Lawrence Berkeley National Laboratory

Lawrence Berkeley National Laboratory

Title:
COMMUNICATION: FROM MOLECULES TO MARS
Author:
Calvin, Melvin
Publication Date:
08-01-1962
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Submitted f o r Pub. in Bulletin AIBS

U C R L 10424

UNIVERSITY O F CALIFORNIA
Lawerence Radiation Laboratory
Berkeley, California
C o n t r a c t No. W - 7 4 0 5 - e n g - 4 8

COMMUNICATION: F R O M M O L E C U L E S T O M A R S
Melvin Calvin

A u g u s t 1962

U C R L 10424

Melvin Calvin
Department of Chemistry & Lawrence Radiation ~ a b o r a t o r ~ * *
University of California, Berkeley 4 , California
Abstract
August 23, 1962
An analysis i s made of the energetic, molecular, m x r o m o l e c u l a r and
organizational steps which appear

to be e s s e n t i a l for the development of

a living c e l l f r o m a nonliving origin.

Accepting the c u r r e n t view of the

primitive atmosphere of the e a r t h , experimental demonstration for the

formation of the fundamental molecules of living o r g a n i s m s (amino acids,
fatty acids, purines and pyrimadines) under the influence of available
energy s o u r c e s ( u l t r a v i o k light, ionishg radiation and electric discharge)

is presented.
The combination of t h e s e small units and the polymers via the univers a l dehydration condensation reaction under the influence of py rophosphate
o r carbon- to-nitrogen multiple bonds i s experimentally provided. These
macromolecules a r e shown to a s s u m e specific configuratione resulting
f r o m intrinsic f a c t o r s in their s t r u c t u r e , and mechanisms for information
t r a n s f e r and energy t r a n s f e r by virtue of these ordered s t r u c t u r e s a r e
described.

The aggregation of bifunctional molecules a t interfaces to

give o r d e r e d membranous s t r u c t u r e s is indicated a s the possible source

for the c e l l wall enclo5ures, thus completing the prebiotic phase.

UCRL 10424

Since this sequence of events on a molecular level may be expected to

occur whenever and wherever the initial conditions a r i s e , we a r e led to
e xpect the appearance of life of this type elsewhere in the universe.

Some

of the evidence that i s presently a t hand regarding such e x t r a t e r r e s t r i a l

life i s presented, and the promise of m o r e definitive information, a t l e a s t

about the solar system, seems to be forthcoming.

Tok published in the AIBS Bulletin

Ib

**

Presented a t meeting of American Institute of Biological Sciences,

Corvallis, Oregon, August 28, 1962.

The preparation of this paper was sponsored by the U. S. Atomic

Energy Commission.

COMMUNICATION: FROM MOLECULES TO MARS

M elvin Calvin

D e p a r t m e n t of C h e m i s t r y and L a w r e n c e Radiation L a b o r a t o r y
University of California, B e r k e l e y 4, California

**

INTRODUCTION

Z v e r s i n c e m a n became consciods of himself i t s e e m s he has been

concerned with wonder a t his own n a t d r e . In f a c t , the d e g r e e to which
he h a s left evidence of t h i s c o n c e r n is frequently taken a s a m e a s u r e of
h i s p r o g r e s s toward hurnanhood.

Very e a r l y i n his speculations about

h i s own n a t u r e , he recognized t h a t he was a m e m b e r of a l a r g e c l a s s of

objects on the s u r f a c e of the e a r t h which w e r e called "living1' a s d i s tinguished f r o m those which w e r e not.
Very soon, a s a c o r o l l ~ r yo r exrcnsion of his c o n c e r n f o r this own
n a t u r e , he t h e r e f o r e becama i n t e r e s t e d i n the n a t u r e of llfe and living
things t h e m s e l v e s .

In the c o u r s e of h i s h i s t o r y , b o ~ hancient and m o d e r n ,

he produced a n e n o r m o u s v a r i e t y of notions about both the n a t u r e of life

and h i s r e l a t i o n to i t . But it h a s only been i n the l a s t c e n t u r y since the
dominant s u c c e s s of D < r w i n i a nthought that m a n h a s been i n a position
t o begin to d e v i s e p a t t e r n s of ~ h o u g h twithin the f r a m e w o r k of what we

**

T h e p r e p a r a t i o n of t h i s paper was s p o n s o r e d by the U.S. Atomic

Energy Commiesion.

call rational s c i e n c e today.

In fact, i t hae only been i n the l a e t t w o

o r t h r e e decades. that both the biochemical and bi: phyeical, a s well

as c h e m i c a l and physical and a s t r o n o m i c a l , knowledge has reached the

level that h a s enabled him t o e s c a p e the r e q u i r e m e n t f o r u s e of such
t e r m s a s "fields", "gradients", and "eeeences" and r e p l a c e them with the
m o r e s e v e r e l y and a c c u r a t e l y defined t e r m s of chemical reaction, t r a n s formations, m o l e c u l e s and t h e i r interactions, c r y s t a l s , and m o l e c u l a r
f i l m s , about whose n a t u r e w e need not g u e 8s.
This expanded p a r t i c u l a r knowledge about the atomic and m o l e c u l a r
constituents of which living things a r e constructed, together with an inc r e a s e d understanding of the way in which t h e s e m o l e c u l e s ( u s e d in the
m o s t general s e n s e ) i n t e r a c t with e a c h o t h e r , that i s , communicate with
e a c h o t h e r so a s t o cooperate in the production of what w e now recognize
at least
a s living o r g a n i s m s , has h a 4 two very interesting r e s u l t s , among
o t h e r s . l'he f i r s t of these h a s been to stimulate s c i e n t i s t s to c r e a t e
hypothetical s c h e m e s leading i r o m the p r i m e v a l nonliving e a r t h to the

1-7

p r e s e n t day

and, consequently, induce them t o devise experimental

areas i n t h e i r l a b o r a t o r i e s for testing some of t h e s e e c h e m e s a t various

points a t which they might be amenable to experimental l a b o r a t o r y

tests.

i'he d e g r e e of s u c c c s s of a v a r i e t y o f t h e s e e x p e r i m e n t s h a s ,

i n t u r n , modified the original c o n s t r u c t s , and even l e d to new e x p e r i -

m e n t s , both in biology and in c h e m i s t r y , p a r l i c u l a r l y the l a t t e r .

Up until now, dl o u r knowledge about tho nature of tho extrat e r r e s t r i a l universe has been baaed entiroly upon tho infonnrtioa that b a
bean c a r r i e d to us b y tlectromagnetic radiation (until rscontly only
visible light, now we m a y add radiofrequency waves) from elrowhero.
However, we a r e about to begin ( o r , in fact, have already begun) an exploration of the space beyond the reachea of the e a r t h ' r atmoephere and
will soon be exploring not only our own satellite, the Moon, but our two
n e a r e s t planetary neighbors, Venus and M a r s .

H e r s we will be able to

get direct first-hand information not only about the nature of t h t materialo

of which these objects a r e constructed, but a l s o about the possible exietence on their surface either of m a t t e r which we woulg be willing to call
living, o r of m a t t e r which might have ultimately given riee to living
things, o r be the residue of living things.

This will add immeasurably

not only to our intellectural horizons but directly to the knowledge of

the nature of the t e r r e s t r i a l organisms a s well.

We a r e even beginning

t o discuss seriously and make a f e w small attempts at communications with

e x t r a t e r r e s t r i a l organisms who might have not only o u r minimal power
of understanding but perhaps even powers i a r beyond those which w e
know.

11

It therefore s e e m s appropriate to say a f e w words both about the

present state of our knowledge of chemical evolution on the e a r t h and the
generation of molecular communitiee which give r i s e to terrestrial o r g a n i s m ~ ,a s well a s what little we know of the existence of corresponding organiams eleewhere.

TERRESTRIAL CKEMICAL EVOLUTION

What Ie a Living System'!

In any discuseion of such a broad, all-encompassing subject ao
t h i s we a r e always faced with the problem of trying to define the m a t e r l a l

e y e l a m to which w e a r e willing to a t t r i b u t e the adjective "living."

Per-

sonally, I feel that this h a s a c e r t a i n d e g r e e of subjective a r b i t r a r i n e e o

about i t , s i n c e t h e r e a r e those who would be willing to allow the u s e of
t h i s t e r m for s y s t e m s which would not be acceptable to o t h e r s . I'hie
p e c u l i a r c h a r a c t e r i s t i c of the problem immediately allows us to recognize
that the q u a l i t i e s , o r p r o p e r t i e s , which we r e q u i r e of a m a t e r i a l s y s t e m
a r e of the n a t u r e of a continuous aggregation in t i m e along which no s h a r p
l i n e of d e m a r c a t i o n need n e c e s s a r i l y e x i s t .

