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Signal transduction and signal amplification are both important mechanisms used within biological signalling pathways. Inspired by this process, we have developed a signal amplification methodology that utilises the selectivity and high activity of enzymes in combination with the robustness and generality of an organometallic catalyst, achieving a hybrid biological and synthetic catalyst cascade. A proligand enzyme substrate was designed to selectively self-immolate in the presence of the enzyme to release a ligand that can bind to a metal pre-catalyst and accelerate the rate of a transfer hydrogenation reaction. Enzyme-triggered catalytic signal amplification was then applied to a range of catalyst substrates demonstrating that signal amplification and signal transduction can both be achieved through this methodology.

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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 present study explores the microstructural characteristics and electrochemical responses of four metastable beta Ti-Nb-Mo alloys for biomedical implantation. They were synthesized by the cold crucible levitation melting technique, and compositions were selected to keep the molybdenum equivalency close to 12 wt% Moeq. For the sake of comparison, Ti12Mo was also investigated. Microstructural characterization reveals that all the alloys are beta (body-centred cubic structure), and the surface is composed by beta equiaxial grains with dimensions in the range of tens to hundreds mum. The corrosion resistance (potentiodynamic polarization and electrochemical impedance spectroscopy) of the alloys was determined in 0.9 wt% NaCl saline solution at 25 C. The materials spontaneously form a passivating oxide film on their surface, and they are stable for polarizations up to +1.0 VSCE. No evidence of localized breakdown of the oxide layers is found for polarizations more positive than those encountered in the human body. The passive layers show dielectric characteristics, and the wide frequency ranges displaying capacitive characteristics occur for both higher niobium contents in the alloy and longer exposures to the saline solution. The insulating characteristics of the oxide-covered surfaces were investigated by scanning electrochemical microscopy operated in the feedback mode, using ferrocene-methanol as redox mediator. Both z-approach curves and amperometric images were taken over the surface of the samples both at their open circuit potential and polarized. It has been found that Ti8Nb10Mo and Ti16Nb8Mo exhibit the lowest activity towards electron transfer. The new Ti-Nb-Mo ternary alloys are regarded to be potential candidates for biomedical application on the basis of both their microstructural characteristics and their corrosion resistance in saline solution with chloride content equivalent to body fluids.

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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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The prevalence of solvent effects in heterogeneous catalysis in condensed media has motivated developing theoretical assessments of solvent structures and their interactions with reaction intermediates and transition states. COA of Formula: C11H3FeO, You can get involved in discussing the latest developments in this exciting area about 1273-86-5

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The efficient and simple routes for the synthesis of various ferrocenyl derivatives from ferrocenylcarbinols and N,N?-thiocarbonyldiimidazole (TCDI) are described. It involves grinding the two substrates in a Pyrex tube with a glass rod at room temperature. The reaction of ferrocenylmethanol (1a) provided S,S-bis(ferrocenylmethyl)dithiocarbonate (1b), whose crystal structure and a plausible mechanism for its formation are also reported. The reaction of 1-ferrocenyl-1-phenylmethanol (2a) and 1-ferrocenylbutanol (2b) gave the products 2c and 2d, respectively. The reaction of omega-ferrocenyl alcohols 4-ferrocenylphenol (3a) and 6-ferrocenylhexan-1-ol (3b) yielded the products 3c and 3d, respectively. Reaction of 1,1?-ferrocenedimethanol (3e) afforded 3f in moderate yield, and by contrast, it was not similar to 1b. Reaction of [4-(trifluoromethyl)phenyl]methanol (4a) provided the thiocarbonate 4b in good yield.

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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 synthesis of a phosphonic-acid-functionalized porphyrin is presented and a procedure for the reproducible assembly of the porphyrins into thin films on glass or conductive glass surfaces is described. The assembly scheme, which utilizes established zirconium phosphonate (ZrP) chemistry, yields highly oriented films (normal to the surface) of well-defined thicknesses. In the lateral direction (plane parallel to the surface) the porphyrins interact by edge-on-edge contact and are characterized by significant porosity. Electrochemical redox-probe experiments indicate the existence of openings or pores of several angstroms in width in both monolayer and multilayer ZrP porphyrin films. Micropatterned versions of the films, capable of diffracting visible light, have also been prepared and have been used for the direct evaluation of film thicknesses via atomic force microscopy.

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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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Controlled switching of the spin state of transition metal ions, particularly of FeII and FeIII, is a prerequisite to achieve selectivity, efficiency, and catalysis in a number of metalloenzymes. Here we report on an iron(III) porphyrin with a photochromic axial ligand which, upon irradiation with two different wavelengths reversibly switches its spin state between low-spin (S = 1/2) and high-spin (S = 5/2) in solution (DMSO-acetone, 2:598). The switching efficiency is 76% at room temperature. The system is neither oxygen nor water sensitive, and no fatigue was observed after more than 1000 switching cycles. Concomitant with the spin-flip is a change in redox potential by ~60 mV. Besides serving as a simple model for the first step of the cytochrome P450 catalytic cycle, the spin switch can be used to switch the spin-lattice relaxation time T1 of the water protons by a factor of 15.

