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Covalent immobilization of amino-beta-cyclodextrins on glassy carbon electrode in aqueous media

In the present work, the application of the amine electrooxidation method to achieve the grafting of amino beta-cyclodextrins (CD-amines) on glassy carbon electrodes (GCE) in aqueous media has been investigated. The results indicate that the electrooxidation procedure of CD-amines on GCE effects their covalent immobilization without the need of additional linkers or intermediates. Cyclic voltammograms of ferricyanide proved that the immobilized CDs cover at a large extent the GCE surface. This immobilization is due to real grafting and not the result of a weak physisorption interaction. Indeed, the presence of contributions characteristic of amide groups and the absence of peaks typical of amine groups in the XPS N 1s spectra of the modified GCE, support the evidence of the covalent bonding of the CDs to the glassy carbon surface through amide bond formation. Electrochemical experiments demonstrated that ferrocenemethanol and bentazon can be encapsulated within the cavity of the CDs immobilized on GCEs via the formation of inclusion compounds. Overall, the results of the present work show that this simple amine-electrooxidation strategy is suitable to immobilize CDs on glassy carbon surfaces while maintaining their inclusion abilities and, therefore, open the door to design cheap and simple electrochemical sensors for environmental applications.

Covalent immobilization of amino-beta-cyclodextrins on glassy carbon electrode in 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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Electrochemical behaviour of ferrocenes in tributylmethylphosphonium methyl sulfate mixtures with water and 1,2-dichloroethane

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 ¡Á 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 ¡Á 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 ¡Á 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.

Electrochemical behaviour of ferrocenes in tributylmethylphosphonium methyl sulfate mixtures with water and 1,2-dichloroethane

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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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Localized electrochemical characterization of organic coatings: A brief review

Local electrochemical techniques such as scanning electrochemical microscopy, scanning vibrating electrode technique, local electrochemical impedance spectroscopy, scanning Kelvin probe technique, and scanning ion-selective electrode technique have gained significant attention in organic coating research. These techniques have enhanced our understanding of the fundamental processes of corrosion at defects and underneath coatings. Each of these techniques employ unique measurement strategy to provide important local information about coatings, their protective properties, defects, and failure mechanisms. In this brief review, the basic principles of these techniques and the nature of information that has been extracted from these techniques to study organic coatings are discussed.

Localized electrochemical characterization of organic coatings: A brief review

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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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Reactions of ferrocenyl amines and alcohols with hexachlorocyclotriphosphazene

The reactions of ferrocenyl methanol, ferrocenyl 2-propanol and N-methyl-2-ferrocenylmethylamine with chlorocyclophosphazenes have been examined. The pentachlorocyclotriphosphazene derivative of ferrocenylmethanol undergoes rapid decomposition via a phosphazene-phosphazane rearrangement, however when the alcohol function is beta to the cyclopentadienyl ring modest yields of N3P3Cl5OCHMeCH2C5H 4FeCp may be obtained. By way of contrast N-methyl-2-ferrocenylmethylamine gives a broad range of stable derivatives, N3P3Cl6-n[NMeCH2C5H 4FeCp]n(n=1-3). The substitution process follows a predominantly trans non-geminal pathway. The corresponding reaction with the butylmethacrylate derivative, N3P3Cl5O(CH2) 4OC(O)CMe=CH2 leads to the unexpected geminal product, 2,2?-N3P3Cl4[O(CH2) 4OC(O)CMe=CH2]NMeCH2C5H 4FeCp. Polymers containing the 2-ferrocenylmethylamine function have been obtained by reactions of poly(dichlorophosphazene) with the ferrocenylamine and by radical addition polymerization of the aforementioned mixed ferrocenylamino butylmethacrylphosphazene. The new materials have been characterized by standard methologies including 31P NMR spectroscopy, cyclic voltametry and gel permeation chromatography.

