A Prebiotic Surface Catalysed Photochemically Activated Synthesis of a-Lipoic Acid

AUTHOR(S):

TITLE

A Prebiotic Surface Catalysed Photochemically Activated Synthesis of a-Lipoic Acid

ABSTRACT

Catalysts such as Mg.porphin may coordinate alkynes such as ethyne and catalyse their photchemically activated oligomerization. The multicentre catalyst may also form a charge transfer adduct with anions such as hydrogen disulphide anion centred on its magnesium ion. Both adducts may exhibit net negative charges which determine their orientations when subject to the magnetic field of exciting radiation. The preferred orientation determines the asymmetry of the adducts when they bond to form a complex. The negatively charged complex may then loose hydrogen anion to become neutral. Subsequent reaction with hydroxyl radicals to form a 1,1’-dihydroxy complex allows enolisation to form the carboxylic acid. Further hydrogenation and activation allows the separation of the a-lipoic acid from the catalyst. 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

Ethyne, hydrogen disulphide, a-lipoic acid, Mg.porphin

REFERENCES

[1] J.D.Loudon in E.H.Rodd (Ed.), Chemistry of Carbon Compounds,Vol.1VA, Elsevier Publ.Comp. 1957, pp.333.

[2] A.Volpi and F.Toffoli, Therapeutic dosage and physicochemical constants of bases and acids, Boll. Chim. Farm., 118, 1979, pp.594-609.

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

[4] E.E.Conn and P.K.Stumpf, Outlines of biochemistry, Wiley Int.1972.

[5] J.D.Carreau, Biosynthesis of lipoic acid via unsaturated fatty acids, Methods Enzymology, 62, 1979, pp.152-8.

[6] L. J. Reed, I. C. Gunsalus, G. H. F. Schnakenberg, Q.F. Soper, H.E. Boaz, S. F. Kern, and T. V. Parke, J. Am. Chem. Soc., 75 (6), 1953, pp. 1267–1270.

[7] N.Aylward, and N.R.Bofinger, Possible origin for porphin derivatives in prebiotic chemistry - a computational study, Orig.Life Evol. Biosph.,35, No.4, pp345-368,2005.

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

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

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

[11] 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.

[12] 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.

[13] 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

[14] 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: A contemporary reassessment based on an unpublished 1958 Stanley Miller experiment, OLEB, 41, No.3, 2011, pp. 201–212.

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

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

[17] 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.

[18] L.P.Christensen and K.Brandt, Bioactive polyacetylenes in food plants of the Apiacae family: occurrence, bioactivity and analysis, J.Pharm. Biomed.Analysis, 41, 2006, pp.683-693.

[19] 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.

[20] 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.

[21] T.Moeller, Inorganic Chemistry, J.Wiley, 1952

Cite this paper

Nigel Aylward. (2018) A Prebiotic Surface Catalysed Photochemically Activated Synthesis of a-Lipoic Acid. International Journal of Biochemistry Research, 3, 31-39