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Ferrocene Derivatives, Part 67 57Fe-NMR Spectroscopy of Ferrocenes

57Fe NMR-spectra of 28 mono and disubstituted ferrocenes with a natural abundance of 57Fe have been measured relative to internal ferrocene.Most of the resonances appear at the high frequency side.The shielding influence of the various substituents is discussed qualitatively. 57Fe shifts are very sensitive to ring tilting as occurring in <3>ferrocenophanes. – Keywords: 57Fe Shifts; Hybridization influence on chemical shifts; Ring tilting

Ferrocene Derivatives, Part 67 57Fe-NMR Spectroscopy of Ferrocenes

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Bioencapsulation within synthetic polymers (Part 1): Sol-gel encapsulated biologicals

Since its inception a decade ago, sol-gel encapsulation has opened up an intriguing new way to immobilize biological materials. An array of substances, including catalytic antibodies, DNA, RNA, antigens, live bacterial, fungal, plant and animal cells, and whole protozoa, have been encapsulated in silica, metal-oxide, organosiloxane and hybrid sol-gel polymers. The advantages of these ‘living ceramics’ might give them applications as optical and electrochemical sensors, diagnostic devices, catalysts, and even bioartificial organs. With rapid advances in sol-gel precursors, nanoengineered polymers, encapsulation protocols and fabrication methods, this technology promises to revolutionize bioimmobilization. Copyright (C) 2000 Elsevier Science Ltd.

Bioencapsulation within synthetic polymers (Part 1): Sol-gel encapsulated biologicals

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
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An amperometric biosensor based on lactate oxidase immobilized in laponite-chitosan hydrogel on a glassy carbon electrode. Application to the analysis of l-lactate in food samples

A biosensor based on the immobilization of lactate oxidase (LOx) on a glassy carbon electrode modified with laponite/chitosan hydrogels for the quantification of l-lactate in alcoholic beverages and dairy products is presented. Ferrocene-methanol (FcMe) is used as artificial mediator. The purpose of this work is to determine the best hydrogel composition from the analytical point of view. The characterization of the hydrogels was carried out by CV, amperometry and EIS. According to permeabilities and charge transfer resistances for ferrocyanide (used as molecular probe) as well as the enzymatic behavior of the enzyme for l-lactate, the best laponite/chitosan mass ratio found was 25/50. The distinct features of the bioelectrode are its long stability, its ability to reject or minimize most interferents including ascorbic acid, and its excellent analytical response, which allowed the reduction of the enzyme content below 0.5 U, for a sensitivity of (0.326 ¡À 0.003) A cm -2 M-1, with a time response lower than 5 s and a detection limit of (3.8 ¡À 0.2) ¡Á 10-6 M. Our l-lactate biosensor was validated by comparison with a standard spectroscopic method.

An amperometric biosensor based on lactate oxidase immobilized in laponite-chitosan hydrogel on a glassy carbon electrode. Application to the analysis of l-lactate in food samples

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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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Au nanoparticles/hollow molybdenum disulfide microcubes based biosensor for microRNA-21 detection coupled with duplex-specific nuclease and enzyme signal amplification

An ultrasensitive electrochemical biosensor for detecting microRNAs is fabricated based on hollow molybdenum disulfide (MoS2) microcubes. Duplex-specific nuclease, enzyme and electrochemical?chemical?chemical redox cycling are used for signal amplification. Hollow MoS2 microcubes constructed by ultrathin nanosheets are synthesized by a facile template-assisted strategy and used as supporting substrate. For biosensor assembling, biotinylated ssDNA capture probes are first immobilized on Au nanoparticles (AuNPs)/MoS2 modified electrode in order to combine with streptavidin-conjugated alkaline phosphatase (SA-ALP). When capture probes hybridize with miRNAs, duplex-specific nuclease cleaves the formative duplexes. At the moment, the biotin group strips from the electrode surface and SA-ALP is incapacitated to attach onto electrode. Then, ascorbic acids induce the electrochemical?chemical?chemical redox cycling to produce electrochemical response in the presence of ferrocene methanol and tris (2-carboxyethyl) phosphine. Under optimum conditions, the proposed biosensor shows a good linear relationship between the current variation and logarithm of the microRNAs concentration ranging from 0.1 fM to 0.1 pM with a detection limit of 0.086 fM (S/N=3). Furthermore, the biosensor is successfully applied to detect target miRNA-21 in human serum samples.

Au nanoparticles/hollow molybdenum disulfide microcubes based biosensor for microRNA-21 detection coupled with duplex-specific nuclease and enzyme signal amplification

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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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Metal complexes of biologically important ligands. CLXVI [1] metal complexes with ferrocenylmethylcysteinate and 1,1?-ferrocenylbis- (methylcysteinate) as ligands

A series of complexes of transition metal ions (Cr3+, Mn 2+, Co2+, Ni2+, Cu2+, Zn 2+) and of lanthanide ions (La3+, Nd3+, Gd 3+, Dy3+, Lu3+) with the anions of ferrocenylmethyl-L-cysteine [(C5H5)Fe(C5H 4CH(R)SCH2CH(NH3+)CO 2-] (L1) and with the dianions of 1,1?-ferrocenylbis(methyl-L-cysteine) [Fe(C5H 4CH(R)SCH2CH(NH3+) CO 2-)2] (R = H, Me, Ph) (L2) as N,O,S-donors were prepared. With the monocysteine ferrocene derivative L 1 as ligands complexes [MIIL12] or [CrIIIL12]Cl type complexes are formed whereas the bis(cysteine) ligand L2 yields insoluble complexes of type [ML2]n, presumably as coordination polymers. The magnetic moments of [MnIIL2]n, [PrIIIL 2]n(OH)n and [DyIIIL 2]n(OH)n exhibit “normal” paramagnetism.

