Table Of ContentCOSMOCHEMICAL EVOLUTION AND THE ORIGINS OF LIFE
VOLUME II
CONTRIBUTED PAPERS
COSMOCHEMICAL EVOLUTION
AND THE ORIGINS OF LIFE
PROCEEDINGS OF THE FOURTH INTERNATIONAL CONFERENCE ON
THE ORIGIN OF LIFE AND THE FIRST MEETING OF THE
INTERNATIONAL SOCIETY FOR THE STUDY OF THE ORIGIN OF LIFE,
BARCELONA, JUNE 25-28, 1973
VOLUME II: CONTRIBUTED PAPERS
Edited by
J. ORO
Departments of Biophysical Sciences and Chemistry, University of Houston,
Houston, Texas, and Universidad Autbnoma de Barcelona, Barcelona
S. L. MILLER
Department of Chemistry, University of California, San Diego, California
C. PONNAMPERUMA
Laboratory of Chemical Evolution, Department of Chemistry,
University of Maryland, College Park, Maryland
and
R. S. YOUNG
Head of Planetary Biology, NASA, Washington, D.C.
D. REIDEL PUBLISHING COMPANY
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Library of Congress Catalog Card Number 74-77967
ISBN-I3: 978-94-010-2284-2 e-ISBN-I3: 978-94-010-2282-8
DOl: 10.1007/978-94-0 10-2282-8
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T ABLE OF CONTENTS
PART I/ORGANIC COSMOCHEMISTRY
JAMES G. LAWLESS and ETT A PETERSON / Amino Acids in Carbonaceous
Chondrites 3
HANS E. SUESS / Remarks on the Chemical Conditions on the Surface of the
Primitive Earth and the Probability of the Evolution of life 9
MIKIO SHIMIZU / Molten Earth and the Origin of Prebiological Molecules 15
DUWAYNE M. ANDERSON and AMOS BANIN / Soil and Water and Its Rela-
tionship to the Origin of Life 23
RICHARD Y. MORIT A / Microbial Contributions to the Evolution of the
'Steady State' Carbon Dioxide System 37
A. s. LOPUCHIN / Structure of Biogenic Origin from Early Precamoriam
Rocks of Euro-Asia 45
PART II / ABIOTIC ORGANIC SYNTHESIS
SHIN-SHYONG TSENG and SHER WOOD CHANG (Photochemical Synthesis of
Simple Organic Free Radicals on Simulated Planetary Surfaces - an ESR
Study 61
s. YUASA and M. ISHIGAMI / High Frequency Discharge Experiment 75
G. TOUPANCE,F. RAULIN, andR. BUVET /FormationofPrebiochemicaICom
pounds in Models of the Primitive Earth's Atmosphere. I: CH -NH and
4 3
CH4 - N 2 Atmospheres 83
F. RAULIN and G. TOUPANCE / Formation of Preb iochemical Compounds in
Models of the Primitive Earth's Atmosphere. II:CH -H S Atmospheres 91
4 2
w. K. PARK, A. R. HOCHSTIM, and c. PONNAMPERUMA / Organic Synthesis
by Quench Reactions 99
A. BAR-NUN / Shock Synthesis of Amino Acids II 109
G. H. LOEW and S. CHANG / Quantum Chemical Study of the Thermodynamics,
Kinetics of Formation and Bonding ofH CN: Relevance to Prebiotic Chem-
2
istry 117
MOHINDRA s. CHADHA, PETER M. MOL TON, and CYRIL PONN AMPER UMA /
Aminonitriles: Possible Role in Chemical Evolution 127
PART III / ABIOTIC ORGANIC SYNTHESIS AND
INTERACTIONS: POLYMERS
HARUHIKO NODA, HIROSHI MIZUTANI, and HIROYUKI OKIHANA /
Macromolecules and the Origin of Life 139
