Directed electron transfer

In bulk chemical reactions, an oxidizer (electron acceptor) and fuel (electron donor) react to form products resulting in direct electron transfer and the release or absorption of energy as heat. By special arrangements of reactants in devices called batteries, it is possible to control the rate of reaction and to accomplish the direct release of chemical energy in the form of electricity on demand without intermediate processes. [Pg.505]

Oxidation—Reduction. Redox or oxidation—reduction reactions are often governed by the hard—soft base rule. For example, a metal in a low oxidation state (relatively soft) can be oxidized more easily if surrounded by hard ligands or a hard solvent. Metals tend toward hard-acid behavior on oxidation. Redox rates are often limited by substitution rates of the reactant so that direct electron transfer can occur (16). If substitution is very slow, an outer sphere or tunneling reaction may occur. One-electron transfers are normally favored over multielectron processes, especially when three or more species must aggregate prior to reaction. However, oxidative addition... [Pg.170]

Although all the types of corrosion discussed in this section result in the oxidation of metal and some involve direct electron transfer, they can be understood without reference to electrochemistry. [Pg.895]

A large number of other sensitizers has been investigated for use in photolytic de-diazoniation. The excited states of these compounds (S ) react either by direct electron transfer (Scheme 10-97), as for pyrene, or by reaction with an electron donor with formation of a sensitizer anion radical which then attacks the diazonium ion (Scheme 10-98). An example of the second mechanism is the sensitization of arenedi-azonium ions by semiquinone, formed photolytically from 1,4-benzoquinone (Jir-kovsky et al., 1981). [Pg.280]

Further improvements can be achieved by replacing the oxygen with a non-physiological (synthetic) electron acceptor, which is able to shuttle electrons from the flavin redox center of the enzyme to the surface of the working electrode. Glucose oxidase (and other oxidoreductase enzymes) do not directly transfer electrons to conventional electrodes because their redox center is surroimded by a thick protein layer. This insulating shell introduces a spatial separation of the electron donor-acceptor pair, and hence an intrinsic barrier to direct electron transfer, in accordance with the distance dependence of the electron transfer rate (11) ... [Pg.177]

Barium and strontium salts of polystyrene with two active end-groups per chain were prepared by Francois et al.82). Direct electron transfer from tiny metal particles deposited on a filter through which a THF solution of the monomer was percolated yields the required polymers 82). The A.max of the resulting solution depends on the DPn of the formed oligomers, being identical with that of the salt of polymers with one active end-group per chain for DPn > 10, but is red-shifted at lower DPn. Moreover, for low DPn, (<5), the absorption peak splits due to chromophor-chromophor interaction caused by the vicinity of the reactive benzyl type anions. [Pg.117]

Direct Electron Transfer. We have already met some reactions in which the reduction is a direct gain of electrons or the oxidation a direct loss of them. An example is the Birch reduction (15-14), where sodium directly transfers an electron to an aromatic ring. An example from this chapter is found in the bimolecular reduction of ketones (19-55), where again it is a metal that supplies the electrons. This kind of mechanism is found largely in three types of reaction, (a) the oxidation or reduction of a free radical (oxidation to a positive or reduction to a negative ion), (b) the oxidation of a negative ion or the reduction of a positive ion to a comparatively stable free radical, and (c) electrolytic oxidations or reductions (an example is the Kolbe reaction, 14-36). An important example of (b) is oxidation of amines and phenolate ions ... [Pg.1508]

Diols (pinacols) can be synthesized by reduction of aldehydes and ketones with active metals such as sodium, magnesium, or aluminum. Aromatic ketones give better yields than aliphatic ones. The use of a Mg—Mgl2 mixture has been called the Gomberg-Bachmann pinacol synthesis. As with a number of other reactions involving sodium, there is a direct electron transfer here, converting the ketone or aldehyde to a ketyl, which dimerizes. [Pg.1560]

