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< THE DARK SECRET OF LIFE >
Reflections on the chemico-biological role of interstellar black material and the appearance of life in the universe.
Summary.
Simple
organic molecules have been identified among the grains of interstellar
clouds. In
our view, heterocyclic polymers must also be present in space. Their
synthesis is presumed to occur during certain evolutionary stages of
stars. Similarly the presence of acetylene black in space is predicted. A
triple role has been assigned to these black materials: -
supporting structures of interstellar grains through mechanical,
electrical and optical properties (charge transfer, diffraction and
absorption of radiation, transformation of light into current); -
accumulators of chemical energy; -
space storehouses of C, H, N (from which simple oxygenated and/or
nitrogenated molecular fragments, “biogenetic bricks”, are built). In
fact, the black materials can be considered as solid compact parcels of C,
H, N and allow simultaneous transport of these key elements avoiding
losses (oxygen, the fourth key element, is shipped as frozen water H2O). These
polycyclic blacks are split into smaller fragments by
"photolysis" (similar reactions occur on Earth by laser beam and
other radiation). These fragments are later recombined with oxygen
radicals, obtained from frozen H2O.
Oxygenated and/or nitrogenated biomonomers are formed accordingly (equal
or similar to those already known on our planet). The
properties of prebiotic, biotic and spatial black matter are compared and
discussed. Special reference is given to conductivity, the
graphitic-fullerene structure and to surface and interstitial properties.
Consequently, the hypothesis that prebiotic melanins were instrumental as
enzymatic prototypes during the process of self-assembling primigenous
organic molecules is developed and supported. It
is supposed that the organic black matter in the interstellar clouds
protects organic material from cosmic rays and
regulates the ion/radical/molecule balance. The
nature of black particles is many fold: from one point of view they are
instrumental in assembling atoms and molecules, from another in generating
new molecular species by self destruction. A
unique architectonic principle appears to act on organising living and
interstellar matter: cosmic tensegrity. 1
- Preface In
interstellar space there is solid black matter. Numerous
nitrogenated, sulphurated and oxygenated organic molecules known on Earth
are found to be associated with black
matter: these are of different types and complexities and always almost in
radical and/or ionic form, stabilised by the particular interstellar
environment. It is possible to think that this mixture of organic
molecules has its origins in black particles. From
the composition of the degradation material one can deduce that the black
material is composed of carbon, polycyclic carbon (graphite, fullerenes)
and of polyheterocyclic carbon (N,S,O). Almost
all the terrestrial black materials widespread in nature (carbon,
graphite, melanins) and the synthesised blacks (polycondensed
heterocycles) are sensitive to different physical agents (FAB,, LASER,
pyrolysis, etc,): under such action they explode and fragment into smaller
pieces. It is possible that this terrestrial chemical behaviour finds a
parallel in the interstellar black material. The organic molecules,
therefore, have origins in the explosive photolysis of the interstellar
black particles. (1) 2 -Natura enim simplex est During
the last 50 years, the vision of the universe has undergone more than
drastic changes. Initially
we inherited the reassuring image of a placid, bucolic world from Ptolemey
and the ancient Egyptians, with a tranquil Earth at the centre kissed by
the sun and venerated by other planets. Copernicus
brutally woke us up from this idyllic vision which had lasted millennia
and suddenly the Earth has been forced to run a breathless circle around
the sun as well as up and down the universe. Today
we have made a further leap towards a neurotic cosmos, towards a universe
which tends towards an infinite dispersion, sudden fruit of an enormous
catastrophe with the monstrous name of Big Bang. (2) Beyond
the provincial Milky Way, which was once mistaken for the immutable
expression of an eternal order, there are apocalyptic dramas: stellar
explosions, collisions of stars and comets, gigantic encounters between
galaxies. The sun and the stars, the perfect spheres which faithfully
accompanied merchants and navigators over millennia, are today hydrogen
bombs, patiently waiting their inevitable end. Sooner or later they will
finish as they started, in catastrophe. Fear of the apocalypse has given
way to mathematics and the cold, rational certainty of the inevitable end.
Divine providence has packed its bags, hope is dead and buried. The
galaxies are born and die like prehistoric animals, like cosmic dinosaurs.
The universe, once only order and peace, boils, is agitated, flaps in
spasms of geneses and convulsions of agony. The depth of the blue coloured
sky, where we had transferred Olympus, is today the theatre of nova,
supernova and of their explosions. Mad elementary particles, quarks,
atoms, ions and molecules with no fixed abode alternate with storms of
deathly rays. Condensation of energy into matter, and vice versa the
annihilation of the same material, are the order of the day. Flashes of
mortal light dance across the dense clouds of dark matter, of gasses and
of cosmic dust which obscure our view. These clouds will sooner or later
collapse giving life to stars and planets. (Fig. 1). Fig.
