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A highly regioselective Ni-catalyzed hydroalkoxylation of 1,3-dienes is reported. The use of a (P,N) ligand is essential in achieving high levels of selectivity. The optimized protocol operates under particularly mild conditions, it provides access to a broad range of structurally diverse allylic ethers, and tolerates a number of sensitive functional groups.

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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 method for the preparation of magnetic porous carbon materials (MPMs) with high specific surfaces was developed using hydroxymethylferrocene through the combination of chloromethylation, hypercross-linked polymerization, and vacuum carbonization. The MPMs were mainly composed of porous carbon and iron nanoparticles. The specific surface and maximum specific saturation magnetization of MPMs were 295.90 m2/g and 7.45 emu/g, respectively. Furthermore, organic dyes, organic pesticides, and antibiotics were chosen as model adsorbates to test the adsorption properties of MPMs. The adsorption capacity of MPMs for methyl red was up to 199.54 mg/g at 120 min, and the adsorption isotherm was proved to fit the Langmuir isotherm model. The reuse results confirmed that MPMs had an excellent regenerative capacity and reusability stability. Moreover, MPMs showed superior removal efficiency for the rice field pesticides (emamectin benzoate, imidacloprid) and antibiotics (ampicillin). The above observations demonstrated that MPMs were universal to organic pollutants and would be one of the most promising candidates in the water purification filed.

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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 in feedback mode was used to monitor changes in the surface state of a polymeric film applied on a metallic substrate when exposed to an aqueous electrolytic environment. The protected metal consisted of a carbon steel substrate coated with a polyurethane-based polymeric film. SECM measurements performed in the presence and absence of chloride anions permitted a specific effect caused by Cl- anions at early exposures to be detected. Significant surface roughening is observed for immersion times shorter than 1 day when the electrolyte contains chloride ions. Additionally, the growth of an individual blister could also be investigated.

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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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Titanium and alloys with titanium as the major component are widely used for making biomedical implants, such as artificial dental roots. In our laboratory, we have studied the kinetics of the self-healing reaction of the TiO2 film that forms on the surface of such an implant. Amperometric SECM approach curves were recorded over the surface of a grade 4 titanium (Ti G4) dental implant sample at specific times after the metal surface had been exposed to an air-saturated buffer solution. A ferrocene methanol redox mediator and a platinum microelectrode tip (r = 12.5 mum) were used in the experiments. The effective rate coefficient (keff) values for the mediator regenerating surface reaction were estimated using Wittstock’s method from the approach curves recorded at different time points. Decreasing values of keff over time indicated an increasing rate of formation of the passivating TiO2 film.

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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 viability and activity of HeLa cells were probed using scanning electrochemical microscopy (SECM). The feedback generated by HeLa cells during scanning depends on the electrochemical mediator. Living HeLa cells generated positive feedback when ferrocene methanol (FcMeOH) was oxidized at the tip, showing that the cells reduced FcMeOH+. The positive feedback with FcMeOH changed to negative feedback when the HeLa cells were exposed to toxic treatments, i.e. CN- or UVC radiation, suggesting that FcMeOH+ reduction can be used to monitor cell activity. Living HeLa cells also accumulate FcMeOH after exposure times of a few h, but the presence of mM concentrations of FcMeOH has no apparent effect on the cell viability. The effect of Ag+ (known to be toxic to bacteria at the 10 muM level) on HeLa cells was probed using the FcMeOH as an indicator. The activity of the HeLa cells was not affected in a culture medium containing Ag+ up to 10 mM. The uptake of Ag+ by living and dead HeLa cells was small and nearly the same, indicating that even at high Ag+ concentrations in the culture medium, only a small amount of Ag+ is accumulated within the cells.

