Download Active Carbohydrate Oligomers of Bacteria in Anoxic Environments

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ACTIVE CARBOHYDRATE OLIGOMERS OF BACTERIAS IN ANOXIC ENVIRONMENTS. Yasunori MIURA,
Department of Chemistry and Earth Sciences, Faculty of Science,Yamaguchi University, Yoshida, Yamaguchi 753, Japan.
A new type of oligomers SO3 was found in natural and synthetic materials from L-lactic acid monomer (C3H6O3) by
heating to 180° Celcius and rapix mixing under decreased pressure [1–3] . Oligomers with various degrees of
polymerization are obtained from 2 to 23 in formaulae (C3H4O2)z with open ring structure and with characteristic
biological activity , as observed in supramolecule.[4]. The oligomer SO3 provides significant clue for analyzing the origin of
life [5–9] arizing from copying system and enzyme-like activity in anaerobic and photosynthetic bacterias on anoxic waterplanets of the Earth and Mars.
1. Chemical evolution of life
Chemical evolution of life [5–9] can be summarized in the following steps:
(a) Conversion of inorganic CO2, H2O to organic compounds (CH2O)n by fermentation
of spheroidal prokaryotes, or by primitive photosynthesis.
(b) Conversion of inorganic CO2, H2O and N2 to simple organic monomers of HCHO and
HCN, sugars, animo acids and bases, and nuclleic acids and proteins.
(c) Conversions of protein and nucleic acids to life precursors and primitive organisms.
Although the monomers (CH2O)n are important energy]transporting molecules, intermediate organic oligomers with
biological activity have not been reported previously in terrestrial rocks [6,7] or meteorites [11], nor in synthetic
experiments [5,8].
Inspite of important roles of sugars and RNA or DNA giant molecules, there are few detailed study of carbohydrate
molecules with biological activity from low to high degrees of polymerization. A large amount of carbohydrate oligomers
can be explained more detailed reaction in the above (1) process.
2. Various primitive life materilas
The following various species of primitive life are considered to be formed in primordial Earth and Mars [13,].
(a) Anaerobic bacteria (3.8Ga to ca.2.9Ga), (b) Photosynthetic bacteria (3.3Ga to 2.9Ga),
(c) Anaerobic prokaryotes (2.9Ga to 2.4Ga), (d) Aerobic prokaryotes by modern
photosynthesis (1.8Ga to ca.1.0Ga), (e) Eukaryotes (1.5Ga to 1.3Ga, 0.8Ga to 0.7Ga, and
0.5Ga to 0.0), and (f) Algue and metazoants (0.7Ga to o.5Ga).
Before producing first primitive life on the Earth and Mars, it takes ca. 1 Ga due to its complex chemical evolution.
During anaerobic or photosynthetic bacterias, the main organic materials are (CH2O)n composition as follows (cf. Table 1):
nCO2 + nH2O -> (CH2O)n + nO2 (n:integer)
--------------------------------(1)
3. New carbohydrate oligomers with characteristic ring structure
Trace amount of lactic acid oligomers SO3 have been extracted from human organisms [1–3]. Large amounts of
synthetic SO3 are formed from L-lactic acid monomer with inert gas of nitrogen , rapid stirrer (360 rpm) and with 180°C
for 10 h. After cooling the molten solution , the fractions of lactic acid oligomers are measured by the proton-NMR (HNMR), high performance liquid chromatography (HPLC), and Field-desorption mass spectrometry (FD-MS) to obtain the
polymerization indices (z) of the oligomers.
Two types of the oligomer were obtained as a closed ring CR (C3H4O2)z, and an open chain OC {(C3H4O2)z-H2O].
Comput program CHEM3D for enegy-minimizing indicates that z=5 oligomers have a zig-zag ring structure CR with a
large cavity , or chain feature OC, and that the z=11 oligomers have a C-shaped curled ring CR with an open chain, or
simple curled chain featurre OC. The closed ring structures are confirmed by adding Na ions or H2O molecule into the
vacant hole of the ring structure CR.
