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Freezing of Aqueous Solutions and Chemical Stability of Amorphous Pharmaceuticals: Water Clusters Hypothesis

Molecular mobility has been traditionally invoked to explain physical and chemical stability of diverse pharmaceutical systems. Although the molecular mobility concept has been credited with creating a scientific basis for stabilization of amorphous pharmaceuticals and biopharmaceuticals, it has become increasingly clear that this approach represents only a partial description of the underlying fundamental principles. An additional mechanism is proposed herein to address 2 key questions: (1) the existence of unfrozen water (i.e., partial or complete freezing inhibition) in aqueous solutions at subzero temperatures and (2) the role of water in the chemical stability of amorphous pharmaceuticals. These apparently distant phenomena are linked via the concept of water clusters. In particular, freezing inhibition is associated with the confinement of water clusters in a solidified matrix of an amorphous solute, with nanoscaled water clusters being observed in aqueous glasses using wide-angle neutron scattering. The chemical instability is suggested to be directly related to the catalysis of proton transfer by water clusters, considering that proton transfer is the key elementary reaction in many chemical processes, including such common reactions as hydrolysis and deamidation.

Freezing of Aqueous Solutions and Chemical Stability of Amorphous Pharmaceuticals: Water Clusters Hypothesis

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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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Scanning electrochemical microscopy for the investigation of localized degradation processes in coated metals

Scanning electrochemical microscopy has been employed to obtain spatially-resolved information regarding surface topology, water uptake and blister formation at intact coatings, as well as the onset and progress of corrosion reactions within coating defects. Topographical lines and maps as well as chronoamperometric plots were measured during operation in the feedback mode. Next, the release of metal ions at the anodic sites and the consumption of oxygen at the cathodic sites developed in holidays could be monitored during operation in the generator-collector mode. Furthermore, the surface topography of defective coatings was imaged by using the redox competition mode.

Scanning electrochemical microscopy for the investigation of localized degradation processes in coated metals

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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

 

Brief introduction of Ferrocenemethanol

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A disposable Protein A-based immunosensor for flow-injection assay with electrochemical detection

Low-cost disposable immunosensors were produced by covalent binding of Protein A or G on graphite-polystyrene screen-printed electrodes, and they were used in a fully automated flow-injection analysis (FIA) system, allowing the kinetics of IgG binding to Protein A or G to be improved by forced convection. The displacement of rabbit IgG bound to Protein A or G by mouse IgG isotypes (IgG1 or IgG(2a)) was studied. A FIA immunoassay of mouse IgG(2a) was performed at a Protein A-based immunosensor with a good sensibility (down to 0.02mugml-1) and a total assay time of 19min. It was shown that the immunosensor combines the advantages of being reusable for more than 30 assay cycles in flow-injection analysis, and disposable when necessary. Copyright (C) 2000 Elsevier Science B.V.

A disposable Protein A-based immunosensor for flow-injection assay with electrochemical detection

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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

 

Some scientific research about Ferrocenemethanol

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Electrochemistry in bicontinuous microemulsions based on control of dynamic solution structures on electrode surfaces

Bicontinuous microemulsions (BMEs, Winsor III), also called middle-phase microemulsions, are low-viscosity, isotropic, thermodynamically stable, and spontaneously formed mixtures of water, oil, and surfactants. They are unique solution media for electrochemistry. Here, we introduce the recent progress in the electrochemistry of BMEs from their fundamental aspects to their practical applications. Electrochemistry using BMEs has two irreplaceable properties: the coexistence of hydrophilic and lipophilic species with high self-diffusion coefficients; and the dynamic deformation of structures at an oil/water/electrode ternary interface, which is easily changed according to the property of the electrode surface. Electrochemical contact with the micro-saline and oil phases in a BME is alternately or simultaneously achieved by controlling the hydrophilicity and lipophilicity of the electrode surfaces. The selective electrochemical analysis of hydrophilic and lipophilic antioxidants in liquid foods without extraction demonstrated as the use of the unique ternary solution structures of BME on solid surfaces.

Electrochemistry in bicontinuous microemulsions based on control of dynamic solution structures on electrode surfaces

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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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Dinuclear platinum(II) complexes containing ferrocenylalkyl-thiolate and -selenolate ligands

Alkylation reactions of [Pt2(mu-S)2(PPh 3)4] with haloalkylferrocenes FcCH2Cl, Fc(CH2)6Br and Fc(CH2)11Br [Fc = (eta5-C5H5)Fe(eta5-C5H4)] gave the cationic mu-thiolate complexes [Pt2(mu-S){mu-S(CH2) nFc}(PPh3)4]+ (n = 1, 6, 11), isolated as PF6 and/or BPh4 salts, and characterised by ESI mass spectrometry, NMR spectroscopy, microelemental analysis, and by an X-ray structure determination on [Pt2(mu-S){mu-SCH2Fc} (PPh 3)4]PF6. The complex contains the typical folded {Pt2(mu-S)2} core with an axial ferrocenylmethylthi-olate ligand. The corresponding selenolate complex [Pt 2(mu-Se){mu-SeCH2Fc}(PPh3) 4]+ was similarly obtained by alkylation of [Pt 2(mu-Se)2(PPh3)4] with FcCH 2Cl, and isolated as PF6 and BPh4 salts. The attempted liberation of FcCH2SH from [Pt2(mu-S){mu- SCH2Fc}(PPh3)4]+ using Na 2S was not successful.

