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A dual-stream flow injection method has been developed for electrochemical detection of ferrocene derivatives in flow streams. The method is based on a previously described electrochemical amplification method in which currents for analyte oxidation are enhanced by rapid analyte regeneration via a solution-phase electron exchange reaction with a sacrificial reagent. The use of two independent flow channels in the present method, one to carry the analyte and another to supply the sacrificial reagent, eliminates the necessity of spiking samples and calibration standards with sacrificial reagent to avoid injection transients. Hydrodynamic voltammograms were recorded for a series of injections of hydroxymethylferrocene (HMFc, a model ferrocene analyte) into the carrier stream in the presence and absence of ferrocyanide (which serves as sacrificial reagent) in the reagent stream. From these voltammograms an optimum detection potential for HMFc of +0.8 V versus Ag|AgCl|KClsat was selected. Two different concentrations of sacrificial reagent were tested for a range of HMFc concentrations between 1 × 10-3 and 1 × 10-8 M for which both unamplified and amplified peaks could be detected. An amplification factor of approximately 300 was obtained for a 1 × 10-8 M HMFc injection with 2 × 10-4 M ferrocyanide present in the reagent stream.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Tuning the energy of the frontier orbitals of an adsorbed molecule to match the Fermi level of the electrode is a fundamental requirement for efficient charge injection in molecular electronic devices. In this paper, we present electrochemical, impedimetric, spectroscopic, and scanning electrochemical microscopy (SECM) data that were used to study the effects of the adsorption of 4?-mercaptobiphenylcarbonitrile (HS2PCN) on the work function of gold. The adsorption process was studied and indicated the formation of a loosely packed self-assembled monolayer (SAM, DeltaGads = -43.3 kJ mol-1) following the immersion of the gold substrate in an ethanolic solution of HS2PCN. An increase in the immersion time resulted in the accumulation of negative charge density on the gold surface ascribed to the bonding dipoles resulting from the charge rearrangement at the metal-SAM interface that generates interfacial dipoles as a result of a charge-transfer process. As a consequence, a modification of about 1.2 eV is estimated in the work function of the gold surface modified with HS2PCN. Electron-transfer rate constants (k0), as measured via SECM, showed a strong dependence on the net charge of the redox probes and increased on going from negatively (ca. 1.14 × 10-3 cm s-1) to positively charged species (>1.0 cm s-1). Such behavior is ascribed to the polarity of the interface of the HS2PCN SAM on gold, which is negatively charged because of the electron-withdrawing property of the nitrile fragment.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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A novel liquid-junction-removed reference electrode system was developed for simultaneous multiplex amperometry using a closed bipolar electrode. The liquid junction between the reference cell and the sample cell was replaced by a bipolar electrode to ensure electron conductivity in lieu of ionic conductivity in conventional systems. Under the condition where the redox reaction of the analyte at the bipolar electrode in the sample cell was a limiting process, voltammetric and amperometric measurements were performed for quantitative detection of the analytes. After characterization of the system, a chip-type device was fabricated with six sample cells and one reference cell. Simultaneous determination of ferrocene methanol was conducted in six solutions in the 0.1?0.5 mM range. This is the first demonstration of the simultaneous multiplex determination of analytes with a liquid-junction-removed system. Although the potential control problem (which is different to the liquid potential problem of conventional liquid junction) still remains because of the increase of the solid?liquid interface, this system is expected to solve some problems associated with the liquid junction of the reference electrode, including sample contamination by chloride ions and the complicated process of fabricating a reference electrode on a chip.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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The magnitude of the current steps due to blocking collisions is shown to be proportional to the square of the particle size, the concentration of the redox mediator, and inversely proportional to the size of the indicator electrode. A theoretical model and a simple analytical expression have been developed that allow for estimation of the average value of the current step magnitude in blocking collisions. Thus, it is now possible to directly relate the size of the analyte to the size of the average current step without worrying about the edge effect. It is proposed that by using the developed model and equations one could monitor the state of analyte species in solution, i.e., whether it is aggregated or not.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Sixfold substitution reaction of hexachlorocyclotriphosphazene with 4-ferrocenylphenol gave a covalent hexaferrocenyl cluster in which all six ferrocene units were electrochemically equivalent. On the other hand, reaction of hexachlorocyclotriphosphazene with ferrocene methanol produced ferrocene aldehyde in high yield.