rod-like core with three phenyl rings connected to a fourth phenyl ring via a flexible spacer are reported. The molecules are abbreviated as monomer, dimer, and trimer as they comprised one, two, and three pairs of core and spacer combinations linked to ring IV, respectively. Hot-stage optical polarizing microscopy and differential scanning calorimetry studies confirmed that all of them exhibit an enantiotropic nematic phase with additional monotropic or enantiotropic smectic mesophases. Large values of 13C-1H dipolar couplings of the order of 11 kHz are observed for all the cases for the terminal carbon C1 of the core unit. These high values indicated that the corresponding CH vector is collinear with the long axis of the molecule, which itself is aligned parallel to the magnetic field. In contrast, the terminal carbon of the ring IV (C19/C17) exhibits a relatively smaller value in the range of 2.0-2.5 kHz, reflecting the divergent local dynamics at different sections of the mesogens. The orientational order parameters of the phenyl rings computed from the 13C-1H dipolar couplings have been used to obtain the conformation of the mesogens in the nematic phase. It is concluded that the dimer and trimer exhibit C2 and C3 symmetry with the ring IV connected by spacers tilted away from the symmetry axis by 35.9 and 90° for the two cases, respectively. This leads to the interesting tripod-like molecular shape for the trimer in the nematic phase rather than the planar representation of the λ shape.

Synthesis of Dendrimers Liquid Crystalline Materials based on 1,3,5-triphenylbenzene

In this study, new compounds of discotic liquid crystalline dendrimers are prepared which is derived from 1,3,5-triphenylbenzene. The synthesis of these compounds shows the effect of dendrimer unit on the mesogenic properties. The structures of prepared compounds characterized by using spectroscopic method e.g. FT-IR and 1HNMR. The liquid crystalline phases of prepared compounds was identified by using the hot-stage polarizing optical microscope (POM) and differential scanning calorimeter (DSC).

Cytotoxic Anti-Cancer Activity of Certain Thermotropic Liquid Crystalline Poly (Ester-Amides) Containing 2, 6-Bis (Benzylidene)Cyclohexanone Moiety in the Main Chain

Five thermotropic liquid crystalline poly(ester-amides) were synthesized by polycondensation method. The poly(ester-amides) were synthesized from varying dicarboxylic acids with a common diamine namely 4,4'-diaminobenzene and a common diol namely 2,6-bis(4-hydroxybenzylidene))cyclohexanone. For qualitative characterization, viscosity measurements and solubility data were used for these synthesized poly(ester-amides). The spectroscopic techniques such as FT-IR, 1H NMR, 13C NMR were performed to investigate the microstructural features of these synthesized poly(ester-amides). The thermal phase transition behavior of these poly(ester-amides) were studied by Differential Scanning Calorimetry (DSC) and Hot-stage Optical Polarized Microscopy (HOPM). The degree of crystallinity was assessed by X-ray diffraction (XRD) patterns. Scanning Electron Microscopic (SEM) technique was used to illustrate the morphology of these poly(ester-amides). The copolymer synthesized was subjected into in vitro anti-cancer activity studies against human breast cancer (MCF-7) cell line.
 Keywords: Bisbenzylidenecyclohexanone; poly(ester-amides); polycondensation; thermotropic liquid crystalline properties; cytotoxicity, anticancer.

Synthesis and Characterization of Certain Photoactive Liquid Crystalline Poly(ester amides) from 2,5-Pyridine Dicarboxylic Acid

A new series of four photo-crosslinkable thermotropic liquid crystalline poly(ester amides) were synthesized by direct polycondensation of 2,5-pyridine dicarboxylic acid with two different varying diols and diamines. Two diamines employed in the synthesis were 4,4′-diaminodiphenyl methane and 1,4-diaminobenzene. The arylidene diols 2,5-bis(4-hydroxy-3-methoxybenzylidene)cyclopentanone and 2,6-bis(4-hydroxy-3-methoxybenzylidene)cyclohexanone were also used. The synthesized poly(ester amides) were characterized by qualitative solubility test, FT-IR, 1H and 13C NMR spectra. The monomeric moieties were found to be well incorporated in the polymer back bone. The molecular weight of the polymer was assessed by gel permeation chromatography (GPC). The thermal phase transition behavior and liquid crystallinity of the poly(ester amides) were investigated by differential thermogravimetry (DTG) and hot stage optical polarized microscopy (HOPM), respectively. Interestingly, these poly(ester amides) in dimethylacetamide were found to possess photo-crosslinking characteristics when irradiated by UV light. These polymeric materials may find utility value in optical information storage devices.

