Mahdi Roohnikan

Nanoparticle/liquid crystal (NP/LC) composites can be stabilized by hydrogen bonding, a relatively strong, yet reversible interaction allowing for the annealing of defects. Previously, nanocomposites based on 4-hexylbenzoic acid (6BA) and ZrO2 NPs with pendant carboxylic acid groups were investigated, leading to problems of particle aggregation due to intra- and inter-particle hydrogen bonding. Here we report the synthesis of NP–LC composites based on different hydrogen bond acceptor and donor… Show more

Nanoparticle/liquid crystal (NP/LC) composites can be stabilized by hydrogen bonding, a relatively strong, yet reversible interaction allowing for the annealing of defects. Previously, nanocomposites based on 4-hexylbenzoic acid (6BA) and ZrO2 NPs with pendant carboxylic acid groups were investigated, leading to problems of particle aggregation due to intra- and inter-particle hydrogen bonding. Here we report the synthesis of NP–LC composites based on different hydrogen bond acceptor and donor groups, promoting NP–LC coupling and reducing aggregation due to NP–NP interactions. Specifically, we developed a mechanochemical, solvent-free approach for efficient functionalization of ZrO2 NPs with (3-(pyridin-4-yl)propyl)phosphonic acid (3-PPA), leading to NPs with pendant pyridine groups that act as hydrogen bond acceptors only. This is the first example of using hydrogen bonded heterosynthons to tune the LC–NP interactions. The miscibility of the pyridine-functionalized NPs with 4-hexylbenzoic acid (6BA), a strong hydrogen bond donor, versus trans-4-butylcyclohexanecarboxylic acid (4-BCHA), a weaker hydrogen bond donor, was characterized by polarized optical and fluorescence microscopies. The specificity of the NP/LC acceptor/donor hydrogen bonds improves the miscibility over the NP/LC dispersions based on COOH dimer interactions only. The different effect of the NPs on the 4-BCHA properties as compared to 6BA can be related to the relative strengths of the COOH-pyridine hydrogen bonds. Show less

Nanoparticle-liquid crystal (NP-LC) composites based on hydrogen bonding were explored using a model system. The ligand shells of 3 nm diameter zirconium dioxide nanoparticles (ZrO2 NPs) were varied to control their interaction with 4-n-hexylbenzoic acid (6BA). The miscibility and effect of the NPs on the nematic order as a function of particle concentration was characterized by polarized optical microscopy (POM), fluorescence microscopy and 2H NMR spectroscopy. Nonfunctionalized ZrO2 NPs have… Show more

Nanoparticle-liquid crystal (NP-LC) composites based on hydrogen bonding were explored using a model system. The ligand shells of 3 nm diameter zirconium dioxide nanoparticles (ZrO2 NPs) were varied to control their interaction with 4-n-hexylbenzoic acid (6BA). The miscibility and effect of the NPs on the nematic order as a function of particle concentration was characterized by polarized optical microscopy (POM), fluorescence microscopy and 2H NMR spectroscopy. Nonfunctionalized ZrO2 NPs have the lowest miscibility and strongest effect on the LC matrix due to irreversible binding of 6BA to the NPs via a strong zirconium carboxylate bond. The ZrO2 NPs were functionalized with 6-phosphonohexanoic acid (6PHA) or 4-(6-phosphonohexyloxy)benzoic acid (6BPHA) which selectively bind to the ZrO2 NP surface via the phosphonic acid groups. The miscibility was increased by controlling the concentration of the pendant CO2H groups by adding hexylphosphonic acid (HPA) to act as a spacer group. Fluorescence microscopy of lanthanide doped ZrO2 NPs showed no aggregates in the nematic phase below the NP concentration where aggregates are observed in the isotropic phase. The functionalized NPs preferably concentrate into LC defects and any remaining isotropic liquid but are still present throughout the nematic liquid at a lower concentration. Show less

The mesomorphic, thermoptic and glass-forming properties of 4-[6-((cholesteryloxy) carbonyl)oxy hexyloxy] benzoic acid (Ch-BA) have been investigated as a novel supramolecular hydrogen-bonded cholesteric mesogen. Fourier transform infrared and 1H nuclear magnetic resonance studies have confirmed the chemical structure and the hydrogen-bond formation between the mesogens. According to polarising optical microscope observations, the compound exhibited smectic and chiral nematic phases… Show more

The mesomorphic, thermoptic and glass-forming properties of 4-[6-((cholesteryloxy) carbonyl)oxy hexyloxy] benzoic acid (Ch-BA) have been investigated as a novel supramolecular hydrogen-bonded cholesteric mesogen. Fourier transform infrared and 1H nuclear magnetic resonance studies have confirmed the chemical structure and the hydrogen-bond formation between the mesogens. According to polarising optical microscope observations, the compound exhibited smectic and chiral nematic phases. Differential scanning calorimetry indicated an unexpected glass transition (T g) around 32°C and a liquid crystalline region between 32 and 122°C, in which the cholesteric phase appeared at 80°C. As a result of the glass formation, samples of Ch-BA which were rapidly cooled below the T g were found to preserve the long-range ordering of the liquid crystalline state and retained the iridescent colours of the cholesteric phase. These results led to the conclusion that the formation of identical dimers by intermolecular hydrogen-bonding of the terminal carboxylic acids accompanying the lateral packing of the rigid cores, built a trimeric arrangement and this was responsible for the macromolecular behaviour of Ch-BA, despite its relatively simple structure and low molecular weight. Show less