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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This work presents the design, preparation, and characterization of a novel glucose electrochemical biosensor based on the immobilization of glucose oxidase (GOX) into a nylon nanofibrous membrane (NFM) prepared by electrospinning and functionalized with multiwalled carbon nanotubes (CNT). A disc of such GOX/CNT/NFM membrane (40 mum in thickness) was used for coating the surface of a glassy carbon electrode. The resulting biosensor was characterized by cyclic voltammetry and chronoamperometry, with ferrocene methanol as mediator. The binding of GOX around the CNT/NFM greatly enhances the electron transfer, which results in a biosensor with a current five times higher than without CNT. The potential usefulness of the proposed biosensor was demonstrated with the analysis of glucose in commercial beverages and along the monitoring of the brewing process for making beer, from the mashing to the fermentation steps.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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A new method was introduced to research the corrosion resistance of enamel coatings which were sintered at different temperatures in this paper.1-4 Scanning electrochemical microscopy (SECM) conjunction with capacitance-potential test and Mott-Schottky analysis technique were used to study the coating failure process and semiconductor conduction behavior of enamel coating in 3.5wt.% NaCl solution. The high strength steel (SAPH440) was selected as the metal substrate. The coatings which were sintered at different temperatures on the high strength steel were analyzed and their corrosion behaviors and microstructures were also measured by potentiodynamic polarization curves, Mott-Schottky analysis technique and scanning electrochemical microscopy.5-10 In this paper, five kinds of enamel coatings were prepared on high strength steel. The SECM results show that the Faraday current of the microprobe tip gradually decreases with the soaking time increasing, which indicates that the coatings become failure slowly with the invasion of water and aggressive ions. At the same time, the tip current was homogeneous during the immersion process, which reflected that the surface of the sample remained stable, no obvious bulges appeared. Capacitance-potential test and Mott-Schottky analysis7,8 show that the external ions and water molecules gradually penetrate into the coating; coating showed characteristics of n-type semiconductor as time increases, the capacitance increases gradually, the space charge layer thickness decreases, slope of Mott-Schottky curve decreased gradually which indicates that the failure of coating in the process of soaking slowly with the charge carrier density increases.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Reductive amination of ferrocenecarbaldehyde with several primary and secondary amines in the presence of sodium triacetoxyborohydride was studied. This method was used for the synthesis of new ferrocenylmethylamines, viz., N-(ferrocenylmethyl)isoleucine methyl ester, N,N-bis(ferrocenylmethyl)glycine ethyl ester, and N-(3,5-dibenzyloxybenzyl)-N-(ferrocenylmethyl)methylamine. The latter is a potential precursor of a dendrimer with the chiral ferrocenyl plane in the core.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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This chapter summarizes research work showing that electrostatic interactions may have considerable effects on the stability of complexes formed by the cucurbit[n]uril hosts. Focusing primarily on work carried out by the author’s research group with the cucurbit[7]uril (CB[7]) molecular receptor, this review highlights the role played by electrostatic interactions involving the host cavity portals, in which considerable negative charge density accumulates due to the carbonyl oxygens lacing the portal rims. Electrostatics are responsible for diminished binding affinities between CB[7] and a number of anionic guests containing one or more carboxylate groups. These electrostatic interactions can be used effectively to control the average location of CB[7] along axle-type guests having terminal -COOH groups as a function of their state of protonation, leading to switchable pseudorotaxane systems. They can also be utilized to advantage to develop favorable lateral interactions between CB[7] and other molecular receptors, which results in systems showing cooperative self-assembly.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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A novel photoelectrochemical cell consisting of a set of organic thin films which generate photocurrents in opposite directions was fabricated. The polythiophene film containing 5,10,15,20-tetraphenylporphyrin (TPP) and fullerene (C60) generated anodic photocurrents in the presence of ferrocene, while that containing TPP alone generated cathodic photocurrents under aerobic condition. The combination of these two film-modified electrodes showed a better cell performance than the simple sum of these two independent photoelectrochemical cells. A push-pull type, double-driven photoelectrochemical cell is proposed in this paper.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion