A New Supramolecular Tetraruthenated Cobalt (II) Porphyrazine Displaying Outstanding Electrocatalytical Performance in Oxygen Evolution Reaction.

A new supramolecular electrocatalyst for Oxygen Evolution Reaction (OER) was synthesized from a central multibridging cobalt tetrapyridylporphyrazine (CoTPyPz) species by attaching four [Ru(bpy)2Cl]+ groups. Both CoTPyPz and the tetraruthenated cobalt porphyrazine species, TRuCoTPyPz, form very homogenous molecular films just by dropcasting their methanol solutions onto GCE electrodes. Such films exhibited low overpotentials for O2 evolution, e.g., 560 e 340 mV, respectively, displaying high stability, typically exceeding 15 h. The kinetic parameters obtained from the Tafel plots showed that the peripheral complexes are very important for the electrocatalytic activity. Hyperspectral Raman images taken along the electrochemical process demonstrated that the cobalt center is the primary active catalyst site, but its performance is enhanced by the ruthenium complexes, which act as electron-donating groups, in the supramolecular system.

Orange-Emitting ZnSe: Mn2+ quantum dots as nanoprobes for macrophages

The biocompatibility, bionanointeraction, uptake efficiency, and entry pathway of luminescent nanomaterials are the key factors to understand development of an efficient bionanoprobe. The foremost objective of this work is to explore the potential of 3-mercaptopropionic acid (3-MPA) capped ZnSe:xMn2+ (x = 5, 10, and 15 mol %) quantum dots (QDs) for the development of bionanoprobe used in future biological and clinical applications. For this purpose, highly intense orange-emitting activator Mn2+ ion doped ZnSe QDs were synthesized via a high-temperature organometallic method and rendered water-soluble by a ligand exchange approach. The morphological and physicochemical characterizations displayed the ultrasmall zinc-blend cubic crystal structure of QDs with an elliptical shape nanocrystals and average diameter of 4 nm. The luminescent nanomaterials exhibited orange emission centered at 584 nm under excitation at 385 nm. The biocompatibility, time-dependent cellular uptake, and the uptake mechanism of QDs were studied in RAW 264.7 macrophages, accomplished by various cytotoxicity assays, CytoViva hyperspectral enhanced dark-field and dual-mode fluorescence (DMF) microscopy, and transmission electron microscopy (TEM) images. The cytotoxicity study did not confirm any noticeable deleterious effect of QDs within incubation for 6 h. The fluorescence images of cells incubated with QDs showed efficient emission, which is a manifestation that QDs are photochemically stable in the intracellular environment. The cellular uptake findings demonstrated that the QDs were predominantly internalized via clathrin- and caveolae-mediated pathways. After the uptake, QDs aggregates appeared inside the vesicles in the cytoplasm, and their number and size gradually increased as a function of time. Nevertheless, the fluorescent QDs presented remarkable colloidal stability in various media, biocompatibility within the designated time, efficient time-dependent uptake, and distinct entry pathway in RAW macrophages, suggesting promising candidates to explore for the development of future bionanoprobes.

Unravelling the nature of the spongy dark material in aged Turkevich gold nanoparticles colloidal solutions by CytoViva® dark-field imaging and HRTEM analysis.

Turkevich gold nanoparticles colloidal solutions undergo further changes after ageing for several weeks or months, and in most cases a spongy dark material can be observed suspended in the red solution. CytoViva® dark-field microscopy images and high resolution transmission electron micrographys (HRTEM) of the strange body played a central role and revealed a fibrous structure, consistent with cellulose, as commonly found in the cell-walls of many fungi. Surprisingly, the interior of the fibers are filled with gold nanoparticles, responsible for the high contrasting images obtained in this work. The fungi were replicated in the laboratory, characterized by Infrared Microscopy (FTIR) and revealed an ability to grow in gold-citrate media, even in dark and anaerobical conditions.

Hyperspectral dark-field microscopy of gold nanodisks.

The light scattering properties of hexagonal and triangular gold nanodisks were investigated by means of Cytoviva hyperspectral dark-field microscopy, exploring the huge enhancement of the scattered waves associated with the surface plasmon resonance (SPR) effect. Thanks to the high resolution capability of the dark-field microscope, the SPR effect turned it possible to probe the individual nanoparticles directly from their hyperspectral images, extrapolating the classical optical resolution limit, and providing their corresponding extinction spectra. Blue spectral shifts involving the in-plane dipolar modes were observed for the hexagonal gold nanodisks in relation to the triangular ones, allowing their spectroscopic differentiation in the dark-field images.

Effect of cations/polycations on the efficiency of formation of a hybrid bilayer membrane that mimics the inner mitochondrial membrane.

