a functional approach to the origin of life problem

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t t t :l J{ tfi tl t /g\ 'l- i;{ t ,t : ':i 'I ? "fl-, *. :7 e .f g & & B fi F h t J : il tl 1i t. 1i I A Functional Approach to the Origin of Life Probtrem Krishna Bahadur', S. Ranganayaki', Clair Folsome' and Adolph Smithg i-1 ' t-,' '; lChemistry Department, University of Allahabad zlaboratory for Primordial Biology, University of Hawaii, Honolulu, Hl 96822 sPhysics Department; r:L4rcordia University, Montreal, now at Amr-.i.,.,;search Center, 239-12, Motrett Field, NASA, California, 94035 Offprint from National Acarlemy of Sciences, Intlia : Golden Jubilee Commemoration Volume, 1980

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"A functional approach to the Origin of Life problem" by Krishna Bahadur

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A Functional Approachto the Origin of

Life Probtrem

Krishna Bahadur', S. Ranganayaki', Clair Folsome'and Adolph Smithg

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lChemistry Department, University of Allahabadzlaboratory for Primordial Biology, University of Hawaii,Honolulu, Hl 96822sPhysics Department; r:L4rcordia University,Montreal, now at Amr-.i.,.,;search Center,239-12, Motrett Field, NASA, California, 94035

Offprint from

National Acarlemy of Sciences, Intlia : Golden Jubilee Commemoration Volume, 1980

2 Bahadur Ranganayaki Folsome & Smith

1. Tne PnosLnN{ IN ORIGIN oF LIFE SruoIEs

To explain how life began is surely one of the most fundamental aspects

of biological research, yet today we see studies in origrn of life generally as

an esoteric field away from the main stream. whi' ? For one thing there

has been little progress in the field in the past decade. During the 1950's

with the announcement of the Miller-Urey experiment i1953) origin of lifebecame a much discussed subject which found its way into standard text'

books. During the succeeding decade a variety of presumed prebiotic experi-

ments in which various energy sources such as light, electric discharges, and

acoustic shock waves were carried out. A wide variety of simple biochemicals

were found to be products in these experiments. Some work was done on

polymers but most of the work centered about identifying and listing the

smaller organic molecules such as amino acids and nucleic acid bases formed

from simple precursors.

The gap between a collection of biochemicals and the properties which

are intrinsic to the simplest living organism remained just as large after two

decades. There has also been the objection that origin of life work is mean-

ingless because it is largely a matter of conjecture as to what rheconditions

on a prebiological earth were ; hence the relevance ofany simulation experi-

ment was suspect.

we want to question the fundamental assumptions of present-day work

and to suggest an alternative simplifying approach which bridges the gap

'between biochemicals and simple cell functions. Experimental resulis which

demonstrate the utility of a functional approach to the origin of life problem

wiil be presented.

2. MooBnN losA,s oN OntctN oF LIFE

Modern ideas on the origin of life come from the theories of oparin3s

and Haldanezs. They assume a primitive, reducing atmosphere (methane,

ammonia, hydrogen and water) so that complex molecules could arise. The

reducing atmosphere was thought necessary so that organic moiecules would

not be oxidized. With sources of high energy in this atmosphere (electric

discharge, UV, etc.) it was thought that a variety of organic molecules would

be produced. Since there were rto organisms to consume these molecules,

they accumulated in the primitive oceans to form a prirnordial "soup". There

is a great difference of opinion on the concentration of the supposed soup

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-the Origin of Life Problem 3

from nearly zeto|' or an amino acid concentration of l0-7 Mle to one

gram per iiter.At this point, the heterotrophic hypothesis, originally advanced by Horo-

witz26 isinvoked.By some chance a primitive organism is assumed to have

arisen out of the soup mixture and this primitive organism used the soup

components for further metabolism and growth. Based upon the heterotro-

phic concept, Oparin adduces his concept of coacervates which arise from

cornplicated molecules and then absorb various compounds from the envi'

ronment. In this way, the coacervates are conceived as evolving into prim-

itive cells.

Fox has synthesised microspheres starting from heated dry amino acids

and has formed some sort of cell-like macromolecular structures and pro-

teinoids. FIowever, his experimental conditions seem not to be geologically

plausible and the arbitrary properties he lists as being lifelike are not from

any one microsphere preparation but rather from many different microsphe-

res pi-oduced under different conditions. In a summary of the prevailing

heterotrophic hypothesis, Keosian2T writes :

