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The syntheses, structures, electrochemical properties of the series of ferrocenylalkyl azoles, FcAlkAz, as well as the antitumor activity of ferrocenylmethyl benzimidazole (8) have been studied. Above mentioned compounds were investigated by the method of cyclic voltametry. All of them exhibited a reversible one-electron oxidation-reduction wave owing to the ferrocene-ferrocenium redox couple with a positive shift (0.50-0.65 V) compared with that of ferrocene (0.42 V). The X-ray determination of molecular structures of 1-(ferrocenylmethyl)imidazole (4), 1-(ferrocenylbenzyl)imidazole (7) and 1-(ferrocenylmethyl)bezimidazole (8) was carried out. Compound 4 with imidazolyl substituent was found to be present in N-protonated form. Antitumor activity of 1-(ferrocenylmethyl)benzimidazole (8) against some solid tumor models such as adenocarcinoma 755 (Ca755), melanoma B16 (B16) and Lewis lung carcinoma was studied. The antitumor activity of compound 8 was compared with cisplatin effectiveness against some experimental tumor systems.

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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 planar bidirectional valveless peristaltic micropump for controlling biological sample fluids was designed with a very simple structure and fabricated employing MEMS technologies including deep reactive ion etching (DRIE) process in silicon, chemomechanical polishing (CMP), and silicon-glass anodic bonding. The proposed micropump was able to control the flow bidirectionally at the rate of ?12mul/min (20nl/stroke) for water and ?60mul/min (100nl/stroke) for air with an operation frequency of 10Hz at a voltage of 120Vpp. Actuation modeling of the PZT-glass actuator was performed using the CoventorWare, and the simulation results agreed well with the experimental measurements. In addition, the fabricated micropump was used in the setup for flow-type analysis and was found adequate in the electrochemical immunosensing by biocatalyzed precipitation.

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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 virus-based nanostructuring strategy is proposed for improving the catalytic performance of integrated redox enzyme electrodes. Random arrays of adsorbed filamentous fd bacteriophage particles, used as scaffolds, are assembled onto gold electrode surfaces. The viral particles are endowed with functionally coupled enzymatic and redox properties, by the sequential immunological assembly of quinoprotein glucose dehydrogenase conjugated antibodies and ferrocene PEGylated antibodies on their protein shell. The resulting virus-scaffolded enzyme/redox mediator integrated system displays a large enhancement in the catalytic current generated per enzyme molecule (i.e., in enzymatic turnover) as compared with nonscaffolded integrated glucose oxidizing enzyme electrodes. The mechanism underlying the observed scaffolding-induced catalytic enhancement is deciphered. Confinement of the mediator on the viral scaffold enables fast electron transport rate and shifts the enzyme behavior into its most effective cooperative kinetic mode.

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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 the present work, the application of the amine electrooxidation method to achieve the grafting of amino beta-cyclodextrins (CD-amines) on glassy carbon electrodes (GCE) in aqueous media has been investigated. The results indicate that the electrooxidation procedure of CD-amines on GCE effects their covalent immobilization without the need of additional linkers or intermediates. Cyclic voltammograms of ferricyanide proved that the immobilized CDs cover at a large extent the GCE surface. This immobilization is due to real grafting and not the result of a weak physisorption interaction. Indeed, the presence of contributions characteristic of amide groups and the absence of peaks typical of amine groups in the XPS N 1s spectra of the modified GCE, support the evidence of the covalent bonding of the CDs to the glassy carbon surface through amide bond formation. Electrochemical experiments demonstrated that ferrocenemethanol and bentazon can be encapsulated within the cavity of the CDs immobilized on GCEs via the formation of inclusion compounds. Overall, the results of the present work show that this simple amine-electrooxidation strategy is suitable to immobilize CDs on glassy carbon surfaces while maintaining their inclusion abilities and, therefore, open the door to design cheap and simple electrochemical sensors for environmental applications.

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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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Ruthenium(ii) carbonyl complexes with phosphine-functionalized PNS type thiosemicarbazone ligands [RuCl(CO)(EPh3)(L)] (1-6) (E = P or As, L = 2-(2-(diphenylphosphino)benzylidene) thiosemicarbazone (PNS-H), 2-(2-(diphenylphosphino)benzylidene)-N-methylthiosemicarbazone (PNS-Me), 2-(2-(diphenylphosphino)benzylidene)-N-phenylthiosemicarbazone (PNS-Ph)) have been synthesized and characterized by elemental analysis and spectroscopy (IR, UV-Vis, 1H, 13C, 31P-NMR) as well as ESI mass spectrometry. The molecular structures of complexes 1, 2 and 6 were identified by means of single-crystal X-ray diffraction analysis. The analysis revealed that all the complexes possess a distorted octahedral geometry with the ligand coordinating in a uni-negative tridentate PNS fashion. All the ruthenium complexes (1-6) were tested as catalyst for N-alkylation of heteroaromatic amines with alcohols. Notably, complex 2 was found to be a very efficient and versatile catalyst towards N-alkylation of a wide range of heterocyclic amines with alcohols. Complex 2 can also catalyze the direct amination of 2-nitropyridine with benzyl alcohol to the corresponding secondary amine. Furthermore, a preliminary examination of performance for N,N-dialkylation of diamine showed promising results, giving good conversion and high selectivity. In addition, N-alkylation of ortho-substituted anilines (-NH2, -OH and -SH) led to the one-pot synthesis of 2-aryl substituted benzimidazoles, benzoxazoles and benzothiazoles, also revealing the catalytic activity of complex 2. This journal is the Partner Organisations 2014.

