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Dunathan stereoelectronic hypothesis is a concept in chemistry to explain the stereospecefic cleavage of bonds using pyridoxal phosphate. This occurs because stereoelectronic effects controls the actions of the enzyme.
History
Before the correlation between fold type and reaction correlation of proteins were understood, Harmon C. Dunathan, a chemist at Haverford College proposed that the bond that is cleaved using pyridoxal is perpendicular to the system. Though an important concept in bioorganic chemistry, it is now known that enzyme conformations play a critical role in the final chemical reaction.
Mode of action
The transition state is stabilized by the extended pi bond network (formation of anion). Furthermore hyperconjugation caused by the extended network draws electrons from the bond to be cleaved, thus weakening the chemical bond and making it labile The sigma bond that is parallel to the pi bond network will break. The bond that has the highest chance of being cleaved is one with the largest HOMO-LUMO overlap. This effect might be effected by electrostatic effects within the enzyme.
Applications
This was seen in transferase and future interests lie in decarboxylation in various catalytic cycles.
References
- Silverman, Richard B. (2002). The organic chemistry of enzyme-catalyzed reactions (Rev. ed.). San Diego, Calif. : Acad. Press. ISBN 9780126437317.
- "MacKay Web". Archived from the original on 2015-02-25. Retrieved 2015-01-28.
- "Stereoelectronic".
- "Chem 654: Four Specialized Adaptations In Catalytic Proteins" (PDF). University of Alaska Fairbanks. 6 October 2011. Archived from the original (PDF) on 2 February 2015. Retrieved 9 November 2022.
- Toney, Michael D. (November 2011). "Controlling reaction specificity in pyridoxal phosphate enzymes" (PDF). Biochimica et Biophysica Acta (BBA) - Proteins and Proteomics. 1814 (11): 1407–1418. doi:10.1016/j.bbapap.2011.05.019. PMC 3359020. PMID 21664990. Retrieved 9 November 2022.
- http://faculty.washington.edu/gelb/Chp9.ppt
- Mohammed Shahid; et al., eds. (2011). Biomedical aspects of histamine current perspectives. Dordrecht: Springer. ISBN 9789048193493.
- "Archived copy" (PDF). Archived from the original (PDF) on 2015-02-02. Retrieved 2015-01-28.
{{cite web}}: CS1 maint: archived copy as title (link) - Eliot, Andrew C.; Kirsch, Jack F. (June 2004). "Pyridoxal Phosphate Enzymes: Mechanistic, Structural, and Evolutionary Considerations" (PDF). Annual Review of Biochemistry. 73 (1): 383–415. doi:10.1146/annurev.biochem.73.011303.074021. PMID 15189147. Retrieved 9 November 2022.
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