1 - Constellation of the Centaur: Bok’s Globules This
frightening picture is not the product of a sick mind. It was conceived
one piece at a time, after the recent progress of astro-physics and
physics together with the new space vectors. Spectroscopy, already amply
used in the study of the structure of materials, and radioastronomy (3), used to scrutinise spaces, has demonstrated that empty interstellar
space does not exist. Space contains a confusion of complex organic and
inorganic molecules. Surprising results have been reached thanks to recent
measurements made outside the Earth’s atmosphere, a fortunate filter of
space radiation. So
that today we know that at thousands of light years from us, there are
many of the composites necessary for the synthesis of macromolecules like
proteins and peptides. Products which will play a highly relevant role in
the appearance of life. Today
we also know that these “biological bricks” existed in space before
our solar system and our planet. Therefore,
life came to Earth from far away shores, or developed on earth and other
hospitable planets, parting from the same building bricks. The
discussion on how and where life arose is still open. On
this question, which has an antique flavour, we later propose a new reply,
even if we remain the ashes and dust of stars. (4) 3
- From space garbage to tensegrity Space
is not empty, as the ancients believed when admiring the depth of the sky
on starry nights. Space is occupied by material, although it is rarefied
and with a non-uniform distribution between stars, planets and galaxies. The
interstellar material
(5) of our
galaxy and perhaps of the entire universe is composed of hydrogen (70%)
and helium (28%) in the gaseous state. Only a very small part (2%) is
formed of tiny solid particles, called cosmic dust or interstellar grains.
Among these elements like O, C, N, Ni, S, Al and Fe and also various
organic and inorganic molecules have been identified. An
important role in the evolution of the interstellar material is played by
these grains, responsible for the absorption and diffraction of radiation,
grain/grain collisions, absorption of various substances on their surfaces
and electrical conductance. These latter properties allow electrical
charge transfer inside the molecular clouds, regulating the ion/molecule
interaction, in turn a source of further reactions. Thanks to their
optical properties, the grains also play a role as filters in protecting
the organic molecules from the demolishing action of electromagnetic
radiation and of various corpuscles. The
grains are amorphous and heterogeneous. According to spectroscopic
analyses, they are formed by silicon oxides, water ice H2O, ammonia ice NH3,
mixed ices of H2O
+ NH3,
various forms of carbon (fuligines, graphites, fullerenes) polyarenes
(polycyclic aromatic hydrocarbons), silica carbon and metallic oxides. Of
all these products, the most interesting for us are certainly the
carboneous products, from which life sooner or later took form. The grains
are subject to growth and reduction. One could say that they “live”
their inorganic, but organised, life. Their dimensions increase in the
dense clouds, by chemical reaction with gaseous types absorbed on the
surface (H2O; NH3, CH3OH, CO, etc). A reduction of dimension comes about, instead, from the
increase in temperature of the coating, radiation with cosmic rays,
grain-grain collisions or nearing a newly formed star. The surface of the
grains represents a valid site of synthesis through photofragmentation and
association between atoms and radicals. The
chemical reactions in the gaseous phase are often disadvantaged because of
the high rarefaction of the components and of the low temperature which
makes the binary and ternary interactions between neutral molecules
improbable. The reactions on the surface of the grains therefore become a
necessary alternative for the chemistry of space. The
carboneous material of the clouds derives from nuclear fusion inside the
giant stars. We can imagine how these “furnaces” have produced the
carbon, oxygen and nitrogen from which we are made, from hydrogen and
helium, by erupting burning fumes into the frozen space.(6) These
then converge into interstellar clouds, where there are demolished and
chemically recombined until they form a biogene molecule. Our
cradle of life seems to lie precisely in these immense clouds which seem
real space laboratories. Living organisms are composed of four key
elements C, H, O, and N while various other elements (S, P, Fe) are
present in small quantities or traces. The appearance of the first forms
of life, even if still simple and primitive, presume that these four
elements have already encountered long before, in the right place and at
the right time. Today
one thinks that this four-way meeting, a possible but improbable event,
happened in the interstellar grains, where carbon and hydrogen were
supplied by the photolysis of PAH (Polycyclic Aromatic Hydrocarbon), the
oxygen from that of water ice and the nitrogen from the nitrogen ice also
present. Therefore,
PAH, H2O
and NH3
would be the three ingredients from which the first organic molecules at
the base of every further reaction derive. However,
the heterocyclic blacks, to which we shall shortly return, have not been
identified in space, to date, and neither have they been mentioned as a
probable simultaneous source of organic molecules. Among
the various carboneous products, radioastronomy has identified some
specific unsaturated aliphatics, worthy of particular attention: the
cyanopolyines.(7) The
fact that types, so reactive on Earth survive in space is surprising, but
can be understood considering the temperature, rarefaction and
photoprotection exercised by the grains and by the black particles. The cyanopolyines are linear homologues of acetylene CH CH added onto a nitrile radical -C N. Their being found in space finds agreement in the presence of free acetylene and cyanhydric acid HCN. These very reactive compounds can cyclize in determined conditions, forming nitrogen heterocyclic and, from these, their black polymers.
Figure
2 - Cyanopolyines determined in interstellar space Acetylene
itself can polymerise in the laboratory, giving rise to linear chains
(acetylene blacks) or cyclic products (aromers, oligomers, aromatics of
benzene). These are variously coloured products with electrical
conductivity (8)
(Figure 3) Figure
3 - Aromatic polycondensed hydrocarbons The
aromers (C6H4)n
are not very common on Earth because of their poor stability. During the
formation process of the polycyclic hydrocarbons those with a non-linear
structure are preferred. On this theme it should be noted that in the
series of aromers, the aromatic character diminishes with an increase in
molecular weight, while the olephinic and instability properties increase.