VI TABLE OF CONTENTS
SALVATORE ANDINI, ETTORE BENEDETTI, LUCIANO FERRARA, LIVIO
PAOLILLO, and PIERO ANDREA TEMUSSI / NMR Studies of Prebiotic
Polypeptides 147
CLIFFORD N. MA TTHEWS / The Origin of Proteins: Heteropolypeptides from
Hydrogen Cyanide and Water 155
ALAN W. SCHWARTZ, M. VAN DER VEEN, T. BISSELING, and G. J. F. CHIT
TENDEN / Prebiotic Nucleotide Synthesis-Demonstration of a Geologically
Plausible Pathway 163
M. HALMANN / Models of Preb iological Phosphorylation 169
ELISABETH ET AIX and RENE BUVET / Conditions of Occurrence for Pri-
meval Processes of Transphosphorylations 175
PART IV / STRUCTURAL AND THERMODYNAMIC CONSIDERATIONS
ON THE ORIGIN OF LIFE
WILLIAM A. BONNER and JOSE J. FLORES / Experiments on the Origins ofOp-
tical Activity 187
K. D. HAEGELE, P. Y. HOWARD, and w. PARR / A Technique for the Determi-
nation of Enantiomeric Amino Acids in Biological Samples 195
DUANE L. ROHLFING / Coacervate-Like Microspheres from Lysine-Rich
Proteinoid 203
P. DECKER / Evolution in Bioids: Hypercompetitivity as a Source of Bistability
and a Possible Role of Metal Complexes as Prenucleoprotic Mediators of
Molecular Asymmetry 211
MASAMI HASEGAWA and TAKA-AKI YANO / Entropy of the Genetic In-
formation and Evolution 219
c. A. BOGDANSKI/Physical Foundations of the Probability of Biogenesis 229
M. MCCABE / Some Physical Parameters Controlling Cell Size During the Evo-
lution of the Procaryons 239
PART V / EARLY BIOCHEMICAL EVOLUTION
E. BRODA / The Beginning of Photosynthesis 247
N. V. KARAPETY AN / Evolution of Photo systems of Photosynthetic Organisms 253
v. M. KUTYURIN / Evolution of Oxygen by Plants in Relation to Biosphere
Evolution 257
A. G. CAIRNS-SMITH / Ambiguity in the Interpretation of Abiotic Syntheses 265
VLADIMIR NOV A.K and VLASTIMIL LIEBL / On the Question of the Origin and
Evolution of the Genetic System 269
JAMES C. LACEY, JR., ARTHUR L. WEBER, and WILLIAM E. WHITE, JR. / A
Model for the Coevolution of the Genetic Code and the Process of Protein
Synthesis: Review and Assessment 273
TABLE OF CONTENTS VII
PART VI/MISCELLANEOUS PAPERS
KONG-YI HONG, JANE-HUEY HONG, and RALPH S. BECKER / Hot Hy
drogen Atoms: Initiators of Reactions of Interest in Interstellar Chemistry
and Evolution 287
s. YU ASA and 1. ORO / Role of Weak Bases on the Prebiotic Formation of Het-
erocyclic Compounds 295
E. STEPHEN-SHERWOOD, D. G. ODOM, and J. ORO / The Prebiotic Synthesis of
Deoxythymidine Oligonucleotides 301
L. E. ORGEL / A Possible Step in the Origin of the Genetic Code 309
A. GINER-SOROLLA and A. BENDICH / The Emergence of Carcinogens During
the Evolution of Living Systems 315
INDEX OF SUBJECTS 325
PART I
ORGANIC COSMOCHEMISTRY
AMINO ACIDS IN CARBONACEOUS CHONDRITES
JAMES G. LAWLESS and ETTA PETERSON
Ames Research Center, NASA, Planetary Biology Division, Moffett Field, Calif. 94035, U.S.A.
