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Redox enzymes, which catalyze electron transfer reactions in living organisms, can be used as selective and sensitive bioreceptors in biosensors, or as efficient catalysts in biofuel cells. In these bioelectrochemical devices, the enzymes are immobilized at a conductive surface, the electrode, with which they must be able to exchange electrons. Different physicochemical methods have been coupled to electrochemistry to characterize the enzyme-modified electrochemical interface. In this Review, we summarize most efforts performed to investigate the enzymatic electrodes at the micro- and even nanoscale, thanks to microscopy techniques. Contrary to electrochemistry, which gives only a global information about all processes occurring at the electrode surface, microscopy offers a spatial resolution. Several techniques have been implemented; mostly scanning probe microscopies like atomic force microscopy, scanning tunneling microscopy, and scanning electrochemical microscopy, but also scanning electron microscopy and fluorescence microscopy. These studies demonstrate that various information can be obtained thanks to microscopy at different scales. Electrode imaging has been performed to confirm the presence of enzymes, to quantify and localize the biomolecules, but also to evaluate the morphology of immobilized enzymes, their possible conformation changes upon turnover, and their orientation at the electrode surface. Local redox activity has also been imaged and kinetics has been resolved.

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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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We want to report on syntheses and test reactions of some ferrocenic compounds which could be used as derivatizing reagents for peptides and proteins in order to detect them electrochemically after an HPLC analysis run.Among the tested compounds we found the 3-ferrocenylpropionic anhydride as the most suitable reagent for this purpose.It is a stable compound which can be prepared with high yields from 3-ferrocenylpropionic acid.Its reaction products with peptides and proteins are highly electroactive which is essential for the sensibility and selectivity of the method.

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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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Application of 1273-94-5, Chemistry graduates have much scope to use their knowledge in a range of research sectors, including roles within chemical engineering, chemical and related industries, healthcare and more. 1273-94-5, Name is 1,1′-Diacetylferrocene, molecular weight is 262.0412. In an Article,once mentioned of 1273-94-5

Circular dichroism spectra in the IR range (VCD = vibrational circular dichroism) and in the UV range (ECD = electronic circular dichroism) have been recorded for both enantiomers of simple mono-substituted ferrocenes containing chiral pendants: 1-acetoxyethylferrocene, 1, 1-methoxyethylferrocene, 2, and 1-hydroxyethylferrocene, 3; the related disubstituted 1,1?-bis(1-hydroxyethyl)ferrocene, 4, was also considered. These two types of spectra, with the support of DFT calculations, concur to unequivocally confirm the absolute configuration for 1-4. In particular, our computational results point out the clear advantage of using an anharmonic oscillator model for the interpretation of VCD spectra of chiral ferrocenes. Interesting conformational properties are either confirmed or established by the technique, like the eclipsed conformation of the two cyclopentadienyl rings and an intra-molecular interaction involving the OH for 3. For 4, NMR, VCD and IR spectra are compatible with dimer formation and in this case a distorted conformation is predicted. Of utmost importance for the absolute configuration assignment in mono-substituted ferrocenes, we were able to identify a diagnostic VCD band at 950 cm-1 and a (low intensity) ECD band that clearly indicate the absolute configuration of the whole series.

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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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Various metalloligands and inorganic-organic hybrid bridging ligands have been incorporated in polynuclear complexes and bimetallic coordination polymers. Ferrocene, exhibiting redox activity and facile chemical modification, is a versatile metalloligand component. However, most metal complexes with ferrocene-containing ligands form discrete low-dimensional chelate complexes or coordination polymers. Thus, we designed and synthesized ferrocene-based multidentate ligands, 1,2-di(4-pyridylthio)ferrocene (L1) and 1,2-di(2-pyridylthio)ferrocene (L2). Here we report the synthesis and structures of molecular square complexes and coordination polymers containing L1, which reacted with M(hfac)2 (hfac = 1,1,1,5,5,5-hexafluoroacetylacetonate) and AgCF3SO3 to yield molecular square complexes [M(hfac)2(L1)]2·2C6H5CH3 [M = Ni (1) and Co (2)] and [Ag(CF3SO3)(L1)(H2O)0.5]2·2CH2Cl2·H2O (3). The molecular square units comprise two metal ions bridged by two ligands. Isomorphic complexes 1 and 2 accommodate two toluene molecules above and below the molecular square. L1 reacted with Cu(hfac)2 and CuI to yield zigzag, {[Cu(hfac)2(L1)]}n·0.25n(CH2Cl2) (4), and ribbon-shaped, {[Cu4I4(L1)2]}n (5), coordination polymers. In 4, L1 behaves as a bidentate N,N-ligand bridging the CuII ions, while in 5 it acts as a tridentate S,N,N-ligand linking the stepped-cubane Cu4I4 units. L1 reacted with AgX to form two-dimensional coordination polymers {[Ag(ClO4)(L1)]}n (6) and {[Ag(L1)]PF6}n (7), in which it acted as a tetradentate S,S,N,N-ligand. These complexes have topologies based on multidentate coordination of 1,2-substituted L1.