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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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Two new ferrocenylsubphthalocyanine dyads with ferrocenylmethoxide (2) and ferrocenecarboxylate (3) substituents directly attached to the subphthalocyanine ligand via the axial position have been prepared and characterized using NMR, UV-vis, and magnetic circular dichroism (MCD) spectroscopies as well as X-ray crystallography. The redox properties of the ferrocenyl-containing dyads 2 and 3 were investigated using the cyclic voltammetry (CV) approach and compared to those of the parent subphthalocyanine 1. CV data reveal that the first reversible oxidation is ferrocene-centered, while the second oxidation and the first reduction are localized on the subphthalocyanine ligand. The electronic structures and nature of the optical bands observed in the UV-vis and MCD spectra of all target compounds were investigated by a density functional theory polarized continuum model (DFT-PCM) and time-dependent (TD)DFT-PCM approaches. It has been found that in both dyads the highest occupied molecular orbital (HOMO) to HOMO-2 are ferrocene-centered molecular orbitals, while HOMO-3 as well as lowest unoccupied molecular orbital (LUMO) and LUMO+1 are localized on the subphthalocyanine ligand. TDDFT-PCM data on complexes 1-3 are consistent with the experimental observations, which indicate the dominance of pi-pi* transitions in the UV-vis spectra of 1-3. The excited-state dynamics of the dyads 2 and 3 were investigated using time-correlated single photon counting, which indicates that fluorescence quenching is more efficient in dyad 3 compared to dyad 2. These fluorescence lifetime measurements were interpreted on the basis of DFT-PCM calculations.

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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 (SECM) is an electrochemical technique that is used to measure redox activity local to the surface of a sample. The incorporation of shear force (SF) feedback into SECM enables the concurrent acquisition of topographical data. Contemporary SECM measurements require a redox mediator (such as ferrocene methanol (FcMeOH)) for electrochemical measurements; however, redox mediators are detrimental to chemically sensitive materials such as biological cells. In this article, nanoscale polypyrrole membranes doped with dodecylbenzene sulfonate (PPy(DBS)) are deposited at the tip of highly sensitive ultra-microelectrodes (UME) to demonstrate a novel modification of the contemporary SECM?SF imaging technique that operates in the absence of a redox mediator. This technique leverages the redox activity of a PPy(DBS) membrane to locally detect changes in cation concentration. In conjunction with SF imaging, the PPy(DBS) membrane can (i) detect changes in distance from the surface by measuring changes in ion concentration of the diffusion shell, or (ii) detect local cation flux due to cell function when kept at a constant distance from the cell surface through SF-imaging techniques. Therefore, we predict this technique to enable high resolution mapping of surface cation concentrations and impact the field of biological imaging.

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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 paper deals with the development of different formats of screen-printed array of electrodes. The arrays consist of a silver pseudo-reference electrode surrounded by four or eight radially distributed working electrodes. Two different commercially available inks were used to fabricate the working electrode (WE) surfaces: a carbon-based ink and a gold-based ink. Due to their low curing temperature, the inks were screen-printed onto an inert plastic substrate. The electrochemical characterisation of these arrays is shown; reproducibility of the arrays as well as the batch-to-batch reproducibility were also assessed. As model case, the four WE array was used as platform to develop an electrochemical genosensor. Analytical parameters such as linearity range, reproducibility and detection limit of the genosensor were evaluated. Preliminary results on real samples were also reported.

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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 injection analysis (FIA) system suitable for measurements of glucose in blood serum is developed. In the proposed FIA system, a new kind of glucose sensor based on composite polymer films and well-immobilized enzyme was fabricated. An electrochemical technique of scanning electrochemical microscopy (SECM), and electrochemical impedance spectroscopy (EIS) were used for the characterization of the newly fabricated biosensor. A wide linear range of 0.1-50 mM for glucose detection was reported in virtue of the new configuration of the sensor and the developed FIA system. The reproducibility of signals was quite good with relative standard deviation (RSD) values for n = 4 injections (typically 5.7%). Animal blood serum was directly injected and assayed in this simulative physiological system. Good analytical recovery of glucose spiked into serum samples, with recoveries in the range of 96.7-105.0%, was exhibited. Under optimized conditions, detection of serum glucose for normal people and diabetics using our proposed method is possible.

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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 iron complex [Fp][OTf] {Fp+ = [Fe(CO)2(Cp)] +, OTf- = SO3CF3-} is an efficient catalyst for the direct substitution of the OH group in ferrocenylmethanol [Fc-CH2OH] by thiols, aromatic amines, diphenylphosphane, and carbon nucleophiles (furan, pyrrole, and indole). This approach offers a convenient route to ferrocenes containing side chains with different functional groups. The advantages of the method are associated with the use of a catalyst based on iron, which is a nontoxic and readily available transition metal, and in the direct OH substitution, which produces water as the only byproduct. Direct substitution of the OH group in ferrocenylmethanol by S, N, P, and C nucleophiles containing an active hydrogen atom (thiols, aromatic amines, diphenylphosphane, furan, pyrrole, indole) can be accomplished by use of the iron catalyst [Fe(CO)2(Cp)][OTf] (Cp = cyclopentadienyl, OTf = SO3CF3). 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