Larisa Klapshina

Institute of organometallic chemistry of RAS

An irreversible addition reaction of benzylmercaptan to the macrocycle of the cyanoarylporphyrazine family (Ar = p-MeOPh and Nph) was established for the first time. The reaction proceeds along the polarized peripheral semi-isolated double bonds of the macrocycle and takes place under mild conditions. Mass spectrometry and 1H NMR spectroscopy confi...

Today we see an increasing demand for new fluorescent materials exhibiting various sensory abilities due to their broad applicability ranging from the construction of flexible devices to bioimaging. In this paper, we report on the new fluorescent pigments AntTCNE, PyrTCNE, and PerTCNE which consist of 3–5 fused aromatic rings substituted with tricy...

Photodynamic therapy (PDT) is a rapidly developing modality of primary and adjuvant anticancer treatment. The main trends today are the search for new effective photodynamic agents and the creation of targeted delivery systems with the function of controlling the release of the agent in the tumor. Recently, the new group of cyanoarylporphyrazine dy...

Tumor cells are well adapted to grow in conditions of variable oxygen supply and hypoxia by switching between different metabolic pathways. However, the regulatory effect of oxygen on metabolism and its contribution to the metabolic heterogeneity of tumors have not been fully explored. In this study, we develop a methodology for the simultaneous an...

The current efforts in photodynamic therapy (PDT) of brain cancer are focused on the development of novel photosensitizers with improved photodynamic properties, targeted specific localization, and sensitivity to the irradiation dose, ensuring the effectiveness of PDT with fewer side effects for normal nerve tissue. Here, we characterize the effect...

To mitigate side effects in systemic administration, anticancer drugs are encapuslated in nanocontainers. The nanocontainers are impermeable through normal vessel walls but can permeate and retain in the tumor, albeit their diffusive transport in the tumor interstitium towards pharmacological targets is drastically hindered by the tumor microenviro...

New water-soluble polynorbornenes P1–P4 containing oligoether, amino acid groups and luminophoric complexes of iridium(III) were synthesized by ring-opening metathesis polymerization. The polymeric products in organic solvents and in water demonstrate intense photoluminescence in the red spectral region. The polymers P1 and P3 with 1-phenylisoquino...

Despite the significant relevance of photodynamic therapy (PDT) as an efficient strategy for primary and adjuvant anticancer treatment, several challenges compromise its efficiency. In order to develop an "ideal photosensitizer" and the requirements applied to photosensitizers for PDT, there is still a need for new photodynamic agents with improved...

The prospective strategy for treatment of cancer is based on the application of nano-sized macromolecular carriers, which are able penetrate inside and can be accumulated within tumor tissue. In this work graft copolymers of cellulose and poly(methacrylic acid) has been prepared and tested as a nanocontainers for the delivery of drug to tumor. For...

Using the example of a polymer formed from the T-monomer RFOCH2Si(ORF)3 (RF = CH2CF3), it was shown that rapid hydrolysis of this type of compounds with a linear fluorinated substituent leads to the formation of largely ordered polysiloxanes. A comparison of the interatomic distances obtained from the pair function of the radial distribution of ele...

Photodynamic therapy (PDT) is based on the production of the cytotoxic reactive oxygen species (ROS) by light irradiation of a photosensitizer dye in the presence of molecular oxygen. Along with photochemical ROS production, it becomes evident that PDT induces massive secondary production of ROS which is registered long after the irradiation is com...

The immunogenicity of dying cancer cells determines the efficacy of anti-cancer therapy. Photodynamic therapy (PDT) can induce immunogenic cell death (ICD), which is characterized by the emission of damage-associated molecular patterns (DAMPs) from dying cells. This emission can trigger effective anti-tumor immunity. Only a few photosensitizers are...

Polysiloxane based on N-2-hydroxy-1,1-di(hydroxymethyl)ethyl-N´-3-triethoxysilylpropylurea was synthesized. The polymer forms small nanoparticles and their associates in water. The latter can retain poorly soluble luminophore and hydrophobic gadolinium complex. The doped particles are capable of interacting with proteins. Aqueous suspensions based...

