Day: August 18, 2021

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We report biodegradable electroactive polymer (EAP)-based materials and their application as drug delivery devices. Copolymers composed of oligoaniline-based electroactive blocks linked to either polyethylene glycol or polycaprolactone blocks via ester bonds were synthesized in three steps from commercially available starting materials and isolated without the need for column chromatography. The physicochemical and electrochemical properties of the polymers were characterized with a variety of techniques. The ability of the polymers to deliver the anti-inflammatory drug dexamethasone phosphate on the application of electrochemical stimuli was studied spectroscopically. Films of the polymers were shown to be degradable and cell adhesive in vitro. Such EAP-based materials have prospects for integration in implantable fully biodegradable/bioerodible EAP-based drug delivery devices that are capable of controlling the chronopharmacology of drugs for future clinical application.

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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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Much attention has been focused on electrochemically active bacteria (EAB) in the application of bioelectrochemical systems (BESs). Studying the EAB biofilm growth mechanism as well as electron transfer mechanism provides a route to upgrade BES performance. But an effective bacterial growth monitoring method on the biofilm scale is still absent in this field. In this work, electrode-attached bacterial biofilms formed by Shewanella oneidensis MR-1 were dynamically monitored through a microelectrode method. For S. oneidensis MR-1, a respiratory electron transport chain is associated with the secretion of riboflavin, severing as the cofactor to the outer membrane c-type cytochromes. The biofilm growth was monitored through adopting riboflavin as an electrochemical probe during the approach of the microelectrode to the biofilm external surface. This method allows in vivo and in situ biofilm monitoring at different growth stages without destructive manipulation. Furthermore, the biofilm growth monitoring results have been proved to be relatively accurate through observation under confocal laser scanning microscopy. We further applied this method to investigate the effects of four environmental factors (the concentrations of dissolved oxygen, sodium lactate, riboflavin as well as the electrode potential) on S. oneidensis MR-1 biofilm development.

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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 chameleonic, redox-switchable carrier molecule: A [4,4]ferrocenophane ligand can selectively recognize Mg2+ ions through complexation. This ligand can transport and release Mg2+ ions by application of an external electrochemical stimulus across a CH2Cl2 liquid membrane (see picture). Furthermore, dramatic color changes are seen, which allow the potential for “naked-eye” detection. (Chemical Equation 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 oxidation of primary azides to aldehydes constitutes a convenient but underdeveloped transformation for which no efficient methods are available. Here, we demonstrate that engineered variants of the hemoprotein myoglobin can catalyze this transformation with high efficiency (up to 8500 turnovers) and selectivity across a range of structurally diverse aryl-substituted primary azides. Mutagenesis of the ‘distal’ histidine residue was particularly effective in enhancing the azide oxidation reactivity of myoglobin, enabling these reactions to proceed in good to excellent yields (37-89%) and to be carried out at a synthetically useful scale. Kinetic isotope effect, isotope labeling, and substrate binding experiments support a mechanism involving heme-catalyzed decomposition of the organic azide followed by alpha hydrogen deprotonation to generate an aldimine which, upon hydrolysis, releases the aldehyde product. This work provides the first example of a biocatalytic azide-to-aldehyde conversion and expands the range of non-native chemical transformations accessible through hemoprotein-mediated catalysis.

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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

Chemical research careers are more diverse than they might first appear, name: Ferrocenemethanol, as there are many different reasons to conduct research and many possible environments. In a article, mentioned the application of 1273-86-5, Name is Ferrocenemethanol, molecular formula is C11H3FeO

Hydrogen peroxide (H2O2) is an important molecule within the human body, but many of its roles in physiology and pathophysiology are not well understood. To better understand the importance of H2O2 in biological systems, it is essential that researchers are able to quantify this reactive species in various settings, including in vitro, ex vivo and in vivo systems. This review covers a broad range of H2O2 sensors that have been used in biological systems, highlighting advancements that have taken place since 2015.