R a t h e r than t r y to define that

p a r t i c u l a r concatenation of p r o p e r t i e s of a m o l e c u l a r s y s t e m which
might be acceptable to everyone a s living, I would ratherlecognize
the difficulty of satisfying everyone, and simply take two of the qualities
which everyone will a g r e e a r e c e r t a i n l y basic a t t r i b u t e s of a living
s y s t e m and t r y to d e s c r i b e the sequence of events which might have
produced them f r o m nonliving origins.
'l'hese two p r o c z s s e s which I think mosl, if not a l l of u s , would
a g r e e upon a s being p e r q u i s i t e s of present-day living s y s t e m s a r e
( 1 ) t h e i r ability to t r a n s f a r and t r a n s t o r m energy in a directed way
and ( 2 ) t h e i r ability to r e m e m b e r how to do this, once having l e a r n e d

it, and to t r a n s f e r o r communicate that information to another e y s t e m

like itself which it c a n c o n s t r u c t .

H e r e w* have, then, two of the p r i n c i -

pal p r o b l e m s of the biologist trying to underetand a living o r g a n i s m in

molecularr t e r m e .

These a r e , r e s t a t e d : (1) The t r a n e f e r and t r a n e -

f o r m a t i o n of energy and (2) the communication and t r a n s f o r m a t i o n of

In the l a r g e r s e n s e , I suppose, the second ability includes

information.
the f i r s t .

The genetic information contains not only the d i r e c t i o n s f o r

the construction of new o r g a n i s m s but f o r t h e i r function as well, and

i t i s rhis function which i s l a r g e l y a m a t t e r of e n e r g S f r a n s f e r and

transformation.

Wlolecular C o n s ~ r u c t i o n
In any c a s e , the rriaterials of which the living o r g a n i s m i s cons t r u c t e d a r e known

KO

us ( o r a t l e a s t a good m a n y of

hem a r e ) , and one

of the c h a r a c t e r i s t i c s of these m a t e r i a l t , iu the e c s e n t i a l r e q u i r e m e n t

that they be constituted, a t l e a s t in parL, of polymeric molecules in o r d e r
that the information s t o r a g e and t r a n s f e r Le possible. i'he energy t r a n s f o r m a t i o n a s well s e e m s dependent upon such n i a c r o m o l e c u l a r , o r pseudocrystalloidal, structures.

L u r evolutionary problem c a n now be deflned

in m o l e c u l a r Lermb a s the devising oi p r o c e s s e s which will no1 only give

r i s e to the simple m o l e c u l a r s t r u c t u r a l components of living things and,
i n addition,

LO

nlac rorriolecules associated with them, but to their

functional relationshipa, that i s , energy t r a n s f o r m a t i o n relationships,

a s well.

The

ITIOSL

common e l e m e n t s of the universe, namely, h m o g e n , carbon,

oxygsn and nitrogen, a r e a l s o the m o s t common o n e s in t e r r e s t r i a l living

o r g a n i s m s , and some relationship between t h e s e a t o m s , the biologically
i m p o r t a n t molccules and the p o l y m e r s derived f r o m them is shown in
F i g u r e 1.

The chemical bonds which must be c r e a t e d i n o r d e r t o m a n u -

f a c t u r e the simple m o l e c u l e s r e q u i r e d f o r the c o n s t r u c t i o n of living

o r g a n i s m s , such a s a m i n o a c i d s , s u g a r s , purine-pyrimidine b a s e s , fatty
and hydroxy acid, and the l i k e , involve a wide v a r i e t y of types ( s e e
F i g u r e 1 and F i g u r e 3 ) . T h e s e include C-H, N-13, 0 - H , C-N, C - 0 , C - N,

C - 0, and perhaps o t h e r l e s s widespread types. The s t e p f r o m the s i m p l e

m o l e c u l e s to the polyrriers a p p e a r s t o be p r i m a r i l y of a single type,
namely, the formation of e i t h e r a C - v o r C-I< (and possibly a P-0)
bond with a concomitant l o s s , o r zliminatiun, oi. a water molecule;
w e s h a l l come back to t h i s r e m a r k a b l y unllorm rdaction l a t e r .

T h e catalytic and e n e r g y t r a n s f e r r i n g functions which today a r e s o

highly efficient weri: p r e s u m a b l y evolved in the s a m e m o l a c u l e s and by
s i m i l a r m e c h a n i s m f r o m the v e r y primitive e n e r g y t r a n s f e r r i n g and
catalytic functions oi

ha p r i m e v a l molecules and ions p r e s a n t in the

f o r m a t i o n of the e a r t h itself.

12

ATOM

MOLECULE

POLYMER

Hydrogen

Amino Acid --,

Carbon

Sugar

Cellulose, Starch ,etc.

0 xygen

Base

[~ucleicAcid

N itrogen

Acid

Lipid

F i g u r e 1. Schematic representation, in chemical t e r m s , of the

set of transformations which have to be accomplished from the
atoms to produce the s t r u c t u r e of the cell.

The Time Scale and the Stacting Material

W e mut now turn to the question of the starting material that was
available to ur and the time available to achieve the transformation0 from
that starting m a t e r i a l into the forms we now recognize.
The time available since the formation of the e a r t h s e e m s to be
something of the o r d e r of 4 . 5 to 5 billion years, and the logarithmic

chart, w~::A ~omebenchm a r k s on i t , i s shown in Figure 2.

It i s in-

tere*.ting to note that the period marked Chemical Lvolution, p r e s u r n ~ b l y

Leginning with the formation of the e a r t h in i t s present; shape, and the
period marked Organic dvolution, beginning with the appearance of rnolec u l a r syetems which w e would call alive, a r e shown to overlap in the
region of 2 billion years ago, roughly halfway through the age of the
earth.

A n interesting calculation can be m a d e conczrning the two

stages of evolution which might be separated ac such a point. The earliest

stage of Chemical Evolution leading up to the appearance of the f i r s t micellular organisms would thus occupy some 2. 5 billion y e a r s . The
climb from the prirritive

unicellular organisms to the modern mulri-

cellular organisms required the remaining 2 billion years.

T h e r e i s now m o r e reason f o r thio particular division than was o r i ginally a t hand when it was made.

It now appears that unicellular o r -

ganisms resembling blue-green algae in form havj been found in 6Lrata

whose age i s not l e s s than

.7 billion years.

13,14

UCRL-10424

IN
MILLIONS
OF YEARS

GEOLOGIC
ERA

EVENTS

Earliest Vertebrates
Earliest known Fossils
(Cambrian)
Organic Evolution

Chemical Evolution

Formation of the
present earth

5000

Figure 2.

Genesis of the Universe

T i m e s c a l e for t o t a l evolution.

An e s t i m a t e of the complexity of the unicellular system might be

made i n t e r m s of the number of molecules that have to be organized to

produce one.

Roughly this amounts to l o l o molecules for a cell of

approximately one m i c r o diameter.

Noc all of these molecules are

different, that i s , some of these l o 1 molecules would be made up of a

much s m a l l e r number of different v a r i e t i e s .

A s i m i l a r calculation f o r

the next transition f r o m the unicellular level to the intelligent organism

such as m a n gives a corresponding number of c e l l s in the whole organism,
again lo1'.
10"

So i t i s not surprising that the time r e q u i r k d to organize

moleculen into a single cell and the time to organize 101 c e l l s

into a full-fled ged lrrssl

should have been rough1.y the same o r d e r of

magnitude.

The evolution of highly efticient mechanism for the storage and

t r a n s f e r of information (and energy conversion) took place during the
f i r s t phase of this evolutionary time sequence and was dependent upon
the properties inherent in the macrorrlolecules (nucleic acids, proteins)
which a p p e a r e d during that period.

Similarly, the evolution of effi-

cient mechanisme for the control and ordered'development of the information contained in the t r a n s f e r r e d molecules w a s based upon the propertiea

of the information t r a n s f e r r i n g system itself, and proba liy took place

l a r g e l y during the second period, giving r i s e to all the phenomena of
growth and differentiation of multicellular o r g a n i s m s as w e know them

toddy. This r e q u i r e s , of course, that such control mechanisms were alr e a ry inherently present, even in the unicellular organisms.
iVhile we have developed, in the past decade, a m o r e o r l e s s consistent understanding of the nature of information t r a n s f e r on a molec u l a r basis, we a r e only just beginning to understand the way in which
that information manifests itself i n growth. development and differcntiation of c e l l s and t i s s u e s on a molecular basis. This seeme to be a problem
of molecular communication of the nucleus of the cell (the information
storage vault with its environment through the intermediary of the cytoplamic constituents ( s e e F i g u r e

1 7 ).

It i s quite obvious that an

understanding of the mechanism of this communication problem i s of

g r e a t importance to u s

f o r practical a s well a s philosophical reasonra.

W e now r e t u r n to the question of the natuleof the actual organic

s t a r t i n g m a t e r i a l s f r o m which all this was derived.

P e r h a p s the simplest

way to begin w i l l be to recognize that the primeval e a r t h had accumulated

i n i t , o r on it, the very s a m e organic m a t e r i a l s which a r e widespread
throughout the s o l a r system and the galaxy a s well, namely, the very
s i m p l e s t compounds of carbon, hydrogen, oxygen and nitrogen. 15,16
It is presumed that these were l a r g e l y dominated by hydrogen and,
t h e r e f o r e , were generally in t h e i r most reduced f o r m s .

These m a t e r -

i d s a r e represented by the molecules in the top row of Figure 3 and

the molecules with which we have to work a r e thus methane, ammonia,
water, and a l a r g e amount of hydrogen, and perhaps some c a r b o n
monoxide and carbon dioxide.

