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Electrochemical grafting of a water-insoluble diazonium salt in aqueous media onto an electrode surface was achieved by host-guest complexation. 1-(2-Bisthienyl)-4-aminobenzene (BTAB) was solubilized in a water/beta- cyclodextrin solution (beta-CD). The corresponding diazonium salt was generated in situ then electroreduced. This process leads to the attachment of bithiophene or short oligothiophene groups to the electrode surface. The modified surfaces were analyzed by cyclic voltammetry (CV), scanning electrochemical microscopy (SECM), X-ray photoelectron spectroscopy (XPS), infrared reflection absorption spectroscopy (IRRAS), and atomic force microscopy (AFM). The electrochemical investigations show that the waterbased modified surface is similar to one generated in acetonitrile without beta-CD. Thus, the attached organic layer behaves like an electrochemical switch (above some threshold potential, a soluble external probe is oxidized, but the oxidized form cannot be reduced). The modified surfaces consist of grafted bisthienylbenzene (BTB) and cyclodextrins that can be removed from the surface. This procedure may be considered as a new means of creating a surface made of submicrometric holes in an organic semiconducting layer.

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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 MOFs, [H2N(CH3)2][Zn3(TATB)2(HCOO)]·HN(CH3)2·DMF·6H2O (1) and Zn-HKUST-1 (2), were investigated as potential hosts to encapsulate Fe(III) heme (Fe(III) protoporphyrin IX = Fe(III)PPIX). Methyl orange (MO) adsorption was used as an initial model for substrate uptake. MOF 1 showed good adsorption of MO (10.3 ± 0.8 mg g-1) which could undergo in situ protonation upon exposure to aqueous HCl vapor. By contrast, MO uptake by 2 was much lower (2 ± 1 mg g-1), and PXRD indicated that structural instability on exposure to water was the likely cause. Two methods for Fe(III)PPIX-1 preparation were investigated: soaking and encapsulation. Encapsulation was verified by SEM-EDS and showed comparable concentrations of Fe(III)PPIX on exposed interior surfaces and on the original surface of fractured crystals. SEM-EDS results were consistent with ICP-OES data on bulk material (1.2 ± 0.1 mass % Fe). PXRD data showed that the framework in 1 was unchanged after encapsulation of Fe(III)PPIX. MO adsorption (5.8 ± 1.2 mg g-1) by Fe(III)PPIX-1 confirmed there is space for substrate diffusion into the framework, while the UV-vis spectrum of solubilized crystals confirmed that Fe(III)PPIX retained its integrity. A solid-state UV-vis spectrum of Fe(III)PPIX-1 indicated that Fe(III)PPIX was not in a mu-oxo dimeric form. Although single-crystal XRD data did not allow for full refinement of the encapsulated Fe(III)PPIX molecule owing to disorder of the metalloporphyrin, the Fe atom and pyrrole N atoms were located, enabling rigid-body modeling of the porphine core. Reaction of 2,2?-azino-bis(3-ethylbenzothiazoline)-6-sulfonic acid (ABTS) with H2O2, catalyzed by Fe(III)PPIX-1 and -2, showed that Fe(III)PPIX-1 is significantly more efficient than Fe(III)PPIX-2 and is superior to solid Fe(III)PPIX-Cl. Fe(III)PPIX-1 was used to catalyze the oxidation of hydroquinone, thymol, benzyl alcohol, and phenyl ethanol by tert-butyl-hydroperoxide with t1/2 values that increase with increasing substrate molecular volume.

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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 convenient protocol has been developed for the hydrogenation of metallo-protoporphyrin IX dimethyl esters (MPPDMEs) to their mesoporphyrin analogues using CoCl2-NaBH4 reagent system. Metallo-porphyrin complexes were found to perform as self-catalysts in this procedure. This method provides several advantages such as safe and simple procedure, short reaction time, high yields and low cost. Copyright

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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 propose an innovative nanoarchitecture for the development of electrochemical biosensors based on the non-covalent functionalization of multi-walled carbon nanotubes (MWCNTs) with the lectin Concanavalin A (ConA) and the site-specific supramolecular binding of glycobiomolecules. As proof-of-concept, we propose the use of two glycoenzymes, glucose oxidase (GOx) and horseradish peroxidase (HRP), for building mono and bienzymatic glucose biosensors. The selected conditions for the preparation of the dispersion were 1.5 mg MWCNTs in 1.0 mL of 2.0 mg mL?1 ConA sonicated for 5.0 min with sonicator probe. The monoenzymatic glucose biosensor was prepared by casting GCE with the MWCNTs-ConA dispersion (GCE/MWCNTs-ConA) followed by the interaction with GOx (GCE/MWCNTs-ConA/GOx), while the bienzymatic one was obtained by interaction of GCE/MWCNTs-ConA with GOx + HRP (GCE/MWCNTs-ConA/GOx-HRP). The best analytical performance was obtained with the bienzymatic biosensor from the amperometric response at -0.050 V in the presence of 1.0 × 10-4 M hydroquinone. The sensitivity was (2.22 ± 0.03) muA mM?1 (which was 5.2 times higher than the one obtained with the monoenzymatic biosensor) and a detection limit of 0.31 muM. The reproducibility was 5.4% and the biosensor was challenged with human blood serum showing an excellent correlation with the values reported by the laboratory.

