A. S. Merekalov

Opto-mechanical effect in photoactive nematic side-chain liquid-crystalline elastomers.

The mechanical behaviour of monodomain nematic side-chain liquid-crystalline elastomers containing azoderivatives as pendant groups or crosslinkers has been studied under UV irradiation and in the darkness at different temperatures. From the evaluation of the opto-mechanical experiments, the mechanical efficiency, kinetic rates, activation energies and the isomerization mechanism of the azocompounds in the liquid-crystalline matrix could be determined, as well as the effect of the chemical constitution of the azobenzene derivatives and their role in the elastomeric network.

Liquid-crystalline polymer composites with CdS nanorods: structure and optical properties.

We report on the structure, uniaxial orientation, and photoluminescent properties of CdS nanorods that form stable nanocomposites with smectic C hydrogen-bonded polymers from the family of poly(4-(n-acryloyloxyalkoxy)benzoic acids. TEM analysis of microtomed films of nanocomposites reveals that CdS nanorods form small domains that are homogeneously distributed in the LC polymer matrix. They undergo long-range orientation with the formation of one-dimensional aggregates of rods when the composite films are uniaxially deformed. The Stokes photoluminescence was observed from CdS NRs/LC polymer composites with emission peak located almost at the same wavelength as that of NRs solution in heptane. An anti-Stokes photoluminescence (ASPL) in polymer nanocomposites was found under the excitation below the nanoparticles ground state. The mechanism of ASPL was interpreted in terms of thermally populated states that are involved in the excitation process. These nanocomposites represent an unusual material in which the optical properties of anisotropic semiconductor nanostructures can be controlled by mechanical deformation of liquid-crystalline matrix.

Phase separation effects and the nematic–isotropic transition in polymer and low molecular weight liquid crystals doped with nanoparticles

Properties of the nematic–isotropic phase transition in polymer and low molecular weight liquid crystals doped with nanoparticles have been studied both experimentally and theoretically in terms of molecular mean-field theory. The variation of the transition temperature and the transition heat with the increasing volume fraction of CdSe quantum dot nanoparticles in copolymer and low molecular weight nematics has been investigated experimentally and the data are interpreted using the results of the molecular theory which accounts for a possibility of phase separation when the system undergoes the nematic–isotropic transition. The theory predicts that the nematic and isotropic phases with different concentrations of nanoparticles may coexist over a broad temperature range, but only if the nanoparticle volume fraction exceeds a certain threshold value which depends on the material parameters. Such unusual phase separation effects are determined by the strong interaction between nanoparticles and mesogenic groups and between nanoparticles themselves.

Liquid crystal acrylate-based networks : polymer backbone-LC order interaction

Abstract New synthetic pathways to poly- and monodomain acrylate-based networks via gamma-irradiation and chemical crosslinking are described. Strain-induced orientation transitions and phase behavior are studied by X-ray scattering, differential scanning calorimetry and optical microscopy. Analysis of the observed phenomena is given in terms of crosslinking conditions, network topology, structure and spatial distribution of crosslinks. The pretransitional behavior and the observed shifts in clearing point Tn–i are in good agreement with theoretical predictions. The reorientation process in monodomain networks is regulated via strain gradients generated by external mechanical field. The variation in geometrical shape of the samples gives an opportunity to control and realize two different reorientation mechanisms: uniform director rotation and reorientation via stripe domains. Gamma-irradiation is found to be a powerful tool for fixation of any current distribution of poly- and monodomain regions within the LC film. ‘Macroscopic memory’ of the information recorded on the films is observed and discussed.

Photoluminescence properties of cadmium-selenide quantum dots embedded in a liquid-crystal polymer matrix

The photoluminescence properties of cadmium-selenide (CdSe) quantum dots with an average size of ∼3 nm, embedded in a liquid-crystal polymer matrix are studied. It was found that an increase in the quantum-dot concentration results in modification of the intrinsic (exciton) photoluminescence spectrum in the range 500–600 nm and a nonmonotonic change in its intensity. Time-resolved measurements show the biexponential decay of the photoluminescence intensity with various ratios of fast and slow components depending on the quantum-dot concentration. In this case, the characteristic lifetimes of exciton photoluminescence are 5–10 and 35–50 ns for the fast and slow components, respectively, which is much shorter than the times for colloidal CdSe quantum dots of the same size. The observed features of the photoluminescence spectra and kinetics are explained by the effects of light reabsorption, energy transfer from quantum dots to the liquid-crystal polymer matrix, and the effect of the electronic states at the CdSe/(liquid crystal) interface.