U C R L - 10424

HI

H-o
Water

H-CIN

O=C=O
Carbon
dioxide

Q
It
H-C-OH

H ~ d r m ~ a n i c Formic acid
acid

'?

H-6-H
I

H
I
H

Methane

Hydrogen

N-H

H
H - ~ O HOCH2-C=O
Formaldehyde

Glycolaldehyde

Ammonia

CH3-C-OH
Acetic acid

NH2
Succinic ocid

Glycine

Alanine

""'2
Aspartic acid
MU-16089-A

Figure 3.

P r i m e v a l and primitive organic molecules.

Enerev Sources

In o r d e r f o r these molecules to undergo t r a n s f o r m a t i o n s , a s o u r c e

of energy m u s t be provided, and h e r e we have a wide v a r i e t y to choose
f r o m . The sources.of e n e r g y and t h e i r possible availabilities are shown
17

in Table 1.

The principal s o u r c e of e n e r g y that could be u s e d by such

TABLE
I-ENERGY

AVAILABLE FOR S Y N T H E S I S O F ORGANIC

COMPOUNDS
Energy
(in 10" cal/yr)

Sowcc of Energy

1)ecay of K4"
in earth's crust a t present
1)ecay of K"' in earth's crust 1.3 x 10" years ago
Decay of I<"' in earth's crust 2.6 x 10" years ago
U!traviolet light of wavelength below 1500 A
Ultraviolet light of wavelength below 2000
L!ltraviolet light of wavelength below 2500 X
I-ight~~i~~g

a n aggrzgation of r r i o l e c u l e ~secrris to ~e 1l;ht

o r shorter.

3adioactivity i n the e a r t h ' :

o i w a v e l e n g ~ hof

2000

c r u s t , e l e c t r i c d i s c h a r g e s in

the a t m o s p h e r e and cosm-ic radiatio,i a r e secondary and t e r i l a r y sources

of e n e r g y f o r t h e s e t r a n s f o r n a t i o n s as w e l l .

At this stage i n o u r knowledge of the c h e d c a l transformations induced

by such high energy radiations, including ultraviolet, the r e does not

appear to be any q a r k e d s y s t e m a t i c difference between the proclucte

from one type of high e n e r g y radiation and those of another, a t Peast
among theas.

And so we will c a l l equally upon experiments which have

been performed with a l l of these energy s o u r c e s .

Initial Transformations
The e a r l i e s t etxperimenta designed to t e s t the notions h e r e introduced w e r e done using a high energy alpha particle beam on the cyclotron

and ware reported in 1951.

H e r e i t was shown chat carbon dioxidi dia-

solved in water and i r r a d i a t e d in the presence of f e r r o u s iron and hydrogen could produce a variety of reduced carbon compounds, including f o r maldehyde and f o r m i c acid.
Since then s i m i l a r experiments have been performed with other
energy s o u r c e s with the same s t a r t i n g m a t e r i a l s and demonstrating not
only that particles but ultraviolet light

1U

reduced carbon under these conditions.

and gamma rays19 can produce

ladn next m a j o r

s t e p was taken

when Miller introduced ammonia into these reaction s y s t e m s , together

with reduced carbon in the form of methane.

Here the energy source

was e l e c t r i c discharge, and M i l l e r was able to dsmonstrate very c l e a r l y

the appearance of amino acids a s m a j o r products under such conditions.
Ultraviolet light has been used f o r a s i m i l a r demonstration.

20

Y,10

The p r e s e n c e of HCN was i n f e r r e d f r o m the appearancz of anrill:,

acids in Miller's e a r l y experiments.

Its quantitative demonatration w d -

achieved in a n e l e c t r o n bombardment of a s i m i l a r m i x t u r e of methane,

ammonia, hydrogen.and water.

21

'The i m p o r t a n c e of HCN as a n e a r l y

product in these r e a c t i o n s a r i s e s f r o m the r e c e n t demonstration of

the formation of adenine when a n ammoniacal solution of I3CN i s allowed
to stand. 22'23 A v a r i e t y of o t h e r biologically i m p o r t a n t simple molecules

haia s i n c e been d e m o n s t r a t e d to a r i s e in solutions of ammonium cyanide

under v e r y m i l d conditions.

24,25

Thus we see that the molecules of the

p r i m e v a l e a r t h shown in the f i r s t row of F i g u r e 3 can v e r y readily be

and i n fact have been

--

-- t r a n s f o r m e d into the p r i m i t i v e o r ~ a n i cm o l e c d e s

shown i n the second r o w , by any of the energy s o u r c e s which w e know to

have been available.
Not only c a n we g s n e r a t e important biological n ~ o i e c u l e u , such a s
amino a c i d s and purine and pyrimidine b a s e s , f r o m HCN and o t h e r s of
these s i m p l e m o l e c u l e s by b a s e c a t a l y s i s , but the s u g a r e themselves are
now v e r y e a r i l y d e r i v a b l e , again b y base c a t a l y s i s , from
g e n e r a t e d by the methods just d e s c r i b e d .

he formaldehyde

I t h a s long been known that

the t r e a t m e n i of aqueous forrnaldehyde v ~ i i hl i m e o r limesrone will produce

a m i x t u r e of c a r b o h y d r a t e s which has bean given the name formose ( f i gure 4).

M o r e recently, this reaction has been examined with modern

analytical tools and the p r e f e r e n c e for c e r t a i n s u g a r s and s u g a r configurations h a s been d e m o n s t r a t e d . 2 6 a L7

'That such f o u r - , f i v e - , s i x - ,

C =O
LH20H

F;WH
C=O

LHOH
hI-l20H

*
CH20H
I
C=o
~HOH

AHOH

&+OH
A

-7

CH20H
I
C=O
~HOH

~HOH

AHOH
I

C
\

CH20H

-,

I'
K=O
~HOH

AHOH
LHOH
&H$H

I,

F i g u r e 4. Route t o c a r b o h y d r a t e s a s a r e s u l t of t r e a t m e n t of
f o r m a l d e h y d e with l i m e o r l i m e s t o n e .

HC=O
1

CHOH

AHOH

~HOH

AHOH
I

CH20H

and seven-carbon s u g a r s m a y be generated d i r e c t l y by electron bombardment

of the methane -ammonia-water -hydrogen s y s t e m was shown by comparison

of radioautographs of tha products of such an i r r a d i a t i o n using c

with the products of l i m e treatment of formaldehyde i s shown i n F i g u r e

5.

21

That a wide variety of other ccrrrmpounds a r e a l s o f o r m e d under these

conditions has been demonstrated and is spectacularly evident in a radioautograph of these products shown in F i g u r e 6.

Most of these d i s c r e t e

s p o t s have not yet been identified. The analysis of such a mixture is

given i n T L ) b l e2.

A distribution of products resulting from the sparking

of methane-ammonia-water-hydrogen m i x t u r e taken f r o m ~ i l l a r ~i s'

shownin Table 3.

T A ~ I2-F II)ESTIFICATION OF C O M P O U N D S FROM I R R A D I A T I O N

ESI'I'HIBIEST FROM C l i - L A B E L E D M E T H A N E ,
AMMONlA, A N D W A T E R
Experiment M22 "CH,, XH,, H1O, P H , ( N I I , P O , ) x
Acid fraction
Basic fraction
Nonionic fraction

.-

45.5%
17.44%

--

21.3%

separation on Dowex 1
and L)owex 50
-

0.45% of total
0.203% of basic fraction
0.03470 of total
0.105~%
of basic fraction
0.01870 of total
2.21% of acid f r a c t m
Lactic acid
0.99% of total
Tlic I?LW urihwwn other dominating acids (not including lactic) accomt ior 2'1%
a ~ ~17.8%,
tl
res11ectively, of the acid fraction.
0.2% of basic fraction
Glycine
0.0370 of total
1.07% of basic fraction
a-Alanine
0.18% of total
0.2%
of basic fraction
Aspartic acid
0.03% of total

The hc*ou ~ ~ k n o w(not

n urea or guanidine) dominating basic compounds (ninhydrin
positive) account for 20.!)70 and 11.9% of the basic fraction.

U C R L - 10424

F i g u r e 5. N e u t r a l f r a c t i o n of e x p e r i m e n t s M30 a n d M31 i n
c o m p a r i s o n to " f o r m o s e " f r o m f o r m a l d e h y d e and CaO.
Solvent: ethyl a c e t a t e - p y r i d i n e - w a t e r 10:3:3.

UCRL- 10424

F i g u r e 6. R a d i o a u t o g r a p h of c h r o m a t o g r a m of n o n v o l a t i l e
r e s i d u e of e x p e r i m e n t M 2 2 . 2 1

'TaLle 3.