Thermal/photophysical properties of cyanobiphenyl based unsymmetrical molecules: synthesis and evaluation

Abstract New set of mesogens based on cyanobiphenyl at one side and other side arms containing three or four phenyl rings linked through alkyl spacer and ester groups were synthesized via convergent approach. All the synthesized mesogens and their intermediates were structurally well characterized using FT-IR, 1H NMR, 13C NMR and CHNS analysis. The mesophase characterization carried out using the combination of hot stage-polarizing optical microscopy (POM), differential scanning calorimetry (DSC) and X-ray diffraction (XRD) techniques. The structural changes made in the mesogens i.e. increase of terminal chain length and aromatic groups with ester groups show decreasing the transition temperatures and phase stability to a wide temperature range. Nematic and smectic phases were observed for the mesogens with short/long terminal chain length.

Synthesis, characterization and photo – switching properties of azobenzene mesogen containing poly (ether - ester) s from cashew nut shell liquid

Poly(ether - ester)s containing azobenzene mesogen were prepared from cardanol, a natural renewable resource and waste of the cashew industry. The azobenzene group containing cardanol (HPPP) was synthesized by the coupling reaction between diazotized aminophenol and cardanol. Further, it was alkylated with 3 – bromopropanol by Williamson’s etherification process to 3- {4- [4-(3- hydroxy propoxy) phenylazo] -3- pentadecyl phenoxy} propan – 1 – ol(3-HPPP). This dihydroxy compound was characterized by CHN analyzer, UV and 1H and 13C - NMR spectroscopies. A series of azobenzene mesogen containing poly (ether – ester)s were synthesized from 3-HPPP and various aliphatic and aromatic diacid chlorides by solution polycondensation technique. The molecular structure of the monomer and polymers was confirmed by FTIR, 1H and 13C - NMR spectral analyses. These polymers were studied for their thermal stability and photochemical properties. Thermal properties were evaluated by TGA and DSC. Hot-stage optical polarizing microscopy (HOPM) study showed that most of the polymers exhibit smectic and highly ordered band structure. The photo-switching property of azopolymers was investigated using UV – Vis spectroscopy and noticed that trans to cis isomerization occurs within 35 s in DMF, whereas reverse process takes place in 4 h in DMF solvent.

Synthesis and characterization of wide range mesogenic esters based on asymmetrical 2,5-disubstituted 1,3,4-thiadiazole

ABSTRACTA homologous series of new 13 esters, 4-(5-(p-tolyl)-1,3,4-thiadiazol-2-yl)-phenyl-4-alkoxybenzoate, (IVn), based on 1,3,4-thiadiazole core has been synthesized. The structures of these esters were confirmed by Fourier transform infrared spectroscopy, proton nuclear magnetic resonance and mass techniques. Their mesophases behavior was investigated with hot-stage polarizing optical microscope and differential scanning calorimetry. The thermal stability for most of these derivatives was measured by thermal gravimetric analysis. All the target esters showed enantiotropic mesomorphic behaviors with nematic and nematic/smectic C phases. The phase transition temperatures and liquid crystalline properties were affected by the nature of heterocyclic ring and the length of the alkoxy chain. Only the nematic phase was observed in the first 10 derivatives, (n = 1–10), while the last 3, (n = 12, 16 and 18) showed nematic and smectic C phases. These compounds demonstrated high liquid crystalline ranges, both in heating and cooling cycles. The mesomorphic results obtained were compared with the reported analogs of similar constituents.

Synthesis and Characterization of New Mesomorphic Azo Compounds and Study their Photoluminesecence Properties

The preparation of a new Azo compounds of highly conjugated dimeric and polymeric liquid crystal to achieve the crystalline characteristics Which have structures assigned based on elemental analysis, IR 1HNMR and CHNS-O while mesogenic properties have been set for DSC and hot-stage polarizing optical microscopy. The compounds show enantiotropicnematic phase being displayed. The compounds show photoluminescence properties in the organic solution at room temperature, with the fluorescence band centered around 400 nm.

Synthesis of aromatic liquid crystals with asymmetric diester based on rod-like multi-ring system by two-step esterification method

ABSTRACTA novel method of two-step esterifications was developed to synthesize compounds with asymmetric double ester groups. By using this method, six rod-like double ester compounds were prepared with p-hydroxy benzaldehyde, p-hydroxy benzoic acid bicyclohexyl carboxylic acid, cyclohexyl benzoic acid and biphenyl carboxylic acid substituted by n-propyl and n-pentyl as main reactants. The structures and properties of target compounds were confirmed by IR, MS, 1H NMR, elemental analysis, differential scanning calorimetry (DSC) and hot stage polarizing optical microscope (HS-POM). Typical yields of the target molecules were more than 70%. All the molecules have mesophases with the textures of nematic type, indicating a rod-like molecule with a longer rigid skeleton can keep its mesophases. There was no clearing point observed for any of the derivatives before they decomposed so that the temperature ranges of the mesophases could not be determined. The energy differences between frontier molecular orbitals (HOMO-LUMO) (Eg) of the compounds were calculated by cyclic voltammetry (CV). The terminal ring system has an obvious influence on the energy levels and the energy gaps (Eg).

