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Electrochemical investigation of the influence of thin SiOx films deposited on gold on charge transfer characteristics

The paper reports on the investigation of the electrochemical behavior of a thin gold film electrode coated with silicon dioxide (SiOx) layers of increasing thickness. Stable thin films of amorphous silica (SiOx) were deposited on glass slides coated with a 5 nm adhesion layer of titanium and 50 nm of gold, using plasma-enhanced chemical vapor deposition (PECVD) technique. Scanning electrochemical microscopy (SECM) and electrochemical impedance spectroscopy (EIS) were used to investigate the electrochemical behavior of the interfaces. In the case of SECM, the influence of the SiOx thicknesses on the electron transfer kinetics of three redox mediators was investigated. Normalized current-distance curves (approach curves) were fitted to the theoretical model in order to find the effective heterogeneous first order rate constant (keff) at the sample. EIS was in addition used to confirm the diffusion barrier character of the SiOx interlayer.

Electrochemical investigation of the influence of thin SiOx films deposited on gold on charge transfer characteristics

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Reference£º
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

 

Awesome Chemistry Experiments For Ferrocenemethanol

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Self-assembled monolayers of 1-alkenes on oxidized platinum surfaces as platforms for immobilized enzymes for biosensing

Alkene-based self-assembled monolayers grafted on oxidized Pt surfaces were used as a scaffold to covalently immobilize oxidase enzymes, with the aim to develop an amperometric biosensor platform. NH2-terminated organic layers were functionalized with either aldehyde (CHO) or N-hydroxysuccinimide (NHS) ester-derived groups, to provide anchoring points for enzyme immobilization. The functionalized Pt surfaces were characterized by X-ray photoelectron spectroscopy (XPS), static water contact angle (CA), infrared reflection absorption spectroscopy (IRRAS) and atomic force microscopy (AFM). Glucose oxidase (GOX) was covalently attached to the functionalized Pt electrodes, either with or without additional glutaraldehyde crosslinking. The responses of the acquired sensors to glucose concentrations ranging from 0.5 to 100 mM were monitored by chronoamperometry. Furthermore, lactate oxidase (LOX) and human hydroxyacid oxidase (HAOX) were successfully immobilized onto the PtOx surface platform. The performance of the resulting lactate sensors was investigated for lactate concentrations ranging from 0.05 to 20 mM. The successful attachment of active enzymes (GOX, LOX and HAOX) on Pt electrodes demonstrates that covalently functionalized PtOx surfaces provide a universal platform for the development of oxidase enzyme-based sensors.

Self-assembled monolayers of 1-alkenes on oxidized platinum surfaces as platforms for immobilized enzymes for biosensing

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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

 

A new application about Vinylferrocene

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Oxidative ring-opening of ferrocenylcyclopropylamines to N-ferrocenylmethyl beta-hydroxyamides

The in situ reduction of ferrocenyl cyclopropylimines to the corresponding amines triggers a facile oxidative ring-opening to yield the formal four-electron oxidation products: N-ferrocenylmethyl beta-hydroxyamides. This process is believed to proceed via generation of a ferrocinium ion in the presence of air, leading to facile formation of a distonic radical cation that is ultimately trapped by oxygen.

Oxidative ring-opening of ferrocenylcyclopropylamines to N-ferrocenylmethyl beta-hydroxyamides

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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

 

Extracurricular laboratory:new discovery of 1,1′-Ferrocenedicarboxaldehyde

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From ferrocenecarbonitriles to ferrocenylimines: Synthesis, structure, and reaction chemistry

From the reaction of [PtCl2(N-CMe)2] with FcC-N (1) (Fc = Fe(eta5-C5H4)(eta5-C 5H5)) complex [PtCl2(FcC-N)(N-CMe)] (2) was obtained, which on subsequent treatment with 1 gave trans-[PtCl 2(N-CFc)2] (trans-3). The latter complex and the appropriate cis isomer (cis-3) were also accessible when [PtCl2] or [PtCl2(N-CMe)2] is reacted with a 2.6-fold excess of 1. Appropriate treatment of [PtCl2(N-CMe)2] with two equivalents of 1-acetyl-1′-cyanoferrocene (4) produced trans-[PtCl 2(Fe(eta5-C5H4CN)( eta5-C5H4C(O)Me))2] (trans-5). Coordination polymer [PtCl2(Fe(eta5-C5H 4CN)2)]n (7) was obtained by combining [PtCl2(N-CPh)2] with [Fe(eta5-C 5H4CN)2] (6). However, when 7 was reacted with PPh3 for deaggregation, [PtCl2(PPh3) 2] was formed. Addition of FcC-CLi (8-Li) to trans-3 gave pentametallic trans-[Pt(C-CFc)2(NH-CnBuFc)2] (10) via trans-[Pt(C-CFc)2(N-CFc)2] (9). When trans-3 is reacted with two equivalents of nBuLi in the absence of FcC-CH (8), trans-[PtCl2(NH-CnBuFc)2] (11) was obtained, which decomposed to FcC(-NH)nBu (12), giving FcC(O)nBu (13). Electrochemical measurements of the nitrile platinum complexes show no redox separation for the oxidation of the Fc and Fe(eta5-C 5H4)2 moieties. Compared with the noncoordinated ferrocenecarbonitriles, a shift to higher potentials is observed. In contrast, for 10 four well-separated redox events (-185, -90, +460, +545 mV) were found, which could be assigned to the oxidation of the Fc units. UV-vis/NIR spectroscopy allowed to determine an IVCT absorption (numax = 6495 cm-1, epsilonmax = 270 L¡¤mol-1¡¤cm-1, Deltanu1/2 = 2270 cm-1) for 10+, classifying this mixed-valent species as a weakly coupled class II system according to Robin and Day, while no IVCT transitions were observed for 10n+ (n = 2, 3). The structures of trans-3, cis-3, 10, and FcC(O)tBu (15) in the solid state were determined by single-crystal X-ray diffraction. Although the bond distances and angles of trans-3 and cis-3 are similar, the cis isomer crystallizes as a dimer possessing Pt-Pt distances within the sum of the van der Waals radii.

