Aston Labs

Amino acids aggregate into non covalent entities upon electrospray ionization (ESI) from concentrated solutions or sublimation followed by corona discharge ionization of the solid. Among the naturally occurring amino acids, serine (Ser) has been most extensively studied for its ability to assemble into octameric clusters (Ser₈) which are distinguished by their remarkable stability and their preference for homochirality.

Objectives

To study the chemistry of the amino acid clusters and their relevance to the origin of homochiral life.

Key findings

• Ser₈ shows remarkable stability compared to the neighboring clusters and strong homochiral preference (i.e. when produced from racemic mixtures, the homochiral clusters are favored).
• Chiral amplification of Ser has been demonstrated through collection of the octameric cluster ions generated through ESI-MS of non-racemic Ser solutions by ion soft landing. The soft-landed material is enriched in the major enantiomer.
• Transmission of chirality from Ser₈ to other biomolecules such as amino acids and sugars was observed by mass spectrometry.

Personnel

• Dr. R. Graham Cooks (Professor)
• Richard Perry (Graduate Student)
• Marcela Nefliu (Graduate Student)
• Chunping Wu (Graduate Student)
• Jonell N. Smith (Graduate Student)
• Anthony B. Costa (Graduate Student)

Funding

• National Science Foundation
• Department of Energy

Publications

• R. Graham Cooks, D. Zhang, Kim J. Koch, F. C. Gozzo and M. N. Eberlin, "Chiroselective Self-Directed Octamerization of Serine: Implications for Homochirogenesis" Anal. Chem. 2001, 73, 3646 -3655 doi: 10.1021/ac010284l
• R. Hodyss, R. R. Julian and J. L. Beauchamp, Chirality, 2001, 13, 703-706.
• Zoltan Takats, Sergio C. Nanita, Gitta Schlosser, Karoly Vekey, R. Graham Cooks “Atmospheric Pressure Gas-Phase H/D Exchange of Serine Octamers” Anal. Chem. 2003, 75, 6147-6154. doi: 10.1021/ac034284s
• Zoltan Takats, Sergio C. Nanita, Gitta Schlosser, Karoly Vekey and R. Graham Cooks "Amino Acid Clusters Formation by Sonic Spray Ionization", Anal. Chem. 2003, 75, 1514 -1523. doi: 10.1021/ac0260793
• Zoltan Takats, Sergio C. Nanita and R. Graham Cooks, “Serine Octamer Reactions: Indicators of Prebiotic Relevance” Angew. Chem. 2003, 115, Nr. 30, 3645-3647 [Angew. Chem. Int. Ed. 2003, 42, No. 30, 3521-3523]. doi: 10.1002/anie.200351210

• Zoltan Takats and R. Graham Cooks, “Thermal Formation of Serine Octamer Ions” Chem. Commun., 2004, 444-445. doi: 10.1039/b316768b
• Sergio C. Nanita, Zoltan Takats, Sunnie Myung, David E. Clemmer, and R. Graham Cooks, "Chiral Enrichment of Serine via Formation, Dissociation and Soft-Landing of Octameric Cluster Ions" J. Am. Soc. Mass Spectrom. 2004, 15(9), 1360-1365. doi: 10.1016/j.jasms.2004.06.010
• R. R. Julian, S. Myung and D. E. Clemmer, J. Am. Chem. Soc., 2004, 126, 4110-4111.
• U. Mazurek, O. Geller, C. Lifshitz, M. A. McFarland, A. G. Marshall and B. G. Reuben, J. Phys. Chem. A, 2005, 109, 2107-2112.
• Pengxiang Yang, Ruifeng Xu, Sergio C. Nanita, and R. Graham Cooks, "Thermal Formation of Homochiral Serine Clusters and Implications for the Origin of Homochirality", Journal of the American Chemical Society, 2006, 128(51), 17074-17086, doi: 10.1021/ja064617d
• Nanita, Sergio C.; Cooks, R. Graham, "Serine Octamers: Cluster Formation, Reactions, and Implications for Biomolecule Homochirality", Angewandte Chemie International Edition, 2006, 45(4), 554-569, doi: 10.1002/anie.200501328
• Sergio C. Nanita, Ewa Sokol and R. Graham Cooks, "Alkali Metal-Cationized Serine Clusters Studied by Sonic Spray Ionization Tandem Mass Spectrometry", Journal of the American Society of Mass Spectrometry, 2007, 18, 5, 856-868, doi: 10.1016/j.jasms.2007.01.003
• Perry, R. H., Wu, C., Nefliu, M., and Cooks, R. G., <"Serine Sublimes with Spontaneous Chiral Amplification", Chemical Communications, 2007, 1071-1073, doi: 10.1039/b616196k