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A series of glucose bioelectrodes were prepared by glucose oxidase (GOx) immobilization into laponite hydrogel films containing DNA bioinspired polycations made of vinylbenzyl thymine (VBT) and vinylbenzyl triethylammonium chloride (VBA) with general formulae [(VBT)m(VBA)n] 25n+ with m=0, 1 and n=2, 4, 8, deposited onto glassy carbon electrode. The bioelectrodes were characterized by chronoamperometry, cyclic voltammetry and electrochemical impedance spectroscopy. Results indicated that the electrochemical properties of the laponite hydrogel films were largely improved by the incorporation of thymine-based polycations, being proportional to the positive charge density of the polycation molecule. After incorporation of glucose oxidase, the sensitivity of the bioelectrode to glucose increased with the positive charge density of the polycation. Additionally, the presence of the vinylbenzyl thymine moiety played a role in the long-term stability and reproducibility of the bioelectrode signal. As a consequence, the [(VBT)(VBA)8]258+ was the most appropriate polycation for bioelectrode preparation and glucose sensing, with a specific sensitivity of se=176 mA mmol-1 L cm-2 U-1, almost two-order of magnitude larger than other laponite immobilized GOx bioelectrodes reported elsewhere. These features were confirmed by testing the bioelectrode for a selective determination of glucose in powder milk and blood serum samples without interference of either ascorbic or uric acids under the experimental conditions. The present study demonstrates the suitability of DNA bioinspired water-soluble polycations [(VBT)m(VBA)n]25n+ for enzyme immobilization like GOx into laponite hydrogels, and the preparation of highly sensitive and stable bioelectrodes on glassy carbon surface.

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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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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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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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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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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 the present manuscript, the electrochemical behavior of cytochrome c (cyt-c) immobilized onto a phenolic terminated self assembled monolayer (SAM) on a gold electrode is investigated using cyclic voltammetry (CV) and scanning electrochemical microscopy (SECM). The tunneling electron transfer (ET) rate constant between the immobilized protein and the underlying electrode surface, and also the bimolecular ET rate constant between the immobilized protein and a probe has been obtained using approach curves that were obtained by SECM. The approach curves were recorded at different substrate overpotentials in the presence of various concentrations of ferrocyanide as a probe and various surface concentrations of cyt-c; then the standard tunneling ET and bimolecular rate constants are obtained as 3.4 ± 0.3 s-1 and (2.0 ± 0.5) × 107 cm3 mol-1 s-1, respectively.

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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 series of 1H-1,2,3-triazole linked Ferrocenyl-methoxy-methyl-Isatin conjugates was synthesized and assayed for their anti-proliferative activities against estrogen-responsive as well as estrogen non-responsive cell lines. The non-cytotoxic conjugate 7l, with an optimum combination of octyl chain as spacer and methyl-substituent at the C-5 position of isatin, proved to be a promising hit with an IC50 value of 14.62 muM against MCF-7 and 79.63 muM against MDA-MB-231 cells, respectively. The observed anti-proliferative activities of active conjugates were further corroborated via docking studies carried out on estrogen receptor subtypes alpha and beta.

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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 scanning electrochemical microscope (SECM) in the feedback and generation-collection modes was used to investigate the regeneration of photoexcited dye cations at the semiconductor/electrolyte interface in a dye-sensitized solar cell (DSSC) based on ZnO/D149. An effective dye regeneration rate constant kox of 9.55 × 107 cm 9/2 mol-3/2 s-1 was obtained from feedback mode experiments at different wavelengths and light intensities on ZnO/D149 electrodes. Illuminated regions of the dye-sensitized electrodes could be differentiated from non-illuminated regions by local imaging in SECM generation-collection experiments with I- as redox mediator. We also report SECM feedback measurements on non-illuminated dye-sensitized electrodes to investigate the electron transfer kinetics of dissolved redox couples at the underlying FTO substrate.

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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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Electrodeposition of Sn from supercritical difluoromethane has been performed into anodic alumina templates with pores down to 3 nm in diameter and into mesoporous silica templates with pores of diameter 1.5 nm. Optimized deposits have been characterized using X-ray diffraction, scanning electron microscopy, and scanning transmission electron microscopy (bright field, high-angle annular dark field, and energy-dispersive X-ray elemental mapping). Crystalline 13 nm diameter Sn nanowires have been electrodeposited in symmetric pore anodic alumina. Direct transmission electron microscopy evidence of sub 7 nm Sn nanowires in asymmetric anodic alumina has been obtained. These same measurements present indirect evidence for electrodeposition through 3 nm constrictions in the same templates. A detailed transmission electron microscopy study of mesoporous silica films after Sn deposition is presented. These indicate that it is possible to deposit Sn through the 1.5 nm pores in the mesoporous films, but that the nanowires formed are not stable. Suggestions of why this is the case and how such extreme nanowires could be stabilized are presented.

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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