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In this paper we describe the synthesis, the electrochemical behaviour as well as the linear and nonlinear optical (NLO) properties of two push-pull derivatives bearing pyranylidene electron donating fragment, pyrimidine/methyl pyrimidinium electron withdrawing moiety and a ferrocene part in the pi-conjugated bridge. The properties of these two compounds were compared to their analogues without ferrocene or pyranylidene fragments. Experimental results were completed with DFT calculations to gain further insight into the intramolecular charge transfer (ICT). All the results indicate a significant charge transfer through the ferrocene unit. The ICT is however more limited than in all organic analogues.

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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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A carbon nanotube (CNT)-modified electrode was fabricated by dropping a dispersion of multi-walled CNTs in water-soluble and amphiphilic phospholipid polymer with both dispersing ability and anti-biofouling property onto a Au electrode. A poly(2-methacryloyloxyethyl phosphorylcholine-co-n-butyl methacrylate) (PMB) composed from 50 mol% of 2-methacryloxylethyl phosphorylcholine and 50 mol% of n-butyl methacrylate (PMB50) was used as dispersing reagent for CNTs. The dispersion of water-insoluble material by PMB50 and its antifouling effects in electrochemical analysis were investigated. The CNT-modified electrode showed an anodic peak potential that was shifted negatively and an increase in the current value for the electrolytic oxidation of nicotinamide adenine dinucleotide. In addition, the charge on PMB50 did not inhibit the electrochemical reaction of the redox compounds K3[Fe(CN)6], [Ru(NH3)6]Cl3, and hydroxymethylferrocene. Cyclic voltammetry of K3[Fe(CN)6] in 4 % bovine serum albumin (BSA) using a bare Au electrode, the anodic peak current was reduced to 47 % of that without BSA. In contrast, the antifouling effect of the PMB50-coated electrode meant that the current was only reduced to 70 % of that without BSA.

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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, a biomolecular calculation system was developed based on electrochemiluminescence (ECL) and fluorescence emission (FL) of luminol and cyclic voltammetry (CV) of ferrocene methanol (FMA). When triethylamine (TEA) was added in luminol solution as a coreactant, a great ECL peak at 1.1 V was observed. While the further addition of enzymatic system, esterase/ethyl butyrate (EB), would significantly lower the ECL response. On the other hand, TEA could quench the FL signal of luminol at 430 nm, while the injection of esterase/EB in the luminol solution could enhance the FL signal. Furthermore, FMA exhibited a CV peak pair at 0.2 V and could decrease the ECL signal greatly in the luminol/TEA solution. Based on these interesting results, a 3-input and 5-output biomolecular logic gate was established with TEA, FMA and esterase/EB as inputs and the ECL, CV and FL signals as outputs. Moreover, some nonarithmetic logic devices, such as an encoder, a decoder, a 3-input keypad lock and two dual transfer gates were elaborately designed on the same platform. This work presented a new example of how the complexity of biocomputing system could be enhanced either by increasing the number of outputs of traditional logic gates or by fabricating some nonarithmetic logic devices based on the same simple electrochemical system.

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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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A sustainable and green route to access diverse functionalized ketones via dehydrogenative?dehydrative cross-coupling of primary and secondary alcohols is demonstrated. This borrowing hydrogen approach employing a pincer N-heterocyclic carbene Mn complex displays high activity and selectivity. A variety of primary and secondary alcohols are well tolerant and result in satisfactory isolated yields. Mechanistic studies suggest that this reaction proceeds via a direct outer-sphere mechanism and the dehydrogenation of the secondary alcohol substrates plays a vital role in the rate-limiting step.

