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Graphene Quantum Dots Electrochemistry and Development of Ultrasensitive Enzymatic Glucose Sensor

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 ¡Á 10-9 m2 s-1 and 3 ¡Á 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. Graphene Quantum Dots Electrochemistry and Development of Ultrasensitive Enzymatic Glucose Sensor We¡¯ll also look at important developments in the pharmaceutical industry because understanding organic chemistry is important in understanding health, medicine, the role of 1273-86-5, and how the biochemistry of the body works.Related Products of 1273-86-5

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Redox-Controlled Voltage Responsive Micelles Assembled by Noncovalently Grafted Polymers for Controlled Drug Release

Voltage responsive micelles prepared from noncovalently grafted amphiphilic polymers were reported. The noncovalent amphiphilic polymers were prepared through the host-guest interaction between beta-cyclodextrin (beta-CD) grafted dextran (Dex-CD) and ferrocene (Fc) terminated poly(?-caprolactone) (PCL-Fc). Because of the presence of Fc groups, the inclusion complex between Fc and beta-CD can be reversibly controlled by an external stimulating voltage, leading to reversible formation and disassembly of the micelles. The occurrence of the inclusion complex between Fc and beta-CD was confirmed by cyclic voltammetry (CV) and the 2D NOESY spectrum. Furthermore, meloxicam was selected as a model drug to test the controlled release performance of these voltage responsive micelles. It was found that the release rate and the final cumulative release amount of meloxicam can be effectively controlled by the external voltage, which may be of use in controlled drug delivery.

Redox-Controlled Voltage Responsive Micelles Assembled by Noncovalently Grafted Polymers for Controlled Drug Release

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Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Metastable beta Ti-Nb-Mo alloys with improved corrosion resistance in saline solution

The present study explores the microstructural characteristics and electrochemical responses of four metastable beta Ti-Nb-Mo alloys for biomedical implantation. They were synthesized by the cold crucible levitation melting technique, and compositions were selected to keep the molybdenum equivalency close to 12 wt% Moeq. For the sake of comparison, Ti12Mo was also investigated. Microstructural characterization reveals that all the alloys are beta (body-centred cubic structure), and the surface is composed by beta equiaxial grains with dimensions in the range of tens to hundreds mum. The corrosion resistance (potentiodynamic polarization and electrochemical impedance spectroscopy) of the alloys was determined in 0.9 wt% NaCl saline solution at 25 C. The materials spontaneously form a passivating oxide film on their surface, and they are stable for polarizations up to +1.0 VSCE. No evidence of localized breakdown of the oxide layers is found for polarizations more positive than those encountered in the human body. The passive layers show dielectric characteristics, and the wide frequency ranges displaying capacitive characteristics occur for both higher niobium contents in the alloy and longer exposures to the saline solution. The insulating characteristics of the oxide-covered surfaces were investigated by scanning electrochemical microscopy operated in the feedback mode, using ferrocene-methanol as redox mediator. Both z-approach curves and amperometric images were taken over the surface of the samples both at their open circuit potential and polarized. It has been found that Ti8Nb10Mo and Ti16Nb8Mo exhibit the lowest activity towards electron transfer. The new Ti-Nb-Mo ternary alloys are regarded to be potential candidates for biomedical application on the basis of both their microstructural characteristics and their corrosion resistance in saline solution with chloride content equivalent to body fluids.

