Glassy carbon electrode modified with a film of tetraruthenated nickel(ii) porphyrin located in natural smectite clay's interlayer for the simultaneous sensing of dopamine, acetaminophen and tryptophan.

A supramolecular complex µ-meso-tetra(4-pyridyl) porphyrinate nickel(ii)tetrakis[bis(bipyridine)(chloro)ruthenium(ii)] ([NiTPyP{Ru(bipy)2Cl}4]4+) was intercalated into the interlayer space of natural smectite clay (shortened as Ba) collected in a Cameroonian deposit at Bagba hill. Physicochemical characterization of the resulting material using ultraviolet-visible spectroscopy (UV-vis), Fourier transform infrared (FTIR) spectroscopy, and X-ray diffraction (XRD) confirmed the intercalation of the porphyrin within the interlayer space of the clay. The intercalated clay was then used to form a stable thin film onto a glassy carbon electrode (GCE) by drop casting a suspension of the hybrid material. The GCE modified with the intercalated organoclay endowed the electrode with a larger electrochemically active surface area, good stability, high selectivity, and sensitivity toward dopamine (DA), acetaminophen (AC) and tryptophan (Trp). In addition, it was observed that the modified electrodes exhibited good and pH-dependent electrocatalytic properties toward these analytes. The simultaneous determination of DA, AC and Trp at [NiTPyP{Ru(bipy)2Cl}4]4+-Ba/GCE was thus possible without the interference of one analyte on the others, and the resulting calibration curve exhibits two segments for the three analytes. For DA, AC and Trp, the detection limits were found to be 0.8 µM, 0.3 µM and 0.3 µM, respectively. The [NiTPyP{Ru(bipy)2Cl}4]4+-Ba/GCE modified electrodes were successfully applied for the determination of AC in Paracetamol, a commercial product, and Trp in real pharmaceutical formulation samples.

Quantum-Dot-Based Iron Oxide Nanoparticles Activate the NLRP3 Inflammasome in Murine Bone Marrow-Derived Dendritic Cells.

Inflammasomes are cytosolic complexes composed of a Nod-like receptor, NLR, the adaptor protein, ASC, and a proteolytic enzyme, caspase-1. Inflammasome activation leads to caspase-1 activation and promotes functional maturation of IL-1ß and IL-18, two prototypical inflammatory cytokines. Besides, inflammasome activation leads to pyroptosis, an inflammatory type of cell death. Inflammasomes are vital for the host to cope with foreign pathogens or tissue damage. Herein, we show that quantum-dot-based iron oxide nanoparticles, MNP@QD, trigger NLRP3 inflammasome activation and subsequent release of proinflammatory interleukin IL-1ß by murine bone marrow-derived dendritic cells (BMDCs). This activation is more pronounced if these cells endocytose the nanoparticles before receiving inflammatory stimulation. MNP@QD was characterized by using imaging techniques like transmission electron microscopy, fluorescence microscopy, and atomic force microscopy, as well as physical and spectroscopical techniques such as fluorescence spectroscopy and powder diffraction. These findings may open the possibility of using the composite MNP@QD as both an imaging and a therapeutic tool.

Magnetic alignment of rhodamine/magnetite dual-labeled microtubules probed with inverted fluorescence microscopy.

Molecular machines, as exemplified by the kinesin and microtubule system, are responsible for molecular transport in cells. The monitoring of the cellular machinery has attracted much attention in recent years, requiring sophisticated techniques such as optical tweezers, and dark field hyperspectral and fluorescence microscopies. It also demands suitable procedures for immobilization and labeling with functional agents such as dyes, plasmonic nanoparticles and quantum dots. In this work, microtubules were co-polymerized by incubating a tubulin mix consisting of 7 biotinylated tubulin to 3 rhodamine tubulin. Rhodamine provided the fluorescent tag, while biotin was the anchoring group for receiving streptavidin containing species. To control the microtubule alignment and consequently, the molecular gliding directions, functionalized iron oxide nanoparticles were employed in the presence of an external magnet field. Such iron oxide nanoparticles, (MagNPs) were previously coated with silica and (3-aminopro-pyl)triethoxysilane (APTS) and then modified with streptavidin (SA) for linking to the biotin-functionalized microtubules. In this way, the binding has been successfully performed, and the magnetic alignment probed by Inverted Fluorescence Microscopy. The proposed strategy has proved promising, as tested with one of the most important biological structures of the cellular machinery.

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.

Analytical determination of gold ions based on ranelate induced nanoparticle formation.

