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The surface of a platinum electrode has been modified with platinum nanoparticles (PtNPs) and the enzyme sulfite oxidase (SOx), was entrapped on its surface in an ultrathin polypyrrole (PPy) film. The PtNPs, with a diameter of 30?40 nm, were deposited on the Pt electrode by cycling the electrode potential 20 times from -200 to 200 mV at a sweep rate of 50 mV.s-1. Morphological evidence of the successful incorporation of SOx and the presence of PtNPs were obtained by scanning electron microscopy. Also, the electrochemical behavior of the PtNPs/PPy-SOx film was examined by cyclic voltammetry, chronopotentiometry, electrochemical impedance spectroscopy and potentiometry. Under optimized conditions, the biosensor achieved a sensitivity of 57.5 mV.decade-1, a linear response that extends from 0.75 to 65 muM of sulfite, a detection limit of 12.4 nM, and a response time of 3?5 s. The biosensor was successfully applied to the determination of sulfite in wine and beer samples. [Figure not available: see fulltext.]

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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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Grafting Ti(=NtBu)(Me2Pyr)2(py)2 (Me2Pyr= 2,5-dimethylpyrrolyl, py=pyridine) onto the surface of silica partially dehydroxylated at 700 C gives the well-defined silica-supported Ti imido complex (?SiO)Ti(=NtBu)(Me2Pyr)(py)2, which is fully characterized by IR and solid-state NMR spectroscopy as well as elemental and mass balance analyses. While stoichiometric imido-transfer reactivity is typical for Ti imides, the obtained surface complex is unique in that it enables catalytic transformations involving Ti imido and oxo intermediates. In particular, it efficiently catalyzes imidation of carbonyl compounds with N-sulfinylamines by oxo/imido heterometathesis.

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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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Hydrogen peroxide (H2O2) is an important target material for detecting biomolecules including acetylcholine (ACh), glutamate (Glu), and glucose. In this study, we report on H2O2 detection under biological environments based on the redox reaction. The redox potential change caused by the reaction between the electron mediators of ferrocenes and H2O2 catalyzed by horseradish peroxidase (HRP) was measured using a gold electrode connected to a source follower circuit. The mediators were either dissolved in sample solutions using ferrocenyl methanol (FcMeOH) or immobilized on the sensor surface in the form of 11-ferrocenyl-1- undecanethiol (11-FUT). H2O2 detection under biological environments was demonstrated in both samples. The overall outputs in the 11-FUT-immmobilzed electrodes were lower than those in the samples with dissolved FcMeOH. The detection range of H2O2 was from 10-5 to 10-3 M for the samples with dissolved FcMeOH, while it was from 10-4 to 10-2 M for the 11-FUT-immobilized electrodes. It was suggested that the oxidation of the mediators by H2O2 insufficiently took place in the 11-FUT-immobilized electrodes, leading to the lower outputs.

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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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An efficient synthetic approach to the synthesis of ferrocenyl heterocyclic derivatives in dilute solutions has been developed. The new compounds were characterised by means of IR, UV, and 1H NMR, spectroscopy and elemental analysis. The structure of complex I was studied by X-ray single-crystal diffraction. The synthesized compounds have a potential of new enzyme models and molecular recognition hosts.

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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 study describes the molecular-level design of a new type of filtration membrane made of crosslinked cyclodextrins?inexpensive macrocycles of glucose, shaped like hollow truncated cones. The channel-like cavities of cyclodextrins spawn numerous paths of defined aperture in the separation layer that can effectively discriminate between molecules. The transport of molecules through these membranes is highly shape-sensitive. In addition, the presence of hydrophobic (cavity) and hydrophilic (ester-crosslinked outer part) domains in these films results in high permeances for both polar and nonpolar solvents.

