Konstantin Mochalov

Optically and Electrically Controlled Circularly Polarized Emission from Cholesteric Liquid Crystal Materials Doped with Semiconductor Quantum Dots

Novel types of electro- and photoactive quantum dot-doped cholesteric materials have been engineered. UV-irradiation or electric field application allows one to control the degree of circular polarization and intensity of fluorescence emission by prepared quantum dot-doped liquid crystal films.

Interaction of CdSe/ZnS core-shell semiconductor nanocrystals in solid thin films

The optical properties of CdSe/ZnS semiconductor nanocrystals with the core-shell structure are studied upon visible-laser excitation in a wide range of flux densities. It is demonstrated that the dimensional quantization effect is preserved in the films with a limiting high concentration of nanocrystals. A strong bathochromic shift of the absorption and luminescence peaks relative to the peak positions in the corresponding spectra of nanocrystals in films with a relatively low concentration of nanocrystals and solutions is caused by a high concentration of nanocrystals and the dipole moment related to the asymmetry of the nanoparticles. The shift is varied from 35 to 50 nm depending on the film thickness. The luminescence spectra of the films remain unchanged upon an increase in the laser intensity to 1 × 106 W/cm2. The laser action on the nanoparticle films is studied at intensities (5 × 106−1 × 109 W/cm2) higher than the damage threshold.

Glass-forming photoactive cholesteric oligomers doped with quantum dots: novel materials with phototunable circularly polarised emission

Novel glass-forming photoactive cholesteric mixtures doped with CdSe quantum dots were prepared and studied. The photooptical and fluorescent properties of these materials were studied. The possibility of phototuning of circularly polarised emission using ultraviolet irradiation was demonstrated.

Resonance energy transfer in self-organized organic/inorganic dendrite structures

Hybrid materials formed by semiconductor quantum dots and J-aggregates of cyanine dyes provide a unique combination of enhanced absorption in inorganic constituents with large oscillator strength and extremely narrow exciton bands of the organic component. The optical properties of dendrite structures with fractal dimension 1.7-1.8, formed from J-aggregates integrated with CdTe quantum dots (QDs), have been investigated by photoluminescence spectroscopy and fluorescence lifetime imaging microscopy. Our results demonstrate that (i) J-aggregates are coupled to QDs by Förster-type resonant energy transfer and (ii) there are energy fluxes from the periphery to the centre of the structure, where the QD density is higher than in the periphery of the dendrite. Such an anisotropic energy transport can be only observed when dendrites are formed from QDs integrated with J-aggregates. These QD/J-aggregate hybrid systems can have applications in light harvesting systems and optical sensors with extended absorption spectra.

Quasi-nanowires from fluorescent semiconductor nanocrystals on the surface of oriented DNA molecules

Ordered structures in the form of quasi-nanowires were obtained from CdSe/ZnS fluorescent semiconductor nanoparticles of spherical (quantum dots) or rodlike (quantum rods) form by their electrostatic deposition on DNA molecules with subsequent stretching of the molecules on a solid substrate. Positively charged nanoparticles were fixed along the negatively charged backbones of DNA molecules by electrostatic interactions in an aqueous solution of a mixture of DNA with quantum particles at different stoichiometric ratios. Strands of single DNA molecules with quantum particles fixed along them were immobilized and stretched on hydrophobic surfaces using the molecular combing technique. It is shown that, by varying the nanoparticle charge and the stoichiometry of complexes of DNA with particles, it is possible to create fluorescent structures with predetermined morphology and properties.

DNA structural alterations induced by bis-netropsins modulate human DNA topoisomerase I cleavage activity and poisoning by camptothecin

Bis-netropsins (bis-Nts) are efficient catalytic inhibitors of human DNA topoisomerase I (top I). These DNA minor groove binders are considered to serve as suppressors of top I-linked DNA breaks, which is generally believed to be related to their affinity to DNA. In this study, it was found that bis-Nts exhibit sequence-specificity of suppression of the strong top I-specific DNA cleavage sites and that this sequence-specificity is determined by differential ligand-induced structural alterations of DNA. Raman scattering analysis of bis-Nts interactions with double-stranded oligonucleotides, each containing the site of specific affinity to one of bis-Nts and a distinctly located top I degenerate consensus, demonstrated that bis-Nts induce not only structural changes in duplex DNA at their loading position, but also conformational changes in a distant top I-specific DNA cleavage site. The ability to alter the DNA structure correlates with the anti-top I inhibitory activities of the ligands. In addition, DNA structural alterations induced by bis-Nts were shown to be responsible for modulation of the camptothecin (CPT)-mediated DNA cleavage by top I. This effect is expressed in the bis-Nts-induced enhancement of some of the CPT-dependent DNA cleavage sites as well as in the CPT-induced enhancement of some of the top I-specific DNA cleavage sites suppressed by bis-Nts in the absence of CPT.

