Electron transfer chemistry

Quinone methides have been shown to be important intermediates in chemical synthesis,1 2 in lignin biosynthesis,3 and in the activity of antitumor and antibiotic agents.4 They react with many biologically relevant nucleophiles including alcohols,1 thiols,5-7 nucleic acids,8-10 proteins,6 11 and phosphodiesters.12 The reaction of nucleophiles with ortho- and /iara-quinone methides is pH dependent and can occur via either acid-catalyzed or uncatalyzed pathways.13-17 The electron transfer chemistry that is typical of the related quinones does not appear to play a role in the nucleophilic reactivity of QMs.18... 

Secondly, Fig. 5 shows that the polymeric rate constants parallel values of heterogeneous rate constants that have been observed for the electrochemical reactions of solutions of the corresponding dissolved porphyrin monomers. (The slope of the line is 0.5). This re-emphasizes what was said above, that measurements of electron hopping in polymers can give rate constants that are meaningful in the context of the metalloporphyrin s intrinsic electron transfer chemistry. 

Han W, Durantini EN, Moore TA, Moore AL, Gust DRP, Leatherman G, Seely GR, Tao N, Lindsay S (1997) STM contrast, electron-transfer chemistry, and conduction in molecules. J Phys Chem B 101 10719-10725... 

Elements of Molecular and Biomolecular Electrochemistry An Electrochemical Approach to Electron Transfer Chemistry, By Jean-Michel Saveant Copyright 2006 John Wiley Sons, Inc. 

This book is based on the Baker Lectures that I gave at Cornell in the fall of 2002. It stems from the idea that electrochemistry might be one of the best approaches to electron transfer chemistry, as illustrated by the work of many researchers all over the world. 

In addition to the nature of the accompanying reactions the prediction that electron transfer chemistry triggers a radical chemistry or an acid-base chemistry depends on the redox characteristic of transient intermediates, such as unstable radicals. The methods that may be used to achieve this difficult task are described and illustrated by experimental examples. 

A. Photoinduced Electron Transfer Chemistry of Iminium Salts. 710... 

DR. JOHN MALIN (National Science Foundation) I have been ruminating on a couple of points related to substitutional and electron transfer chemistry. I have been struck by the tremendous difference in the level of sophistication between theoretical treatments of electron transfer and what people know and can say about substitution. I think Professor Swaddle brought out some hopeful thoughts. It s going to be interesting to see what the theoreticians can do for us in understanding substitution processes. 

R. Sharma, J. H. Baik, C. J. Perera, M. S. Strano, Anomalously large reactivity of single graphene layers and edges toward electron transfer chemistries, Nano Lett., vol. 10, pp. 398-405, 2010. 

Wang, Q.H.,etal., Understanding and controlling the substrate effect on graphene electron-transfer chemistry via reactivity imprint lithography. Nature Chemistry, 2012. 4(9) p. 724-732. 

D Souza, F., et al., Self-assembled single-walled carbon nanotube-.Zinc-porphyrin hybrids through ammonium ion-crown ether interaction Construction and electron transfer. Chemistry - A European Journal, 2007.13(29) p. 8277-8284. 

Mariano PS (ed) (1991 and 1992) Advances in Electron Transfer Chemistry, vols 1-3. JAI Press, Greenwich Connecticut... 

G. B. Schuster, in Advances in Electron Transfer Chemistry (Ed. P. S. Mariano), JAI Press... 

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