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A multiresponsive two-arm ferrocene-based chemosensor molecule for selective detection of mercury

The preparation, electrochemical, electronic, and cation sensing properties of an indole-ferrocene-indole triad, are presented. A salient feature of this new structural motif is that the redox-active organometallic fragment is linked to the indole rings by unsaturated nitrogen functionalities. Triad 4 behaves as a highly selective dual-redox and chromogenic chemosensor molecule for Hg 2+ cations: the oxidation redox peak is anodically shifted (DeltaE1/2 = 210 mV), and the low energy band of the absorption spectrum is red-shifted (Deltalambda = 120 mm), upon complexation with this metal cation. This change in the absorption spectrum is accompanied by a dramatic colour change from orange to green which allows the potential for “naked eye” detection. 1H NMR as well as DFT calculations have been carried out to get information about the molecular sites which are involved in bonding.

A multiresponsive two-arm ferrocene-based chemosensor molecule for selective detection of mercury

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Reference£º
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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Incorporation of a ferrocene unit in the pi-conjugated structure of donor-linker-acceptor (D-pi-A) chromophores for nonlinear optics (NLO)

In this paper we describe the synthesis, the electrochemical behaviour as well as the linear and nonlinear optical (NLO) properties of two push-pull derivatives bearing pyranylidene electron donating fragment, pyrimidine/methyl pyrimidinium electron withdrawing moiety and a ferrocene part in the pi-conjugated bridge. The properties of these two compounds were compared to their analogues without ferrocene or pyranylidene fragments. Experimental results were completed with DFT calculations to gain further insight into the intramolecular charge transfer (ICT). All the results indicate a significant charge transfer through the ferrocene unit. The ICT is however more limited than in all organic analogues.

Incorporation of a ferrocene unit in the pi-conjugated structure of donor-linker-acceptor (D-pi-A) chromophores for nonlinear optics (NLO)

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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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Mussel-Inspired Electro-Cross-Linking of Enzymes for the Development of Biosensors

In medical diagnosis and environmental monitoring, enzymatic biosensors are widely applied because of their high sensitivity, potential selectivity, and their possibility of miniaturization/automation. Enzyme immobilization is a critical process in the development of this type of biosensors with the necessity to avoid the denaturation of the enzymes and ensuring their accessibility toward the analyte. Electrodeposition of macromolecules is increasingly considered to be the most suitable method for the design of biosensors. Being simple and attractive, it finely controls the immobilization of enzymes on electrode surfaces, usually by entrapment or adsorption, using an electrical stimulus. Performed manually, enzyme immobilization by cross-linking prevents enzyme leaching and was never done using an electrochemical stimulus. In this work, we present a mussel-inspired electro-cross-linking process using glucose oxidase (GOX) and a homobifunctionalized catechol ethylene oxide spacer as a cross-linker in the presence of ferrocene methanol (FC) acting as a mediator of the buildup. Performed in one pot, the process takes place in three steps: (i) electro-oxidation of FC, by the application of cyclic voltammetry, creating a gradient of ferrocenium (FC+); (ii) oxidation of bis-catechol into a bis-quinone molecule by reaction with the electrogenerated FC+ and (iii) a chemical reaction of bis-quinone with free amino moieties of GOX through Michael addition and a Schiff’s base condensation reaction. Employed for the design of a second-generation glucose biosensor using ferrocene methanol (FC) as a mediator, this new enzyme immobilization process presents several advantages. The cross-linked enzymatic film (i) is obtained in a one-pot process with nonmodified GOX, (ii) is strongly linked to the metallic electrode surface thanks to catechol moieties, and (iii) presents no leakage issues. The developed GOX/bis-catechol film shows a good response to glucose with a quite wide linear range from 1.0 to 12.5 mM as well as a good sensitivity (0.66 muA/mM cm2) and a high selectivity to glucose. These films would distinguish between healthy (3.8 and 6.5 mM) and hyperglycemic subjects (>7 mM). Finally, we show that this electro-cross-linking process allows the development of miniaturized biosensors through the functionalization of a single electrode out of a microelectrode array. Elegant and versatile, this electro-cross-linking process can also be used for the development of enzymatic biofuel cells.

Mussel-Inspired Electro-Cross-Linking of Enzymes for the Development of Biosensors

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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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Deciphering the Magnitude of Current Steps in Electrochemical Blocking Collision Experiments and Its Implications

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.

Deciphering the Magnitude of Current Steps in Electrochemical Blocking Collision Experiments and Its Implications

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Reference£º
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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Synthesis, electrochemistry and complexation studies of new redox active bisferrocene acyclic and macrocyclic thioethers

The syntheses and electrochemical studies of new bisferrocene acyclic and macrocyclic ligands are described.Preliminary coordination investigations with palladium(II) and rhodium(I) transition metals produced, in most cases, polymeric complex species.Mono- and bi-metallic copper(II) complexes of two macrocyclic ligands and a nickel(II) complex of an acyclic analogue have been isolated and characterized.