Laser-induced photoprocesses in solutions and films of the CdSe/ZnS nanoparticles

The photophysical properties of solutions and films with relatively high concentrations of CdSe/ZnS nanoparticles are studied in the presence of the visible laser irradiation in a wide range of power densities. The short-wavelength wing detected in the photoluminescence spectra of the solutions of quantum dots is due to the selective laser excitation of small-size nanoparticles. A comprehensive analysis of the anti-Stokes photoluminescence of the nanoparticles in solutions and films indicates the thermal mechanism of this phenomenon. The dimensional quantization effect, narrow spectra, and a relatively high luminescence yield are retained in the films with a high nanoparticle concentration. The luminescence spectra of the films remain unchanged when the laser flux density increases to 1 × 106 W/cm2. The effect of the laser radiation on the nanoparticle films is studied at the flux densities exceeding the damage threshold (5 × 106–1 × 109 W/cm2).

High-resolution 3D structural and optical analyses of hybrid or composite materials by means of scanning probe microscopy combined with the ultramicrotome technique: an example of application to engineering of liquid crystals doped with fluorescent quantum dots

Combination of nanometer-scale 3D structural analysis with optical characterization of the same material is a challenging task. Its results may be important for nanophotonics, materials science, and quality control. We have developed a new technique for complementary high-resolution structural and optical characterization followed by optical spectroscopic and microscopic measurements accompanied by reconstruction of the 3D structure in the same area of the sample. The 3D structure is reconstructed by combination of ultramicrotomic and SPM techniques allowing the study of the 3D distribution of implanted nanoparticles and their effect on the matrix structure. The combination of scanning probe nanotomography (SPN) and optical microspectroscopy makes it possible to direct estimate how the 3D structural characteristics of materials affect their macroscopic optical properties. The technique developed has been applied to the engineering of materials made from cholesteric liquid crystals and fluorescent quantum dots (QDs). These materials permit photochemical patterning and image recording through the changes in the dissymmetry factor of circular polarization of QD emission. The differences in the polarisation images and morphological characteristics of the liquid crystal matrix have proved to be correlated with the arrangement of the areas of homogeneous distribution and nonhomogeneous clustering of QDs. The reconstruction of the 3D structure of the liquid crystal matrix in the areas of homogeneous QD distribution has shown that QDs embedded into cholesteric liquid crystal matrices do not perturb their periodic planar texture. The combined optical/SPM/ultramicrotome technique will be indispensable for evaluating the effects of inorganic nanoparticles on the organisation of organic and liquid crystal matrices, biomedical materials, cells, and tissues.

Novel cholesteric materials doped with CdSe/ZnS quantum dots with photo- and electrotunable circularly polarized emission

Optical materials based on cholesteric liquid crystals (LCs) doped with fluorescent CdSe/ZnS quantum dots (QDs) have been developed and demonstrated to have a wide photonic band gap. It has been shown that the fluorescence emission of QDs embedded in LCs is circularly polarized and that the dissymmetry factor of this polarization may be optically or electrically controlled via conformational changes in the helical structure of the LC matrix. The possibility of photochemical patterning or image recording using these materials has been demonstrated; the recorded information can be read through changes in the dissymmetry factor of circular polarization of QDs emission. The developed photo- and electro-active materials with a controlled degree of fluorescence circular polarization may be used as on-demand single photon sources in photonics, optoelectronics, and quantum cryptography, as well as for development of nanophotonic systems capable of low-threshold lasing.

Modulation of quantum dot photoluminescence in porous silicon photonic crystals as a function of the depth of their penetration

Photonic crystals doped with fluorescent nanoparticles offer a plenty of interesting applications in photonics, laser physics, and biosensing. Understanding of the mechanisms and effects of modulation of the photoluminescent properties of photonic crystals by varying the depth of nanoparticle penetration should promote targeted development of nanocrystal-doped photonic crystals with desired optical and morphological properties. Here, we have investigated the penetration of semiconductor quantum dots (QDs) into porous silicon photonic crystals and performed experimental analysis and theoretical modeling of the effects of the depth of nanoparticle penetration on the photoluminescent properties of this photonic system. For this purpose, we fabricated porous silicon microcavities with an eigenmode width not exceeding 10 nm at a wavelength of 620 nm. CdSe/CdS/ZnS QDs fluorescing at 617 nm with a quantum yield of about 70% and a width at half-height of about 40 nm were used in the study. Confocal microscopy and scanning electron microscopy were used to estimate the depth of penetration of QDs into the porous silicon structure; the photoluminescence spectra, kinetics, and angular fluorescence distribution were also analyzed. Enhancement of QD photoluminescence at the microcavity eigenmode wavelength was observed. Theoretical modeling of porous silicon photonic crystals doped with QDs was performed using the finite-difference time-domain (FDTD) approach. Theoretical modeling has predicted, and the experiments have confirmed, that even a very limited depth of nanoparticle penetration into photonic crystals, not exceeding the first Bragg mirror of the microcavity, leads to significant changes in the QD luminescence spectrum determined by the modulation of the local density of photonic states in the microcavity. At the same time, complete and uniform filling of a photonic crystal with nanoparticles does not enhance this effect, which is as strong as in the case of a very limited depth of nanoparticle penetration. Our results will help to choose the best technology for fabrication of efficient sensor systems based on porous silicon photonic crystals doped with fluorescent nanoparticles.