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The size of the diamond particle is tailored to nanoscale (nanodiamond, ND), and the ND surface is engineered targeting specific (electrochemical and biological) applications. In this work, we investigated the complex surface redox chemistry of immobilized ND layer on conductive boron-doped diamond electrode with a broad experimental parameter space such as particle size (nano versus micron), scan rate, pH (cationic/acidic versus anionic/basic), electrolyte KCl concentration (four orders of magnitude), and redox agents (neutral and ionic). We reported on the significant enhancement of ionic currents while recording reversible oxidation of neutral ferrocene methanol (FcMeOH) by almost one order of magnitude than traditional potassium ferricyanide (K3Fe(CN)6) redox agent. The current enhancement is inversely related to ND particle diameter in the following order: 1 mum << 1000 nm < 100 nm < 10 nm ? 5 nm < 2 nm. We attribute the current enhancement to concurrent electrocatalytic processes, i.e. the electron transfer between redox probes and electroactive surface functional (e.g. hydroxyl, carboxyl, epoxy) moieties and the electron transfer mediated by adsorbed FcMeOH+ (or Fe(CN)6 3+) ions onto ND surface. The first process is pH dependent since it depends upon ND surface functionalities for which the electron transfer is coupled to proton transfer. The adsorption mediated process is observed most apparently at slower scan rates owing to self-exchange between adsorbed FcMeOH+ ions and FcMeOH redox agent molecules in diffusion-limited bulk electrolyte solution. Alternatively, it is hypothesized that the surface functionality and defect sites (sp2-bonded C shell and unsaturated bonds) give rise to surface electronic states with energies within the band gap (midgap states) in undoped ND. These surface states serve as electron donors (and acceptors) depending upon their bonding (and antibonding) character and, therefore, they can support electrocatalytic redox processes in the presence of specific redox-active molecules via feedback mechanism. Apparently, FcMeOH+ tended to have electrostatic affinity for negatively charged ND surface functionalities, corroborated by present experiments. We also attempted to study biocatalytic process using model metalloprotein (cytochrome c; Cyt c) immobilized on ND particles for investigating interfacial electron transfer kinetics and compared with those of functionalized graphene (graphene oxide; GO and reduced GO). The findings are discussed in terms of interplay of sp3-bonded C (ND core) and sp2-bonded C (ND shell and graphene-based systems). Interested yet? This just the tip of the iceberg, You can reading other blog about 1273-86-5 .Reference of 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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This review analyzes electrochemical biosensors for the determination of lactate (lactic acid) and pyruvate (pyruvic acid) concentrations in liquid samples, especially in the blood serum. The biosensor systems for the simultaneous determination of both substances and commercial variants of the biosensors are presented, and the biosensors for medical diagnostics are highlighted. The information concerning the necessity of separate and simultaneous determination of lactate and pyruvate, as well as lactate to pyruvate ratio, is given; the traditional methods for the determination of these substances are briefly described. Lactate dehydrogenase and lactate oxidase are shown to be most commonly used in the biosensors for lactate detection. Pyruvate oxidase and living cells are used in the biosensors for pyruvate detection. Different methods of the enzymes immobilization are presented, as well as strategies for enhancement of the biosensor sensitivity. An additional requirement for practical applications is the biosensor resistance to electroactive interferents, inhibitors, biofouling, and electrode passivation; thus, the variants of solving these problems in the biosensors for lactate and pyruvate detection are analyzed.

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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 new form of high surface bioelectrode based on electrospun gold microfiber with -immobilized glucose oxidase was developed. The gold fibers were prepared by electroless deposition of gold nanoparticles on a poly(acrylonitrile)-HAuCl4 electrospun fiber. The material was characterized using electron microscopy, XRD and BET, as well as cyclic voltammetry and biochemical assay of the immobilized enzyme. The surface area of the gold microfibers was 2.5 m2/g. Glucose oxidase was covalently crosslinked to the gold surface using cystamine monolayer and glutardialdehyde, and portrayed characteristic catalytic currents for oxidizing glucose using a ferrocene methanol mediator. Limit of detection of glucose is 0.1 mM. The K m of the immobilized enzyme is 10 mM, in accordance with other reports of immobilized glucose oxidase. The microfiber electrode was reproducible and showed correlation between fiber weight, cathodic current and enzymatic loading.

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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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Ferrocenylalkyl nitro-imidazoles (4a-h, 5a-h) were prepared via the regiospecific reaction of the alpha-(hydroxy)alkyl ferrocenes, FcCHR (OH) (1a?h; Fc = ferrocenyl; R = H, Me, Et, Pr, i-Pr, Ph, ortho-Cl-Ph, ortho-I-Ph), with nitro-imidazoles in aqueous organic medium (H2O-CH2Cl2) at room temperature in the presence of HBF4, within several minutes in good yields. X-ray structural data for racemic (R,S)-1-N-(benzyl ferrocenyl)-2-methyl-4-nitroimidazole (5f) were determined. The resulting enantiomers were resolved into enantiomers by analytical HPLC on modified amylose or cellulose chiral stationary phases. The viabilities of 4b, 4d, 5b, 5c in vitro, and in experiments in vivo antitumor effects of 1-N-ferrocenylethyl-4-nitroimidazole (4b) against murine solid tumor system Ca755 carcinoma were evaluated.