The oxidation of Zn metai by Cu ions is an exampie of direct electron transfer. A copper ion accepts two eiectrons when it coiiides with the surface of the zinc strip. Direct electron transfer occurs when electrons are transferred during a coiiision between the species being oxidized and the species being reduced, as shown by the moiecuiar views in Figure 19-5. [Pg.1370]

Electrochemistry is the coupling of a chemical redox process with electron flow through a wire. The process represented in Figure 19-7 is electrochemical because the redox reaction releases electrons that flow through an external wire as an electrical current. On the other hand. Figure 19-5 shows a redox process that is not electrochemical, because direct electron transfer cannot generate an electrical current through a wire. [Pg.1374]

A physical barrier blocking direct electron transfer... [Pg.1375]

In the past it had been a popular belief that the electrochemical reduction of any inorganic or organic substance involves the primary electrochemical formation of a special, active form of hydrogen in the nascent state (in statu nascendi) and subsequent chemical reaction of this hydrogen with the substrate. However, for many reduction reactions a mechanism of direct electron transfer from the electrode to the substrate could be demonstrated. It is only in individual cases involving electrodes with superior hydrogen adsorption that the mechanism above with an intermediate formation of adsorbed atomic hydrogen is possible. [Pg.234]

Nanni, E.J., Stallings, M.D. and Sawyer, D.T. (1980). Does superoxide ion oxidised catechal, tocopherol and ascorbic acid by direct electron transfer. J. Am. Chem Soc. 102, 448. [Pg.51]

Figure 17.4 Cartoon representation of strategies for studying and exploiting enzymes on electrodes that have been used in electrocatalysis for fuel cells, (a) Attachment or physisorption of an enzyme on an electrode such that redox centers in the protein are in direct electronic contact with the surface, (b) Specific attachment of an enzyme to an electrode modified with a substrate, cofactor, or analog that contacts the protein close to a redox center. Examples include attachment of the modifier via a conductive linker, (c) Entrapment of an enzyme within a polymer containing redox mediator molecules that transfer electrons to/from centers in the protein, (d) Attachment of an enzyme onto carbon nanotubes prepared on an electrode, giving a large surface area conducting network with direct electron transfer to each enzyme molecule.

Figure 17.12 Direct electrocatal3ftic oxidation of D-fnictose at a glassy carbon electrode painted with a paste of Ketjen black particles modified with D-fructose dehydrogenase from a Gluconobacter species. The enzyme incorporates an additional heme center allowing direct electron transfer from the electrode to the flavin active site. Cyclic voltammograms were recorded at a scan rate of 20 mV s and at 25 + 2 °C and pH 5.0. Reproduced by permission of the PCCP Owner Societies, from Kamitaka et al., 2007.

Hagen WR. 1989. Direct electron-transfer of redox proteins at the bare glassy-carbon electrode. Eur J Biochem 182 523-530. [Pg.631]

Kakehi N, Yamazaki T, Tsugawa W, Sode K. 2007. A novel wireless glucose sensor employing direct electron transfer principle based enzyme fuel cell. Biosens Bioelectron 22 2250-2255. [Pg.632]

Kamitaka Y, Tsujimura S, Setoyama N, Kajino T, Kano K. 2007. Fructose/dioxygen biofuel cell based on direct electron transfer-type bioelectrocatalysis. Phys Chem Chem Phys 9 1793-1801. [Pg.632]

Okuda J, Yamazaki T, Fukasawa M, Kakehi N, Sode K. 2007. The application of engineered glucose dehydrogenase to a direct electron-transfer-type continuous glucose monitoring system and a compartmentless biofuel cell. Anal Lett 40 431 -440. [Pg.633]

Minero, C., Mariella, G., Maurino, V., and Pelizzetti, E. (2000) Photocatalytic transformation of organic compounds in the presence of inorganic anions. 1. Hydroxyl-mediated and direct electron-transfer reactions of phenol on a titanium dioxide-fluoride system. Langmuir,... [Pg.124]

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