Luminita Marin

New Thermotropc Liquid Crystalline Polyazomethines Containing Luminescent Mesogens

Thermotropic liquid crystalline polyazomethines containing 1,3,4‐oxadiazole chromophors have been synthesized. These polymers are semiflexible liquid crystalline compounds containing luminescent mesogens. Thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), polarized optical microscopy (POM), and wide angle X‐ray diffraction (WAXD) have been used to evaluate their thermal and mesomorphic properties. The target polyazomethines present liquid crystalline behavior with classical calamitic textures, large mesophase range, and high thermal stability. The investigation of the optical properties of the synthesized polymers, in solution and solid state, confirmed a blue fluorescence.

Polymer-dispersed liquid crystal composites for bio-applications: thermotropic, surface and optical properties

Polymer-dispersed liquid crystal (PDLC) systems based on polysulfone as carrying matrix and 4-cyano-4ʹ-pentylbiphenyl (5CB) liquid crystal (LC) were obtained as thin transparent films. The PDLC films were prepared by solvent- and thermally induced phase separation methods, with various compositions in the two components. Information on the phase separation was obtained by polarised light optical microscopy, differential scanning calorimetry and scanning electron microscopy. The PDLC composites show well-defined droplets of submicrometric size, around 650 nm for a medium content of LC and around 250 nm for a low one. The droplets show a radial configuration and a homeotropic alignment of the LC molecules within. By contact angle measurement and surface free energy calculations, it was established that self-assembling of aliphatic units of the two composite components, at droplet interface, is the driving force of the homeotropic alignment. Moreover, these data indicated the potential biocompatibility of the studied composites. The photophysical behaviour shows a better light emission of the PDLCs containing bigger droplets.

Antifungal vanillin–imino-chitosan biodynameric films

Vanillin-chitosan biodynamers have been prepared and structure-morphology correlations revealed the pathway of progressive incorporation of the aldehyde onto chitosan backbones. Such dynamic biopolymers or biodynamers, generated from reversibly interacting components, offer the possibility to address the dynamic covalent behaviour of the reversible imine-bond formation/hydrolysis equilibria between vanillin and chitosan polymeric backbones. The reaction takes place with very low conversion in acidic aqueous solutions (7-12%), but the imine bond formation is amazingly improved (∼80%) when the reaction takes place while solution-solid state transition and solid state phase-organization events occur. The chitosan-vanillin biopolymeric films described here present interesting Candida albicans antifungal activity compared with other common bacterial strands, which suggests the implementation of these biocompatible materials as thin layer protecting systems for medical devices.

Thermotropic and optical behaviour of new PDLC systems based on a polysulfone matrix and a cyanoazomethine liquid crystal

The thermotropic and optical characterisations of a novel polymer dispersed liquid crystal (PDLC) system based on polysulfone UDEL P-1700 as polymer matrix and a low molecular weight liquid crystal compound containing a mesogenic azomethine core and a cyano-substituent were investigated. The PDLC samples were prepared by solvent-induced phase separation (SIPS) and thermally induced phase separation (TIPS) methods using various compositions in the two components. Information on the morphology and phase structure was obtained by polarising optical microscopy, differential scanning calorimetry and X-ray diffraction measurements. PDLC systems with well-defined droplets were obtained for the composite with medium content of liquid crystal compound. The optical characterisation of these materials was performed by analysing their UV–visible absorption and photoluminescence emission as a function of the liquid crystal aggregation degree.

Synthesis and characterization of new azomethine derivatives exhibiting liquid crystalline properties

Azomethine liquid crystals (LCs), constituted by symmetric and asymmetric bithiophene or fluorene units as chromophores, were designed and synthesised. Their thermotropic behaviour was investigated using optical microscopy, differential scanning calorimetry, and wide angle X‐ray diffraction. A lowering of transition temperatures was obtained by the introduction of the lateral methyl group as compared with unsubstituted compounds. The observed LC phases possess the classical textures of calamitic LCs. The optical properties of the target compounds were evaluated, both in solution and in solid state. A blue fluorescence was observed for fluorene containing compounds and a green fluorescence was observed for analogous bithiophene containing compounds. The introduction of a methyl lateral group onto the aromatic rings led to a remarkable increase in the solution emission properties.

