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In the present work, we have included for the first time diamond nanoparticles (DNPs) in a sol-gel matrix derived from (3-mercaptopropyl)-trimethoxysilane (MPTS) in order to improve electron transfer in a lactate oxidase (LOx) based electrochemical biosensing platform. Firstly, an exhaustive AFM study, including topographical, surface potential (KFM) and capacitance gradient (CG) measurements, of each step involved in the biosensing platform development was performed. The platform is based on gold electrodes (Au) modified with the sol-gel matrix (Au/MPTS) in which diamond nanoparticles (Au/MPTS/DNPs) and lactate oxidase (Au/MPTS/DNPs/LOx) have been included. For the sake of comparison, we have also characterized a gold electrode directly modified with DNPs (Au/DNPs). Secondly, the electrochemical behavior of a redox mediator (hydroxymethyl-ferrocene, HMF) was evaluated at the platforms mentioned above. The response of Au/MPTS/DNPs/LOx towards lactate was obtained. A linear concentration range from 0.053 mM to 1.6 mM, a sensitivity of 2.6 muA mM-1 and a detection limit of 16 muM were obtained. These analytical properties are comparable to other biosensors, presenting also as advantages that DNPs are inexpensive, environment-friendly and easy-handled nanomaterials. Finally, the developed biosensor was applied for lactate determination in wine samples.

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The polarizability alpha, and second hyperpolarizability, gamma, of some ferrocene derivatives are determined by using an optimized semiempirical approach.The bonding in ferrocene has been investigated through the study of the above polarization properties.The results from the ferrocene derivatives have been correlated with the corresponding substituted benzenes.Scales have been presented, where the derivatives are classified according to their polarization properties.The effect of delocalized ? electrons, charge transfer, and geometry variations on alpha and gamma are commented upon.Selected results of various other properties (e.g., the first hyperpolarizability) are used to demonstrate that some mechanisms (e.g., charge transfer) and changes in geometry may have widely different effects on the molecular properties.Common trends and patterns of behavior are recognized and discussed.The reported results are in good agreement with the experimentally determined ones.

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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 number of ether- and thioether-substituted ferrocenes (1,1?-bis(1,3-dioxane-2-yl)ferrocene 1, 1,1?-bis(5-methyl-1,3- dioxane-2-yl)ferrocene 2, 1,1?-bis(4-methyl-1,3-dioxane-2-yl)ferrocene 3, 1,1?-bis[(R)-(-)-4-methyl-1,3-dioxane-2-yl]ferrocene 4, 1,1?-bis(4,6-dimethyl-1,3-dioxane-2-yl)ferrocene 5, and 1,1?-bis(1,3-dithiane-2-yl)ferrocene 6) were synthesised by direct condensation of 1,1?-diformylferrocene with the corresponding diols or dithiols. The crystal structures of 1, 5a, 5b, and 6 were determined by X-ray diffraction studies. Electrospray ionisation mass spectrometry was used to investigate the binding behaviour of 1 and 6 toward alkali as well as transition metal cations. The dioxane-containing species 1 showed high affinity toward Li+ and Na+, whereas the dithiane derivative 6 bound, as expected, preferentially to Hg2+. The Royal Society of Chemistry 2003.

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The new family of Ruthenium(II)-arene complexes of lidocaine of formula [RuII(eta6-p-cymene)Cl(LC)](PF6), 1, [RuII(eta6-p-cymene) (C[tbnd]CFc) (LC)](PF6), 2, [RuII(eta6-p-cymene) (C[tbnd]CFcIP) (LC)](PF6), 3 (LC: lidocaine, FcC[tbnd]CH: ferrocenyl acetylene, C[tbnd]CFcIP: 1?-(phenanthro[9,10-d]imidazole) ferrocenyl-1-acetylene) were prepared and characterized by ESI-MS spectrometry, elemental analysis, IR,1H and13C NMR spectroscopy. The photocytotoxicity of 1?3 was studied with visible light (400?700 nm) against a panel of human cancer cell lines namely, A-375 (human melanoma), HeLa (human cervical cancer) and MCF-7 (human breast cancer) cancer cells. The photoactivity follows the order 1 < 2 < 3 with 2 and 3 having IC50values in A-375 (melanoma) cells in the low micromolar range. These complexes interact with calf thymus DNA. The photocleaving pUC19 DNA of complexes with visible light (400?700 nm) was studied and the results exhibited the active involvement of superoxide and hydroxyl radicals as the reactive oxygen species (ROS) in the DNA photocleavage reactions. These complexes interact with calf thymus DNA via intercalative mode that binding constants vary in the order: 3 > 2 > 1. The complexes 2 and 3 were photoactivated in A-375 cells by visible radiation and analyzed by alkaline single-cell gel electrophoresis.

