Archives for Chemistry Experiments of Ferrocenemethanol

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New ferrocene modified retinoic acid with enhanced efficacy against melanoma cells: Via GSH depletion

Malignant melanoma is a highly lethal disease, and advanced stages of melanoma have proven to be resistant to many chemotherapeutic drugs. Cancer stem cells (CSCs) and high levels of intracellular glutathione (GSH) have been proven to play important roles in drug resistance. Retinoic acid (RA) is a promising anticancer agent, which can inhibit proliferation and induce differentiation of CSCs, but its clinical use has been limited by its water insolubility and weak cancer cell killing effect when used alone. Herein, by combining RA and ferrocene, a new type of derivative of retinoic acid (FCRA) was synthesized and then oxidized by FeCl3. The oxidized FCRA (FCRA+) was exploited as a novel anticancer agent. Compared with RA, FCRA+ not only has improved water solubility and stronger anti-cancer effect to melanoma cells through depleting intracellular GSH of the cancer cells, but also can inhibit proliferation and induce differentiation of melanoma CSCs, such as free RA. Therefore, FCRA+ has better application prospects than RA and may replace RA for clinical applications.

New ferrocene modified retinoic acid with enhanced efficacy against melanoma cells: Via GSH depletion

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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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Host-Guest Complexation of Perethylated Pillar[6]arene toward Ferrocene Derivatives Both in Solution and Solid State: Different Binding Modes Induced by Minor Structural Changes of Guests

Herein, novel host-guest properties between perethylated pillar[6]arene and four kinds of ferrocene derivatives were fully investigated. NMR titrations, 2D NOESY NMR spectroscopy, and ESI-MS are used to confirm that they indeed formed stable inclusion complexes. Two precious single-crystal structures were obtained and showed that ferrocene derivatives with different chemical structures exhibit different binding modes with perethylated pillar[6]arenes.

Host-Guest Complexation of Perethylated Pillar[6]arene toward Ferrocene Derivatives Both in Solution and Solid State: Different Binding Modes Induced by Minor Structural Changes of Guests

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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 flow-through column electrolytic cell for supercritical fluid chromatography*

A novel flow-through column electrolytic cell was proposed as a detector to obtain current signals for supercritical fluid chromatography. The electrochemical cell consisted of two electrodes and its holder, and a working and a counter electrode were fabricated from 192 carbon strings, which were composed of 400 carbon fibers of 10?mum in diameter filled into a heat-shrinkable tube. These electrodes were placed in the center of a holder made from polyether ether ketone blocks and they were separated by polytetrafluoroethylene membrane filters. To evaluate the sensitivity of this cell, a standard solution of ferrocene was injected into the supercritical fluid chromatography system connected to the electrolytic cell. The ferrocene was eluted through a silica gel column using a mixture of a mobile phase of supercritical CO2 and a modifier of methanol containing ammonium acetate. The current peak area of ferrocene correlated to the ferrocene concentration in the range of 10?400?mumol/L (r?=?0.999). Moreover, the limit of detection on the column estimated from a signal-to-noise ratio of 3 was 9.8 ¡Á?10?13?mol.

A flow-through column electrolytic cell for supercritical fluid chromatography*

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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 Ferrocenemethanol

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Vinyl sulfone: A versatile function for simple bioconjugation and immobilization

The easy functionalization of tags and solid supports with the vinyl sulfone function is a valuable tool in omic sciences that allows their coupling with the amine and thiol groups present in the proteogenic residues of proteins, in mild and green conditions compatible with their biological function.

