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Mediated fuel cells are electrochemical devices that produce power in a manner similar to that of conventional proton exchange membrane fuel cells (PEMFCs). They differ from PEMFCs in their use of redox mediators dissolved in liquid electrolyte to conduct oxidation of the fuel or reduction of the oxidant, typically O2, in bulk solution. The mediators transport electrons (and often protons) between the electrode and the catalysts or chemical reagents in solution. This strategy can help overcome many of the challenges associated with conventional fuel cells, including managing complex multiphase reactions (as in O2 reduction) or the use of challenging or heterogeneous fuels, such as hydrocarbons, polyols, and biomass. Mediators are also commonly used in enzymatic fuel cells, where direct electron transfer from the electrode to the enzymatic active site can be slow. This review provides a comprehensive survey of historical and recent mediated fuel cell efforts, including applications using chemical and enzymatic catalysts.

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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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Enzymes are biological catalysts with many industrial applications, but natural enzymes are usually unsuitable for industrial processes because they are not optimized for the process conditions. The properties of enzymes can be improved by directed evolution, which involves multiple rounds of mutagenesis and screening. By using mathematical models to predict the structure?activity relationship of an enzyme, and by defining the optimal combination of mutations in silico, we can significantly reduce the number of bench experiments needed, and hence the time and investment required to develop an optimized product. Here, we applied our innovative sequence?activity relationship methodology (innov’SAR) to improve glucose oxidase activity in the presence of different mediators across a range of pH values. Using this machine learning approach, a predictive model was developed and the optimal combination of mutations was determined, leading to a glucose oxidase mutant (P1) with greater specificity for the mediators ferrocene?methanol (12-fold) and nitrosoaniline (8-fold), compared to the wild-type enzyme, and better performance in three pH-adjusted buffers. The kcat/KM ratio of P1 increased by up to 121 folds compared to the wild type enzyme at pH 5.5 in the presence of ferrocene methanol.

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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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Ferrocenylmethy 1,2-dithiolane-3-pentanoate, which can be used to modify a gold electrode surface, was prepared by a condensation reaction with hydroxymethylferrocene and 1,2-dithiolane-3-pentanoic acid (D, L-alpha-lipoic acid). The condensation product has an 1,2-dithiolane ring which adheres to gold surfaces and a ferrocenyl group which is a redox site. The ferrocene rings on the modified electrode were electroactive in both acetonitrile and aqueous media.

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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 complexation of trimethyl(ferrocenylmethyl)ammonium hexafluorophosphate 1*(BF6), heptyldimethyl(ferrocenylmethyl)ammonium bromide 2*(Br) and ferrocenylmethanol 3 by sulfonated calix<6>arene host was investigated in aqueous media using electrochemical and 1H NMR spectroscopic techniques; the binding interactions between the calixarene host and the surveyed guests are similar to those operating in the complexation of organic compounds by cyclodextrin or cyclophane in aqueous media.

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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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Layered transition metal dichalcogenides (TMDs) have received a great deal of attention due to fact that they have varied band gap, depending on their metal/chalcogen composition and on the crystal structure. Furthermore, these materials demonstrate great potential application in a myriad of electrochemical technologies. Heterogeneous electron transfer (HET) abilities of TMD materials toward redox-active molecules occupy a key role in their suitability for electrochemical devices. Herein, we introduce a promising biosensing strategy based on improved heterogeneous electron transfer rate of WS2, WSe2, and WTe2 nanosheets exfoliated using tert-butyllithium (t-BuLi) and n-butyllithium (n-BuLi) intercalators decorated with vertically aligned TiO2 nanoplatelets. By comparison of all the nanohybrids, decoration of TiO2 on t-BuLi WS2 (TiO2@t-BuLi WS2) results in the fastest HET rate of 5.39 × 10-3 cm s-1 toward ferri/ferrocyanide redox couple. In addition, the implications of decorating tungsten dichalcogenides (WX2) with TiO2 nanoplatelets in enzymatic biosensor applications for H2O2 detection are explored. TiO2@t-BuLi WS2 outperforms all other nanohybrid counterparts and is demonstrated to be an outstanding sensing platform in enzyme-based biosensor with wide linear range, low detection limit, and high selectivity. Such conceptually new electrocatalytic detection systems shall find the way to the next generation biosensors.

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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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To immobilize enzymes at the surface of a nanoparticle-based electrochemical sensor is a common method to construct biosensors for non-electroactive analytes. Studying the interactions between the enzymes and nanoparticle support is of great importance in optimizing the conditions for biosensor design. This can be achieved by using a combination of analytical methods to carefully characterize the enzyme nanoparticle coating at the sensor surface while studying the optimal conditions for enzyme immobilization. From this analytical approach, it was found that controlling the enzyme coverage to a monolayer was a key factor to significantly improve the temporal resolution of biosensors. However, these characterization methods involve both tedious methodologies and working with toxic cyanide solutions. Here we introduce a new analytical method that allows direct quantification of the number of immobilized enzymes (glucose oxidase) at the surface of a gold nanoparticle coated glassy carbon electrode. This was achieved by exploiting an electrochemical stripping method for the direct quantification of the density and size of gold nanoparticles coating the electrode surface and combining this information with quantification of fluorophore-labeled enzymes bound to the sensor surface after stripping off their nanoparticle support. This method is both significantly much faster compared to previously reported methods and with the advantage that this method presented is non-toxic. [Figure not available: see fulltext.].

