Archives for Chemistry Experiments of 1273-86-5

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Diamond nanoparticles based biosensors for efficient glucose and lactate determination

In this work, we report the modification of a gold electrode with undoped diamond nanoparticles (DNPs) and its applicability to the fabrication of electrochemical biosensing platforms. DNPs were immobilized onto a gold electrode by direct adsorption and the electrochemical behavior of the resulting DNPs/Au platform was studied. Four well-defined peaks were observed corresponding to the DNPs oxidation/reduction at the underlying gold electrode, which demonstrate that, although undoped DNPs have an insulating character, they show electrochemical activity as a consequence of the presence of different functionalities with unsaturated bonding on their surface. In order to develop a DNPs-based biosensing platform, we have selected glucose oxidase (GOx), as a model enzyme. We have performed an exhaustive study of the different steps involved in the biosensing platform preparation (DNPs/Au and GOx/DNPs/Au systems) by atomic force microscopy (AFM), field emission scanning electron microscopy (FE-SEM) and cyclic voltammetry (CV). The glucose biosensor shows a good electrocatalytic response in the presence of (hydroxymethyl)ferrocene as redox mediator. Once the suitability of the prototype system to determine glucose was verified, in a second step, we prepared a similar biosensor, but employing the enzyme lactate oxidase (LOx/DNPs/Au). As far as we know, this is the first electrochemical biosensor for lactate determination that includes DNPs as nanomaterial. A linear concentration range from 0.05mM to 0.7mM, a sensitivity of 4.0muAmM-1 and a detection limit of 15muM were obtained.

Diamond nanoparticles based biosensors for efficient glucose and lactate determination

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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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Rational design of a redox-labeled chiral target for an enantioselective aptamer-based electrochemical binding assay

A series of redox-labeled L-tyrosinamide (L-Tym) derivatives was prepared and the nature of the functional group and the chain length of the spacer were systematically varied in a step-by-step affinity optimization process of the tracer for the L-Tym aptamer. The choice of the labeling position on L-Tym proved to be crucial for the molecular recognition event, which could be monitored by cyclic voltammetry and is based on the different diffusion rates of free and bound targets in solution. From this screening approach an efficient electroactive tracer emerged. Comparable dissociation constants Kd were obtained for the unlabeled and labeled targets in direct or competitive binding assays. The enantiomeric tracer was prepared and its enantioselective recognition by the corresponding anti-D-Tym aptamer was demonstrated. The access to both enantiomeric tracer molecules opens the door for the development of one-pot determination of the enantiomeric excess when using different labels with well-separated redox potentials for each enantiomer. Trace compounds: Redox tracers have been synthesized for enantioselective electrochemical ligand binding assays by relying on the combined use of an oligonucleotide-aptamer receptor with the detection of the redox label. A rational step-by-step optimization procedure has been developed leading to a redox-labeled L-tyrosinamide derivative (see figure) conserving the high affinity towards the aptamer.

Rational design of a redox-labeled chiral target for an enantioselective aptamer-based electrochemical binding assay

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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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Selective oxidations of activated alcohols in water at room temperature

Allylic and benzylic alcohols can be selectively oxidized to their corresponding aldehydes or ketones in water containing nanoreactors composed of the designer surfactant TPGS-750-M. The oxidation relies on catalytic amounts of CuBr, bpy, and TEMPO, with N-methyl-imidazole; air is the stoichiometric oxidant. the Partner Organisations 2014.

Selective oxidations of activated alcohols in water at room temperature

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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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Synthesis and electrochemical behavior of the ferrocenyl units assembled on imidoalane and carbaalane clusters

Hydroalumination reaction was effectively carried out on ferrocenylnitrile in the synthesis of imidoalane cluster [HAlNCH2C5H 4FeCp]6 (3). Compound 3 exhibits a reversible electrochemical behavior. In the presence of ferrocenylmethanol, meta thesis reactions were carried out on [HAlNCH2(C4H 3S)]6 (4) and [HAlNCH2Ph]6 (5) in the synthesis of [CpFeC5H4CH2OAlNCH 2(C4H3S)]6 (6) and [CpFeC 5H4CH2OAlNCH2Ph]6 (7). The ferrocenylmethoxide groups present in these two compounds show a single reversible oxidation wave, which suggests their electrochemical equivalence. Electrochemical studies were also carried out on the carbaalane [(AlH) 2(FcCCAl)4(AlNMe3)2(CCH 2Ph)6] (9), which exhibited a considerably broadened wave with shoulders preceding the main anodic and cathodic peak, and it can be assigned to weak electronic interactions between the individual ferrocenyl sites.

Synthesis and electrochemical behavior of the ferrocenyl units assembled on imidoalane and carbaalane clusters

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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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Intramomolecular hydrogen bonds and conformations of ferrocenyl- and nonamethylferrocenylcarbinols

The character of intramolecular hydrogen bonds in ferrocenyl- and nonamethylferrocenylcarbinols has been determined from their IR spectra and on the basis of molecular mechanics calculations.The intramolecular hydrogen bonds of the OH…Fe type are formed when the steric requirements of the substituents at the carbinol carbon atom and Cp rings make the corresponding conformations energetically favourable.The correlation of proton-donating ability of the ferrocenyl- and nonamethylferrocenylcarbinols relative to the stability of intramolecular hydrogen bonds is discussed.

