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Chemoselective and atom-economical methods for the synthesis of ferrocene diethenyl ethers have been developed via direct base-catalyzed addition of 1,1?-bis(hydroxymethyl)ferrocene to various acetylenes. This ferrocene diol has been shown to be capable of adding to acetylene (KOH/DMSO, 70-80 C, 1-3 h), propyne (KOH/DMSO, 70 C, 12 h), phenylethyne (KOH/DMSO, 20-25 C, 48 h), alkylpropiolates (DABCO, 10 mol%/CH 2 Cl 2, 20-25 C, 0.5 h), and acylacetylenes (DABCO, 1 mol%/CH 2 Cl 2, 20-25 C, 0.5 h) to afford the corresponding diethenyl ethers in 73-98% yields.

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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 a novel, simple and facile approach is described to construct highly stable glucose oxidase (GOx) multilayer onto glassy carbon (GC) electrode using thiourea (TU) as a covalent attachment cross-linker. The layer by layer (LBL) attachment process was confirmed by cyclic voltammetry, electrochemical impedance spectroscopy and Fourier transform infrared reflection spectroscopy (FT-IR-RS) techniques. Immobilized GOx shows excellent electrocatalytic activity toward glucose oxidation using ferrocenemethanol as artificial electron transfer mediator and biosensor response was directly correlated to the number of bilayers. The surface coverage of active GOx per bilayer, heterogeneous electron transfer rate constant (ks) and Michaelis-Menten constant (KM), of immobilized GOx were 1.50 × 10-12 mol cm-2, 9.2 ± 0.5 s-1 and 3.42(±0.2) mM, respectively. The biosensor constructed with four-bilayers of TU/GOx showed good stability, high reproducibility, long life-time, fast amperometric response (5 s) with the high sensitivity of 5.73 muA mM -1 cm-2 and low detection limit of 6 muM at concentration range up to 5.5 mM.

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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 native oxide film on the biphasic alloy Ti6Al4V was studied with scanning electrochemical microscopy (SECM). This alloy is commonly used for biomedical applications due to its biocompatibility and mechanical properties. The heterogeneously composed, n-semiconducting oxide film is of particular interest as biological systems are in contact only with these oxides and immunological rejection mechanisms may be connected to their electrochemical properties. Auger electron spectroscopy showed that the elemental composition of the oxide films on the alpha and Beta phase differ from each other. Approach curves were recorded above individual grains of the alpha phase in the feedback mode with several redox mediators. They were selected to cover a wide range of redox potentials for a better understanding of the surface kinetics of the oxide layer. The electron-transfer kinetics changed strongly depending on the redox potential of the mediator with respect to the energetic position of the bandgap of the oxide film. Predictions about the value of the flatband potential on an individual phase were derived from these experiments. Furthermore, SECM images were recorded to laterally resolve different electrochemical properties of the oxide film originating from the heterogeneous composition of the oxide on both phases.

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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 growth of B-CNW with different boron doping levels controlled by the [B]/[C] ratio in plasma, and the influence of boron on the obtained material’s structure, surface morphology, electrical properties, and electrochemical parameters, such as -DeltaE and k, were investigated. The fabricated boron-doped carbon nanowalls exhibit activity toward ferricyanide redox couple, reaching the peak separation value of only 85 mV. The flatband potential and the concentration of boron carriers were estimated in the B-CNW samples using the Mott-Schottky relationship. It was shown that the vertically oriented carbon planes are characterized by p-type conductivity and very high hole-acceptor concentration (3.33 × 1023 cm-3 for a highly doped sample), which provides high electrical conductivity. The enhanced electrochemical performance of B-CNWs electrodes is an advantageous feature that can be applied in ultrasensitive detection or energy storage devices. (Graph Presented).

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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 substitution reaction of ferrocenyl alcohol with various nucleophiles catalyzed by cerium ammonium nitrate (CAN) was investigated. This CAN-mediated direct carbon-carbon bond formation provides the corresponding products in moderate to high yields with relatively lower catalyst loading (5 mol %) at room temperature. It demonstrated a convenient synthetic protocol for the ferrocene functionalities. Crown Copyright