Metastable beta Ti-Nb-Mo alloys with improved corrosion resistance in saline 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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Conductivity and electrochemistry of ferrocenyl-imidazolium redox ionic liquids with different alkyl chain lengths

Electroactive ionic liquids obtained by modifying imidazolium with ferrocenyl moiety and alkyl chains of different lengths (n = 1, 4, 8 and 12) were studied in their pure form and dissolved in ethylene/diethylene carbonates (EC/DEC) solvent. Bis(trifluoromethanesulfonyl) imide (TFSI) was used as the anion. The conductivity of the pure ionic liquids (0.1 to 0.04 mS cm?1) was found to decrease with the increase in alkyl chain length as expected from larger van der Waals interactions. The conductivities of carbonate solutions of redox ionic liquid (50% vol.) were less affected by the chain length but were strongly dependent on the presence of Li ions due to their coordination with TFSI, providing viscous solutions (86-111 cP) which decreased the self-diffusion of the redox imidazolium by a factor of 6. The equilibrium potential of the RIL dissolved in the carbonate solvent was not affected by the alkyl chain length, but mass transport by migration caused a distortion in cyclic voltammograms for highly concentrated solutions.

Conductivity and electrochemistry of ferrocenyl-imidazolium redox ionic liquids with different alkyl chain lengths

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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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Electrocatalytic processes promoted by diamond nanoparticles in enzymatic biosensing devices

We have developed a biosensing platform for lactate determination based on gold electrodes modified with diamond nanoparticles of 4 nm of nominal diameter, employing the enzyme lactate oxidase and (hydroxymethyl)ferrocene (HMF) as redox mediator in solution. This system displays a response towards lactate that is completely different to those typically observed for lactate biosensors based on other nanomaterials, such as graphene, carbon nanotubes, gold nanoparticles or even diamond nanoparticles of greater size. We have observed by cyclic voltammetry that, under certain experimental conditions, an irreversible wave (E0 = +0.15 V) appears concomitantly with the typical FeII/FeIII peaks (E0 = +0.30 V) of HMF. In this case, the biosensor response to lactate shows simultaneous electrocatalytic peaks at +0.15 V and +0.30 V, indicating the concurrence of different feedback mechanisms. The achievement of a biosensor response to lactate at +0.15 V is very convenient in order to avoid potential interferences. The developed biosensor presents a linear concentration range from 0.02 mM to 1.2 mM, a sensitivity of 6.1 muA mM-1, a detection limit of 5.3 muM and excellent stability. These analytical properties compare well with those obtained for other lactate-based biosensors that also include nanomaterials and employ HMF as redox mediator.

Electrocatalytic processes promoted by diamond nanoparticles in enzymatic biosensing devices

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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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Sandwich-type microRNA biosensor based on magnesium oxide nanoflower and graphene oxide?gold nanoparticles hybrids coupling with enzyme signal amplification

An ultrasensitive sandwich-type electrochemical biosensor for microRNA (miRNA) detection is developed based on magnesium oxide (MgO) nanoflower and graphene oxide?gold nanoparticles (GO?AuNPs) hybrids coupling with electrochemical?chemical?chemical (ECC) detection system. In this bioassay system, MgO nanoflowers and AuNPs are modified on electrode to act as sensing platform. The thiolated capture probe is then self-assembled onto AuNPs/MgO substrate via formation of Au-S bonds. Subsequently, a biotinylated DNA signal probe is conjugated to GO?AuNPs hybrids. When miRNA-21 is added, a sandwich complex is formed and a lot of signal indicators streptavidin-conjugated alkaline phosphatases (SA-ALP) are immobilized upon electrode by the specific reaction between avidin and biotin. Finally, ECC reaction is performed in the system to improve detection signal. The proposed sandwich-type assay benefits from advantages of sandwich-type structure for enhanced sensitivity and specificity, MgO nanoflowers/AuNPs as sensing platform and GO?AuNPs hybrids as signal carriers for signal amplification, and ECC as a sensitive detection system for low detection limit. This biosensor exhibits a good dynamic ranging from 0.1 to 100 fM and a low detection limit of 50 aM (S/N = 3) toward target miRNA-21.

Sandwich-type microRNA biosensor based on magnesium oxide nanoflower and graphene oxide?gold nanoparticles hybrids coupling with enzyme signal amplification

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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 electrodes: Preparation, characterization, and electrochemical behavior

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¡Á larger than a bare gold electrode and 2¡Á 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.

