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In this work we report for the first time the use of the enzyme glucose oxidase (GOx) to efficiently disperse multiwall carbon nanotubes (CNT) and to confer biorecognition properties to the dispersed nanotubes. The optimum dispersion was obtained by sonicating for 15 min 1.0 mg/mL CNT in 1.0 mg/mL GOx solution prepared in 50:50 ethanol/water. The dispersion was evaluated by Scanning Electron Microscopy (SEM), Infrared (FT-IR) and Ultraviolet-visible (UV-vis) Spectroscopy. The electrochemical characterization of glassy carbon electrodes (GCE) modified with the dispersion (by dropping) was performed by Electrochemical Impedance Spectroscopy (EIS), Cyclic Voltammetry (CV), and Amperometry. The amount of electroactive GOx deposited on GCE (GCE/CNT-GOx) was 1.02 × 10-10 mol cm-2 and the rate constant for the electron transfer between FAD center and the electrode was (2.9 ± 0.1) s-1 according to Laviron and (9.2 ± 1.3) s-1 considering the model proposed by Albery. The enzyme demonstrated to keep its biocatalytic activity even after dissolution in 50/50 v/v, ethanol-water solution and sonication for 15 min using either ferrocene methanol or oxygen as redox mediators. The sensitivity to glucose at 0.700 V obtained for seventeen electrodes prepared with 6 different dispersions was (3.2 ± 0.2) × 102 muA M-1, (r = 0.997), with an R.S.D. of 6.0%. The sensitivity remained highly constant after 30 days at room temperature (25 C) and 4 C, with average values of (3.21 ± 0.07) × 102 muA M-1, r = 0.9992 and (3.59 ± 0.08) × 102 muA M-1, r = 0.9990, respectively. The GCE/CNT-GOx can be used as platform to build supramolecular architectures for biosensing through the self-assembling of polyelectrolytes, opening the doors to new and exciting possibilities for the development of biosensors.

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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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Hydrogen peroxide (H2O2) is a highly relevant metabolite in many biological processes, including the oral microbiome. To study this metabolite, we developed a 25 mum diameter, highly sensitive, nonenzymatic H2O2 sensor with a detection limit of 250 nM and a broad linear range of 250 nM to 7 mM. The sensor used the synergistic activity of the catalytically active Pt nanoparticles on a high surface area multiwalled carbon nanotube and conducting ionic liquid matrix to achieve high sensitivity (2.4 ± 0.24 mA cm-2 mM-1) for H2O2 oxidation. The unique composite allowed us to miniaturize the sensor and couple it with a Pt electrode (25 mum diameter each) for use as a dual scanning electrochemical microscopy probe. We could detect 65 ± 10 muM H2O2 produced by Streptococcus gordonii (Sg) in a simulated biofilm at 50 mum above its surface in the presence of 1 mM glucose and artificial saliva solution (pH 7.2 at 37 C). Because of its high stability and low detection limit, the sensor showed a promising chemical image of H2O2 produced by Sg biofilms. We were also able to detect 30 muM H2O2 at 50 mum above the biofilm in the presence of the H2O2-decomposing salivary lactoperoxidase and thiocyanate, which would not otherwise be possible using an existing H2O2 assay. Thus, this sensor can potentially find applications in the study of other important biological processes in a complex matrix where circumstances demand a low detection limit in a compact space.

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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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Three novel monomers based on carbazole-3, 4-ethoxylenedioxythiophene and redox groups were synthesized and characterized. Their polymer films were obtained by electropolymerization. Cyclic voltammetry and spectroelectrochemistry of the polymer films showed that they possessed multi-electrochromic property. The presence of ferrocene and 2,2,6,6-tetramethyl-1-piperidinyloxy units not only changed the films? colour but also improved their switching time due to their excellent electrochemical properties. Additionally, the polymer films also possessed a reasonable transmittance change, which made them promising candidates for use in electrochromic devices.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
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Paracyclophanes containing one or two ferrocene units can be efficently synthesized directly from 1,1′ -di(hydroxymethyl)ferrocene and aromatic dithiols.In the reaction with di(4,4′ -dimercaptomethylphenyl)methane the mononuclear paracyclophane was formed, while with the dithiophenols di(4,4′ -dimercaptophenyl)methane and di(4,4′ -dimercaptophenyl)ether, cyclophanes bearing two ferrocene units were obtained.For comparison three open-chain analogues were also prepared.

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Mono and doubly alkynyl substituted ferrocene complexes, [Fc(CH2OCH2C{triple bond, long}CH)n], 2-3 (2: n = 1; 3: n = 2; Fc = ferrocene) have been synthesized from the room temperature reaction of mono and 1,1?-dihydroxymethyl ferrocene, Fc(CH2OH)n, 1a-b (1a: n = 1; 1b: n = 2) and propargyl bromide, in modest to good yields. These new ferrocene derivatives have been characterized by mass, IR, 1H, 13C NMR spectroscopy, and molecular structures of compound 2 and 3 were unequivocally established by single crystal X-ray diffraction study. The crystal structure analysis revealed that 2 and 3 consist of infinite 1D zig-zag hydrogen bonded chains and 2D microporous hydrogen bonded network of molecules, linked by intermolecular C-H···O hydrogen bonding. The molecular structures of both 2 and 3 are further stabilized by C-H···pi interactions.

