Nanoheterogeneous catalysis in electrochemically induced olefin perfluoroalkylation.

Ni-catalyzed electroreductive olefin perfluoroalkylation affords both monomeric and dimeric products depending on the reaction media. Recycling of the catalyst can be achieved by immobilization of a (bpy)NiBr2 complex on silica nanoparticles decorated with anchoring amino-groups. Switching the homogeneous and heterogeneous catalysts is found to be one more factor to control the product ratio. This catalytic technique is both green and atom economical and combines the advantages of nanoheterogeneous catalysis and electrocatalysis.

Tb(III)-doped silica nanoparticles for sensing: effect of interfacial interactions on substrate-induced luminescent response.

The present work introduces the easy modification of the water-in-oil microemulsion procedure aimed at the doping of the Tb(III) complexes within core or shell zones of the silica nanoparticles (SNs), which are designated as "core-shell", "shell", and "core". The dye molecules, chelating ligands, and copper ions were applied as the quenchers of Tb(III)-centered luminescence through dynamic or/and static mechanisms. The binding of the quenchers at the silica/water interface results in the quenching of the Tb(III) complexes within SNs, which, in turn, is greatly dependent on the synthetic procedure. The luminescence of "core" SNs remains unchanged under the binding of the quenchers at the silica/water interface. The quenching through dynamic mechanism is more significant for "core-shell" and "shell" than for "core" SNs. Thus, both "core-shell" and "shell" SNs have enough percentage of the Tb(III) complexes located close to the interface for efficient quenching through the energy transfer. The quenching through the ion or ligand exchange is most efficient for "core-shell" SNs due to the greatest percentage of the Tb(III) complexes at the silica/water interface, which correlates with the used synthetic procedure. The highlighted regularities introduce the applicability of "core-shell" SNs used as silica beads for phosphatidylcholine bilayers in sensing their permeability toward the quenching ions.

The energy transfer based fluorescent approach to detect the formation of silica supported phosphatidylcholine and phosphatidylserine containing bilayers.

The work introduces the quenching of silica coated Tb(III) complexes by merocyanine 540 (MC540) and copper ions as a tool to reveal the adsorption of phosphatidylcholine (PC) and phosphatidylserine (PS) at various PS:PC ratio onto silica nanoparticles doped with Tb(III) complex. The binding of MC540 with PC-based bilayers and copper ions with PS-based ones are the basis of their use as organic and inorganic probes to sense PS:PC ratio in silica supported mixed bilayers. The enrichment of mixed bilayers by PS results in the displacement of MC540 anions, while it enhances the binding with copper ions. The displacement or binding of probe ions results in the diverse luminescence response of Tb(III)-centred luminescence. The reestablishment of the steady state and time resolved luminescence is observed, when MC540 anions are applied as probes. The use of copper ions as probes results in the opposite quenching effect. The developed route enables to discriminate the formation of the phospholipids bilayers onto silica surface from those in the bulk of solution under various concentration conditions.

Determination of fluoroquinolone antibiotics through the fluorescent response of Eu(III) based nanoparticles fabricated by layer-by-layer technique.

The present work introduces the determination of fluoroquinolone antibiotics (FQs) in aqueous solutions through the fluorescent response of Eu(TTA)3 and [Eu(TTA)(3)1] (TTA(-) and 1 are thenoyltrifluoroacetonate and phosphine oxide derivative) complexes encapsulated into the polyelectrolyte capsules fabricated through layer-by-layer deposition of poly(sodium 4-styrenesulfonate) (PSS) and polyethyleneimine (PEI). The variation of luminescent core, polyelectrolyte deposition and concentration conditions reveals two modes of fluorescent response on FQs of diverse structure namely the sensitization and quenching of Eu(III) centered luminescence. The obtained regularities reveal the ternary complex formation and the ligand exchange occurring at the interface of polyelectrolyte coated [Eu(TTA)(3)1] based colloids as the reasons of the diverse fluorescent response of Eu(III) centered luminescence on FQs. The factors affecting the fluorescent response have been revealed, which are: the content of luminescent core, the mode of polyelectrolyte deposition, concentration and structure of FQs. The discrimination of moxifloxacin and lomefloxacin from levofloxacin, ofloxacin, difloxacin, perfloxacin through the quenching of Eu(III) luminescence in PSS-[Eu(TTA)(3)1] colloids has been revealed.

Complex formation of d-metal ions at the interface of Tb(III)-doped silica nanoparticles as a basis of substrate-responsive Tb(III)-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.