|
Key words: melanins, fullerene, cosmoids, cosmochemistry, X-rays, LASER, black particles, interstellar
matter, Bok globules.
Black matter is found universally, especially in the amorphous state. All the black matter known to
date, from the lithosphere and biosphere to the cosmos, generally has the same chemical and physical
properties. These include electron paramagnetic resonance (EPR); electrical properties; changes in
surface properties under the effects of an electric field; the X-ray diffraction spectrum [1]; sensitivity to
radiation inducing photo-ionization and photolysis [2]; explosion and fragmentation under the effects
of LASER, pyrolysis, or fast atom bombardment [3-5]. The physical properties of black particles, and
some of the chemical ones too, do not depend on the structure and nature of the melanogen.
An extensive polyconjugated radical-polaronic system can be found in all pigments, known as Little's
spine [6]. The atoms are arranged in hexagons or pentagons, which are assembled in sandwiches in
layers 3.4Å apart, like graphite in the open form, or giant fullerenes in the closed form. Black material
has certain striking chemical properties: it is sensitive to H2O2 and halogens, it irreversibly loses CO2
and H2O on heating; it can bind organic products, drugs, ions and gas. From many viewpoints the
melanins resemble activated charcoal in their chemical-physical behaviour.
Radioastronomy has shown there are organic molecules in the black dust clouds in the Milky Way.
Some of these molecules are very simple, like acetonitrile, or acetylene systems like the polyines.
Acetylene molecules like HC5N, HC7N, and HC9N have been detected by spectroscopic analysis. Giant
red stars also emit enormous amounts of carbon dust into the surrounding space, suggesting there
may be some links between the acetylene structures and the soot formation [7, 8]. This implies that
interstellar space may look black not just because of the lack of light, or because strong gravitational
fields prevent light escaping [9], but also because of the presence of black matter in the solid state.
This matter would be in continual transformation under the action of radiation.
Graphite, which is found in interstellar space, breaks up under the action of LASER rays in a setting
simulating certain parts of the cosmos, producing a series of fullerenes [7b], including the well-known
C60. LASER light also fragments black particles and melanin. The LASER in mass spectrometry
(MALDI-TOF) does not give molecular peaks for melanin, but there are subproducts which might be
interesting in cosmochemistry [5].
The figure 1 shows a photograph of dark interstellar clouds among the nebulae crowding the
constellation of the Centaurus. These clouds, known as "Bok globules", are normally associated with
protostellar formation [10, 11].
The photography is of great interest because it represent the "time" of Earth formation.
Figure 1
Speculation on the chemistry of interstellar black matter
1/26/02 http://www.tightrope.it/nicolaus/13.htm
These dark clouds in space may contain black particles formed from benzene structures or
heterocyclic polycondensate, like terrestrial melanins. More than 100 different molecules have been
found in the space: H2 and CO being among the most abundant; molecules like CH3NH2, CH3OH,
CH3CH2OH, HC6CN, HC9N, HNCO, CH3CN, CH2CHCN, CH2CO, H2CO, HCNS, CS, COS, CH3SH,
CH2S, acetylene, ethylene, methane, silane, acetylene compounds, polycondensed aromatic systems,
hexamethylenetetamine (HMT), porphyrins, microdiamonds, amorphous carbon [7, 12, 13, 16] and
graphite [9, p.630]. The different molecules might be partly produced by the explosion of
polycondensate systems like those shown in Figure 2, similar to the laboratory procedures for
pyrolysis or atom bombardment [4].
Sulphated and oxygenated molecules might come, similarly, from thiophene or furane systems.
Figure 2
Page 2 of 6 Cosmochemistry
1/26/02 http://www.tightrope.it/nicolaus/13.htm
Mixtures of these materials are found in tars; they are made up of hexagonal and pentagonal rings
and (except for pyrrole black) are little-known electrical conductors [14] on account of difficulties in
isolating and purifying them. Spectroscopic and spectrophotometric analysis of these material is a
potentially useful way of investigating cosmochemistry and interstellar black matter.