,,Life at its origin is envisioned by some as a simplified version of a

present-day 'primitive' heterotroph-simplified not in the reduction

of metabolites or metabolic pathways, but in the substitution ofrhese by simpler substances and simpler reactions supposedly per-

forming the same functions. One need only scan the claims ofchemical evolution over the past two decades to see the trend. There

seems to be a general belief in an abiotic mechanism in a prebiotiQ -Soup. However, the harmonious coordination of separate reactions \//into a smoothly functioning, interconnected metabolic network in

even the simplest heterotroph is the result of untold millions of

years of evolution. Turning that evolutionary clock backwards is

not just a matter of substituting simple substances forcomplexones

or simple reactions for complex pathways. The concept that all parts

of the first living thing pre'existed, and that its formation was

simply a matter of spontaneous generation therefrorn is a mathe-

matical absurdity, not probability. All present approaches to a

solution of the problem of the origin of life are either irrelevant or

lead into a blind alley. Therein lies the crisis."

we present a conceptual and experirnental approach which is based on

wellknown catalytic properties of minerals in cell-sized domains, uses an

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4 Bahadur Ranganayaki Folsome & Smith

autotrophic model, and has already yielded results which narrow the gapbetween biochemicals and the functions manifested by living cells.

3. THn AurorRopHrc Hypornnsrs

The place of autotrophy in origin of life theory has been given scantattention. Geochemists have objected to the concept of a primitive soupon several grounds. one major objection has been that the "primitive soup"should have resulted in formation of large areas containing organic sedi-ments but no such areas have been found. In a recent review, Brooks andShaw17 conclude :

"We can conclude with some certainty that :

(a) There never was any substantial amount of ,primitive soup' onEarth when ancient Precambrian sediments were formed ; and that

(b) If such a 'soup' ever existed it was only for a brief period of time.If we subtract the idea of a substantial amount of ,primitive soup'and a long period of time from the basic concept of Chcmical Evo-lution Theory, there is very little time left."

If there were not any 'primitive soup' we must assume that the first orga-nisms were autotrophic, that is, they obtained their carbon from COn andtheir nitrogen from atmospheric N". cairns-smithas proposed that the firstorganisms were clay-like. The minerals of the clay would catalyze the for-mation of new materials and act as templates for replication.

About the chemical nature of the living system Piriee 5 holds that proteinsare necessary for present-day cells because they are enzymes and catalyzemany biochemical reactions. But many metallic ions also show enzyme-likeactivity and it is possible that to begin with these might have been perform-ing the work of protein enzymes. Bernalla was of the opinion that theremight have been organisms which had only inorganic catalysts in the placeof proteins and such organisms might have been sluggish but could havecertainly performed all the functions of life. According to Smirnovaas manyinorganic substances have physical properties commonly found in organicsubstances and it is quite possible to conceive organisms made of theseinorganic substances only. Bernalls writes "unless itis desired topushbackthe doctrine of special creation to the creation of enzymes and co-enzymes(there is a school that would take one of these, namely the co-enzymes inthe polymerised form as nucleic acid) as the beginning of life, unless thenwe are prepared to take such an easy way out, we must assume that before

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-the Origin of Life Problem 5

there were enzymes to carry out the catalytic reactions in metabolism there

were some other agents that did it, not so well' but sufficiently well for the

slow time of the origin of life'" These evolve to produce protein-nucleic

acid cellular life which we now observe on the earth' Bahadurs'6 has sugges-

ted a probable locale for these forms of life' These microstructures could

haveshownthefunctionalpropertiesoflivingSystemasclay-likemodels.One of the important u'ptti' of the problem of origin of life is to study

the physico-chemical factors which brought the molecules which formed

the earliest living systems together' kept them held together and arranged

them in some specifi" puttt'i that couid show the properties of biological

order.A recent review of autotrophic origin by Hartman2a uses a-.scheme in

whichclays,transitionmetuls,disulfide'dithiols'ultravioletradiationandcyanide ion from a frimitive metabolic 'system which uses COn and N'

fixation and which could evolve in a simple environment. He looks at inter-

mediary metabolism, and examines the central role of the citric acid cycle'

and concludes that the main problem of starting the cycle is one of carbon

dioxide fixation. He considers that nitrogen fixation could have been ac-

complishedbymolybdenumcomplexesintheprimitiveorganismsifastrongreductantwereavailable.Ithasbeenobservedthatthemixturesofjeewanuwhich start with simfle substances have almost all the acids of the Krebs'

cycleaa. It has br"i ..,ggt'ted that Krebs' cycle was perhaps the most

elementarY form of metabolism'

4. Tne FuNcrIoxal AppnoAcH To Onlctt'c or Lll,r

We present here an approach to origin of life which emphasises the

matter-energyflowswhicharefundamentaltoalllivingorganismsandtheirecologies. In the course of the many prebiotic experiments' microstructures

have appeared but generally these structures and their properties have been

ignored. The reasoi for this has not been a case of oversight but rather is'

in line with the mainstream of procedure in biochemistry. A major activity

ofbiochemistshasbeentheseparation,identificationandpurificationofvarious biochemicals involved in each stage of metabolism of a structured

once-functioning sYstem'

In the first Miller-Urey experiments polymeric material in the form of

microstructures was observed' Yet surprisingly these structures were not

studied systematically until recently2o' In the 1963's' a series of articles by

Golden Jubilee Commemoration Volume' 1980

6 Bahadur Ranganayaki Folsome & Smith

Bahadur and coworkersl's'd'z'e on microstructures formed from transitionmetals, ammoniurn phosphate, biological minerals and formaldehl,de appear_ed. These structures were called "Jeewanu,,(a Sanskrir q,ord for particresof life). various catarytic properties of these particres *,ere reported butthese were largely ignored.

