If Yockey's analysis is correct, then it seems Loeb has been denied
his proper place in history due to a mis-translation of carbon
dioxide !
I would also be interested in opinions from geologists, geochemists,
paleontologists (I'm fishing for the appropriate "expert" category)
regarding lack of evidence for the soup in the 3.8 billion year
old Isua rocks. I did a little research on this awhile back and
found some references where "experts" were expecting to find geological
evidence for the soup.
Also, the meteorite bombardment seems significant to me. Earlier on,
these meteorite impacts were capable of sterilizing the entire planet
and even vaporizing the oceans. Their subsidence coincides (on a
geological time scale of course) with the first evidence of life.
This would indicate that the appearance of life was very rapid and
would also indicate that the "soup" (if there was one) should still
be around.
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Subject: Priority of Walther Loeb on "Miller" Spark Discharge Experiment
(Chemical Evolution)
From: hpyockey@aol.com (HPYockey)
Date: 19 Feb 1996
Ian Vaithjilingam asked for details on how to do the spark discharge
experiments to generate amino acids in a presumed atmosphere of the early
Earth.
Thos who believe in the experiment are barking up the wrong tree.
The atmosphere of the early earth was
not as Miller supposed. It was neutral not reducing. There never was a
primeval soup. See my comment on this in "Information in bits and bytes"
BioEssays v17 pp85-88 (1995)
I will send reprints if you send me your snail mail address.
The Miller-Urey experiment was not even original. The whole thing was done
by Walther Loeb in 1913 many years before Miller was born. Loeb's
publications make it clear that he was the first man to produce an amino
acid in the classic "possible prebiotic reducing (sic) atmosphere" of
carbon dioxide, ammonia and water by means of an electrical discharge.
The references to Walther Loeb's work are as follows:
Ueber das Verhalten des Formamids unter der Wirkung der stillen
Entlandung. Ein Beitrag zur Frage der Stickstoff-Assimilation
Berichte der deutschen chemischen Gesellschaft volume 46 (1913) pages
684-697
In English: The Effect of Silent Discharge on the Reactions of Formamide.
A Contribution to the Question of Nitrogen Assimilation published in the
Reports of the German Chemical Society (1913).
Upon reading Loeb's papers, I found that he knew exactly what he was
doing. The first sentence in this paper announced the purpose of the work
that led to the formation of glycine in the silent electric discharge:
"The question of natural nitrogen fixation is especially interesting in
that it presents the source of the first organic nitrogen containing
product for the formation of albumin bodies (that is, proteins)."
Lob concludes his paper by saying:
"There is no doubt that according to previous results the amino acid found
here is glycine.
Here succeeding for the first time, an amino acid has been produced
artificially from the input products of the natural synthesis, which in
any case, in the simplest phase, plays a role in the formation of natural
protein as the final products of the natural synthesis of carbonic acid
[carbon dioxide], ammonia and water without application of other
materials, purely through supplying a special energy form that remains in
close connection with the radiation."
How could Loeb say more clearly that he was working on a "prebiotic"
experiment to synthesize "prebiotic elements of protein"?
Stanley Miller is usually credited for being the first to find amino acids
in a "prebiotic experiment," but as he admitted in his 1955 paper,
biochemists, in particular Walther Loeb, had been exploiting the effects
of electric discharges in organic compounds, especially the fixation or
assimilation of nitrogen and carbon dioxide, long before he was born (ne
1930). Stanley Miller, in his 1955 paper, "Production of some organic
compounds under possible primitive Earth conditions". Journal of the
American Chemical Society volume 77, pp2351-2361 (1955). cited the 1913
reference in which Lob reported finding glycine in the silent discharge.
He mistakenly stated that Loeb used carbon monoxide in his silent electric
discharge tube. If that had that been the case it would give the
impression that Loeb was not interested in finding "prebiotic compounds"
in the electric discharge. Upon actually reading Loeb's papers in German,
I found that he plainly had not carried out his experiments in carbon
monoxide but rather in damp carbon dioxide and ammonia, the same
environment often presumed (mistakenly) by Miller and Urey and many others
to have been that of the early Earth. This false impression is due to a
mistranslation and that may be why Loeb's priority in this work has been
ignored. The German word for carbon monoxide is Kohlenoxyd, the word for
carbon dioxide is Kohlensaeure (literally, carbonic acid)-terms that are
easy enough to tell apart.
As late as 1983 Miller and Schleschinger J. Mol. Evol. v19 pp376-382 quote
Loeb's 1913 paper as using carbon monoxide not the correct carbon dioxide.
Detailed references can be found to Loeb's work in "The Electrochemistry
of gases and other dielectrics by G. Glockler and S. C. Lind John Wiley
(New York) 1939. This book mistranslates Kohlensaere as carbon monoxide.
Perhaps this is the source of Miller's mistranslation in Miller
"Production of some organic compounds under possible primitive Earth
conditions". Journal of the American Chemical Society volume 77,
pp2351-2361 (1955).
Glockler and Lind is a compilation of abstracts of paper on
electrochemistry. It has a complete list of Loeb's papers and those of
many others on the question of the formation of organic materials under
the silent electrical discharge.