Imino-chitosan biopolymeric films. Obtaining, self-assembling, surface and antimicrobial properties

The paper reports the preparation of twelve imino-chitosan biopolymer films by acid condensation of the amino groups of chitosan with various aldehydes, in aqueous medium, followed by slow water removal. FTIR spectroscopy has shown drastic conformation changes of chitosan macromolecular chains—from a stiff coil to a straight one, while wide angle X-ray diffraction evidenced a layered morphology of the biopolymer films. Contact angle and surface free energy determination indicated a higher biocompatibility of the new biopolymers as compared to the chitosan parent, while the microbiological screening demonstrated their self-defense properties against common and virulent pathogen agents. It was concluded that the reversibility of imine forming promotes the self-assembling of imino-chitosan biopolymer films into a lamellar morphology and, on the other hand, the slow release of the antimicrobial aldehyde in the microbiological culture. The obtained results demonstrate that chitosan polyamine is a challenging workbench to functional biodynamic materials.

SOLID‐STATE PROPERTIES OF MESOMORPHIC COPOLYMERS CONTAINING OXADIAZOLE AND FLUORENE UNITS

A series of copolymers containing oxadiazole and fluorene cromophores was synthesized by polycondensation of a diacid chloride incorporating one diphenylsilane linkage and a mixture of aromatic diamines containing oxadiazole and fluorene moieties. The solubility, thermal behavior, and photoluminescence ability of the thin polymer films were studied and compared with related heterocyclic polymers. These polymers are semicrystalline and form plastic mesophases in the first heating run, which brings about new ordered melted state processing opportunities. They exhibited blue photoluminescence in nanometric films, thus being promising candidates for manufacturing electroluminescent devices.

Novel luminescent liquid crystalline polyazomethines. Synthesis and study of thermotropic and photoluminescent properties

Novel semiflexible polyazomethines containing chromophoric units into azomethine mesogenic core have been synthesised by condensation of a flexible dialdehyde with mesogenic diamines containing fluorene, antraquinone, pyrimidine, azobenzene and benzophenone. The thermotropic behaviour of the resulting polyazomethines was assessed by differential scanning calorimetry, polarised light microscopy and investigations of the miscibility relations. While the pure polyazomethines showed a birefringent viscous texture difficult to be ascribed, by mixing with a liquid crystal dimer, clear Schlieren or marbled textures were observed, indicating a nematic mesophase. The polymers exhibited violet, blue or yellow light emission.

Symmetric Liquid Crystal Dimers Containing a Luminescent Mesogen: Synthesis, Mesomorphic Behavior, and Optical Properties

New thermotropic liquid crystalline dimers containing chromophoric units into calamitic mesogens have been synthesized and studied. Cyan, pyrrole, indole and diphenyl moieties were chosen as chromophoric units. The thermotropic behavior of the dimers was monitored by polarized light microscopy, differential scanning calorimetry, and variable temperature X-ray diffraction measurements. The photophysical properties were studied by UV-vis and photoluminescence spectroscopy. All the dimers have mesomorphic behavior and emit violet, indigo, or blue light, in solution and film.

New symmetric azomethinic dimer: the influence of structural heterogeneity on the liquid crystalline behaviour

The paper deals with the study of the thermotropic liquid crystalline properties of a new azomethinic symmetric dimer and some of its structural heterogeneous mixtures with one of its reagents. Their thermotropic behaviour was monitored by polarised light microscopy, differential scanning microscopy and variable temperature X-ray diffraction measurements. The influence of the structural heterogeneity on the mesomorphic behaviour was established and some similarities with the mesomorphic behaviour of the polydisperse polymers were underlined.