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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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Three-dimensional printed multi-purpose electrochemical devices for X-ray absorption spectroscopy are presented in this paper. The aim of this work is to show how three-dimensional printing can be a strategy for the creation of electrochemical cells for in situ and in operando experiments by means of synchrotron radiation. As a case study, the description of two cells which have been employed in experiments on photoanodes for photoelectrochemical water splitting are presented. The main advantages of these electrochemical devices are associated with their compactness and with the precision of the three-dimensional printing systems which allows details to be obtained that would otherwise be difficult. Thanks to these systems it was possible to combine synchrotron-based methods with complementary techniques in order to study the mechanism of the photoelectrocatalytic 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

 

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The first 2-phospha[3]ferrocenophanes containing stereogenic carbon atoms in the three-atom bridge have been synthesised from phenylphosphane by stereospecific ring-closing phosphanation reactions. Either alpha-substituted 1,1?-bis-(hydroxymethyl)ferrocenes or the corresponding 2-oxa-[3]ferrocenophanes have been used as diastereomerically pure starting materials. The resolution of 1,2,3-triphenyl-[2]phosphaferrocenophane has been achieved by chromatographic separation of the diastereomeric adducts of a chiral cyclopalladate complex. The X-ray crystal structures of two 2-phospha[3]ferrocenophane-borane complexes are also reported. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.

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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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Ferrocene-based Lewis bases have found utility as metalloligands in a wide variety of applications. The coordination chemistry of cyanoferrocenes however, is underexplored. Herein, we describe a new synthetic protocol for the generation of cyanoferrocenes. The coordination chemistry of these metalloligands to [Cu(NCMe)4][PF6], [(PPh3)2Cu(NCMe)2][PF6] and [(dppf)Cu(NCMe)2][PF6] salts has been explored, providing crystallographic evidence of cluster and polymeric forms of 1,1?- and 1,2-dicyanoferrocene complexes. The stability of the complexes and ligand dissociation were found to be strongly solvent-dependent.

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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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Chemical engineers ensure the efficiency and safety of chemical processes, adapt the chemical make-up of products to meet environmental or economic needs, and apply new technologies to improve existing processes. Quality Control of Ferrocenemethanol. Catalysts allow a reaction to proceed via a pathway that has a lower activation energy than the uncatalyzed reaction. Introducing a new discovery about 1273-86-5, Name is Ferrocenemethanol

Electron transfer (ET) reactions in ionic liquid (IL)|organic solvent (1,2-dichloroethane, DCE) and IL|water mixtures were investigated using a Pt disk ultramicroelectrode (UME) along with ferrocene (Fc) and ferrocenemethanol (FcCH2OH) redox probes as electroactive species dissolved in the respective mixtures. The IL utilized was tributylmethylphosphonium methyl sulfate (P4441CH3SO4). The diffusion coefficient of each redox species was determined at each incremental increase of DCE or water to the IL using a chronoamperometric technique that is concentration independent. The IL|DCE mixture exhibited little change in the Fc diffusion coefficient, DFc, up to a DCE mole fraction (chiDCE) of 0.5; the observed value, 2.0 × 10-8 cm2 s-1, agrees well with that typically reported for ILs in the literature. After which, the DFc quickly rose to a value commonly found in conventional molecular solvents, 1.3 × 10-5 cm2 s-1 (at chiDCE = 0.8). An analogous result was not observed for IL|water mixtures using FcCH2OH, such that DFcCH2OH varied from 0.2 to 1.2 × 10-9 cm2·s-1 at a chiH2O of 0 to 0.8. It was proposed that a large increase in the DFc in the IL|DCE mixture versus DFcCH2OH in the IL|water series was owing to P4441CH3SO4’s more hydrophobic character. Its hydrophobicity was quantified by measuring the formal ion transfer potentials of the IL component ions at a water|DCE immiscible interface.

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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 doxorubicin – hemin interaction was studied by absorption and emission spectroscopy. The absorption spectra outline two processes, in function of the concentration range of hemin. The fluorescence emission of doxorubicin shows a pronounced hypochromic effect in presence of hemin. The best fit was obtained using an (1:1) and (1:2) interaction for both methods. The doxorubicin – hematoporphyrin and doxorubicin – FeIII systems were also investigated in similar experimental conditions, in order to outline the possible binding sites involved in the interaction. The quenching effect of hematoporphyrin is smaller than that of hemin, the binding parameters indicated an (1:1) interaction and are smaller than the corresponding values for hemin. For the doxorubicin – FeIII system, the association constants for (1:1) and (1:2) complexes are in a reasonable agreement in both methods used. Our results are consistent with a two site binding model, where the Fe III ions of hemin are involved to a higher extent than the planar porphyrin moiety in the hemin – doxorubicin interaction.

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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 highest nonlinear optical bulk efficiency for a 2-(4-nitro-phenyl)ethenylferrocene (140 times that of urea) has been achieved for E-4 owing to a favourable noncentrosymmetrical packing in which all molecules are perfectly aligned (P1 space group).

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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