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Koiti Araki

Publications and source records attributed to Koiti Araki.

12 recordsLinked to original sources
PubMed2006

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.

Fluorescence↗
PubMed2006

Determination of n-octanol/water partition and membrane binding of cationic porphyrins.

Porphyrin and their derivatives are being systematically studied as photosensitizers for photodynamic therapy. The ability to predict their membrane partition properties is of key importance to unveil their in vivo activity and applications. Several n-octanol/water partition coefficients (logP(OW)) of porphyrin derivatives have been reported in the literature but large discrepancies have been observed. Reproducible and reliable logP(OW) data for a series of 20 cationic meso-phenyl(pyridyl)porphyrin derivatives were determined by correlating logP(OW) with the partition coefficients measured in a more adequate n-butanol/water system. Linear correlations as a function of the number of positively charged groups bound to the periphery of the porphyrin rings were found within each series. A significant effect of the stereochemistry and nature of the positively charged substituents was also observed, but diminished steadily converging to a similar value in the mono-substituted derivatives. Binding constants to liposomes were shown to be proportional to logP(OW), except for the cis-isomers of doubly charged porphyrins. The cis-isomer presented smaller logP(OW) and higher membrane affinity. The effect was explained based on the amphiphilic nature of the cis-porphyrin.

1-Octanol↗
PubMed2006

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.

Journal Article↗
PubMed2006

Preparation of very reactive thiol-protected gold nanoparticles: revisiting the Brust-Schiffrin method.

The preparation and properties of tert-dodecanethiol protected gold nanoparticles amenable to very rapid surface functionalization by associative mechanism is described. The new material can be easily prepared by controlling the reaction time, because only a limited but enough number of tert-dodecanethiol to stabilize the gold clusters is bond to the surface until about an hour. Accordingly, it can be isolated as a solid and handled much like the highly stabilized Brust-Schiffrin analogues, but reacted very rapidly with any molecular species containing one or multiple functional groups such as thiol, disulfide, pyridine, etc. These characteristics are ideal for the preparation of a variety of new organic-inorganic hybrid nanomaterials by coordinative self-assembly. This possibility was illustrated using meso-tetra(4-pyridyl)porphyrin, which promptly bonded to the reactive protected gold nanoparticles generating a solid that can be grown as thin films with layer-by-layer control on a suitably modified surface.

Adsorption↗
PubMed2006

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.

Computers, Molecular↗
PubMed2005

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.

Journal Article↗
PubMed2005

Cobalt oxide/tetraruthenated cobalt-porphyrin composite for hydrogen peroxide amperometric sensors.

A new composite material constituted by mu-{5,10,15,20-tetra(4-pyridyl)porphyrinato cobalt(iii)}-tetrakis-{chloro-bis-(2,2'-bipyridine)ruthenium(ii)} complex (or CoTRP) and cobalt oxide, exhibiting high stability and sensitivity for the quantification of hydrogen peroxide, was obtained by the electrochemical polymerization of the tetraruthenated cobalt porphyrin in alkaline medium. The optimized experimental conditions for the preparation of the modified glassy carbon electrodes and for analysis of H2O2 were carefully determined. Fast sequential analysis (120 determinations h(-1)) in a wide linear dynamic range (5.0 x 10(-7) mol L(-1) to 2.0 x 10(-3) mol L(-1)), with high sensitivity and low detection limit (2.0 x 10(-7) mol L(-1)), was achieved by using these electrodes and the batch injection analysis (BIA) technique. Such characteristics allied to a good stability were explored for the specific determination of hydrogen peroxide in six commercial cosmetics and pharmaceutical product samples, giving results in excellent agreement with those obtained by the spectrophotometric method.

Carbon↗
PubMed2004

Bridging nanogap electrodes by in situ electropolymerization of a bis(terthiophenylphenanthroline)ruthenium complex.

A novel complex containing a 3,8-bis[terthiophenyl-(1,10-phenanthroline)] ligand coordinated to [Ru(bpy)(2)] was synthesized and characterized by electrochemical and spectroscopic techniques. The complex was shown to be a suitable starting material for the electrodeposition of functionalized molecular wires between nanogap electrodes to generate stable molecular nanodevices. Temperature-dependent nonlinear I-V curves were obtained at 80-300 K. The material can also be deposited on indium tin oxide (ITO) to form compact electrochromic films at surface concentrations lower than approximately 1 x 10(-8) mol cm(2); however, a more loosely bond fibrous form is preferentially deposited at higher surface concentrations.

Journal Article↗
PubMed2004

Electrospray mass and tandem mass spectrometry of homologous and isomeric singly, doubly, triply and quadruply charged cationic ruthenated meso-(phenyl)m-(meta- and para-pyridyl)n (m + n = 4) macrocyclic porphyrin complexes.

Ten homologous or isomeric singly, doubly, triply and quadruply charged cationic macrocyclic complexes I-Va, bn+ (n = 1-4) formed by the coordination of [Ru(bipy)2Cl]+ to the pyridyl N-atoms of a series of meso-(phenyl)m-(meta or para-pyridyl)n-porphyrins (m + n = 4) were transferred to the gas phase and structurally characterized by electrospray ionization (ESI) mass (MS) and tandem mass (MS/MS) spectrometry. Previously known to be stable in solution and in the solid state, I-Va, bn+ are found to constitute also a new class of stable, long-lived multiply charged gas-phase ions with spatially separated charge sites. Increasing intramolecular electrostatic repulsion from Ia, b+ to IVa, b3+ facilitates in-source and tandem collision-induced dissociation (CID). However, for the quadruply charged ions Va, b4+, electrostatic repulsion is alleviated mainly by ion pairing with the CF3SO3- counterion forming the salt clusters [Va,b/CF3SO3]3+ and [Va,b/(CF3SO3)2]2+ with reduced charge states. Ion-pairing that yields [IVa,b/CF3SO3]2+ is also observed as a minor ESI process for the triply charged ions IVa, b3+. The gaseous ions I-Va, bn+ (n = 2, 3 or 4) dissociate by sequential 'charge partitioning' with the formation of two cationic fragments by the release of [Ru(bipy)2Cl]+. The meta (a) and para (b) isomers and the positional isomers II2+ and III2+ display nearly identical ESI-MS and ESI-MS/MS spectra. ESI-MS/MS of I-Va, bn+ shows that the Ru-py(P) is, intrinsically, the weakest bond since this bond breaks preferentially upon CID.

Cations↗
PubMed2003

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.

Journal Article↗