5
Yields in m o l e s (x10 ) f r o m s p a r k i n g a rnixiure or' C H

4'

N H 3 , H 2 0 and Hz. 710 rng of carbon w a s added a s CH

4'

Gly-;
~,ne

63

Succinic acid

Glycolic acid

56

A s p a r t i c acid

0.4

Glutamic acid

0.6

Yarcosine
Alanine

34

Iminodiacetic acid

5.5

Lactic acid

31

Iminoacecic-propionic acid

1. 5

N -Methylalanine

233

Forrriic acid

4 -Amino-n-butyric a c i d 5

Acetic acid

i5

,A-Aminoisobutyric acid 0 . 1

Propionic a c i d

13

.-A-Hydroxybutyric a c i d

f -Alanine

15

Urea

2.0

N -WJ ethyl u r e a

1.5

It is thus quite c l e a r that any of t h e s e high e n e r s y radiation s o u r c e s

o p e r a t i n g on the p r i m e v a l m o l e c u l e s of the e a r t h ' s s u r f a c e can and do

produce the s i m p l e o r g a n i c m a t e r i a l s , including m a n y new c a r b o n c a r b o n bonds, f r o m which ;he polymeric m a t e r i a l s m a y t h e m s e l v e s u l t i m a t e l y be d e r i v e d . 'These s i m p l e m a t e r i a l s include amino acids, c a r b o h y d r a t e s , purine-pyrimidine b a s e s , fatty acida, hydroxy a c i d s , a l c o h o l s
a n d the like.

It ie f r o m t h e s e , now, that we mu st begin

LO

build both

the m o r e selective c a t a l y t i c agents r e q u i r e d f o r the m o r e e f i i c i e n t e n e r g y

t r a n s f o r m a t i o n a s well a s the m a c r o m o l e c u l e s which help in thie proceeP
and which a r e e esential f o r information s t o r a g e and communication.

The evolution of catalytic syeteme, such a s the iron porphyrins, has

bean discussed in some detail eleewhercs.

Suffice it to say that there is

ample evidence for the gradual selection by autocatalytic mechanisms of

increasingly m o r e efficient catalytic eyetems.

Notable among those

is, of course, the ability of iron in various chemical combinations to

a c t as a catalyat f o r a wide variety of redox reactions. The evolution
of the i r o n porphyrins undoubtedly took place by a n autocatalytic responsa
to the need f o r such redox catzlyats, particularly resulting from the gen-

e r a t i o n of hydrogen paroxids, and poseibl y oxygen, by the high energy

radiation decomposition of water, and the escape of hydrogen.

Polymerization
One of the outstanding characteristic a of living organisms has often

been described a s the high degree of organization which they show, and
this particularly in t e r m s of the specific macromolecule^ of which they
a r e constructed. The formation of all of these macromolecules, specified
i n the polymer column of Figure 1, involves the s a m e reaction, namely,
the condensation of two simple molecules with the elimination of water

between them.

&'hen such molecules a r e polyfunctional, that i s , have

two functional ends, they can do this at both ends.

It i s clear that a

polymer results. The essential feature of each of these reactions i s ehown

in Figure 7. The formation of lipid indicated on Figure 1 but not shown

on F i g u r e 7 is a simple esterification reaction involving t h e elimination

U C R L - 10424

PROTEINS

NUCLNC

ACIDS f 3 STAGES) RNA

POLYMER

SHOWN - DNA

LACKS

OH

ON

2'

POS/T/ON

y42

POLYMER

F i g u r e 7.

Dehydration r e a c t i o n s leading t o b i o p o l y m e r s .

of water b e t w ~ e sa fatty acid ~abrboleylerrad glysesut alcohol group.

we

have already seen how the m o n s m ~ s i srnrhrid@required for the con-

struction of thase polymerrs may be f ~ m d

In

recent year@i t

has been poeefbh to dsmonstrate the direct non-

waapatlc dshydrstion raaction in all of t h e m eystmno to produce polym e r s , At firot these roactiono ware c a r r i e d out In nonaqueouer media,

but more recently they have been aucceaeful even in water, and it is the
tsargants which are capable: af doing thia which we muet eeek, since these

are tbe

v a r y reactions which today are functioning in tbe living arganiem.

The principal agent f o r these dehydration reactions in the modern

organitam i e the pyrophoaphatf~linkage (at leaet this i s the one we lcnqw

today), generally in the form of adenosine triphoophate. T h e accumulation

af palyphosphcaric acid and its derivativae in simple organirma ruch as

a& p a s t @ ' i s also v a r y eugpeetive.

Some years ago For was

able to demanetrate that the formation oi polypaptidea in a mixture of

molten amipo acide with e x c e a e glutamic acid was enhanced by the

preeancrr of phoephoric anhpdr ide 32' J3 More recently, a still milder

i s t of condition5 w a s devised by Schrarnm, which waa able to scconiplieh

tMr dehydration, using a derivativa of phoephoric anhydride m a d e with

&ethyl ether,

34

'This reagent, whose structure i a as yet nat known, might

very well be a di- o r tetra-ethyl e s t e r of tetrapdyph~sphatcaderived from

p5v'40io)*a s ahown in Figure

8. Schramm has uassd this reagent

" POLYPHOSHATE ESTER"

( First

Stage)

F i g u r e 8. F o r m a t i o n a n d p o s s i b l e s t r u c t u r e of "polyphosphate
ester. "

not only to make polypeptides i r o m amino acids but to dehydrate oknple

monosaccharideti to produce polysaccharides and, finally, to induce a
oequence of t h r e e dehydration reactiona, shown in the bottom of Figure

7, leading f r o m the purine baee, into rugar, all the way to the polynucleotidse.

As yet, the high polymers and the efficient reactiona have

only been achieved in nonaqueous media such a s dimethyl fonnamide.

Still another route to polymers in aqueous salution has recently
been demonstrated by Markham and his associates for polypeptides.

24

Although the polymerization of HCN in a n aqueous ammoniacal solution

ha8 long been known, it remained for the stimulus of questions such a8 the
ones we have discussed Lo show not only the presence of purine and
pyrimidine bases, as well a s amino acids, i n such a reaction mixture,
but still m o r e recently the demonstration of polypeptides a s well. 2 3 . 2 4 , 35
That this was indeed a polymerization of preformed amino acids was demonstrated by adding labeled amino acids to the polymerization mixture
and finding them in the polyrne r s

W s can thus formulate still another dehydration mechanism involv-

ing the u s e of HCN a s the dehydrating agent which would be analogous to

the use of the carbodiirnides for the same purpoeo (Tigurc 9). 36 It w i l l
be interesting to watch the development of our knowledge of modern bio-

logical s y s t e m s to s e e if any such dehydration mechanisms as this a r e

found among them.

The p r i m i t i v e o r i g i n o f t h e s e d e h y d r a t i n g a g e n t s i s r e a d i l y u n d e r stood.

Vie h a v e a l r e a d y s e e n t h a t HCN i s o n e o f t h e p r i n c i p a l p r o d u c t s o f

t h e i n t e r a c t i o n o f h i g h energy r a d i a t i o n with t h e primeval t e r r e s t r i a1

atmosphere.

I t i s a l s o w e l l known t h a t any a q u e o u s p h o s p h a t e s o l u t i o n

which i s a l l o w e d t o d r y a t t e m p e r a t u r e s a p p r o a c h i n g 100' C g i v e s r i s e
t o t h e f o r m a t i o n o f a p o l y p h o s p h a t e which i t s e l f i s n o t e x t r e m e l y r a p i d l y
h y d r o l y z e d upon r e d i s s o l v i n g .

I t i s t h i s r e s i : , > ~ . : c ct o i m m e d i a t e h y d r o l y s i s

w i t h w a t e r o f b o t h t h e p y r o p h o s p h a t e and t h e c a r b o n - n i t r o g e n m u l t i p l e
bond which g i v e s r i s e t o t h e i r s p e c i f i c a b i l i t y t o c o u p l e monomers w i t h
t h e absorption o f water.

UCRL- 10424

POLY - +PEPTIDES et,.

I1

H2N-CH-C-NH-CH-C02H
I

'?I

R2

-H+

0~9-NH2-F;H-C02H
H2N-C-H
I
R2

Figure 9. Possible mechanism of peptide formation with

HCN a s dehydrating agent.

GENERATION OF ORDXR AND N E W IFJFOfU/lhl'IiiIu'

Perhaps one of the m o s t outstanding c h a r a c t e r i s t i c s of ihe two

biopolymers with which we a r e dealing, namely, the proteins and the
nueleic acids, i s the f a c t that once having been put together they have in
t h e i r very structural relationships the intrinsic ability to a r r a n g e themaelvee in a highly o r d e r e d a r r a y . 'This arrangement is completely
analogous to the crystallization of small molecules out of solution.
However, in the case of the polymers it does not involve a precipitation from ~ o l u t i o nbut eimply an arrangement i n a very highly ordered
a r r a y of the long polymeric chain in which the individual units stand in a
v e r y specific and pseudocrystalline a r r a y with respect to each other.

In

the c a s e of the polypeptide this a r r a y tends to be a helical one which i s

stabilized, a t l e a s t in p a r t , by the formation of hydrogen bonds between the
amide hydrogen and the amide carbonyl several peptide residues removed. 37
This structure i s shown in Figure 10, and the demonstration that this
s t r u c t u r e i s spontaneously formed may be made in a variety of w a y s .
such demonstration may be done with

a,

One

synthetic polymer whose m i c r o -

s t r u c t u r e i s completely known, namely, polyglutamic acid.

aaey to show that when the carboxyl groups at the ends
represented in Figure 10 by R1, R2, ecc.,

Q% the

H e r e it i s

si

are all ionized by adjusting

the pH to something above 7, the electrostatic repulsion of the

ends is sufficient to overcome the organizing force of the helix, and the

U C R L - 10424

I----------

RI

R2

1
-N-!-c-N-!-c-N-4-c-N-!-CON
I
I
I I I 1111
0
II

I H H O I H H

F i g u r e 13.

