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In this work, a novel redox capacitor was designed for signal amplification in electrochemical detection. It was fabricated by co-electrodeposition of a conducting polymer, sulfonated polyaniline (SPAN) and chitosan on a glass carbon electrode, and its function was evaluated for being a localized source to transfer electron between FcCOOH (Fc) and Ru(NH3)6Cl3 in solution via redox cycling. Furthermore, the electrochemical detection of chloramphenicol, a broad-spectrum antibiotic was performed using the redox capacitor in the presence of Fc. A significant amplification in cathodic current response of chloramphenicol was obtained through a continuous redox-cycling reaction. The performance of the amplifying signal responded linearly to chloramphenicol in a concentration range of 0.05 to 50.0 mumol L?1 with a low detection limit of 0.01 mumol L?1. The proposed approach exhibited good reproducibility and stability, and could be used for detection of chloramphenicol in eye drops by standard addition method with the recoveries from 96.5 % to 103.0 %.

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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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Hierarchical porous gold films with a well-defined bimodal architecture have been made by electrodepositing gold at a constant current around a close-packed assembly of raspberry-like latex spheres (1200/60 nm) followed by template removal. Electrodeposition was stopped when the gold was either layer or 1 layer thick as evident from oscillations in the potential vs time traces. Scanning electron microscopy (SEM) images show the hierarchical pore structure with an ensemble of small ?20 nm openings located in a large ?1200 nm diameter macropore. Prior to electrochemical characterization, the electrodes were cleaned either chemically and/or via UV radiation and X-ray photoelectron spectroscopy (XPS) was used to evaluate the presence of residual polystyrene. Of the three cleaning methods investigated, sonication in chloroform-acetone followed by UV radiation proved best. The surface area of the hierarchical porous gold electrodes, determined by integrating the area under the gold oxide peak, was 4× larger than a bare gold electrode and 2× larger than a macroporous gold electrode prepared using unimodal, 1200 nm diameter latex spheres as the template. The electrochemical performance of the electrodes relative to the macroporous gold and flat gold was undertaken using cyclic voltammetry. The results show that the non-Faradaic current scales linearly with electrode area while the Faradaic current of a diffusing electrochemically reversible redox probe (ferrocene methanol) does not. For an adsorbed redox couple (ferrocene hexanethiol), the voltammetric wave shapes and surface coverage were different for the different electrodes.

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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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Graphene quantum dots (GQDs) – zero-dimensional materials – are sheets of a few nanometers in lateral dimension and exhibit quantum confinement and edge site effects where sp2-bonded carbon nanocore surrounded with edged plane functional moieties is promising as advanced electroactive sensing platforms. In this work, GQDs are synthesized by solvothermal and hydrothermal techniques, with optimal size of 5 nm. Their potential in fundamental (direct electron transfer) and applied (enzymatic glucose biosensor) electrochemistry are demonstrated. Glucose oxidase (GOx) immobilized on glassy carbon (GC) electrodes modified with GQDs are investigated by means of cyclic voltammetry, differential pulse voltammetry, and amperometry. Well-defined quasi-reversible redox peaks observed under various electrochemical parameters helped to determine diffusion coefficient (D) and first-order electron transfer rate (kET). The cyclic voltammetry curves showed homogeneous ion transport for GQD with D ranging between 8.45 × 10-9 m2 s-1 and 3 × 10-8 m2 s-1 following GO < rGO < GQD < GQD (with FcMeOH as redox probe) < GOx/rGO < GOx/GO < HRP/GQDs < GOx/GQDs. The developed GOx-GQDs biosensor responds efficiently and linearly to the presence of glucose over concentrations ranging 10 muM and 3 mM with limit of detection 1.35 muM and sensitivity 0.00769 muA muM-1·cm-2 as compared with rGO (0.025 muA muM-1 cm-2, 4.16 muM) and GO (0.064 muA muM-1 cm-2, 4.82 muM) nanosheets. The high performance and stability of GQDs is attributed to sufficiently large surface-to-volume ratio, excellent biocompatibility, abundant hydrophilic edge site density, and partially hydrophobic planar sites that favors GOx adsorption on the electrode surface and versatile architectures to ensure rapid charge transfer and electron/ion conduction (<10 ms). We also carried out similar studies with other enzymatic protein biomolecules on electrode surfaces prepared from GQD precursors for electrochemical comparison, thus opening up potential sensing applications in medicine as well as bio-nanotechnology. Therefore, this conceptually novel strategy might open impressive avenues to establish green and sustainable chemistry platforms. In my other articles, you can also check out more blogs about 1273-86-5 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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Supramolecular encapsulation is known to alter chemical properties of guest molecules. We have applied this strategy of molecular encapsulation to temporally control the catalytic activity of a stable copper(I)?carbene catalyst. Encapsulation of the copper(I)?carbene catalyst by the supramolecular host cucurbit[7]uril (CB[7]) resulted in the complete inactivation of a copper-catalyzed alkyne?azide cycloaddition (CuAAC) reaction. The addition of a chemical signal achieved the near instantaneous activation of the catalyst, by releasing the catalyst from the inhibited CB[7] catalyst complex. To broaden the scope of our on-demand CuAAC reaction, we demonstrated the protein labeling of vinculin with the copper(I)?carbene catalyst, to inhibit its activity by encapsulation with CB[7] and to initiate labeling at any moment by adding a specific signal molecule. Ultimately, this strategy allows for temporal control over copper-catalyzed click chemistry, on small molecules as well as protein targets.

