T. N. Nekrasova

Photophysical and electrical properties of polyphenylquinolines containing carbazole or indolo[3,2-b]carbazole fragments as new optoelectronic materials

Photophysical and electrical properties of new synthesized 2,6-polyphenylquinolines (PPQs) containing an oxygen or phenylamine bridging group between quinoline cycles and, as an arylene radical, alkylated derivatives of carbazole or indolo[3,2-b]carbazole are studied. It is shown that the photosensitivity for new PPQs is 104–105 cm2/J and the photogeneration quantum yield of free carriers is as high as 0.15. Photophysical parameters increase with the phenylamine bridging group in place of the oxygen one and when using indolocarbazole instead of carbazole. It is found that a film of polyphenylquinoline containing an oxygen bridging group and an alkylcarbazole fragment in the polymer repeat unit exhibits “white” luminescence. Both electron and hole transport with a mobility of ∼10−6 cm2/(V s) are detected in films of all studied polymers. The conductivity value and type can be controlled by varying the chemical structure of the (oxygen or phenylamine) bridging group between PPQ cycles and by choosing carbazole or indolo[3,2-b]carbazole derivatives as an arylene radical.

Specifics of structural organization and properties of lysine dendrimers of different generations and related supramolecular structures

Lysine dendrimers of different generations containing covalently attached anthracene-based luminescent labels (one label per six dendrimer molecules) and fifth-generation heterodendrimers containing various amino acid units located between lysine fragments were synthesized. Homodendrimers were studied by means of the polarized luminescence technique. It was found that the packing density of lysine fragments in macromolecules increases with an increase in the generation number. Their capability of forming supramolecular structures changes in this case; the number of polymacromolecular associates produced in the solution and on the polymer matrix in interpolymer complexes decreases and their complexing power in the reaction with low-molecular-mass compounds increases. It was found that dendrite molecules acquire a looser structure on passing to heterodendrimers and their complexing ability varies in the corresponding manner; the number of polymacromolecular associates in the solution and on the polymer matrix in the interpolymer complexes increases and binding of low-molecular-mass compounds is reduced.

Structural and dynamic characteristics of a star-shaped calixarene-containing polymer in aqueous solutions: the formation of mixed-shell micelles in the presence of poly(methacrylic acid)

Structural and dynamic characteristics of a star-shaped polymer with a central tert-butylcalix[8]arene core and poly(N-isobutyryl ethylenimine)-ω-piperazine arms in aqueous solutions were studied via the polarized-luminescence method. To conduct investigations, a luminescent label of the anthracene structure was attached to the polymer. It has been shown that polymer macromolecules are in an aggregate state in water. The aggregate comprises about 5 macromolecules. During mixing of the star-shaped polymer with macromolecules of un-ionized poly(methacrylic acid), a mixed-shell micelle in which poly(methacrylic acid) units interact with both poly(N-isobutyryl ethylenimine)-ω-piperazine moieties and isobutyl fragments incorporated into the core of the micelle is formed.

Water-soluble complexes of poly(N-vinylamides) of various structures with C60 and C70 fullerenes

By the example of the interaction of fullerene C60 and poly(N-vinylpyrrolidone), the effect of formation conditions of water-soluble fullerene-containing donor-acceptor polymer systems on their composition and structure has been studied. On the basis of these results, a new technique has been developed for preparing water-soluble polymer systems of this kind with the use of o-dichlorobenzene as a component of the reaction medium. This technique has been employed to prepare water-soluble fullerene-containing complexes of poly(N-vinylamides) of various structures (polymers and copolymers of N-vinylpyrrolidone and N-vinylcaprolactam) containing up to 3–5 wt % of C60 and C70 fullerenes. These values are 3–6 times higher than those described previously.

Model system for multifunctional delivery nanoplatforms based on DNA-Polymer complexes containing silver nanoparticles and fluorescent dye

Creation of multifunctional nanoplatforms is one of the new approaches to complex treatment and diagnosis with the monitoring of the curative process. Inclusion of various components into the drug delivery system may reduce toxicity and enhance or modify the therapeutic effects of medicines. In particular, some properties of metal nanoparticles and nanoclusters provide the ability to create new systems for treatment and diagnosis of diseases, biocatalysis and imaging of objects. For example, the ability of metal nanoparticles to enhance the quantum yield of luminescence can be used in bioimaging and therapy. The aim of the research was to construct and examine a multicomponent system based on DNA-polycation compact structure with the inclusion of silver nanoparticles and luminescent dye as a model system for delivery of genes and drugs with the possibility of modification and enhancement of their action.

