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Covalent immobilization of glucose oxidase (GOx) on oxidized silicon (SiO2) surfaces is detailed in view of producing interfaces with a simple, controlled and reproducible procedure that could be used in bioanalytical applications as those based on SECM detection. The procedure is based first on the formation of an amino-terminated propyl layer on a SiO2 substrate followed by addition and cross-linking of a polyoxyethylene bis(diglycidylether) and GOx mixture. The epoxide groups of the cross-linker react with amino groups allowing both the cross-linking with the enzyme (reaction with the free amino groups of the lysine residues) and the covalent attachment of the enzyme layer on the amino groups bound to the surface. SECM in feedback mode analysis provides a characterization of the modified surface and the measurement of the enzymatic activity depending on the concentrations of glucose and mediator. Kinetics analysis indicates that GOx maintains a large enzymatic activity and that the active enzymes remain reachable after their incorporation in the layer with the advantages of a robust immobilization.

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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 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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The present invention provides two ferrocene pyridine derivative and its synthesis method, wherein ferrocene single arm pyridine derivatives FeL1 and ferrocene double-arm pyridine derivatives FeL2 can be used for Cu2 + And Cr3 + Detection. (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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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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Isonicotinyl and pyrazinyl ferrocenyl-derived complexes were prepared using various hydrazides and ferrocenyl aldehydes. Three heterobimetallic complexes were also synthesized from the Schiff base-derived isonicotinyl ferrocene complex using various platinum group metal dimers based on ruthenium, rhodium and iridium. All complexes were evaluated in vitro for antimycobacterial and antiparasitic activity. Against Mycobacterium tuberculosis H37Rv, the platinum group metal complexes showed glycerol-dependent antimycobacterial activity. The antiplasmodial activities against the NF54 chloroquine-sensitive strain of Plasmodium falciparum of some compounds were moderate, while some complexes also showed promising activity against Trichomonas vaginalis. Incorporation of the ferrocenyl-salicylaldimine moiety resulted in enhanced antimicrobial activity compared to the non-ferrocenyl compound in some cases. The bimetallic iridium-ferrocene isonicotinyl complex exhibited superior antitrichomonal activity relative to its organic counterpart, isoniazid. Furthermore, all these compounds, when screened on several normal flora bacteria of humans, showed no effect on the microbiome, emphasizing the selection of these compounds for these pathogens. The promising antimicrobial activities of the complexes thus supports incorporation of ferrocene as part of existing antimicrobial therapies in order to alter their biological activities favorably.

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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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Protonation of p-xylylaminomethylferrocene (1) and n- hexylaminomethylferrocene (2) by HCl and NH4PF6 forms the ferrocenylmethyl(alkyl)ammonium salt. Inclusion of the compounds by dibenzo[24]crown-8 (DB24C8) produces [2]pseudorotaxanes, [(DB24C8)(1-H)] +(PF6) and [(DB24C8)(2-H)]+(PF6), respectively. X-ray diffraction of the former product indicates an interlocked structure composed of the axis and the macrocyclic molecule. Intermolecular N-H…O and C-H…O interactions and stacking of the aromatic planes are observed. [(DB24C8)(1-H)]+(PF6), in the solid state, is characterized by IR spectroscopy and elemental analyses. A similar reaction of 1,1?-bis(p-xylylaminomethyl)ferrocene (3) forms a mixture of [2] and [3]pseudorotaxanes, [(DB24C8)(3-H2)]2+(PF 6)2 and [(DB24C8)2(3-H2)] 2+(PF6)2. The latter product having two DB24C8 molecules is isolated and characterized by X-ray crystallography. Formation of these pseudorotaxanes in a CD3CN solution is evidenced by 1H NMR and mass spectrometry. Electrochemical oxidation of 1-3 at 0.4 V (vs Ag+/Ag) in the presence of TEMPOH (1-hydroxy-2,2,6,6- tetramethylpiperidine) and DB24C8 affords the corresponding pseudorotaxanes. The ESR spectrum of the reaction mixture indicates the formation of a TEMPO radical in high yield. Details of the conversion of the dialkylamino group of the ligand to the dialkylammonium group are investigated by using a flow electrolysis method linked to spectroscopic measurements. The proposed mechanism for the reaction involves the ferrocenium species, formed by initial oxidation, which undergoes electron transfer from nitrogen to the Fe(III) center, producing a cation radical at the nitrogen. Transfer of hydrogen from TEMPOH to the cation radical and inclusion of the resulting dialkylammonium species by DB24C8 yields the pseudorotaxanes.

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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