Vinyl sulfone: A versatile function for simple bioconjugation and immobilization

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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

 

Extracurricular laboratory:new discovery of Ferrocenemethanol

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Photoinduced charge transfer in short-distance ferrocenylsubphthalocyanine dyads

Two new ferrocenylsubphthalocyanine dyads with ferrocenylmethoxide (2) and ferrocenecarboxylate (3) substituents directly attached to the subphthalocyanine ligand via the axial position have been prepared and characterized using NMR, UV-vis, and magnetic circular dichroism (MCD) spectroscopies as well as X-ray crystallography. The redox properties of the ferrocenyl-containing dyads 2 and 3 were investigated using the cyclic voltammetry (CV) approach and compared to those of the parent subphthalocyanine 1. CV data reveal that the first reversible oxidation is ferrocene-centered, while the second oxidation and the first reduction are localized on the subphthalocyanine ligand. The electronic structures and nature of the optical bands observed in the UV-vis and MCD spectra of all target compounds were investigated by a density functional theory polarized continuum model (DFT-PCM) and time-dependent (TD)DFT-PCM approaches. It has been found that in both dyads the highest occupied molecular orbital (HOMO) to HOMO-2 are ferrocene-centered molecular orbitals, while HOMO-3 as well as lowest unoccupied molecular orbital (LUMO) and LUMO+1 are localized on the subphthalocyanine ligand. TDDFT-PCM data on complexes 1-3 are consistent with the experimental observations, which indicate the dominance of pi-pi* transitions in the UV-vis spectra of 1-3. The excited-state dynamics of the dyads 2 and 3 were investigated using time-correlated single photon counting, which indicates that fluorescence quenching is more efficient in dyad 3 compared to dyad 2. These fluorescence lifetime measurements were interpreted on the basis of DFT-PCM calculations.

Photoinduced charge transfer in short-distance ferrocenylsubphthalocyanine dyads

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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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Adsorption/desorption of hydrogen on Pt nanoelectrodes: Evidence of surface diffusion and spillover

Nanoelectrochemical approaches were used to investigate adsorption/desorption of hydrogen on Pt electrodes. These processes, which have been extensively studied over the last century, remain of current interest because of their applications in energy storage systems. The effective surface area of a nanoelectrode was found to be much larger than its geometric surface area due to surface diffusion of adsorbed redox species at the Pt/glass interface. An additional peak of hydrogen desorption was observed and attributed to the spillover of hydrogen from the Pt surface into glass. The results were compared to those obtained for underpotential deposition of copper on Pt nanoelectrodes.

Adsorption/desorption of hydrogen on Pt nanoelectrodes: Evidence of surface diffusion and spillover

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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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Combination of gold and iridium catalysts for the synthesis of N-alkylated amides from nitriles and alcohols

An alternative and efficient approach for the synthesis of N-alkylated amides from nitriles and alcohols was proposed and accomplished. By the combination of [(IPr)Au(NTf2)] (IPr = 1,3-bis(diisopropylphenyl)imidazol-2-ylidene) and [CpIrCl2]2 (Cp = eta5-pentamethylcyclopentadienyl), a series of nitriles were first hydrated to give amides, in which the resulting amides were further N-alkylated with a variety of alcohols as alkylating agents to afford N-alkylated amides with good to excellent yields. Compared with previous methods for the synthesis of N-alkylated amides from nitriles and alcohols as starting materials, this protocol could be accomplished with high atom economy under more environmentally benign conditions.

Combination of gold and iridium catalysts for the synthesis of N-alkylated amides from nitriles and alcohols

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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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Chapter 4: Scanning electrochemical microscopy (SECM): Fundamentals and applications in life sciences