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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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Electrochemical studies of the free ferrocenylphosphine ligands FcCH2PR2 (Fc=(eta5-C5 H5)Fe(eta5-C5H4); R=Ph, CH2OH and CH2CH2CN) and some phosphine oxide, phosphine sulfide, phosphonium and metal derivatives are described. The free ligands exhibit complex voltammetric responses due to participation of the phosphorus lone pair in the redox reactions. Uncomplicated ferrocene-based redox chemistry is observed for PV derivatives and when the ligands are coordinated in complexes cis-PtCl2[FcCH2P(CH2OH) 2], PdCl2[FcCH2P(CH2OH) 2], [Au{FcCH2P(CH2OH)2} 2]Cl, RuCl2(eta6-C10 H14)[FcCH2P(CH2OH)2] and RuCl2(eta6-C10H14) (FcCH2PPh2). The reaction pathways of the free ligands after one-electron oxidation have been examined in detail using voltammetry, NMR spectroscopy and electrospray mass spectrometry. Direct evidence for formation of a P-P bonded product is presented.

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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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Alkylation reactions of [Pt2(mu-S)2(PPh 3)4] with haloalkylferrocenes FcCH2Cl, Fc(CH2)6Br and Fc(CH2)11Br [Fc = (eta5-C5H5)Fe(eta5-C5H4)] gave the cationic mu-thiolate complexes [Pt2(mu-S){mu-S(CH2) nFc}(PPh3)4]+ (n = 1, 6, 11), isolated as PF6 and/or BPh4 salts, and characterised by ESI mass spectrometry, NMR spectroscopy, microelemental analysis, and by an X-ray structure determination on [Pt2(mu-S){mu-SCH2Fc} (PPh 3)4]PF6. The complex contains the typical folded {Pt2(mu-S)2} core with an axial ferrocenylmethylthi-olate ligand. The corresponding selenolate complex [Pt 2(mu-Se){mu-SeCH2Fc}(PPh3) 4]+ was similarly obtained by alkylation of [Pt 2(mu-Se)2(PPh3)4] with FcCH 2Cl, and isolated as PF6 and BPh4 salts. The attempted liberation of FcCH2SH from [Pt2(mu-S){mu- SCH2Fc}(PPh3)4]+ using Na 2S was not successful.

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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 electrochemical kinetics for the oxidation of ferrocenemethanol (FcCH2OH) over the whole composition range of dimethyl sulfoxide (DMSO)-water solutions of different viscosities (I·) containing 50.0 mM (CH3)4NClO4 (TMAP) at a Pt microelectrode was studied using scanning electrochemical microscopy (SECM). The measured diffusion coefficient, DFcCH2OH, as well as the standard rate constant of the heterogeneous electron transfer, k0, as a function of solution composition, showed a minimum at about a DMSO molar fraction (xDMSO) of 0.33, corresponding to the mixture with the maximum solution viscosity. The largest k0 value found, 2.06 A± 0.31 cm s-1 in pure water (electrolyte) medium, was about 15 times larger than that obtained in the solution of xDMSO = 0.33 (0.14 A± 0.02 cm s-1). A good linear correlation between ln k0 and ln I· was observed within the solution composition range of 0.10 a¿¿ xDMSO a¿¿ 0.60. An excellent linear correlation between ln k0 and ln I¿L, the longitudinal relaxation time, was also obtained with a slope equal to 1.0 when xDMSO = 0-0.60. Unusually small rate constants found in the solutions of xDMSO a¿¥ 0.70 were attributed to adsorption effects at the tip and the substrate electrode. The k0 obtained for the present system was generally found to be inversely proportional to the viscosity of the solution and directly proportional to the diffusion coefficient of the electroactive species.

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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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Ferrocenylmethanol acrylate (FcMA)-immobilized polystyrene latex particles were synthesized by copolymerizing FcMA and styrene in the presence of polystyrene latex suspensions with eight different diameters ranging from 0.084 to 1.7 mum. The amounts of the ferrocenyl moiety loaded on one particle were proportional to the radii, a. The proportionality suggests the uniform distribution of the ferrocenyl moiety over the particle, of which concentration was 0.18 M. The aqueous suspensions, which were stable in the presence of a surfactant, exhibited reversible voltammetric waves for the ferrocenyl moiety. The peak current was controlled by diffusion of the latex particles. The efficiency of the reaction was obtained from the ratio of the observed current to the theoretical one which was estimated from the number of the ferrocenyl moieties and the diffusion coefficient of the particle by the Stokes-Einstein relation. The ratio was proportional to a-0.47, whereas it might be a0 for an ideal particle without any size effect. This relation was explained in terms of the contribution of rotational diffusion of redox particles.

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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 study is on current developments concerning ferrocene (FC) and its derivatives on the basis of electrochemical biosensors and sensors. The distinct physiochemical characteristics of FC have enabled the development of new sensor devices, specifically electrochemical sensors. Several articles have focused on the implementation of FC as an electrode constituent while discussing its electrochemical behavior. Furthermore, typical FC-design-based biosensors and sensors are considered as well as practical examples. The favorable design of FC-based biosensors and general sensors needs adequate control of their chemical and physical characteristics in addition to their surface immobilization and functionalization.

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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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Concurrent mapping of chemical reactivity and morphology of heterogeneous electrocatalysts at the nanoscale allows identification of active areas (protrusions, flat film surface, or cracks) responsible for productive chemistry in these materials. Scanning electrochemical microscopy (SECM) can map surface characteristics, record catalyst activity, and identify chemical products at solid-liquid electrochemical interfaces. It lacks, however, the ability to distinguish topographic features where surface reactivity occurs. Here, we report the design and fabrication of scanning probe tips that combine SECM with atomic force microscopy (AFM) to perform measurements at the nanoscale. Our probes are fabricated by integrating nanoelectrodes with quartz tuning forks (QTFs). Using a calibration standard fabricated in our lab to test our probes, we obtain simultaneous topographic and electrochemical reactivity maps with a lateral resolution of 150 nm.

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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