Synthesis and Characterization of New Mesomorphic Azo Compounds and Study their Photoluminesecence Properties

The preparation of a new Azo compounds of highly conjugated dimeric and polymeric liquid crystal to achieve the crystalline characteristics Which have structures assigned based on elemental analysis, IR 1HNMR and CHNS-O while mesogenic properties have been set for DSC and hot-stage polarizing optical microscopy. The compounds show enantiotropicnematic phase being displayed. The compounds show photoluminescence properties in the organic solution at room temperature, with the fluorescence band centered around 400 nm.

Synthesis, Photo-sensitive and Electrochemical Properties of Rod-like Aromatic Aldehyde with Azo Bridge

Abstract Eight new rod-like liquid crystal molecules composed by a long rigid core of three six-member rings (cyclohexane ring or benzene ring), azo, ester and terminal aldehyde groups have been prepared. These rod-like liquid crystalline molecules were designed to construct new structures to further study photo-isomerization in their mesophases. All the compounds have been characterized based on their basic spectral data, differential scanning calorimeter (DSC) and hot stage polarizing optical microscope (HS-POM). The result showed that all the molecules, even those with the shortest terminal methyl group, have liquid crystalline properties. Their mesophases are nematic within the temperature ranges from 85 to 145°C. They exhibit photo-sensitivities not only in methanol solutions but also in a mesophase when exposed to UV light. The highest occupied orbital (HOMO) and the lowest unoccupied orbital (LUMO) and the differences between the frontier molecular orbitals (Eg) of these compounds were determined by cyclic voltammetry. The effect of even-odd carbon number of the terminal straight alkyl chain on the UV spectral data and the Eg were observed. The difference between the Eg of these compounds are in excellent agreement with the difference of their maximum absorption wavelength in UV spectra.

Spectral and physicochemical characterization of dysprosium-based multifunctional ionic liquid crystals.

We report on the synthesis and characterization of multifunctional ionic liquid crystals (melting points below 100 °C) which possess chirality and fluorescent behavior as well as mesomorphic and magnetic properties. In this regard, (1R,2S)-(-)-N-methylephedrine ((-)MeEph), containing a chiral center, is linked with variable alkyl chain lengths (e.g., 14, 16, and 18 carbons) to yield liquid crystalline properties in the cations of these compounds. A complex counteranion consisting of trivalent dysprosium (Dy(3+)) and thiocyanate ligand (SCN(-)) is employed, where Dy(3+) provides fluorescent and magnetic properties. Examination of differential scanning calorimetry (DSC) and hot-stage polarizing optical microscopy (POM) data confirmed liquid crystalline characteristics in these materials. We further report on phase transitions from solid to liquid crystal states, followed by isotropic liquid states with increasing temperature. These compounds exhibited two characteristic emission peaks in acetonitrile solution and the solid state when excited at λex = 366 nm, which are attributed to transitions from (4)F9/2 to (6)H15/2 and (4)F9/2 to (6)H13/2. The emission intensities of these compounds were found to be very sensitive to the phase.

Synthesis of Multiring Azo-Benzoic Acid Liquid Crystalline Molecules and Their Special Photosensitive Property

10 new rod-like azo benzoic acid liquid crystals belonged to three series have been prepared, in which trans-cyclohexyl benzene, biphenyl or bi-trans-cyclohexyl carboxylic acid mesogenic cores with ethyl, n-propyl, n-butyl or n-pentyl substituents were connected with azo benzoic acid. Meantime, a simple method was developed in synthesizing compounds bearing both ester and carboxyl groups in one-step reaction. All these compounds have been characterized on the basis of their spectral data, differential scanning calorimeter (DSC) and hot stage polarizing optical microscope (HS-POM). All these compounds have higher thermo-stability. 8 of these compounds have liquid crystalline properties. Their temperature ranges of mesophase have not been obtained, resulting from all the compounds decomposed before their clearing points. Although these compounds are photosensitive in solution under illumination of UV light (365nm), they can't do trans-cis isomerization in their mesophses, indicating the super stabilities of the trans isomer in mesophase.