Conformational and dynamic characteristics of copolymers of N,N-dimethylaminoethyl methacrylate and 2-deoxy-2-methacrylamido-D-glucose

The conformational and relaxation properties of N,N-dimethylaminoethyl methacrylate and 2-deoxy-2-methacrylamido-D-glucose copolymers in solutions are studied by the methods of molecular hydrodynamics (sedimentation, diffusion, viscometry), polarized luminescence, and flow birefringence. Kuhn-Mark-Houwink equations are obtained, and Kuhn statistical segment lengths at various degrees of protonation of amino groups are estimated. It is found that there is a correlation between the Kuhn statistical segment length and the intramolecular mobility of the copolymers.

Interpolymer complexes of poly(N-vinylpyrrolidone) with copolyimide-grafted side chains of poly(methacrylic acid)

The process of formation and structural organization of interpolymer complexes formed by macromolecules of poly(N-vinylpyrrolidone) and poly(methacrylic acid) chains grafted onto polyimide in solution is investigated via the method of polarized luminescence. A luminescent label of anthracene structure is covalently bound to both polymers. Relaxation times characterizing intramolecular mobility of each of the components in their interpolymer complex are measured in relation to the composition of the system.

Carbazole-containing polyphenylquinolines as a basis for optoelectronic materials with white luminescence

The photophysical properties of poly-2,2′-(1-dodecyl carbazole-4,7-yl)-6,6′-(oxy)-bis-(4-phenylquinoline) in a solution, as a film, and in a poly(methyl methacrylate) or poly-N-vinylcarbazole host matrix have been studied. Considerable positive solvatochromism in the photoluminescence spectra, compared with solvatochromism in the absorption spectra, indicates that the dipole moment of the donor-acceptor complex increases in the excited state. Calculations show that the dipole moments of the complex in the ground and excited states differ by more than an order of magnitude. Upon transition to films, photoluminescence is observed in the entire visible spectral range (white luminescence). The intensity of the white luminescence grows by an order of magnitude when the polymer is dispersed in a poly(methyl methacrylate) matrix. The integrated photosensitivity and parameters of the photogeneration process (quantum yield of carrier photogeneration, quantum yield of free carrier formation, and thermalization radii) have been determined.

Luminescence of Ln3+ lanthanide complexes in polymer matrices

The photoluminescence properties of Tb3+ and Eu3+ complexes with polymer ligands containing various kinds of complexing groups—namely, carboxyl (5–20 mol %), pyridylquinoline (5 mol %), or pyridylnaphthyl (5 and 10 mol %) groups—in solution and block are considered. The chemical structure of a neutral comonomer (methyl methacrylate; styrene; isopropyl-, phenyl-, or benzylmethacrylamide; and N-vinylamides) in polymer ligands is varied. The intensity of photoluminescence is dependent not only on the chemical nature of a complexing group but also the chemical nature of a neutral comonomer and a spacer. Variation in the nature of a comonomer and a ligand makes it possible to prepare complexes in which a high luminescence of a low-molecular-mass complex is preserved and advantages inherent in a polymer complex are acquired. The effect of the nature of the polymer matrix (photoactive and photoinert) on the efficiency of electronic-excitation energy transfer is ascertained. The data on the photoluminescence of metal-polymer complexes that are based on polymer ligands containing vinylcarbozole units and that possess hole conductivity make it possible to regard them as materials for electroluminescence. The intensity of photoluminescence of these complexes is related to the competition of oppositely directed photophysical processes in a macromolecule: formation of excimers and migration of electronic excitation energy. An analysis of the published data and of the results of the authors shows that detailed studies of these polymer systems in solution and in matrices are needed to gain insight into the relationship between photo- and electroluminescence properties of metal-polymer complexes, because the matrix plays different roles in photoluminescence and electroluminescence (inner filter or conduction); as a consequence, the emission spectra may differ appreciably. It is shown that the efficiency of electroluminescence may be improved if the transfer of energy from the lanthanide ligand in a complex to the conducting matrix is decreased.

Water-soluble polymer derivatives of cholesterol

New cholesterol-containing water-soluble polymers based on N-methacryloyl aminoglucose and N-vinylpyrrolidone are synthesized by free-radical copolymerization and polymer-analogous transformations. Binary and ternary copolymers of various composition containing N-allylamine and N,N,N-trimethylaminoethyl methacrylate methyl sulfate units and cholesterol residues are prepared. Luminescently labeled copolymers of the same composition are obtained. Effects of the nature of polymers and the amount of cholesterol in them on the intramolecular mobility of macromolecules in solution are studied with polarized luminescence. When 2–4 mol % of cholesterol residues are incorporated into the copolymer, the intramolecular mobility of macromolecules decreases, thus indicating formation of intramolecular compact structures via interaction of nonpolar cholesterol groups. In copolymers containing charged groups, these structures are looser than those in neutral copolymers. It is shown that macromolecules of cholesterol-containing polymers of various types can interact with each other. 1 This work was supported by the Russian Foundation for Basic Research (project no. 08-03-00324) and the Council for Grants of the President of the Russian Federation for Support of Leading Institutes of Higher Education (NSh-4391.2008.3).