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The review is concerned with studies on peculiar features of supramolecular organization of phthalocyanines (Pc) bearing complex-forming substituents (15-crown-5, 2-oxyphenylphosphonic acid residues) in organized aqueous microheterogeneous media based on cationic and anionic surfactants, bile salts (BS) including sodium deoxycholate (SDC), as well as polyelectrolytes and amphiphilic polymers including a phosphate buffer (pH 7.4). Organized, SDC-based fluorescence-active phthalocyanine-containing hydrogels obtained for the first time are also considered. In vitro accumulation and localization of Pc in human cervical adenocarcinoma cells, HeLa, as well as the photochemical and sensitizing properties of Pc including light cytotoxicity and photoinduced generation of reactive oxygen species were demonstrated taking octa-crown-substituted magnesium phthalocyaninate as an example.

The behavior of crown- and phosphoryl-containing magnesium and zinc phthalocyaninates in solutions of synthetic and natural surfactants is studied. In a phosphate buffer (рН 7.4), zinc phthalocyaninate bearing oxy(pentyloxy)phosphoryl groups in peripheral substituents of the macrocycle is in aggregated state. According to absorption and fluorescence spectroscopy data, adding oppositely charged synthetic and natural surfactants leads to monomerization of this compound. The degree of monomerization of magnesium octa[(4´-benzo-15-crown-5)oxy]-phthalocyaninate in a microheterogeneous medium is affected by the concentration of sodium cholate and ionic strength. Fluorescence-active supramolecular gels based on sodium deoxycholate were prepared using phosphoryl-containing zinc phthalocyaninate.

Methods of absorption and fluorescence spectroscopy and, in some cases, small angle X-ray scattering, are used to study solubilization and supramolecular organization of octa[(4'-benzo-15-crown-5)-oxy]phthalocyanines (Pc), H2cr8Pc, and Mgcr8Pc in an aqueous medium in the presence of polyelectrolytes, sodium polystyrene sulfonate, and sodium carboxymethyl cellulose or their mixtures with anionic surfactants: sodium dodecyl benzene sulfonate and sodium deoxycholate. The obtained results indicate the appearance of a monomeric, fluorescent state of Mgc8Pc in the presence of sodium polystyrene sulfonate and at the further increase in its concentration with an increase in the solution ionic strength and addition of anionic sodium deoxycholate. In all cases, the monomeric state of Mgcr8Pc is confirmed by the data of fluorescence spectroscopy. Photobleaching of Mgcr8Pc solubilized in the monomer form is observed in aqueous micellar solutions of sodium dodecylsulfate and sodium dodecyl benzene sulfonate. In the presence of PSS/NaCl, aqueous solutions of Mgcr8Pc were also studied using dynamic light scattering and small-angle X-ray scattering.

This work is dedicated to low-molecular hydrogels based on biodegradable sodium deoxycholate (SDC) and lysine hydrochloride (lys × HCl) with magnesium octa-[(4'-benzo-15-crown-5)-oxy]phthalocyaninate (Mgcr8Pc) as the active component, namely, their synthesis, spectral properties of gel-solubilized Mgcr8Pc, its release from the gel etc. Addition of Mgcr8Pc occurs both via the mixing of the components and via its diffusion from the aqueous solution into the phase of the formed SDC/lys × HCl gel. Mgcr8Pc-containing hydrogels are thermoreversible. The state of Mgcr8Pc in the SDC/lys × HCl/NaCl gel at the room temperature and in the melt is studied using spectral methods. Gel melting releases Mgcr8Pc in the form of a micelle-bound monomer. The presence of the Mgcr8Pc monomer phase in the phthalocyanine-carrying supramolecular hydrogel causes fluorescent activity of the latter.

Crown-containing Pc Mg[(B15C5O)8Pc], Mg[(B15C5O)4Pc], and Mg[(15C5)4Pc] are in the monomolecular state in solutions of synthetic anionic surfactants: sodium dodecylsulfate and sodium dodecylbenzenesulfonate. In micellar solutions of bile-acid salts, molecular organization of crown-substituted Pc with different methods of introduction of crown groups into the macrocycle and their different numbers changes their state from predominantly monomeric for Mg[(B15C5O)8Pc] in the presence of NaCl to the aggregated one in the case of Mg[(15C5)4Pc)]. Magnesium phthalocyaninate with annulated (15-crown-5)-fragments, Mg[(15C5)4Pc], is characterized by the highest sensitivity to the structure of the micelle-forming biocompatible surfactant.

