Other Articles by Author(s)

Nigel Aylward

Author(s) and WSEAS

Nigel Aylward

WSEAS Transactions on Biology and Biomedicine

Print ISSN: 1109-9518
E-ISSN: 2224-2902

Volume 15, 2018

Notice: As of 2014 and for the forthcoming years, the publication frequency/periodicity of WSEAS Journals is adapted to the 'continuously updated' model. What this means is that instead of being separated into issues, new papers will be added on a continuous basis, allowing a more regular flow and shorter publication times. The papers will appear in reverse order, therefore the most recent one will be on top.

A Prebiotic Surface Catalyzed Photochemically Activated Synthesis of Vitamin B12

AUTHORS: Nigel Aylward

Download as PDF

ABSTRACT: The four stereospecific pyrroline derivatives present in the corrin structure of Vitamin B12 may be oligomerized to form a corrin structure or a porphin structure. The analogous porphin structure is formed with a lower activation energy and favourable free energy change. The corresponding corrin structure requires a greater activation energy and gives a less favourable free energy change. The resulting corrin structure may then chelate a metal ion and accept a propyne adduct in a stereospecific manner which subsequently binds metaphosphoric acid. The charge transfer adduct is cleaved by the partially hydrolyzed cyanopropyne substituent of ring D. The corrin structure is then free to bind five carbon monoxide molecules to form aziridin2one adducts. These can be photochemically activated to form the α-D-ribose and add a hydrogen ion. A carbonyl reaction site is then available to bond with the rare 5,6-dimethyl benzimidazole base. Further hydrogenation frees the sugar and rotation allows the bonding of the rare base to the metal ion. 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: Pyrroline monomers, corrin, porphin, α-D-rbose, 5,6-dimethyl benzimidazole, Vitamin B12.


[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 SulfurContaining 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.CouturierTamburelli, 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.

[20] N.Aylward. A Prebiotic Surface Catalyzed Photochemically Activated Synthesis of Corrin Derivatives: A and B Monomers. International Journal of Biochemistry Research, 3, 2018, pp.10- 19.

[21] N. Aylward. (2018) A Prebiotic Surface Catalyzed Photochemically Activated Synthesis of Corrin Derivatives: C and D Monomers. International Journal of Biochemistry Research, 3, 2018, pp.1-9

[22] F.K.Fong, Light Reaction Path of Photosynthesis, Springer-Verlag, 1982.

[23] R.H.A.Plimmer and W.J.N.Burch, XLIV-Esters of phosphoric acid. Part 11. The action of ethyl metaphosphate on alcohols, ammonia and some amino compounds. J.Chem.Soc.(resumed), Issue 0, 1929, pp.292.

WSEAS Transactions on Biology and Biomedicine, ISSN / E-ISSN: 1109-9518 / 2224-2902, Volume 15, 2018, Art. #8, pp. 68-80

Copyright © 2018 Author(s) retain the copyright of this article. This article is published under the terms of the Creative Commons Attribution License 4.0

Bulletin Board


The editorial board is accepting papers.

WSEAS Main Site