The aim of the study was to compare the relevance of ovarian adenocarcinoma spheroids with that of a monolayer culture for assessing photodynamic effect of the tetrakis(4-benzyloxyphenyl)tetracyanoporphyrazine photosensitizer. Materials and methods: The work was performed on SKOV-3 human ovary adenocarcinoma cells grown in vitro in a monolayer cu...

Photodynamic therapy is a clinically approved procedure for targeting tumor cells. Though several different photosensitizers have been developed, there is still much demand for novel photosensitizers with improved properties. In this study we aim to characterize the accumulation, localization and dark cytotoxicity of the novel photosensitizers deve...

Polymers containing oligoether groups, amino acid fragments, and luminophore complexes of iridium(III) in side chains are synthesized by metathesis polymerization. The photophysical properties of the compounds obtained are studied. The iridium-containing copolymers show intense green, blue-green, and red photoluminescence, and the color is determin...

A method for synthesis of hyperbranched polysiloxane based on N-methyl-N-(2,3,4,5,6- pentahydroxyhexyl)-N´-(3-triethoxysilylpropyl)urea is proposed. In water, the polymer forms nanoparticles capable of holding low soluble luminophores (tetracyanotetraarylporphyrazines) due to non-covalent interaction. Intensively luminescent stable aqueous suspensi...

Novel fluorescent dyes of the cyanoarylporphyrazine series containing peripheral triazole groups have been synthesized. Their photophysical properties and the local viscosity effect on the fluorescence have been studied. The experiments with cell cultures have revealed rapid accumulation of the dyes in the cells cytoplasm. Photo- and dark cytotoxic...

A survey of the studies dealing with the development of new porphyrazine type tetrapyrrole dyes promising for the application in photonics and biophotonics is presented. An original synthetic approach to the template assembly of the porphyrazine macrocycle at room temperature in high yield has been proposed. A porphyrazine macrocycle containing eig...

Copolymers with oligoether units and luminophoric iridium(III) complexes in the side chains have been synthesized via metathesis polymerization. The copolymers containing different luminophoric iridium(III) complexes have exhibited strong green, blue-green, or red photoluminescence. The copolymers are soluble in water, forming micelles with average...

Tetra(aryl)tetracyanoporphyrazines are the promising group of dyes for photodynamic therapy of tumors with unique combination of photosensitizer properties and sensitivity of fluorescence parameters to the environment viscosity. However, in vivo application of such hydrophobic photosensitizers requires using of drug carriers ensuring efficient deli...

Hydrolysis of N-methyl-N-(2,3,4,5,6-pentahydroxyhexyl)-N′-(3-triethoxysilylpropyl)urea gave water-soluble polysiloxane nanoparticles. They can be used for the preparation of intensely luminescent stable aqueous suspensions of water-insoluble or poorly soluble compounds (Eu(BTFA)3 · 6H2O complex and tetracyano-tetraaryl-porphyrazines) for biomedical...

We report a series of novel red-emitting cyanoaryl porphyrazine pigments which are found to be an excellent platform for bimodal tumor diagnostic agents and intracellular viscosity sensors. They also work as efficient PDT sensitizers upon irradiation with red light.

A queous nanosuspensions containing polymer nanoparticles loaded with drugs can be used as drug delivery system. They are able to increase the bioavailability of the compounds which are insoluble or slightly soluble in water. The neecessary requirement for such the polymeric systems is the high content and availability of the functional groups whic...

Background: A promising strategy for cancer diagnosis and therapy is the development of an agent for multimodal imaging and treatment. In the present paper we report on two novel multifunctional agents prepared on the porphyrazine pigment platform using a gadolinium (III) cation chelated by red-fluorescent tetrapyrrole macrocycles (GdPz1 and GdPz2...

New porphyrazine bases containing peripheral benzyloxyphenyl groups have been synthesized by the template method. The procedure includes condensation of aromatic aldehydes with malononitrile, transformation of arylmethylidenemalononitriles to arylethenetricarbonitriles, template assembly of porphyrazine macrocycle on bis(indenyl)ytterbium(II) compl...

The microscopic viscosity plays an essential role in cellular biophysics by controlling the rates of diffusion and bimolecular reactions within the cell interior. While several approaches have emerged that have allowed the measurement of viscosity and diffusion on a single cell level in vitro, the in vivo viscosity monitoring has not yet been reali...