Reactions of ferrocenyl amines and alcohols with hexachlorocyclotriphosphazene

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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

 

Extracurricular laboratory:new discovery of Ferrocenemethanol

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Electrochemical detection of amyloid-beta oligomer with the signal amplification of alkaline phosphatase plus electrochemical-chemical-chemical redox cycling

Soluble amyloid-beta oligomer (AbetaO) is believed to be a reliable molecular biomarker for the diagnosis of Alzheimer’s disease (AD) because of its high toxicity for neuronal synapse and higher concentration level in cerebrospinal fluid sample from AD patient than from control individual. At present, it is critical to develop a simple method for AbetaO detection with low cost as well as high sensitivity and selectivity. In this work, we reported an antibody-free electrochemical method for the detection of AbetaO based on the specific interaction between AbetaO and PrP(95-110) peptide, a segment of cellular prion protein. Specifically, cysteine-containing PrP(95-110) peptide was first immobilized on a gold electrode for the capture of AbetaO. Then, alkaline phosphatase-conjugated PrP(95-110) was used for the recognition of the captured AbetaO and the generation of electroactive species. Furthermore, an “outer-sphere to inner-sphere” electrochemical-chemical-chemical (ECC) redox cycling using ferrocene methanol as the redox mediator was employed to enhance the detection sensitivity. As a result, a detection limit of 3 pM for equivalent monomer was achieved. The amenability of this method to AbetaO analysis in a biological matrix was demonstrated by assays of AbetaO in serum samples.

Electrochemical detection of amyloid-beta oligomer with the signal amplification of alkaline phosphatase plus electrochemical-chemical-chemical redox cycling

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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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Synthesis and characterization of new ferrocene-containing ionic liquids

A series of several new families of ferrocene-containing imidazolium salts were synthesized by etherification of ferrocene methanol, acylation of ferrocene, and amide coupling of ferrocene carboxylic acid. The etherification was achieved by an acid-catalyzed procedure and very good yields of between 86-93-% were obtained. Next to the nature of the linkage itself, the lengths of the alkyl chains linking the ferrocenyl moiety and the imidazolium group and the nature of the counterions were also varied. Interestingly, a gamma-effect can be observed for the ether compounds but this effect was only visible in 13C NMR spectroscopy. These new redox-active ionic liquids were fully characterized by FTIR, 1H, 19F, and 13C NMR spectroscopy, and by MS, HRMS and elemental analysis. A novel series of ferrocenated ionic liquids with different spacer species between the ferrocenyl moiety and the imidazolium group have been developed. The spacer units have been established by amide coupling, etherification and acylation. The latter reaction is strongly influenced by the chain length of the acid chloride and a gamma-effect is observable for the ether compounds. Copyright

Synthesis and characterization of new ferrocene-containing ionic liquids

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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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Reduced graphene oxides: Influence of the reduction method on the electrocatalytic effect towards nucleic acid oxidation

For the first time a critical analysis of the influence that four different graphene oxide reduction methods have on the electrochemical properties of the resulting reduced graphene oxides (RGOs) is reported. Starting from the same graphene oxide, chemical (CRGO), hydrothermal (hTRGO), electrochemical (ERGO), and thermal (TRGO) reduced graphene oxide were produced. The materials were fully characterized and the topography and electroactivity of the resulting glassy carbon modified electrodes were also evaluated. An oligonucleotide molecule was used as a model of DNA electrochemical biosensing. The results allow for the conclusion that TRGO produced the RGOs with the best electrochemical performance for oligonucleotide electroanalysis. A clear shift in the guanine oxidation peak potential to lower values (~0.100 V) and an almost two-fold increase in the current intensity were observed compared with the other RGOs. The electrocatalytic effect has a multifactorial explanation because the TRGO was the material that presented a higher polydispersity and lower sheet size, thus exposing a larger quantity of defects to the electrode surface, which produces larger physical and electrochemical areas.

