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In this work, we report the modification of a gold electrode with undoped diamond nanoparticles (DNPs) and its applicability to the fabrication of electrochemical biosensing platforms. DNPs were immobilized onto a gold electrode by direct adsorption and the electrochemical behavior of the resulting DNPs/Au platform was studied. Four well-defined peaks were observed corresponding to the DNPs oxidation/reduction at the underlying gold electrode, which demonstrate that, although undoped DNPs have an insulating character, they show electrochemical activity as a consequence of the presence of different functionalities with unsaturated bonding on their surface. In order to develop a DNPs-based biosensing platform, we have selected glucose oxidase (GOx), as a model enzyme. We have performed an exhaustive study of the different steps involved in the biosensing platform preparation (DNPs/Au and GOx/DNPs/Au systems) by atomic force microscopy (AFM), field emission scanning electron microscopy (FE-SEM) and cyclic voltammetry (CV). The glucose biosensor shows a good electrocatalytic response in the presence of (hydroxymethyl)ferrocene as redox mediator. Once the suitability of the prototype system to determine glucose was verified, in a second step, we prepared a similar biosensor, but employing the enzyme lactate oxidase (LOx/DNPs/Au). As far as we know, this is the first electrochemical biosensor for lactate determination that includes DNPs as nanomaterial. A linear concentration range from 0.05mM to 0.7mM, a sensitivity of 4.0muAmM-1 and a detection limit of 15muM were obtained.

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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 conversion of alpha-ferrocenylalkyl-O-methyl ethers into the corresponding alcohols was successfully achieved by solvolysis in water/acetone mixtures. The content of water in the solvent markedly influenced the reaction rates. The reactivity of structurally different classes of ferrocenyl ethers was evaluated and in most cases high yields of ferrocenyl alcohols or diols were obtained in a few hours without any additive. Deprotection of less reactive substrates was accelerated in the presence of montmorillonite. The method is simple, environmentally benign and valuable in providing easy access to a variety of ferrocenyl derivatives through the use of the -O-methyl ether protective group.

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Grafting Ta(=NtBu)(CH2CMe2Ph)3 onto the surface of silica partially dehydroxylated at 300C leads to the formation of the surface imido complex (?SiO)2Ta(=N tBu)(CH2CMe2Ph) as a major species, which was characterized with EXAFS, 13C CP/MAS NMR, diffuse reflectance FTIR, elemental analyses, and chemical reactivity. The obtained material acts as an efficient heterogeneous catalyst for various oxo/imido heterometathesis transformations: imidation of ketones and DMF with N-sulfinylamines and condensation of N-sulfinylamines into sulfurdiimines and phenyl isocyanate into diphenylcarbodiimide.

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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 synthesis and characterization of ferrocenylimidazole complexes of platinum(II) and palladium(II) are described. Reaction of ferrocenylimidazoles with K2MCl4 (M = Pd, Pt) using a biphasic system of dichloromethane and ethanol/water provided the corresponding complexes 2a-2j in good yields. New synthetic routes for the synthesis of ferrocenylbenzylethers 2k-2o, bis(4-ferrocenylbenzyl)carbonate [2p] and 4-ferrocenylbenzylacetate [2q] are also described. These products were obtained by the reaction of 4-ferrocenylbenzyl-1H-imidazole-carboxylate and K2PtCl4 under various conditions. Compounds 2k-2o were also obtained by alternative routes which do not involve the use of a platinum salt. The crystal structures of 2b, 2q and plausible mechanisms for the formation of 2k, 2p and 2q are reported.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
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The ferrocene-derived acids FcCH2CH2E(O)(OH)2 [4, E=P; 10, E=As; Fc=Fe(eta5-C5H5)(eta5-C5H4)] have been synthesized by the reaction of FcCH2CH2Br with either P(OEt)3 followed by hydrolysis, or with sodium arsenite followed by acidification. Reaction of FcCH2OH with (EtO)2P(O)Na gave FcP(O)(OEt)(OH), which was converted to FcCH2P(O)(OH)2 (3) by silyl ester hydrolysis using Me3SiBr-Et3N followed by aqueous work-up. Similarly, the known phosphonic acid FcP(O)(OH)2 and the new derivatives 1,1?-Fc?[P(O)(OH)2]2 [Fc?=Fe(eta5-C5H4)2] and 1,1?-Fc?[CH2P(O)(OH)2]2 (7) have been synthesized via their corresponding esters. X-ray crystal structure determinations have been carried out on 3 and 7, and the hydrogen-bonding networks discussed. Electrospray mass spectrometry has been employed in the characterization of the various acids. Phosphonic acids give the expected [M-H]- ions and their fragmentation at elevated cone voltages has been found to be dependent on the acid. FcP(O)(OH)2 fragments to [C5H4PO2H]-, but in contrast Fc(CH2)nP(O)(OH)2 (n=1, 2) give Fe{eta5-C5H4(CH2)nP(O)O2]- ions, which are proposed to have an intramolecular interaction between the Fe atom and the phosphonate group. In contrast, arsonic acid (10), together with PhAs(O)(OH)2 for comparison, undergo facile alkylation (in methanol or ethanol solvent), and at elevated cone voltages (e.g. 60 V) undergo carbon-arsenic bond cleavage giving [CpFeAs(O)(OR)O]- (R=H, Me, Et) and ultimately [AsO2]- ions.