Efficient drug delivery can be assigned to tasks that attract the most acute attention of researchers in the field of anticancer drug design. We have reported the first case of using amphiphilic polymer brushes as nanocontainers for photosensitizer delivery to cancer cells. Regular graft‐copolymers of hydrophobic polyimides with hydrophilic polymet...

New tetraaryltetracyanoporphyrazines have been obtained in the form of metal complexes and free bases via template assembly of a variety of aryltricyanoethylenes as structural units of the macrocycle, and photophysical properties of the products have been studied. The unique high sensitivity of the fluorescent properties to viscosity has been demon...

Porphyrazines have recently emerged as a useful class of tetrapyrroles suitable for photodynamic therapy of cancer (PDT) with excellent uptake and retention properties in vivo. Here we demonstrate that the photophysical properties of cyano-phenyl porphyrazin pz1 are strongly viscosity dependent, i.e. the fluorescence lifetime and the quantum yield...

An approach to the synthesis of new regular graft-copolymers polyimide (PI)-graft-polymethacrylic acid is elaborated, including (1) synthesis of multicenter PI macroinitiators, (2) controlled ATRP of tert-butylmethacrylate on the prepared macroinitiators, and (3) protonolysis of tert-butyl ester groups of side chains of the resulting PI-graft-poly(...

A photocurable polymeric luminescent composition doped by a new ytterbium tetra(4-fluorophenyl)tetracyanoporphyrazine complex capable of efficiently absorbing and reemitting light in a wide spectral range is developed. Defect-free organic glasses obtained with the use of this composition were applied as waveguides in the creation of laboratory mode...

The ytterbium tetraphenyltetracyanoporphyrazine complex (YbPz) has been studied as a potential photosensitizer for fluorescence diagnostics and photodynamic therapy of cancer. A water-miscible formulation of YbPz has been prepared using PEG 6000. The new compound shows intense absorption and fluorescence in the “optical window” of biological tissue...

The tetraphenyltetracyanoporphyrazine complex of ytterbium has been studied as a potential photosensitizer for fluorescence diagnostics and photodynamic therapy (PDT) of cancer. It has been shown that the new compound has an intensive absorption and fluorescence in the "tissue optical window". In particular, the absorption maximum of the complex is...

The reaction of perylene-3,4,9,10-tetracarboxylic acid dianhydride with 3-aminopropyltriethoxysilane and hexamethyldisilazane was investigated. A possibility of obtaining a new dye resistant to UV light and heating (up to 300°C), consisting of structural fragments of perylene-3,4,9,10-tetracarboxydiimede, diethoxysiloxane, and 3-aminopropylethoxysi...

The preparation and properties are described of two types of novel PEG-organized nanoparticles including silica-modified uniform disk-shaped nanoparticles doped with a fluorescent ytterbium cyanoporphyrazine complex; a large enhancement of red emission for both types of nanoparticles is observed in physiological liquids owing to their binding to bi...

The preparation is described of a novel highly emissive ytterbium complex with a proposed unusual structure obtained by reaction of tricyanovinylbenzene (TCNVB) with bis(indenyl)ytterbium(II) in THF. The reaction occurs under extremely mild conditions, the tetraphenyltetracyanoporphyrazine macrocycle being assembled in high yield from TCNVB buildin...

The preparation is described of a novel highly emissive ytterbium complex with a proposed unusual structure obtained by reaction of tricyanovinylbenzene (TCNVB) with bis(indenyl)ytterbiumll) in THF. The reaction occurs under extremely mild conditions, the tetraphenyltetracyanoporphyrazine macrocycle being assembled in high yield from TCNVB building...

New fuctionalized ligand 3-(3′-triethoxysilylpropylaminocarbonyl)pent-2-on-3-en-4-ol (EtO)3SiCH2·CH2CH2NHC(O)-C[C(O)CH3][=C(OH)CH3] (I) containing ketoenol and triethoxysilyl groups is synthesized from 3-triethoxysilylpropyl isocyanate (EtO)3SiCH2CH2CH2N=C=O and acetylacetone. The reaction is accompanied by the formation of 2-(3′-triethoxysilylprop...

A novel facile synthetic route to the metal-template assembly of a tetrapyrrollic framework from tetracyanoethylene (TCNE) and tricyanovinylbenzene (TCNVB) structural units through reaction of TCNE and TCNVB with metal π-sandwich complexes has been developed. The reactions occur under extremely mild conditions, the porphyrazine macrocycles being as...

Two types of transparent high-optical-quality organic glasses (rigid and flexible, 40 × 40 × 2.2 mm in size) containing 0.6–3.2 mass % europium tris(benzoyltrifluoroacetonate) (0.1–0.6 mass % of Eu) were obtained from photopolymerizing compositions using the technique of layer-by-layer photopolymerization. The glasses are characterized by a high le...

A method for the synthesis of polyphosphosiloxane by the thermal condensation of an equimolar mixture of trimethyl phosphate and (3-aminopropyl)triethoxysilane at 200 °C was developed. The reaction affords ethanol and polyphosphosiloxane-{Si(OEt)[(CH2)3NR1R2]-O-P(O)(OMe)-O}n-(R1 = H, Me; R2 = Me), whose composition and structure were confirmed by 1...

The cubic nonlinear-optical susceptibility of solutions and films of new metalloorganic polymers is studied by the z-scan method using 1064-nm, 40-ps laser pulses. The contribution of the electronic susceptibility is measured with the help of probe beams with circular and linear polarisations. The greatest electronic susceptibility amounting to — 9...

Tetracyanoethylene (TCNE) is a very important starting compound in modern synthetic and materials chemistry. The great variety of its numerous reaction modes and chemical versatility have been surveyed in a very recent fundamental review by Miller. It was particularly emphasized that a wide array of products based on TCNE is available and that the...

3-(3′-Triethoxysilylpropyl)pentane-2,4-dione, (EtO)3SiCH2CH2CH2C[-C(O)CH3]2 (I), was synthesized from 3-allylpentane-2,4-dione, CH2 = CH-CH2-C[-C(O)CH3]2, and triethoxysilane, (EtO)3SiH, in the presence of Speier’s catalyst. The silylation occurred mainly at the terminal C atom of the allyl group. The corresponding europium(III), terbium(III), and...

Novel non-linear optical polymeric film-producing nanocomposites based on bis(arene)chromium complexes incorporated into CN-containing matrices have been developed. Measurements by the spectrally resolved two-beam coupling method with a femtosecond range of pulse widths (central wavelength 795-800 nm) confirmed that the test composites exhibited a...

Transparent luminescent sol–gel films have been prepared from the complexes of EuIII and TbIII with the new ligand 3-(3′-triethoxysilylpropyl) pentane-2,4-dione synthesised by the reaction of 3-allylpentane-2,4-dione with triethoxysilane in the presence of Speier catalyst.

Novel non-linear optical polymeric film-producing nanocomposites based on bis(arene)chromium complexes incorporated into a CN-containing matrix have been developed. Polymeric nanocomposite precursors were prepared by the reaction of Cr(EtnC6H6−n)2 (n = 1,2,3) with CN-containing vinyl monomers (acrylonitrile, crotononitrile or ethyl 2-cyanopropenoat...

Original Russian Text: V.V. Semenov, A.Yu. Nerovnya, V.A. Egorov, N.F. Cherepennikova, L.G. Klapshina, A.I. Kirillov, T.I. Lopatina, W.E. Douglas, G.A. Domrachev, 2006, published in Doklady Akademii Nauk, 2006, Vol. 407, No. 4, pp. 489–492.

Novel nonlinear optical polymeric film-producing nanocomposites based on bis(arene)chromium complexes incorporated into a CN-containing matrix have been developed. Polymer-precursors were prepared by the reaction of Cr(EtnC6H6?n)2 mixtures (n = 1,2,3) with CN-containing vinyl monomers (acrylonitrile, crotononitrile and ethylcyanoacrylate). The nonl...

Fluorescence and fluorescence excitation spectra of phosphorus-containing organosilicon ligands O = PX2NHR (X = NMe2, OPh; R = CH2CH2CH2Si(Oet)3 and their Eu(III) complexes in acetonitrile solutions and in films are studied. In UV region (285–420 nm), bis(dimethylamido)triethoxysilylpropylamidophosphate (X = NMe2) and diphenyltriethoxysilylpropylam...

The spectroscopic characteristics of hybrid organic-inorganic films and solutions of ethoxysilicon-containing amidophosphate ligands in acetonitrile have been investigated. Inhomogeneous broadening of the absorption and fluorescence spectra which is characterized by the spectral dependence of the fluorescence and fluorescence excitation bands on th...

