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A carbon microfiber (7 mum diameter) is employed herein as an electroanalytical sensor. The fabricated sensor is cheap, is disposable, and requires only 150 muL of samples. The carbon fiber is surface-mounted onto an inert surface to overcome the problems of the fragility of the microwire and the possible interference of convective force due to the nonrigid nature of the wires, as well as to improve the reproducibility in length and the amperometric responses. As the cylindrical electrode is supported on a surface, the diffusion of redox-active species to the electrode is partially blocked by the substrate. A theoretical model is developed to account for this hindered diffusion. The mass-transport regime is altered from “linear” at very short time, where the amperometric responses of the supported microwire closely resemble that of an isolated free-standing cylinder (current alpha electrode area), to “convergent” at long time where its response now tends toward that of a hemicylinder of equal radius. The model is validated using chronoamperometry and cyclic voltammetry of an ideal outer-sphere redox probe, reversible ferrocene methanol oxidation. The fabricated microwire electrode is further applied to the system of irreversible 2-nitro-5-thiobenzoate oxidation used in the detection of reduced glutathione (GSH). The microwire electrode shows significantly higher ratio of Faradaic to non-Faradaic currents as compared to microdisk, macrodisk or carbon nanotube modified electrodes. Using the fabricated microwire, GSH can be detected with the sensitivity of 0.7 nA muM-1 and the limit of detection of 0.5 muM (3 sB/m). (Figure Presented).

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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 enzyme pyruvate oxidase (PyOD) covalently immobilized on an original conducting copolymer poly(5-hydroxy-1,4-naphthoquinone-co-5-hydroxy-3-thioacetic-1,4-naphthoq uinone acid) can be recycled under anaerobic conditions, at +0.1 V versus SCE. It is first demonstrated that the quinone group is an efficient co-substrate for PyOD in homogeneous conditions, then this efficiency is preserved when the quinone group is embedded in the polymer structure. The copolymer remains efficient even in aerated media. The low working potential avoids side-oxidations of interfering species as ascorbic acid or salycilate.

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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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Novel ferrocene-oligothiophenylene-cyanoacrylic acid in the form of donor-spacer-acceptor dyads was synthesized. The compound with a single unit of thiophenylene showed the lowest energy transition in neutral state. For radical cations, the lowest energy transition appears red-shifted along with the increased number of thiophenylene units. These results suggested that the electronic structure of radical cations is significantly different from that of neutral molecules.

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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 redox-active cyanomanganese carbonyl ligands cis- and trans-[Mn(CN)(CO)2{P(OR)3}(dppm)] (R = Ph or Et dppm = Ph2PCH2PPh2) reacted with ZnBr2, CdI2 and Hg(NO3)2 to give the tetrahedral (at M) complexes [X2M{(mu-NC)MnLx}2] [MX2 = ZnBr2, CdI2 or Hg(NO3)2; Lx = cis- or trans-(CO)2{P(OR)3}(dppm); R = Ph or Et]; similarly [Mn(CN)(NO)PPh3)(eta-C5H4Me)] gives [X2M{(mu-NC)MnLx}2] {MX2 = ZnBr2 or CdI2 Lx = (NO)-(PPh3)(eta-C5H4Me)}. Treatment of [Br2Zn{(mu-NC)MnLx}2] [Lx = trans-(CO)2{P(OEt)3}(dppm)] 4 with TlPF6 in the presence of 1 or 2 equivalents of trans-[Mn(CN)(CO)2{P(OEt)3}(dppm)] gave the tetra- and penta-metallic complexes [BrZn{(mu-NC)MnLx}3][PF6] 13 and [Zn{(mu-NC)MnLx}4][PF6]2 14 [Lx = trans-(CO)2{P(OEt)3}(dppm)] respectively. Differential pulse volammetry showed that 4, 13 and 14 are oxidised to weakly interacting mixed-valence complexes. The reaction of trans-[Mn(CN)(CO)(dppm)2] with ZnBr2 or CdX2 (X = Br or I) in thf gave the bimetallic species [X2(thf)M(mu-NC)Mn(CO)(dppm)2] (MX2 = ZnBr2 or CdI2) and [Br2Cd(mu-NC)Mn(CO)(dppm)2] which are oxidised by [Fe(eta-C5H5)2][PF6] to the MnII complexes [X2(thf)M(mu-NC)Mn(CO)(dppm)2][PF6] and [Br2Cd(mu-NC)Mn(CO)(dppm)2][PF6]. The crystal structures of the tetrahedral polynuclear complexes [I2Cd{(mu-NC)MnLx}2] [Lx = trans-(CO)2{P(OEt)3}(dppm)] 9 and [Br2(thf)Zn(mu-NC)Mn(CO)(dppm)2] 15 are reported, and the importance of steric effects (as quantified by cone angles) in the behaviour of cyanomanganese carbonyl ligands is noted.

