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Redox enzymes, which catalyze electron transfer reactions in living organisms, can be used as selective and sensitive bioreceptors in biosensors, or as efficient catalysts in biofuel cells. In these bioelectrochemical devices, the enzymes are immobilized at a conductive surface, the electrode, with which they must be able to exchange electrons. Different physicochemical methods have been coupled to electrochemistry to characterize the enzyme-modified electrochemical interface. In this Review, we summarize most efforts performed to investigate the enzymatic electrodes at the micro- and even nanoscale, thanks to microscopy techniques. Contrary to electrochemistry, which gives only a global information about all processes occurring at the electrode surface, microscopy offers a spatial resolution. Several techniques have been implemented; mostly scanning probe microscopies like atomic force microscopy, scanning tunneling microscopy, and scanning electrochemical microscopy, but also scanning electron microscopy and fluorescence microscopy. These studies demonstrate that various information can be obtained thanks to microscopy at different scales. Electrode imaging has been performed to confirm the presence of enzymes, to quantify and localize the biomolecules, but also to evaluate the morphology of immobilized enzymes, their possible conformation changes upon turnover, and their orientation at the electrode surface. Local redox activity has also been imaged and kinetics has been resolved.

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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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We want to report on syntheses and test reactions of some ferrocenic compounds which could be used as derivatizing reagents for peptides and proteins in order to detect them electrochemically after an HPLC analysis run.Among the tested compounds we found the 3-ferrocenylpropionic anhydride as the most suitable reagent for this purpose.It is a stable compound which can be prepared with high yields from 3-ferrocenylpropionic acid.Its reaction products with peptides and proteins are highly electroactive which is essential for the sensibility and selectivity of the method.

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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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Three-dimensional printed multi-purpose electrochemical devices for X-ray absorption spectroscopy are presented in this paper. The aim of this work is to show how three-dimensional printing can be a strategy for the creation of electrochemical cells for in situ and in operando experiments by means of synchrotron radiation. As a case study, the description of two cells which have been employed in experiments on photoanodes for photoelectrochemical water splitting are presented. The main advantages of these electrochemical devices are associated with their compactness and with the precision of the three-dimensional printing systems which allows details to be obtained that would otherwise be difficult. Thanks to these systems it was possible to combine synchrotron-based methods with complementary techniques in order to study the mechanism of the photoelectrocatalytic 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

Chemical engineers ensure the efficiency and safety of chemical processes, adapt the chemical make-up of products to meet environmental or economic needs, and apply new technologies to improve existing processes. Quality Control of Ferrocenemethanol. Catalysts allow a reaction to proceed via a pathway that has a lower activation energy than the uncatalyzed reaction. Introducing a new discovery about 1273-86-5, Name is Ferrocenemethanol

Electron transfer (ET) reactions in ionic liquid (IL)|organic solvent (1,2-dichloroethane, DCE) and IL|water mixtures were investigated using a Pt disk ultramicroelectrode (UME) along with ferrocene (Fc) and ferrocenemethanol (FcCH2OH) redox probes as electroactive species dissolved in the respective mixtures. The IL utilized was tributylmethylphosphonium methyl sulfate (P4441CH3SO4). The diffusion coefficient of each redox species was determined at each incremental increase of DCE or water to the IL using a chronoamperometric technique that is concentration independent. The IL|DCE mixture exhibited little change in the Fc diffusion coefficient, DFc, up to a DCE mole fraction (chiDCE) of 0.5; the observed value, 2.0 × 10-8 cm2 s-1, agrees well with that typically reported for ILs in the literature. After which, the DFc quickly rose to a value commonly found in conventional molecular solvents, 1.3 × 10-5 cm2 s-1 (at chiDCE = 0.8). An analogous result was not observed for IL|water mixtures using FcCH2OH, such that DFcCH2OH varied from 0.2 to 1.2 × 10-9 cm2·s-1 at a chiH2O of 0 to 0.8. It was proposed that a large increase in the DFc in the IL|DCE mixture versus DFcCH2OH in the IL|water series was owing to P4441CH3SO4’s more hydrophobic character. Its hydrophobicity was quantified by measuring the formal ion transfer potentials of the IL component ions at a water|DCE immiscible interface.

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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 mechanism of electron transfer of ferrocenylmethanol through the self-assembled monolayer (SAM) of mercaptosuccinic acid (MSA) on gold was investigated. A key finding is that the hydrogen-bonded FcMeOH plays the role of a mediator in the electron transfer involving the physically adsorbed glucose oxidase at the MSA SAM surface. The space-conformation of the hydrogen-bonding between FcMeOH and MSA was obtained by computational methods. The FcMeOH interacts with MSA via the strong hydrogen bond with the short distance around 1.9 A at two different binding sites, approving the statements of hydrogen-bonding. The intermolecular hydrogen-bonding between redox mediator (FcMeOH) and the artificial self-assembled monolayer (MSA) is evident, and the mechanistic study of heterogeneous electron transfer kinetics is meaningful for the biosensor applications.