Synthesis, electrochemistry and complexation studies of new redox active bisferrocene acyclic and macrocyclic thioethers

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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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Synthetic Route of 1293-65-8, A catalyst don’t appear in the overall stoichiometry of the reaction it catalyzes, but it must appear in at least one of the elementary reactions in the mechanism for the catalyzed reaction. 1293-65-8, Name is 1,1′-Dibromoferrocene, molecular formula is C10Br2Fe. In a Article£¬once mentioned of 1293-65-8

A new synthesis of diferrocenylketones

Diferrocenylketone (I) and <1.1>ferrocenophane-1,12-dione (II) have been obtained in 86percent and 13percent yields, respectively, via a simple route analogous to the Barbier synthesis involving N,N-disubstituted carbamylchlorides and the appropriate bromoferrocene derivatives.

A new synthesis of diferrocenylketones

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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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Selectivity mechanisms at self-assembled monolayers on gold: Implications in redox recycling amplification systems

Redox recycling systems enable marked improvement of electrochemical detection capabilities. Enhanced sensitivity is achieved by employing a sacrificial redox species that recycles the analyte back to its original oxidation state through a catalytic homogeneous electron transfer. Repetition of the cycle leads to multiple heterogeneous electron transfer events for each analyte molecule, serving to enhance the transduced signal. The success of redox recycling is intimately linked to the selectivity of heterogeneous electron transfer: the analyte should undergo a fast reaction while the sacrificial species should ideally be excluded from contributing directly to the current. This requirement stems from the relationship between selectivity and detection limit in that the direct heterogeneous electrolysis of the sacrificial additive can increase the background current which can degrade detection capabilities. Earlier work has shown that electrodes with suitable selectivity can be constructed using alkanethiolate monomolecular films on gold, with various ferrocenes (FcX) serving as a model analyte and ferrocyanide (Fe (CN)64 -) acting as the recycling agent [A.J. Bergren, M.D. Porter, J. Electroanal. Chem. 585 (2005) 172, A.J. Bergren, M.D. Porter, J. Electroanal. Chem. 591 (2006) 189, P.T. Radford, M. French, S. E. Creager, Anal. Chem. 71 (1999) 5101, P.T. Radford, S.E. Creager, Anal. Chim. Acta 449 (2001) 199, S.E. Creager, P.T. Radford, J. Electroanal. Chem. 500 (2001) 21]. The work herein investigates the origins of the selectivity for this system by analysis of the different pathways (e.g., electron transfer kinetics, size-exclusion, and partitioning) that can suppress the heterogeneous electrolysis of Fe (CN)64 -, while maintaining that for FcX at a rapid level. Comparisons of experimental data to expectations derived from model assessments are used to evaluate the relative importance of each possibility. The properties (i.e., size and hydrophobicity) of several FcX molecules and Fe (CN)64 – are also examined to provide additional insight into the processes that are important in creating a potent redox recycling system. These results show how the inherent differences in the heterogeneous electron transfer reaction rates can dictate the kinetic selectivity of the system. These findings indicate that partitioning augments the kinetic selection for the FcX / Fe (CN)64 – system, leading to the high level of observed selectivity.

Selectivity mechanisms at self-assembled monolayers on gold: Implications in redox recycling amplification systems

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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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Synthesis of unsymmetrical 1,1?-disubstituted ferrocenes. Formation of ferrocenophanes via intramolecular cycloaddition

Unsymmetrical 1,1?-disubstituted ferrocenes bearing appropriate substituents for intramolecular cycloadditions were synthesized conveniently starting from 1,1?-ferrocenedicarbaldehyde. Ferrocenenitrone derivatives reacted in an intramolecular regioselective manner affording ferrocenophanes.

Synthesis of unsymmetrical 1,1?-disubstituted ferrocenes. Formation of ferrocenophanes via intramolecular cycloaddition

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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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Electrochemical activity of new ferrocene-labelled PNA monomers to be applied for DNA detection: Effects of the molecular structure and of the solvent

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.

Electrochemical activity of new ferrocene-labelled PNA monomers to be applied for DNA detection: Effects of the molecular structure and of the solvent

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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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Related Products of 1273-94-5, Because a catalyst decreases the height of the energy barrier, its presence increases the reaction rates of both the forward and the reverse reactions by the same amount.1273-94-5, Name is 1,1′-Diacetylferrocene, molecular formula is C14H6FeO2. In a article£¬once mentioned of 1273-94-5

Synthesis, spectroscopic studies of binuclear Ruthenium(II) carbonyl thiosemicarbazone complexes containing PPh3/AsPh3 as Co-ligands: DNA binding/cleavage

The ruthenium(II) ferrocenyl heterocyclic thiosemicarbazone complexes of the type [RuCl(CO)(EPh3)]2L (where E = P/As; L = binucleating monobasic tridendate thiosemicarbazone ligand) have been investigated. Strutural features were determined by analytical and spectral techniques. Binding of these complexes with CTDNA by absorption spectral study indicates that the ruthenium(II) complexes form adducts with DNA and has intrinsic binding constant in the range of 3.3 ¡Á 104 – 1.2 ¡Á 105 M?1. The complexes exhibit a remarkable DNA cleavage activity with CT-DNA in the presence of hydrogen oxide and the cleavage activity depends on dosage.

Synthesis, spectroscopic studies of binuclear Ruthenium(II) carbonyl thiosemicarbazone complexes containing PPh3/AsPh3 as Co-ligands: DNA binding/cleavage

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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