Controllable synthesis of metal hydroxide and oxide nanostructures by ionic liquids assisted electrochemical corrosion method

Cu(OH)(2) nanowires have been synthesized by anodic oxidation of copper through a simple electrolysis process employing ionic liquid as an electrolyte. Controlling the electrochemical conditions can qualitatively modulate the lengths, amounts, and shapes of Cu(OH)(2) nanostructures. A rational mechanism based on coordination self-assembly and oriented attachment is proposed for the selective formation of the polycrystalline Cu(OH)(2) nanowires. In addition, the FeOOH nanoribbons, Ni(OH)(2) nanosheets, and ZnO nanospheres were also synthesized by this route, indicative of the universality of the electrochemical route presented herein. The morphologies and structures of the synthesized nanostructures have been characterized by transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM), powder X-ray diffraction (XRD). Fourier transform infrared spectra (FT-IR), and thermogravimetric (TG). (C) 2007 Elsevier Masson SAS. All rights reserved

Magnetic control of bioelectrocatalytic processes based on assembled iron oxide particles

A facile magnetic control system was designed in bioelectrocatalytic process based on functionalized iron oxide particles. The iron oxide particles were modified with glucose oxidase, and ferrocene dicarboxylic acid was used as electron transfer mediator. Functionalized iron oxide particles can assemble along the direction of applied magnetic field, and the directional dependence of the assembled iron oxide particles can be utilized for device purposes. We report here how such functionalized magnetic particles are used to modulate the bioelectrocatalytic signal by changing the orientation of the applied magnetic field. (C) 2008 Elsevier B.V. All rights reserved.

Phosphonate-Functionalized Polyfluorene as a Highly Water-Soluble Iron(III) Chemosensor

An anionic, phosphonate-functionalized polyfluorene, i.e., poly(9,9-bis(3'-phosphatepropyl)fluorene-alt-1,4-phenylene) sodium salt (PFPNa), has been synthesized by copolymerization of phosphonic acid-substituted 2,7-dibromofluorene and phenyldiboronic ester via direct Suzuki polycondensation reaction in DMF/water. Polymer PFPNa is highly soluble and emissive in water with a solubility of 60 mg/mL and a photoluminescence quantum yield of 75%. The absorption and fluorescence spectra of PFPNa are strongly dependent on pH value owing to the partial protonation of phosphate groups and the aggregation of the polymer chains.

Cesium hydroxide doped tris-(8-hydroxyquinoline) aluminum as an effective electron injection layer in inverted bottom-emission organic light emitting diodes

We demonstrate highly efficient inverted bottom-emission organic light-emitting diodes (IBOLEDs) by using cesium hydroxide (CsOH) doped tris-(8-hydroxyquinoline) aluminum (Alq(3)) as the electron injection layer on indium tin oxide cathode, which could significantly enhance the electron injection, resulting in a large increase in luminance and efficiency. The maximum luminance, current efficiency, and power efficiency reach 21 000 cd/cm(2), 6.5 cd/A, and 3.5 lm/W, respectively, which are 40%-50% higher in efficiency than that of IBOLEDs with cesium carbonate (Cs2CO3) doped Alq(3) as the electron injection layer, where the efficiencies are only 4.5 cd/A and 2.2 lm/W.

The mechanism of formic acid electro oxidation on iron tetrasulfophthalocyanine-modified platinum electrode

The mechanism of formic acid electrooxidation on iron tetrasulfophthalocyanine (FeTSPc) modified Pt electrode was investigated with electrochemical methods. It was found that a "third-body" effect of FeTSPc on Pt electrode predominates during the electrooxidation process based on unusual electrochemical results. The modification leads formic acid electrooxidation to take place through a desired direct pathway, in which the mechanism is proposed to be the gradual dehydrogenation of formic acid and the reaction of formate with hydroxyl species.

