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Multichannel Front-End for Electrochemical Sensing of Metabolites, Drugs, and Electrolytes

A multi-channel front-end for electrochemical sensing is presented. It consists of a multiplexed four-channel readout interface supporting amperometric, voltammetric, and potentiometric measurements. The electronic interface is co-designed according to the target biomarker specifications, and exhibits excellent linearity in both current and voltage sensing. The sensing front-end is characterized with lactate, paracetamol, and lithium sensing, yielding sensitivity of {1.2} pm {0.3}, mu {A}/textit {mM} , {69.6} pm {2}, textit {nA}/mu {M} , and {55.6},textit {mV}/textit {decade} , respectively. These performances are comparable with the ones obtained with a bulky commercial Autolab potentiostat. Moreover, the limit of detection achieved are of {37}pm {8},mu {M} , {2.1}pm {1.22},mu {M} , and {11}pm {3.5},mu {M} , respectively, for the aforementioned sensors. These values are more than one order of magnitude lower than the relevant detection range. This successful characterization demonstrates the ability of the proposed system to monitor, in a broader sense, metabolites, drugs, and electrolytes. The programmability, versatility and portability of the front-end interface paves the way for a continuous monitoring of different families of biomarkers, suitable for advanced healthcare diagnosis and wearable physiology.

Multichannel Front-End for Electrochemical Sensing of Metabolites, Drugs, and Electrolytes

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Reference£º
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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Amperometric Biosensors for Tyramine Determination Based on Graphene Oxide and Polyvinylferrocene Modified Screen-printed Electrodes

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¡Á10?7 to 1.2¡Á10?4 M and from 9.9¡Á10?7 to 1.1¡Á10?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.

Amperometric Biosensors for Tyramine Determination Based on Graphene Oxide and Polyvinylferrocene Modified Screen-printed Electrodes

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Reference£º
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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C-N Bond Formation Catalyzed by Ruthenium Nanoparticles Supported on N-Doped Carbon via Acceptorless Dehydrogenation to Secondary Amines, Imines, Benzimidazoles and Quinoxalines

Ruthenium nanoparticles (NPs) supported on N-doped carbon (Ru/N?C) were prepared by the pyrolysis of cis-Ru(phen)2Cl2 loaded onto carbon powder (VULCAN XC72R) at 800 C. Ru/N?C NPs (0.2 mol% Ru) selectively catalyzed either acceptorless dehydrogenation coupling (ADC) or auto-transfer-hydrogen (ATH) reactions of amines with alcohols to imines and secondary amines. Such selectivity could be controlled by the choice of alkali metal ion associated with the base. Under similar catalytic conditions, the ADC cross-coupling of diamines with primary alcohols or diols afforded the corresponding benzimidazoles and quinoxalines in good to excellent yields. This catalytic system displayed good activity, recyclability, and wide applicability to a diverse range of substrates.

C-N Bond Formation Catalyzed by Ruthenium Nanoparticles Supported on N-Doped Carbon via Acceptorless Dehydrogenation to Secondary Amines, Imines, Benzimidazoles and Quinoxalines

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Reference£º
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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Enantioselective addition of diethylzinc to ferrocene carbaldehyde-reaction outcome by using natural compound based catalysts

The efficiency of the alkaloids quinine, cinchonine, cinchonidine and ephedrine, the aminoalcohols prolinol, and alaninol, as well as the aminoacids proline, and phenylalanine as catalysts for the enantioselective addition of diethylzinc to ferrocene carbaldehyde and benzaldehyde has been studied. The addition reactions proceeded with acceptable yields and low to moderate enantioselectivities. The side products ferrocenyl methanol and 1-ferrocenyl-1- propanone, observed during the additions to ferrocene carbaldehyde were isolated and characterized.

Enantioselective addition of diethylzinc to ferrocene carbaldehyde-reaction outcome by using natural compound based catalysts

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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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Ionic hydrogenation of acylferrocenes using zinc borohydride: An efficient, mild method for the preparation of alkylferrocenes

An effective mild procedure for the reductive deoxygenation of alpha-ferrocenyl aldehydes, ketones, and alcohols into the corresponding alkylferrocenes is described using a combination of zinc borohydride and zinc chloride. This is the first example of such reactivity of zinc borohydride. The present method allows the synthesis of alkylferrocenes bearing terminally functionalized pendant chains.

Ionic hydrogenation of acylferrocenes using zinc borohydride: An efficient, mild method for the preparation of alkylferrocenes

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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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Synthesis and characterization of ferrocene containing block copolymers

Narrowly dispersed diblock copolymers containing poly(methyl methacrylate) [PMMA] or poly(nonafluorohexyl methacrylate) [PF9MA] as the first block and poly(ferrocenylmethyl methacrylate) [PFMMA] as the second block, were prepared by anionic polymerization for the first time. Disordered bulk morphologies in the case of PMMA-b-PFMMA were observed and explained in terms of low Flory?Huggins interaction parameter (chi ? 0.04). In the case of PF9MA-b-PFMMA hexagonally packed cylinder morphology (HEX) was substantiated from TEM and SAXS observations. Furthermore, high incompatibility between PF9MA and PFMMA blocks allowed for the formation of well-ordered ferrocene containing cylinders on silica substrate upon exposure of the thin films to a saturated solvent vapor. It was shown that the cylinder orientation, parallel or perpendicular to the surface, could easily be controlled by appropriate choice of the solvent and without the need for preliminary surface modification, for example by means of grafted brush layer.

