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Detection of proteins on membranes and in microchannels using copper staining combined with scanning electrochemical microscopy

Scanning electrochemical microscopy (SECM) and copper staining are combined to achieve visualisation of proteins on surfaces. Proteins are adsorbed on a polyvinylidene fluoride (PVDF) membrane or on a polyethylene terephthalate (PET) surface and stained using a standard protocol involving copper salts. Salts are then reduced to copper and detected by SECM with ferrocene methanol as a redox mediator in aqueous solution. During the SECM scan, the potential is held at a value at which the oxidation of the redox mediator occurs and a positive feedback current is detected when scanning over copper clusters. A negative feedback is observed elsewhere. This method enables unspecific protein adsorption mapping on polymeric membranes and into microchannels without any requirement of enzymatic activity or affinity to a labelled secondary reporter.

Detection of proteins on membranes and in microchannels using copper staining combined with scanning electrochemical microscopy

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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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Anion recognition by highly sterically encumbered 1,2-diborylferrocenes

The syntheses and structural characterization of sterically encumbered 1,2-diborylferrocenes are reported, together with an investigation of their anion recognition capabilities with respect to fluoride and cyanide. Surprisingly, 1,2-fc(BMes2)2 is found to be highly selective for CN-, with the uptake of F- being shown to be not only thermodynamically less favorable but also kinetically much slower.

Anion recognition by highly sterically encumbered 1,2-diborylferrocenes

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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, chemical reactivity and electrochemical behaviour of mono- and difluoro metallocenes

We report the synthesis of mono- and 1,1?-difluoro-substituted metallocenes (ferrocene, ruthenocene) and of asymmetrical 1,1?-disubstituted ferrocenes with one substituent being fluorine. Lithiation of metallocenes and subsequent addition of the fluorinating agent NFSI gave the fluorinated metallocenes after optimization of the experimental conditions. All new compounds were comprehensively characterized and the cyclic voltammograms of fluoro- and 1,1?-difluoroferrocene were recorded and compared to other mono- and dihalogenated ferrocenes. Half-wave potentials of +106 mV and +220 mV vs. FcH0/+ were obtained for monofluorinated species and difluorinated ferrocene, respectively. Both values are remarkably low compared to the other halogenated ferrocenes (Cl, Br, and I). Finally, 1-bromo-1′-fluoro-ferrocene turns out to be an ideal starting material for further fluoro-substituted ferrocene derivatives.

Synthesis, chemical reactivity and electrochemical behaviour of mono- and difluoro metallocenes

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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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A novel side-chain ferrocene-containing polymer by combination of Cu(0)-mediated SET-LRP of acrylonitrile and post-modification

Well-defined side-chain ferrocene-containing polymers have been synthesized by post-modification of well-defined polyacrylonitrile (PAN). PAN prepared by Cu(0)-mediated single-electron transfer living radical polymerization was further modified using sodium azide and ammonium chloride (NH4Cl) to yield polymeric materials with vinyltetrazole units. Side-chain ferrocene-containing polymer was prepared by vinyltetrazole units and hydroxymethylferrocene after Mitsunobu reaction. FTIR, 1H NMR, UV?Vis spectroscopy and thermogravimetric analysis were used to identify the structure of the target product. After linked the ferrocene unit, the final polymer showed typical redox property?with?a?more negative?redox?potential (E1/2).

A novel side-chain ferrocene-containing polymer by combination of Cu(0)-mediated SET-LRP of acrylonitrile and post-modification

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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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Sensitive detection of serum creatinine based on beta-cyclodextrin- ferrocenylmethanol modified screen-printed electrode

Ferrocenylmethanol (Fc-OH) is included in beta-cyclodextrin (beta-CD) to form the beta-CD-Fc-OH complex by host-guest supramolecular interaction. beta-CD dissociates from the beta-CD-Fc-OH complex due to the conversion of Fc-OH to Fc+-OH under a stimulus of oxidant. In our study, Fc-OH is oxidized after a series of enzymatic reactions of creatinine, which blocks the other means for oxidation of Fc-OH. And the background noise is reduced for testing for serum creatinine (sCr). The chronoamperometry signal for creatinine (with a constant potential -0.3 V vs. Ag/AgCl) increases linearly in the 1 – 1000 muM range, with a limit of detection as low as 0.5 muM. The amperometric potential of -0.3 V greatly prevents the interference of various redox substances in serum. The biosensor was used to test 120 clinical specimens and the results showed a linear correlation with the biochemical analyzer (R2 = 0.9885). The biosensor could be applied to clinical trials and offers good prospects for clinical sCr detection.