From ferrocenecarbonitriles to ferrocenylimines: Synthesis, structure, and reaction chemistry

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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

 

Top Picks: new discover of 1273-94-5

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Formation of functionalized [3]ferrocenophane derivatives by an enamine condensation reaction

Treatment of 1,1?-diacetylferrocene (10) with excess piperidine and a stoichiometric amount of TiCl4 in pentane leads to CC-coupling of the two functional groups at the ferrocene framework. This enamine condensation reaction leads to the formation of the 1,3-connected dienamine-bridged [3]ferrocenophane system 13a. Complex 13a was characterised by X-ray crystal structure analysis. The analogous TiCl4-mediated coupling and condensation reactions of 10 with morpholine, pyrrolidine or methyl-isopropylamine yield the corresponding substituted [3]ferrocenophane systems 13b-d.

Formation of functionalized [3]ferrocenophane derivatives by an enamine condensation reaction

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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

 

Top Picks: new discover of 1,1′-Diacetylferrocene

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1,1?-Bis(pyrazol-3-yl)ferrocene: A Clip Ligand That Forms Supramolecular Aggregates and Prismatic Hexanuclear Coinage Metal Complexes

Two ferrocene derivatives with appended pyrazole substituents, namely, 1,1?-bis(5-methyl-1H-pyrazol-3-yl)ferrocene (H2LH) and 1,1?-bis(5-trifluoromethyl-1H-pyrazol-3-yl)ferrocene (H2LF), were synthesized. In solid state they form distinct H-bonded dimers with orthogonal (H2LH, C2 symmetry) or antiparallel (H2LF, C2h symmetry) arrangement of the two ferrocene/pyrazole hybrid molecules. Supramolecular dimerization was also detected in solution at low temperatures, though diffusion-ordered spectroscopy and variable-temperature NMR spectroscopy revealed several dynamic processes. Redox potentials of the ferrocene derivatives are affected by the nature of the pyrazole substituent (Me, CF3). In their deprotonated form [LR]2-, both ferrocene/pyrazole hybrids serve as ligands and form oligonuclear CuI, AgI, and AuI complexes that were identified by matrix-assisted laser desorption ionization mass spectrometry. X-ray crystallography revealed the structures of Cu6L3H and Ag6L3F, which both contain two parallel and eclipsed [M(mu-pz)]3 metallamacrocycles (M = Cu, Ag) linked by three ferrocene units. MI…MI distances between the two triangular M3N6 decks are shorter in Ag6L3F (3.28-3.30 vs 3.44-3.51 A in the case of Cu6L3H), indicating substantial intramolecular closed-shell Ag(d10)-Ag(d10) interactions. However, Cu6L3H features close intermolecular Cu…Cu contacts as short as 3.37 A. Moessbauer data for both the ligands and complexes were collected, and electrochemical properties were measured; preliminary luminescence data are reported. (Figure Presented).

1,1?-Bis(pyrazol-3-yl)ferrocene: A Clip Ligand That Forms Supramolecular Aggregates and Prismatic Hexanuclear Coinage Metal Complexes

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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

 

Archives for Chemistry Experiments of 1271-48-3

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Highly efficient iridium catalysts based on C2-symmetric ferrocenyl phosphinite ligands for asymmetric transfer hydrogenations of aromatic ketones

A series of chiral modular C2-symmetric ferrocenyl phosphinite ligands have been synthesized in good yields by using 1,1?-ferrocenedicarboxyaldehyde and various amino alcohols as starting materials, and applied in the iridium(III)-catalyzed asymmetric transfer hydrogenations of aromatic ketones to give the corresponding secondary alcohols with good enantioselectivities and reactivities using 2-propanol as the hydrogen source (up to 98% ee and 99% conversion). The substituents on the backbone of the ligands were found to have a significant effect on both the activity and enantiomeric excess. The structures of these complexes have been clarified by a combination of multinuclear NMR spectroscopy, IR spectroscopy, and elemental analysis.