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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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Ferrocenylmethanol (1) (= FcCH2OH) is easily deprotonated upon treatment with NaN(SiMe3)2 in toluene solution to give the unsolvated sodium alkoxide Na (2) (Fc = Ferrocenyl). 2 is a useful intermediate in the preparation of early transition metal and lanthanide derivatives containing the ferrocenylmethoxide ligand.The new alkoxides Cp2M(OCH2Fc)2 (3: M = Zr; 4: M = Hf), (FcCH2O)3Ln (5: Ln = Sm; 6: Ln = Yb) and Cp2Sm(OCH2Fc) (7) have been obtained by treatment of 2 with the corresponding metal halides.The chelate-stabilized ytterbium(III) thiolates 2YbCl (9) and 3Yb (10) were synthesized by reacting anhydrous YbCl3 with the appropriate amounts of Li (8).

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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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Scanning electrochemical microscopy has been employed to obtain spatially-resolved information regarding surface topology, water uptake and blister formation at intact coatings, as well as the onset and progress of corrosion reactions within coating defects. Topographical lines and maps as well as chronoamperometric plots were measured during operation in the feedback mode. Next, the release of metal ions at the anodic sites and the consumption of oxygen at the cathodic sites developed in holidays could be monitored during operation in the generator-collector mode. Furthermore, the surface topography of defective coatings was imaged by using the redox competition mode.

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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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Chemical engineers work across a number of sectors, processes differ within each of these areas, but chemistry and chemical engineering roles are found throughout, creation and manufacturing process of chemical products and materials. Computed Properties of C11H3FeO. Catalysts allow a reaction to proceed via a pathway that has a lower activation energy than the uncatalyzed reaction. Introducing a new discovery about 1273-86-5, Name is Ferrocenemethanol

The extracellular electron transfer of Shewanella oneidensis MR-1 (MR-1) has been extensively studied due to the importance of the biosensors and energy applications of bioelectrochemical systems. However, the oxidation of metal compounds by MR-1, which represents the inward extracellular electron transfer from extracellular electron donors into the microbe, is barely understood. In this study, MR-1 immobilized on an electrode electrocatalyzes the oxidation of [Fe(CN)6]4- to [Fe(CN)6]3- efficiently and selectively. The selectivity depends on midpoint potential and overall charge(s) of redox molecules. Among 12 investigated redox molecules, the negatively charged molecules with high midpoint potentials, i.e., [Ru(CN)6]4- and [Fe(CN)6]4-, show strong electrocatalysis. Neither reference bacteria (Escherichia coli K-12 nor Streptococcus mutans) electrocatalyze the oxidation of [Fe(CN)6]4-. The electrocatalysis decays when MR-1 is covered with palladium nanoparticles presumptively involved with cytochromes c. However, cytochromes c MtrC and OmcA on MR-1 do not play an essential role in this process. The results support a model that [Fe(CN)6]4- donor electrons to MR-1 by interacting with undiscovered active sites and the electrons are subsequently transferred to the electrode through the mediating effect of [Fe(CN)6]4-/3-. The selective electron uptake by MR-1 provides valuable and fundamental insights of the applications of bioelectrochemical systems and the detection of specific redox molecules.

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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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For the first time, the synthesis, characterization, and analytical application for hydrogen peroxide quantification of the hybrid materials of Co2TiO4 (CTO) and reduced graphene oxide (RGO) is reported, using in situ (CTO/RGO) and ex situ (CTO+RGO) preparations. This synthesis for obtaining nanostructured CTO is based on a one-step hydrothermal synthesis, with new precursors and low temperatures. The morphology, structure, and composition of the synthesized materials were examined using scanning electron microscopy, X-ray diffraction (XRD), neutron powder diffraction (NPD), and X-ray photoelectron spectroscopy (XPS). Rietveld refinements using neutron diffraction data were conducted to determine the cation distributions in CTO. Hybrid materials were also characterized by Brunauer-Emmett-Teller adsorption isotherms, Scanning Electron microscopy, and scanning electrochemical microscopy. From an analytical point of view, we evaluated the electrochemical reduction of hydrogen peroxide on glassy carbon electrodes modified with hybrid materials. The analytical detection of hydrogen peroxide using CTO/RGO showed 11 and 5 times greater sensitivity in the detection of hydrogen peroxide compared with that of pristine CTO and RGO, respectively, and a two-fold increase compared with that of the RGO+CTO modified electrode. These results demonstrate that there is a synergistic effect between CTO and RGO that is more significant when the hybrid is synthetized through in situ methodology.

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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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Cucurbit[n]urils have been supported on graphene to develop sensitive and selective electrodes. The electrochemical response of modified electrodes containing graphene or graphene plus cucurbiturils has been studied for three probe molecules including hydroxymethylferrocene, ferrocyanide and methylviologen. It was found that the properties of these modified electrodes are derived from an increase in electron mobility and catalytic activity imparted by graphene and the selective complexation and molecular recognition due to cucurbit[n]urils. These properties of the graphene/cucurbit[n]urils modified electrodes have been applied for the electrochemical detection of relevant biomolecules as tryptophan at 0.69×10-7 M concentration.

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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