The steady-state fluorescence, fluorescence excitation spectra and fluorescence lifetime of pentacoordinate [8-(dimethylamino-κN)-1-naphthalenyl-κC]diethynylmethylsilicon as a function of excitation and emission wavelengths were investigated in solvents of various polarities at room temperature. Inhomogeneous spectral broadening and biexponential d...

The photoconductivity and electro-optic response of a self-organised nanostructured poly[(ethynediyl)(arylene)(ethynediyl)silylene]/N-ethylcarbazole/polyphenylsilsesquioxane composite have been investigated with a cw diode laser at a wavelength of 1500 nm. For electric field 25 V µm-1 and beam intensity 18 W cm-2, the photosensitivity was 0.5 pS cm...

Using new, high-sensitivity methods to determine the cubic optical susceptibility in the femtosecond range of laser pulse widths, the presence of large coefficients of cubic nonlinearity of electronic type is revealed in new organometallic polymers. Measurement methods based on two-wave mixing of laser pulses in the sample are compared with respect...

The spectroscopic characteristics of new -linked polymers, whose main chain contains tetracoordinated silicon, acetylene groups, and 1,4-biphenyl or 2,7-fluorene, in chloroform have been investigated. It has been established that the spectral features of the absorption, fluorescence, fluorescence excitation, and fluorescence polarization spectra of...

Three new silicon- and fluorine-containing ligands, namely bis(dimethylamido)(3-triethoxysilylpropylamido)phosphate O=P(NMe2)2NHCH2CH2CH2Si(OEt)3, diphenyl(3-triethoxysilylpropylamido)phosphate O=P(OPh)2NHCH2CH2CH2Si(OEt)3, and tris(3,3,3-trifluoropropyl)phosphine oxide O=P(CH2CH2CF3)3 are synthesized. The erbium and ytterbium complexes with amine,...

The new complexes of erbium and ytterbium with amine, phosphate and phosphine oxide ligands Ln(NH2R)3Cl, Ln[O=P(NMe2)2NHR]3Cl3, Ln[O=P(OPh)2NHR]3Cl3, [R=CH2CH2CH2Si(OEt)3], Ln[O=P(OPh)3]3Cl3, Ln[O=P(CH2CH2CF3)]3Cl3 and Ln[O=P(CH=CHPh)3]3Cl3 have been synthesised, and their absorption spectra have been measured in both films and solutions.

The paper presents the results of a study of the spatial structure of Si-containing [poly(ethynediyl-arylene-ethynediyl-silylene)] composites in the nanometer scale, as well as of an optical study of photorefractive effects in the visible and near-infrared ranges in these composites. The compositions have been examined using transmission/diffractio...

Spectroscopic characteristics, i.e. absorption, fluorescence, fluorescence excitation spectra, fluorescence decay time, fluorescence polarization degree of novel silicon-containing organic polymers including main chain anthracene groups were investigated. Three kinds of emission spectra were revealed and assigned to polaron–exciton, anthracene and...

Self-organisation through π-stacking occurs in poly[(ethynediyl)(arylene)(ethynediyl)silylene]–N-ethylcarbazole–poly(phenylsilsesquioxane) compositions giving rise to nanostructured hybrid layered materials exhibiting photorefraction at telecommunication wavelengths. To our knowledge, this is the first such material to be reported the poly[(ethyned...

In this paper spectroscopic characteristics of two new carbosilane polymers 1 and 2 containing anthracene and acetylene units in their main chain is discussed. To investigate excitation energy migration along the polymeric chain we have measured the fluorescence polarization characteristics

The spectroscopic characteristics of novel -conjugated polymers containing four-coordinated silicon, acetylene groups and either 1,4-biphenylene or 2,7-fluorene in the main chain were investigated by steady-state and picosecond laser spectroscopy. The spectral features of absorption, fluorescence excitation spectra, fluorescence lifetime, and fluor...

Novel unique organometallic nanomaterials with high nonlinearities of various types (nonresonant, resonant, photorefractive) have been prepared. Two main kinds of nanomaterials actualizing the different nonlinear-optical processes have been created: 1) polymeric photorefractive nanocomposites with very low glass transition temperatures (ca. 8 deg C...