A ranelate ion, an old antiosteoporotic drug, readily reacts with gold(III) ions generating stable gold nanoparticles (AuNP@Ran). The reaction proceeds rapidly under green conditions and is specific for gold ions at room temperature. Their characteristic color associated with the plasmonic resonance effects allows its use in colorimetric/spectrophotometric analysis, as well as in spot test assays. In addition to the color changes, the gold nanoparticles exhibit surface enhanced Raman scattering (SERS), providing another interesting route for the analytical detection of gold ions. Because of the great simplicity, the ranelate method can be very convenient for monitoring gold ions, especially in metal extraction and hydrometallurgical processes.

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.

A new ferrous diflunisal complex and its effects on biopools of labile iron.

Drugs bearing metal-coordinating moieties can alter biological metal distribution. In this work, a complex between iron(II) and diflunisal was prepared in the solid state, exhibiting the following composition: [Fe(diflunisal)2(H2O)2], (Fe(dif)2). The ability of diflunisal to alter labile pools of both plasmatic and cellular iron was investigated in this work. We found out that diflunisal does not increase the levels of redox-active iron in plasma of iron overloaded patients. However, diflunisal efficiently carries iron into HeLa or HepG2 cells, inducing an iron-catalyzed oxidative stress.

Extraction of Dysprosium Ions with DTPA Functionalized Superparamagnetic Nanoparticles Probed by Energy Dispersive X-ray Fluorescence and TEM/High-Angle Annular Dark Field Imaging.

The extraction of dysprosium (Dy3+) ions from aqueous solution was carried out successfully, using magnetite (Fe3O4) nanoparticles functionalized with diethylenetriaminepentaacetic acid (MagNP@DTPA). The process was monitored by energy dispersive X-ray fluorescence spectroscopy, as a function of concentration, proceeding according to a Langmuir isotherm with an equilibrium constant of 2.57 × 10-3 g(MagNP) L-1 and a saturation limit of 63.2 mgDy/gMagNP. The presence of paramagnetic Dy3+ ions attached to the superparamagnetic nanoparticles led to an overall decrease of magnetization. By imaging the nanoparticles surface using scanning transmission electron microscopy equipped with high resolution elemental analysis, it was possible to probe the binding of the Dy3+ ions to DTPA, and to show their distribution in a region of negative magnetic field gradients. This finding is coherent with the observed decrease of magnetization, associated with the antiferromagnetic coupling between the lanthanide ions and the Fe3O4 core.

Can in vivo surface dental enamelmicrobiopsies be used to measure remote lead exposure?

Measuring lead in the surface dental enamel (SDE) using biopsies is a rapid, safe, and painless procedure. The dental enamel lead levels (DELLs) decrease from the outermost superficial layer to the inner layer of dental enamel, which becomes crucial for the biopsy depth (BD) measurement. However, whether the origin of lead found in SDE is fully endogenous is not yet established. There is also controversy about the biopsy protocol. The aims of this study were to investigate if DELLs are altered by extrinsic contamination (A) and to evaluate the real geometric figure formed by the erosion provoked by biopsy procedure and the respective BD in SDE (B). To accomplish the aim A, lead from 90 bovine incisor crowns lead was determined by graphite furnace atomic absorption spectrometer as a function of exposure time and lead concentration. Two biopsies were performed in each tooth, before and after lead exposure. Six 15-tooth groups differed by exposure time (1 or 30 min) and lead concentrations (A. 0 mg/L-placebo, B. 0.01 mg/L-standard for drinking water, or C. 0.06 mg/L-concentration found in contaminated groundwater). Phosphorus was determined by an inductively coupled plasm optical emission spectrometer to quantify the enamel removed. To compare intakes/losses of lead in SDE among the groups, values of DELL differences between before and after lead exposure were compared by ANOVA (p < 0.05). To attain the objective B, one extracted human permanent tooth was studied by confocal Raman microscopy. Lead measurements and the surface profile were determined. There was no difference in DELL among the groups (p = 0.964). The biopsy bottom surface area, analyzed by microscopy, showed an irregular area, with regions of peaks and valleys, where areas with depth ranging from 0.2 (peaks) to 1.8 µm (valleys) (± 0.1 µm) could be found. BD carried out in vivo is commonly calculated using the cylinder height formula. The real BD was shown to be very similar to already published data. In conclusion, the SDE of erupted teeth does not seem to be susceptible to environmental lead intake, being thus reliable to measure remote exposures to lead.

Ultrasmall cationic superparamagnetic iron oxide nanoparticles as nontoxic and efficient MRI contrast agent and magnetic-targeting tool.

