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Diiron nonacarbonyl oxidized a series of alpha-phenylcarbinols to their corresponding aldehydes and ketones.In addition, this resagent converted 4-methoxybenzyl alcohol to 4-methoxybenzyl ether, albeit in low yield.Under the same reaction conditions, oxidation was a minor with a group of alpha-ferrocenylcarbinols as ether synthesis was the major reaction with those substrates which could not dehydrate; however, stereoselective olefin synthesis predominated when elimination was possible.

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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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Thymol, a potent agent for microbial, fungal, and bacterial disease, has low aqueous solubility and it is genotoxic, i.e., is capable of damaging deoxyribonucleic acid (DNA). This possible problem of DNA toxicity needs to be solved to allow the use of different doses of thymol. This study characterized the inclusion compound containing thymol and beta-cyclodextrin (beta-CD) by measuring the interaction between these two components and the ability of thymol to bind DNA in its free and beta-CD complexed form. The encapsulation approach using beta-CD is particularly useful when controlled target release is desired, and a compound is insoluble, unstable, or genotoxic. The interaction between thymol and DNA has been studied using electrochemical quartz crystal microbalance (EQCM), atomic force microscopy (AFM), and differential pulse voltammetry (DPV). The characterization of the inclusion complex of thymol and beta-CD was analyzed by UV-vis spectrophotometry, cyclic voltammetry, and scanning electrochemical microscopy (SECM). Based on the free beta-CD by spectrophotometry method, the association constant of thymol with the beta-CD was estimated to be 2.8 × 104 L mol?1. The AFM images revealed that in the presence of small concentrations of thymol, the dsDNA molecules appeared less knotted and bent on the mica surface, showing significant damage to DNA. The SECM and voltammetry results both demonstrated that the interaction of thymol-beta-CD complex was smaller than the free compound showing that the encapsulation process may be an advantage leading to a reduction of toxic effects and increase of the bioavailability of the drug.

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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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Synthesis of environmentally-sensitive, and therefore smart hydrogels of micro- and nanosize allowed substantial shortening of time of response of these gels to a change in environmental conditions. This made the hydrogels much more attractive and opened new possibilities of their applications. In this paper we present recent developments in ways of construction of micro- and nanogels, their adaptation to particular needs and possibilities of use. The focus was given to individual, spherical particles and very thin layers of gels on solid supports, including electrodes.

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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 family of 15 ferrocene derivatives has been prepared, most of which are reported for the first time. This includes FcCH2O-3-cholestanyl, 1; FcCH2O(CH2)13CH3, 2; FcCH2O(CH2)15CH3, 3; FcCH2O(CH2)17CH3, 4; FcCH2N[(CH2)17CH3]2, 5; FcCH2O(CH2)8OCH2Fc, 6; FcCH2O(CH2)12OCH2Fc, 7; FcCH2O(CH2)16OCH2Fc, 8; Fc(CH2)22Fc, 9; FcCH2-3,17-beta-estradioxy-CH2Fc, 10; Fc-1,1′-[COO(CH2)16CH3], 11; FcCONH(CH2)17CH3, 12; Fc-1,1′-{CON[(CH2)17CH3]2}2, 13; Fc-1,1′-(COO-3-dihydrocholesteryl), 14; and Fc-1,1′-(COO-3-cholesteryl), 15. Redox potentials for 1-15 have been determined and are in the range 400-450 mV for 2-6 (vs SSCE) and 509 mV for 1, 972 mV for 7, 806 mV for 8, 711 mV for 9, 941 mV for 10, and 945 mV for 11 (vs Ag/AgCl). Upon oxidation with Ce(IV), aqueous suspensions of compounds 1-5 and 7-10 formed stable vesicles after sonication. The charged monomers that formed vesicles afforded aggregates in the 2000-3000 A range that were characterized by laser light scattering and negative stain electron microscopy. In the absence of an oxidizing agent, vesicles failed to form from any of the 15 monomers even after prolonged sonication. Addition of 500 muM aqueous Na2S2O4 solution collapsed the vesicles formed from 1-5 and 7-10, and the original amphiphile monomers were detected afterward by thin layer chromatography. It was concluded from cyclic voltammetry that both ferrocene residues in 8 were oxidized. Vesicles formed from 7-10 represent the first examples of a redox-switched bolaamphiphile.