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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. Related Products of 1273-86-5. 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

Treatment of ferrocenecarboxaldehyde with base at 0 deg C, lithium diisopropylamide (LDA) or n-butyllithium, followed by the addition of trimethylsilylcyanide, produced 1-(diisopropylamino)cyanomethylferrocene, FcCH(N2)(CN) (II) or 1-trimethylsiloxy-n-pentylferrocene.FcCH(nBu)OSiMe3 (IIIa).The reaction of naphthaldehyde, NpCHO, with LDA/Me3SiCN led to formation of 1-(diisopropylamino)cyanomethylnaphthalene, NpCH(CN) suggesting a general new synthesis for cyanoamines.The reaction of ferrocenecarboxaldehyde with Me3SiCN led to the expected silylether FeCH(CN)OSiMe3 (I).An alternative synthesis of ferrocenylmethylsilylethers, FeCH2OSiR3 (IV), involved the reaction of 1-ferrocenylmethanol with R3SiCl in the presence of pyridine.The basicity of the new silylethers III and IV is reported.

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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 rebinding kinetics of CO to protoheme (FePPIX) in the presence and absence of a proximal imidazole ligand reveals the magnitude of the rebinding barrier associated with proximal histidine ligation. The ligation states of the heme under different solvent conditions are also investigated using both equilibrium and transient spectroscopy. In the absence of imidazole, a weak ligand (probably water) is bound on the proximal side of the FePPIX-CO adduct. When the heme is encapsulated in micelles of cetyltrimethylammonium bromide (CTAB), photolysis of FePPIX-CO induces a complicated set of proximal ligation changes. In contrast, the use of glycerol-water solutions leads to a simple two-state geminate kinetic response with rapid (10-100 ps) CO recombination and a geminate amplitude that can be controlled by adjusting the solvent viscosity. By comparing the rate of CO rebinding to protoheme in glycerol solution with and without a bound proximal imidazole ligand, we find the enthalpic contribution to the proximal rebinding barrier, Hp, to be 11 ± 2 kJ/mol. Further comparison of the CO rebinding rate of the imidazole bound protoheme with the analogous rate in myoglobin (Mb) leads to a determination of the difference in their distal free energy barriers: DeltaGD ? 12 ± 1 kJ/mol. Estimates of the entropic contributions, due to the ligand accessible volumes in the distal pocket and the xenon-4 cavity of myoglobin (?3 kJ/mol), then lead to a distal pocket enthalpic barrier of HD ? 9 ± 2 kJ/mol. These results agree well with the predictions of a simple model and with previous independent room-temperature measurements (Tian et al. Phys. Rev. Lett. 1992, 68, 408) of the enthalpic MbCO rebinding barrier (18 ± 2 kJ/mol).

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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 work across a number of sectors, processes differ within each of these areas, but chemistry and chemical engineering roles are found throughout, creation and manufacturing process of chemical products and materials. Application of 1271-51-8. Catalysts allow a reaction to proceed via a pathway that has a lower activation energy than the uncatalyzed reaction. Introducing a new discovery about 1271-51-8, Name is Vinylferrocene

