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

 

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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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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

 

Can You Really Do Chemisty Experiments About 1,1′-Ferrocenedicarboxaldehyde

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Highly enantioselective one-pot synthesis of chiral tri- and tetrasubstituted ferrocenes from 1,1′-ferrocenedicarbaldehyde

Exclusively planar chirality is exhibited by the ferrocenes obtained in a highly enantioselective synthesis in which a chiral aminoamide acts as a temporary protecting/directing group. This method was used to obtain an enantiomerically pure tetrasubstituted ferrocene, which was transformed into the first C2-symmetric disubstituted ferrocenophane [Eq. (1)].

Highly enantioselective one-pot synthesis of chiral tri- and tetrasubstituted ferrocenes from 1,1′-ferrocenedicarbaldehyde

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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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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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Enantioselective Assembly of Congested Cyclopropanes using Redox-Active Aryldiazoacetates

The enantioselective assembly of quaternary stereocenters through sequential functionalization of versatile carbon-atom precursors has the potential to systematize the synthesis of these ubiquitous stereogenic elements. Herein, we report two catalytic processes that allow the realization of this concept in the enantioselective synthesis of cyclopropanes. We demonstrate that C-H functionalization, carbene-transfer, and decarboxylative cross-coupling can sequentially take place in the same carbon atom to obtain highly enantioenriched cyclopropane products. The reactions reported herein give access to redox-active analogues of privileged aryldiazoacetates and demonstrate their enantioselective carbene transfer with a simple and practical rhodium catalyst.

Enantioselective Assembly of Congested Cyclopropanes using Redox-Active Aryldiazoacetates

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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

 

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Synthesis and Structural Characterization of a Bitopic Ferrocenyl-Linked Bis(pyrazolyl)methane Ligand and Its Silver(I) Coordination Polymers

The bitopic ligand 1,1?-bis(dipyrazol-1-ylmethyl)ferrocene, Fe[C 5H4CH(pz)2]2 (1; pz = pyrazolyl ring), has been prepared by the reaction of 1,1?-ferrocenedicarbaldehyde and 1,1?-carbonyldipyrazole. In the solid state, the bis(pyrazolyl) methane moieties are in an antiperiplanar eclipsed orientation. The molecules are organized into a three-dimensional array by pi…pi, weak C-H-…N hydrogen bonding, and C-H…pi interactions. The reactions between 1 and AgBF4, AgPF6, AgSO3CF 3, or AgSbF6 yield {Fe[C5H 4CH(pz)2]2AgBF4}n (2), {Fe[C5H4CH(pz)2]2AgPF 6}n (3), {Fe[C5H4CH(Pz) 2]2AgSO3CF3}n (4), and {Fe[C5H4CH(pz2]2AgSbF 6}n (5), respectively. The solid-state structures consist of coordination polymers with compounds 2 and 3 arranged in helical chains, while the chains in 3¡¤1/2Et2O, 4¡¤1.5C6H 6,5¡¤1/2Et2Et2O, and 5¡¤1/2C 6H6 are nonhelical. In these structures, the ferrocenyl groups adopt a similar orientation, where the angle between CH(pz)2 groups is confined to the range of 85-99 and the silver pyrazolyl coordination spheres are also in very similar distorted-tetrahedral arrangements. Both structural types form three-dimensional supramolecular structures organized by weak hydrogen bonds, pi…pi stacking, and CH…pi interactions. In the helical form, the anions reside in the pockets formed by the close-packed chains, whereas in the nonhelical form, sizable channels, which contain the solvent molecules and the anions, are located between the chains.

Synthesis and Structural Characterization of a Bitopic Ferrocenyl-Linked Bis(pyrazolyl)methane Ligand and Its Silver(I) Coordination Polymers

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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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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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The proportionality constant is the rate constant for the particular unimolecular reaction. the reaction rate is directly proportional to the concentration of the reactant. I hope my blog about 1273-86-5 is helpful to your research. Application of 1273-86-5

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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