Intramomolecular hydrogen bonds and conformations of ferrocenyl- and nonamethylferrocenylcarbinols

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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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Mediated bioelectrocatalysis based on NAD-related enzymes with reversible characteristics

Diaphorase (DI) works as an effective catalyst for the electrochemical oxidation and reduction of NAD with the aid of several quinones or flavins as electron transfer mediators. The redox kinetics between DI and mediators have been expressed by a Butler-Volmer-type equation. NAD-dependent L-lactate dehydrogenase (LDH) catalyzing the redox reaction between L-lactate and pyruvate was coupled to the DI-catalyzed NAD redox system to achieve better understanding of mediated two-enzyme-linked bioelectrocatalysis with reversible characteristics. Under the conditions where the concentration polarization of NAD due to the DI-catalyzed electrochemical reaction is suppressed by the LDH reaction, the NAD concentration dependence of the catalytic current was expressed by an approximate equation involving the enzyme kinetics between DI and NAD. The suppression of the NAD concentration polarization is also useful to observe steady-state catalytic waves of an uphill reaction between DI and the mediator. The oxidation reaction involving the uphill electron transfer from L-lactate to NAD+ is susceptible to a inhibition from pyruvate due to the reversible characteristics of LDH. The present knowledge has led to the strategy to realize a two-way bioelectrocatalysis for the reduction of pyruvate and the oxidation of L-lactate. New potentiometry for the detection of the solution potential governed by the electrochemically inactive pyruvate/L-lactate redox couple has also been demonstrated based on the reversible characteristics of the DI-DLH-linked bioelectrocatalytic system.

Mediated bioelectrocatalysis based on NAD-related enzymes with reversible characteristics

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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

 

Discovery of Ferrocenemethanol

We¡¯ll also look at important developments in the pharmaceutical industry because understanding organic chemistry is important in understanding health, medicine, the role of 1273-86-5, and how the biochemistry of the body works.category: iron-catalyst

In homogeneous catalysis, the catalyst is in the same phase as the reactant. The number of collisions between reactants and catalyst is at a maximum.In a patent, 1273-86-5, name is Ferrocenemethanol, introducing its new discovery. category: iron-catalyst

Real-time electrocatalytic sensing of cellular respiration

In the present work we develop a real-time electrochemical mediator assay to enable the assessment of cell numbers and chemical toxicity. This allowed us to monitor metabolism down to a single cell in a low cost easy to use rapid assay which is not possible with current technology. The developed assay was based on the determination of oxygen. This was made possible via the use of electrochemical mediator ferrocene carboxylic acid (FcA). The FcA showed distinctive catalytic properties in interacting with reactive oxygen species generated from oxygen when compared to ferrocene methanol (FcMeOH). A deeper insight into the chemistry controlling this behaviour is provided. The behaviour is then taken advantage of to develop a cellular aerobic respiration assay. We describe the properties of the FcA system to detect, in real-time, the oxygen consumption of Escherichia coli DH5-alpha (E. coli). We demonstrated that the FcA-based oxygen assay is highly sensitive, and using a population of cells, oxygen consumption rates could be calculated down to a single cell level. More importantly, the results can be accomplished in minutes, considerably outperforming current commercially available biooxygen demand assays. The developed assay is expected to have a significant impact in diverse fields and industries, ranging from environmental toxicology through to pharmaceutical and agrochemical industries.

Real-time electrocatalytic sensing of cellular respiration

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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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Electrochemically driven clathration/declathration of ferrocene and its derivatives by a nanometer-sized coordination cage

The electrochemical, NMR, and crystallographic studies clearly indicate that the clathration and declathration of ferrocene and its derivatives in a self-assmbled Pd(II)-linked nanometer-sized cage can be controlled by the oxidation state of the guest. Namely, the guests are clathrated when they are reduced but declathrated when they are oxidized. The process is rapid on the NMR time scale but slow on the CV time scale. Copyright

Electrochemically driven clathration/declathration of ferrocene and its derivatives by a nanometer-sized coordination cage

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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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Chapter 3 DFT Computations of Transition-Metal Chemical Shifts

Probing the central metal with NMR can provide a wealth of information on the geometrical and electronic structure of transition-metal compounds. Accurate quantum-chemical computations of the salient metal NMR parameters can be a valuable complement to experiments, which are frequently plagued by low sensitivity, poor resolution or other fundamental problems, in particular for quadrupolar nuclei. Current computational approaches are mainly rooted in density functional theory and face different challenges, namely the proper choice of the exchange-correlation functional, and the treatment of relativistic, solvation and dynamical effects. This review summarizes the present state-of-the art of first-principles approaches for computation of transition-metal NMR parameters, calling special attention to the isotropic chemical shifts. Typical accuracies that can be reached for different classes of compounds are given, and illustrative chemical applications are highlighted. Corresponding results are also discussed for the full magnetic shielding and nuclear quadrupole coupling tensors, relevant for solid-state NMR spectroscopy, as well as for indirect spin-spin coupling constants involving transition-metal nuclei. In many cases, the computations can lead to a deeper understanding of the factors influencing the NMR parameters.

Chapter 3 DFT Computations of Transition-Metal Chemical Shifts

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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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PQQ-GDH ? Structure, function and application in bioelectrochemistry

This review summarizes the basic features of the PQQ-GDH enzyme as one of the sugar converting biocatalysts. Focus is on the membrane -bound and the soluble form. Furthermore, the main principles of enzymatic catalysis as well as studies on the physiological importance are reviewed. A short overview is given on developments in protein engineering. The major part, however, deals with the different fields of application in bioelectrochemistry. This includes approaches for enzyme-electrode communication such as direct electron transfer, mediator-based systems, redox polymers or conducting polymers and holoenzyme reconstitution, and covers applied areas such as biosensing, biofuel cells, recycling schemes, enzyme competition, light-directed sensing, switchable detection schemes, logical operations by enzyme electrodes and immune sensing.

PQQ-GDH ? Structure, function and application in bioelectrochemistry

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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