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This account focuses on the application in catalysis of ruthenium and osmium complexes containing 2-(aminomethyl)pyridine (Ampy)-based ligands. The combination of these aminoalkylpyridine ligands with appropriate phosphines affords ruthenium and osmium systems displaying unprecedented high catalytic activity and productivity in a variety of organic transformations such as hydrogenation by hydrogen transfer and dihydrogen, dehydrogenation, racemization, and alkylation.

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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 structure of ferrocene derivative 1 was synthesized with cyanuric chloride and ferrocenemethanol as starting materials. The synthesized compound was fully characterized using 1H NMR, 13C NMR, MS and XRD. Subsequently, the in vitro anticancer effect against A549, HCT116 and MCF-7 cell lines was preliminarily evaluated by the MTT method. The result showed that this compound exhibits good cytotoxic effect on A549, HCT116 and MCF-7 cell lines.

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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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Owing to their fairly high stability under visible irradiation, ferrocene and ferrocenyl derivatives are widely used in luminescent systems. They are classical quenchers of excited states. Both energy and electron transfer may be involved, depending on the nature of the excited species. Inter- or intramolecular quenching are encountered. Applications span from the study of reaction mechanisms to that of organized or biological media. Recently, dyads and polyads designed for their ability to mimic photosynthetic centers or for their photodiode properties have also been obtained. Finally, the incorporation of a ferrocenyl derivative in a luminescent system does not necessarily lead to luminescence quenching. New applications are emerging, in which advantage is taken of the presence of ferrocene acting as a redox center: this gives optically and electrochemically active sensors. The present review encompasses the literature up to November 1999.

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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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PNA oligomers are promising candidates as DNA probes on account of their very high DNA binding power, but they generally require an appropriate electrochemically or spectroscopically active marker. This paper describes the systematic electrochemical characterization of two newly synthesized PNA monomers, derivatised with one or three active ferrocene groups, and of their precursors. Our monomers show high electrochemical activity in spite of their bulkiness; moreover, the systematicity of our investigation affords an interesting analysis of the role of the molecular structure, the degree of functionalization and the working solvent on the electrochemical activity of the organometallic site.

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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 original method combining two conductometric biosensors is proposed for the determination of total lactate, L- and D-lactate in dairy products. The biosensors were prepared through cross-linking of L-lactate oxidase from Pediococcus sp. (LODP) or a combination of LODP and horseradish peroxidase (HRP) at the surface of gold interdigitated microelectrodes using glutaraldehyde (GA) vapors. LODP is reported to catalyze specifically L-lactate oxidation into pyruvate and hydrogen peroxide in solution. In this work, we showed that LODP chiral selectivity was lost following enzyme cross-linking, rendering LODP sensor suitable for total lactate determination. Biosensor sensitivity towards both stereoisomers was 1.16 ± 0.04 muS muM-1. The addition of HRP significantly improved the linear range and stability of LODP biosensor, but also increased its sensitivity, the effect being more pronounced for D-lactate (+381%) than for L-lactate (+260%). This result was attributed to a modification in LODP chiral selectivity combined with the production of additional ions (acetate, H+ and HCO3-) via the HRP-catalyzed oxidation of pyruvate. A method, taking advantage of the difference in D- and L-lactate behaviours and combining the monoenzymatic and bienzymatic biosensors calibration data, was proposed for the calculation of their concentrations in unknown samples. Different parameters (HRP/LODP ratio, exposure time to GA vapors, pH and concentration of measurement medium) were optimized in order to achieve the best compromise between sensitivity and stability of the biosensors. The best limit of detection for L- and D-lactate, calculated as three times the signal to noise ratio was achieved with the bi-enzymatic sensor and was equal to 0.05 muM. LODP/HRP biosensor response towards L-lactate was not significantly affected by glucose, fructose and lactose. The proposed biosensors were finally applied to the determination of total lactate, D- and L-lactate concentrations in yogurt samples. Results were in good agreement with those obtained using a reference colorimetric enzymatic method.

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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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57Fe NMR spectra of 20 ferrocene derivatives with natural abundance of 57Fe have been recorded by the conventional pulse Fourier transform technique using ferrocene as internal standard for the chemical shifts.Shift contributions of the substituents are discussed qualitatively.