The different techniques nowadays applied in life sciences may be considered as individual instruments in a symphony orchestra, each providing different valuable information. Fundamental questions are addressed regarding biomolecules, biomolecule-modified surfaces, live cells and complex biological functions such as cell signaling cascades, influences on cell proliferation, gene expression and cell death. Techniques such as optical microscopy, electrophoresis, chromatographic techniques bulk or on-chip electrochemical measurements and spectroscopic techniques are among the approaches providing bulk information usually averaging over a large number of biological entities. However, for most of the listed techniques either modification or complexing agents may be necessary and/or the obtained information cannot be correlated to structural changes. Fluorescence-based and high-resolution optical techniques provide spatially resolved information down to individual molecules (e.g., single molecule fluorescence) but usually require labeling steps.1 Scanning probe microscopy (SPM) techniques such as atomic force microscopy (AFM),2 scanning electrochemical microscopy (SECM)3 and scanning ion conductance microscopy (SICM)4 yield valuable information when investigating biological samples in respect to topographical and structural analysis of, for example, cells, yet some of them lack chemical and molecular specificity. In particular electrochemical methods5,6 play a dominant role in studying signaling processes as many transmitter molecules are either electroactive molecules (e.g., catecholamines)7 or can be selectively determined using biosensors.8 Ideally, the detection of specific constituents and the response to stimulation and/or changes of the biological sample should be obtained in a temporally and spatially resolved manner. SECM, as introduced by Bard and co-workers,9 is an attractive scanning probe technique for life sciences and related research areas, which was already demonstrated by early investigations on biological samples10,11 and first enzyme activityrelated investigations presented in 1992.12 Since then, SECM evolved into an increasingly popular technique for studying biochemical and bio-related processes. Significant progress has been made over the years in instrumental developments, by introducing new imaging modes and establishing comprehensive theoretical models. While the early years of SECM were certainly shaped by the team of A. Bard and the research groups emerging from this nucleus, not much later research groups in Japan13-15 and Europe16-24 contributed to SECM research in the field of life sciences. In the early twenty-first century, SECM was improved in respect to resolution, introducing new imaging modalities and SECM research expanded to the investigation of DNA,25-27 cells,28,29 membranes30,31 and neurons.32 Returning to the metaphor of an orchestra, the musical development in allegro was not just limited to its leitmotif of SECM, but combinations with other scanning probe techniques such as AFM and SICM or optical techniques enriched the Symphony. Within this chapter an overview on SECM is provided along with the imaging modalities on biologically relevant applications in the life sciences and related research areas with selected examples. As this chapter cannot be comprehensive, the interested reader is directed further to the seminal book Scanning Electrochemical Microscopy.

Chapter 4: Scanning electrochemical microscopy (SECM): Fundamentals and applications in life sciences

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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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Cholesterol oxidase modified gold electrodes as bioanalytical devices

Cholesterol oxidase (ChOx) has been immobilized by direct adsorption on gold electrodes. The resulting ChOx monolayers have been characterized using atomic force microscopy (AFM) under liquid conditions and quartz crystal microbalance (QCM) techniques. The immobilized enzyme retains its catalytic activity, thus spatially resolved mapping of enzymatic activity has been carried out using scanning electrochemical microscopy (SECM). The replacement, in the enzymatic reaction, of the natural electron acceptor (O2) by an artificial mediator has been also evaluated, in particular, hydroxymethylferrocene (HMF), thionin, nile blue and azure A, have been studied as electron acceptors for reduced ChOx. In addition, the influence of the low cholesterol solubility on the experimental conditions using redox mediators was also discussed. Finally, the response of the enzymatic electrode to varying cholesterol concentrations has been obtained by measuring directly the H2O2 generated in the enzymatic reaction. Cholesterol can be determined amperometrically at +0.5 V (versus SSCE) with a detection limit of 60 muM and a sensitivity of 0.13 muA mM-1.

Cholesterol oxidase modified gold electrodes as bioanalytical devices

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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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Catalytic access to ferrocenyl phosphines bearing both planar and central chirality ? A kinetic resolution approach via catalytic asymmetric P(III)?C bond formation

A series of enantioenriched ferrocenyl monophosphines imbued with both central and planar chirality were obtained catalytically (80?99% ee) via the kinetic resolution of 1,2-disubstituted planar chiral ferrocenyl enone racemates. The synthetic approach utilized a chiral palladacycle to facilitate the asymmetric hydrophosphination (AHP) as a means to achieve high stereoselectivity. The enantioenriched ferrocenylphosphine products could be protected and further recrystallized to obtain ees up to 99%. The modularity of the phosphine framework obtained was demonstrated via derivatization of its functional handles via a simple nucleophilic substitution to yield optically pure bisphosphines.

Catalytic access to ferrocenyl phosphines bearing both planar and central chirality ? A kinetic resolution approach via catalytic asymmetric P(III)?C bond formation

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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