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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 this work, binary hydrogel films based on carboxylated multi-walled carbon nanotubes/poly(N,N-diethylacrylamide) (c-MWCNTs/PDEA) were successfully polymerized and assembled on a glassy carbon (GC) electrode surface. The electroactive drug probes matrine and sophoridine in solution showed reversible thermal-, salt-, methanol-and pH-responsive switchable cyclic voltammetric (CV) behaviors at the film electrodes. The control experiments showed that the pH-responsive property of the system could be ascribed to the drug components of the solutions, whereas the thermal-, salt-and methanol-sensitive behaviors were attributed to the PDEA constituent of the films. The CV signals particularly, of matrine and sophoridine were significantly amplified by the electrocatalysis of c-MWCNTs in the films at 1.02 V and 0.91 V, respectively. Moreover, the addition of esterase, urease, ethyl butyrate, and urea to the solution also changed the pH of the system, and produced similar CV peaks as with dilution by HCl or NaOH. Based on these experiments, a 6-input/5-output logic gate system and 2-to-1 encoder were successfully constructed. The present system may lead to the development of novel types of molecular computing systems.

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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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Upon photoirradiation, diphenyl diselenide and diphenyl ditelluride reacted with ethynylferrocene to afford the corresponding bischalcogenated vinylferrocenes. Regioand stereoselectivities were determined by X-ray crystal analysis, and redox properties were investigated by cyclic voltammetry.

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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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Deuterium exchange of certain substituted ferrocenes (under very mild basic conditions) occurs in only the substituted cyclopentadienyl-ring in non-statistical pattern; a ?->? (eta5->eta1) rearrangement mechanism is proposed to account for the novel pattern of exchange.

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Chemoselective and atom-economical methods for the synthesis of ferrocene diethenyl ethers have been developed via direct base-catalyzed addition of 1,1?-bis(hydroxymethyl)ferrocene to various acetylenes. This ferrocene diol has been shown to be capable of adding to acetylene (KOH/DMSO, 70-80 C, 1-3 h), propyne (KOH/DMSO, 70 C, 12 h), phenylethyne (KOH/DMSO, 20-25 C, 48 h), alkylpropiolates (DABCO, 10 mol%/CH 2 Cl 2, 20-25 C, 0.5 h), and acylacetylenes (DABCO, 1 mol%/CH 2 Cl 2, 20-25 C, 0.5 h) to afford the corresponding diethenyl ethers in 73-98% yields.

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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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1,1?-Diacetylferrocene was condensed with aromatic aldehydes without solvent in the presence of solid NaOH. Diacetylferrocene can give good yields of mono- or diene with either one or two molecules of a wide range of aldehydes depending only on the stoichiometry. Cyclization to ferrocenphane does not occur in this condition.

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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