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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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Reaction of Cp4Fe4(CO)4 (1) with RLi and HBF4 in sequence affords Cp3Fe4(CO)4(C5H4R) (R= Me, Bun, and Ph) in moderate yields. Further sequential PhLi/HBF4 treatment of Cp3Fe4(CO)4(C5H4Ph) produces Cp2Fe4(CO)4(C5H4Ph) 2. On the other hand, 1 reacts with lithium diisopropylamide (LDA) and bromoferrocene sequentially to produce a ferrocenylated cluster [Cp3Fe4(CO)4(C5H 4)][(C5H4)FeCp] (3) and a double cluster [Cp3Fe4(CO)4(C5H4)] 2 (2). A similar LDA/dibromoferrocene treatment with 1 leads to 2, [Cp3Fe4(CO)4(C5H 4)][(C5H4)(C5H4Br)Fe] (4), and a ferrocenyl-bridged double cluster [Cp3Fe4(CO)4(C5H4)] 2[(C5H4)2Fe] (5). The new compounds have been characterized by elemental analysis and IR, mass, and NMR spectroscopy.

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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

Chemical research careers are more diverse than they might first appear, Electric Literature of 1271-48-3, as there are many different reasons to conduct research and many possible environments. In a article, mentioned the application of 1271-48-3, Name is 1,1′-Ferrocenedicarboxaldehyde, molecular formula is C12H10FeO2

Reaction of ferrocenecarboxaldehyde 13 and its vinylogue, (E,E)-1-ferrocenyl-4-formyl-1,3-butadiene (16), with nitrofluorenes as CH-acids, results in push-pull compounds of the type Fc-pi-fluorene (8a-g, 12a-e). Similar reaction with bifunctional ferrocene and ruthenocene dicarboxaldehydes results, depending on the fluorene structure, in the products of mono- or di-condensation, OHC-Fc-CH=fluorene (11d,e) or fluorene=CH-Fc-CH=fluorene and fluorene=CH-Rc-CH=fluorene (9a-c, 10a-c). Intramolecular charge transfer (ICT) in compounds 8 results in lowering the rotation barrier around the CH=fluorene double bond and easy E-Z isomerisation in solution. Cyclic voltammetry (CV) experiments show a reversible single-electron oxidation of Fc-CH=fluorenes (8) yielding the cation and two reversible single-electron reduction waves yielding the radical anion and dianion (for 8a-e) which merge into one two-electron reduction wave for 8f-h. ICT was also manifested in the electron absorption spectra of 8-12, and energies of ICT (as well as reduction potentials in CV) were found to display excellent correlation (r?0.99) with Hammett-type substituents constants (sigmap-) in the fluorene moiety. Compounds 8-12 show solvatochromism [8a: lambdaICT=604.5 nm (acetonitrile), 622.5 nm (1,2-dichloroethane)], with, however, no quantitative regularities for 10 solvents of different polarity. Bathochromic shifts of 40-83 nm and an increase in the intensity of ICT bands were observed with lengthening of the pi-bridge between ferrocene and fluorene moieties (8?12) whereas substitution of the ferrocene unit in 9 by the ruthenocene unit (10) resulted to a hypsochromic shift of ca. 100 nm due to decreasing donor ability of the latter metallocene fragment. Acceptor 8a was found to sensitise the photoconductivity of poly-N-(2,3-epoxypropyl)carbazole showing moderate holographic response of the materials. Molecular and crystal structures for ferrocene derivatives 8a, 8g, and 11d were determined by single-crystal X-ray diffraction. Tetranitro derivative 8a shows substantial distortion, caused by steric repulsion between the nitro groups in positions 4 and 5, which precludes the formation of stacks, and pairs of fluorene moieties contact face-to-face (interplanar distance 3.8 A?). In di- and trinitro derivatives 8g and 11d the fluorene moieties are more planar and their crystal packing motifs are similar: fluorene moieties form good stacks, parallel to the x-axis in 8g and the y-axis in 11d, with interplanar separations between fluorene moieties of 3.35-3.36 A? for 8g and alternate separations of 3.52 and 3.55 A? for 11d.