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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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In this work, a sensitive, universal and reusable electrochemical biosensor based on stannic oxide nanocorals-graphene hybrids (SnO2 NCs-Gr) is developed for target DNA detection by using two kinds of DNA enzymes for signal amplification through an autonomous cascade DNA duplication strategy. A hairpin probe is designed composing of a projecting part at the 3?-end as identification sequence for target, a recognition site for nicking endonuclease, and an 18-carbon shim to stop polymerization process. The designed DNA duplication?incision?replacement process is handled by KF polymerase and endonuclease, then combining with gold nanoparticles as signal carrier for further signal amplification. In the detection system, the electrochemical?chemical?chemical procedure, which uses ferrocene methanol, tris(2-carboxyethyl)phosphine and L-ascorbic acid 2-phosphate as oxidoreduction neurogen, deoxidizer and zymolyte, separately, is applied to amplify detection signal. Benefiting from the multiple signal amplification mechanism, the proposed sensor reveals a good linear connection between the peak current and logarithm of analyte concentration in range of 0.0001?1 × 10?11 mol L?1 with a detection limit of 1.25 × 10?17 mol L?1 (S/N=3). This assay also opens one promising strategy for ultrasensitive determination of other biological molecules for bioanalysis and biomedicine diagnostics.

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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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To date, there is an urgent need for cancer treatment to improve in many ways in order to successfully cure all cancers. Retinoic acid (RA) is a promising anti-cancer drug through influencing cancer stem cells (CSCs). Taxol is a chemotherapy drug for many cancers. To increase the anti-cancer effects of RA and taxol, we created a novel RA nanoparticle, FCRAN, which has the ability of carrying a second anti-cancer drug, taxol, using nanotechnological methods. The results of this study demonstrated that this RA nanoparticle was water-soluble and retained the same effects as RA on cancer cells, such as inhibiting the proliferation of CSCs, inducing the differentiation of CSCs, and enhancing the sensitivity of CSCs to chemotherapeutic drugs. In addition, this RA nanoparticle can be used to carry a second anticancer drug, taxol, to become FCRAN/T and synergistically enhance the anti-cancer effects of both drugs in vivo. Interestingly, the FCRAN/T is a targetable anti-cancer nanoparticle in the presence of higher levels of glutathione (GSH) in cancer cells. Our results demonstrate that our novel synthesized nanoparticles not only retain the RA functions, but can also carry a second anticancer drug to play a synergistic anticancer role with good water solubility, in particular FCRAN/T can target cancer cells. Therefore, our novel synthesized targetable anti-cancer nanoparticles have a better application prospect than that of RA or taxol alone.

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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 sandwich-type electrochemical biosensor for microRNA (miRNA) detection is developed based on magnesium oxide (MgO) nanoflower and graphene oxide?gold nanoparticles (GO?AuNPs) hybrids coupling with electrochemical?chemical?chemical (ECC) detection system. In this bioassay system, MgO nanoflowers and AuNPs are modified on electrode to act as sensing platform. The thiolated capture probe is then self-assembled onto AuNPs/MgO substrate via formation of Au-S bonds. Subsequently, a biotinylated DNA signal probe is conjugated to GO?AuNPs hybrids. When miRNA-21 is added, a sandwich complex is formed and a lot of signal indicators streptavidin-conjugated alkaline phosphatases (SA-ALP) are immobilized upon electrode by the specific reaction between avidin and biotin. Finally, ECC reaction is performed in the system to improve detection signal. The proposed sandwich-type assay benefits from advantages of sandwich-type structure for enhanced sensitivity and specificity, MgO nanoflowers/AuNPs as sensing platform and GO?AuNPs hybrids as signal carriers for signal amplification, and ECC as a sensitive detection system for low detection limit. This biosensor exhibits a good dynamic ranging from 0.1 to 100 fM and a low detection limit of 50 aM (S/N = 3) toward target miRNA-21.

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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 types of transformations (the metal complex protonation and oxidation) have been revealed in the ferrocenylmethanol??2?2??? system (HX = HClO4, CF3COOH) by means of electronic spectroscopy. The efficiency of protonation has been determined from the intensity of the FcCH2 + carbocation absorption band (lambdamax = 600 nm); it depends on the acid strength and relative concentration as well as the solvent nature. Kinetics of ferrocenylmethanol oxidation in dioxane has been studied in the presence of trifluoroacetic acid. Two alternative reaction mechanisms have been proposed, differing in the coordination type of the reagents.

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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