Reduced graphene oxides: Influence of the reduction method on the electrocatalytic effect towards nucleic acid oxidation

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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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Modification of Gold’s Work Function upon Adsorption of Mercaptobiphenylcarbonitrile: Experimental Evidence for a Theoretical Prediction

Tuning the energy of the frontier orbitals of an adsorbed molecule to match the Fermi level of the electrode is a fundamental requirement for efficient charge injection in molecular electronic devices. In this paper, we present electrochemical, impedimetric, spectroscopic, and scanning electrochemical microscopy (SECM) data that were used to study the effects of the adsorption of 4?-mercaptobiphenylcarbonitrile (HS2PCN) on the work function of gold. The adsorption process was studied and indicated the formation of a loosely packed self-assembled monolayer (SAM, DeltaGads = -43.3 kJ mol-1) following the immersion of the gold substrate in an ethanolic solution of HS2PCN. An increase in the immersion time resulted in the accumulation of negative charge density on the gold surface ascribed to the bonding dipoles resulting from the charge rearrangement at the metal-SAM interface that generates interfacial dipoles as a result of a charge-transfer process. As a consequence, a modification of about 1.2 eV is estimated in the work function of the gold surface modified with HS2PCN. Electron-transfer rate constants (k0), as measured via SECM, showed a strong dependence on the net charge of the redox probes and increased on going from negatively (ca. 1.14 ¡Á 10-3 cm s-1) to positively charged species (>1.0 cm s-1). Such behavior is ascribed to the polarity of the interface of the HS2PCN SAM on gold, which is negatively charged because of the electron-withdrawing property of the nitrile fragment.

Modification of Gold’s Work Function upon Adsorption of Mercaptobiphenylcarbonitrile: Experimental Evidence for a Theoretical Prediction

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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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Kinetic rotating droplet electrochemistry: A simple and versatile method for reaction progress kinetic analysis in microliter volumes

Here, we demonstrate a new generic, affordable, simple, versatile, sensitive, and easy-to-implement electrochemical kinetic method for monitoring, in real time, the progress of a chemical or biological reaction in a microdrop of a few tens of microliters, with a kinetic time resolution of ca. 1 s. The methodology is based on a fast injection and mixing of a reactant solution (1-10 muL) in a reaction droplet (15-50 muL) rapidly rotated over the surface of a nonmoving working electrode and on the recording of the ensuing transient faradaic current associated with the transformation of one of the components. Rapid rotation of the droplet was ensured mechanically by a rotating rod brought in contact atop the droplet. This simple setup makes it possible to mix reactants efficiently and rotate the droplet at a high spin rate, hence generating a well-defined hydrodynamic steady-state convection layer at the underlying stationary electrode. The features afforded by this new kinetic method were investigated for three different reaction schemes: (i) the chemical oxidative deprotection of a boronic ester by H2O2, (ii) a biomolecular binding recognition between a small target and an aptamer, and (iii) the inhibition of the redox-mediated catalytic cycle of horseradish peroxidase (HRP) by its substrate H2O2. For the small target/aptamer binding reaction, the kinetic and thermodynamic parameters were recovered from rational analysis of the kinetic plots, whereas for the HRP catalytic/inhibition reaction, the experimental amperometric kinetic plots were reproduced from numerical simulations. From the best fits of simulations to the experimental data, the kinetics rate constants primarily associated with the inactivation/reactivation pathways of the enzyme were retrieved. The ability to perform kinetics in microliter-size samples makes this methodology particularly attractive for reactions involving low-abundance or expensive reagents.

Kinetic rotating droplet electrochemistry: A simple and versatile method for reaction progress kinetic analysis in microliter volumes

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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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Ultrathin micropatterned porphyrin films assembled via zirconium phosphonate chemistry

The synthesis of a phosphonic-acid-functionalized porphyrin is presented and a procedure for the reproducible assembly of the porphyrins into thin films on glass or conductive glass surfaces is described. The assembly scheme, which utilizes established zirconium phosphonate (ZrP) chemistry, yields highly oriented films (normal to the surface) of well-defined thicknesses. In the lateral direction (plane parallel to the surface) the porphyrins interact by edge-on-edge contact and are characterized by significant porosity. Electrochemical redox-probe experiments indicate the existence of openings or pores of several angstroms in width in both monolayer and multilayer ZrP porphyrin films. Micropatterned versions of the films, capable of diffracting visible light, have also been prepared and have been used for the direct evaluation of film thicknesses via atomic force microscopy.

Ultrathin micropatterned porphyrin films assembled via zirconium phosphonate chemistry

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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