Elena R. Ranyuk

Diaminoanthraquinone-linked polyazamacrocycles: efficient and simple colorimetric sensor for lead ion in aqueous solution.

A new colorimetric molecular sensor based on a 1,8-diaminoanthraquinone signaling subunit exhibits efficient binding for lead ion in water and allows naked-eye detection.

A new approach for the synthesis of 18F-radiolabelled phthalocyanines and porphyrins as potential bimodal/theranostic agents

The synthesis of a series of new fluorinated phthalocyanines and porphyrins as potential bimodal probes is evaluated. In these complexes, zinc phthalocyanine functions as a fluorescence imaging moiety while attachment of an aliphatic chain of different lengths bearing a tosylate group permits introduction of fluorine via nucleophilic substitution of the tosylate group. Using short-lived [18F]fluoride gives the analogous 18F-radiolabelled tracer rendering the bimodal probe suitable for both fluorescence and PET imaging.

Palladium-catalyzed amination in the synthesis of nitrogen and oxygen heterocycles containing fragments of cholane and quinoline

By Mitsunobu reaction from 3,24-cholanediol and 2-hydroxy-8-chloroquinoline 24-(8-chloroquinolinyl-2-oxy)cholan-3-ol and 3,24-di(8-chloroquinolinyl-2-oxy)cholane were synthesized. These compounds were brought into reactions of palladium-catalyzed amination with propanediamine, oxaalkane diamines, and N,N′-bis(3-aminopropyl)ethylenediamine to obtain macrocycles of various structures, linear mono- and bis(steroid) derivatives of trioxaalkane diamine, and also cholane bis(oxaalkandiamine) derivative. The dependence was demonstrated of macrocyles and cyclooligomers yield on the polyamine nature. 4-Hydroxy-7-chloroquinoline afforded only 24-(7-chloroquinolinyl-4-oxy)cholan-3-ol.

Synthesis of nitrogen- and oxygen-containing macrocycles by palladium-catalyzed amination of 3,24-bis(6-chloropyridin-2-yloxy)cholane

Abstract3,24-Bis(6-chloropyrdin-2-yloxy)cholane prepared from cholane-3,24-diol by the Mitsunobu reaction was successfully used to synthesize various polyaza macrocycles via palladium-catalyzed amination with linear polyamines. The contribution of side formation of cyclic oligomers was found to depend on the polyamine nature.

Preparation, characterization and photophysical properties of hybrid materials from rare earth complexes of phosphonato-substituted DOTAM derivatives

Europium complexes [Eu.L]X33 (X = SO3CF3, NO3) of (diethoxyphosphorylnaphthyl)-substituted DOTAM were prepared and incorporated into titania and zirconia inorganic matrices. Zirconia revealed an appropriate matrix to achieve an efficient sensitization of emitting lanthanides.

Palladium-catalyzed amination in the synthesis of macrocyclic compounds containing 1,3-disubstituted adamantane fragments

Palladium-catalyzed amination of 1,3-dibromobenzene, 2,6-dibromopyridine, 3,3′-dibromobiphenyl, 2,7-dibromonaphthalene, and 1,8-dichloroanthracene with an equimolar amount of 2,2′-(adamantane-1,3-diyl)diethanamine resulted in the formation of macrocyclic compounds containing one or several adamantane and one or several aromatic fragments. The reactions of 2,2′-(adamantane-1,3-diyl)diethanamine with excess 1,3-dibromobenzene, 2,6-dibromopyridine, 1,8-dichloroanthracene, and 1,8-dichloroanthraquinone gave the corresponding N,N′-diaryl derivatives. Polyaza macrocycles incorporating adamantane, aromatic, and 4,7,10-trioxatridecane-1,13-diamine fragments, were obtained by palladium-catalyzed amination of the N,N′-diaryl derivatives with 4,7,10-trioxatridecane-1,13-diamine.

Towards sensory Langmuir monolayers consisting of macrocyclic pentaaminoanthraquinone

A pentaazamacrocycle incorporating an intracyclic anthraquinone fragment (PENTAQ) was synthesized with the aim of forming metal-responsive Langmuir monolayers. PENTAQ allows a good discrimination by naked eye of copper ions in methanol–water solutions (50 : 50 v/v). Spectrophotometric investigations of the protonation and Cu2+ binding properties of PENTAQ were undertaken in order to gain a deeper insight into the pH-dependent speciation as well as the color changing process. PENTAQ monolayers at air/water and air/methanol–water interfaces were prepared according to the Langmuir procedure. The structure of the monolayers can be tuned by varying the pH of the aqueous subphase, since it was found that the relative orientation at the interface of the aromatic lipophilic and polyazaalkyl hydrophilic fragments is critically dependent upon the protonation state of the immersed pentaazamacrocyclic chain. In situ fiber-optic UV-vis measurements revealed the formation of H-aggregates in the PENTAQ monolayer deposited on a water subphase at pH = 5.5. The ability of these films to detect copper(II) in the aqueous or methanol–water (20 : 80 v/v, pH = 9.8) subphase was explored by combining several experimental techniques, including pressure–area measurements (π–A isotherms), in situ UV-vis absorption spectrophotometry, and XPS spectroscopy.

Palladium-catalyzed amination in the synthesis and modification of acyclic oxadiamino cholane derivatives

Palladium-catalyzed reactions of 24-(haloaryloxy)cholanes and 3,24-bis(haloaryloxy)cholanes with excess oxadiamines gave the corresponding mono- and bis(oxadiamino)-substituted cholanes which were subjected to palladium-catalyzed arylation with 1,3-dibromobenzene, 2,6-dibromopyridine, 1,8-dichloroanthracene, 9-bromoanthracene, 1-chloroanthracene, and 1-chloroanthraquinone. The results of these reactions were found to strongly depend on the haloarene nature. The arylation with 1,3-dibromobenzene and 2,6-dibromopyridine led to the formation of new macrocyclic compounds containing one cholane, one arene, and two oxadiamine fragments.

Synthesis of porphyrin-bis(polyazamacrocycle) triads via Suzuki coupling reaction

Suzuki–Miyaura cross-coupling reaction has been used for the synthesis of tricyclic architectures based on trans-A2B2-porphyrins and bisaminal-protected polyazamacrocycles which are linked directly or by a p-phenylene spacer. This modular approach allowed the synthesis of ligands with various substituted porphyrin macrocycles and bisaminal-protected tetraazamacrocycles possessing different cavity sizes. These molecules can be assembled into dimers using a DABCO linker. Deprotection of these compounds afforded porphyrin-bis(polyazamacrocycle) triads.