R4

R3

0
II

Protein structure.

helix ie destroyed.

When the side chain carboxyls a r e neutralized, a t

pHte below 5, the helix can reform, and these two states a r e reflected
i n a variety of properties, among them the absorption spectrum ( F i g u r e
1 1). 38 When the helix i s formed. the paptide linkages interact with
each other, giving r i s e to decrease of absorbance and splitting into two
bands, which show very clearly in the curve below pH 5.

A s i m i l a r molecular crystallization phenomenon occurs in the

polynucleotides and m a y be demonstrated again by a wide variety of
methods, of which I will h e r e only use one, namely, the change in a b sorption spectrum when the polymer i s ordered, a s opposed to when it i s
disordered.

Here the transition between o r d e r and disorder is a l s o

reversible and has been achieved by a change in temperatures ( F i g u r e

12).

The curve at 9 9 . 4 O ~shows the absorption primarily of the purine-

pyrimidine bases when t h e r e i s relatively little interaction between them,

a s would be the c a s e in the bases alone.

When the temperature i s lowered,

the helical configuration i s reformed, and the absorption decrease i s

shown by the absorption at 2 2 . 8 ' ~ . 'I'his decrease in absorption upon
assuming the helical configuration, due to the interaction of the bases
with each other lying in parallel planes, i s known a s hyperchromism and
has recently been used a s a m e a s u r e of the degree of o r d e r in a particular
eample. The polynucleotide system, however, han in it not only the tendency f o r intrinsic o r d e r in the form of the helix, but because of the
nature of the bases and the geometry of their hydrogen bonds, i n t s r -

U C R L - 10424

TINOCO, HALPERN ond

SIMPSON, 1962

76-

0
*

=-

POL YGL UTAMIC

A CID

4-

E
k J

3-

2-

F i g u r e 11. Absorption s p e c t r u m of polyglutamic a c i d in both

h e l i c a l and r a n d o m coil f o r m s .

Random Coil
( t = 99.4OCj

SPECTRUM OF NATl VE
CALF THYMUS DNA uno

F i g u r e 12.

H y p e r c h r o m i s m on nucleic acid.

dction between them gives r i s e to a specificity in rhe p z i r i r ~ ~

"1 ,

L,L-

bases as shown in F i g u r a 13 in which thymine p a i r s with i i ~ e n i n eand

cytosine p a i r s with guanine.

'This b a s e pairing ~ p e c i f i c i r y ,together

with the i n t e r a c t i o n s responsible ior the helical structure, give r i s e

to the principle of complemenrary b a s e s t r a n d s of nucleic acid upon w h i c h
the whole s t r u c t u r e of bioreplication i s b a s e d . 3 Y *40 Thus in F i y r e 14
the s t r a n d on t h e l e f t induces the formation of the complementary
s t r a n d , on the right, which, in turn, gives r i s e to the original s t r a n d .

This type of m o l e c u l a r communication c a n thus account f o r the reproduction

of m o l e c u l e s belonging t o the s a m e c l a s s , such a s c h r o m o s o m e duplication involves. This influence of a p a r t i c u l a r base sequence on i t s own
replication h a s long s i n c e been d e m o n s t r a t e d in the r e q u i r e m e n t of the
enzymatic s y n t h e s i s of deoxyribonucleic acid (DNA).

*'

f o r the p r o -

eence of a p r i m e r D N A molecule which not only provides the i n f o r m a t i o n

r e q u i r e d f o r the s y n t h e s i s of the new sequence but a l s o catalyzes i t .
A s i m i l a r r e l a t i o n s h i p h a s been d e m o n s t r a t e d f o r ribonucleic

a c i d (RNA) r e p l i c a t i o n on a D N A template ( m e s s e n g e r R N A ) .

4L,43

In f a c t , the c a t a l y t i c and information control of the polymerization o f

b a s e s to produce a polynucleotide h a s even been demonstrated in t h e
nonenzymatic p o l y m e r i z a t i o n of uridine phosphate in the p r e s e n c e of
polyadenylic a c i d ; this i s shown in F i g u r e 15. 3 4 H e r e , again, I think
i t i e e a s y to see how p r i m i t i v e catalytic

and information

t r a n s f e r s y s t e m s on a m o l e c u l a r level m a y be evolved by a p r o c e s s

U C R L -10424

F i g u r e 13.

M o l e c u l a r d r a w i n g of c o m p o n e n t s of DNA.

U C R L - 10424

c-p\sugar -T

c
sugar -G
\

...H... A - s u y x
\

pl

...H... C- sugar
'P
p\
c sugar -G ...H... c - sugar
\P \
'P
r sugar - A ...H ... T - sugar
'P
'P \
c
sugar - C ...H... G - sugar
\
'P
p\
sugar -C ...H ... G - sugar

>
>

F i g u r e 14. B a s e p a i r i n g f o r DNA r e p l i c a t i o n a n d R N A t e m p l a t e
formation.

Schramm e t

a l . , 1962

F i g u r e 15. P o l y m e r i z a t i o n of uridine monophosphate in the p r e s e n c e ( A ) and i n the a b s e n c e ( B ) , of polyadenylic acid. (The

d e c r e a s e of f r e e uridine monophosphate was m e a s u r e d c h r o matographically).
A b c i s s a : Time ( h o u r s )
70f r e e uridine monophosphate ( r e f e r r e d to the
Ordinate:
amount of s t a r t i n g m a t e r i a l ) .

of m o l e c u l a r scleccion, just a s we! have s u g g e s t e a i t s u c c s r r ~ n c ai ~ :

...

e n e r g y t r a n s f e r catalytic s y s t e m s .
The question of the r e l a t i o n s h i p between the linear sequences a i
b a s e s i n a nucleic acid and the l i n e a r sequenca of amino acids i n thz
protein, as shown in F i g u r e 16, i s s t i l l with u s .

Ilowever, a g r e a t

deal of p r o g r e s s h a s been m a d e toward rhe elucidation of that m o l e c u l a r

communication problem in r e c e n i m o n t h s .

14,45,46

A sequence of evsr;:,

as i t now s e e m s to take place i s i l l u s t r a t e d in Figure

by the reaction sequences f r o m 1 to 1 I .

ii'

The essential. recognition fiiep

which involves the c r o s s -over between tne two types of polymers is

Step 6 in which the active amino a c i d is hung on one of the specific
t r a n r f e r RNA1s, having a different and specific

base

- - presumably t h r e e

-- sequence corresponding to a a c h amino acid,

Group 8 of F i g u r e 17.

a s shown i n

All the r e m a i n i n g cornrnunication steps involve

b a s e p a i r i n g of e i t h e r DNA o r RNA.
vv'e a r e only just now beginning to understand the m e c h a n i s m s by

which the nuclear DNA which gives r i s e to the m e s s e n g e r RNA (Step 2,

RNA template, F i g u r e 17) i s c o n t r o l l e d .

This control mechanism is

d i a g r a m a t i c a l l y r e p r e s e n t e d in the upper left hand c o r n e r of F i g u r e 17,

according to the t h e o r i e s of J a c o b and Munod.

47,48

'The e s s e n t i a l f e a t u r e

h e r e i s the m e c h a n i s m provided for the interaction of m a t e r i a l s f r o m

outside the c e l l with the genetic a p p a r a t u s in the nucleus via inducer o r

U C R L - 10424

PROT E IN

NUCLEIC ACID

A - sugar
\

l
C- sugarp
'P
c - sugar
'P
T- sugar
'P
G - sugar

>

1
1
P'
G -sugar 1

F i g u r e 16.

S t r u c t u r e of p r o t e i n a n d n u c l e i c acid.

U C R L - 10424

r.

CELL

INDUCER
OR

\\

TEMPLATE
RNA

RIBOSOME
11

/o
f--------

PROTEIN,
ENZYME, etc.

RNA

F i g u r e 17.

c o - r e p r e s r o r acting with tho repreeoor oubotance which appears i n the

cytoplasm.

Preournably it i s through ruch mochmismo a e this that the

f i r s t and obvioue external e f f e c t s of what appear to be genetically controlled processes m a y be found. It m a y be that the thalidomids effect
on tho growth and differentiation of human embryos a s well a s the morls
longmtanding problema such o r drug addiction and the long t e r m effects of
imecticidee will ultimate1 y be understood in theae termn.

The Next Level of Organization

Just as the o r d e r e d a r r a y observed in the structura of the polymer
waa dependent upon the monomers of which it i s made and their a r r a n g e -

ment, so the o r d e r in which polymere m a y themselves be organized is

built right into the s t r u c t u r e of the polyrnero.

Here, however, we a r e

on l e s s clearly defined chemical and structural grounds and much m o r e hoa

yot to ba done before we will understand i t s detailed mechanismm.
that such fa the case i s amply demonstrable.