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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 result showed that such a combination of chemo- and biocatalysis improved the catalytic yield more than two times compared with that of sole metal catalysis. We will look forword to the important role of 1273-86-5, and how the biochemistry of the body works.Application In Synthesis of Ferrocenemethanol

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The different techniques nowadays applied in life sciences may be considered as individual instruments in a symphony orchestra, each providing different valuable information. Fundamental questions are addressed regarding biomolecules, biomolecule-modified surfaces, live cells and complex biological functions such as cell signaling cascades, influences on cell proliferation, gene expression and cell death. Techniques such as optical microscopy, electrophoresis, chromatographic techniques bulk or on-chip electrochemical measurements and spectroscopic techniques are among the approaches providing bulk information usually averaging over a large number of biological entities. However, for most of the listed techniques either modification or complexing agents may be necessary and/or the obtained information cannot be correlated to structural changes. Fluorescence-based and high-resolution optical techniques provide spatially resolved information down to individual molecules (e.g., single molecule fluorescence) but usually require labeling steps.1 Scanning probe microscopy (SPM) techniques such as atomic force microscopy (AFM),2 scanning electrochemical microscopy (SECM)3 and scanning ion conductance microscopy (SICM)4 yield valuable information when investigating biological samples in respect to topographical and structural analysis of, for example, cells, yet some of them lack chemical and molecular specificity. In particular electrochemical methods5,6 play a dominant role in studying signaling processes as many transmitter molecules are either electroactive molecules (e.g., catecholamines)7 or can be selectively determined using biosensors.8 Ideally, the detection of specific constituents and the response to stimulation and/or changes of the biological sample should be obtained in a temporally and spatially resolved manner. SECM, as introduced by Bard and co-workers,9 is an attractive scanning probe technique for life sciences and related research areas, which was already demonstrated by early investigations on biological samples10,11 and first enzyme activityrelated investigations presented in 1992.12 Since then, SECM evolved into an increasingly popular technique for studying biochemical and bio-related processes. Significant progress has been made over the years in instrumental developments, by introducing new imaging modes and establishing comprehensive theoretical models. While the early years of SECM were certainly shaped by the team of A. Bard and the research groups emerging from this nucleus, not much later research groups in Japan13-15 and Europe16-24 contributed to SECM research in the field of life sciences. In the early twenty-first century, SECM was improved in respect to resolution, introducing new imaging modalities and SECM research expanded to the investigation of DNA,25-27 cells,28,29 membranes30,31 and neurons.32 Returning to the metaphor of an orchestra, the musical development in allegro was not just limited to its leitmotif of SECM, but combinations with other scanning probe techniques such as AFM and SICM or optical techniques enriched the Symphony. Within this chapter an overview on SECM is provided along with the imaging modalities on biologically relevant applications in the life sciences and related research areas with selected examples. As this chapter cannot be comprehensive, the interested reader is directed further to the seminal book Scanning Electrochemical Microscopy.

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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 containing carbon-carbon and carbon-nitrogen double bonds of the long-chain conjugated system of the ferrocene derivative and its preparation and use, its structure is: The ferrocene derivative has good second-order and third-order non-linear optical activity, can be used as the photoelectric material role. (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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The chemical modification of an sp2 hybridized carbon surface in a controllable manner is very challenging but also crucial for many applications. An inverse electron demand Diels?Alder (IEDDA) reaction using microcontact printing technique is introduced to spatially control the modification of a highly ordered pyrolytic graphite (HOPG) surface under ambient conditions. The covalent modification was characterized by Raman spectroscopy, XPS, and SECM. Tetrazine derivatives can effectively react with an HOPG surface and with microcontact printing methods resulting in spatially patterned surfaces being produced with micrometer-scale resolution.

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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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Multilayer films made of poly(diallyldimethylammonium) (PDDA), gold nanoparticles (AuNP) of 10 nm diameter and lactate oxidase (LOx), were built for the first time, by layer-by-layer (LBL) assembly technique onto both quartz and gold substrates. The surface plasmon resonance (SPR) band of AuNP was used for monitoring the film growth and adsorption kinetics on PDDA monolayer supported onto quartz substrate. In the case of polycrystalline gold surfaces, electrochemical characterization was performed by means of cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The latter system was used as bioelectrode for L-lactate quantification, showing a short time response (<10 s) with high sensitivity of 63 ± 3 muA mM?1cm?2, detection limit of 0.47 muM and linear range between 0.001 mM and 0.25 mM. This bioelectrode was also tested for L-lactate analysis in yogurt and fermented milk, and it was checked that typical interfering as glucose and citric, acetic and ascorbic acids do not play a role. Present results indicate that self-assembled multilayers made of PDDA/AuNP/LOx are suitable thin films for electroanalytical determination of L-lactate in real samples. I am very proud of our efforts over the past few months, and hope to 13790-39-1 help many people in the next few years. .Electric Literature of 1273-86-5

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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Single-entity electrochemistry mainly focuses on the properties of single nanoscale systems, which provides a new avenue of studying electrochemical processes at the nanoscale rather than in complex ensemble systems. Stochastic collision nanoelectrochemistry (SCNEC), which has emerged as a convenient and fast single-entity electrochemical analysis method, has gone through significant improvements over the past few years. As a powerful tool for the establishment of multiple analytical strategies, SCNEC has broad applications in electrochemical analysis, catalysis, biosensing, and so forth. This technique is especially promising for the rapid analysis of a single entity with respect to size, concentration, aggregation, and kinetic studies. In this Minireview, we summarize the basic principles and experimental techniques of SCNEC and give a brief overview of the cutting-edge developments in SCNEC over the past 3 years.

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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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A nickel(0)-catalyzed hydroalkenylation of imines with styrene and its derivatives is described. A wide range of aromatic and aliphatic imines directly coupled with styrene and its derivatives, thus providing various synthetically useful allylic amines with up to 95 % yield. The reaction offers a new atom- and step-economical approach to allylic amines by using alkenes instead of alkenyl-metallic reagents. Experiments and DFT calculations showed that TsNH2 promotes the proton transfer from the coordinated olefin to the imine, accompanied by a new C?C bond formation.

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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