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The catalytic activity of low-dimensional electrocatalysts is highly dependent on their local atomic structures, particularly those less-coordinated sites found at edges and corners; therefore, a direct probe of the electrocatalytic current at specified local sites with true nanoscopic resolution has become critically important. Despite the growing availability of operando imaging tools, to date it has not been possible to measure the electrocatalytic activities from individual material edges and directly correlate those with the local structural defects. Herein, we show the possibility of using feedback and generation/collection modes of operation of the scanning electrochemical microscope (SECM) to independently image the topography and local electrocatalytic activity with 15-nm spatial resolution. We employed this operando microscopy technique to map out the oxygen evolution activity of a semi-2D nickel oxide nanosheet. The improved resolution and sensitivity enables us to distinguish the higher activities of the materials? edges from that of the fully coordinated surfaces in operando. The combination of spatially resolved electrochemical information with state-of-the-art electron tomography, that unravels the 3D complexity of the edges, and ab initio calculations allows us to reveal the intricate coordination dependent activity along individual edges of the semi-2D material that is not achievable by other methods. The comparison of the simulated line scans to the experimental data suggests that the catalytic current density at the nanosheet edge is ?200 times higher than that at the NiO basal plane.

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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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Glucocorticoids are used during prostate cancer (PCa) treatment. However, they may also have the potential to drive castration resistant prostate cancer (CRPC) growth via the glucocorticoid receptor (GR). Given the association between inflammation and PCa, and the anti-inflammatory role of heme oxygenase 1 (HO-1), we aimed at identifying the molecular processes governed by the interaction between HO-1 and GR. PCa-derived cell lines were treated with Hemin, Dexamethasone (Dex), or both. We studied GR gene expression by RTqPCR, protein expression by Western Blot, transcriptional activity using reporter assays, and nuclear translocation by confocal microscopy. We also evaluated the expression of HO-1, FKBP51, and FKBP52 by Western Blot. Hemin pre-treatment reduced Dex-induced GR activity in PC3 cells. Protein levels of FKBP51, a cytoplasmic GR-binding immunophilin, were significantly increased in Hemin+Dex treated cells, possibly accounting for lower GR activity. We also evaluated these treatments in vivo using PC3 tumors growing as xenografts. We found non-significant differences in tumor growth among treatments. Immunohistochemistry analyses revealed strong nuclear GR staining in almost all groups. We did not observe HO-1 staining in tumor cells, but high HO-1 reactivity was detected in tumor infiltrating macrophages. Our results suggest an association and crossed modulation between HO-1 and GR pathways.

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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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Olefinplatinum(II) ?-complexes can be synthesized by the following methods: (i) heating a solution of an olefin, alcohol or alkyl acetate and PtCl62- in acetic acid; (ii) light irradiation of a solution of PtCl62- and an olefin in acetone, and (iii) light irradiation of a solution of PtCl42- and an olefin in aqueous acetone.The possible mechanisms of the thermal and photoinduced reactions are discussed.

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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 design and operation of biosensors is not trivial. For instance, variation in the output signal during monitoring of analytes can not usually be controlled. Hence, if such control were possible, and could be triggered on demand, it would greatly facilitate system design and operation. Herein, we report the design of two types of voltamperometric immunosensors, in which the magnitude of the current output signal (differential pulse voltammetry [DPV]) can be increased or decreased as needed. The designed systems use monoclonal and polyclonal anti-human IgG antibodies, conjugated to monopodal ferrocene-modified gold nanoparticles that are casted onto screen-printed carbon electrodes (Ab/mFcL/AuNPs/SPCEs). Upon addition of human IgG as antigen, the systems exhibit opposite responses according to the Ab: the current decreases when monoclonal Ab is used, whereas it increases when polyclonal Ab is used. We attributed the former response to inhibition of electron-transfer (due to the formation of a protein layer), and the latter response, to a global increase in electron transfer (induced by the aggregation of gold nanoparticles). These effects were confirmed by studying a custom-made lipoic acid-based bipodal ligand, which confirmed that the increase in current is effectively induced by the aggregation of the modified nanoparticles (pAb/mFcL/AuNPs). Both sensors have large dynamic ranges, although the pAb-based one was found to be 3.3-times more sensitive. Tests of selectivity and specificity for ovalbumin, alpha-lactalbumin and serum bovine albumin showed that the immunosensors are highly selective and specific, even in the presence of up to 1000-fold levels of potentially competitive proteins. The limit of detection for human IgG using the pAb/mFcL/AuNP bioconjugate was estimated to be 0.85 ng/mL. The pAb/mFcL/AuNPs-based biosensor has used to determine amounts of human IgG in real sample.

