Maria V. Mukhina

Intrinsic Chirality of CdSe/ZnS Quantum Dots and Quantum Rods.

A new class of chiral nanoparticles is of great interest not only for nanotechnology, but also for many other fields of scientific endeavor. Normally the chirality in semiconductor nanocrystals is induced by the initial presence of chiral ligands/stabilizer molecules. Here we report intrinsic chirality of ZnS coated CdSe quantum dots (QDs) and quantum rods (QRs) stabilized by achiral ligands. As-prepared ensembles of these nanocrystals have been found to be a racemic mixture of d- and l-nanocrystals which also includes a portion of nonchiral nanocrystals and so in total the solution does not show a circular dichroism (CD) signal. We have developed a new enantioselective phase transfer technique to separate chiral nanocrystals using an appropriate chiral ligand and obtain optically active ensembles of CdSe/ZnS QDs and QRs. After enantioselective phase transfer, the nanocrystals isolated in organic phase, still capped with achiral ligands, now display circular dichroism (CD). We propose that the intrinsic chirality of CdSe/ZnS nanocrystals is caused by the presence of naturally occurring chiral defects.

Preparation of chiral quantum dots

Chiral quantum dots (QDs) are expected to have a range of potential applications in photocatalysis, as specific antibacterial and cytotoxic drug-delivery agents, in assays, as sensors in asymmetric synthesis and enantioseparation, and as fluorescent chiral nanoprobes in biomedical and analytical technologies. In this protocol, we present procedures for the synthesis of chiral optically active QD nanostructures and their quality control using spectroscopic studies and transmission electron microscopy imaging. We closely examine various synthetic routes for the preparation of chiral CdS, CdSe, CdTe and doped ZnS QDs, as well as of chiral CdS nanotetrapods. Most of these nanomaterials can be produced by a very fast (70 s) microwave-induced heating of the corresponding precursors in the presence of D- or L-chiral stabilizing coating ligands (stabilizers), which are crucial to generating optically active chiral QDs. Alternatively, chiral QDs can also be produced via the conventional hot injection technique, followed by a phase transfer in the presence of an appropriate chiral stabilizer. We demonstrate that the properties, structure and behavior of chiral QD nanostructures, as determined by various spectroscopic techniques, strongly depend on chiral stabilizers and that the chiral effects induced by them can be controlled via synthetic procedures.

The chiral nano-world: chiroptically active quantum nanostructures

Chirality is one of the key factors in molecular recognition, therefore the development of new chiral nanoparticles is of great interest to many fields of scientific endeavour including chemistry, biochemistry, pharmacology and medicine. Knowledge of the fundamental concepts relevant to chirality in nanosystems is also very important for further advancement of nanoscience and nanotechnology in general. Over the past years, the use of stereospecific chiral stabilising molecules has opened a new avenue to the area of nanocrystal research. In this review article we present some recent advances in the development of various chiroptically active quantum nanostructures and discuss the latest progress in various approaches for the preparation of these nanostructures. We also consider the intrinsic chirality in quantum nanostructures due to the presence of chiral defects such as screw dislocations and discuss the structure-property relationship. Furthermore, the corresponding potential applications of these chiral nanomaterials has been analysed for key areas: sensing, cytotoxicity mediation and cell imaging, asymmetric catalysis and enantiomeric separation, circular polarised light emitting devices and spintronics. Finally, we provide an outlook for the future development of chiroptically active quantum nanostructures.

Electrically controlled polarized photoluminescence of CdSe/ZnS nanorods embedded in a liquid crystal template

A novel homogeneous composite material, consisting of luminescent CdSe/ZnS quantum nanorods, embedded in the nematic liquid crystal 5CB, has been prepared. Liquid crystal cells and free-standing stretched polymer films incorporating this composite material were characterized using polarized micro-photoluminescence and electro-optical measurements under an applied electric field. A liquid crystal induced, macroscopic orientation of the nanorods in a thin layer of the material has been demonstrated. A conventional liquid crystal cell, filled with this composite, exhibits 40% modulation of the nanorods photoluminescence intensity when subjected to an external electric field. These results indicate that quantum nanorods may have practical applications in photonic devices.

Molecular Recognition of Biomolecules by Chiral CdSe Quantum Dots.

Molecular recognition is one of the most important phenomena in Chemistry and Biology. Here we present a new way of enantiomeric molecular recognition using intrinsically chiral semiconductor nanocrystals as assays. Real-time confocal microscopy studies supported by circular dichroism spectroscopy data and theoretical modelling indicate an ability of left-handed molecules of cysteine and, to a smaller extent, histidine and arginine to discriminate between surfaces of left- and right-handed nanocrystals.

Anisotropy of optical transitions in ordered ensemble of CdSe quantum rods

We report on the observation of spectral dependence of absorption anisotropy in a CdSe quantum rod (QR) ensemble, which is aligned in a polymer film with a nanocrystal concentration of 2×10(-5) M. The experimental data on the polarization direction and anisotropy factor were obtained for the lowest excitonic transition and the second group of transitions in the QR. The nonzero constant value of anisotropy was investigated for the high-energy transitions, and is evidence of the one-dimensional confinement in the QR.

Circular Dichroism of Electric-Field-Oriented CdSe/CdS Quantum Dots-in-Rods

Here we report anisotropy of intrinsic chiroptical response in CdSe/CdS quantum dot-in-rod systems. These nanostructures being oriented in an external electric field demonstrate dependence of circular dichroism signal on the orientation of the nanocrystals. The type of circular polarization in these nanostructures correlates with preferential direction of linear polarization, and the degree of circular polarization is the maximal for the first circular dichroism band corresponding to the absorption band edge. We also support our experimental data with a theoretical model. Using this model, we show a direct connection between theoretically derived morphological parameters of twisting in nanocrystals lattices and calculated from experimental data parameters of circular dichroism anisotropy.

Liquid-crystal composites with controlled photoluminescence of CdSe/ZnS semiconductor quantum rods

Liquid-crystal (LC) composites based on a combination of different acrylates and pentylcyanobiphenyl and containing CdSe/ZnS semiconductor quantum nanorods have been investigated. Samples of electro-optical cells with planar or homeotropic structures (depending on the acrylate type) have been obtained. The morphology of LC composite formation has been studied using luminescence techniques. It is shown that these composites are gel-like LC media, where the formation of dispersed and network structures in the cells plays a stabilizing role. The role of the electron transfer reactions during polymerization and the features of the kinetics of the Freedericksz effect (reorientation in an electric field) are discussed.

Anisotropy of light absorbed by an ensemble of CdSe quantum nanoplates

The anisotropy of the optical properties of CdSe quantum nanoplates is investigated, using the methods of absorption spectroscopy. It is experimentally established that the optical properties of the quantum nanoplates are anisotropic. Spectral dependences are obtained for the absorption anisotropy of ensembles of nanocrystals ordered in a stretched polymer film. A technique has been developed for creating elastic polymer films made from polyvinyl butyral with a high concentration of quantum nanoplates.

Photoinduced anisotropy in an ensemble of CdSe/ZnS quantum rods

The photoluminescence anisotropy in initially disordered quantum rod ensemble induced by selective photochemical reaction under continuous irradiation with polarized light is demonstrated. A specific long-time relaxation of the photoinduced anisotropy in darkness, which is attributed to rotational diffusion of nanocrystals, is observed in the minutes time scale after an extended period of irradiation. The observed bi-exponential evolution of the photoluminescence intensity under continuous irradiation suggests the development of two photoinduced processes such as photopassivation of surface defects and photooxidation of the quantum rod surface.