.Ieewanu are photochemically synthesized particres formed in srerilizedaqueous mixtures containing simple organic source as formaldehl.de, inorga_nic nitrogen and minerals cornmonry found in cells. These particles havedefinite boundary warl and intricate internar structures2e'r.. They are verysimilar to the present-day cell in chemical composition and diff.-r from thecommon microorganisms that they cannot be grorvn on an). known bacte-rial cult're mediume'6'7. These particres mulripry by budding aird the smarlbuds grow to maturity size and bud again. wherever organic materiars andnecessary inorganic substances are present, sunlight synthesized amino acids,peptides, sugars and such other biochemicals and the transitionai metarcoordination complexes with ligand as these biochemicals wirh the help of

I lurfacl ol semi-conductor could organise in the form of microstructures ancl

il fOfm jeeWanUz'e o' 3 o' 44' 46' 47' 5 11 6 5' 5 a' i s

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Bahadur and Ranganayakie photochemicalry produced another varietyof these particles by the interaction of ammonium rnolybdate, diammoniumhydrogen phosphate, rninerals commonly found in ceils and formaldehyde inaqueous mixtures which have 31.21% of molybdenum.

In the jeewanu the properties of growth, multiprication and metabolicactivity are observed in a natural way, once the experiments are set and nospecific chemicals are needed for any specific property1,2,s,7.

These particles with high molybdenum content have a number of amincracids iri free form and in combinecr form as peptides, and sugars as ribose,deoxyribose, lructose and glucose. They have distinct bcundary walr andintricateinternalstructure. TheinternalsfrustLrrescanbeclearlyviewedunderhigh magnification. The particles under phase-contrast microscope revealtheboundary walland the internal structure of theparticlesclearlyro. Theseparticles multiply by budding (Bahadur and Ranganayaki 1970).

on separation of the particles from the mixture, extraction withchroro-form : methanol : : 80 : 20 in a soxhlet yierds a viscous yellow liquid. Thiscontains an ethyl alcohor solubre compound which on chromatography givesthe test for phospholipidrz. on hydrorysis of the particres with perchroric

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-the Origin of Life Problem 7

acid or formic acid in a sealed tube the products give the tests for nucleic

acid baser as adenine, guanine, cytosine, thymine and uracil2e'3e. If the

particles are kept in lNsodium hydroxide for 24 hours, filtered and the

hltrate acidified with dilute acetic acid a white precipitate is obtained which

on subsequent hydrolysis gives the test of nucleosidesao'

The particles can be fixed with chromic acid and subsequently stained

with gentian violet and then eosin. In the central portion chromatin-like

blue structures are seen and the portion outside the central zone stains red

with eosin, Lke cytoplasms. lt has been reported that the malerials of the

particles on diges..ion with hydrochloric acid show strong optical activitye.

Briggsa6 reported esterase and phosphatase activity in these particles.

BahadurandRanganayakigreportedurease-like,ATP-aselikeandperoxi-dase-like activity in these photochemically formed microstructures' Jeewanu

are sensitive to the presence oi antibiotics in the irradiative mixtureal'36'

Presence of sulphur drugs also affect their growths6'

The factors which are responsible for the natural formation of objects with

a definite morphology have been discussed by Bahadur3'5'7' The molecules

of different chemicals are brought together and are first beld by coacervate

formingfactors.IfthiscontainsmacromoleculeswithlowM.W.,moleculesattached by various intermolecular forces, such as van der Waals forces'

hydrogen bonding, hydrophobic bonding, molecular bonding and others'

and also many other molecules adsorbed' absorbed and held together by

electrostatic forces, on crystallisation, a highly deformed crystal is formed

and the whole thing results in a molecular mesh having wide gapsand pass-

ages through which small environmental molecules have specific permeability'

The various gaps contain different molecules held in this deformed crystal

structure and remain active chemically and also catalytically. The whole

structure attempts to acquire a spatio-energetic pattern representing the state

of minimum energy and it results in biological looking structures. The outer

material forms a boundary wall and tbe aggregate appears to have anintri'

cate internal structure. Ifthis structure is present in an appropriate environ-

ment, containing molecules which can form its body material' and if it has

asourceofenergy,whichmaypreferablybeobtainedbyirradiation'theenvironnrental molecules enter the aggregatethrough the appropriate passa'

gesintheboundarywallfromtheoutermaterialoftheaggregate,interactand finally result in the material from whichthe aggregateis formeds'a'5',7.