A series of ferrocenyl-arene dyads, Fc-C=C-Ar, trans-Fc-CH=CH-Ar, and Fc-CH=CH-CH=CH-Ar (Ar = phenyl, 1-naphthyl, 2-naphthyl, 9-phenanthryl, 9-anthryl, 1-pyrenyl, 3-perylenyl) have been synthesized. Their structures and spectroelectrochemical properties are discussed. The molecular structures of several have been determined by X-ray diffraction and the observed structures compared with global free-energy minimized calculated structures. In the solid state all ethynyl dyads have the aromatic ring orthogonal to the ferrocenyl cyclopentadienyl rings, whereas calculations predict a coplanar orientation. Calculated and observed structures agree for the ethenyl dyads with the rings orthogonal and coplanar for the anthryl and pyrenyl dyads, respectively. In most cases the solid-state structures are stabilized by offset pi-stacking interactions between the polycyclic hydrocarbon rings. The two bands in the electronic spectra of the neutral dyads are due to the individual aryl and ferrocenyl end-groups. Upon oxidation at the [Fc]+/0 couple, the ferrocenyl transition is replaced by LMCT bands at lower energy and a new weak band in the NIR assigned to a Fc+ ?aryl transition; these assignments are supported by resonance Raman spectra, and the energy of the Fc+? aryl transition correlates with the ionization energy of the aryl group. These are therefore electrochromic dyads.

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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, after optimizing the original aptamer sequence by truncation and site-directed mutagenesis, a simple and sensitive colorimetric aptasensor was established for detecting the widespread food-borne pathogen Vibrio parahemolyticus (V. parahemolyticus). The detection strategy was based on the competition for an V. parahemolyticus specific aptamer between its complementary DNA (cDNA) and V. parahemolyticus. The aptamer-conjugated magnetic nanoparticles (MNPs) were used as capture probes, and the G-quadruplex (G4) DNAzyme was employed as the signal amplifying element. Under optimal conditions, a wide linear detection range (from 102 to 107 cfu/mL) was available, and the detection limit could be as low as 10 cfu/mL. This method was also used to detect V. parahemolyticus in contaminated salmon samples, and the results showed good consistency with those obtained from standard plate counting method. Therefore, this novel aptasensor could be a good candidate for sensitive and selective detection of V. parahemolyticus without complicated operations.

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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 work across a number of sectors, processes differ within each of these areas, but chemistry and chemical engineering roles are found throughout, creation and manufacturing process of chemical products and materials. Computed Properties of C11H3FeO. 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

The extracellular electron transfer of Shewanella oneidensis MR-1 (MR-1) has been extensively studied due to the importance of the biosensors and energy applications of bioelectrochemical systems. However, the oxidation of metal compounds by MR-1, which represents the inward extracellular electron transfer from extracellular electron donors into the microbe, is barely understood. In this study, MR-1 immobilized on an electrode electrocatalyzes the oxidation of [Fe(CN)6]4- to [Fe(CN)6]3- efficiently and selectively. The selectivity depends on midpoint potential and overall charge(s) of redox molecules. Among 12 investigated redox molecules, the negatively charged molecules with high midpoint potentials, i.e., [Ru(CN)6]4- and [Fe(CN)6]4-, show strong electrocatalysis. Neither reference bacteria (Escherichia coli K-12 nor Streptococcus mutans) electrocatalyze the oxidation of [Fe(CN)6]4-. The electrocatalysis decays when MR-1 is covered with palladium nanoparticles presumptively involved with cytochromes c. However, cytochromes c MtrC and OmcA on MR-1 do not play an essential role in this process. The results support a model that [Fe(CN)6]4- donor electrons to MR-1 by interacting with undiscovered active sites and the electrons are subsequently transferred to the electrode through the mediating effect of [Fe(CN)6]4-/3-. The selective electron uptake by MR-1 provides valuable and fundamental insights of the applications of bioelectrochemical systems and the detection of specific redox molecules.

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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 efficient synthesis of various diborylalkenes such as 1,1-, trans-1,2-, and cyclic 1,2-diborylalkenes from alkenes and diboron was achieved for the first time. Selective preparation of di- and monoborylalkenes was also realized by the appropriate choice of reaction conditions. The reaction was found to proceed via a new mechanism of dehydrogenative borylation through a monoborylpalladium complex bearing an anionic PSiP-pincer ligand as a key intermediate, which realized the efficient borylation without sacrificial hydroboration or hydrogenation of the alkene.

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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