For example, it has not been possible to isolate the terminal heptacene in
the pure state. The acetylene black (35) formed by a linear aliphatic
chain (radical-polarone system) and, having excellent electrical
conductivity in doped state, can be considered a prototype of the black
organic polymers (melanins). Acetylene forms easily from hydrogen and
carbon at high temperatures and is present in space. It seems probable,
therefore, that one also finds its direct transformation product,
acetylene black, in the clouds. This black polymer could play a relevant
role in electric charge transfer in the clouds and contribute to causing
their dark colour. It also represents a potential store of carbon, from
which to take fragments, by photolysis, for the synthesis of biogene
molecules. The
combustion of acetylene and other products has been amply studied in the
laboratory(9), confirming that in these conditions one has the formation
of aromatic polycondensated types, fullerenes and fuligines. Therefore it
is credible that similar polycondensated materials form in the extreme
conditions of the “stellar laboratory”. The polyarenes, derived from
combustion, are very common on Earth
(10,11) but
fortunately at low concentrations (cancerogenes).(12) It
has been estimated that 2% of the carbon present in the interstellar
clouds is in the form of polyarenes(13), which represent the prevalent
organic molecules in the universe.(14) These
estimates could be redimensioned if the presence of black nitrogenated
polymers in space is confirmed. Unlike
the aromers, the PAH are not very reactive and have very high fusion
points (one may observe that during the determination of the fusion point
the thick glass capillary melts before the product). They belong to
complex cyclic systems and the number of the possible composites is truly
enormous. The physico-chemical and biological properties, like stability
and reactivity, vary according to the steric positioning of the rings and
the grade of alkylation. Both
the polyarenes and the aromers are virtual polymers of acetylene and it is
probable that they are formed in the giant stars by dimerization of dienes
and polycondensation of acetylene derivatives. Besides, on Earth they are
found in the tars from the distillation of carbon and in the residues of
petroleum refining.(15) In
these sources they are accompanied by the analogous polycyclics with one
or more nitrogen, oxygen or sulphur atom. In the stellar and terrestrial
synthesis, the preference towards one composite rather than another is
determined by thermodynamic parameters and not only by chance. A confusion
of highly reactive compounds (radical methynics HC
; methylenics H2C=;
acetylene HC
CH; dienes CH2=CH-CH=CH2;
ethylenes CH2=CH2; etc) in
competition among themselves, takes chemistry back to the first dawn,
when, under the influx of very high temperatures, powerful radiation and
the absence of oxygen, prebiotic reactions were the norm. Among the many
possible structures those which are more stable (and more aromatic) and
with a higher probability of surviving in the
conditions of space have been proposed for the interstellar PAH
(Fig 4), in agreement with radioastronomy measurements. Fig
4 - Structures of polycondensated aromatic hydrocarbons (PAH, polyarenes)
identified in space by radiospectroscopy. The
polyarenes are sensitive to light and oxygen. Under the
combined action of these two agents they form highly mutagenic
oxygenated products (e.g. benzopyrene) in the Earth’s atmosphere. With
organic molecules and salts, they can form charge transfer complexes:
these are excellent conductors of electricity and could catalyse various
reactions in interstellar clouds. From
what has been described one has the picture of a space “crowded” with
various organic molecules. It has also been postulated that many
photoreactions occur in the grains, forming oxygenated aliphatic
composites (aldehydes, alcohols, acids, etc) which are key products for
the synthesis further of biomonomers and polymers.(16) The
nitrate products, except for a few exceptions (N H3, HCN, cyanopolyines, etc), have been given little importance, to date,
despite their representing one of the main chapters in the chemistry of
living forms (proteins, polypeptides, alkaloids, etc). Considering that
most of the biomonomers undoubtedly have their origins in space, it would
seem logical to find the roots of those nitrates in space too. We
turn therefore our attention to this topic and try to find a reply to
three fundamental questions: 1.
Is there a valid scientific basis for the presence of nitrated organic
products in space? 2.
In what forms is it probable that they are found in space? 3.
What relationship is there between the cosmic products and the terrestrial
ones? *** Inside
giant stars all the chemical elements starting from hydrogen and helium
are formed by nuclear fusion. Carbon,
hydrogen, oxygen, nitrogen, C, H, O, N, are the four elements key of
living organisms: “for there to be life” they must be found close
together and in the appropriate forms.(17) The
carboneous stars, during the last stages of their evolution, are rich in
C, H, N. It is easy to imagine that in these conditions various
nitrogenated heterocycles (pyrrol, indol, pyridine, quinoline,
isoquinoline, etc) are formed from acetylene and nitrogen. Similarly,
oxygenated or sulphated polycycles (furane, benzofurane, benzothiophene,
etc) are generated from acetylene and oxygen or sulphur . The
possibility of reactions between the carbon and the other simple elements
like hydrogen, sulphur, oxygen and nitrogen have been amply studied and
now belong to the repertoire of classical chemistry. The
hydrocyanic acid HCN, obtained in the pure state by Gay Lussac in 1881,
can be synthesised from the elements by making a gaseous mixture of
hydrogen and nitrogen run across a voltaic arch with high temperature
(1800°C) carbon electrodes. Passing
acetylene C2H2
across red-hot glass tubes, Berthelot demonstrated the formation of
benzene C6H6
obtained by trimerization and cyclization. If
one makes a flow of acetylene, heated to at least 300°C, pass over
pyrite, one can isolate thiophene H4C4S (Steinkopf)
in high yields. In
a completely analogous way, using ferrous oxide as a catalyst and an
oxygen donor, the furane H4C4O
forms from acetylene. In
favourable conditions (high temperature, metals, nitrogen) acetylene and
butadiene cyclize giving rise to the pyrrol H5C4N, which
represents an important component of various animal and vegetable products
like polypeptides and proteins, haemoglobin, chlorophyll, nicotine,
atropine, cocaine and many others. Therefore,
we can give a positive reply to the first question of the above section:
On a theoretical plane, it seems probable that nitrogenated organic
products and in particular nitrogenated heterocycles (also sulphurated and
oxygenated) form in the course of the stellar chemical reactions and are
erupted into sidereal space. *** The
nitrogenated heterocycles like pyrrole and indole, like also their
sulphurated or oxygenated isosters (thiophene, furane) and their
derivatives tend to polymerise. This phenomenon is accentuated in the
presence of certain catalysts and is highly favoured by temperature and
light. The polymerisation yields amorphous black materials, conductors of
electricity and characterised by a graphite(18) or a giant fullerene type
structure. It
is therefore probable that simple heterocyclics, once formed in the stars,
are quickly transformed into the corresponding black polymers (polycyclic
heterocyclic blacks), and as such are released into space (Fig. 5). Acetylene
+ Nitrogen CH
CH
N2 Pyrrole H5C4N Indole H7C8N Pyridine H5C5N Quinoline H7C9N Isoquinoline H7C9N Pyrrole-black
Indole-black
Pyridine-black
Quinoline-black
Isoquinoline-black
(HC4N)n
(HC8N)n
(HC5N)n
(HC9N)n
(HC9N)n Fig.
