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Test structure and measurement system for characterising the electrochemical performance of nanoelectrode structures

This paper presents a complete test structure and characterisation system for the evaluation of nanoelectrode technology. It integrates microfabricated nanoelectrodes for electrochemical measurements, 3D printing and surface tensionconfined microfluidics. This system exploits the inherent analytical advantages of nanoelectrodes that enables their operation with small volume samples, which has potential applications for onwafer measurements.

Test structure and measurement system for characterising the electrochemical performance of nanoelectrode structures

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Effect of tensile stress on the passivity breakdown and repassivation of AISI 304 stainless steel: A scanning Kelvin probe and scanning electrochemical microscopy study

The interplay between mechanical stresses and electrochemical reactions may lead to stress corrosion cracking or hydrogen embrittlement for many materials. In this work, the effect of the tensile stress on the electrochemical properties of AISI 304 stainless steel was studied using scanning Kelvin probe (SKP) in air and scanning electrochemical microscopy (SECM) in an aqueous 0.5 M Na2SO4 electrolyte. The measurements were performed under load- and load-free conditions. No influence of the elastic stress on the electrochemical potential of the steel was found. In contrast, the plastic strain induces dislocations and dislocation pile-ups, which emerge to the surface. The formation of new active surfaces is accompanied by an increase in the roughness and a 150?200 mV decrease in the steel potential. After activation, the potential increased due to passivation of the emerging surfaces by a newly grown oxide film, which took place under both the load and load-free conditions and followed a time dependence of ? = A log t + B. Formation and then passivation of the new surfaces increased and then decreased the reduction current of the mediator in the SECM measurements. The effect of residual stress stored in the steel due to the development of dislocations on the reactivity of the re-passivated surface was investigated.

Effect of tensile stress on the passivity breakdown and repassivation of AISI 304 stainless steel: A scanning Kelvin probe and scanning electrochemical microscopy study

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
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A method of cyclic amine alpha – catalysed synthesis (by machine translation)

The invention discloses a method for synthesizing alpha – cyclic amine method, which comprises the following steps: in the reaction container, joins the alkone, the compound is mellow, iridium complex catalyst, tertiary amyl alcohol base and a solvent, the reaction mixture in the air reflux reaction, after the reaction to cool to room temperature, the solvent is removed by rotary evaporation, then through the column separation, to obtain the target compound. The invention uses an N? C? N ligand complex three tooth iridium, reaction only need to add 0.2 equivalent of carbonate, in the air, reaction only needs 10 – 12 hours, demonstrating the obvious advantages; therefore, the reaction in accordance with the requirement of green chemistry, has broad prospects of development. (by machine translation)

A method of cyclic amine alpha – catalysed synthesis (by machine translation)

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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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Supramolecular Interactions between beta-Cyclodextrin and the Nucleobase Derivatives of Ferrocene

Novel conjugates of ferrocene with uracil, 5-fluorouracil, tegafur, or acyclovir are reported. Their synthesis involved (i) the azide-alkyne 1,3-dipolar cycloaddition or (ii) the formation of the ester linkage. For the first time, we present an in-depth insight into the supramolecular interactions between beta-cyclodextrin and ferrocene-nucleobase derivatives. Spectroscopic and voltammetric analyses performed within this work suggested that the ferrocene or adamantane unit of the conjugates interacted with the beta-cyclodextrin’s inner cavity. The methods applied for the supramolecular studies included 1H-1H ROESY NMR, 1H NMR titration, Fourier-transform infrared spectroscopy, cyclic voltammetry, fluorescence spectra titration, and 1H DOSY NMR. 1H DOSY NMR was also employed to evaluate the apparent binding constants for all the complexes. The ferrocene-acyclovir conjugate Fc-5 featured the highest apparent binding constant value among all the complexes tested.

Supramolecular Interactions between beta-Cyclodextrin and the Nucleobase Derivatives of Ferrocene

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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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Enhanced light harvesting efficiencies of bis(ferrocenylmethyl)-based sulfur rich sensitizers used in dye sensitized TiO2 solar cells

In this work, the photosensitizing properties of ferrocene (Fc)-based compounds FcCH2CS3CH2Fc (1) and FcCH 2SSCH2Fc (2) were investigated and significant enhancement in the light harvesting efficiency was observed compared to those achieved with previously reported compounds from our lab. The compounds were fully characterized by spectroscopy and X-ray crystallography, and their electrochemical properties studied. DSSCs based on these dyes display efficiencies comparable to those of a standard cell based on N719 under similar experimental conditions. These studies demonstrate that ferrocenyl-based sulfur rich compounds with proper orientation of the Fc groups assisted via suitable linkers, together with desired redox properties and visible region electronic absorption features could constitute a new class of photosensitizers targeting light driven reactions.