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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 reaction of nitrones with 1,2-dibromotetrafluoroethane affording bromodifluoroethyl-substituted hydroxylamines is described. The process is performed in the presence of a ruthenium photocatalyst and ascorbic acid as a stoichiometric reducing agent and is mediated by blue light irradiation. The fluroalkylation products can undergo chemoselective transformations involving either N?O or C?Br bonds furnishing various tetrafluorinated compounds. (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 growth of B-CNW with different boron doping levels controlled by the [B]/[C] ratio in plasma, and the influence of boron on the obtained material’s structure, surface morphology, electrical properties, and electrochemical parameters, such as -DeltaE and k, were investigated. The fabricated boron-doped carbon nanowalls exhibit activity toward ferricyanide redox couple, reaching the peak separation value of only 85 mV. The flatband potential and the concentration of boron carriers were estimated in the B-CNW samples using the Mott-Schottky relationship. It was shown that the vertically oriented carbon planes are characterized by p-type conductivity and very high hole-acceptor concentration (3.33 × 1023 cm-3 for a highly doped sample), which provides high electrical conductivity. The enhanced electrochemical performance of B-CNWs electrodes is an advantageous feature that can be applied in ultrasensitive detection or energy storage devices. (Graph 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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Two new ferrocenyl-cymantrenyl bimetallic chalcones, [(CO)3Mn(eta5-C5H4)C(O)CHCH(eta5-C5H4)Fe(eta5-C5H5)] (1) and [{(CO)3Mn(eta5-C5H4)C(O)CHCH(eta5-C5H4)}2Fe] (2) have been synthesized. Their reactivity study with triphenylphosphine and bis-(diphenylphosphino)ferrocene led to the isolation of phosphine substituted bimetallic chalcones (3-6). Single crystal X-ray structural characterization for 1 and its phosphine analogue (3) reveals their different conformational identity with anti-conformation for 1, while syn-conformation for 3. Investigation of antimalarial and antibacterial activities was carried out for compounds 1 and 2 against two strains of Plasmodium falciparum (3D7, K1) and four bacterial strains. TD-DFT calculation was performed for compound 1 and electrochemical properties were studied for bimetallic chalcone compounds by cyclic voltammetric technique.

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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 new efficient approach for the ferrocenylmethylation of various alcohols, OH-, SH- and SeH-acids (carboxylic, thio- and selenophosphinic) as well as 1H-triazoles is elaborated based on the acid-catalyzed reaction with available vinyloxymethylferrocene. The reaction readily occurs under mild conditions to afford product of O-, N-, S- and Se-ferrocenylmethylation of the corresponding nucleophiles in good to high 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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It was found that the adsorption of hematin on the surface of solid carriers (alumogel and graphitized carbon black and alumogel and graphitized carbon black modified with adsorbed lecithin) is a reversible and equilibrium process, because the adsorption and desorption branches of the obtained isotherms coincide. The adsorption isotherms were shown to be of Langmuir type. The corresponding Langmuir equation parameters were calculated. These parameters can be considered effective, because the adsorbate is a solution containing an equilibrium mixture of active monomers and inactive associates (dimers); therefore, the curves of sorption are overall isotherms of adsorption of the equilibrium forms of hematin. A kinetic analysis showed that the redistribution of the composition of the associates in the adsorption layers of hematin on the solid carriers under study is accomplished through the solution.

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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 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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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