We aim in this study to characterize the effect of cations and polycations on the formation of hybrid bilayer membranes (HBMs), especially those that mimic the inner mitochondrial membrane (IMM), with a proper composition of phosphatidylcholine (PC), phosphatidylethanolamine (PE) and cardiolipin (CL) adsorbed on an alkanethiol monolayer. HBMs are versatile membrane mimetics that show promising results in sensor technology. Its formation depends on the fusion of vesicles on hydrophobic surfaces, a process that is not well understood at the molecular level. Our results showed to which extend and in which condition the presence of cations and polycations facilitate the formation of HBMs. The required time for lipid layer formation was reduced several times and the lipid layer reaches the expected thickness of 19.5±1.8 Ǻ, in contrast to only 2±1.5 Ǻ usually observed in the absence of cations. In the presence of specific concentrations of spermine and Ca(2+) the amount of adsorbed phospholipids on the thiol layer increased nearly 70% compared to that observed when Na(+) was used at concentrations 10 times higher. Divalent cations and polycations adsorb specifically on the lipid headgroups destabilizing the hydration forces, facilitating the process of vesicle fusion and formation of lipid monolayers. The concepts and conditions described in the manuscript will certainly help the development of the field of membrane biosensors.

Catalytic properties of thioredoxin immobilized on superparamagnetic nanoparticles.

Thioredoxin (Trx1), a very important protein for regulating intracellular redox reactions, was immobilized on iron oxide superparamagnetic nanoparticles previously coated with 3-aminopropyltriethoxysilane (APTS) via covalent coupling using the EDC (1-ethyl-3-{3-dimethylaminopropyl}carbodiimide) method. The system was extensively characterized by atomic force microscopy, vibrational and magnetic techniques. In addition, gold nanoparticles were also employed to probe the exposed groups in the immobilized enzyme based on the SERS (surface enhanced Raman scattering) effect, confirming the accessibility of the cysteines residues at the catalytic site. For the single coated superparamagnetic nanoparticle, by monitoring the enzyme activity with the Ellman reagent, DTNB=5,5'-dithio-bis(2-15 nitrobenzoic acid), an inhibitory effect was observed after the first catalytic cycle. The inhibiting effect disappeared after the application of an additional silicate coating before the APTS treatment, reflecting a possible influence of unprotected iron-oxide sites in the redox kinetics. In contrast, the doubly coated system exhibited a normal in-vitro kinetic activity, allowing a good enzyme recovery and recyclability.

Probing magnetic and gold nanoparticles by using MAClevers® as ultrasensitive sensors.

Magnetic AFM probes known as MAClevers® were employed for sensing picogram amounts of magnetic nanoparticles, based on the cantilever frequency shifts resulting from the magnetically induced adsorption of mass. By using organothiol functionalized magnetic nanoparticles, this analytical strategy was successfully extended to the detection of gold nanoparticles, as confirmed by confocal Raman microscopy.

Conduction and photoelectrochemical properties of monomeric and electropolymerized tetraruthenated porphyrin films.

The influence of the preparation method on the structure, conduction and photoelectrochemical properties of monomeric and polymeric tetraruthenated porphyrin films on ITO glass and nanocrystalline TiO2 has been investigated. The films were characterized by STM, MAC mode SFM, cyclic voltammetry, electrochemical impedance spectroscopy (EIS) and combined electro-/photoelectrochemical techniques. The electronic diffusion coefficient D(e)C(m)2 of the films differed by three to four orders of magnitude depending on the procedure employed for the deposition process. The photoelectrochemical properties were evaluated either: by depositing the films directly on transparent ITO electrodes, under an applied bias potential and presence of O2 as electron acceptor; or by depositing the porphyrin material on nanocrystalline TiO2 in a Grätzel-type cell. In the first case the porphyrin films exhibited a typical p-type semiconductor behavior described by a Schottky junction model, while in the second the films behaved as a sensitizer of an n-type semiconductor. The photoelectrochemical properties of the porphyrin films and their performance as sensitizer in Grätzel-type cells were found to be strongly dependent on the conductivity and packing characteristics of the material. Semi-empirical calculations were performed by modified MM2 and ZINDO/S methods, in order to simulate the packing and electronic structures of the tetraruthenated porphyrin.

Sensitization of TiO(2) by supramolecules containing zinc porphyrins and ruthenium-polypyridyl complexes.

Modification of wide band gap semiconductor surfaces by a new generation of supramolecular sensitizers combining porphyrin and ruthenium-polypyridyl complexes leads to versatile molecular interfaces, allowing the exploitation of photoinduced charge transfer in photoelectrochemical devices.

Photoelectrochemical properties of supramolecular species containing porphyrin and ruthenium complexes on TiO(2) films.

Modification of wide band gap semiconductor surfaces by a new generation of supramolecular sensitizers, combining porphyrin and ruthenium-phenanthroline complexes leads to versatile molecular interfaces, allowing the exploitation of photoinduced charge transfer in dye sensitized photoelectrochemical cells. meso-Tetrapyridylporphyrin coordinated to two ruthenium complexes converts 21% of the incident photons into current after excitation at the Soret band. In this work we discuss the electron/energy transfer mechanisms involved in the TiO(2) sensitization by these supramolecular species, invoking some theoretical calculations.