Nowadays, the study of well-known sensitizers for photodynamic therapy and search for new ones are intensively conducted. In the present work supramolecular organization of crown-ether and phosphoryl-containing phthalocyanines ({Mgcr8Pc, I, and М[R4Pc] (M = Zn2+, R = -OPhP(O)(OH)(OC5H11), II; M = 2H+, R = -OPhP(O)(OH)(OC5H11), III; M = 2H+, -OPhP(O)(OH)2), IIIa}, respectively) was studied in microheterogeneous media. The role of a metal ion of a macrocycle in monomerization of phosphoryl-containing Pc in the presence of water-soluble poly(N-vinylpyrrolidone) was revealed. Some photobiological properties of compound I as possible photosensitizer with respect to human adenocarcinoma cells, HeLa, were analyzed. So, the light and dark cytotoxicity of I (IC50 dose) was 1.83 μМ and higher than 25 μМ, respectively. The reactive oxygen species (ROS) formation studied with use of fluorescent ROS detector DCFH2 revealed the plateau on the curves of fluorescence intensity vs time after 30 min of irradiation and ROS are almost not produced after the end of irradiation. In HeLa cells, accumulation of compounds I and II as well as fluorescent DCF presence were shown by confocal microscopic images. At concentration of 5 μM, compound I easily penetrates into the cell localizing primarily in the perinuclear region, whereas compound II mainly remains in the periphery of the cells in the fluorescent-active state. The results obtained allow us to continue the study of these interesting compounds.

Investigations of activation of C–H bonds in mild conditions have been analyzed. Much attention is given to the Shilov chemistry. The Shilov system, namely, platinum (II) and (IV) halides in aqueous solution, has demonstrated the ability of homogenous catalysts to activate and functionalize saturated hydrocarbons including methane. Gold containing catalysts are intensely introduced in catalytic chemistry. For the first time, reactions of an aerobic and anaerobic oxidation of methane in the presence of gold complexes in an aqueous environment are also shown. High activity and selectivity in the activation of C–H bonds can be attained by developing catalysts including variously modified nanocarbons, for example, those based on fullerene, fullerene-containing materials and even chemically modified nanodiamonds.

Aggregation of magnesium octa-[(4′-benzo-15-crown-5)oxy]phthalocyaninate (Mgcr8Pc) in solutions of biocompatible anionic surfactant, sodium deoxycholate (SDC), was studied. It was shown using the electron absorption spectra that formation of Mgcr8Pc monomers in micellar solutions of SDC is affected by both increased surfactant concentration and by changes in the ionic strength of solution after sodium chloride is added. The effect of the chemical structure of biocompatible anionic surfactant on monomerization of crown-containing phthalocyanines was identified; this fact opens new possibilities for using this family of compounds for fluorescent diagnosis and photodynamic therapy.

The electrochemical behavior of several methanofullerenes, including methyl-C61-propionic acid esters (Ph-C61-(CH2)2COOC n H2n + 1, n = 1–4, 8), in tetraoctyl- and didodecyldimethylammonium bromide films on conducting glass was studied. A cyclic voltammetry study showed that the introduction of methanofullerene derivatives in a cation matrix led to redox transformations of these compounds at potentials accessible for aqueous solutions. The shift of their formal potentials toward positive values is mainly caused by the electrostatic interactions of the reduction products (methanofullerene anions) with the matrix cations. The chemical stability of the reduction products is provided by their hydrophobic microenvironment in the matrix in all cases. This makes it possible to perform quasireversible redox transformations in neutral aqueous media. The duration of the adjustment of the structure of the coating depends on the solvent used for its preparation, the length of the alkyl radical in the ester group of methanofullerene, and the length of the alkyl chain between the cyclopropane fragment and the COOC n H2n + 1 group. The redox potentials of methanofullerene Ph-C61-(CH2)2COOC2H5 incorporated in the didodecyldimethylammonium bromide film lie in the range of higher negative values relative to the potentials of the compound in the tetraoctylammonium bromide film.

