Vladimir A. Burilov

Complex Formation of d-Metal Ions at the Interface of TbIII-Doped Silica Nanoparticles as a Basis of Substrate-Responsive TbIII-Centered Luminescence

The complex formation of d-metal ions at the interface of Tb(III)-doped silica nanoparticles modified by amino groups is introduced as a route to sensing d-metal ions and some organic molecules. Diverse modes of surface modification (covalent and noncovalent) are used to fix amino groups onto the silica surface. The interfacial binding of d-metal ions and complexes is the reason for the Tb(III)-centered luminescence quenching. The regularities and mechanisms of quenching are estimated for the series of d-metal ions and their complexes with chelating ligands. The obtained results reveal the interfacial binding of Cu(II) ions as the basis of their quantitative determination in the concentration range 0.1-2.5 μM by means of steady-state and time-resolved fluorescence measurements. The variation of chelating ligands results in a significant effect on the quenching regularities due to diverse binding modes (inner or outer sphere) between amino groups at the interface of nanoparticles and Fe(III) ions. The applicability of the steady-state and time-resolved fluorescence measurements to sense both Fe(III) ions and catechols in aqueous solution by means of Tb(III)-doped silica nanoparticles is also introduced.

Supramolecular assemblies of triblock copolymers with hexanuclear molybdenum clusters for sensing antibiotics in aqueous solutions via energy transfer

The work introduces the supramolecular assembly of triblock copolymers, namely (PEO)13(PPO)30(PEO)13 (L64), (PPO)14(PEO)24(PPO)14 (17R4), (PPO)8(PEO)22(PPO)8 (10R5) and (PEO)21(PPO)67(PEO)21 (P123) with novel cluster complexes [K(diglyme)(CH3CN)]2[Mo6I14] (1) and [K2(diglyme)(CH3CN)5][Mo6I14] (2) as a route to increase their water solubility. Dynamic light scattering and photophysical measurements reveal the decisive influence of the arrangement of PEO and PPO blocks and of their length on both colloidal and photophysical properties of these solutions. ES-MS data reveal [Mo6I14]2− clusters as the predominant form in aqueous solutions of L64 and P123. The steady state and time resolved luminescence data indicate concentration dependent sensitizing of the Mo-centered luminescence through the energy transfer from difloxacin to [Mo6I14]2− mediated by the ion-pairing. The impact of both arrangement and length of PEO and PPO blocks in the luminescent response of [Mo6I14]2− to difloxacin is discussed. The aqueous solutions of L64 at pH 4 provide the optimal conditions for the sensing of difloxacin through the cluster luminescence.

A facile synthetic route to convert Tb(III) complexes of novel tetra-1,3-diketone calix[4]resorcinarene into hydrophilic luminescent colloids

The work presents the synthesis of a novel calix[4]resorcinarene cavitand bearing four 1,3-diketone groups at the upper rim and its complex formation with Tb(III) ions in DMF and DMSO solutions. Electrospray ionization mass spectra, 1H NMR, UV-Vis and luminescence spectra indicate a long (three hours at least) equilibration time for the complex formation between the cavitand and Tb(III) in alkaline DMF and DMSO solutions. These results are explained by the restricted keto–enol conversion, resulting from the steric hindrance effect of the methylenedioxy-groups linking the benzene rings within the cavitand framework. A facile synthetic route to convert luminescent Tb(III) complexes of various stoichiometries into luminescent hydrophilic colloids is disclosed in this work. The route is based on the reprecipitation of the Tb(III) complexes from DMF to aqueous solutions with further polyelectrolyte deposition without prior separation of the luminescent complexes. The luminescent colloids exhibit high stability over time and in buffer systems, which is a prerequisite for their applicability in analysis and biolabeling.

Temperature induced phase separation of luminescent silica nanoparticles in Triton X-100 solutions

The aggregation and cloud point behavior of Tb(III)-doped silica nanoparticles has been studied in Triton X-100 (TX-100) solutions at various concentration conditions by fluorimetry, dynamic light scattering, electrophoresis and transmission electron microscopy methods. The temperature responsive behavior of nanoparticles is observed at definite concentration of TX-100, where the aggregation of TX-100 at the silica/water interface is evident from the increased size of the silica nanoparticles. The reversible dehydration of TX-100 aggregates at the silica/water interface should be assumed as the main reason of the temperature induced phase separation of silica nanoparticles. The distribution of nanoparticles between aqueous and surfactant rich phases at the phase separation conditions can be modified by the effect of additives.

