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AUTHOR(S):

Nigel Aylward

 

TITLE

A Prebiotic Surface Catalyzed Photochemically Activated Synthesis of Corrin Derivatives: A and B Monomers

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ABSTRACT

Alkynes such as but-2-ynimine, propyne and ethyne form weak charge-transfer, ?^2 -alkynyl complexes, with surface catalysts such as Mg.porphin in which the alkynyl group is positively charged and the porphin has a negative charge. The enthalpy changes are -0.040, -0.002 and -0.018 h, respectively. However, if the adduct is excited to a higher energy state it may migrate to form a weak charge transfer bond with the nitrogen atom of an adjacent pyrrole unit. If the catalyst, Mg.porphin accepts two adducts they may have opposite charges. The di-adduct complexes may bond leading to high energy products in which the orientation is determined by the exciting radiation. Subsequent reactions with nucleophiles such as cyanoacetylene and methyl cyanide anions may give derivatives of pyrroline that can oligomerize to tetramers that can cyclise to corrin derivatives. The reactions have been shown to be feasible from the overall enthalpy changes in the ZKE approximation at the HF and MP2 /6-31G* level.

KEYWORDS

Mg.porphin , but-2-ynimine, propyne, ethyne, corrin derivatives

REFERENCES

[1] T.S. Stevens, in Rodd,E.H.(ed), Chemistry of Carbon Compounds, Elsevier, Amsterdam, Vol.IV B, 1959, pp.1151

[2] IUPAC Commission on Biochemical Nomenclature (CBN), 2nd edition, Portland Press, 1992, pp. 272-277.

[3] R.Banerjee and S.W. Ragsdale, Ann. Rev. Biochem.72, 2003, pp.209-247.

[4] R.B.Jordan, Reaction Mechanisms of Inorganic and Organometallic Systems. Oxford, 2007

[5] A.L.Lehninger, Biochemistry,Worth, New York ,1975.

[6] N.Aylward, and N.R.Bofinger, Possible origin for porphin derivatives in prebiotic chemistry - a computational study, Orig.Life Evol. Biosph., 35, No.4, 2005, pp.345-368.

[7] S.L.Miller and L.E.Orgel, The Origins of Life on Earth, Prentice-Hall Inc.,Englewood Cliffs, N.J., 1975.

[8] D.W.Clarke and J.P.Ferris, Photodissociation of cyanoacetylene : application to the atmospheric chemistry on Titan, Icarus, vol.115, 1995, pp.119-125.

[9] K.Seki, M.He, R.Liu and H.Okabe, Photochemistry of cyanoacetylene at 193.3 nm., J.Phys.Chem.,100 ,1996, pp.5349-5353.

[10] N.N.Aylward, and N.R.Bofinger, Carbon monoxide clusters in the formation of D-sugars and L-amino-acids in prebiotic molecular evolution on Earth, in G.Palyi, C.Zucchi, L.Cagliotti, eds., Progress in Biological Chirality, Elsevier, Oxford (GB), 2004, ch2, pp.429.

[11] N.N. Aylward, The synthesis of terpenes in prebiotic molecular evolution on Earth, in WSEAS New Aspects of Biomedical Electronics and Biomedical Informatics. Eds. C.A.Long, P.Anninos, T.Pham, G.Anastassopoulos, N.E.Mastorakis, 2008, pp.202-207.

[12] E T. Parker, H. J. Cleaves, M. P. Callahan, J. P. Dworkin, D. P. Glavin, A. Lazcano, J. L. Bada, Prebiotic Synthesis of Methionine and Other Sulfur-Containing Organic Compounds on the Primitive Earth: OLEB, 41,No.3, 2011, pp. 201–212.

[13] Gaussian98, Users Reference,Gaussian Inc.,Carnegie Office Park, Bldg.6., Pittsburgh, PA 15106, USA, 1998.

[14] W.J.Hehre, L.Random, P.V.R. Schleyer, and J.A.Pople, Ab Initio Molecular Orbital Theory, Wiley, New York.,1986.

[15] J.A.Pople, H.B.Schlegel, R.Krishnan, D.J. DeFrees, J.S. Binkley, M.J. Frisch, R.A.Whiteside, R.J.Hout and W.J.Hehre, Molecular orbital studies of vibrational frequencies, Int.J.Quantum Chem. Symp. vol.S15, 1981, pp.269-278.

[16] Z.Guennoun, A.Coupeaud, I.Couturier-Tamburelli, N.Pietri, S.Coussan, J.P.Aycard, Acetylene/cyanoacetylene complexes:simulation of the Titan’s atmosphere chemistry, Chem.Phys.,300 2004, pp.143-151.

[17] K.I. Öberg, V.V. Guzmán, K. Furuya, C.Qi, Y. Aikawa, S.M. Andrews, R.Loomis and D,. J. Wilner The comet-like composition of a protoplanetary disk as revealed by complex cyanides, Nature , 520, 2015, pp.198–201

[18] D.G.Whitten,I.G.Lopp and P.D.Wildes, Fluorescence of zinc and magnesium etioporphyrin 1. quenching and wavelength shifts due to complex formation, J.Am.Chem.Soc.,90,1968, pp.7196-7200.

[19] N. Aylward, A Prebiotic Surface Catalysed Synthesis of Alkyl Imines,in WSEAS Int. Conf. on Biomedical Electronics and Biomedical Informatics. Moscow, Russia, August 20-22, 2009, pp.52-59.

Cite this paper

Nigel Aylward. (2018) A Prebiotic Surface Catalyzed Photochemically Activated Synthesis of Corrin Derivatives: A and B Monomers. International Journal of Biochemistry Research, 3, 10-19

 

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