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Theoretical Investigation of the Gas Phase Cu+-Activated Fragmentation of D-Alanine
Corresponding Author(s) : Tao Hong Li
Asian Journal of Chemistry,
Vol. 25 No. 15 (2013): Vol 25 Issue 15
Abstract
The gas phase Cu+-activated fragmentation of D-alanine was theoretically investigated at B3LYP and MP2 levels. The experimentally observed products can be rationalized by the mechanism as: Cu++D-alanine ® h2 (NH2, C=O) complex ® Ca-COOH bond insertion ® O=C-OH bond insertion ® H migration from -NH2 to -OH ® [CH3CHNH-(H2O)Cu(CO)]+. Dissociations of the final intermediate in different forms produce the products corresponding to loss of H2O, CO and H2O + CO, respectively. Another product channel leading to elimination of HCOOH was also identified but it is energetically less favourable than the first one. By comparing the Cu+ + alanine reaction with previously studied Cu+ + phenylalanine reaction, it was concluded that different a-amino acids may share common reaction mechanisms for the same product channels. Different side chains change the reactivity but do not change the mechanisms significantly.
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References
Q.P. Lei and I. Amster, J. Am. Soc. Mass Spectrom., 7, 722 (1996).
W.X. Cheng, H.Y. Chen, Y.P. Zhang, Y. Feng, T.H. Li and H. Cao, Acta Chim. Sin., 65, 1956 (2007).
T.H. Li, C.M. Wang, X.Y. Liu and X.G. Xie, Chin. Chem. Lett., 19, 881 (2008).
T.H. Li, C.M. Wang, S.W. Yu, X.Y. Liu, X.H. Li and X.G. Xie, Chem. Phys. Lett., 463, 334 (2008).
T.H. Li, C.M. Wang and X.G. Xie, J. Phys. Org. Chem., 24, 292 (2011).
A.D. Becke, J. Chem. Phys., 98, 5648 (1993).
C. Lee, W. Yang and R.G. Parr, Phys. Rev. B, 37, 785 (1988).
G.A. Petersson and M.A. Laham, J. Chem. Phys., 94, 6081 (1991).
M.J. Frisch, M. Head-Gordon and J.A. Pople, Chem. Phys. Lett., 166, 281 (1990).
T. Clark, J. Chandrasekhar and P.V.R. Schleyer, J. Comp. Chem., 4, 294 (1983).
M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman, J.A. Montgomery, Jr., T. Vreven, K.N. Kudin, J.C. Burant, J.M. Millam, S.S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G.A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox, H.P. Hratchian, J.B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R.E. Stratmann, O. Yazyev, A.J. Austin, R. Cammi, C. Pomelli, J.W. Ochterski, P.Y. Ayala, K. Morokuma, G.A. Voth, P. Salvador, J.J. Dannenberg, V.G. Zakrzewski, S. Dapprich,A.D. Daniels, M.C. Strain, O. Farkas, D.K. Malick,A.D. Rabuck, K. Raghavachari, J.B. Foresman, J.V. Ortiz, Q. Cui, A.G. Baboul, S. Clifford, J. Cioslowski, B.B. Stefanov, G. Liu,A. Liashenko, P. Piskorz, I. Komaromi, R.L. Martin, D.J. Fox, T. Keith, M.A. Al-Laham, C.Y. Peng, A. Nanayakkara, M. Challacombe, P.M.W. Gill, B. Johnson, W. Chen, M.W. Wong, C. Gonzalez, and J.A. Pople, Gaussian 03, Revision C.02, Gaussian, Inc., Wallingford CT (2004).