Allsuchabiogenicmorphologicalstructuremaynotbeabletoshowthe

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properties of biologicar order, but those which bappened to be in the en_vironment to allow the flow of energy appropriate for them could showthese properties. of such innumerable particles those which depended onsuch materials which were continuously being formed in the mixture-sayby photochemical process-continued their riving activity and the restceased their functions soon after the supply of the n.".rrury moleculeswas finisheds,6,7.

Many such microstructures are observed in ores and rocks and are repor-ted as silicate particles' found in sedimentary rocks and are described asmicrofossils and observed in carbonaceous chondrites and mentioned as"organised Elements". Many of these may be models of the earliest struc-tures in which life was expressed.

The presence of transitional m.etal in these microstructures which mighteasily form coordination compreies with ligands as amino acid, peptide,nucleic acid bases courd make these structures extremely reactive for anumber of chemical transfornrations.

rn 1971, microstructures resurting from ultraviolet irradiation of ammo_nium thiocyanate and ferrous surphate were reported to show pH changesupon further irradiationdl.Earlier microstructures have been produced by the action of urtravioletlight on aqueous mixture of ammonium thiocyanate and formardehydezs,4e'5o' This mixture was modified by introducinga mineral sorutioncontain-

ing sodium chloride, potassium sulphate, carcium acetate, magnesium sul-phate and potassium dihydrogen phosphate. In addition to this mineralsolution the concenrration of which was as usually usedin microbialcultureexcess of potassium hydrogen phosphate and calcium acetate was added toprovide a more inorganic base. In another mixture ferric chloride wasadded' Three sets of two such mixtures were prepared. one set of iron andnon-iron containing mixtures was exposed to artificial electric right froma 100'watt electric bulb, another was covered with several folds of thickblack cloth as the dark set and the third was similarly covered with blackcloth and kept in a lead chamber of l inch thick solid lead walls. Moremicrostructures were formed in the mixtures exposed to light. The mixturesbowed the formation of amino acids and peptides. More synthesis of aminoacid was observed in the exposed mixture, lesser in the mixture kept in darkand least in the mixtures kept in lead chamber. Ferric chroride containingmixtures showed formation of more amino acids than the mixtures without

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ferric chloride. In each mixture cellJike microstructure formation was ob-served which showed the presence of amino acids and peptides.

The experiments indicate that for the formation of microstructureschemical reactions as well as irradiation are helpful and the coordinationcomplexes of transitional elements with ligands as amino acids and peptides

as suggested by Beck13 together withthecatalyticfunctions of theinsolublecompounds of semi-conductor elements with their increasing surface as

suggested by Tsigdinos and SwansonsT, were effective in these processes.

In an attempt to study the "obvious", the simplest microstructures inprebiotic experiments, we consider globally the metabolism of the simplestliving cells, the blue-green algae. We can view the flows into a blue-greenalgae as Figure 1.

Energy InputLi9 h't

Motter Inputs

N.

Fig.1

Global matter-energy flows in a blue-green algae.

The global overview suggested several catalytic properties to search forin the microstructures, i.e. nitrogenase activity, carbon dioxide reduction,water photolysis. Since transition metai complexes have been intensivelystudied for their catalytic properties in promoting the above reactions, we

decided that the microstructures studied by Bahadur would be a good start-ing point since they contain transition metals closely associated with organiccompounds.

5. Exppruurr.rrA,r, REsuLrs

Molybdenum complexes with amino acid and small peptide ligands havebeen reported by Schrauzeras to have nitrogenase activity, so this functionwas selected for initial testing.

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10 Bahadur Ranganayaki Folsome & Smith

As jeewanu are synthesised photochemically a search of the functional

properties of splitting of water in sunlight and utilisation of hydrogen thus

produced is obvious. A typical jeewanu mixture is prepared as follows :

i vol of 4% wlv of ammonium molybdate solution, 2 vol of 3lwlv of

diammonium hydrogen phosphate solution and 1 vol of mineral solution

prepared by dissolving 20 ml of each of sodium chloride, potassium sulphate,

calcium acetate, magnesium sulphate, manganese sulphate and potassium

dihydrogen phosphate and 50 mg of ferrous sulphate in 100 ml of distilled

water are mixed together and the mixture is cotton plugged and sterilised.

Aftercoolinglvolof36/'offormaldehydeisaddedinthenaixtureaseptically and the mixture is exposed to sunlight under sterilised conditions

for 15 hr giving five hr exposure each day for three days' The mixture is

shaken once each day by gentle whirling motion to disperse the sediments

in the whole mixture. After the exposure the jeewanu formed in the mixture

are separated from the mixture by filtration, dried in a desiccator and used

for different exPeriments.