Highly efficient iridium catalysts based on C2-symmetric ferrocenyl phosphinite ligands for asymmetric transfer hydrogenations of aromatic ketones

Sometimes chemists are able to propose two or more mechanisms that are consistent with the available data. Recommanded Product: 1,1′-Ferrocenedicarboxaldehyde, If a proposed mechanism predicts the wrong experimental rate law, however, the mechanism must be incorrect.Welcome to check out more blogs about 1271-48-3, in my other articles.

Reference£º
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

 

Archives for Chemistry Experiments of 1273-86-5

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Electron transfer kinetics of cytochrome c immobilized on a phenolic terminated thiol self assembled monolayer determined by scanning electrochemical microscopy

In the present manuscript, the electrochemical behavior of cytochrome c (cyt-c) immobilized onto a phenolic terminated self assembled monolayer (SAM) on a gold electrode is investigated using cyclic voltammetry (CV) and scanning electrochemical microscopy (SECM). The tunneling electron transfer (ET) rate constant between the immobilized protein and the underlying electrode surface, and also the bimolecular ET rate constant between the immobilized protein and a probe has been obtained using approach curves that were obtained by SECM. The approach curves were recorded at different substrate overpotentials in the presence of various concentrations of ferrocyanide as a probe and various surface concentrations of cyt-c; then the standard tunneling ET and bimolecular rate constants are obtained as 3.4 ¡À 0.3 s-1 and (2.0 ¡À 0.5) ¡Á 107 cm3 mol-1 s-1, respectively.

Electron transfer kinetics of cytochrome c immobilized on a phenolic terminated thiol self assembled monolayer determined by scanning electrochemical microscopy

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Reference£º
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

 

New explortion of 1273-86-5

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Counting the number of enzymes immobilized onto a nanoparticle-coated electrode

To immobilize enzymes at the surface of a nanoparticle-based electrochemical sensor is a common method to construct biosensors for non-electroactive analytes. Studying the interactions between the enzymes and nanoparticle support is of great importance in optimizing the conditions for biosensor design. This can be achieved by using a combination of analytical methods to carefully characterize the enzyme nanoparticle coating at the sensor surface while studying the optimal conditions for enzyme immobilization. From this analytical approach, it was found that controlling the enzyme coverage to a monolayer was a key factor to significantly improve the temporal resolution of biosensors. However, these characterization methods involve both tedious methodologies and working with toxic cyanide solutions. Here we introduce a new analytical method that allows direct quantification of the number of immobilized enzymes (glucose oxidase) at the surface of a gold nanoparticle coated glassy carbon electrode. This was achieved by exploiting an electrochemical stripping method for the direct quantification of the density and size of gold nanoparticles coating the electrode surface and combining this information with quantification of fluorophore-labeled enzymes bound to the sensor surface after stripping off their nanoparticle support. This method is both significantly much faster compared to previously reported methods and with the advantage that this method presented is non-toxic. [Figure not available: see fulltext.].

Counting the number of enzymes immobilized onto a nanoparticle-coated electrode

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Reference£º
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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Synthesis and characterisation of ferrocenyl-phosphonic and -arsonic acids

The ferrocene-derived acids FcCH2CH2E(O)(OH)2 [4, E=P; 10, E=As; Fc=Fe(eta5-C5H5)(eta5-C5H4)] have been synthesized by the reaction of FcCH2CH2Br with either P(OEt)3 followed by hydrolysis, or with sodium arsenite followed by acidification. Reaction of FcCH2OH with (EtO)2P(O)Na gave FcP(O)(OEt)(OH), which was converted to FcCH2P(O)(OH)2 (3) by silyl ester hydrolysis using Me3SiBr-Et3N followed by aqueous work-up. Similarly, the known phosphonic acid FcP(O)(OH)2 and the new derivatives 1,1?-Fc?[P(O)(OH)2]2 [Fc?=Fe(eta5-C5H4)2] and 1,1?-Fc?[CH2P(O)(OH)2]2 (7) have been synthesized via their corresponding esters. X-ray crystal structure determinations have been carried out on 3 and 7, and the hydrogen-bonding networks discussed. Electrospray mass spectrometry has been employed in the characterization of the various acids. Phosphonic acids give the expected [M-H]- ions and their fragmentation at elevated cone voltages has been found to be dependent on the acid. FcP(O)(OH)2 fragments to [C5H4PO2H]-, but in contrast Fc(CH2)nP(O)(OH)2 (n=1, 2) give Fe{eta5-C5H4(CH2)nP(O)O2]- ions, which are proposed to have an intramolecular interaction between the Fe atom and the phosphonate group. In contrast, arsonic acid (10), together with PhAs(O)(OH)2 for comparison, undergo facile alkylation (in methanol or ethanol solvent), and at elevated cone voltages (e.g. 60 V) undergo carbon-arsenic bond cleavage giving [CpFeAs(O)(OR)O]- (R=H, Me, Et) and ultimately [AsO2]- ions.

Synthesis and characterisation of ferrocenyl-phosphonic and -arsonic acids

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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