Hierarchical porous gold electrodes: Preparation, characterization, and electrochemical behavior

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
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Supported Microwires for Electroanalysis: Sensitive Amperometric Detection of Reduced Glutathione

A carbon microfiber (7 mum diameter) is employed herein as an electroanalytical sensor. The fabricated sensor is cheap, is disposable, and requires only 150 muL of samples. The carbon fiber is surface-mounted onto an inert surface to overcome the problems of the fragility of the microwire and the possible interference of convective force due to the nonrigid nature of the wires, as well as to improve the reproducibility in length and the amperometric responses. As the cylindrical electrode is supported on a surface, the diffusion of redox-active species to the electrode is partially blocked by the substrate. A theoretical model is developed to account for this hindered diffusion. The mass-transport regime is altered from “linear” at very short time, where the amperometric responses of the supported microwire closely resemble that of an isolated free-standing cylinder (current alpha electrode area), to “convergent” at long time where its response now tends toward that of a hemicylinder of equal radius. The model is validated using chronoamperometry and cyclic voltammetry of an ideal outer-sphere redox probe, reversible ferrocene methanol oxidation. The fabricated microwire electrode is further applied to the system of irreversible 2-nitro-5-thiobenzoate oxidation used in the detection of reduced glutathione (GSH). The microwire electrode shows significantly higher ratio of Faradaic to non-Faradaic currents as compared to microdisk, macrodisk or carbon nanotube modified electrodes. Using the fabricated microwire, GSH can be detected with the sensitivity of 0.7 nA muM-1 and the limit of detection of 0.5 muM (3 sB/m). (Figure Presented).

Supported Microwires for Electroanalysis: Sensitive Amperometric Detection of Reduced Glutathione

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A carbon nanotube/poly [Ni-(Protoporphyrin IX)] composite for amperometric detection of long chain aliphatic amines

Poly [Ni-Protoporphyrin] film (pNiPP), containing multiwall carbon nanotubes (MWCNT) was used to cover a glassy carbon electrode. The hybrid material (pNiPP/MWCNT) successfully combines the permselectivity of pNiPP with the high conductivity of MWCNT.The modified electrode was used to perform amperometric detection of long chain aliphatic amines (LCAA) in order to prevent the passivation effect of the aliphatic chain. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) demonstrated that the pNiPP/MWCNT facilitates the electron transfer reaction. The charge transfer resistance (Rct) values were significantly lower by up to one order of magnitude compared to the bare electrode. Differential pulse polarography (DPP) showed a marked decrease of the overpotential generated by the aliphatic chain. The calibration of the amperometric peak area vs. concentrations of derivatized LCAA exhibits a linear response within the range of 0.018 and 28muM and correlation coefficient (R2) higher than 0.999 (n=5). The quantitation limit of the pNiPP/MWCNT electrode is about 400 times lower than the UV-visible detection. RSD of 7.2%, 5.8%, 2.5% and 2.3% was obtained for concentrations of 0.028, 0.28, 2.8 and 28muM of ferrocenyl octadecylamine. A solution of sphingosine, 0.23muM, was exclusively detected with HPLC-ECD with pNiPP/MWCNT electrode.

A carbon nanotube/poly [Ni-(Protoporphyrin IX)] composite for amperometric detection of long chain aliphatic amines

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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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Covalent binding of biorecognition groups to solids using poly(hydromethylsiloxane) as linkage

By activating Si-H bonds, poly(hydromethylsiloxane) can be covalently bound in a first step to various metal or polymer surfaces. In a second step, unreacted Si-H bonds can be brought to react with organic compounds having adequate functional groups such as double or triple bonds, carbonyl or hydroxyl groups. This scheme is used to bind biorecognition groups to solids. The novel concept is demonstrated by attaching a newly synthesized biotin derivative to Au. It is shown that the immobilized biotin is capable of binding streptavidin.

Covalent binding of biorecognition groups to solids using poly(hydromethylsiloxane) as linkage

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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