Abstract. For almost 20 years laboratory experiments have advanced the concepts of chemical evolution,
particularly with regard to formation of the amino acids. What has been generally lacking is concrete
natural evidence for this chemical evolution hypothesis. The recent development of sophisticated analytical
techniques and availability of carbonaceous chondrites with a minimum of terrestrial contamination has
resulted in the identification of amino acids which provide strong evidence for a natural extraterrestrial
chemical synthesis. Since the initial find in the Murchison meteorite (a type II carbonaceous chondrite)
of both protein and nonprotein amino acids and amino acids with nearly equal abundances of D and L
isomers, further studies have been carried out. These studies have revealed the presence of at least 35 amino
acids; the population consists of a wide variety of linear, cyclic and polyfunctional amino acids which
shows a trend of decreasing concentration with increasing carbon number. Investigations of the Murray
meteorite (a type II carbonaceous chondrite) has produced similar results, but studies of the Orgueil
meteorite (a type I carbomiceous chondrite) show only a limited suite of amino acids, some of which
appear to be indigenous while others appear to be terrestrial contaminants. A sample of the Murchison
meteorite was extracted with D 0 and in addition to 'free' amino acids, showing no deuterium incorpora
2
tion, some amino acids showed the presence of deuterium suggesting either a 'precursor(s)' or hydrogen
deuterium exchange which require(s) formation of carbon-hydrogen bonds.
1. Introduction
One of the most important classes of compounds in the scheme of chemical evolu
tion is the amino acids. Since the initial identification of these compounds as products
of an electrical discharge in an atmosphere of methane, ammonia, and water, many
investigators have contributed to an extensive body of literature concerning their
production in simulated prebiotic experiments. This abundance of data provides
an impressive experimental base for the hypothesis of chemical evolution. Since the
laws of chemistry are believed to be universal, there should be natural evidence for
the chemical evolutionary process. Meteorites, particularly carbonaceous chon
drites, appear to provide such evidence. Recently, Kvenvolden et al. (1970) identified
amino acids - as well as other compounds - in the Murchison meteorite, a type
II carbonaceous chondrite. The suite of amino acids found included protein and
nonprotein amino acids, with many of these amino acids having nearly equal amounts
of both the D and the L isomers. Subsequent investigations of the Murchison and
other meteorites (Kvenvolden et al., 1971; Cronin and Moore, 1971; Oro et al.,
1971a; Lawless et at., 1971; Oro et al., 1971b; Lawless et al., 1972) have substan
tiated this finding and provided the strongest evidence to date for the indigenous
nature of complex organic molecules in extraterrestrial samples. The recent develop
ment of sophisticated analytical techniques, particularly the combined gas chromato
graph-mass spectrometer (GC-MS), has been instrumental in the success of these
investigations. This paper reports on the use of GC-MS to characterize further the
amino acids found in extracts of the Murchison meteorite.
4 JAMES G. LAWLESS AND ETTA PETERSON
2. Experimental
Two separate samples of the Murchison meteorite were analyzed. The first 5.1 g
sample was refluxed with deuterated water (D 20) for 20 hr. The D 20 extract was
charged on a Dowex 50 (H +) ion exchange column and eluted with H 0 and 2N
2
NH 0H. A second 10 g sample of pulverized meteorite was refluxed with H 0 for
4 2
20 hr. The H 0 extract was evaporated to dryness and refluxed with 6N HCI for
2
20 hr. The hydrolyzate was evaporated to dryness, redissolved in H 0, and charged
2
on a Dowex 50 (H +) ion exchange column. The column was successively eluted
with HP and 2NNHpH. In each case the NH 0H eluate was evaporated to
4
dryness, and the N-trifluoroacetyl-D-2-butyl ester derivatives of the amino acids
were prepared (Pollock et at., 1965; Pollock and Oyama, 1966). These compounds
were analyzed by gas chromatography (Perkin-Elmer 900) using a flame ionization
detector and a 150 ft x 0.02 in wall coated (UCON 75-H-90000) capillary column.
The column was programmed from 100° to 150°C at 1°C min Procedural blanks
-1.
showed no amino acids.
The same column and gas chromatographic conditions were used in the GC-MS
analysis where the gas chromatograph was interfaced to a CEC 21-491 mass spec
trometer through a membrane separator. As each compound eluted from the gas
chromatograph and passed into the mass spectrometer, its mass spectrum was ob
tained using 70 eV electrons by taking successive scans at 4 s per decade. The co
variant mass spectral peaks were then plotted and the identity of the compound
determined. This GC-MS system is capable of identifying as little as 20 x 10 g
-9
of the N-trifluoroacetyl-D-2-butyl ester derivative of an amino acid injected onto
the gas chromatographic column.