Bychangingtheconcentrationsofthedifferentconstituentsofthemixtures and introducing different semi-conductors or transitional metal

soluble salts in the mixtures different types of jeewanu can be prepared'

These samples ofjeewanu were found to contain material with ferredoxin-

like activitysT. Jeewanu have ability to transfer electrons to hydrogenase

from sodium dithionite as well as from the chloroplast system. The activity

of these compounds are listed in the Table No. l. The particles are very stable

in air at room temperature'

Type and concentrationof mediator

Micromoles Hn evolved Per hour

per mg chloroPhYll25' 10000 lux

100 m M Dithionite30'

J I, I mg/ml.J,II, 1 mg/ml.J III, 1 mg/ml.J IV, 1 mg/ml.15 m M Spinach ferredoxin1'25 m methyl viologen

4'11'01'01'840

0

2'4l'31'0r'7

Not determined50

Table No. 1

H" Evolution by various samples of Jeewanu(J) with the

hYdrogenase from C. Pasteutianum

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Ferredoxinisessentiallormanybiologicalelectrontransferprocessesand all the living cells have ferredoxin in them' A system of chloroplast

withitsintactmembraneandchlorophyll,ferredoxinandhydrogenasecansplit water molecule on exposure to sunlight in many algae' Jeewanu can

beusedinthissystemintheplaceofferredoxinunderlaboratorycondi-tionsse. Systems containing lijrrt narvesting chloroplast membranes and

electron mediators to hydrogenase, to produce hodrogen from water' are

under study for utilising such systems for energy conversion and storage

using sunlight as the p.iria,y energy source' Ferredoxin' cytochrome C" and

N.{DH are the known physiological electron carriers to hydrogenase' ln

some instances these.u,,i.t' can be substituted by viologen dyes' Jeewanu

canmediateelectrontransferfromsodiumditbioniteorilluminatedchloro-ptasts to C, pasteurianum hydrogenase as indicated in Fig' 2

JeewanumixturesshowreversiblephotochemicalelectrontransferT.Thusthe mixture in which jeewanu is produced' on exposure to sunlightbecomes

blue in colour. This biue colour is formed by the reduction of molybdenum

from colourless(ic) stage to blue coloured(ous) stage' If this blue mixture

iscoveredwithblack"tott,uodkeptindarkthemixturebecomescolourless.Theprocessofrnakingthemixturecolouredandcolourlesscanberepeatedagain and again by keeping the mixture in light and dark respectively' Many

ferredoxins have hydroge.irase activity also andso the possibility of splitting

water by jeewanu in piesen'" of light was investigated' It was observed

that so far jeewanu url p""o'in the environmental medium in which they

are prodrrr.d there is no appatent evolution of gas fromthe mixture' How-

ever, if the particles u" "iu'u"d from the environmontal medium in which

,h.yu..produ.eduoOpotindistilledwaterandthemixturevigorouslyshakenandkeptinsunlightbubblesofgasstari'comingoutofthemixtureafter about l5 min of

""-poso'"' This evolution of gas continues for about

three hours and then gradually stops' If the mixtures are given a second

thorough shaking and exposed the evolution of gas continues for the next

oneandhalfhoursbuttheyieldispoor.Alterthisthegasevolutionstopsandnoamountofshakingandexposureproducesanygas.Butifthismixtureiskeptovernighttheparticlesarerevivedandnextdayagainthemixture liberates gu, u, on the flrst day. It is observed that jeewanu are

slowlydestroyedwhenkeptindistilledwaterandresultinacolloidalsus-pension. However, they retain their shape for a long time if kept in very

dilute mineral solution. so for the study of the photolytic evolution of gas

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TlME ( MIN )

Frg 2

The system, contained C. Pasteurianunt hydrogenase and the componentsmentioned under Fig. except Ferredoxin. (1) with 30.lr'Moles of FD/2ML,

(2) with 30 N Mole FD +4 MG RA I in 2 ML,(3) with 2 MG RA I in2ML'(4) *t'n o t$lXf

i#"1't"t",,gnf) *un no right and

from water usually dilute mineral solution is used. The results of theseexperiments will be published elsewhere.

It has been observed that the jeewanu water mixture evolves gas forabout 20 to 30 days and then slowly the evolution stops. Then no treatmentproduces gas. The evolution of gas by jeewanu is optimum if a certainperiod of exposure is given in the formation of jeewanu. For the m-ixturedescribed here the optimum exposure piriod is 24 hr exposure to sunlight.It is done by giving4 days'exposure ofsix hours each day. Ifthe exposureperiod is considerably shorter or longer, then the particles showed lessevolution of gas. The evolution of gas decreases with the aging of theparticles and is maximum when freshly prepared.