Synthesis and characterization of ferrocene containing block copolymers

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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 effects of drying time and relative humidity on the stability of sol-gel derived silicate films in solution

The stability of thin silicate films in solution has been evaluated as a function of drying time and drying conditions using scanning probe microscopy and an electrochemical probe technique. In these experiments, the silicate films were spin coated on various substrates using a sol formed by the acid catalyzed hydrolysis and condensation of tetramethoxysilane. The silicate films were then dried under a relative humidity of 25, 50, or 75% for 3, 12, 24, or 48 h. After drying, the films were immediately placed in a solution of potassium nitrate or a solution of a redox probe, specifically ferrocene methanol, ruthenium hexaammine, or cobalt phenanthroline. Cyclic voltammetry in conjunction with atomic force microscopy was used to monitor the disruption in gel structure as the films sat in aqueous solution. The stability of each film was found to be essentially independent of the substrate it was coated on but a strong function of the length of the drying time and the relative humidity under which it was dried. Films that were dried at 25% humidity for 48 h stayed on the electrode for several days. In contrast, films that were dried at 75% humidity for 3 h fell off the electrode within 24 h.

The effects of drying time and relative humidity on the stability of sol-gel derived silicate films in solution

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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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Mediated Catalytic Voltammetry of Holo and Heme-Free Human Sulfite Oxidases

Herein, we report the electrocatalytic voltammetry of holo and heme-free human sulfite oxidase (HSO) mediated by the synthetic iron complexes 1,2-bis(1,4,7-triaza-1-cyclononyl)ethane iron(III) bromide, ([Fe(dtne)]Br3.3H2O), potassium ferricyanide (K3[Fe(CN)6]), and ferrocene methanol (FM) at a 5-(4?-pyridinyl)-1,3,4-oxadiazole-2-thiol (Hpyt) modified gold working electrode. Holo HSO contains two electroactive redox cofactors, comprising a mostly negatively charged cyt b5 (heme) domain and a Mo cofactor (Moco) domain (the site of sulfite oxidation), where the surface near the active site is positively charged. We anticipated different catalytic voltammetry based on either repulsive or attractive electrostatic interactions between the holo or heme-free enzymes and the positively or negatively charged redox mediators. Both holo and heme-free HSO experimental catalytic voltammetry has been modeled by using electrochemical simulation across a range of sweep rates and concentrations of substrate and both positive and negatively charged electron acceptors ([Fe(dtne)]3+, [Fe(CN)6]3? and FM+), which provides new insights into the kinetics of the HSO catalytic mechanism. These mediator complexes have almost the same redox potential (all lying in the range +415 to +430 mV vs. NHE) and, thus, deliver the same driving force for electron transfer with the Mo cofactor. However, differences in the electrostatic affinities between HSO and the mediator have a significant influence on the electrocatalytic response.

Mediated Catalytic Voltammetry of Holo and Heme-Free Human Sulfite Oxidases

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Reference£º
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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Hydrogen and Atom Transfer Activity of Saffron Extracts by Square Wave Voltammetry

Saffron is an edible spice with highly appreciated sensory and antioxidant properties. One of the most representative redox species found in saffron extracts is crocin, whose content is used to evaluate the quality and value of the resulting spice. In this study, a voltammetry method based on the direct detection of crocin at a bare glassy carbon electrode is presented. The principle of the method is based on the monitoring of the anodic wave exhibited by crocin (0.1?1.0 mM) after its mixing with the azo radical initiator AAPH (20 mM) in ethanol:acetonitrile (1 : 1) solution. The decay rate of the anodic peak (E=+434 mV vs. Ag/Ag+), as a result of the consumption of crocin by AAPH, was used as index of the hydrogen transfer capacity and, thus, of its antioxidant activity. With a decay rate of k=0.02 h?1, crocin exhibits only a weak antioxidant activity in comparison with tocopherols (k=0.13 h?1), but still sufficient to protect against the oxidation of safranal, a further redox species found in saffron extracts and mainly responsible for its flavor. The proposed approach was finally applied to discriminate saffron extract samples from different geographical origins. The proposed approach is suitable to characterize the quality of saffron extracts and estimate its antioxidant properties.

Hydrogen and Atom Transfer Activity of Saffron Extracts by Square Wave Voltammetry

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Reference£º
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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Fluorescence quenching reaction of chlorophyll a by tris(acetylacetonate)iron(III) in various solvents

Chlorophyll a is known as the prevailing light absorbing pigment giving a strong absorption and fluorescence emission in visible region. Quenching reactions of the chlorophyll a fluorescence by Fe(acac)3 were precisely investigated in various organic solvents which are benzene toluene, ethanol, methanol, dmf, dmso and acetonitrile. Electron transfer performance of chlorophyll a by Fe(acac)3 was investigated from oxidative quenching reaction. Herein, the simplified Rehm-Weller relationship was used to calculate the free energy change of the photo-induced electron transfer reaction. Emission intensity decreased when the concentration of Fe(acac)3 quencher was increased. Non-linear Stern-Volmer plots are found to be affected by inner filter effect more than the ground state complex formation. Rate of quenching reactions (kq) were determined from the Stern-Volmer equation with corrected inner filter effect. The rates of quenching reactions occurred faster in high viscous solvents.

Fluorescence quenching reaction of chlorophyll a by tris(acetylacetonate)iron(III) in various solvents

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Reference£º
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