It is clear that Loeb thought his discovery of the formation, by means of
electrical energy, of biologically important substances such as glycine,
formic acid, formaldehyde, butyric acid, fatty acids and other compounds
was significant: See also Walther Loeb and A. Sato Zur Frage der
Elektrokultur I Mitteilung Die Einflussung von Enzymreaction durch die
stille Entlandung
Biochemische Zeitschrift volume 69 pp1-35 (1915) He and Sato had this to
say:(my translation)
"On the ground of these relationships and practical knowledge one must
conclude further that electrical energy has an important meaning in life
reactions, that the knowledge of its role can be furthered only through a
long series of special undertakings.
The application of silent discharge is especially proper for such
undertakings on physical and chemical grounds. On physical grounds, while
under avoidance of higher temperature, the electrical energy unites with
ultraviolet ray exposure, especially as Warburg has shown previously. On
chemical grounds relatively strong chemical effects are experienced
(ausgeuebt).
And now to come to my own investigations, I wish to mention from the
earlier preparation of biologically important processes:
1. The assimilation of carbonic acid (H2CO3) higher than formaldehyde up
to glykolaldehyde from damp carbonic acid.
2. The synthesis of fatty acids that are brought up by the assimilation
of carbonic acid.
3. The synthesis of glycine from carbonic acid (H2CO3), water and ammonia
from the intervening steps of formamids, a reaction that can be the first
phase of nitrogen fixation on the way to protein.
4. The hydrolyzing of starch.
5. The deamination of glycine.
Walther Loeb, and others in his time, noted that they often found polymers
of various kinds in their discharge chambers, just as did Stanley Miller
and others many years later. Loeb reported in 1909 that he had frequently
smelled the unpleasant and characteristic odor of butyric acid during
investigations of the behavior of nitrogen in the presence of simple
organic compounds under the influence of the silent discharge. He thought
that the connection of the silent discharge reaction might be related to
fermentation processes.
Walther Loeb died after a brief illness on 3 February 1916, at the age of
44.
Miller has never given up the "primeval soup" although the atmosphere of
the early earth is now known not to have been reducing.
Would there not be geological evidence in rocks of 4 to 3. 8 billion years
old, if there had been such a soup? All methods of simulating the
formation of amino acids and other 'building blocks' leave a tarry
polymeric material as their most abundant product. Carbon that has once
composed living matter is slightly enriched in carbon 12. No chemical
reaction, heat, pressure or other treatment to which these ancient rocks
may have been subjected can change one of these isotopes to another. Thus
the carbon isotope ratio is a reliable and indestructible fingerprint to
determine whether carbonaceous material, including kerogen, came from
living organisms or by inorganic chemistry from a primordial carbon
source.
Sedimentary rocks at Isua in Greenland have been dated at 3.8 billion
years ago, a time near the end of the late heavy bombardment. They do
indeed contain kerogen. Schidlowski (Nature 333, pp313-318; 1988) reported
that all carbon in these rocks divides distinctly into two groups, one
high in carbon 13 and one depleted in carbon 13 with respect to the
isotope ratio found in atmospheric carbon dioxide. The kerogen of the very
old Isua rocks is depleted in carbon 13. This is just what is expected if
the kerogen had been derived from cyanobacteria-like microorganisms
capable of photosynthesis of carbon dioxide and nitrogen by means of an
enzyme system to form living matter. Schopf Science 260 640-646 (1993),
Moore Nature 367 322-323 (1994)
According to the standard model of the origin of life, there are two paths
the carbon would follow in the primeval soup. The first is toward forming
the ancient protobiont, the remains of which would go to kerogen. The
second, and the much more abundant amount, is the tarry material generated
in all origin of life simulation experiments. No kerogen from the tarry
material left over from the generation of the 'building blocks' of life is
found. The significance of the very old kerogen in the Isua rocks in
Greenland is that there never was a primeval soup and that living matter
must have existed abundantly on Earth before 3.8 billion years ago.
Lazcano and Miller J. Mol. Evol v39 pp546-554 (1994) admitted that: "Late
accretion impacts may have killed off life on our planet as late as 3.8
billion years ago." The date of the Isua kerogen (3.8 billion years old)
shows that life was swarming at that time. There is simply not enough time
between the last sterilizing impact event for the generation of a primeval
soup and for the appearance of a proto biont that must have had the
enzymes capable of assimilating both carbon dioxide and nitrogen.
For further comment and references on the non existence of a primeval soup
in the oceans on the early Earth see Chapters 8, 9 and 10 in Information
Theory and Molecular Biology, Cambridge University Press (1992); BioEssays
v 85-88 (1995) and Journal of Theoretical Biology v176 349-355 (1995).
Best regards Hubert P. Yockey
Einstein: "God does not play craps with the world."
Bohr: "Einstein, stop telling God what to do!"
The gods actually did cast lots for the world as Homer tells us (Illiad )
See comment on page 88 of Information Theory and Molecular Biology
Cambridge University Press (1992)
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Brian Harper |
Associate Professor | "It is not certain that all is uncertain,
Applied Mechanics | to the glory of skepticism" -- Pascal
Ohio State University |
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