Electron-transfer polymers

Electron transfer polymers were prepared from p-benzoquinone-diols and diisocyanates, in the presence of DBTDL. At room temperature, no reaction of the isocyanate with the benzoquinone took place and the polymers were not cross-linked. 

THERMAL CONDUCTIVITY OF SOME ELECTRON TRANSFER POLYMERS. 

Polymer reagents of this type may be ion-exchange resins (see Section 23.3.3) or electron transfer polymers (oxidation/reduction polymers). Polymer reagents are also used in the Merrifield synthesis of peptides and proteins (see Section 30.3.2). Other polymer reagents, together with their applications, are ... 

Cassidy HG. Electron-transfer polymers (oxidation-reduction polymers). J Polym Sci Macromol Rev 1972 6(l) l-58. 

Electrochemistry is concerned with the study of the interface between an electronic and an ionic conductor and, traditionally, has concentrated on (i) the nature of the ionic conductor, which is usually an aqueous or (more rarely) a non-aqueous solution, polymer or superionic solid containing mobile ions (ii) the structure of the electrified interface that fonns on inunersion of an electronic conductor into an ionic conductor and (iii) the electron-transfer processes that can take place at this interface and the limitations on the rates of such processes. 

In solid state materials, single-step electron transport between dopant species is well known. For example, electron-hole recombination accounts for luminescence in some materials [H]. Multistep hopping is also well known. Models for single and multistep transport are enjoying renewed interest in tlie context of DNA electron transfer [12, 13, 14 and 15]. Indeed, tliere are strong links between tire ET literature and tire literature of hopping conductivity in polymers [16]. 

In addition to conventional applications in conducting polymers and electrooptical devices, a number of recent novel applications have emerged. Switching of DNA electron transfer upon single-strand/double-strand hybridization fonns the basis for a new medical biosensor teclmology. Since the number of base pairs of length 20... 

The size-exclusion and ion-exchange properties of zeoHtes have been exploited to cause electroactive species to align at a zeoHte—water interface (233—235). The zeoHte thus acts as a template for the self-organization of electron transfer (ET) chains that may find function as biomimetic photosynthetic systems, current rectifiers, and photodiodes. An example is the three subunit ET chain comprising Fe(CN)g anion (which is charge-excluded from the anionic zeoHte pore stmcture), Os(bipyridine)3 (which is an interfacial cation due to size exclusion of the bipyridine ligand), and an intrazeoHte cation (trimethylamino)methylferrocene (F J ). A cationic polymer bound to the (CN) anion holds the self-assembled stmcture at an... 

A compound which is a good choice for an artificial electron relay is one which can reach the reduced FADH2 active site, undergo fast electron transfer, and then transport the electrons to the electrodes as rapidly as possible. Electron-transport rate studies have been done for an enzyme electrode for glucose (G) using interdigitated array electrodes (41). The following mechanism for redox reactions in osmium polymer—GOD biosensor films has... 

Among the dynamical properties the ones most frequently studied are the lateral diffusion coefficient for water motion parallel to the interface, re-orientational motion near the interface, and the residence time of water molecules near the interface. Occasionally the single particle dynamics is further analyzed on the basis of the spectral densities of motion. Benjamin studied the dynamics of ion transfer across liquid/liquid interfaces and calculated the parameters of a kinetic model for these processes [10]. Reaction rate constants for electron transfer reactions were also derived for electron transfer reactions [11-19]. More recently, systematic studies were performed concerning water and ion transport through cylindrical pores [20-24] and water mobility in disordered polymers [25,26]. 

The initiating radicals are assumed to be SCN, ONO or N3 free radicals. Tris oxalate-ferrate-amine anion salt complexes have been studied as photoinitiators (A = 436 nm) of acrylamide polymer [48]. In this initiating system it is proposed that the CO2 radical anion found in the primary photolytic process reacts with iodonium salt (usually diphenyl iodonium chloride salt) by an electron transfer mechanism to give photoactive initiating phenyl radicals by the following reaction machanism ... 

Ultrafast photoinduced electron transfer in semiconducting polymers mixed with controlled amounts of acceptors this phenomenon has opened the way to a variety of applications including high-sensitivity plastic photodiodes, and efficient plastic solar cells ... 

The first realization of a conjugated polymer/fullerene diode [89] was achieved only recently after the detection of the ultrafasl phoioinduced electron transfer for an lTO/MEH-PPV/CW)/Au system. The device is shown in Figure 15-18. Figure 15-19 shows the current-voltage characteristics of such a bilayer in the dark at room temperature. The devices discussed in the following section typically had a thickness of 100 nm for the MEH-PPV as well as the fullerene layer. Positive bias is defined as positive voltage applied to the 1TO contact. The exponential current tum-on at 0.5 V in forward bias is clearly observable. The rectification ratio at 2 V is approximately l()4. 

Formation of block polymers is not limited to hydrocarbon monomers only. For example, living polystyrene initiates polymerization of methyl methacrylate and a block polymer of polystyrene and of polymethyl methacrylate results.34 However, methyl methacrylate represents a class of monomers which may be named a suicide monomer. Its polymerization can be initiated by carbanions or by an electron transfer process, the propagation reaction is rapid but eventually termination takes place. Presumably, the reactive carbanion interacts with the methyl group of the ester according to the following reaction... 

Charge transfer kinetics for electronically conducting polymer formation, 583 Charge transport in polymers, 567 Chemical breakdown model for passivity, 236... 

Electron transfer mechanism Butler-Volmer kinetics and, 587 in electronically conducting polymers, 568... 

Szwarc, M. Carbanions, living polymers and electron transfer process. New York Inter-science 1968... 

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