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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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Shaped carbon nanomaterials (SCNMs) were synthesized via the chemical vapour deposition (CVD) technique by using typical metallocenes (ferrocene, nickelocene, cobaltocene, and ruthenocene), and more interestingly, by use of novel ferrocenyl imidazolium derivatives, containing -Cl (FcImCl), -NO2 (FcImNO2) and -CH3 (FcImCH3) substituents as catalysts. Acetonitrile was applied both as a carbon and nitrogen source at temperatures 800?900 C. The SCNMs, namely, carbon nanotubes (CNTs), carbon spheres (CS), carbon fibres (CF) and amorphous carbons (ACs) were obtained in varying ratios depending on the catalyst and carbon sources. The ferrocenyl imidazolium catalysts produced nitrogen-doped CNTs (N-CNTs) with bamboo-like structures. The yields of various reactions were temperature-dependent, with the highest amount of N-CNTs obtained at 850 C. In all samples, the composition was mainly of CS and N-CNTs except for nickelocene at 800 C that gave CFs as a ?minor? product. Ferrocene and nickelocene in acetonitrile produced well-aligned N-CNTs while cobaltocene and ruthenocene gave ‘spaghetti-like? structures. In the case of ferrocenyl imidazolium catalyst, a coiled N-CNTs morphology was produced from FcImCl catalyst. Also, higher percentage of N-CNTs with traces of CS were obtained from the FcImCl and FcImCH3 catalysts in acetonitrile at 850 C, while higher percentage of CS and AC were obtained for FcImNO2 catalyst. In all the catalysts, the use of acetonitrile promoted nitrogen-doping (samples with more disordered and with smaller outer-diameters). Thus, this study demonstrates that the synthesis of N-CNTs from nitrogen-containing ferrocenyl imidazolium compounds as catalyst sources, provided higher percentage of N-CNTs which can be suitable for various application.

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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 easy functionalization of tags and solid supports with the vinyl sulfone function is a valuable tool in omic sciences that allows their coupling with the amine and thiol groups present in the proteogenic residues of proteins, in mild and green conditions compatible with their biological function.

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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 paper describes the electrochemical reduction of nitrite ion in neutral aqueous solution mediated by tetraruthenated metalloporphyrins (Co(II), Ni(II) and Zn(II)) electrostatically assembled onto a Nafion film previously adsorbed on glassy carbon or ITO electrodes. Scanning electron microscope (SEM-EDX) and transmission electron microscopy (TEM) results have shown that on ITO electrodes the macrocycles forms multiple layers with a disordered stacking orientation over the Nafion film occupying hydrophobic and hydrophilic sites in the polyelectrolyte. Atomic force microscopy (AFM) results demonstrated that the Nafion film is 35 nm thick and tetraruthenated metalloporphyrins layers 190 nm thick presenting a thin but compacted morphology. Scanning electrochemical microscopy (SECM) images shows that the Co(II) tetraruthenated porphyrins/Nf/GC modified electrode is more electrochemically active than their Ni and Zn analogues. These modified electrodes are able to reduce nitrite at -660 mV showing enhanced reduction current and a decrease in the required overpotential compared to bare glassy carbon electrode. Controlled potential electrolysis experiments verify the production of ammonia, hydrazine and hydroxylamine at potentials where reduction of solvent is plausible demonstrating some selectivity toward the nitrite ion. Rotating disc electrode voltammetry shows that the factor that governs the kinetics of nitrite reduction is the charge propagation in the film.

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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 ultrasensitive electrochemical biosensor for detecting microRNAs is fabricated based on hollow molybdenum disulfide (MoS2) microcubes. Duplex-specific nuclease, enzyme and electrochemical?chemical?chemical redox cycling are used for signal amplification. Hollow MoS2 microcubes constructed by ultrathin nanosheets are synthesized by a facile template-assisted strategy and used as supporting substrate. For biosensor assembling, biotinylated ssDNA capture probes are first immobilized on Au nanoparticles (AuNPs)/MoS2 modified electrode in order to combine with streptavidin-conjugated alkaline phosphatase (SA-ALP). When capture probes hybridize with miRNAs, duplex-specific nuclease cleaves the formative duplexes. At the moment, the biotin group strips from the electrode surface and SA-ALP is incapacitated to attach onto electrode. Then, ascorbic acids induce the electrochemical?chemical?chemical redox cycling to produce electrochemical response in the presence of ferrocene methanol and tris (2-carboxyethyl) phosphine. Under optimum conditions, the proposed biosensor shows a good linear relationship between the current variation and logarithm of the microRNAs concentration ranging from 0.1 fM to 0.1 pM with a detection limit of 0.086 fM (S/N=3). Furthermore, the biosensor is successfully applied to detect target miRNA-21 in human serum samples.

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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 review (with 210 references) summarizes recent developments in the design of voltammetric chemical sensors and biosensors based on the use of carbon nanomaterials (CNMs). It is divided into subsections starting with an introduction into the field and a description of its current state. This is followed by a large section on various types of voltammetric sensors and biosensors using CNMs with subsections on sensors based on the use of carbon nanotubes, graphene, graphene oxides, graphene nanoribbons, fullerenes, ionic liquid composites with CNMs, carbon nanohorns, diamond nanoparticles, carbon dots, carbon nanofibers and mesoporous carbon. The third section gives conclusion and an outlook. Tables are presented on the application of such sensors to voltammetric detection of neurotransmitters, metabolites, dietary minerals, proteins, heavy metals, gaseous molecules, pharmaceuticals, environmental pollutants, food, beverages, cosmetics, commercial goods and drugs of abuse. The authors also describe advanced approaches for the fabrication of robust functional carbon nano(bio)sensors for voltammetric quantification of multiple targets. [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