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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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This work reports the reduction of a large variety of aldehydes and ketones with the system PhSiH3/[CpRu(PPh3)2Cl] in good to excellent yields and high chemoselectivity. The catalyst [CpRu(PPh3)2Cl] can be used in at least 12 catalytic cycles with excellent catalytic activity and several substrates were reduced under solvent free conditions.

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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 water-soluble dinuclear Cp?Ir complex bearing 4,4?,6,6?-tetrahydroxy-2,2?-bipyrimidine as a bridging ligand was found to be a highly effective catalyst for the alpha-alkylation of ketones with alcohols in pure water. In the presence of catalyst (0.5 mol%), a series of desirable products were obtained with high reaction economy under environmentally benign conditions. The importance of the hydroxy group in the ligand for catalytic hydrogen transfer was confirmed by mechanism experiments. Furthermore, the application of this catalytic system for the synthesis of a biologically active molecule donepezil in pure water has been accomplished. Notably, this research would facilitate the progress of C-C bond-forming reactions in water catalyzed by water-soluble metal-ligand bifunctional catalysts.

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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 complex Fc(CH=CH)2C?C-TMS (Fc = ferrocenyl) was obtained from Wittig olefination of FcCH2PPh3Br with TMS-C?CCH=CHCHO in THF. The conjugated monometallic diene can be desilylated to give Fc(CH=CH)2C?CH, which reacted with RuHCl(CO)(PPh3)3 to produce Fc(CH=CH)3RuCl(CO) (PPh3)2. Treatment of the latter complex with PMe 3, 4-phenylpyridine (PhPy), 2,6-(Ph2PCH2) 2C5H3N (PMP), and KTp (Tp = hydridotris(pyrazolyl)borate) gave Fc(CH=CH)3RuCl(CO)(PMe 3)3, Fc(CH=CH)3RuCl(CO)(PhPy)(PPh 3)2, Fc(CH= CH)3RuCl(CO)(PMP), and Fc(CH=CH)3RuTp(CO)(PPh3), respectively. The structures of Fc(CH=CH)2C?CH and Fc(CH=CH)3RuCl(CO)(PMe 3)3 have been confirmed by X-ray diffraction.

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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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Inclusion behavior of negatively charged host molecules, thiacalix[4]arene-p-tetrasulfonate (TC4AS) and [6]arene-p-hexasulfonate (TC6AS), toward (ferrocenylmethyl)trimethylammonium (FcCH2NMe3+), hydroxymethylferrocene (FcCH2OH), ferrocenecarboxylic acid (FcCOOH), and 1,1?-ferrocenedicarboxylic acid (Fc(COOH)2) was studied in aqueous solutions (pH 7.0) with cyclic voltammetry. Upon increasing the concentration of TC4AS to 4-fold of each guest, the anodic peak current density (jp,a) decreased, suggesting inclusion of the ferrocenyl guests in TC4AS. Also oxidation half-wave potential (E1/2) of FcCH2NMe3+, FcCH2OH, and FcCOOH was shifted to cathodic direction, showing preferential inclusion of the oxidative state. Inclusion of neutral guests such as FcCH2OH and Fc+COO- implies that hydrophobic interaction between TC4AS and the guests is the chief driving force for formation of host-guest assembly. The decrease of E1/2 for each guest was in the order: FcCH2NMe3+ > FcCH2OH > FcCOOH, suggesting that electrostatic interaction controls the preference toward oxidative form of the guest. Dicarboxylic Fc(COOH)2 showed decrease of jp,a but increase of E1/2 upon inclusion, suggesting TC4AS preferred reduced form Fc(COOH)2 to oxidized form Fc+(COO-)2. TC6AS behaved similarly to TC4AS but with larger decrease in of E1/2 and jp,a. The larger shift of E1/2 for inclusion of FcCOOH, the oxidative form of which is also neutral (Fc+COO-), than that attained with TC4AS endorses main role of hydrophobic interaction between TCnAS (n = 4, 6) and ferrocenyl guest molecules. Having the most preferential electrostatic interaction, kinetically stable complex was formed between TC6AS and FcCH2NMe3+.

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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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Atomically thin graphene electrodes enable the modulation of interfacial reactivity by means of underlying substrate effects. Here we show that plasmonic excitation of microscopic arrays composed of 50 nm Au nanoparticles situated underneath a graphene interface results in localized enhancements on the electrochemical readout. We used scanning electrochemical microscopy (SECM) in the feedback and H2O2 collection modes to identify the role of the generated plasmons on the electrochemical response. Using electrochemical imaging, supported by finite-element method simulations, we confirmed that a temperature rise of up to ?30 K was responsible for current enhancements observed for mass transfer- limited reactions. On single-layer graphene (SLG) we observed a shift in the onset of H2O2 generation which we traced back to photothermal induced kinetic changes, raising ko? from 1.1 × 10-8 m/s to 2.2 × 10-7 m/s. Thicker 10-layer graphene electrodes displayed only a small kinetic difference with respect to SLG, suggesting that photothermal processes, in contrast to hot carriers, are the main contributor to the observed changes in interfacial reactivity upon illumination. SECM is demonstrated to be a powerful technique for elucidating thermal contributions to reactive enhancements, and presents a convenient platform for studying sublayer and temperature-dependent phenomena over individual sites on electrodes.

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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