Fully dispersible, cationic ultrasmall (7 nm diameter) superparamagnetic iron oxide nanoparticles, exhibiting high relaxivity (178 mM(-1)s(-1) in 0.47 T) and no acute or subchronic toxicity in Wistar rats, were studied and their suitability as contrast agents for magnetic resonance imaging and material for development of new diagnostic and treatment tools demonstrated. After intravenous injection (10 mg/kg body weight), they circulated throughout the vascular system causing no microhemorrhage or thrombus, neither inflammatory processes at the mesentery vascular bed and hepatic sinusoids (leukocyte rolling, adhesion, or migration as evaluated by intravital microscopy), but having been spontaneously concentrated in the liver, spleen, and kidneys, they caused strong negative contrast. The nanoparticles are cleared from kidneys and bladder in few days, whereas the complete elimination from liver and spleen occurred only after 4 weeks. Ex vivo studies demonstrated that cationic ultrasmall superparamagnetic iron oxide nanoparticles caused no effects on hepatic and renal enzymes dosage as well as on leukocyte count. In addition, they were readily concentrated in rat thigh by a magnet showing its potential as magnetically targeted carriers of therapeutic and diagnostic agents. Summarizing, cationic ultrasmall superparamagnetic iron oxide nanoparticles are nontoxic and efficient magnetic resonance imaging contrast agents useful as platform for the development of new materials for application in theranostics.

Fluorescent tetraruthenated porphyrins embedded in monolithic SiO2 gels by the sol-gel process.

In this work silica gels have been prepared by a sol-gel method using tetraethylorthosilicate as gel precursor. The tetraruthenated porphyrins H2(3-TRPyP), Co(3-TRPyP), and H2(4-TRPyP) were incorporated into the systems during gel formation without problems commonly found in the process, such as aggregation. Spectroscopic studies of the resulting silica gels revealed the presence of absorption bands in the range 200-400 nm associated with the transitions of the groups ruthenium-bipyridine, along with the Soret band at the same wavelengths observed in solution. The porphyrins were found to preserve fluorescence emission properties in the range 650-700 nm even after the aging period. Study of the thermal behavior and decomposition kinetics evidenced that the porphyrin H2(4-TRPyP) is the least stable of the group and that all compounds decompose according to first-order kinetics.

Polymetallated porphyrin ultrathin films as transducing elements for molecular devices and logic gates.

Meso-tetrapyridylporphyrins peripherally coordinated to four ruthenium complexes, such as [Ru(bpy)2Cl] and [Ru(5-ClPhen)2Cl] (bpy = 2,2'-bipyridine; Phen = 1,10-phenanthroline), provide a versatile class of molecular materials in which the complexes act as co-factors, inducing electronic effects and acting as electron-transfer relays and electron pools or sinks, depending upon their oxidation state. These cationic porphyrins can be assembled into thin films by conventional methods, or into organized layer-by-layer structures by combining with negatively charged tetrasulfonated porphyrins or phthalocyanines. Their electrocatalytic and photoelectrochemical properties have been successfully exploited in chemical sensors. Their usefulness in molecular logic gates are being demonstrated by using modified transparent conducting electrodes in miniaturized flow injection cells. In such designs, the chemical, electrochemical, and light inputs can be readily combined to perform the basic logic functions, such as AND, OR, and NOT, for molecular computing.

Interaction of 2- and 4-mercaptopyridine with pentacyanoferrates and gold nanoparticles.

2-Mercapto- and 4-mercaptopyridine (2- and 4MPy) react with the [Fe(CN)(5)(H(2)O)](3-) complex, forming the S-coordinated [Fe(CN)(5)(2MPy)](3-) and the N-coordinated [Fe(CN)(5)(4MPy)](3-) complexes. The rates of formation and dissociation of the [Fe(II)(CN)(5)(2MPy)](3-) complex were determined as k(f) = 294 dm(3) mol(-1) s(-1) and k(d) = 0.019 s(-1) by means of stopped-flow technique. The equilibrium constants for the iron(II) and -(III) species were calculated as K(f)(II) = 1.5 x 10(4) mol(-1) dm(3) and K(f)(III) = 1.3 x 10(6) mol(-1) dm(3), in comparison with 2.6 x 10(5) and 3.4 x 10(4) mol(-1) dm(3), respectively, for the 4MPy isomer. In the presence of gold nanoparticles, both 2- and 4MPy can displace the stabilizing citrate species, leading to substantial aggregation in aqueous solution, as deduced from the surface-enhanced Raman spectroscopy effect and from the decay of the 520-nm plasmon band accompanied by the rise of the characteristic exciton band at 650 nm. The [Fe(CN)(5)(4MPy)](3-) complex promotes strong stabilization of the gold nanoparticles by interacting through the S atom. On the other hand, the labile [Fe(CN)(5)(2MPy)](3-) complex induces aggregation, delivering the 2MPy ligand to the gold nanoparticles.

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.