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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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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 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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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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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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A series of ruthenium(II) complexes incorporating a thiosemicarbazone chelate tethered with a diphenylphosphine pendant have been studied. Thus, [(PNS-Et)RuCl(CO)(PPh3)] (1), [N,S-(PNS-Et)RuH(CO)(PPh3)2] (2) and [(PNS-Et)RuCl(PPh3)] (3) were synthesized by reactions of various RuII precursors with 2-(2-(diphenylphosphino)benzylidene)-N-ethylthiosemicarbazone (PNS-Et). However, complexation of PNS-Et with an equimolar amount of [RuCl2(dmso)4] resulted in two different entities [(PNS-Et)RuCl(dmso)2] (4) and [(PNS-Et)2Ru] (5) with different structural features in a single reaction. All the RuII complexes have been characterized by analytical and various spectroscopic techniques. Compounds 1-5 were recrystallized, and the X-ray crystal structures have been reported for 1, 2 and 5. In the complexes 1 and 3-5 the ligand coordinated in a tridentate monobasic fashion by forming PNS five- and six-membered rings, whereas in 2, the ligand coordinated in a bidentate monobasic fashion by forming a strained NS four-membered ring. Furthermore, compounds 1-5 showed catalytic activity in N-alkylation of heteroaromatic amines. Notably, complexes 1-3 were found to be very efficient catalysts toward N-alkylation of a wide range of heterocyclic amines with alcohols. In the presence of a catalytic amount of 2 with 50 mol% of KOH, N1,C5-dialkylation of 4-phenylthiazol-2-amine has been investigated. Reaction of in situ generated aldehyde with amine yields the N1,C5-dialkylated products through the hydride ion transformation from alcohol. Complexes 1-3 also catalyzed a variety of coupling reactions of benzyl alcohols and sulfonamides, which were realized often with 99% isolated yields. Advantageously, only one equivalent of the primary alcohol was consumed in the 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 performances of a single microband electrode probing within a microfluidic channel, the passage of a concentration front of electroactive species,were investigated. Optimal conditions in terms of device geometries and hydrodynamic flow were delineated to allowamperometric detectionswith high temporal resolution. These conditions correspond to specific regimes reflecting the complex coupling between diffusional and convective transport. Experimental current responses were in excellent agreement with the theoretical predictions. A new concept of microchannel electrodes acting as concentration probes was thus successfully demonstrated.

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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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Abstract: Regioselective synthesis of bis-ferrocenylpyrazole derivatives in biphasic aquatic?organic system under catalysis with HBF4 was carried out. The regioselectivity of these reactions depending on the electronic effects of substituents in pyrazole moiety was studied. Graphical abstract: [Figure not available: see fulltext.]

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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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To study the direct electron transfer (DET) of the multicofactor enzyme cellobiose dehydrogenase (CDH) in regard to its orientation on an electrode surface, a recently published, maleimide-based immobilization method was used in combination with site-directed mutagenesis to establish different orientations on an electrode surface. CDH from Myriococcum thermophilum was chosen for this study because its protein structure is resolved and the factors influencing the movement of its mobile cytochrome domain (CYT) are established. Seven CDH variants with a surface-exposed cysteine residue in different spatial positions were generated for site-specific maleimide coupling. Surface plasmon resonance and cyclic voltammetry showed that all CDH variants, but not the wild-type CDH, bound covalently to gold electrodes or glassy carbon electrodes and were catalytically active. For DET, the CYT domain needs to move from the closed-state conformation, where it obtains an electron from the catalytic flavin adenine dinucleotide (FAD) cofactor to the open state where it can donate an electron to the electrode. We therefore hypothesized that the mobility of the CYT domain and its distance to the electrode is central for DET. We found that the uniform spatial orientations of CDH influenced DET as follows: An orientation of the two-domain enzyme on the side, with CYT in proximity to the electrode, resulted in high DET currents. Orientations with a bigger distance between CYT and the electrode, or orientations where CYT could not swing back to the dehydrogenase domain to form the closed enzyme conformation, reduced DET. In the latter case, calcium ions that stabilize the closed conformation of CDH fully recovered DET. The study demonstrates that a mobile CYT domain can compensate unfavorable orientations of the catalytic domain to a great extent and allows CDH as a multicofactor enzyme to transfer electrons even in awkward orientations. The mobile CYT domain reduces the anisotropy of DET, which is also essential for CDH’s physiological function as an extracellular, electron-transferring enzyme.

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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 series of novel 2-ferrocenyl-3,4-dihydropyrans were synthesized in good to excellent yields through three-component reaction of vinylferrocene, 1,3-dicarbonyl compound and formaldehyde near room temperature under catalyst-free conditions. The obtained ferrocenyl dihydropyrans can also react readily with indole in the presence of alum, providing a ring-opening product in high yield, and this result opens an effective way to access a new class of complex ferrocenyl derivatives.

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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