Syndiotactically enriched 1,2-selective polymerization of 1,3-butadiene initiated by iron catalysts based on a new class of donors

A series of phosphoryl (P=O) contained compounds: triethylphosphate (a), diethyl phenyl phosphate (b), ethyldiphenylphosphate (c) triarylphosphates (d and h-m), triphenylphosphine oxide (e), phenyl diphenylphosphinate (f) and diphenyl phenylphosphonate (g) have been prepared. Iron catalysts, which are generated in situ by mixing the compounds with Fe(2-EHA)(3) and (AlBu3)-Bu-i in hexane, are tested for butadiene polymerization at 50 degrees C. Phosphates donated catalysts have been, unprecedently, found to conduct extremely high syndiotactically (pentad, rrrr=46.1-94.5%) enriched 1,2-selective (1,2-structure content=56.2-94.3%) polymerization of butadiene.

Living polymerization of 1,3-butadiene by a Ziegler-Natta type catalyst composed of iron(III) 2-ethylhexanoate, triisobutylaluminum and diethyl phosphite

Living characteristics of facilely prepared Ziegler-Natta type catalyst system consisting of iron(III) 2-ethylhexanoate, triisobutylaluminum and diethyl phosphite have been found in the polymerization of 1,3-butadiene in hexane at 40 degrees C. The characteristics have been well demonstrated by: a first-order kinetics with respect to monomer conversion, a narrow molecular weight distribution (M-w/M-n = 1.48-1.52) of polybutadiene in the entire range of polymerization conversion and a good linearity between M-n and the yield of polymer. Feasible post-polymerization of 1,3-butadiene and block co-polymerization of 1,3-butadiene and isoprene further support the living natures of the catalyst bestowed with.

Fabrication of Iron Oxide Core/Gold Shell Submicrometer Spheres with Nanoscale Surface Roughness for Efficient Surface-Enhanced Raman Scattering

A method to synthesize Fe3O4 core/Au shell submicrometer structures with very rough surfaces on the nanoscale is reported. The Fe3O4 particles were first modified with uniform polymers through the layer-by-layer technique and then adsorbed a lot of gold nanoseeds for further Au shell formation. The shell was composed of a large number of irregular nanoscale An particles arranged randomly, and there were well-defined boundaries between these Au nanoparticles. The Fe3O4 core/Au shell particles showed strong plasmon resonance absorption in the near-infrared range, and can be separated quickly from solution by an external magnet.

Origin of improvement in device performance via the modification role of cesium hydroxide doped tris(8-hydroxyquinoline) aluminum interfacial layer on ITO cathode in inverted bottom-emission organic light-emitting diodes

It has been found that cesium hydroxide (CsOH) doped tris(8-hydroxyquinoline) aluminum (Alq(3)) as an interfacial modification layer on indium-tin-oxide (ITO) is an effective cathode structure in inverted bottom-emission organic light-emitting diodes (IBOLEDs). The efficiency and high temperature stability of IBOLEDs with CsOH:Alq(3) interfacial layer are greatly improved with respect to the IBOLEDs with the case of Cs2CO3:Alq(3). Herein, we have studied the origin of the improvement in efficiency and high temperature stability via the modification role of CsOH:Alq(3) interfacial layer on ITO cathode in IBOLEDs by various characterization methods, including atomic force microscopy (AFM), ultraviolet photoemission spectroscopy (UPS), X-ray photoemission spectroscopy (XPS) and capacitance versus voltage (C-V). The results clearly demonstrate that the CsOH:Alq(3) interfacial modification layer on ITO cathode not only enhances the stability of the cathode interface and electron-transporting layer above it. which are in favor of the improvement in device stability, but also reduces the electron injection barrier and increases the carrier density for current conduction, leading to higher efficiency.

The adsorption of dopamine on gold and its interactions with iron(III) ions studied by microcantilevers

The adsorption of dopamine (DA) molecules on gold and their interactions with Fe3+ were studied by a microcantilever in a flow cell. The microcantilever bent toward the Au side with the adsorption of DA due to the change Of Surface stress induced by the intermolecular hydrogen bonds of DA or the charge transfer effect between adsorbates and the Substrate. The interaction process between DA adsorbates and Fe3+ was revealed by the deflection curves of microcantilever. As indicated by the appearance of a variation during the decline of curves, two steps were observed in the curve at relative high concentrations of Fe3+. In this case, Fe3+ reacted with DA molecules only in the outer layers and the complexes removed with solution. Then Fe3+ reacted further with DA molecules forming the surface complex in the first layer next to the gold. At this stage, the stability Of Surface complexes was time dependent, i.e., unstable initially and stable finally. This may be due to the surface complexes change from mono-dentate to bi-dentate complexes. In another case, i.e., at relative low concentration of Fe3+, only the first step was observed as indicated by the absence of a variation.