5 - Total synthesis of some heterocyclics and their black polymers from
acetylene and nitrogen Graphite
is a stable product, even though sensible to the action of LASER rays.
These manage to explode its structure giving rise to smaller fragments
with the characteristic cage conformation of fullerenes (to take on this
new closed form, the plane of the open structure of the graphite, formed
by a net of hexagonal parallels, curves, restricting a certain number
of hexagons into pentagons). In
interstellar space, the graphite and the black polymers (indole black,
pyrrole black, acetylene black, etc) undergo bombardment by high energy
electromagnetic and corpuscular radiation able to demolish them into
smaller fragments. With similarity to what happens in the laboratory on
Earth, it is probable that these are transformed also into fragments with
nitrogenated fullerene - graphite structures. In these, the pentagons
necessary for the closure of the cage are represented by the pyrrol rings,
isosters of the cyclopenthane. The
substitution of some carbon atoms with nitrogen in a computerised model of
C60
leads to the formation of a nitrogenated fullerene, C53N7,
in which quinoline units are present. The calculated geometric
optimisation does not produced deformations of the initial soccer-ball
type structure. The model shows how a giant fullerene structure is
possible for synthetic and natural blacks. For the giant fullerenes one
predicts diffraction spectra of X-rays similar to those predicted for
graphite structures. For this reason we believe it probable that black
pigments and their fragments from photodemolition are found in space.
These conclusions give an answer to the second of the questions we asked
at the beginning of the section. The black polymers are excellent
electrical conductors, an important property for the evolution of
molecular clouds, and the dark colour may also be caused by the presence
of black material. The
experimental verification of these claims may be possible in a short time,
(first decade of the 21st century) when it may be possible to put our
hands on samples of interstellar material (19). In
the meanwhile, it would be worth verifying the spectroscopic properties of
the black pigments in the laboratory, and comparing them with what has
been collected from radioastronomy to date. The
presence of nitrogenated molecules of the base form HCnN in space has also been shown. These have been attributed a cyanopolynic
structure. It
is interesting to note how this same base formula corresponds to some
black pigments, derived by polycondensation of heterocycles (pyridine
black HC5N,
quinoline and isoquinoline HC9N). At
this point it is possible to draw a further conclusion, confirming that in
space (besides the well known polyarenes, graphite, fuligines and aromers)
there are most probably also: -
acetylene black -
blacks of heterocyclic polycyclics (pyrrol black, indol, pyridine,
quinoline, isoquinoline etc,) -
nitrogenated and non-nitrogenated fragments, deriving from photodemolition
of the heterocyclic blacks. Most
of these heterocyclic materials form charge transfer complexes able to
move electrical charges towards the inside of molecular clouds and vice
versa to catalyse further chemical reactions. These
materials are all black (acetylene black, pyrrole, indole, pyridine etc).
This helps to explain the dark colour of the interstellar clouds. The
black polymers can be considered as compact molecules with which it is
possible to transport ternary mixtures with bases of carbon, hydrogen and
nitrogen simultaneously in space. In the right place and at the right
moment it is possible to have simple nitrogenated and/or oxygenated
organic molecules, identical to those which compose living organisms, from
these modules, through photodisassociation and recombination. (Fig. 6) (
www,tightrope.it/nicolaus/13.htm ) and Link 5. *** According
to various research, the interstellar
grains are composed of a nucleus of silica oxide covered by a mantle of H2O
ice and NH3
ice. Polyarenes and other simple molecules are trapped in this icebox. As
already mentioned, we believe that other non-identified carboneous
materials should also be found in the grains. These including the black
pigments of polycondensed heterocycles, acetylene black and their
fragmentation products. These black materials, undergoing high energy
cosmic radiation are fragmented and recombined, up to obtaining, with the
help of H2O ice, simple oxygenated organic molecules CH2O,
CH3OH,
C2H5OH,
etc and nitrogenated molecules HCN, CH3CN, etc. These molecules in turn are trapped and will take part in
further fragmentations and combinations. According to this model, the
grains act as a support for the chemical reactions in the solid phase.