However,

F o r example, a eolution

of protein molecules made from collagen can be reprecipitated by eimply

adjueting the medium to produca large aggregates of these molecules
oarily visible in an electron microscope which have a structure indistinguishable f r o m the original cullagan fibrils (Figure 18). Similar
ltcrystallization" phenomena may be obtrerved with other shaped moleculrs

on a somewhat higher level; for example, the crystallization of virumes,

both of the rod and epherical type.

U C R L - 10424

FILAMENTS OF COLLAGEN, a protein which is usually found

in long fibrils. were dispersed by placing t h e m i n dilute acetic

FIBRILS O F COLLAGEN formed spontaneously out of filaments

a hove
surh 08lhose ehown
when 1 per cent of sodium

acid. This elertron micrograph, which enlarges the filamen~z75.000

times, was m a d e by Jerome Gross of the Harvard Medical School.

chloride was added to the dilute nvetir arid. TIlrrc long fihrils are
identical i n appearance with thosc of coll;i~enbrlore dirprrsion.

F i g u r e 18. S t r u c t u r e of collagen. Top: f i l a m e n t s of collagen,

a p r o t e i n which i s usually found in long f i b r i l s , w e r e d i s p e r s e d by placing t h e m i n dilute a c e t i c acid. This e l e c t r o n
m i c r o g r a p h , which e n l a r g e s the f i l a m e n t s 75,000 t i m e s ,
was m a d e by J. G r o s s of the H a r v a r d Medical School. Bottom: F i b r i l s of collagen f o r m e d spontaneously out of f i l a m e n t s such a s t h o s e shown above when 1% of sodium
chloride was added t o t h e dilute a c e t i c acid. T h e s e long
f i b r i l s a r e identical i n appearance with those of collagen
before dispersion.

Something r e s e m b l i n g this c r y s t a l l i z a t i o n of s p h z r i c a l v i r u s a s
a p p e a r s to show in the visible s t r u c t u r e s which can be s e e n in :he plant
49

c h l o r o p l a s t e ( F i g u r e 19). H e r e i s a viaible o r d e r e d a r r a y of p a r t i c l e s ,
e a c h about 200 A in: d i a m e t e r .

Whether this s t r u c t u r e c a n be r e c o n s t i -

tuted f r o m the s e p a r a t e d p a r t i c l e s r e m a i n a yet t o be d e m o n s t r a t e d .

The relationship between the energy converting a p p a r a t u s which the
plants uee t o tranraform light e n e r g y and the energy convercing a p p a r a t u s
which both plants and a n i m a l s m e f o r converting chemical e n e r g y i s
c l e a r l y ehown in F i g u r e 20 in which a r e shown both the c h l o r o p l a s t s

and the mitochondria in a single plant c d l .

That the cwo s t r u c t u r e s a r e

functionally r e l a t e d , a s well as s t r u c t u r a l l y r e l a t e d , seems c l e a r . 5 0

Both involve v e r y s i m i l a r elac t r o n transpor:: s y s t e m s , such a s the cytoc h r o m e s , flavins and quinones a s well a s their a s s o c i a t e d proteins.
M o r e recently s t i l l another molecule in this e l 3 c ~ r o nr r a n s p o r t chain

has been demonstratsci i n h;lostridiunl b a c t e r i a b y Carnahan and his

associates

51

which s e a m s to be v e r y c l e a r l y related, if not identical,

to the phoiopyridine nuclsoiide r e d u c t a s e which has been isolated f r o m

c h l o r o p l a s t s by San 13ietrc. some years ago. 52 This l a t t e r molecule
was, according t o San P i e t r o , the one responsible for the t r a n s f e r of the
initialiy photoexciced e l s c r r o n to pyridine nccleotide, and i t s demonstration
i n nonphotosynthetic o r g a n i s m s a s s o c i a t e d with hydrogen evolurion and
a b s o r p t i o n i s just a n o t h e r link in the chain recognizing the v e r y c l o s e
s t r u c t u r a l , functional and evolutionary relation between the nonphoto-

U C R L - 10424

Figure 19. Electron micrograph of "quantasomes" 5 3 from

spinach chloroplasts.

Tobacco

chloroplasts

showing

quantasomes

in

section

Weier,

F i g u r e 20. E l e c t r o n m i c r o g r a p h of Elodea chloroplasts,

showing mictochondria (Buvat).

1962

synthetic and the photosynthetic o r g a n i s m s , but on the molecular

l e v e l . A l a b o r a t o r y d e m o n s t r a t i o n of the coupling of these t w o m o l s c u l a r s y s t e m s (hydrogen and pyridine nucieotide r e a c t i o n s ) buch a s

exists naturally i n s o m e organisms ( ~ c e n e d s s r n u s has

) ~ ~been published
r e c e n t l y by Arnon and c o - w o r k e r s .
I hus

55

w e have in o u r m o l e c u l a r evolution v e r y n e a r l y r e e c h e d the

morphological and anatomical level with which evolutionary studieb have

long been concarnad.

It it; no1 diffic-dt to s e e ihat the m o l e c u l a r s e l e c t i o n

processes which w e h a m called upon to develop both the e n e r g y t r a n s f e r

and Information t r a n s f e r s y s t e m s on ~ h t molecular
:
level a r e completely
analogous co the u e l e c ~ i o nsyotenlb that have been used on the m u c h
higher l e v e l of s t r u c t u r e , and, m o r e recently of biochemical function
to d e m o n s t r a t e the n a t u r e of the svulu~icrnaryproce3s under he p r e s s u r e
of natural selection.

The Cell M e m b r a n e
fi e

cannot v e r y well ~ e r m i n a t ethe d i s c u s s i o n of chemical and

biological evolution without saying a few words relating the a a r l i e r p r o c e s s e s to the development of the c e l l u l a r s t r u c t u r e itself. The principal
r e q u i r e m e n t would seem to be s o m e m e c h a n i s m f o r the a p p e a r a n c e of a
c e l l u l a r m e m b r a n e to e n c a s e a l l the biological a p p a r a t u s which w e have
dicscussed, and much m o r e b e s i d e s .

F o r this we m u s t c a l l upon the

s a m e kinds of spontaneous s e l f - o r d e r i n g m o l e c u l a r s y s t e m s that we have

used f o r the e n e r g y and information t r a n s f e r r i n g p r o c e s s e s e a r l i e r .

However, the development of o u r knowledge of such m e m b r a n e s y s t e m s ,

both in physical-chemical t e r m s a s well a s in biological t e r m s , i s m u c h
m o r e r u d i m e n t a r y than we would like to have it.
I t i s , n e v e r t h e l e s s , = l r a a d y possible to d e m o n s t r a t e the s a m e
kind of o r d e r i n g p r o c e s s e s that have o c c u r r e d for theother two functions.

The m o l e c u l e s involved h e r e , however, a r e not water soluble m a t e r i a l s

but r a t h e r w a t e r insoluble m a t e r i a l s , o r m o l e c u l e s , which have only one
se p e n t wate P soluble, the o t h e r segment being hydrophobic and m o r e

likely to i n t e r a c t w i ~ ha s i m i l a r hydrophobic i r a g m e n i than with water.

Thie type of s t r u c t u r a l f e a t u r e i s typical of the biologically widespread
lipids which we now know to be i m p o r t a n t in the s t r u c t u r e of biological
membranes.

It h a s long been known that such bifunctional m o l e c u l e s f o r m m e m b r a n o u s l a y e r s spontaneously a t the w a t e r - a i r interface

-- f o r example,

fatty a c i d s , s o a p s , and the like. r h a t such m a t e r i a l s m a y f o r m double

l a y e r m e m b r a n e s between water and a lipid l a y e r has a l s o been established.
I would like to introduce h e r e a n example of this spontaneous m e m b r a n e ,
o r double m e m b r a n e , f o r m a t i o n , a case with which I happen to he p e r -

ona ally i n t e r e s t e d , n a m e l y , the c a s e of chlorophyll i t s e l f . H e r e the

hydrophilic porphyrin head is attached to a hydrophobic, o r lipophilic,
phytol tail, and the two together have the e s s e n t i a l element of s t r u c t u r e
which we mentioned e a r l i e r .

In f a c t , if they a r e s p r e a d out e i t h e r a t a

w a t e r - a i r i n t e r f a c e o r a water -oil interface they spontaneously take up

a n o r d e r e d a r r a y which might be thought of a s a two-dimensional c r y s t a l

l a t t i c e in the same s e n s e that the protein o r nucleic acid helix might be

called a one-dimensional c r y s t a l . 'This w a s d e m o n s t r a t e d by the change
i n absorption s p e c t r u m shown in F i g u r e 21. 56 The molecule i n a solvent

has a noticeably d i f f e r e n t s p e c t r u m f r o m the m o l a c d e formed in a l a y e r

a t a w a t e r - a i r i n t e r f a c e o r a water-oil i n t e r f a c e .

It is interesting to

nore that the s p e c t r u m of these chlorophyll lwers a t e i t h e r a w a t e r - a i r

o r water-oil i n t e r f a c e i s v e r y n e a r l y the s a m e a s the s p e c t r u m of c h l o r o phyll in the quantasorrie s and larnellae shown in F i y u r s s 19 and 20, suggasting that h e r e the chlorophyll is s i m i l a r l y arrayed.
Still m o r e recently a m u c h m o r e complex m e m b r a n e E t r u c t u r e has
been r e c o n a i t u t e d f r o m lipids of biological o r i g i n and shown not only to
have a 60 A double l a y e r e d s t r u c t u r e but t o have a l e c t r i c and selective

functionality as well.