3. Results and Discussion
Cronin and Moore (1971) observed a marked increase in the concentration of most
of the amino acids as a result of acid hydrolysis of the Murchison meteorite aqueous
extract. They pointed out that the state of the amino acids prior to extraction and
the chemical reactions which they may undergo during extraction were not known.
In order to understand further what might be happening during the extraction
procedure, a sample of the Murchison meteorite was extracted with D 0 and the
2
resulting amino acids derivatized and analyzed by GC-MS. If carbon-hydrogen bond
formation occurs during extraction and involves the extraction solvent, use of D 20
would result in carbon-deuterium bond formation which could be detected in the
mass spectra of the derivatized amino acids. The results of this experiment are sum
marized by the mass spectral data presented in Table I. First, it should be noted
that with the exception of p-aminoisobutyric acid, all of the amino acids which were
found in previous studies of the Murchison meteorite (Kvenvolden et al., 1970;
Kvenvolden et al., 1971; Oro et at., 1971a; Cronin and Moore, 1971) and the Murray
meteorite (Cronin and Moore, 1971; Lawless et at., 1971) have been identified in
AMINO ACIDS IN CARBONACEOUS CHONDRITES 5
TABLE I
Major fragment ions of the amino acids found in the Murchison meteorite D 0 extractt
2 .. ..
.• 1~t"0: <c '~~;d .~"~~& i6"ro,' t ' ~."~.-"""-- J~~ ~,~~h ~I~i c]th~~~2~ .!~ .N~. .!~ ..~~. i~:.\:!l .!~~ .2.N.:g1 ~,!,.,.~~~~~~ ..'~~"~"\"-! :].~\":!l :i~~~;~Ji :~~"&;g~"J' " ~~
100 8 6
102 3 1 2
103 3 4 3
104 3 6
110 13
112 10 17
113 5
11ft 11 9 15 12
115 14
116 8 7
120 10 27 12
126 6 11 7 48 40 100 75 17 21 4 24 31 19
127 2 3 3 34 16 87 100 45 44 2 5
128 10 8 14 52 100 100 4
129 5 13 46 49 2
130 5 2 3 3
138 10 10
139 1 18 16 11 42 21
140 3 3 100 100 64 38 96 8 11 16 27
141 3 87 99 19 24 13 4 8 1 1
142 20 42 2 4 3 5 4 4
143 2 11 25 25
144 100 100
145 41 47
146 3 3
147 1 1
152 2 3 6 6 2 1 2 51
153 25 8 5 10 12 19 6 2 2 1 10 33
154 100 34 100 100 100 18 15 73 45 10 8 29 17
155 16 3 18 78 65 12 17 15 42 31 20 7
156 2 19 18 7 5 12 48 42
157 3 2 3 4 1 3 3
164 2
165
166 9 7 3 2 4 5 11 9 110~
167 4 3 1 2 5 7 6 22
168 100 100 21 29 100 100 100 3
169 12 56 8 16 95 21 77 1
170 12 2 4 24 4 25
171 10 14 3
172
173
180 2 3 4 5 100 6 73
181 23 5 14 16 52
182 14 14 15 15 100 2 100 17
183 2 2 5 5 33 14
184 12 5 16 4 70
185 1 2 13 6 7 8 75
186 14 12 14
187 5 10
188 3
194 1 3 8 6
195 2 1 1
196 5 14 18
197 1 3 9
198 100
199 11 30 62
200 17 9 22
201 4
207 2
208 6
209 1
211 4
212 1 11~~
213
214 20
225 17
226 100
227 I 33
228 16 I
tEach mass spectrum is normalized to the most abundant ion above role 100.
*D ata from successive scans of the GC peak showing partial chromatographic separation of nondeuterated and deuterated species.
** A synthesized sample of alanine with approximately 75% D4 shows no mass spectral differences between direct probe and GC-MS methods of
sample introduction.