4. Active carbohydrate oligomers as enzyme-like characteristics
Among (CH2O)n carbohydrates of folmaldehyde(n=1), acetic acid(n=2), lactic acid (n=3), ribose (n=5) and glucose(n=6),
characteristic oligomer structuire and biological activity can be found only in lactic acid (n=3) oligomer. The lactic acid
monomer has three distinct characteristics of recyclic process: (a) change from monomer to oligomer and polymer by
Workshop on Early Mars (1997)
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natural dehydration [12], (b) alteration from polymer to monomer by natural hydrolysis, and (c) replacement from organic
monomer to inorganic compounds of water and carbon dioxide by primitive fermentation or photosynthesis in anoxic
condition as shown in the equation (1).
The supramolecule (C3H4O2)z derived from (C3H6O3) has an effects similar to recognition
of elemetnts or molecules, transformation and translocation of an enzyme-like reaction as the
following characteristics:
(a) host (by oligomers CR) and guest (by Na, H2O and oligomer OC) relation by
carbohydrate compounds similar to biological effect by enzyme of protein compounds.
This suggests that life-precursors can evolve from the main composition of carbohydrate
by slow polymerization during the first chemical evolution of the origin of the life.
(b) Production of chemical energy from oligomers (CH2O)n to lactic acid monomers by
enzyme-like reaction in the CR ring structure.
This indicates that chemical energy by SO3 fermentation can produce in anoxic
condition among (C3H6O3)z and materilas expressed in the equation (1).
This result suggests that the SO3 fermentation in anaerobic bacteria does not
require formation of phosphorous compounds (ATP or ADP) during primitive Earth and
mars.
(c) The ring CR structure can duplicate it to polylactic acid ([1–3,12].
This indicates that primitive copying ability starts by polymerization from monomer to
oligomers or polymers before establishing dublication ability such as the RNA or DNA
complex.
References:
[1] Y.Miura(1996): Proc. 29th ISAS Lunar and Planet.Sympo. (ISAS, Japan), 29, 289–292.
[2] Y.Miura(1996) : In Japan. Governm.Report KK-B1 of Formation and metamorphic process
of primordial organisms in the solar system (Hokkaido Univ), Grain Formation Workshop
Vol.XVIII, 5–8.
[3] Y.Miura(1997): Proc. new Frontiers in Biochemical fluid Engineering (JSME, Japan), pp.4
(accepted for publication November 2, 1996).
[4] J.-M.Lehn (1995): Supramolecular Chemistry, 271pp. VCH, Weinheim, Germany.
[5] S.L.Miller (1953): Science, 117, 528-529.
[6] M.R.Walter , R.Buick and J.Dunlop (1980): Nature, 284, 443–446.
[7] J.W.Schopf (1993): Science, 260, 640–646.
[8] C.Chyba and C.Sagan(1992): Nature, 355, 125–132.
[9] D.S.McKay, E.K.Gilson, K.H.Thomas-Keprta, H.Vali, C.S.Romanek, S.J.Clemett,
X.D.F. Chillier, C.R.Maechilling and R.N. Zare (1996): Science, 273, 924–930.
[10] Y.Miura(1994): Astro.Soc. Pacific Conf. Series, 63, 259–264.
[11] R.Hayatsu, S.Matsuoka, R.G.Scott, M.H.Studier and E.Anders (1977): Geochim.
Cosmochim. Acta, 41, 1325–1339.
[12[]D.K.Gilding and A.M. Reed (1979): Polymer, 20, 1459–1646.
[13] J.W.Schopt (1977): Precambrian Research, 5, 143–173.
Table 1. Characteristic cyclic system of SO3 oligomers in primitive Earth and Mars [1,9,10].
----------------------------------------------------------------------------------Water and carbon dioxide -> (anaerobic or primitive photosynthetic bacterias) ->
-> (CH2O)n monomers -> (CH2O)3 -> (dehydration) ->
-> SO3 lactic acid oligomer -> (copying) -> polylactic acid ->
-> (hydrolysis) -> Lactic acid monomer -> Water and CO2 ->
-----------------------------------------------------------------------------------