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The gas evolved by the photolysis of water was collected and was found

to be a mixture of hydrogen and oxygen. Greater amount of gas was obtained

whensomeairwaskeptover the irradiated aqueous mixture of jeewanu and

water and was smaller when the air above the mixture is evacuated. An

atmosphere of nitrogen above the irradiated mixture produces gas which

contains more than one volume of oxygen for 2 volumes of hydrogen pro-

duced. It was because some of the hydrogen is used up for fixation of nitro-

gen. If a slow current of the gas is maintained through the irradiated

mixture with the same gas circulating again and again though the mixture

with a pyrogallol-alkali mixture in the circuit to remove the oxygen formed,

the liberation of gas continues for a long time and the circulating gas goes

on increasing in volume.It was further observed that jeewanu and water mixture have nitrogen'

ase-like activity. That is, if acetylene is kept over the aqueous mixture ofjeewanu and water containing a little mineral solution and glucose, and the

mixture is exposed to artificial light from a Xenon lamp, acetylene slowly

gets converted into ethylene and acetylene ethylene ratio slowly increases

with increasing period of exposure6 2 as indicated in Fig. 3. On passing

nitrogen through a mixture of jeewanu and water, molecular nitrogen is

fixed and more fixation is observed when only nitrogen is passed through

the mixture and lesser when a mixture of nitrogen, oxygen of the compo-

sition of air is passed throughls'42.It was further observed that if carbon dioxide is passed through a mix'

ture of jeewanu, mineral solution and water and the outcominggas is pass-

ed through distilled water, this water starts showing the properties of un-

saturated organic compounds collected in it as indicated by its ability to deco-

lourise cold aqueous permanganate solution and bromine water. The un-

saturation increases with increasing period of irradiation.4l It was observed

that if sodium bicarbonate, jeewanu, water and mineral solution is exposed

to sunlight the bicarbonate carbon gets converted into organic carbon.al

carbon dioxide fixation using 1ac containing Hco; was investigated and

it was.observed that the bicarbonate carbon is convertedd 3 to organic carbon.

That in these processes of nitrogen and carbon dioxide fixation it is the

hydrogen of the water molecule which is obtained by the splitting of water

molecule and not the hydrogen from any organic material present in jeewanu

was investigated using DrO.us They selected the reaction of nitrogen fixa-

tion and created acetylene atmosphere over the jeewanu, water mixture and

Golden Jubilee Commemoration Volume, 1980

l4 Bahadur Ranganayaki Folsome & Smith

01231.56709- MAY 31 Tll'lE li\t DAYS JUNE 6 JUNE 9

Fig.3

Acetylene to Ethylene reduction by feewanu preparedfromGlyiine + L - Cyiteine + I : 2 i I : I +Fe Xenon irradiationI mg of particies in I ml 0'1 M gluclse solution.Conlrol of particles in dark showed O

. Control of acetylene+glucose showed OO particle suspension about 40 cm from Xenon lamp.X barticle suspension about 50 cm from Xenon lamp'No stirring

observed that the hydrogen of the ethylene formed was mostly deuterium

indicating photolytic decomposition of water andutilisation of theliberated

hydrogen for its reduction of acetylene'

The particles produced in the ammonium thiocyanate, formaldehyde-mixture having additional mineral solution as described earlier show the

formation of red cell-like structure if ammonium molybdate was added in

the mixture within a fewhours of exposuretosunlight. Redcolouredmicro-

structures are formed on exposure to sunlight.4 2 These particles also indicate

iiberation of gas when the particles are separated from their environment

and a mixture of the particles and water is exposed to sunlight.

Conclusion

The e-arlier living systems might have been primitive autotrophs. There

was not.enough organic material on the earth during the emergence of life

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-the Origin of Life Problem

on the earth. The atmosphere was, in allprobability,composedofnitrogen,

carbon dioxide and water vapours and solar energy was the chief source of

energy available' Sott o"u of semi-conducting elements had abiliry of

breaking water molecules absorbed on their surface into bydrogen and

oxygen by the UV radiation of the sun' Some of these could flx molecular

nitrogen and carbon dioxide by the hydrogen thus produced The oxygen

simultareously produced made tlie atmosphere less and less permeable to

UV. Some of these reducpd nitrogen and organic molecules formed by the

reduction of carbon dioxide combined and formed compounds as amino

acid, peptides and nucleic acid bases' The transitional metal coordinalion

complexes utilising these biochemicals as ligands acted as catalysts for a

number of reactions'