Enhanced light harvesting efficiencies of bis(ferrocenylmethyl)-based sulfur rich sensitizers used in dye sensitized TiO2 solar cells

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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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Scanning electrochemical microscopy for the fabrication of copper nanowires: Atomic contacts with quantized conductance, and molecular adsorption effect

Scanning electrochemical microscopy, SECM, is proposed as a tool for the fabrication of copper nanowires. In a first step, configuration based on two electrodes, a platinum UME (cathode) and a copper substrate (anode), operating in the SECM configuration was employed. For nanowires generated in water the conductance changes stepwise and varies by integer values of the conductance quantum G0. The formation of atomic contacts is supported by the ohmic behavior of the I-V curve. It depends neither on the UME tip radius nor on the initial gap size between tip and substrate. Atomic contacts generated in aqueous solutions of sodium dodecyl sulfate (SDS) below the critical micellar concentration (CMC) have conductances below 1G0 attributed to molecular adsorption on the contact. In some cases, the nanowires have low conductance, 0.01G0. The corresponding I-V curve shows tunneling rather than ohmic behavior, suggesting that molecular junctions are formed with a few surfactant molecules trapped between the two electrodes. Finally, copper nanowires with quantized conductance have been generated using the SECM operating in a four-electrode setup. Thanks to the reference electrode, this configuration leads to better control of the potential of each working electrode; this setup will make it possible to evaluate the conductance variation and/or modulation upon electrochemical stimuli.

Scanning electrochemical microscopy for the fabrication of copper nanowires: Atomic contacts with quantized conductance, and molecular adsorption effect

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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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Tuneable superbase-catalyzed vinylation of alpha-hydroxyalkylferrocenes with alkynes

Superbase-catalyzed (KOH/DMSO suspension as a catalyst) vinylation of hydroxymethyl- and hydroxyethylferrocenes with terminal and internal alkynes (acetylene, propyne, phenylacetylene, 3-ethynylpyridine, 1-propyn-1-yl-benzene, diphenylacetylene) affords hitherto unknown vinyl ethers of ferrocene in 30-93% yields depending on the alkyne structure and the tuneable ratio of reactants/KOH/DMSO. The vinylation smoothly proceeds under mild conditions (70-90 C, 0.25-13 h). With unsubstituted acetylene the process is readily realized under atmospheric pressure (yield of the corresponding vinyl ethers is 81-90%) though under pressure (initial pressure at room temperature is 10-13 atm, maximum pressure is 13-16 atm at the reaction temperature) the yield is close to quantitative (93%). The synthesized compounds were characterized using 1H and 13C NMR, and IR spectroscopy, as well as X-ray diffraction analysis.

Tuneable superbase-catalyzed vinylation of alpha-hydroxyalkylferrocenes with alkynes

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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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FERROCENYLTRITHIOCARBONATES I. DIRECT ACCESS FROM alpha-FERROCENYLCARBINOLS BY A SNi MECHANISM. ABSOLUTE X-RAY STRUCTURE DETERMINATION OF (R)-FERROCENYLMETHYLMETHANE S-METHYLTRITHIOCARBONATE

Ferrocenyltrithiocarbonates (I) are readily obtained by treating alpha-ferrocenylcarbinols (II) successively with sodium hydride, carbon disulfide and alkyl halide.Formation of I occurs by intramolecular nucleophilic displacement of oxygen by sulfur with retention of configuration.This is supported by the nature of the other products formed and by the X-ray structure determination of an optically active compound I, which was refined to R = 0.038.The title compound of R configuration was obtained from (R)-ferrocenylmethylmethanol.

FERROCENYLTRITHIOCARBONATES I. DIRECT ACCESS FROM alpha-FERROCENYLCARBINOLS BY A SNi MECHANISM. ABSOLUTE X-RAY STRUCTURE DETERMINATION OF (R)-FERROCENYLMETHYLMETHANE S-METHYLTRITHIOCARBONATE

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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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Development of a miniaturized injection cell for online electrochemistry?capillary electrophoresis?mass spectrometry

Abstract: The elucidation of oxidation or reduction pathways is important for the electrochemical characterization of compounds of interest. In this context, hyphenation of electrochemistry and mass spectrometry is frequently applied to identify products of electrochemical reactions. In this contribution, the development of a novel miniaturized injection cell for online electrochemistry?capillary electrophoresis?mass spectrometry (EC?CE?MS) is presented. It is based on disposable thin-film electrodes, which allow for high flexibility and fast replacement of electrode materials. Thus, high costs and time-consuming maintenance procedures can be avoided, which makes this approach interesting for routine applications. The cell was designed to be suitable for investigations in aqueous and particularly non-aqueous solutions making it a universal tool for a broad range of analytical problems. EC?CE?MS measurements of different ferrocene derivatives in non-aqueous solutions were carried out to characterize the cell. Oxidation products of ferrocene and ferrocenemethanol were electrochemically generated and could be separated from the decamethylferricenium cation. The importance of fast CE?MS analysis of instable oxidation products was demonstrated by evaluating the signal of the ferriceniummethanol cation depending on the time gap between electrochemical generation and detection. Graphical abstract: [Figure not available: see fulltext.].

Development of a miniaturized injection cell for online electrochemistry?capillary electrophoresis?mass spectrometry

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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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Ferrocenylmethylphosphonate formation. Synthesis, spectroscopy and molecular structure

Reaction of ferrocenylmethanol, FcCH2OH, with beta-cyano-N,N-diisopropyl chlorophosphoramidite in dichloromethane yields the ferrocenylmethylphosphonate derivative, FcCH2P(O)(N(iPr)2)(OCH2CH2CN), 2a. The crystal and molecular structure of 2a is presented. 31P NMR data suggest that this is formed from FcCH2OP(N(iPr)2)(OCH2CH2CN) via a Michaelis-Arbusov-type rearrangement. Similar behaviour was also observed for 1,2-phenylene chlorophosphite and diethyl chlorophosphite.

Ferrocenylmethylphosphonate formation. Synthesis, spectroscopy and molecular structure

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
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