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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 flow-through column electrolytic cell was proposed as a detector to obtain current signals for supercritical fluid chromatography. The electrochemical cell consisted of two electrodes and its holder, and a working and a counter electrode were fabricated from 192 carbon strings, which were composed of 400 carbon fibers of 10 mum in diameter filled into a heat-shrinkable tube. These electrodes were placed in the center of a holder made from polyether ether ketone blocks and they were separated by polytetrafluoroethylene membrane filters. To evaluate the sensitivity of this cell, a standard solution of ferrocene was injected into the supercritical fluid chromatography system connected to the electrolytic cell. The ferrocene was eluted through a silica gel column using a mixture of a mobile phase of supercritical CO2 and a modifier of methanol containing ammonium acetate. The current peak area of ferrocene correlated to the ferrocene concentration in the range of 10?400 mumol/L (r = 0.999). Moreover, the limit of detection on the column estimated from a signal-to-noise ratio of 3 was 9.8 × 10?13 mol.

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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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Diverse series of isatin?ferrocene conjugates were synthesized via Cu-promoted azide?alkyne cycloaddition reaction with an aim of probing their antiproliferative structure?activity relationship against MCF-7 (estrogen receptor positive) and MDA-MB-231 (triple negative) cell lines. Among the synthesized conjugates, isatin?ferrocenes proved to be more potent against MCF-7, whereas ferrocenylmethoxy?isatins exhibited activity against MDA-MB-231 cell lines. However, the introduction of chalcone moiety among these hybrids resulted in the complete loss of activity against the tested cell lines, as evident by isatin?ferrocenylchalcones. The conjugates 5a and 9c proved to be the most potent among the series against MCF-7 and MDA-MB-213 cell lines, exhibiting IC50 values of 31.62 and 20.26 muM, respectively.

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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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We describe the catalytic voltammograms of the periplasmic arsenite oxidase (Aio) from the chemolithoautotrophic bacterium Rhizobium sp. str. NT-26 that oxidizes arsenite to arsenate. Electrochemistry of the enzyme was accomplished using its native electron transfer partner, cytochrome c552 (cyt c552), as a mediator. The protein cyt c552 adsorbed on a mercaptoundecanoic acid (MUA) modified Au electrode exhibited a stable, reversible one-electron voltammetric response at + 275 mV vs NHE (pH 6). In the presence of arsenite and Aio the voltammetry of cyt c552 is transformed from a transient response to an amplified sigmoidal (steady state) wave consistent with an electro-catalytic system. Digital simulation was performed using a single set of parameters for all catalytic voltammetries obtained at different sweep rates and various substrate concentrations. The obtained kinetic constants from digital simulation provide new insight into the kinetics of the NT-26 Aio catalytic mechanism.

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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 encapsulation of redox mediators (i.e. ferrocene methanol, potassium ferricyanide) within the nanostructured network of organically modified silicate (ormosil) on a electrode surface is studied. The redox electrochemistry of modified electrodes made by sol-gel processing of 3-aminopropyltrimethoxysialne (3-APTMS) and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane containing aqueous solution of desired redox mediators (potassium ferricyanide or ferrocene methanol) on electrode surface is reported. The synthetic protocol of ormosil film preparation on electrode surface also enables the encapsulation of titania (TiO2) and palladium when suitable precursors of the same are incorporated during sol-gel processing. The ormosil films are characterized by Atomic force spectroscopy, EDX and cyclic voltammetry. The modified electrodes of three different types (Ormosil, Ormosil-TiO2, and Ormosil-TiO 2-Pd) together with either ferrocene methanol or potassium ferricyanide are made to understand the redox behaviour of these electron transfer mediators present within nanostructured domain useful in electrochemical sensing with following major findings: (1) the redox electrochemistry of ormosil-encapsulated ferrocene methanol/potassium ferricyanide show gradual improvement in reversible electrochemical behavior in the order of Ormosil-TiO2-Pd > Ormosil-TiO2 and Ormosil; (2) the presence of TiO2-Pd in ormosil shows better catalytic activity as compared to that of made with only TiO2 toward ascorbic acid (AA) oxidation; (3) ferrocene methanol encapsulated ormosil has been found relatively more efficient mediator as compared to that of potassium ferricyanide toward AA oxidation. The findings justify the novel approach on the fabrication of porous chemically modified electrode of suitable nanogeometry for electroanalytical applications.

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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