These will happen at temperatures near absolute zero, under the action of
cosmic radiation comparable in intensity to terrestrial LASER rays. In
these conditions one can make selective reactions at photosensible
molecular sites (targets) eliminating the background noise of vibrations
and thermic movements. The forced fragmentation of the black material will
bring a myriad of radicals, able to react with the water molecules in ice,
captating the oxygen. This will give rise to oxygenated nitrogenated and
mixed compounds, keys for forming biomonomers and polymers. In the grains
aliphatic products, aromatic products and oxygenated heterocyclics form,
Among these are : CH3OH,
C2H5OH,
HCHO, CH3CHO,
HCOOH, CH3COOH,
NH3,
CH3NH2,
C2H5NH2,
HCN, CH3CN,
HC(NH2)COOH,
CH3CH(NH2)COOH. Fig.
6 - Explosive photodemolition of the black particles. Parting
from a few simple products the stream of the organic molecules will follow
like a flood, and from this will come life. In the biological synthesis of
biopolymers (polysaccarids, proteins, lipids and others), solar energy is
transformed into chemical energy. Consuming
these products, the organisms acquire the building blocks of living
material and recover part of the accumulated energy. The macromolecules
therefore play a triple role of: -
Support structures for the organisms, -
Accumulators of energy, -
Stores (reservoirs) of building blocks of living material. Life
on earth was built on these simple principles. Something
similar happens in the cosmos. When the stars synthesise the base
elements, and from then on, the organic polymers, in fact they transform
nuclear energy into chemical energy. After
the expulsion from the stars the organic polymers navigate in space also
playing a triple role, as: -
Support materials using their mechanical electrical and optical properties
(charge transfer, diffraction of radiation, transformation of light into
electrical charge); -
Accumulators and distributors of energy (chemical); -
Stores of molecular fragments, (simple and complex molecules). The
reactions in the stars occur at very high temperatures and pressures, in
reducing environments. This is the ideal site for the chemistry of carbon,
and nitrogen. The oxygen, instead, where it is formed, is soon trapped in
water molecules. The
chemistry of interstellar space is the chemistry of cold. It occurs in the
grains at temperatures near to absolute zero, in solid systems (ice),
under the action of cosmic rays and in the presence of oxygen in the water
molecules of H2O
ice. It is a chemistry in which the bonds break and reform with great
precision. The
screen of dark material, the low temperature, the absence of free oxygen
gas and of gravity allow the survival of radicals and even highly reactive
molecules. The
chemistry of the biotic era, instead, is of a refined sophistication. It
is the chemistry of enzymes in antiradical functions. It is a chemistry
which loves moderate temperatures, watery environments, atmospheres rich
in oxygen. It is the chemistry which has tamed oxygen, the most aggressive
of the terrestrial elements. Despite
the considerable differences these three chemistries are made similar by
the same principles: “natura enim simplex est”. Cosmic order has
stamped the biological world, has moulded the living world according to a
unique architectonic principle. Wherever one turns ones eyes in the living
world there are chemical reactions. Plants and certain bacteria fix the
solar energy synthesising complex substances from simple materials. Other
organisms decompose these materials into simpler structures, using the
energy they contain. In every cell there are intense chemical processes
(reduction, oxidation, hydrolysis, synthesis, etc). The
chemical composition of plants is simple. The biochemical architecture of
the living things is based on a few pillars C, H, O, N, S, P, etc. This
sparse array ramifies into a myriad of molecular composites: binary with a
base of only carbon hydrogen (the hydrocarbons), ternary with a base of
carbon, oxygen and hydrogen (carbohydrates, fats etc), quaternary with a
base of carbon, hydrogen, oxygen, nitrogen (the amminoacids, the peptides,
polypeptides, proteins, nucleic acids, alkaloids, lipoproteins, etc) and
so on. Living
beings possess a unique characteristic, reproducibility. Another salient
property is the specificity of the single structures and the relationship
between the structures and a biological role. The
surprising variety of living forms and the individuality of the various
organisms can be conducted to the individuality of some macromolecules,
the proteins. However, these are nothing but combinations and permutations
of a few amminoacids, invariant for various millions of years. In
all the organisms, fuel is transformed into carbonic dioxide CO2 and water H2O through few reactions. The production and use of energy, on the part of
the cells, has the same mechanism in many animal species, from protozoons
to mammals. Returning
to the star at this point a spontaneous question arises, about the role of
interstellar smog, that black
tinted garbage of the space which is among the most deadly of cocktails.