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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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Horse-chestnut ethanolic extract was tested as potential corrosion inhibitor of bronze in simulated acid rain. The extract was analysed by FTIR, GC?MS and HPLC-PDA, and its anti-corrosion behaviour studied using a multiscale electrochemical approach by polarization curves, EIS and scanning electrochemical microscopy, along with SEM-EDS. 94 % inhibition efficiency was attained by developing a surface physisorbed film. A novel methodology for kinetic evaluation of dynamic adsorption of inhibitive species on metal surface is proposed using SECM, achieving good agreement with results from conventional electrochemical techniques. Excellent adsorption-desorption kinetic constants (ka = 0.102 s?1 mol?1 L; kd = 3.33 × 10-5 s?1) were determined.

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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 electrochemical properties of Ti20Mo alloys prepared using different fabrication procedures, namely cold crucible levitation melting (CCLM) and powder sintering, were investigated using linear potentiodynamic polarization and EIS measurements. The surface condition was established using AFM, with the observation of a more porous surface finish in the case of powder sintering. A major effect of surface conditioning on the corrosion resistance of Ti20Mo alloys was observed, where the compact finish exhibits a superior corrosion resistance in chloride-containing saline solutions. Less insulating surfaces towards electron exchange resulted for the more porous finish as revealed by scanning electrochemical microscopy (SECM).

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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 review is divided into two parts; the first one summarizes the main features of surface modification by diazonium salts with a focus on most recent advances, while the second part deals with diazonium-based biosensors including small molecules of biological interest, proteins, and nucleic acids.

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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 series of redox-labeled L-tyrosinamide (L-Tym) derivatives was prepared and the nature of the functional group and the chain length of the spacer were systematically varied in a step-by-step affinity optimization process of the tracer for the L-Tym aptamer. The choice of the labeling position on L-Tym proved to be crucial for the molecular recognition event, which could be monitored by cyclic voltammetry and is based on the different diffusion rates of free and bound targets in solution. From this screening approach an efficient electroactive tracer emerged. Comparable dissociation constants Kd were obtained for the unlabeled and labeled targets in direct or competitive binding assays. The enantiomeric tracer was prepared and its enantioselective recognition by the corresponding anti-D-Tym aptamer was demonstrated. The access to both enantiomeric tracer molecules opens the door for the development of one-pot determination of the enantiomeric excess when using different labels with well-separated redox potentials for each enantiomer. Trace compounds: Redox tracers have been synthesized for enantioselective electrochemical ligand binding assays by relying on the combined use of an oligonucleotide-aptamer receptor with the detection of the redox label. A rational step-by-step optimization procedure has been developed leading to a redox-labeled L-tyrosinamide derivative (see figure) conserving the high affinity towards the aptamer.

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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 reports the successful application of bamboo-like multiwalled carbon nanotubes (bCNT) non-covalently functionalized with calf-thymus double stranded DNA (dsDNA) as a robust platform (bCNT-dsDNA) to build electrochemical biosensors. The “model system” proposed here as a proof of concept was an enzymatic biosensor devoted to glucose quantification obtained by layer-by-layer self-assemby of polydiallyldimethylammonium (PDDA) and glucose oxidase (GOx) at glassy carbon electrodes (GCE) modified with bCNT-dsDNA (GCE/bCNT-dsDNA/(PDDA/GOx)n). The influence of GOx and PDDA assembling conditions and the effect of the number of PDDA/GOx bilayers (n) on the performance of the resulting biosensor is critically discussed. The supramolecular architecture was characterized by electrochemical impedance spectroscopy from the charge transfer resistance of quinone/hydroquinone and potassium ferrocyanide/potassium ferricyanide; by cyclic voltammetry from the surface concentration of GOx using ferrocene methanol as enzyme regenerator; by amperometry from the response of the enzymatically generated hydrogen peroxide; and by surface plasmon resonance from the changes in the plasmon resonance angle. The analytical parameters obtained with GCE/bCNT-dsDNA/(PDDA/GOx)3 for the amperometric quantification of glucose at 0.700 V were: sensitivity of (265 ± 7) muA mM-1 cm-2, linear range between 0.25 and 2.50 × 10-3 M, detection limit of 50 muM, repeatability of 3.6% (n = 10), and negligible interference from maltose, galactose, fructose and manose. The biosensor was successfully used for the sensitive quantification of glucose in beverages and a medicine 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 reaction of alpha-hydroxyferrocenylalkyl derivatives and vinylferrocene with 1,5-disubstituted tetrazoles in methylene chloride-aqueous acid HX (X = BF4, ClO4) two-phase systems gives a mixture of 1,3,5- and 1,4,5-trisubstituted tetrazolium salts, the fraction of the 1,3,5-isomers prevailing. The synthesized salts are readily dealkylated under the action of bases to give the above starting compounds. Heating of 3(4)-(ferrocenylmethylene)-1,5-pentamethylenetetrazolium and 3(4)-(ferrocenylmethylene)-2-methyl-1-phenyltetrazolium tetrafluoroborates in anhydrous methanol or ethanol in the presence of catalytic amounts of alkali gives rise to ferrocenylcarbinol ethers. Other nuclephiles (pyridine, triphenylphosphine, sodium thiocyanate, sodium p-toluenesulfinate, dibenzoylmethane) also react with the above tetrazolium salts, forming ferrocenylmethylation products. Heating of equimolar amounts of 3(4)-(ferrocenylmethylene)-1,5-pentamethylenetetrazolium or 3(4)- (ferrocenylmethylene)-2-methyl-1-phenyltetrazolium perchlorates with mercury(II) perchlorates in anhydrous ethanol results in mercuration of the starting tetrazolium salts, involving hydrogen substitution in the methylene or methyl groups bound to tetrazolium carbon atoms. The condensation of the same salts with p-N,N-(dimethylamino)nitrosobenzene, leading to azomethine formation, occurs under similar conditions.

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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