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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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Diaphorase (DI) works as an effective catalyst for the electrochemical oxidation and reduction of NAD with the aid of several quinones or flavins as electron transfer mediators. The redox kinetics between DI and mediators have been expressed by a Butler-Volmer-type equation. NAD-dependent L-lactate dehydrogenase (LDH) catalyzing the redox reaction between L-lactate and pyruvate was coupled to the DI-catalyzed NAD redox system to achieve better understanding of mediated two-enzyme-linked bioelectrocatalysis with reversible characteristics. Under the conditions where the concentration polarization of NAD due to the DI-catalyzed electrochemical reaction is suppressed by the LDH reaction, the NAD concentration dependence of the catalytic current was expressed by an approximate equation involving the enzyme kinetics between DI and NAD. The suppression of the NAD concentration polarization is also useful to observe steady-state catalytic waves of an uphill reaction between DI and the mediator. The oxidation reaction involving the uphill electron transfer from L-lactate to NAD+ is susceptible to a inhibition from pyruvate due to the reversible characteristics of LDH. The present knowledge has led to the strategy to realize a two-way bioelectrocatalysis for the reduction of pyruvate and the oxidation of L-lactate. New potentiometry for the detection of the solution potential governed by the electrochemically inactive pyruvate/L-lactate redox couple has also been demonstrated based on the reversible characteristics of the DI-DLH-linked bioelectrocatalytic system.

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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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Vicinal diamines are a common structural motif in bioactive natural products, therapeutic agents, and molecular catalysts, motivating the continuing development of efficient, selective, and sustainable technologies for their preparation. We report an operationally simple and environmentally friendly protocol that converts alkenes and sodium azide?both readily available feedstocks?to 1,2-diazides. Powered by electricity and catalyzed by Earth-abundant manganese, this transformation proceeds under mild conditions and exhibits exceptional substrate generality and functional group compatibility. Using standard protocols, the resultant 1,2-diazides can be smoothly reduced to vicinal diamines in a single step, with high chemoselectivity. Mechanistic studies are consistent with metal-mediated azidyl radical transfer as the predominant pathway, enabling dual carbon-nitrogen bond formation.

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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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Regioselectivity of ferrocenylalkylation reaction of mercaptoheterocycles with ferrocenylcarbinoles in biphasic aqueous-organic media was studied. The structures of compounds were assigned on the basis of NMR spectra and 1H/13C heteronuclear correlations. X-ray determination of molecular structures of 1-(ferrocenyl(phenyl)methyl)pyrrolidine-2-thione 5f, 4, 5-dihydro-1-(1-ferrocenylmethyl)-1H-imidazole-2-thiol 7a and 4, 5-dihydro-1-(1-ferrocenyl-2methylpropyl)-1H-imidazole-2-thiol 7e were carried out.

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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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Reactions of Cp2TiMe2, with the ester derivatives of organometallic sandwich compounds (n5-RC5H4)Fe(n5-C5H5) and (n5-RC5H4)Co(n4-C4Ph4) (R=ester groups) gave products having R=C(CH2)Me, instead of the expected vinyl ethers indicating conversion of the ester units by Cp2TiMe2 to methyl ketones followed by methylenation. A reaction of Cp2TiMe2 with the diester (n5-RC5H4)Co(n4-C4Ph3R)(R=C(O)OMe) also gave similar results. The study has also been successfully extended to metal sandwich derived amides, thio and seleno esters. By controlling the amount of Cp2TiMe2, the reactions were also stopped at the methyl ketone stage and the methyl ketones were isolated in good yields and characterized. The method provides an easy and direct access to convert organometallic sandwich derived esters and related compounds to 1-methylvinyl derived products.

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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 invention relates to a double-allyl three-carbon ester ferrocene monomer and its preparation method. In order to 1, 1 ‘- double-(1 – methoxy – 3 – butenyl) ferrocene and 1 – methoxy – 1 – (trimethyl siloxy) – 2 – methyl – 1 – propylene as the raw material, at the low temperature, boron trifluoride ether complex adds by drops three, to obtain 1, 1’ – double-[1 – (1 – methoxy carbo- acid radical – 1 – methyl – ethyl) – 3 – ene butyl] ferrocene compound; diene propyl substituted three-carbon methyl ester ferrocene not only can be used for the melt polycondensation of the polyester, but also has the double bond giving it take part in the polymerization reaction capability of the, therefore is a novel ferrocene base monomer. (by machine translation)

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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