At first sight it may seem erupted
from gigantic forges. At a closer look it demonstrates a design and a
target. Among
the dark clouds light is reemerges, lifting the veil on the great mystery,
it is no longer completely secret. *** 4
- From a black tinted firmament to
the skin and the brain On
Earth nature is painted in many colours. Transcending purely aesthetic
values, the colours play a unique role in the communication between
different worlds (animal, vegetable and mineral). Colour
is an instrument of communication. The mechanism with which colour is
formed is physical. It happens through the change of the state of the
electrons in material. Colour
is an electrical phenomenon. Light and electricity are easily transformed
from one to the other. They are two aspects of the same nature. A
grating, a prism or a drop of dew all decompose the light into colours of
the rainbow and each of these colours corresponds to a frequency of an
electromagnetic wave. A body appears white because it reflects all the
light, black if instead it absorbs it. In sunlight white seems fresh,
while black burns. Black is not, therefore, a colour, on a par with the
others. There is a precise relationship between the colours and the
structures of colourants, and the pigments are classified on the basis of
their structure: carontinids, pteridins, porphyrines and so on. The
black pigments are an exception. They are regrouped according to their
colour which is not a colour, neglecting the extreme differences of many
of them. This is black tinted chaos. The terrestrial black materials,
unlike those in space of a binary (C, H) or ternary (C, H, N) nature, are
in general oxygenated. They are easily obtained by polymerising simple
molecules and are named after the substances which have generated them: acetylene black,
benzene black, aniline, pyrrole, thiophene, indole, pyridine, quinoline,
isoquinoline, etc. Those
produced by living organisms are well represented both in the animal
(eyes, skin, hair, etc) and the vegetable (seeds, flowers, fruit, woods,
etc) kingdoms. They were called melanins(20) and often derive from
aromatic systems and polyhydroxylated heterocyclics.(21) Leaving
aside the precursor which has generated them and for this reason also
their substitutes, the melanins present properties typical of black
materials and these can be conducted to the nature of the solid state.
Black materials are spread in all the universe and is almost always
amorphous and non-crystalline. From the lithosphere and biosphere to the
cosmos, they possess interesting chemical and physical properties both for
the implications for the vital processes and for the study of
astrochemistry. These properties include: -
EPR (Electronic Paramagnetic Resonance); -
Electrical and sound waves conductivity (36); -
Modification of surface properties under the action of electrical and
magnetic fields; -
X-ray diffraction spectrum
(22) -
Sensitivity to radiation which produce ionisation and lysis of the
covalent bonds
(23) -
Fragmentation of the structure on fast atomic bombardment, LASER rays,
pyrolisis, oxidation -
Formation of charge transfer complexes -
Permeability to gas and liquids. The
melanins are “fruits of the Earth” and for this reason almost always
oxygenated The earth is the planet of oxygen; oxygen is life. The melanins
are ternary (C, H, O) or quaternary (C, H, N, O) or more complex (C, H, N,
O, S, ...) composites. Life, complexity and the melanins are the fruit of
living organisms. The
black polycyclic heterocycles are the offspring of the stars and navigate
in space. We can call them “space melanins”. They are almost always
ternary composites (C, H, N). They are constructed according to the same
principle and this relationship is given away by their structure. The
oxygen distinguishes the two classes without changing, though, some
fundamental properties. Similar
or different structure, similar or different
role? *** A
guiding concept is recognised in the structure of all the pigments. They
all have an extended polyconjugated radical-polaronic system called the
Little spine (24), in which unpaired electrons create conduction bands. The black
particles are amorphous semiconductors and have electrical conductability,
which can be modified by doping. Under X-rays the melanins present a
diffraction spectrum which is similar to that of graphite, or of the giant
fullerenes. The
strict relationship between melanins and graphite is expressed in the
colour black, in the EPR signal, in the electrical conductability and in
the sensibility to oxygen, to name some of the parameters. The relation is
so strict as to be able to consider graphite in some sense the simplest
natural melanin or the “Protomelanin” of the prebiotic era. Like
other black particles, the melanins are sensitive to light
(photoionization and photolysis) and to LASER rays (Light Amplification by
Stimulated Emission of Radiation), which provokes a real explosion of the
structure. This property finds multiple practical uses: in dermatology (25) for the transformation of black skin into white, in cleaning of
monuments and art works. The
collapse of the black particles has been studied for the purpose of
cosmo-chemistry, among other things, by bombarding graphite with LASER
(the experiment brought about the discovery of the famous C60 (26). It
does not seem that there has been further investigation to see whether a
similar reaction occurs in the interstellar black dust. Despite this it
seems reasonable that electromagnetic fragmentation plays a not
indifferent role in the photolysis of the black heterocyclic polymers
present in space. Effectively the small organic molecules associated to
the black material indicate that there is fragmentation in course. The
melanins have origins in the hydroxylated (orthodiphenoles) of aromatic
systems like benzene, indol, pyrrol, pyridine, quinoline. DOPA,
Dopachrome, DHI (5,6-Dihydroxyindole), DHICA
(5,6-Dihydroxyindol-2-carboxylic acid), dopamine, adrenaline, serotonine,
5,6-dihydroxytriptamine, 5,6-dihydroxy-7-methyl-tetrahydroxyquinoline
(linole salt) (27), are some of the substances, which play a role in neurotransmission
in living organisms, and which have the properties of producing black
particles (melanogenesis) in turn having a biological role. Melanogenesis
is a complex reaction of an enzymatic and
radical type. The first phase consists of the formation of the
oligomers, in which polyconjugated chains assembled according to the
scheme of the Little spine (acetylene-black) are present. The second phase
is characterised by the self-assembly of the various units up to reaching
graphite structures. This model is universal and is valid for the melanins
on Earth and those in space (in the former case it is useful to consider
the role of oxygen and of the enzymes operating on Earth). The
melanins are able to bond various substances and ions both by salification
(carboxyls, nitrogen bases) and by coordination in typical porphyrine
complexes or thanks to interstitial processes. Also the various gasses and
water can be trapped by the melanins (absorption) as happens in the case
of active carbon and the small fullerenes (C60 and C70) with some noble gasses. The entrapment of oxygen and water can suggest
new biological roles for the melanins as matrixes for guided reactions. The
porphyrine system allows the formation of various complexes, helping to
explain the affinity for ions and metals, the peroxydase activity, the
absorption of gas, the coordination of the water molecules and the
electrical conductivity. These
