Electron donors/acceptors, chemical

Morokuma K 1977. Why Do Molecules Interact The Origin of Electron Donor-Acceptor Complexes, Hydrogen Bonding, and Proton Affinity. Accounts of Chemical Research 10 294-300. 

Electrode etymology of, 2 potential of, 123 work function of, 138,203, 340 Electron acceptor adsorbate chemical potential of, 208 definition of, 24 isotherm, 309 Electron donor adsorbate chemical potential of, 208 definition of, 24 isotherm, 309... 

Senesi and Testini [147,156] and Senesi et al. [150,153] showed by ESR the interaction of HA from different sources with a number of substituted urea herbicides by electron donor-acceptor processes involves organic free radicals which lead to the formation of charge-transfer complexes. The chemical structures and properties of the substituted urea herbicides influence the extent of formation of electron donor-acceptor systems with HA. Substituted ureas are, in fact, expected to act as electron donors from the nitrogen (or oxygen) atoms to electron acceptor sites on quinone or similar units in HA molecules. 

There are a number of different enthalpic interactions that can occur between polymer and packing, and in many cases multiple interactions can exist depending on the chemical structure of the polymer. Enthalpic interactions that are related to water-soluble polymers include ion exchange, ion inclusion, ion exclusion, hydrophobic interactions, and hydrogen bonding (12)- Other types of interactions commonly encountered in SEC, as well as in all other chromatographic separations, are dispersion (London) forces, dipole interactions (Keeson and Debye forces), and electron-donor-acceptor interactions (20). 

In the absence of electron donor-acceptor interactions, the London dispersive energy is the dominant contributor to the overall attractions of many molecules to their surroundings. Hence, understanding this type of intermolecular interaction and its dependency on chemical structure allows us to establish a baseline for chemical attractions. If molecules exhibit stronger attractions than expected from these interactions, then this implies the importance of other intermolecular forces. To see the superposition of these additional interactions and their effect on various partitioning phenomena below, we have to examine the role of dispersive forces in more detail,... 

Figure 11.1. Schematic views of various ways in which an organic chemical, i, may sorb to natural inorganic solids (a) adsorption from air to surfaces with limited water presence, (b) partitioning from aqueous solutions to the layer of vicinal water adjacent to surfaces that serves as an absorbent liquid, (c) adsorption from aqueous solution to specific surface sites due to electron donor-acceptor interactions, (d) adsorption of charged molecules from aqueous solution to complementarily charged surfaces due to electrostatic attractions, and (e) chemisorption due to surface bonding or inner sphere complex formation.

The aforementioned theories arc concerned wilh Ihc size and shape of odorant molecules, but differ in certain underlying concepts. For example, accommodating for functional groups, electron donor-acceptor characteristics, as well as Ihc sorptive nature of odorants on sensor sites. The vibration Iheory largely concentrates on the far-infrared and Raman spectral characteristics of odoriferous substances. The remaining theories concentrate on structural and behavior characteristics of odorant molecules, stressing direct interactions physically, chemically, and biologically wilh the olfactory sensor system. 

A reasonable model has been proposed to accommodate these results (2/y 23). The presence of quinoid functions in lignin would give rise to electron donor-acceptor complexes with existing phenolic groups. These complexes, like quinhydrone, would form stable radical anions (semiquinone anions) on basification, according to the scheme shown below. Both biological and chemical oxidation would create more quinone moieties, which in turn would increase the contribution of Reactions 1 and 2. Alternately, enzymatic (< ) and/or alkaline demethylation 16) would produce... 

Lately one has been able to encounter experimental studies more frequently denoted Chemical Force Microscopy , CMF. This includes various attempts to observe tip-surface interactions which are specific to the chemical constitution of the surface. Mostly, CFM involves modification of the tip by a surface layer with molecules which contain particular functional groups, i.e. hydrophilic or hydro-phobic moieties, hydrogen bonding groups, ionic substituents and molecular units which can undergo electron-donor-acceptor interactions. However, sometimes the term Chemical Force Microscopy is just used for any method which can provide a material specific contrast. Depending on the specificity, CFM provides valuable information on the nanoscale composition complementary to other surface characterisation methods which are sensitive to the chemical con-... 

Electron transfer profoundly affects chemical reactivity by inverting normal electron densities in electron donor/acceptor pairs and therefore activating previously inaccessible reaction modes. The basic principles have been widely discussed in several reviews [69-72]. 

A sacrificial donor (acceptor) is a molecular entity that acts as the electron donor (acceptor) in a photoinduced electron transfer process and is not restored in a subsequent redox process, but is destroyed by irreversible chemical conversion [29]. 

Photoinitiated electron transfer reactions are among the earliest photochemical reactions documented in the chemical literature and (ground state) electron donor-acceptor interactions have been known for over one hundred years. Some aspects of plant photosynthesis were already known to Priestly in the eighteenth century. The photooxidation of oxalic acid by metal ions in aqueous solution was discovered by Seekamp (UVI) in 1803 and by Dobereiner (Fe,n) in 1830. The electron donor-acceptor interactions between aromatic hydrocarbons and picric acid were noticed by Fritzsche in the 1850s the quinhydrones are even older,... 

The two mechanisms proposed by Coughlin can better explain many of the experimental results obtained to date. However, an electron donor-acceptor mechanism cannot be completely ruled out because it could explain tbe irreversible or chemical adsorption of phenohc compounds. Thus, it is well known that the adsorption of phenolic compounds is pardy physical and partly chemical. 

The [3 + 2] photocycloaddition (Scheme 6.79) usually involves the ground-state alkene and the Si excited state of an electron-donor substituted benzene derivative, often via an exciplex intermediate.807,809 811,816 The discrimination between the ortho- and metacycloaddition pathways is dependent on the electron donor acceptor properties of the reaction partners and the position and character of the reactants substituents.807 The reaction typically produces many regio- and stereoisomers however, a suitable structure modification can reduce their number. Intermolecular and intramolecular versions of the reaction are presented in Scheme 6.88 (a) photolysis of the mixture of anisole and 1,3-dioxole (226) leads to the formation of two stereoisomers, exo- and endo-221, in mediocre ( 50%) chemical yields 830 (b) four different isomers are obtained in the intramolecular photocycloaddition of an anisole derivative 228. 831... 

Another class of interacting forces are the so-called chemical forces (Prausnitz 1969). In contrast to the physical forces these forces are counterbalanced. Typical examples are the covalent bonds, electron donor-acceptor interactions, acidic solute - basic solvent interactions. Association and solvatation are effects well-known to every chemist. 

The most difficult chemical step in precursor Z synthesis is the cleavage of the C2 -C3 bond with subsequent insertion of the C8 atom. While the mechanistic details of this process are unknown, it appears that strict radical transfer from dAdo to 5 -GTP must occur with significant rearrangement of active site molecules in a manner that prevents unwanted side reactions. The C-terminal [4Fe S] cluster may play an important, heretofore unidentified role during catalysis, either functioning as an electron donor/acceptor system or coordinating reaction intermediates. 

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