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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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The two related compounds (R = OEt or ferrocenyl C5H4FeC5H5, Fc), have been prepared, the first by insertion of ethyl ethynyl ether (CH<*>COEt) into and the second by oxidative addition of ethenylferrocene (CH2 = CHFc) to respectively.Spectroscopically both compounds are similar to known related compounds with alkyl- or aryl-substituted vinyl ligands.A single-crystal X-ray structural study of each was made in an attempt to detect any structural effects of ?-donation by the substituents at the vinylgroup, such as was observed for .The latter compound has been shown to have a zwitterionic structure with an alkylidene bridge between two osmium atoms rather than the normal mu,eta2-vinyl mode of bonding.The two compounds studied here have essentially normal mu,eta2-vinyl bridges, but with some distortion towards the alkylidene bonding type, more pronounced for R = OEt.

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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

As a society publisher, everything we do is to support the scientific community – so you can trust us to always act in your best interests, HPLC of Formula: C12H10FeO2, and get your work the international recognition that it deserves. Introducing a new discovery about 1271-48-3, Name is 1,1′-Ferrocenedicarboxaldehyde

A selection of metallocene inclusion compounds with channel structured MOFs (MOF = Metal-Organic Framework) were obtained via solvent-fee adsorption of the metallocenes from the gas-phase. The adsorbate structures ferrocene 0.5@MIL-53(Al) (MIL-53(Al) = [Al(OH)(bdc)]n with bdc = 1,4-terephthalate), ferrocene0.25@MIL-47(V) (MIL-47(V) = [V(O)(bdc)]n), cobaltocene0.25@MIL-53(Al), cobaltocene0.5@MIL-47(V), 1-formylferrocene0.33@MIL-53(Al) , 1,1?dimethylferrocene0.33@MIL-53(Al), 1,1?- diformylferrocene0.5@MIL-53(Al) were determined from powder X-ray diffraction data and were analyzed concerning the packing and orientation of the guest species. The packing of the ferrocene guest molecules inside MIL-47(V) is significantly different compared to MIL-53(Al) due to the lower breathing effect and weaker hydrogen bonds between the guest molecules and the host network in the case of MIL-47(V). The orientation of the metallocene molecule is also influenced by the substituents (CH3 and CHO) at the cyclopentadienyl ring and the interaction with the bridging OH group of MIL-53(Al). The inclusion of redox active cobaltocene into MIL-47(V) leads to the formation of a charge transfer compound with a negatively charged framework. The reduction of the vanadium centers is stoichiometric. The resulting material is a mixed valence compound with a V3+/V4+ ratio of 1:1. The new compounds were characterized via thermal gravimetric analysis, infrared spectroscopy, solid state NMR, and differential pulse voltammetry. Both systems are 1D-channel pore structures. The metallocene adsorbate induced breathing effect of MIL-53(Al) is more pronounced compared to MIL-47(V), this can be explained by the different bridging groups between the MO6 clusters. The Royal Society of Chemistry 2010.

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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 ruthenium(II) ferrocenyl heterocyclic thiosemicarbazone complexes of the type [RuCl(CO)(EPh3)]2L (where E = P/As; L = binucleating monobasic tridendate thiosemicarbazone ligand) have been investigated. Strutural features were determined by analytical and spectral techniques. Binding of these complexes with CTDNA by absorption spectral study indicates that the ruthenium(II) complexes form adducts with DNA and has intrinsic binding constant in the range of 3.3 × 104 – 1.2 × 105 M?1. The complexes exhibit a remarkable DNA cleavage activity with CT-DNA in the presence of hydrogen oxide and the cleavage activity depends on dosage.

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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