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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 the (E,E)-1,1?-ferrocene nanostructures having controlled pi-extended conjugation was satisfactory carried out starting of 1?-[2-(1,3-dioxolan)]-1-formylferrocene (1). The molecular unit (E)-1?-[2-(1,3-dioxolan)]-1-[beta-(p-iodophenyl)ethenyl]ferrocene (2), was obtained in excellent yield by treatment of 1 with p-iodobenzyl triphenylphosphonium ylid followed by Z?E isomerization, catalyzed by iodine, in quantitative yield. Compound (E)-2 was transformed in (E)-1?-{2-(1,3-dioxolan)-1-[beta-[4-(3-hydroxy-3-methyl-but-1-ynyl)-phenyl]-ethenyl}ferrocene, (E)-4, by palladium catalyzed cross-coupling with 2-methyl-but-3-yn-2-ol. (E)-4 gives (E)-1-[beta-(4-ethynylphenyl)-ethenyl]-1?-[2-(1,3-dioxolan)]ferrocene (E)-5 by powder sodium hydroxide treatment. The molecular unit (E,E)-1-{beta-[4-(beta-(1?-formylferrocenyl)-ethenyl)-phenylethynyl]-phenyl]-ethenyl}-1?-formylferrocene, (E,E)-6, was synthesized by palladium catalyzed cross-coupling between the p-iodophenyl derivative (E)-2 and their ethynyl derivative (E)-5, in good yield. The (E,E)-1,1?-(p-iodophenyl)ethenyl ferrocene, (E,E)-7, was synthesized by reaction between 1,1?-diformylferrocene and the p-iodobenzyltriphenylphosphonium ylid, as a mixture of isomers which were purely isolated. Moreover, isomerization of the Z,Z and E,Z mixture to the E,E isomer, was induced by sunlight exposure, catalyzed by iodine, in quantitative yield. The (E,E)-1,1?-[beta-(4-ethynylphenyl)-ethenyl]ferrocene, (E,E)-10, was synthesized in good yield, by palladium catalyzed cross-coupling of compound (E,E)-7 with 2-methyl-but-3-yn-2-ol, followed by powder sodium hydroxide treatment.

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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 invention discloses a novel containing nitrogen oxygen free radical ferrocene derivatives preparation method and use thereof, of formula (I) is shown containing nitrogen oxygen free radical of the ferrocene derivative or its pharmaceutically acceptable salt or pharmaceutical composition or solvate. (I) in formula (I) indicated by the ferrocene derivative to a lung cancer cell strain A549 and breast cancer cell MCF – 7 of value-added has very strong inhibiting activity, can be used as a medicine for treating cancer, tumor diseases such as candidate compound or a lead compound. (by machine translation)

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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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An In(OTf)3-catalyzed N-benzylation of amines utilizing benzyl alcohols through direct C-O bond activation has been reported. The reaction was performed in water without any base, additive, ligand or inert gas protection to afford the chem-selective mono- or bis-alkylated aromatic amines in good to excellent yields.

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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 first sumanene-ferrocene probes for efficient and selective caesium cation (Cs+) recognition are reported. The working mechanism of the sumanene moiety as the sensing unit was based on the site-selective cation-pi interaction in its neutral state. The interactions with Cs+ were characterized by high association constant values together with low limits of detection.

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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 influence of the reaction conditions in the polycondensation of 1,1′-diacetylferrocene and 1,1′-bisferrocene with biuret is studied and the optimum parameters for obtaining new ferrocene polymers, polyferrocenyleniminoimides, determined.The synthesized polymers are stable up to 225 deg C and show semiconducting properties.

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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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Respiration, photosynthesis and peroxidase activities of living spherical samples, such as algal protoplasts, breast cancer spheroids and bovine embryos, were characterized with scanning electrochemical microscopy (SECM). The concentration profile of the metabolic product around the spherical sample was directly measured by scanning with a probe microelectrode. According to the spherical diffusion theory, the total mass transfer rate per spherical sample is linear to the multiplication of the sample radius and the concentration difference between the sample surface and the bulk of the solution. Therefore, the sample radius is a key parameter to assess the viability of the living samples. For example, we investigated the respiration and photosynthesis activities as a function of the size of the protoplast (Bryopsis plumosa). The respiration rate was linear to the cube of the sample radius. On the contrary, the photosynthesis rate was linear to the square of the sample radius, suggesting that the former is controlled by the volume of the protoplast, and the latter is controlled by the surface area of the protoplast. We will also discuss the size-dependent activity of the breast cancer spheroids and the bovine embryos. Furthermore, relations between the sample size, the concentration difference, and the oxygen consumption rate of the cryo-preserved bovine blastocysts were investigated.

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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