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A series of ferrocene derivatives, which have diverse redox potentials modulated by functional groups, have been synthesized as potential ?multi-potential? probes. A Hammett constant analysis revealed a linear free energy correlation between the redox potentials and the electron density of the ferrocene derivatives as determined by the choice of functional group used to modify the ferrocene core.

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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 new efficient approach for the ferrocenylmethylation of various alcohols, OH-, SH- and SeH-acids (carboxylic, thio- and selenophosphinic) as well as 1H-triazoles is elaborated based on the acid-catalyzed reaction with available vinyloxymethylferrocene. The reaction readily occurs under mild conditions to afford product of O-, N-, S- and Se-ferrocenylmethylation of the corresponding nucleophiles in good to high 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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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 design and operation of biosensors is not trivial. For instance, variation in the output signal during monitoring of analytes can not usually be controlled. Hence, if such control were possible, and could be triggered on demand, it would greatly facilitate system design and operation. Herein, we report the design of two types of voltamperometric immunosensors, in which the magnitude of the current output signal (differential pulse voltammetry [DPV]) can be increased or decreased as needed. The designed systems use monoclonal and polyclonal anti-human IgG antibodies, conjugated to monopodal ferrocene-modified gold nanoparticles that are casted onto screen-printed carbon electrodes (Ab/mFcL/AuNPs/SPCEs). Upon addition of human IgG as antigen, the systems exhibit opposite responses according to the Ab: the current decreases when monoclonal Ab is used, whereas it increases when polyclonal Ab is used. We attributed the former response to inhibition of electron-transfer (due to the formation of a protein layer), and the latter response, to a global increase in electron transfer (induced by the aggregation of gold nanoparticles). These effects were confirmed by studying a custom-made lipoic acid-based bipodal ligand, which confirmed that the increase in current is effectively induced by the aggregation of the modified nanoparticles (pAb/mFcL/AuNPs). Both sensors have large dynamic ranges, although the pAb-based one was found to be 3.3-times more sensitive. Tests of selectivity and specificity for ovalbumin, alpha-lactalbumin and serum bovine albumin showed that the immunosensors are highly selective and specific, even in the presence of up to 1000-fold levels of potentially competitive proteins. The limit of detection for human IgG using the pAb/mFcL/AuNP bioconjugate was estimated to be 0.85 ng/mL. The pAb/mFcL/AuNPs-based biosensor has used to determine amounts of human IgG in real sample.

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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 catalytic activity of low-dimensional electrocatalysts is highly dependent on their local atomic structures, particularly those less-coordinated sites found at edges and corners; therefore, a direct probe of the electrocatalytic current at specified local sites with true nanoscopic resolution has become critically important. Despite the growing availability of operando imaging tools, to date it has not been possible to measure the electrocatalytic activities from individual material edges and directly correlate those with the local structural defects. Herein, we show the possibility of using feedback and generation/collection modes of operation of the scanning electrochemical microscope (SECM) to independently image the topography and local electrocatalytic activity with 15-nm spatial resolution. We employed this operando microscopy technique to map out the oxygen evolution activity of a semi-2D nickel oxide nanosheet. The improved resolution and sensitivity enables us to distinguish the higher activities of the materials? edges from that of the fully coordinated surfaces in operando. The combination of spatially resolved electrochemical information with state-of-the-art electron tomography, that unravels the 3D complexity of the edges, and ab initio calculations allows us to reveal the intricate coordination dependent activity along individual edges of the semi-2D material that is not achievable by other methods. The comparison of the simulated line scans to the experimental data suggests that the catalytic current density at the nanosheet edge is ?200 times higher than that at the NiO basal plane.

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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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In the present work we report the results concerning the synthesis of Ti-C films obtained by a co-sputtering process of both titanium and graphite targets. The titanium content within the coatings has been adjusted in a wide range, allowing different structures of the films, to be formed. The chemical composition of the films was determined by X-ray photoelectron spectroscopy (XPS). Phase structure was analyzed by grazing angle X-ray diffraction (GXRD), while the morphology and microstructure were investigated by scanning electron microscopy (SEM). The possibility of using the resulting materials for electrochemical applications was also examined. For these purposes, the Ti-C films used as electrodes were investigated in terms of both reactivity and stability. Electrochemical investigations were carried out by using cyclic voltammetry and spectroscopy electrochemical techniques.

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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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Cyclic voltammetry and controlled-potential coulometry show that ferrocenyl alcohols of type (C5H5)Fe(C5H4)C(OH)RR? and ferrocenediols of type Fe[(C5H4)CCR?(OH)]2 undergo quantitative and reversible one-electron oxidation at the metal centre, and that the redox potentials are controlled predominantly by the inductive effects of the substituents at the alpha-carbon. The crystal structure of the new alcohol ferrocenyl(2-furyl)phenylmethanol not only confirms its molecular constitution, but also demonstrates that in the solid state it forms centrosymmetric hydrogen-bonded dimers involving cyclic (OH)2 bridge without any participation of the furan oxygen atom in the hydrogen bonding.

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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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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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Electrochemical experiments were carried out in a nanometer-sized cylindrical thin layer cell (TLC) formed by etching the surface of a disk-type platinum nanoelectrode (5- to 150-nm radius). Using high frequency ac voltage, the surface of such an electrode was etched to remove a very thin (? 1-nm-thick) layer of Pt. The resulting zeptoliter-scale cavity inside the glass sheath was filled with aqueous solution containing redox species, and the etched electrode was immersed in a dry (no external solution) pool of mercury to produce a TLC. Several approaches based on steady-state voltammetry and scanning electrochemical microscopy (SECM) were developed to independently evaluate the electrode radius and the etched volume. The number of redox molecules in the TLC could be varied between one and a few hundred by changing its volume and solution concentration. In this way, the transition between a random and deterministic number of trapped molecules was observed. High quality steady-state voltammograms of ?1 molecules were obtained for different neutral and charged redox species and different concentrations of supporting electrolyte. The analysis of such voltammograms yields information about mass transfer, adsorption, electron transfer kinetics, and double-layer effects on the nanoscale.

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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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Cobalt(II) complexes (5 mol% Co) bearing phosphine-free N?N?N pincer ligands efficiently catalyze C?C coupling of secondary and primary alcohols to selectively form alpha-alkylated ketones with a good functional group compatibility using NaOH (20 mol%) as a base at 120 C. The NH group on the N?N?N?Co(II) precatalyst controls the activity and selectivity. This simple catalytic system is involved in the synthesis of quinolones via the dehydrogenative annulation of 2-aminobenzyl alcohols with secondary alcohols.

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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