The mixture of semi-conductor element insoluble compounds and the

coordination complexes formed slstems with lots of inorganic surface and

littleorganicmaterials'Someofthesedevelopedtheabilityofsplittingwater with visible light and utilising the hydrogen thus produced for the

reduction of atmospheric nitrogen and ca'bon dioxide and the resultant

product acted as,t" "nt'ry material for further development' The flow of

energy from sunlight to tiese biochemicals stabilised these earliest micro'

stiuctures and they developed and evolved with the changing environment

and ihese were the first primitive autotrophs'

The abiiity of some of the microstructures as jeewanu with perfected

property of splitting water moiecules with sunlight and fixation oI nitrogen

and carbon dioxide had advantage over the inorganic minerals because of

the increasing concentration of oxygen in the atmosphere and decreasing

permeability of UV and could show the other functional properties as

growth,multiplicationandmetabolism'Theear|iestlivingsystemmighthave been more rich in inorganic material' With evolution and perfection

of biological function the organisms increased in organic material and de-

creasedininorganicconstituentsthoughacertainminimumisyetessentialand maintained'

REF'ERENCES

-,1: Bahadur, K', Ranganayaki' S'' Verma' H' C'' Srivastava' R' B'' Agarwal' K' M' L"

Pandey, n. S., Saxena, I', Malviya' A' N'' Kumar' V'' Perti' O' N' and Pathak'

H. D. (1963) Vijnana Parishad Anusandhan Patrika' 6 "

63'

Golden Jubitee Commemoration Volume' I9B0

16 Bahadur Ranganayaki Folsome & Smith

'-2, Bahadur, K., Ranganayaki, S., Verma, H' C', Srivastava, R' B', Agarwal' K' M' L"Pandey, R. S., Saxena, I., Malviya, A' N', Kumar, V', Perti' O' N' and Pathak'

H.D. (1964) Zbl. Bakt., tl1 (2\ : 567 -

Bahadur, K. (1964) ZbL Bakt., l1.8 (2): 671'

Bahadur, K., Perti, O. N. and Pathak, H' D' (1965) Agra [Iniv"/' des' (Scf')' 13'3.

4;

5.

'\-.6'

(II) : 197.

Bahadur, K. (1966) "Jeewanu, The

Allahabad.''bahadur, K., RanganaYaki, S., Kumar,

t20 (2) :740.

Protocell", Ramnarainlal Beni Prasad,

A. and Srivastava, P. (1966) Zbl. Bakt"

National Academy of Sciences, India

'..-7. Bahadur, K' (1967) ZbL Bakt.,l2l (2) :291'8. iahadur, K. and Gupta, J. L. (1972) Zbl' Bakt', lTl (2) : 643'

, g..'Bahadur, r. ana Ranganayaki, s. (1970) J. Brit. Interplanetary soc., 23 : 813.'tr0.

Bahadur, K. (1975) Zbt.8akt.,130, (II) :2ll'11. Bahadur, K., Ranganayaki, S', Singh, Y' P' and Kumar' S' (19?5) Revista do

Instituto de Antibioticoso Recfe,15, N (*) : 33'

12. Bahadur et al. G979) (To be published elsewhere)'

13. Beck, M. (1979) Kemiai Kozlemenyck,50 : 223'

14. Bernal, J. D. (1959) Proc. First Int. Symp. on ..The origin of Life on the Earth',,

Moscow, 1957, Pergamon Press, New York, 78'

15. Bernal, J. D. (196i) Oceanography Am' Association for the Advancement of

Science, 95.

16. Briggs, M. H. (1965) Spaceflieht,T 14) :129'

l7.Brooks,J.andShaw,G.(1978)InOriginoflife'Ed'H'Noda'CenterforAca-demic Publications, Japan, 597'

18. Cairns-Smith, A. G' (1966) J ' Theoret' Biol' l0 : 53'

lg. Dose, K. (1975) BiosYstems,6 :224'

20. Folsome, C' (1975) Precambrian Research,2: 263'

2l.Fox,S.andDose,K.(1972)MolecularEvolutionandtheoriginofLife,W.H.Freeman & Co., San Francisco'

22. Gupta, J. L. (1976) Cvtological and Histochemical Studv of Abiogenic Cell-like

Molecular Association, o. pnr. Thesis, Chemistry Department, University of

Allahabad, India.Haldane, J' B. S. (1929) The Origin of Life, Rationalist Annual'

Hartman, H. (1975) J. MoL Evol- 4 : 359'

Herrara, A. L. (1942) Science, 96 : 14'

Horowitz, N. (1945) Proc. Nat' Acad' Sci' tlSA,3l: L53'

Keosian, J. (1978) In Origin of Life, Ed' H' Noda' Center for Academic Publi-

cations, JaPan,569.Kurnar, A. (fSee) Study of Abiogenesis of Amino Acids' D' Phil' Thesis'

Chemistry Department, University of Allahabad, India'

Kumar,S.(1976)AbiogenesisofNucleicAcidBases'D'Phil'Thesis'ChemistryDepartment, University of Allahabad' India'

)7,

24.