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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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Comparative analysis of the specific features of autooxidation of ferrocenylacetic acid (FcCH2COOH) in organic solvents at 30-50C in the absence and in the presence of trifluoroacetic acid (processes 1 and 2 respectively) was carried out. It was shown that both reactions proceed as a sequence of two macrostages, the molecular and the chain radical oxidation of the metal complex. Introduction of acid (HX) in the reaction mixture leads to a significant increase in the rate of the process, in the amount of oxygen per one mole of metal complex absorbed by the reaction mixture, and to the change in the yields of main reaction products like hydroxymethylferrocene, formylferrocene, ferrocenylpyruvic acid, and CO2. On the basis of results of the investigation performed, the kinetic and thermodynamic analysis of primary reactions of the process probable mechanisms of both macrostages in both processes were suggested. The significant effect of approach and orientation on the rate of the molecular oxidation of complex as the bifunctional reagent was noted. An assumption was made that the acid takes place in the molecular oxidation of FcCH2COOH according to two alternative mechanisms differing by the way of its coordination with O2 and the metal complex in the prereactional intermediates. The oxidative transformation of these intermediates leads to the generation of radicals of different nature, Fc+?CH2C(O)OO? and HO 2 ? which initiate the chain radical oxidation of the metal complex.

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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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Lipoic acid derivatives and pharmaceutical formulations containing lipoic acid derivatives are useful in the treatment and prevention of disease characterized by disease cells that are sensitive to lipoic acid derivatives.

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Graphene quantum dots (GQDs), derived from functionalized graphene precursors are graphene sheets a few nanometers in the lateral dimension having a several-layer thickness. They are zero-dimensional materials with quantum confinement and edge site effects. Intense research interest in GQDs is attributed to their unique physicochemical phenomena arising from the sp2- bonded carbon nanocore surrounded with edged plane functional moieties. In this work, GQDs are synthesized by both solvothermal and hydrothermal techniques, with the optimal size of 5 nm determined using high-resolution transmission electron microscopy, with additional UV-Vis absorption and fluorescence spectroscopy, revealing electronic band signatures in the blue-violet region. Their potential in fundamental (direct electron transfer) and applied (enzyme-based glucose biosensor) electrochemistry has been practically realized. Glucose oxidase (GOx) was immobilized on glassy carbon (GC) electrodes modified with GQDs and functionalized graphene (graphene oxide and reduced form). The cyclic voltammetry, differential pulse voltammetry, and electrochemical impedance spectroscopy are used for characterizing the direct electron transfer kinetics and electrocatalytical biosensing. The well-defined quasi-reversible redox peaks were observed under various electrochemical environment and conditions (pH, concentration, scan rate) to determine the diffusion coefficient (D) and first-order electron transfer rate (kET). The cyclic voltammetry curves showed homogeneous ion transport behavior for GQD and other graphenebased samples with D ranging between 8.45 × 10?9 m2 s?1 and 3 × 10?8 m2 s?1 following the order of 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 between 10 muM and 3 mM with a limit of detection of 1.35 muM and sensitivity of 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 relatively high performance and stability of GQDs is attributed to a sufficiently large surface-to-volume ratio, excellent biocompatibility, abundant hydrophilic edges, and a partially hydrophobic plane 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. We very much hope you enjoy reading the articles and that you will join us to present your own research about 1273-86-5, you can contact me at any time and look forward to more communication. Related Products of 1273-86-5

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A direct synthesis of alpha-alkylated arylacetamides from arylacetonitriles and primary alcohols has been accomplished for the first time. In the presence of the rhodium complex [Rh(cod)Cl]2/triphenylphosphine/potassium hydroxide system, the desired alpha-alkylated arylacetamides were obtained in 74-92% yield under microwave conditions. The experimental results in this paper are in sharp contrast with previous reports, where the coupling of arylacetonitriles and primary alcohols produced the alpha-alkylated arylacetonitriles. Mechanistic investigations show that arylacetonitriles are first alpha-alkylated with primary alcohols to produce alpha-alkylated arylacetonitriles, which are further hydrated with the water resulting from the alpha-alkylation step to produce alpha-alkylated arylacetamides. More importantly, this research shows the potential of developing completely atom-economical reactions that involve the hydrogen autotransfer (or hydrogen borrowing) process.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
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Covalent immobilization of glucose oxidase (GOx) on oxidized silicon (SiO2) surfaces is detailed in view of producing interfaces with a simple, controlled and reproducible procedure that could be used in bioanalytical applications as those based on SECM detection. The procedure is based first on the formation of an amino-terminated propyl layer on a SiO2 substrate followed by addition and cross-linking of a polyoxyethylene bis(diglycidylether) and GOx mixture. The epoxide groups of the cross-linker react with amino groups allowing both the cross-linking with the enzyme (reaction with the free amino groups of the lysine residues) and the covalent attachment of the enzyme layer on the amino groups bound to the surface. SECM in feedback mode analysis provides a characterization of the modified surface and the measurement of the enzymatic activity depending on the concentrations of glucose and mediator. Kinetics analysis indicates that GOx maintains a large enzymatic activity and that the active enzymes remain reachable after their incorporation in the layer with the advantages of a robust immobilization.

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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