Dinuclear platinum(II) complexes containing ferrocenylalkyl-thiolate and -selenolate ligands

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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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THE ELECTROPHILIC SUBSTITUTION OF FERROCENE BY PROTONATED CARBONYL COMPOUNDS

The alpha-ferrocenylalkyl carbenium ions are formed from ferrocene and carbonyl compounds in strongly acidic media, in particular mixtures of fluorosulfuric acid and trichloroacetic acid.The alpha-ferrocenylalkyl carbenium ions are scavenged by nucleophiles or bases.The addition of nucleophiles produces the corresponding alpha-substituted ferrocenyl alkanes.Proton abstraction by base from the beta-position leads to the ferrocenylethene derivatives.Such electrophilic substitutions of ferrocene by carbonyl compounds, followed by suitable scavengeing of the alpha-ferrocenylalkyl carbenium ion, form the basis of one-pot syntheses of various ferrocene derivatives.

THE ELECTROPHILIC SUBSTITUTION OF FERROCENE BY PROTONATED CARBONYL COMPOUNDS

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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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Mild hydrolytic cleavage of alpha-ferrocenylalkyl-O-methyl ethers

The conversion of alpha-ferrocenylalkyl-O-methyl ethers into the corresponding alcohols was successfully achieved by solvolysis in water/acetone mixtures. The content of water in the solvent markedly influenced the reaction rates. The reactivity of structurally different classes of ferrocenyl ethers was evaluated and in most cases high yields of ferrocenyl alcohols or diols were obtained in a few hours without any additive. Deprotection of less reactive substrates was accelerated in the presence of montmorillonite. The method is simple, environmentally benign and valuable in providing easy access to a variety of ferrocenyl derivatives through the use of the -O-methyl ether protective group.

Mild hydrolytic cleavage of alpha-ferrocenylalkyl-O-methyl ethers

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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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Ferrocenylalkylation of 2-mercaptobenzoxazoles

Regioselectivity of the HBF4-catalyzed ferrocenylalkylation of 2-mercaptobenzoxazole in two phase aqueous organic solvent mixture was studied. The reaction proceeds regioselectively at the heterocyclic nitrogen atom. Structures of the synthesized compounds were established by 2D NMR technique. Structure of 3-(1-ferrocenylbenzyl)benz[d]oxazol-2-thione was elucidated by X-ray diffraction.

Ferrocenylalkylation of 2-mercaptobenzoxazoles

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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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Tackling the Challenges of Enzymatic (Bio)Fuel Cells

The ever-increasing demands for clean and sustainable energy sources combined with rapid advances in biointegrated portable or implantable electronic devices have stimulated intensive research activities in enzymatic (bio)fuel cells (EFCs). The use of renewable biocatalysts, the utilization of abundant green, safe, and high energy density fuels, together with the capability of working at modest and biocompatible conditions make EFCs promising as next generation alternative power sources. However, the main challenges (low energy density, relatively low power density, poor operational stability, and limited voltage output) hinder future applications of EFCs. This review aims at exploring the underlying mechanism of EFCs and providing possible practical strategies, methodologies and insights to tackle these issues. First, this review summarizes approaches in achieving high energy densities in EFCs, particularly, employing enzyme cascades for the deep/complete oxidation of fuels. Second, strategies for increasing power densities in EFCs, including increasing enzyme activities, facilitating electron transfers, employing nanomaterials, and designing more efficient enzyme-electrode interfaces, are described. The potential of EFCs/(super)capacitor combination is discussed. Third, the review evaluates a range of strategies for improving the stability of EFCs, including the use of different enzyme immobilization approaches, tuning enzyme properties, designing protective matrixes, and using microbial surface displaying enzymes. Fourth, approaches for the improvement of the cell voltage of EFCs are highlighted. Finally, future developments and a prospective on EFCs are envisioned.

Tackling the Challenges of Enzymatic (Bio)Fuel Cells

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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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Nanoarchitectures based on multi-walled carbon nanotubes non-covalently functionalized with Concanavalin A: A new building-block with supramolecular recognition properties for the development of electrochemical biosensors

We propose an innovative nanoarchitecture for the development of electrochemical biosensors based on the non-covalent functionalization of multi-walled carbon nanotubes (MWCNTs) with the lectin Concanavalin A (ConA) and the site-specific supramolecular binding of glycobiomolecules. As proof-of-concept, we propose the use of two glycoenzymes, glucose oxidase (GOx) and horseradish peroxidase (HRP), for building mono and bienzymatic glucose biosensors. The selected conditions for the preparation of the dispersion were 1.5 mg MWCNTs in 1.0 mL of 2.0 mg mL?1 ConA sonicated for 5.0 min with sonicator probe. The monoenzymatic glucose biosensor was prepared by casting GCE with the MWCNTs-ConA dispersion (GCE/MWCNTs-ConA) followed by the interaction with GOx (GCE/MWCNTs-ConA/GOx), while the bienzymatic one was obtained by interaction of GCE/MWCNTs-ConA with GOx + HRP (GCE/MWCNTs-ConA/GOx-HRP). The best analytical performance was obtained with the bienzymatic biosensor from the amperometric response at -0.050 V in the presence of 1.0 ¡Á 10-4 M hydroquinone. The sensitivity was (2.22 ¡À 0.03) muA mM?1 (which was 5.2 times higher than the one obtained with the monoenzymatic biosensor) and a detection limit of 0.31 muM. The reproducibility was 5.4% and the biosensor was challenged with human blood serum showing an excellent correlation with the values reported by the laboratory.

Nanoarchitectures based on multi-walled carbon nanotubes non-covalently functionalized with Concanavalin A: A new building-block with supramolecular recognition properties for the development of electrochemical biosensors

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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