25.26.

27.

28.

29.

a\- .-

;ri

iir

Fffifi'q

ili

I

fi

I

:

-the Origin of Life Problem 17

30. Maurya, H. K. (1927) studies in the Abiogenesis of Amino Acids, D. phil. Thesis,Chemistry Department, University of Allahabad, India.

Jt.

32.Miller, S. L. (1953) Science,lIT :528.Narain, K. (1974) studies in the Abiogenesis and Biopoesis, D. phir. Thesis,Chemistry Depafiment, University of Allahabad, India.

33. oparin, A.r. {1929) proiskhozdenie zhizni, Moscovsky, Robctchii, Moscow.34. orgel, L. E. (1972) origin of Life, Molecules and Naturar Selecion, \viley, New

York.35. Pirie, N. w. (1959) proc. First Int. Symposium on ..The origin of Life on the

Earth", Moscow, 19-24 August, 1957, pergamon press, New york, 1g4-1gi.36. Pradhan, D. N. (1977) Effect of Antibiotics and sulpha drugs on the formation of

abiogenic microstructures, D. phil. Thesis, chemistry Department, University ofAllahabad, India.

37. Rao, K. K', Morris, p. and Hail, D. o. (197s) '.presented at the workshopMeeting on Hydrogenases : Their catalytic activity, structure and function,', held atGottingen, August.

38' Raina, v. (i973) Studies in some Aspects of Abiogenesis of organic compoundsof Biochemical Interest, D. phil. Thesis, chemistry Department, university ofAllahabad, India.

39. Rao, K. K., Ada'rs, M. W. W., Morris, p. and Hall, D. O., Ranganayaki, S. andBahadur, K. (1978) Abstract presented at the BASE symposium, Madurai, India,December.

40. Ranganayaki, S., Raina, v. and Bahadur, K. (1972) J. Brit. Inter. planet, soc.,2s (5): 279.

41. Ranganayaki, S. and Kumar, S. (1979) (To be published elsewhere).42. Ranganayaki, S. et a/. (1979) (To be publishect elsewhere).43. Schrauzer. G. N. (1979) J. Amer. Chem. Soc., l0l,gZ5.44. Sharma, K. (1977) Studies in the .Abiogenesis and Biopoesis, D, phil. Thesis,

Chemistry Department, University of Allahabad, India.45. Sillen. L. G. (t96j) Arkit' Keni,24: 431.

.46. Singh. R. c. (1973) Studies in the Abiogenesis of Enzyme.like Material, D. phil.Thesis. Che:nistr_r' Department, University of Allahabad, India.

47. Singh. \'. P. (i975) srudies in Abiogenesis of phosphoripids, D. phil. Thesis,Chemisrry Departmenr. University of Allahabad, InCia.

-48 smirno'a. -{. \'a. {.1959) proc. First Int. S1'mposium on .,The origin of Life on theEanh", l9-24 -\ugust, 1957, pergamon press, New york, 1g4.

49. Smith, A. E.. Silrer, J. J. and Sreinmann, G. (1969) Experientia,24:36.50. Smith, A. E.. Steinmann, G. and Galand, C. (1969) Experientia,23 13):255.51. Smith, A. E., Raab, K. and Ekpaha-Mensah, T. (1971) Experientia,2T:648.52. Smith, A. E. (1979) (To be published elsew,here).53. Smith, A. E. and Folsome, C. (.1979) (To be published elsewhere).54. srivastava, P. (1967) Studies in the origin and Evolution of Enzymes, D. phil.

Thesis, Chemistry Department, University of Allahabad, India.

Golden Jubilee Commemoration Volutne, 1980

i

J

-,;'"

t{

18 Bahadur Ranganayaki Folsome & Smith

55. Srivastava, V. K. (1970) SrudiesMolecular Associations, D. phil.Allahabad, India.

in Chemical Transformations of AbiogenicThesis, Chemistry Department, University of

56' srivastava, M. (1977) studies in Abiogenesis of Amino Acids, D. phir. Thesis,.Chemistry Department, University ol Allahabad, India.57. Tsigdinos, G. A. and_Swan.on, W. w. <lgjij- na. Eng. Chem. Res. Dev., t7 (3):208.58' upadhyaya, G. (rg77) cytorogicar ano gistoctremicar Studies of seif_sustaining

,ano.l::.u"r.r, D. phil. Thesis, Chemistry Department, Universiry of Allahabad,

59' verma, M. L. (19701 Studies in Abiogenesis of Morecular Association, D. phir.Thesis, chemistry i)epartment, university of Alrahabad, India.

ir I 1,'r;1. i;; t! f l,r i. Yvi

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National Acadeny of Sciences, Inclia

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