Alignment of nanoparticles in polymer matrices

This paper briefly summarizes the state of the art in the field of designing composites containing semiconductor nanoparticles distributed in a polymer matrix. Special attention is focused on (i) nanocomposites based on block copolymers and (ii) LC polymer matrices capable of controlling the localization and alignment of nanoparticles.

Role of the Polymer Matrix on the Photoluminescence of Embedded CdSe Quantum Dots

The photoluminescence (PL) of CdSe quantum dots (QDs) that form stable nanocomposites with polymer liquid crystals (LCs) as smectic C hydrogen-bonded homopolymers from a family of poly[4-(n-acryloyloxyalkyloxy)benzoic acids] is reported. The matrix that results from the combination of these units with methoxyphenyl benzoate and cholesterol-containing units has a cholesteric structure. The exciton PL band of QDs in the smectic matrix is redshifted with respect to QDs in solution, whereas a blueshift is observed with the cholesteric matrix. The PL lifetimes and quantum yield in cholesteric nanocomposites are higher than those in smectic ones. This is interpreted in terms of a higher order of the smectic matrix in comparison to the cholesteric one. CdSe QDs in the ordered smectic matrix demonstrate a splitting of the exciton PL band and an enhancement of the photoinduced differential transmission. These results reveal the effects of the structure of polymer LC matrices on the optical properties of embedded QDs, which offer new possibilities for photonic applications of QD-LC polymer nanocomposites.

Composites based on liquid-crystalline polymers with terminal functional groups and inorganic nanoparticles

A method of controlled radical polymerization via the reversible addition fragmentation chain transfer mechanism is used to synthesize LC polymers with functional terminal thiol groups. These polymers are used to create composites containing gold nanoparticles at a concentration of up to 40 wt % and capable of LC ordering. The structural, thermodynamic, and optical properties of the composites are studied. It is shown that the spatial separation of mesogenic groups and groups responsible for the binding of a macromolecule with nanoparticles makes it possible to considerably widen the concentration range of nanoparticles while preserving the LC state of the composites.

Stable nonequilibrium composites based on liquid-crystalline polymers and cadmium selenide nanoparticles

On the basis of copolymers of 4-methoxyphenyl-4-(6-(acryloyloxyhexyloxy)benzoate with 4-(6-acryloyloxyhexyloxy)benzoic acid, nonequilibrium composites containing nanoparticles (quantum dots) of cadmium selenide at concentrations many times higher than their solubility limit in the liquid-crystalline phase are synthesized. In the resulting material, the polymer matrix undergoes the transition to the liquidcrystalline state before separation into phases with concentrations of nanoparticles corresponding to thermodynamically equilibrium values. Under common conditions, the composites are stable for at least several months.

Immobilization of quantum dots of cadmium selenide on the matrix of a graft liquid-crystalline polymer

A new luminescent composite based on quantum dots of CdSe immobilized on the polymer LC matrix prepared through the graft polymerization of the monomer of 4-(ω-acryloyloxyhexyloxy)benzoic acid on a fluorocarbon support after its preliminary irradiation with vacuum ultraviolet light is elaborated. The structure, composition, and optical characteristics of the prepared composite are studied via the methods of the FTIR spectroscopy, energy-dispersive and wave-dispersive analyses, and luminescence spectroscopy. The CdSe particles are shown to interact with the carboxyl groups of mesogenic fragments of the LC polymer, and this interaction leads to the integration of quantum dots into the ordered LC structure of the composite. As a result of immobilization, the luminescence peak of the quantum dots is shifted toward lower wavelengths owing to the interaction between the nanoparticles and the polymer LC matrix.