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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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Real time measurement of time-correlated ion transport and volumetric changes in electroactive materials is necessary to understand and model mechanoelectrochemistry. Reversible reduction and oxidation of soft electroactive materials such as conducting polymers result in the deformation of the material due to ion transport into and out of the polymer backbone. In cells, ion transport and volumetric expansion are collectively responsible for homeostasis that is essential for life functions and hence, mechanoelectrochemistry of cells is essential to understand cell and developmental biology. The characterization methods required to investigate mechanoelectrochemistry require nanoscale spatial resolution for the imaging of a redox active site in a polymer or a small group of transmembrane proteins in a single cell. Towards this goal, we present an imaging technique using scanning electrochemical microscopy (SECM) hardware with shear-force (SF) feedback for high bandwidth mechanoelectrochemistry characterization. In this proceedings article, we demonstrate this technique referred to as surface-tracked scanning electrochemical microscopy technique (ST-SECM) that is realized by measuring the structural feedback of the glass electrode to position the electrode in 10s of nanometers above the surface of a polypyrrole membrane doped with dodecylbenzenesulfonate (PPy(DBS)). Two ultra-microelectrodes of controlled dimensions (of 20 mum and 30 mum glass diameter) were fabricated using a hydrofluoric acid etching technique and were used to generate a spatially correlated ion storage map of PPy(DBS). We compare the developed technique to a three-dimensional discrete scan over the surface and show that a ST-SECM technique produces a higher resolution and takes approximately 200 fewer minutes as compared to the conventional technique.

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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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Reactive oxygen species (ROS) are vital metabolites in numerous biological functions. Disorders of cellular mechanisms can cause overproduction of ROS and, subsequently, oxidative damage to DNA, proteins, cells and tissues, which is associated with the pathogenesis of a number of neurodegenerative and inflammatory diseases. Development of highly sensitive, relatively simple and fast-to-implement innovative methods to detect oxidative stress requires understanding of how such disorders relate to the level of ROS. This research aimed to apply the biological fluids’ ROS detection method we have developed (using the stable platinum nanoelectrode that allows assessing the level of hydrogen peroxide (H2O2) down to 1 muM) and determine the level of H2O2 in lacrimal and intraocular fluids of rabbits, as well as to investigate how the level of H2O2 changes under the influence of antioxidant therapy. The effect superoxide dismutase (SOD) nanoparticles produce on biological fluids’ ROS level was shown. The level of H2O2 in lacrimal fluid increased 10 and 30 min after instillation of SOD nanoparticles. As for the intraocular fluid, H2O2 concentration starts to grow only 30 min after instillation of SOD nanoparticles, which suggests that the they penetrate the internal structures of the eye gradually. The method seems to be of value in the context of eye diseases diagnosing and treatment.

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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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The invention provides monoferrocenyl compounds of general formula (I). The invention also provides substrates labelled with the compounds, functionalised derivatives of the compounds and methods of using the compounds, functionalised derivatives and labelled substrates in electrochemical assays.

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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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Functional monolayers containing ferrocenylphosphines have been assembled at silicon surfaces by reaction with the hydrogen-terminated layer.

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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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Ferrocenyl-nucleobases are an increasingly important class of complexes with possible applications in biology, pharmacy and material sciences. This review focuses on synthetic methods for ferrocenyl-nucleobases and on the chemical transformations of these compounds. Utilization of ferrocenyl-nucleobases for self-assembly material preparation and as building blocks for XNA synthesis and anticancer and antibacterial agents is also discussed herein. This review shows that the combination of the redox-active biologically artificial ferrocenyl moiety and genetically essential nucleobases leads to conjugates that retain their electrochemical and self-pairing properties. These properties make ferrocenyl-nucleobases attractive objects for further studies and for applications across the entire spectrum of physico-chemical and engineering sciences.

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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 cyclometalated iridium(III) complex containing a N?C?N-coordinating terdentate ligand [Ir(dpyx-N,C,N)Cl(mu-Cl)]2 was found to be a general and highly effective catalyst for the alpha-alkylation of ketones and N-alkylation of amines with alcohols. In the presence of catalyst (1 mol % Ir) and base (0.2-0.5 equiv), a variety of desirable products were obtained in good yields under an air atmosphere. Notably, this research exhibited the new potential of Ir(III) complexes bearing non-Cp? ligand and will facilitate the progress of the hydrogen autotransfer process.

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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