Structural Assignment of Side Chain Liquid Crystalline Monomer and Polymer by 1-D and 2-D Solution NMR Studies

In the present study, the synthesis and characterization of a methacrylic-based side chain liquid crystalline monomer and its polymer were investigated with the aid of both 1-D and 2-D nuclear magnetic resonance (NMR) techniques. The mesophase characteristics of the monomer and polymer were determined by hot-stage optical polarized microscopy (HOPM). The nematic and smectic phases were observed for the monomer and polymer. Furthermore, 13C spin-lattice relaxation time measurements were performed on the above systems in order to monitor molecular dynamics. The present study provides an opportunity to carry out a systematic comparison of the evolution of structural as well as dynamical changes of the monomer and the polymer.

Preparation and characterization of hydrated salts/silica composite as shape-stabilized phase change material via sol–gel process

• A mixture of hydrated salts were adopted as phase change materials. • Phase segregation of the hydrated salts was inhibited. • Subcooling was slightly mitigated. • Thermal cycling performance was greatly improved after PVP coating. A novel shape-stabilized phase change material composite was prepared by impregnating the mixture of hydrated salts (Na 2 SO 4 ·10H 2 O–Na 2 HPO 4 ·12H 2 O) into porous silica matrix obtained by sol–gel process and further coated with polyvinylpyrrolidone (PVP) to improve the thermal cycling performance. The chemical compatibility, morphology and phase change properties were investigated by Fourier transform infrared spectroscopy (FT-IR), scanning electron microscope (SEM), hot-stage polarizing optical microscope (HS-POM) and differential scanning calorimetry (DSC). Confined in the silica matrix, phase segregation of the hydrated salts was inhibited and subcooling was slightly mitigated. No leakage was observed during the solid–liquid phase transition even when the mass ratio of hydrated salts to silica was as high as 70:30. Results showed that the melting enthalpy of the composite can reach 106.2 kJ/kg with the melting temperature at 30.13 °C and there was no significant enthalpy loss after 30 thermal cycles.

Synthesis and mesophase characterization of novel methacrylate based thermotropic liquid crystalline monomers and their polymers

A new series of side chain methacrylate monomers with a three phenyl ring core connected by an ester with a terminal alkoxy chain and hexamethylene spacer are synthesized by a multistep synthetic route. The corresponding polymers are realized by free radical solution polymerization. Two structurally similar mesogens are also synthesized for use as models to study the influence of the methacrylic unit on the mesophase characteristics. The molecular structure of the intermediates, monomers as well as the polymers is unambiguously confirmed by Fourier-transform infrared (FT-IR), solution 1H and 13C nuclear magnetic resonance (NMR) spectroscopy and by elemental analysis. The mesophase characteristics of all of the monomers and polymers are determined by hot-stage optical polarized microscopy (HOPM) and differential scanning calorimetry (DSC). These investigations revealed the existence of enantiotropic nematic (N), smectic A (SA) and smectic C (SC) mesophases. Furthermore, for a representative monomer and polymer, the presence of the smectic phase is confirmed by variable temperature X-ray diffraction (XRD) where a characteristic layer ordering is noticed. The molecular weight of the polymers is determined by gel permeation chromatography (GPC) and the values are found to be typically in the range of 2.0 × 103 to 3.7 × 103. The mesogenic polymers are also found to be stable up to 320 °C by thermogravimetric analysis (TGA).

Multirings Aromatic Aldehyde Liquid Crystal with Azo Linkage and Their Photosensitivity in Mesophase

Ten new rod-like aromatic aldehyde liquid crystalline molecules with azo linkage were synthesized, in which bi(trans-cyclohexyl), cyclohexyl phenyl, and biphenyl carboxylic acid mesogenic cores with terminal ethyl, n-propyl, n-butyl, and n-pentyl substituents were esterified with azo benzoic aldehyde. These molecules were designed in an attempt to construct a series of new azo liquid crystalline molecules to investigate the influence of ultraviolet (UV) light on their mesophase. All compounds have been characterized on the basis of their spectral data, differential scanning calorimeter (DSC), and hot stage polarizing optical microscope (HS-POM). All these compounds exhibited liquid crystalline phase that belonged to nematic and photosensitive properties. Their temperature ranges of mesophase are from 101 °C to 150 °C. Under irradiated 365 nm UV light, they showed photosensitivity in the solvent of methanol. Observed under HS-POM, the UV light also did change the textures of these compounds. The result showed that terminal ethyl is enough for these molecules to exhibit wider temperature range of mesophase, and these new molecules have photosensitivities observed under illumination of UV light not only in solution but also in mesophase due to the change of their structures from trans isomer to cis one.