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Nanoelectrochemical approaches were used to investigate adsorption/desorption of hydrogen on Pt electrodes. These processes, which have been extensively studied over the last century, remain of current interest because of their applications in energy storage systems. The effective surface area of a nanoelectrode was found to be much larger than its geometric surface area due to surface diffusion of adsorbed redox species at the Pt/glass interface. An additional peak of hydrogen desorption was observed and attributed to the spillover of hydrogen from the Pt surface into glass. The results were compared to those obtained for underpotential deposition of copper on Pt nanoelectrodes.

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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 supramolecular assembly of a ferrocene-porphyrin conjugate allowed ferrocene-based electrochemical sensing of the metalloporphyrin axial coordination via a “tail on-tail off” binding process.

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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 syntheses and properties of corannulenes bearing different numbers and types of ferrocenyl groups are described. Six different monoferrocenylated corannulenes were synthesized, and the crystal structure of 1-corannulenyl-1?-(ferrocenyl)benzene was elucidated by single-crystal X-ray analysis. Further, diferrocenylated corannulenes bearing methyl or trifluoromethyl groups are reported. Buckybowls with four and five ferrocenyl substituents were synthesized from tetrabromocorannulene and the symmetrical pentachlorocorannulene. The molecular structure and nutshell-like crystal packing of a tetraferrocenylated corannulene was determined by single-crystal X-ray analysis. Additionally, all compounds presented herein were subjected to electrochemical and optical measurements in solution.

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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 binding properties of two electroactive glutathione-ferrocene conjugates that consist in glutathione attached to one or both of the cyclopentadienyl rings of ferrocene (GSFc and GSFcSG), to Schistosoma japonica glutathione S-transferase (SjGST) were studied by spectroscopy fluorescence, isothermal titration calorimetry (ITC) and differential pulse voltammetry (DPV). Such ferrocene conjugates resulted to be competitive inhibitors of glutathione S-transferase with an increased binding affinity relative to the natural substrate glutathione (GSH). We found that the conjugate having two glutathione units (GSFcSG) exhibits an affinity for SjGST approximately two orders of magnitude higher than GSH. Furthermore, it shows negative cooperativity with the affinity for the second binding site two orders of magnitude lower than that for the first one. We propose that the reason for such negative cooperativity is steric since, i) the obtained thermodynamic parameters do not indicate profound conformational changes upon GSFcSG binding and ii) docking studies have shown that, when bound, part of the first bound ligand invades the second site due to its large size. In addition, voltammetric measurements show a strong decrease of the peak current upon binding of ferrocene-glutathione conjugates to SjGST and provide very similar K values than those obtained by ITC. Moreover, the sensing ability, expressed by the sensitivity parameter shows that GSFcSG is much more sensitive than GSFc, for the detection of SjGST.

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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 lab-on-a-chip electroanalysis, the mass transfer of electroactive species towards the electrode surface limits the detection performance due to the difficulty in applying external convection. In this study, we proposed to integrate miniature acoustic resonator, fabricated by microelectrochemical system, within on-chip electroanalytical platform to improve electrochemical process. Gold film electrochemical sensor chip and acoustic resonator were assembled face-to-face with a polydimethylsiloxane chamber in between. Cyclic voltammetric (CV) responses of ferrocenemethanol were tested under actuation of miniature acoustic resonator at various powers. Resonator’s actuation results in sigmoidal CV curves and the diffusion limited current increases with the rise of applied power on resonator. The advantages of miniature acoustic resonator, including submillimeter small size, mass fabricability, low cost, low energy consumption, as well as outstanding performance towards enhancing electrochemical process, will strongly contribute to the development of highly-sensitive compact sono-electroanalytical devices.

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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 comparison of the analytical characteristics of two tyramine biosensors, based on graphene oxide (GRO) and polyvinylferrocene (PVF) modified screen-printed carbon electrodes (SPCE), is reported. Diamine oxidase (DAOx) or monoamine oxidase (MAOx) was immobilized onto the PVF/GRO modified SPCE to fabricate the biosensors. Surface characteristics and electrochemical behaviour of the modified SPCEs were investigated by atomic force microscopy (AFM), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX) and cyclic voltammetry (CV). Electrode surface composition and experimental variables such as pH and working potential were optimized in order to ensure a high performance. Under optimum experimental conditions, both DAOx/PVF/GRO/SPCE and MAOx/PVF/GRO/SPCE biosensors exhibited wide linear dynamic ranges for tyramine from 9.9×10?7 to 1.2×10?4 M and from 9.9×10?7 to 1.1×10?4 M, respectively. MAOx/PVF/GRO/SPCE biosensor showed higher sensitivity (11.98 muA mM?1) for tyramine determination than the DAOx/PVF/GRO/SPCE biosensor (7.99 muA mM?1). The substrate specifity of the biosensors to other biogenic amines namely histamine, putrescine, spermine, spermidine, tryptamine, beta-phenylethylamine and cadaverine was also investigated. The developed biosensors were successfully used for tyramine determination in cheese 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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Pnictogens are an intensively studied group of monoelemental two-dimensional materials. This group of elements consists of phosphorus, arsenic, antimony, and bismuth. In this group, the elements adopt two different layered structural allotropes, orthorhombic structure with true van der Waals layered interactions and rhombohedral structure, where covalent interactions between layers are also present. The orthorhombic structure is well known for phosphorus and arsenic, and the rhombohedral structure is the most thermodynamically stable allotropic modification of arsenic, antimony, and bismuth. Due to the electronic structure of pnictogen layers and their semiconducting character, these materials have huge application potential for electronic devices such as transistors and sensors including photosensitive devices as well as gas and electrochemical sensors. While photodetection and gas sensing applications are often related to lithography processed materials, chemical sensing proceeds in a liquid environment (either aqueous or non-aqueous) and can be influenced by surface oxidation of these materials. In this review, we explore the current state of pnictogen applications in sensing and electronic devices including transistors, photodetectors, gas sensors, and chemical/electrochemical sensors.

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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 class of phosphorus compounds containing a ferrocenyl unit are obtained from vinylferrocene and phosphono-substituted aromatic halides by using palladium-catalyzed Heck-type reactions. The crystal structure of compound 3a confirms the trans planar geometry of the pi-conjugated system. The electrochemistry and electronic absorption spectra of phosphorus esters 3a,b and acids 4a,b are 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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Porous crystals are excellent materials with potential spatial functions through molecular encapsulation within the pores. Co-encapsulation of multiple different molecules further expands their usability and designability. Herein we report the simultaneous arrangement of up to three different guest molecules, TTF (tetrathiafulvalene), ferrocene, and fluorene, on the pore surfaces of a porous crystalline metal-macrocycle framework (MMF). The position and orientation of adsorbed molecules arranged in the pore were determined by single-crystal X-ray diffraction analysis. The anchoring effect of hydrogen bonds between the hydroxy groups of the guest molecules and inter-guest cooperation and competition are significant factors in the adsorption behaviors of the guest molecules. This finding would serve as a design basis of multicomponent functionalized nanospaces for elaborate reactions that are realized in enzymes.

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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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By activating Si-H bonds, poly(hydromethylsiloxane) can be covalently bound in a first step to various metal or polymer surfaces. In a second step, unreacted Si-H bonds can be brought to react with organic compounds having adequate functional groups such as double or triple bonds, carbonyl or hydroxyl groups. This scheme is used to bind biorecognition groups to solids. The novel concept is demonstrated by attaching a newly synthesized biotin derivative to Au. It is shown that the immobilized biotin is capable of binding streptavidin.

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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