properties and the fact that the melanins (even if different from the
currently studied molecules because of the lack of oxygen) must have
already been present on the Earth in the prebiotic era, has led to the
hypothesis of their having a role in the self-assembly of the first
organic molecules. Acting
as a matrix these materials would offer many advantages, besides the
simple absorption of reagents on the part of the minerals. In contrast
with the monotonous symmetry of a mineral lattice, the black particles can
offer a vast diversity of steric configurations, both with their own
external surfaces and with their porous internal parts. If you look for a
given combination of stereo-specific sites and relative functional groups,
also having the capacity to bond metallic ions, the melanin particles seem
more adapted than minerals like clay and pyrites to be prototypes of a
structure of enzymatic behaviour. In this same environment it should be
recalled that the melanins possess structural characteristics similar to
molecular sieves and to resins with ionic exchange. More explicitly, the
enzyme is a matrix which traps reagents and is provided with a metallic
centre (catalyst). The melanins correspond to this model of a primigeneous
enzyme. The electrical and sound wave conductivity of the melanins, the
fullerenic cages, the surface properties, the unpaired electrons, the
hydration, the interstitial activity and charge reversibly applying an
electrical potential, that is, the electroactivity
of the melanins, thus reveal the other side of their nature. This
is flexible and mutable, completely unexpected from the rigidity of the
structure. Under
the action of heat, powerful radiation and electrical discharges the
melanin matrices take us to the prebiotic era, when carbon derivatives are
organised into simple molecules which become more and more complex
eventually yielding living organisms. *** The
age of our planet is written in its rocks and its birth, connected with
the explosion of a supernova, was certainly traumatic. This
is testified by the radioactive uranium (235U)
still present and by its fission products, as well as by the endless
deposits of heavy metals, these being elements which do not form during
normal stellar evolution, but rather, following violent fusions. From
the geological stratification and the radioactivity of the rocks the start
of the Earth as an independent planet in space, is dated at 4.5 billion
years ago. From
this one deduces, that anaerobic life started 3.6 billion and aerobic 2.5
billion years ago or a little less; therefore there are about 900 million
years between the birth of the planet and that of life the prebiotic era (28). The
atmosphere today is dominated by nitrogen and oxygen,
with small percentages of carbon dioxide CO2, H2, H2S, CH4, NH3, NO2, NO, SO2, O3 (
29). The
atmospheres of Venus and Mars are instead dominated by CO2 with small percentages of oxygen and nitrogen.(30)
Making a comparison with something from everyday life, our
atmosphere is like the mixture of burning gasses which makes a motor car
work, those of Venus and Mars like the exhaust gasses of the same motor.
The first case it is synonymous with life, in the second is exhausted and
sterile. We do not know precisely what the primogeneous atmosphere of the
Earth was like. We can only make guesses. One imagines that it was
reducing and for this reason had the capacity of binding oxygen and
impeding its appearance in the pure state. The oxygen appeared much later,
freed by photosynthesis or micro-organisms. It is a gift from the sun
and from life. From
the reaction of the ferrous ion (Fe++)
with water (H2O), copious
amounts of hydrogen gas (H2) formed which was dispersed in the atmosphere. At the same time hydrogen
was also erupted in great quantities by vulcanoes together with carbon
dioxide (CO2). All
this contributed to making the air and the oceans highly reducing. A
totally different picture to today’s. If today, for example, we threw
the carcass of a car into the sea today, soon we would have little more
than a pile of rust. The oxygen oxidises the iron without pity. In those
times, the car, would, instead, have dissolved without leaving a trace. In
the first five hundred million years of its formation, it seems that the
Earth was bombarded by small planets, asteroids, comets and other residue
of the cloud of the sun. The traces of these apocalyptic collisions are
still obvious in the many small, large and immense, craters so far
discovered in various regions.(31) Besides
the mechanical damage caused by this cosmic “rain”, it is probable
that many simple and complex organic molecules accompanied the downpour,
stored in the grains of the interstellar clouds. These contributed to the
creation of a “protomix” of reagents ready for further combinations,
from biomonomers to biopolymers, on the Earth’s crust, in the sea and in
lake waters. In
the prebiotic era chemical reactions already sketched out in space
occurred on the Earth and others adequate to the profoundly changed
environmental conditions also developed. The temperature passed from
almost absolute zero of space to 20-30° on
Earth. The molecules no longer frozen in the grains became mobile
and superactive with great possibility of remixing in the agitated waters
with strong tides. The kinetic possibility of collisions and reactions
with different partners notably increased. The
now liquid reactions and the weakening acid favoured the dissolving of
basic (amines) substances and reactions of addition and condensation with
other functions (e.g. aldehydes + nitryls ----> amminoacids),
while the reducing environment kept sensitive products (aldehydes,
alcohols, phenols, etc) safe from oxidation. The
water screened the UV rays and actively participated in hydrolysis and
hydration. New possibilities of assembling complex structures were created
at the solid/liquid, solid/gas interfaces between dissolved reagents or
gaseous with inorganic (clay, pyrites) and organic (melanins) matrices. Following
the decomposition of water (H2O) highly
reactive oxygenated radicals formed giving the start to new reactions and
new compounds. The era of oxygen would soon come about. The notable
increase in the temperature stimulated reactions which were previously
blocked for the lack of activating energy, in the new terrestrial
environment. A
mass of metallic ions, free and chelated in fortunate matrices (melanins)
mingled in the marine and lake environments, determining the chemical
cataclysm which gave the biotic era the start of enzymes. The
“prebiotic test-tube” became bigger and bigger, expanding enormously,
taking in by now, lakes, seas and oceans: the biological soup was ready
for cooking. *** Given
that the pot is ready a spontaneous question arises: Will the soup be the
simple outcome of chance or is it, instead, preordained and to some extent
guided? The question is valid, giving an answer is difficult. In nature
there is a continual conflict between the game of chaos and the tendency
to self-organisation. The study of the sciences and of chemistry in
particular moves in the direction of order, seeking an ordering principle
of every phenomenon. We shall examine two concrete examples, one coming
from physics the other from biology. We
have a universe made of hydrogen. In this universe carbon is the element
on which life is based. It is still difficult to understand why such
enormous quantities of this element have formed.(32) The
synthesis of carbon is a sequence of improbable events favoured by energy.
