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In order to investigate the ways in which heterogeneous kinetics at semiconductor electrodes are affected by various combinations of the formal reduction potentials of solution species and the energetic condition of the electrode surface. The authors have measured cyclic voltammetric dark currents in acetonitrile solutions for cobaltocene and a number of ferrocene derivatives at highly doped p-InP electrodes. Proper interpretation of the cyclic voltammetric data requires specific knowledge of the energetics at the semiconductor electrode/solution interface. This information has been derived from capacitance data that was obtained in the same solutions and within the same potential regions as the cyclic voltammetry and with experiments.

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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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Conjugated microporous polymers (CMPs) have full access to the organic synthesis toolbox and feature-rich functionality, structural diversity, and high surface area. We incorporated ferrocene (Fc) into the backbones of CMPs and systematically engineered their optical energy gaps. Compared with the CMPs without Fc units yet adopting a similar molecular orbital level, Fc-based CMPs can sufficiently generate reactive oxygen species (ROS) under visible light. The resultant ROS are able to effectively decompose the absorbed pollutants, including organic dyes and chemical warfare agents. Specifically, Fc-based CMPs significantly outperform commercial TiO2 (P25) in the degradation of methylene blue and are capable of converting 2-chloroethyl ethyl sulfide (a mustard gas simulant) into a completely nontoxic product.

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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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Here we present methodology for fabricating electrochemical flow cells with embedded carbon-composite electrodes in a single step using simultaneous 3D printing of insulating poly(lactic acid) (PLA) and a commercially available graphene?PLA composite. This work is significant because it is the first demonstration that devices capable of fluid handling and electrochemical sensing can be produced in a single fabrication step using inexpensive equipment. We demonstrate the broad utility of this approach using a channel-flow configuration as an exemplary system for hydrodynamic electrochemistry. Unmodified devices were characterized using hydrodynamic electrochemistry, and behave according to the well-established Levich equation. We also characterized the fabrication reproducibility and found that the devices were within 3% RSD. The 3D-printed sensors we employed were subsequently modified by electroplating Au and used under flowing conditions to detect catechol, whose oxidation requires two electrons and two protons and is thus more challenging to analyze than the outer-sphere FcCH2OH. We envision these results will pave the way for the development of highly customized micro-total analysis systems that include embedded electrochemical sensors for a variety of redox-active analytes.

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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 addition of 2,4-dinitrobenzenesulfenyl chloride to alkyl-substituted vinylferrocenes has been investigated in CH2Cl2, 1,1,2,2-tetrachloroethane and acetic acid solutions.Product analyses were carried out by VPC and PMR techniques and reaction rates measured by a spectrophotometric method.The orientation appears to be determined by the structural features of the intermediate episulfonium ion rather than by the site of the primary attack of the electrophile on the starting substrate.A comparison with the results previously obtained with the methoxymercuration reaction has a bearing on the mechanism of the latter reaction.

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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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Stimuli-responsive hydrogels have lately attracted a lot of attention in the chemistry and material fields because of the ?smart? change of their properties under outside stimuli including light, temperature, electric or magnetic field, pH, chemicals, shear stress, and redox reagents. Ferrocenyl (Fc) is often employed as a redox-responsive building unit due to its properties of chemical and electrochemical redox reversibility. This property involves reversible change between hydrophobicity and hydrophilicity, which endows hydrogels with unexpected features. Also, Fc derivatives are used as guest molecules featuring host?guest interactions with macrocyclic host molecules, mainly including cyclodextrins and pillararenes, commonly leading to the formation of supramolecular hydrogels with shape-memory, self-healing and sol?gel transition performances. This review focuses on the fabrication of various kinds of Fc-containing hydrogels and describes their gelling mechanisms, characteristic structures and properties, as well as functional applications. The review is divided into covalently cross-linked hydrogels and supramolecular cross-linked hydrogels. Furthermore, Fc-containing microgels constructed by chemically cross-linked three-dimensional polymer networks that are related to traditional hydrogels are also discussed. Fc-containing hydrogels and microgels are becoming more and more important as advanced functional materials, especially biomedical, shape-memory and self-healing materials.

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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 Ir and Raman spectra of gaseous (C5H5)Fe(C5H4COCH3) and (C5H4COCH3)2Fe were recorded in the frequency range 20-4000 cm-1.Both the gaseous complexes show a Raman absorption at 41 +/- 2 cm-1 which was assigned to the torsional frequency omega0.1 .In these molecules a barrier of 1000 +/- 100 cal/mol restricts the rotation of the cyclopentadienyl ring with respect to the rigid frame.The thermodynamic functions of the gaseous ferrocenes are reported in the temperature range 298-450 deg K.