57

I think that work of this s o r t will eventually

d e m o n s t r a t e unequivocally that the m e m b r a n c s t r a c t u r e r e s u l t s f r o m the

c h a r a c t e r i s t i c s c;f the nlolecqdec. of which thl: xxzmbrans i s constituted.
i'ie musr leave

3;

this poin; our d i s c u s s i o n of chemical and biolo-

gical evolution on che s u r f a c e of the earth, having a r r i v e d at the enclosing

of the ane rgy t r a n s f o r m i n g and information communicating a p p a r a t u s
within a cell wall.

~ d chave,

it would a p p e a r , generated the e s s e n t i a l

e l e m e n t s f o r che developmaat oi m u l t i c a l l u l a r o r g a n i s m s a s well, and the

sequence of events beginning not m u c h i u r t h e r beylind t h i s is actually
r e c o r d e d in the f o s s i l r e c o r d .

UCRL-10424

0. D

Trurnit, Colmano, 1959

I , 2 : chlorophyll a films at water/air interface

F i g u r e 21. F i l m s p e c t r a of chlorophyll a t w a t e r - a i r interface,

and solution s p e c t r u m .

EXTRATERRESTRIAL L I F K

It appears to m e that the information we now have available regarding the nature of molecular evolution which leads up to something which i a
unequivocally acceptable todl of us a s a living organism i s such a s to
i m p r e s s one with the notion that such a sequence, a t l e a s t in i t s e a r l i e r
stages, results from the concatenation of molecules and energy sources,
temperature and environment with it8 variation, which the primitive
e a r t h provided, and i t i s not a. unique accident.

If this be the case,

we can surmise that given a corresponding s e t of molecules, temperature

and environment anywhere d s e in the universe, a similar sequence of

events might have been expected to occur. 58 This does not imply that
the multicellular end-products that we know today would be identical
elsewhere, since the evolutinnary process on the surface of the earth is
f a r from having tried all the possible multiceLlular combinations imaginable.

The time has simply not been available for this at the rate it

can be done. This i s not t r u e f o r the simple atomic and molecular cc-nbinations of the e a r l i e r phases, the exploration of which took place at a
much higher rate.

However, the general pattern of transformation in

the e a r l y phases would be s i m i l a r , and in the l a t e r phases analogous,

to those taking place on the earth, and we have only to answer the
question:

Are there s i m i l a r environments elsewhere T'

Life Z l s e w h e r e in the S o l a r System

'There a r e iwo kinds of d i r e c t information that we have today about
such possibilities i n o u r own s o l a r s y s t e m . T h e s e come to u s in the form
of electromagnetic - r a d i a t i o n s , that i s , light, both visible, i n f r a r e d and
possibly radio waves, and i n the f o r m of the m e t e o r i t e s which we p r e s u m e
have t h e i r o r i g i n in the a s t e r o i d belt between M a r s and J u p i t e r .
The information t h a t i s available to u s f r o m o u r d i r e c t observations
with visible and i n f r a r e d light s e e m s to s u g g e s t quite unequivocally that
the Moon, having no: a t m o s p h e r e , i s not l i k e l y t o have on it living o r g a n i s m s of the type w e know. This i s not to s a y t h a t the Moon has not a c t e d
a s a cold s t o r a g e r e p o s i t o r y of both m o l e c u l e s and f r a g m e n t s which m a y
have been biological, which i t has c a p t u r e d in i t s long sweep through space
accompanying the e a r t h .

59,60

Such m a t e r i a l s captured by the e a r t h it-

self would have been l o n g s i n c e m e t a m o r p h o s e d by the life on it, but m a y

v e r y well be in t h e i r p r i m i t i v e condition on the s u r f a c e of the Moon.
Our next n e a r e s t p l a n e t a r y neighbors, however, have somewhat b e t t e r
p r o s p e c t s . Venus in the s m a l l e r o r b i t n e a r the sun i s definitely w a r m e r ,
but it does have an a t m o s p h e r e and i s v e r y n e a r l y the s a m e s i z e a s the

earth.

I t s a t m o s p h e r e s e e m s to be occupied, a t l e a s t a t its higher

level, by a cloud i m p e n e t r a b l e to visible light.

the actual solid s u r f a c e of che plane^.

We,

t h e r e f o r e , cannot s e e

I s h a l l not t r y to review h e r e the

evidence f o r the n a t u r e of the C y t h e r e a n a t m o s p h e r e .

v a r i o u s reviews

61

A p e r u s a l of

on the subject l e a v e s the i m p r e s s i o n that we do not

really know what the quality of that a t m o e p h e r e i s in a n unequivocal

fashion and we a m thus not severely l i m i t e d in our conclusions.

'The opiical data that a r e available to u s about the s u r f a c e of h l a r s

are somawhat m o r e extensive.

H e r e i t h a s been long since recognized

that t h e r e i s a s e a s o n a l variation in the v i s i b l ? color of v a r i o u s p a r t s of

the s u r i a c e of the planet.

T h e r e is a p o l a r white cap which advances and

r e c e d e s with the s e a s o n , and with i t t h e r e a r e changes a t l o w e r l a t i t u d e s

involving advance and r e c e s s i o n of a d a r k a r e a approximately b o r d e r i n g
the p o l a r white cap and a light a r e a beyond i t . l'he d a r k a r e a i s often
called g r e a n and the light a r e a red, although t h i s i s m o r e a subjective
phenomena that a s p e c t r o s c o p i c one.
Recently the a s t r o n o m e r Sinton has examined the light and d a r k
a r e a s with the i n f r a r e d s p e c t r o m e i e r on the 200-inch telescope, and

has seen a l a r g e r absorption in the 3 . 3 u region in the d a r k a r e a of the

planet than in the light a r e a . 6 z

l h i s he has i n t e r p r e t e d to m e a n that

the d a r k a r e a d o e s indeed contain 6-'W linkages, since the 3 . 5 u region

i.e.,

n e a r 3 0 0 c r n - l , c o r r e s p o n d s approximately t o C - W absorption.

I f this i s indeed trile and if the i n - l n s i ~ yoi ~ h z s eC - r i components of

rhe i n f r a r e d absorption (reflection) do indeed v a r y with the s e a s o n s a s
do the visible changes, then Sinton's observatlnns rrii:,ht v e r y w z l l bz t r : ~
b e s t evidence we have f o r the exiseence of or3a:lic lifc a s u c know i, un
the s u r f a c e of M a r s .

Salisbury

63

has even gone s o far a s to sugges: it;.

m o a t probable n a t u r e to be a broad l z a f e d plant.

L i o w e v e r , we zre vzry

l i m i t e d i n o u r ability to get such inforrr~atisnfrom the e a r t h ' s

The resolving power of t h e r e l e s c u ~ e sw i ~ hr e s p e c t to the

uriact.

eobraphy'ol

M a r s is l i m i t e d when the light has t o go through a n i n f r a r e d apectron-ie~, r

as wall.

'The identification of the IR binds with C-H frequencies leaves

much to be desired, and the identification of the polar white cap a s a snow
cap has also been recently called into question.

It has been suggested

that the white c a p - i s not frozen water a t all but may very well be frozen

N204 instead.

64

Casting even m o r e uncertainty i s the fact that some of

the 3.5 u abeorption seems to correspond fairly closely with one of the
NOZ abaorptione, but there i s not enough of it.

65

F u r t h e r than this,

i f there were a large amount of PdCi in the atmosphere of M a r s with a small

amounts of NOZB the blue-green (or dark) color might very well be due
to tha condensation of small amounts of N203 whose infrared spectrum ie
not yet precisely known. Beyond this, we have observed that a variety
of inorganic carbonates give reflections in this same 3.5 u region. 6 6

W e are thus left with a high degree of uncertainty about the possible
exietence of carbon-based life on M a r s .
However, w e need not remain in this ignorance for very long.

Many of u s will undoubtedly have unequivocal answerB to the questions

nearest celestial
M a r s , Venus and
we have raised about all three of ourbeighbors

--

the Moon

-- certainly within the next decade and possibly much sooner,

in view of what has happened in the l a s t year and particularly in the

l a s t month. We will certainly have orbiting tslescopes which will not be
hampered by the content and fluctuation of the earth's atmosphere, and
we

will thua be able to have a very close look a t the optical propertiee,

particularly of M a r e , in regions which a r e today inaccess jble to ue.

Vie c a n a l s o expect v e r y soon to k m w sorneLhirlt of

he p o s b i l ~ l e

existence of o r g a n i c m a t e r i a l capturcd on the s u r f a c e of tha Bioon, a n d

of i t s nature. \be will probably

no^

have to wait f o r a m a n to land on the

s u r f a c e of the Moon to know the answer to rhis question, since it c a n be

i n s t r u m e n t e d ; i t i s being instrumented in our country and v e r y likely
e l s e w h e r e a s well. Various types of detecting devices f o r organic m a t t e r
a n d i t s c h a r a c t e r will be landed on the s u r f a c e o i the h o o n , and will
t e l e m e t e r t h e i r findings back t o us. Short1y a f t e r that we will undoubtedly
have m e n e i t h e r bringing u s back p i e c e s of the Moon o r a t l e a s t telling

us of what i t i s made.

k s i m i l a r sequence of observations will take place

with r e s p e c t to Venus and M a r s .