The behavior of octa-(benzo-15-crown-5)phthalocyanine (H2cr8Pc), as well as cobalt octa- and tetra-(benzo-15-crown-5)phthalocyaninates (Cocr8Pc and Cocr4Pc), in aqueous solutions containing cationic or anionic surfactants, such as cetyl trimethylammonium bromide (CTAB), sodium carboxymethyl cellulose (Na-CMC), and sodium dodecyl sulfate (SDS), is studied using electronic spectroscopy. The presence of eight benzo-15-crown-5 ether fragments on the periphery of the phthalocyanine ring is shown to facilitate the dissolution of Pc in an aqueous environment. The interactions between CTAB and crown-containing Pc promotes the dissolution of H2cr8Pc; Cocr8Pc; and, to a lesser degree, Cocr4Pc, which is accompanied by the appearance of molecular aggregates, including heteronuclear cofacial dimers. The presence of a metal in the ring is not the necessary condition of the process. In microscopically heterogeneous medium, such as an aqueous SDS-containing solution, H2cr8Pc is present in monomeric form at SDS concentrations close to Ccr and in dimeric form at SDS content below Ccr. Under similar conditions (environment, surfactant), Cocr4Pc can exist in monomeric form at SDS concentrations much high than Ccr. The effect of the size of cation on the form of the crown-containing Pc in an aqueous solution is illustrated by an example of H2cr8Pc. Na-CMC promotes the dissolution of Pc and enables one to produce K+/Mcr8Pc-modified films from aqueous solutions.

Investigations of activation of C–H bonds in mild conditions have been analyzed. Much attention is given to the Shilov chemistry. The Shilov system, namely, platinum (II) and (IV) halides in aqueous solution, has demonstrated the ability of homogenous catalysts to activate and functionalize saturated hydrocarbons including methane. Gold containing catalysts are intensely introduced in catalytic chemistry. For the first time, reactions of an aerobic and anaerobic oxidation of methane in the presence of gold complexes in an aqueous environment are also shown. High activity and selectivity in the activation of C–H bonds can be attained by developing catalysts including variously modified nanocarbons, for example, those based on fullerene, fullerene-containing materials and even chemically modified nanodiamonds.

Using cyclic voltammetry, it is shown that formal reduction potentials of pyridyl-substituted pyrrolidinofullerenes are shifted to negative values as compared with formal potentials of the corresponding redoxtransitions of C60, which indicates weakening of the acceptor properties of the fullerene fragment. NIR spectrophotometric and EPR spectroscopic studies show that cis-2′,5′-di-(4-pyridinyl)pyrrolidino-[3′,4′:1,2][60]fullerene is reduced with 1,8-diazobicyclo[5.4.0]undec-7-ene and morpholine to give a radical anion.

1. A small yield of diphenyl is obtained in the presence of ruthenium hydroxychloride and oxalic acid in 50% ethyl alcohol. 2. The ruthenium hydroxychloride -sodium acetate system in acetic acid is an agent for oxidative combination of phenols. 3. In the presence of ruthenium hydroxychloride as catalyst hydrogen peroxide oxidizes 2,4,6-triterbutylphenol to 2,6-diterbutyl-1,4-benzoquinone and 4-hydroxy-2,4,6-triterbutyl-2,5-cyclohexadiene-1-one and oxidizes phenols (V) and (VI) to products of oxidative combination. 4. In the presence of palladium chloride and sodium acetate in an atmosphere of oxygen (or argon) only the products of oxidative combination of phenols (III) and V are obtained.

1. Organic catalysts of theπ-acceptor type of the reduction of 2,2,6,6-tetramethylpiperidone-4-oxy-1 with 2,6-dimethyl-3,5-dicarbethoxy-1,4-dihydropyridine were found. 2. Catalytic systems includingπ-acceptors were produced. In the presence of the catalytic system ofπ-acceptor and o-naphthoquinone, the reduction of 2,2,6,6-tetramethylpiperidone-4-oxy-1, nitro-compounds, and molecular oxygen with dihydropyridine compounds and cyclohexadiene-1,4 can be conducted. 3. The kinetics of the catalytic reduction of 2,2,6,6-tetramethylpiperidone-4-oxy-l was investigated. It was proposed that the mechanism of the action of the indicated catalysts and catalytic systems involves the formation ofπ-complexes including a reducing agent as the donor.