Metal complexes of biologically important ligands. CLXVI [1] metal complexes with ferrocenylmethylcysteinate and 1,1?-ferrocenylbis- (methylcysteinate) as ligands

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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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Voltammetric sensing based on the use of advanced carbonaceous nanomaterials: a review

This review (with 210 references) summarizes recent developments in the design of voltammetric chemical sensors and biosensors based on the use of carbon nanomaterials (CNMs). It is divided into subsections starting with an introduction into the field and a description of its current state. This is followed by a large section on various types of voltammetric sensors and biosensors using CNMs with subsections on sensors based on the use of carbon nanotubes, graphene, graphene oxides, graphene nanoribbons, fullerenes, ionic liquid composites with CNMs, carbon nanohorns, diamond nanoparticles, carbon dots, carbon nanofibers and mesoporous carbon. The third section gives conclusion and an outlook. Tables are presented on the application of such sensors to voltammetric detection of neurotransmitters, metabolites, dietary minerals, proteins, heavy metals, gaseous molecules, pharmaceuticals, environmental pollutants, food, beverages, cosmetics, commercial goods and drugs of abuse. The authors also describe advanced approaches for the fabrication of robust functional carbon nano(bio)sensors for voltammetric quantification of multiple targets. [Figure not available: see fulltext.].

Voltammetric sensing based on the use of advanced carbonaceous nanomaterials: a review

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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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Nylon nanofibrous membrane for mediated glucose biosensing

This work illustrates how polyamide nanofibrous membranes, prepared by the electrospinning process, can act as a new type of biosensor element. The sensing unit is based on a glassy carbon electrode coated with polyamide nanofibrous membranes, in which glucose oxidase is covalently tethered. The work is carried out by means of transient electrochemical techniques, such as cyclic voltammetry and amperometry, in which ferrocene methanol was employed as mediator. The results show that nanofibrous membranes are an excellent support for the development of biosensors thanks to their high-surface to volume ratio, high porosity and permeability of the cosubstrate and minimal effect on both the biocatalytic kinetics and the selectivity of the biorecognition event. The optimization, characterization, and attractive performance of the nanofibrous biosensor are reported in connection with the detection of glucose in a variety of food beverages.

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Use of a Cyclometalated Iridium(III) Complex Containing a N?C?N-Coordinating Terdentate Ligand as a Catalyst for the alpha-Alkylation of Ketones and N-Alkylation of Amines with Alcohols

A cyclometalated iridium(III) complex containing a N?C?N-coordinating terdentate ligand [Ir(dpyx-N,C,N)Cl(mu-Cl)]2 was found to be a general and highly effective catalyst for the alpha-alkylation of ketones and N-alkylation of amines with alcohols. In the presence of catalyst (1 mol % Ir) and base (0.2-0.5 equiv), a variety of desirable products were obtained in good yields under an air atmosphere. Notably, this research exhibited the new potential of Ir(III) complexes bearing non-Cp? ligand and will facilitate the progress of the hydrogen autotransfer process.

Use of a Cyclometalated Iridium(III) Complex Containing a N?C?N-Coordinating Terdentate Ligand as a Catalyst for the alpha-Alkylation of Ketones and N-Alkylation of Amines with 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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Direct trifluoromethylthiolation of alcohols under mild reaction conditions: Conversion of R-OH into R-SCF3

A direct process for the trifluoromethylthiolation of allylic and benzylic alcohols under mild conditions has been developed. A wide range of free alcohols underwent nucleophilic substitution in the presence of stable CuSCF3 and BF3¡¤Et2O to give the corresponding products in good to excellent yields.

Direct trifluoromethylthiolation of alcohols under mild reaction conditions: Conversion of R-OH into R-SCF3

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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 SIMPLE SYNTHESIS AND PURIFICATION OF 1-FERROCENYLALKYL ALCOHOLS

An alternative method for the preparation of 1-ferrocenylalkyl alcohols has been developed.This involves condensation of ferrocene with carbonyl compounds in concentrated sulfuric acid and addition of the resulting solutions of 1-ferrocenylalkylium ions into aqueous sodium bicarbonate.The mixtures are then treated with thioglycolic acid and the S-(1-ferrocenylalkyl)thioglycolic acids purified via sodium salts and hydrolysed in the presence of copper powder to give 1-ferrocenylalkyl alcohols in good yields.

A SIMPLE SYNTHESIS AND PURIFICATION OF 1-FERROCENYLALKYL 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