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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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Triazole-based novel dendrimers with ferrocenyl surface groups have been achieved through click chemistry, both by divergent and convergent approaches. The presence of more ferrocenyl and triazolyl units in dendrimers 1-4 alters the current potential curve in the voltammogram and also the absorption coefficient in the UV-vis spectrum.

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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 a simple and miniaturized microdroplet chip (muchip) that is constructed with a silica nanochannel (SNC)-assisted electrode array and a hydrophobic paper cover (SNC&P-muchip). Vertically aligned SNCs with uniform pore size of 2?3 nm in diameter and negatively charged surface can significantly accelerate the mass transport of the positively charged tris(2,2′-bipyridyl) ruthenium (II), resulting in a remarkably enhanced electrochemiluminescence (ECL) signal. The SNC-assisted electrode array was coupled to a low cost paper cover to achieve simultaneous detection of six samples in 1 min. The feasibility and universality of the SNC&P-muchip was evaluated by detecting a series of alkaloidal drugs both in buffers and in human serum. The performance of the SNC&P-muchip was fully validated with respect to linearity (0.9999 > R > 0.9939), sensitivity (limits of detection from 1.799 nM to 11.43 nM), and accuracy (recovery rate between 94.38% and 109.12%). The facile and economic SNC&P-muchip shows promising potential for rapid drug detection in complex biofluids.

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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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Transient concentration gradients generated and detected electrochemically in continuous flow microchannels were investigated by numerical simulations and amperometric measurements. Operating conditions including device geometry and hydrodynamic regime were theoretically delineated for producing gradients of various profiles with tunable characteristics. Experiments were carried out with microfluidic devices incorporating a dual-channel-electrode configuration. Under these conditions, high electrochemical performance was achieved both to generate concentration gradients and to monitor their dynamics along linear microchannels. Good agreement was observed between simulated and experimental data validating predictions between gradient properties and generation conditions. These results demonstrated the capability of electrochemical microdevices to produce in situ tunable concentration gradients with real-time monitoring. This approach is versatile for the active control in microfluidics of microenvironments or chemical gradients with high spatiotemporal resolution.

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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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Integrated amperometric biosensors for the determination of l-malic and l-lactic acids were developed by coimmobilization of the enzymes l-malate dehydrogenase (MDH) and diaphorase (DP), or l-lactate oxidase (LOX) and horseradish peroxidase (HRP), respectively, together with the redox mediator tetrathiafulvalene (TTF), on a 3-mercaptopropionic acid (MPA) self-assembled monolayer (SAM)-modified gold electrode by using a dialysis membrane. The electrochemical oxidation of TTF at +100 mV (vs. Ag/AgCl), and the reduction of TTF+ at -50 mV were used for the monitoring of the enzyme reactions involved in l-malic and l-lactic acid determinations, respectively. Experimental variables concerning the biosensors composition and the detection conditions were optimized for each biosensor. Good relative standard deviation values were obtained in both cases for the measurements carried out with the same biosensor, with no need of cleaning or pretreatment of the bioelectrodes surface, and with different biosensors constructed in the same manner. After 7 days of continuous use, the MDH/DP biosensor still exhibited 90% of the original sensitivity, while the LOX/HRP biosensor yielded a 91% of the original response after 5 days. Calibration graphs for l-malic and l-lactic were obtained with linear ranges of 5.2 × 10-7 to 2.0 × 10-5 and 4.2 × 10-7 to 2.0 × 10-5 M, respectively. The calculated detection limits were 5.2 × 10-7 and 4.2 × 10-7 M, respectively. The biosensors exhibited a high selectivity with no significant interferences. They were applied to monitor malolactic fermentation (MLF) induced by inoculation of Lactobacillus plantarum CECT 748T into a synthetic wine. Samples collected during MLF were assayed for l-malic and l-lactic acids, and the results obtained with the biosensors exhibited a very good correlation when plotted against those obtained by using commercial enzymatic kits.

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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 work proposes the use of an electronic tongue based on flow injection coulometry for the rapid determination of the antioxidant capacity of fresh lettuce. The e-tongue consisted of a series of 16 porous carbon electrodes, each poised at a fixed potential from +100 to +850 mV. Each injection leaded to a characteristic hydrodynamic voltammogram, whose profile reflects the composition of antioxidants. The correlation between the peak area recorded by each sensor and the 1,1-Diphenyl-2-picryl-hydrazyl (DPPH) assay was maximum in the range of potentials between +400 and 750 mV (R2>0.97). Accordingly, the charge measured provided a direct and simple index of the antioxidant capacity. The practical utility of such index was initially demonstrated by determining the best extraction conditions. This consisted in freeze-drying of lettuce followed by methanolic extraction. Later, the e-tongue was used to evaluate the effect of storage (one week at 5 C) on lettuce. The e-tongue revealed that lettuce lost up to 25 % of their initial antioxidant activity during storage. However, when lettuce samples were pre-treated with fast cooling or vacuum cooling, the decrease of the antioxidant index was limited to 14 and 15 %. Overall, the e-tongue is a rapid, simple and sensitive method for the determination of the antioxidant capacity of fresh lettuce samples. Indirectly, these findings suggest also that lettuce may serve as potential dietary sources of natural phenolic antioxidants.

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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