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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 Wittig reaction has been identified as a viable route to transition metal monomers.It has been used to synthesize (eta5-C5>Mn(CO)3 from acetylcymantrene and the appropriate phosphorane at room temperature. >(eta5-C5H5)Fe (eta5-C5H5)Fe have been produced from formylferrocene and phosphorane in refluxing benzene.E/Z isomeric ratios were identified for alkenylcymantrenes and are consistent with past Wittig studies.The aldol reaction has been identified as a side route in the Wittig reactions of acetylferrocene and phosphoranes.Carbomethoxyphosphoranes did not produce alkenes at room temperature with nonpolar solvents.

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The synthesis and solution redox properties of several covalently attached ferrocene and tetrathiafulvalene units are reported, together with the X-ray crystal structure of a 1,1′-bis(1,3-dithiole-2-ylidene)-substituted ferrocene derivative.

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

 

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Matrix materials, such as sol-gels and polymers derivatives to contain a redox active material can be used to form electrodes and probes suitable for use in pH meters and other analyte sensing devices.

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We investigate the Faradaic currents of ferrocene species at an electrode-membrane-electrode system. The membrane electrodes system is fabricated by physical sputtering of conductive metal on both sides of a nanoporous alumina membrane. The metal coatings function as working electrodes by connection to a bipotentiostat and reference/counter electrodes in the sample solution. Collection and shielding efficiency studies are carried out at this membrane electrodes system to measure mobility values of charged ferrocene species within nanochannels of alumina membrane. Results indicated high selective electrode response of up to 16 times for positively charged (dimethylaminomethyl)ferrocene (FcN), and neutral ferrocenemethanol (FcMeOH), compared to the negatively charged ferrocenecarboxylic acid (FcCOOH) when the receiver electrode was maintained at negative potentials of 0.5-1.0 V relative to the feed electrode. This is a report on the use of an electrode-membrane-electrode system to achieve selective response towards differently charged redox species, under the condition of high electrolyte concentration (0.1 M, pH 7.0 phosphate buffer).

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
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Suitably blocked carbohydrates containing free thio 4, amino 5, and hydroxyl 10,19 nucleophilic functionalities have been treated with (a) ferrocenecarbonyl chlorides 2 and 3. (b) N,N-dimethylaminomethylferrocene methiodide 12, and (c) ferrocenyl tosylate 16 to form the ferrocenyl sugar derivatives 6,7,8,9,11,13,14,15 and 20.Direct conjugation of a free, water-soluble sugar to ferrocene was achieved by the formation of a Schiff’s base between glucosamine hydrochloride 25 and ferrocene carboxaldehyde 24.The synthesis of ferrocenyl sugars using bridging group technology is exemplified by the conjugation of the thio sugar 4 to ferrocene via the versatile coupling reagent cyanuric chloride 21 to form the s-triazine compound 23.These products have been studied by 1H nmr spectroscopy: chemical shifts, coupling constants, and proton spin-lattice relaxation measurements.

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A cesium fluoride-promoted reductive coupling reaction of acylferrocene tosylhydrazones with arylboronic acids has been developed, producing highly substituted alpha-arylalkylferrocenes in moderate to excellent yields. The reaction employs anionic fluorine to facilitate the cleavage of C?B bond. The developed methodology demonstrates a wide substrate scope and high functional groups tolerance. Moreover, the alpha-arylalkylferrocenes compounds were also obtained on a multi-gram scale.

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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