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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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In this work we studied how backbone chemical modifications, such as 2?-O-methyl, phosphorothioate, l-form nucleotides and locked nucleic acid, on G-quadruplex based DNAzymes would affect their peroxidase activity. Our results indicate that 2?-O-methyl modification facilitates the formation of a perfectly compacted parallel structure and significantly promotes peroxidase activity of G-quadruplex based DNAzymes.

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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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Some bacteria can act as catalysts to oxidize (or reduce) organic or inorganic matter with the potential of generating electrical current. Despite their high value for sustainable energy, organic compound production and bioremediation, a tool to probe the natural biodiversity and to select most efficient microbes is still lacking. Compartmentalized cell culture is an ideal strategy for achieving such a goal but the appropriate compartment allowing cell growth and electron exchange must be tailored. Here, we develop a conductive composite hydrogel made of a double network of alginate and carbon nanotubes. Homogeneous mixing of carbon nanotubes within the polyelectrolyte is obtained by a surfactant assisted dispersion followed by a desorption step for triggering electrical conductivity. Dripping the mixture in a gelling bath through simple extrusion or a double one allows the formation of either plain hydrogel beads or liquid core hydrogel capsules. The process is shown to be compatible with the bacterial culture (Geobacter sulfurreducens). Bacteria can indeed colonize the outer wall of plain beads or the inner wall of the conductive capsules’ shell that function as an anode from which electrons produced by the cells are collected.

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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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We described a hybrid system of scanning electrochemical microscopy (SECM) and scanning ion conductance microscopy (SICM) with ion current feedback nanopositioning control for simultaneous imaging of noncontact topography and spatial distribution of electrochemical species. A nanopipette/nanoring electrode probe provided submicrometer resolution of the electrochemical measurement on surfaces with complex topology. The SECM/SICM probe had an aperture radius of 220 nm. The inner and outer radii of the SECM Au nanoring electrode were 330 and 550 nm, respectively. Characterization of the probe was performed with scanning electron microscopy (SEM), cyclic voltammetry (CV), and approach curve measurements. SECM/SICM was applied to simultaneous imaging of topography and electrochemical responses of enzymes (horse radish peroxidase (HRP) and glucose oxidase (GOD)) and single live cells (A6 cells, superior cervical ganglion (SCG) cells, and cardiac myocytes). The measurements revealed the distribution of activity of the enzyme spots on uneven surfaces with submicrometer resolution. SECM/SICM acquired high resolution topographic images of cells together with the map of electrochemical signals. This combined technique was also applied to the evaluation of the permeation property of electroactive species through cellular membranes.

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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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Background: Metal organic compounds have attracted considerable attention since the advent of Salvarsan, a metal organic compound for the treatment of syphilis. Ferrocene as an effective phenyl bioisostere is becoming a viable platform for drug design by virtue of its redox properties, high lipophilicity and three-dimensional metallocene unit, which may lead to some changes in selectivity toward biological targets compared with phenyl or alkyl groups. Therefore, ferrocene seems to an appropriate candidate for improving the antioxidant activity of drugs. Methods: We synthesized four ferrocenyl-containing curcumin analogues by introducing ferrocenyl groups into the active methylene groups to obtain higher antioxidant activity than the parent ferrocene-substituted curcumin analogues, and their antioxidant activities were evaluated in 2, 2?-azobis (2-amidinopropane hydrochloride) (AAPH) and Cu2+/glutathione(GSH)-induced oxidation of DNA, and in trapping 2, 2?-diphenyl-1-picrylhydrazyl (DPPH), 2, 2?-azinobis(3-ethylbenzothiazoline-6-sulfonate) cationic radicals (ABTS+?) and galvinoxyl radicals. Results: These ferrocenyl-containing curcumin analogues can protect DNA against Cu2+/GSH-induced oxidation, and scavenge 5.7, 6.9, 5.5 and 5.3 radicals in protecting DNA against AAPH-induced oxidation. Compounds (3)~(5) can trap more DPPH, ABTS+? and galvinoxyl radicals than compound (6). The substituents and iron atoms play an antioxidant role in ferrocenyl-containing curcumin analogues. Conclusion: The introduction of ferrocenyl group results in a higher antioxidant activity than the traditional hydroxyl-involved curcumin analogues. The ferrocenyl group is a powerful antioxidative group that could be used to modify natural antioxidants. The electron-accepting group attaching to the phenyl-group could further increase the antioxidant activity. Ferrocene-containing curcumin analogues show higher activities in quenching radicals and protecting DNA against radical-induced oxidation. Therefore, the introduction of ferrocenyl group into the natural antioxidant may contribute to increase the antioxidant activity.

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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