Antioxidant Sensors Based on Iron Diethylenetriaminepentaacetic Acid, Hematin, and Hemoglobin Modified TiO2 Nanoparticle Printed Electrodes

Antioxidant amperometric sensors based on iron-containing complexes and protein modified electrodes were developed. Indium tin oxide glass was printed with TiO2 nanoparticles, onto which iron-containing compounds and protein were adsorbed. When applied with negative potentials, the dissolved oxygen is reduced to H2O2 at the electrode surface, and the H2O2 generated in situ oxidizes Fe-II to Fe-III, and then electrochemical reduction of Fe-III therefore gives rise to a catalytic current. In the presence of antioxidants, H2O2 was scavenged, the catalytic current was reduced, and the decreased current signal was proportional to the quantity of existing antioxidants. A kinetic model was proposed to quantify the H2O2 scavenging capacities of the antioxidants. With the use of the sensor developed here, antioxidant measurements can be done quite simply: put the sensor into the sample solutions (in aerobic atmosphere), perform a cathodic polarization scan, and then read the antioxidant activity values. The present work can be complementary to the previous studies of antioxidant sensor techniques based on OH radicals and superoxide ions scavenging methods, but the sensor developed here is much easier to fabricate and use.

Two-Step Spin-Transition Iron(III) Compound with a Wide [High Spin-Low Spin] Plateau

A new iron(III) coordination compound exhibiting a two-step spin-transition behavior with a remarkably wide [HS-LS] plateau of about 45 K has been synthesized from a hydrazino Schiff-base ligand with an N,N,O donor set, namely 2-methoxy-6-(pyridine-2-ylhydrazonomethyl) phenol (Hmph). The single-crystal X-ray structure of the coordination compound {[Fe(mph)(2)](ClO4)(MeOH)(0.5)(H2O)(0.5)}(2) (1) determined at 150 K reveals the presence of two slightly different iron(III) centers in pseudo-octahedral environments generated by two deprotonated tridentate mph ligands. The presence of hydrogen bonding interactions, instigated by the well-designed ligand, may justify the occurrence of the abrupt transitions. 1 has been characterized by temperature-dependent magnetic susceptibility measurements, EPR spectroscopy, differential scanning calorimetry, and Fe-51 Mossbauer spectroscopy, which all confirm the occurrence of a two-step transition. In addition, the iron(III) species in the high-spin state has been trapped and characterized by rapid cooling EPR studies.

Supramolecular isomerism in zinc hydroxide coordination polymers with pyridine-2,4-dicarboxylic acid: Two polymorphs with centrosymmetric two-dimensional and acentric three-dimensional coordination networks

Reactions of Zn(BF4)(2) and pyridine-2,4-dicarboxylic acid (2,4-pydcH(2)) in the presence of 1,2-bis( 4-pyridyl) ethylene or 1,3-bis(4-pyridyl) propane under hydro(solvo) thermal conditions yielded two polymorphic metal-organic coordination polymers formulated as Zn-2(OH)(2)(2,4-pydc) (1 and 2). Polymorph 1 features a two-dimensional (2-D) layer-like structure that is constructed by 2,4-pydc ligands bridging between the Zn-OH-Zn double-chain units. Each single Zn-OH-Zn chain is composed of mu(2)-OH groups connecting trigonal bipyramidal and tetrahedral Zn centers. Polymorph 2 is a 3-D coordination polymer containing 2-D Zn-OH-Zn sheets that consist of mu(2)- and mu(3)-OH groups and trigonal bipyramidal Zn centers. The sheets are pillared by 2,4-pydc ligands to form an acentric structural architecture. 1 and 2 are rare examples that the two polymorphs exhibit a centrosymmetric 2-D coordination network and an acentric 3-D coordination network, respectively. The different structures lead to differences in photoluminescent properties and thermal stabilities for 1 and 2.