However, the time s c a l e will p r e s u m -

a b l y be somewhat longer.

Meteorite Observations

In the m e a n t i m e , w e have another source of information about the

construction of o u r neighbors in the s o l a r s y s t e m .

If w e a c c e p t the

c u r r e n t a p p a r e n t notion that the o r i g i n of the m e t e o r i t e s l i e s s o m e w h e r e

i n o u r s o l a r s y s t e m ( p r e s u m a b l y in the a s t e r o i d belt), then a c h e m i c a l
examination of t h e i r constitution provides us with s o m e information conc e r n i n g what s u c h bodies m u s t be c o n s t r u c t e d of.
o r g a n i c conetituknts

Aside f r o m t h e i r in-

which a r e c h e m i c a l l y not g r e a t l y different f r o m

t e r r e s t r i a l m a t t e r (althoug m i n e r a l o g i c a l l y and physically they a r e ) , a

c e r t a i n n u m b e r of such m e t e o r i t e s contain organic m a t t e r .

known for o v e r one hundred yearer.

Thi8 has been

However, i t ie only in r e c e n t y e a r s

that the examination of that o r g a n i c m a t e r i a l has been possible on the

m i c r o scale and with precision and detail that has allowed new concluviuns
to be drawn a s to their origin.
Some y e a r s ago we examined the organic constituents of one
recently fallen meteorite (Murray, 19 5O), and came to the ccnclueion
that i t not only contained hydrocarbons (at l e a s t up to C12), which were
purely incidental to our search, but also ultraviolet-absorbing m a t e r i a l
which resembled heterocyclic bases going into the construction of nucleic
acids.

67

These we interpreted to be representing some of the organic

compounds of the primitive s o l a r system upon which chemical evolution

operated.
More recently a m o r e detailed examination of the nature of the
hydrocarbons in meteorites has been made in the m a s s s p e c t r o m e t e r .

68

These seem to have an alternation in hydrocarbon size a s well as a

dominance of the C

and steroids.

21

fragments which suggested their origin in lipids

If indeed these m a t e r i a l s come in with the meteorites

from e x t r a t e r r e s t r i a l sources and do not have their origin on the earth,

that would be very good evidence for the existence of primitive organisms
elsewhere.
A further, m o r e spectacular conclusion has been drawn from a

microecopic examination of a number of meteorites, particularly

Orgueil and Mokoia.

69,70

P a r t i c l e s of various specific and apparently

nonrandom shapes have been claimed a s being the fossil remains of

e x t r a t e r r e s t r i a l microorganisms. 'This result has been disputed and the
reeults variously interpreted.

We have had a look at some of the ground

up b i t s of Orgueil and have s e e n many m o r e o r l e s s r e g u l a r s t r i l c t u r e s ,

one of which i s shown i n F i g u r e 2 2 .

1 feel that we m u s t r e s e r v e judgment

as to the n a t u r e of these p a r t i c l e s 7 1 as wall as t o t h e i r origin. 7 2

P e r h a p s i n the next decade we will not have to depend upon t h e s e
randpm and accidental m e s s e n g e r s from o u t e r s p a c e but will be able to

go and collect s a m p l e s , if not a t will a t l e a s t with some e f f o r t , and thus

have a m o r e likely chance to a r r i v e a t an unequivocal a n s w e r to this
i m p o r t a n t question.

Life i n Other Galactic S y s t e m s

On the s c a l e of the e n t i r e u n i v e r s e w e can explore the possibility
of the existence of life only s t a t i s t i c a l l y .

Accepting the c u r r e n t m o s t

popular t h e o r i e s of the o r i g i n of the s t a r s and the planets around them

i n t e r m s of a gravitationally condensing cloud of m o l e c u l e s (HZ,CH4,

H 0 , N H 3 ) and d u s t (the h e a v i e r e l e m e n t s in v a r i o u s combinations), one

2

cankaake the s t a t i s t i c a l a s s e r t i o n thai: planetary s y s t e m s a r e widespread

throughout the u n i v e r s e .

One c a n even go beyond this and a s s e r r that

t h e r e will be a finite probability of m a n y o i these e x t r a t e r r e s t r i a l s y s t e m s

containing e a r t h - l i k e planets i n those e s s e n t i a l a s p e c t s f o r the evolution
of life, that i s , t e m p e r a t u r e , s i z e , and m o l e c u l a r environment.

73

Thus we a r e l e d to the conclusion that t h e r e m u s t exisc e l s e w h e r e in

the universe not one but many t e r r e s t r i a l type planets upon which, we
t h e r e f o r e conclude, will have evolved living s y s t e m s of a kind that w e
would recognize as such. Given the t i m e s c a l e of 5 to 10 billion ycari;,

U C R L - 10424

F i g u r e 22. E l e c t r o n m i c r o g r a p h of ground up p a r t i c l e s f r o m
Orgueil meteorite.

i t i s c l e a r that s o m e of t h e s e living communicies m a y have existed m u c h

l o n g e r than the one on the e a r t h , and, t h e r e f o r e , one might expect that
mu1 t i c e l l u l a r o r g a n i s m s having had m o r e time m a y have progrer; s ed
f a r beyond the s y s t e m s that we know h e r e .

Of c o u r s e , t h e r e will be

m a n y which have not existed a s long, as well, but i t i s the f o r m e r which

i n t r i g u e 8 our imagination m o r e profoundly.

The kind of intelligence we can recognize a s m a n h a s existed on the

a
s u r f a c e of the e a r t h f o r j v e r y s h o r t p e r i o d in these t e r m s , and we t h e r e f o r e m i g h t expect that in t e r m s of the ability to communicate, s o m e of
t h e s e o t h e r p l a n e t a r y s y s t e m s m a y be inhabited by o r g a n i s m s f a r m o r e
skillful and knowledgeable chan we. T h i s kind of reasoning has a l r e a d y

led to a n a t t e m p t to l i s t e n with o u r own newly acquired radiotelescopes

f o r m e s s a g e s f r o m silch o r g a n i s m s .

7 4 11
r h i s h a s , as yet, been f r u i t l e s s .

Howeva; a bit of c a r e f u l and controlled imagination as to how we might

a c h i e v e s u c h concact has led one of o u r r a d i o a ~ t r o n o r n e r sto~ ~
invent
a p o s s i b l e m e s s a g e which might have a r r i v e d f r o m outside the s o l a r
s y s t e m , and I give i t to you for your own deciphering.

Frank Drake
National Redio hatronwy Observatory
Green Dank, West Virginia

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Some r e k e n c e s to the e a r l i e r laboratory e x p e r i m e n ~ a t i o nin this

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L. E. Mortenson, R. C. Valentine and J. E. Carnaham, An

E l e c t r o n T r a n s p o r t F a c t o r for GIostridium pasteurianum.
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, On Dating Stages in Photochemical tvolution, m

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Raconatitution of Cell AAembran* S t r u c t u r e i n vitro and Itrr
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Acad. Sci. 46, 393 (1960).
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rJn h'iars.

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74.

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F. D. Drake, Periodic Communicatione of the O r d e r of the

Dolphins, 196 2 .

T h i s r e p o r t was p r e p a r e d a s a n a c c o u n t o f Government
sponsored work.
N e i t h e r t h e U n i t e d S t a t e s , n o r t.he Comm i s s i o n , n o r a n y p e r s o n a c t i n g on h e h a l f o f t h e C o m m i s s i o n :

A.

Makes a n y w a r r a n t y o r r e p r e s e n t a t i o n , e x p r e s s e d o r
imp1 i e d , w i t h r e s p e c t t o t h e a c c u r a c y , c o m p l e t , e n e s s ,
o r usefulness of the information contained in
his
r e p o r t , o r t h a t t h e use o f any i n f o r m a t i o n , appar a t u s , method, o r p r o c e s s d i s c l o s e d i n t h i s r e p o r t
may n o t i n f r i n g e p r i v a t e l y owned r i g h t s ; o r

B.

Assumes a n y l i a b i l i t i e s w i t h r e s p e c t t o t h e u s e o f ,
o r f o r damages r e s u l t i n g from t h e u s e o f a n y i n f o r mation, a p p a r a t u s , method, o r p r o c e s s d i s c l o s e d i n
this report.

A s u s e d i n t h e above, "person a c t i n g on b e h a l f o f t h e
C o m m i s s i o n " i n c l u d e s a n y e m p l o y e e o r c o n t r a c t o r o f t h e Cornm i s s i o n , o r employee o f such c o n t r a c t o r , t o t h e e x t e n t t h a t
s u c h employee o r c o n t r a c t o r o f t h e Commission, o r employee
of such contractor prepares, disseminates, o r provides access
t o , any i n f o r m a t i o n p u r s u a n t t o h i s employment o r c o n t r a c t
w i t h t h e Commission, o r h i s employment w i t h s u c h c o n t r a c t o r .