“Clickable” thiacalix[4]arene derivatives bearing polymerizable 1,3-butadiyne fragments: synthesis and incorporation into polydiacetylene vesicles

p-tert-Butylthiacalix[4]arene derivatives in 1,3-alternate stereoisomeric form bearing polymerisable 1,3-butadiyne fragments on the one side and amino/carboxylic groups on another were synthesized using stepwise functionalisation. Calixarene 7 embedded in polydiacetylene nanoparticles showed a selective colorimetric response toward lanthanide ions.

Cyclic voltammetry of tris(2,2′-bipyridine)zinc(ii) diperchlorate detected by electron spin resonance

Electrochemical transformations of the tris(2,2′-bipyridine) complex of zinc(ii) perchlorate were studied by cyclic voltammetry detected by electron spin resonance (DESR CV), which made it possible to indentify the intermediates formed and to monitor the unpaired electron localization in them.

Electrochemical properties of n-sulfonatothiacalyx[4]arene complexes with Fe3+ and [Co(dipy)3]3+ ions

The electrochemical properties of n-sulfonatothiacalyx[4]arene (H4XNa4) complexes with [Co(dipy)3]3+ and Fe3+ ions were studied by means of cyclic voltammetry in aqueous solution at pH 2.5. The observed single-electron reduction of [Co(dipy)3]3+ bound extraspherically to the upper rim and Fe3+ ion bound intraspherically to the lower rim of n-sulfonatothiacalyx[4]arene in binary [Co(dipy)3]3+ · H3X5−, H3X5− · Fe3+, and ternary [Co(dipy)3]3+ · H3X5− · Fe3+ heterometal complexes was more difficult than in the free state. The reversible single-electron transfer to the metal ion results in lower binding energy ([Co(dipy)3]3+, ΔΔG0 = 3.9 kJ/mol) or in full fast dissociation of the complex (Fe3+). The ternary complex in the solution forms the aggregates, in which inner encapsulated Fe(III) and Co(III) ions are not reduced on the electrode. Their quantitative reduction takes place by the relay mechanism of intra- and intermolecular electron transfer through electrochemically generated [Co(dipy)3]2+ outer ions.

Thiacalix[4]arene-functionalized vesicles as phosphorescent indicators for pyridoxine detection in aqueous solution

Amphiphilic tetracarboxylate derivatives of p-tert-butylthiacalix[4]arene were obtained by click reactions of the corresponding azido derivatives with acetylene dicarboxylic acid. Embedding of the amphiphilic tetraacids in DPPC vesicles was studied by DLS, AFM, turbidity techniques and by probing with merocyanine 540. The obtained DPPC–calixarene vesicles are effective antennae for Tb(III) ion luminescence. It allows the use of DPPC–calixarene-Tb(III) vesicles for the selective detection of analytes with a higher affinity for Tb(III) due to cation removal from the calixarenes in the DPPC bilayer. It was found that pyridoxine hydrochloride can be selectively detected at the 7 μM concentration in the presence of a 100 fold excess of different biologically important molecules, like amino acids, adenosine phosphates, sugars, amines and ammonium salts.

The discrimination between phospholipids of diverse structure and phosphacoumarins of various hydrophobicity through fluorescent response of Tb-doped silica nanoparticles decorated by cationic surfactant.

The work represents colloids of silica nanoparticles displaying fluorescent response on biorelevant compounds exemplified by phosphacoumarins and phospholipids. The luminescent properties of the colloids arise from Tb(III) complexes doped into silica nanoparticles (SNs). The noncovalent decoration of SNs by dicationic surfactant with further interfacial binding of dye anions enables to develop colloids programmed to display a substrate induced fluorescent response. The latter results from the quenching of Tb(III) centered luminescence by dye anions through dynamic mechanism and subsequent displacement of quenching anions by the non-quenching substrates from the interface of SNs. Both negative charge and hydrophobicity of substrates are the key factors affecting the selectivity of the substrate induced fluorescent response. The peculiar effects of zwitter-ionic and anionic phospholipids on the fluorescent response have been revealed. The applicability of the fluorescent procedure in the sensing of impurities in commercial phosphatidylcholine is also introduced.

Synthesis and fluorescent properties of thiacalix[4]arenes containing terpyridyl fragments at the lower rim

New thiacalix[4]arenes tetrasubstituted by terpyridyl fragments at the lower rims in the 1,3-alternate stereoisomeric form were synthesized. The molecules interact with EuIII and TbIII in the DMF solution to form highly luminescent nanoscale (21–26 nm) metal-organic structures with the 2: 1 metal-to-ligand stoichiometry and a narrow particle size distribution.