Sensitive detection of serum creatinine based on beta-cyclodextrin- ferrocenylmethanol modified screen-printed electrode

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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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Branch-Selective and Enantioselective Iridium-Catalyzed Alkene Hydroarylation via Anilide-Directed C-H Oxidative Addition

Tertiary benzylic stereocenters are accessed in high enantioselectivity by Ir-catalyzed branch selective addition of anilide ortho-C-H bonds across styrenes and alpha-olefins. Mechanistic studies indicate that the stereocenter generating step is reversible.

Branch-Selective and Enantioselective Iridium-Catalyzed Alkene Hydroarylation via Anilide-Directed C-H Oxidative Addition

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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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Biodegradable Conducting Polymer Coating to Mitigate Early Stage Degradation of Magnesium in Simulated Biological Fluid: An Electrochemical Mechanistic Study

The application of a biodegradable conducting polymer coating based on a polythiophene composite (PTC) to mitigate degradation of magnesium in an in vitro environment is reported. The rationale behind the study is to advance a bioactive coating to control the rapid early stage degradation of the magnesium and prevent inflammatory reactions and physiological complications, while, in the long term, the coating degrades, followed by the full degradation of the magnesium implant. The conducting polymer in this study is deposited on a bioabsorbable medical grade magnesium alloy, AZNd, through layer-by-layer deposition, and the degradation behavior in simulated biological fluid is studied electrochemically. The possibility of a synergistic effect by combining praseodymium conversion coating together with the conducting polymer coating in protecting magnesium is also examined. Results show that the highest level of corrosion mitigation is afforded by the combination of praseodymium conversion and the conducting polymer coating layers. Electrochemical models are advanced to explain the electroactivity of the conducting polymer across the film as well as at the interface with electrolyte and substrate. Based on the physical and electrochemical evidence, the barrier effect is proposed as the main protection mechanism.

Biodegradable Conducting Polymer Coating to Mitigate Early Stage Degradation of Magnesium in Simulated Biological Fluid: An Electrochemical Mechanistic Study

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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 Reactivity of Ferrocenyl-Substituted Allylamine Derivatives

[(2-Ferrocenylvinyl)methyl]dimethylamine (2) was obtained in good yields and with perfect regio- and stereoselectivity by reaction of dimethylmethylideneammonium salts with vinylferrocene. After methylation of amine 2, [(2-ferrocenylvinyl)methyl]trimethylammonium iodide (4) was obtained in high yields and used to transfer the ferrocene-containing allyl group to various amines. By controlling reaction conditions, various linear and branched ferrocenyl-substituted allylamines could be obtained with good yields and selectivities. When anilines were used as substrates against ammonium salt 4, compounds originating from Friedel?Crafts reactions were also obtained, with complete regioselectivity towards the para position.

Synthesis and Reactivity of Ferrocenyl-Substituted Allylamine Derivatives

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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 electrochemical properties of slipped-cofacial porphyrin dimers of ferrocene-functionalized Zn-imidazolyl-porphyrins as potential terminal electron donors in photosynthetic models

A systematic series of ferrocene-functionalized Zn-imidazolyl-porphyrins were synthesized to assemble into the slipped-cofacial porphyrin dimers through imidazolyl-to-zinc complementary coordination as artificial photosynthetic models. Direct substitution at the meso position of the porphyrin ring with ferrocence and octamethylferrocene leads to the characteristic electronic structures, while the ferrocene substituents through phenylene-ethenylene and phenylene-ethylene spacers mitigate the electronic communications. Bathochromic shift of Q band, fluorescence quenching, and redox potentials of porphyrin ring are rationalized by the degree of electron-donating ability of the terminal ferrocenes. the Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2006.

Synthesis and electrochemical properties of slipped-cofacial porphyrin dimers of ferrocene-functionalized Zn-imidazolyl-porphyrins as potential terminal electron donors in photosynthetic models

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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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Ruthenium and osmium complexes containing 2-(aminomethyl)pyridine (Ampy)-based ligands in catalysis

This account focuses on the application in catalysis of ruthenium and osmium complexes containing 2-(aminomethyl)pyridine (Ampy)-based ligands. The combination of these aminoalkylpyridine ligands with appropriate phosphines affords ruthenium and osmium systems displaying unprecedented high catalytic activity and productivity in a variety of organic transformations such as hydrogenation by hydrogen transfer and dihydrogen, dehydrogenation, racemization, and alkylation.

Ruthenium and osmium complexes containing 2-(aminomethyl)pyridine (Ampy)-based ligands in catalysis

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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