It starts with the fusion of two atoms of helium which form beryllium, an
isotope which is so unstable that it must disintegrate quickly and
regenerate helium. But, instead, the beryllium fuses with another atom of
helium and produces carbon. This last reaction is improbable but is
favoured since the combined energy of beryllium + helium (7.370 MeV) is in
fact a little less than that of carbon (7.656 MeV). Reacting with helium
the carbon should, in turn, form oxygen. However, this reaction is not
favoured since the energy level of oxygen (7.1187 MeV) is lower than that
of the two reagents (C+He = 7.1616 MeV) even if only by a little. There is
a low, but sufficient, probability that the energy levels of the sequence
He, Be, C, O are in correspondence with the necessary levels. The energy
balance prevails over the game of chance. Therefore we have a universe
coloured black, as black as coal. According to
Darwin, the first forms of complex life (blue algae, bacteria)
developed in the span of 500 million years, parting from a casual
molecular soup. A short length of time, frankly, for obtaining such
complexity through the game of fortunate chemical reactions and casual
mutations. Chemistry follows precise laws. The molecules, even though free
to oscillate, vibrate, and move randomly and tend to become organised
according to predetermined lines. The
very concepts of chemical valence or of affinity are deterministic.
The atoms are not free to pair up randomly They obey the laws of chemical
bonding, of valence and affinity. The same is true for molecules which are
groupings of atoms, pairing according to a precise design. The degrees of
freedom of atoms and molecules are not infinite. Little is left to luck. The
evolution of material, which started with the elementary particles,
continued with atoms and molecules inside the stars and interstellar
clouds. The planetary ecosystems are made up of populations by diverse
organisms and these are made up by cells, the cells by proteins, the
proteins by molecules and blocks, the molecules by atoms and these from
subatomic particles. Nature
(from quarks to the galaxies and from bacteria to the planetary
ecosystems) tends towards complexity, to self-organisation. The subatomic
particles join in atoms and molecules,
these in biomonomers first and in polymers later, the protobiontics in
structures and pluricellular organisms, which in turn make way for social
and ecological systems.(33) The
creation of this plurality of organisms and structures in such a short
time necessarily reduces the casualness of evolution and alters the
probability of variations in favour of ordered and coherent outcomes. Therefore
it appear more and more realistic that there are interactions between the
physical, chemical and biological aspects of nature. These interactions
which make order prevail over chaos. *** 5
- The dark secret of life Our
vision of the cosmos and life have changed from the start of civilisation
and they have been overturned in the last few years, by the force of
science and technology. Today
we know that the space between the stars and planets is not a vacuum as
was once believed. It is vibrating with material. There are atoms, ions,
simple and complex molecules. Some of these molecules only exist in the
stellar regions, many are well known in the terrestrial world. Among these
there are various composites necessary for the synthesis of proteins,
peptides, carbohydrates, and lipids, the basic macromolecules of living
organisms. The
clouds have lost all their magic characteristics and seem more and more
like huge black coloured stellar garbage cans, gigantic accumulations of
rarefied material, all dust and grains of various size, which live in
their own organised “inorganic life”. The grains grow, diminish in
number and amount, and are in continual evolution. They show important
optical properties (diffraction, absorption of electromagnetic and
corpuscular radiation), electrical properties (charge transference,
photoelectric effect), chemical properties (photolythic reactions,
photosynthetic, dissociation and combination). Singular properties which
evolve and alter notably. In
the grains, real miniature space
laboratories , delicate photochemical reactions occur which are
great importance for the future biogenesis at temperatures near
absolute zero. Complex materials are fragmented and these recombined into
oxygenated and nitrogenated molecules (alcohols, aldehydes, acids,
carboxylics, ammines, nitrils, amminoacids, phenols etc). The
black polymers are excellent conductors and show a pronounced
photoelectric effect (transformation of light into current). This property
is possessed to an even greater measure by charge transfer complexes which
form easily from black polymers. It is reasonable to suppose, therefore,
that these play a role in the evolution of the stellar clouds. All this
assumes particular value considering the stars and planets which form from
the gravitational collapse of stellar clouds. The
black polymers, probably created from polymerisation of acetylene and
nitrogen in the giant stars, play a triple role in these clouds. They are: -
Support structures: mechanical, electrical and optical properties (charge
transference, diffraction and absorption of radiation, transformation of
light into current); |