It is generally acknowledged that biological evolution followed on the heels of molecular chemical
evolution, and this has led to the proposal that there was probably some synthesis of porphyrin-like
substances in prebiotic times [15]. The presence of porphyrin-like sites [1b] in the melanins suggests
that the black particles found on the earth had some sort of catalytic role, in symbiosis with metals.
Compared to minerals they would be ideal candidates for a prototype structure in the pre-enzymatic
era (stereospecific sites, clathrates, ability to bind metals, photoprotection, etc.). The black particles
may also have played a part in forming the primordial atmosphere on earth on account of their ability
to trap and release gases (in a giant fullerene "cage-like" structure?).
Black particles in general are an interesting feature in the evolution of interstellar and biological
matter. They are conductors, which means they can transfer electrical charges from inside molecular
clouds, regulating their chemistry and the ion-radical-molecule equilibria. These properties can be
deduced from the absorption, polarization of stellar light and spectra of the infrared light emitted by
dust [9, 12]. The black particles might also have played a part in prebiotic evolution as atom and
molecule assembly structures, or as generators of other molecular structures that have been
annihilated. The shock waves produced by the supernovae might have the effect - like interstellar
particles when they move faster than 25 km/second - of making the black particles in space explode.
Page 3 of 6 Cosmochemistry
1/26/02 http://www.tightrope.it/nicolaus/13.htm
High-speed ions can cause fragmentation, and mixtures of simple products form. Some of the simple
organic molecules found in black clouds [12] are also among the products of pyrolysis and fast atom
bombardment of sepiomelanin, melanin from hair, tyrosine-melanin, serotonin-melanin, and
tryptamine-melanin [4]. The following compounds have been identified: CH4, CO2, H2O, HCN, CH3Cl,
CH3OH, C4H8, C2H6, COS, CH3CHO, CH3SH, C4H10, H2S, CH3CN, C3H6, methylcyclohexene, pyridine,
toluene, methylpyrrole, ethenylbenzene, phenol, benzoic acid, phenylester, benzaldoxime, 2,3-
dimethylcyclohexanol, 1,2-benzoisothiazol, benzaldehyde, methylindole. The Stardust, Space
Technology 4/Champollion, and Rosetta space missions should transmit analytical data on black dust
in the years 2005, 2006 and 2013 [16] so we should then have more details. The information
presented here, together with whatever we find out from studying terrestrial black matter (tar,
melanin, synthetic black) could be helpful in analysing the samples collected in the various missions.
Chemists see interstellar black matter as having aromatic and polycondensed heterocyclic structures,
some of them similar to substances known on earth. Under the action of radiation black matter explodes,
forming smaller fragments that are easier to identify. Black matter is in continuous evolution, producing
low-molecular-weight organic molecules as it changes that eventually become ice. As an electrical
conductor, black can regulate the chemistry and the balance of ions, radicals and molecules within
interstellar clouds. Black matter helps shield organic matter from radiation. The basic energy for organic
synthesis - heat, ionizing radiation, ultraviolet radiation - comes from the stars. The smallest fragments
resulting from the explosion of black matter probably give rise to organic molecules similar or identical to
some already known on earth.
The cosmochemistry of black matter may stimulate fresh interest on earth in research on the
melanins, which so far has strayed along the wrong paths. Once we have straightened out problems of
purification and extraction [17], further interesting developments can be expected in nanochemistry,
nanobiochemistry and nanophysics of these black particles [5, 18-26].
Melanin is a conductor whose configuration varies under the action of electric or electromagnetic
fields. Melanin assembles the simplest elements and can control the form and function of cell
adhesion [18, 19]. Stellar melanin is a producer of organic molecules, while terrestrial melanin
assembles organic molecules and macromolecules.
Authors' addresses:
B.J.R. Nicolaus
Dell'Accademia Pontaniana
Via Crescitelli 6, I-20052 Monza
R.A. Nicolaus
http://www.tightrope.it/nicolaus
e-mail: rnicolaus@tightrope.it
M. Olivieri
http://www.dichi.unina.it/multimedia/biomolecole/
e-mail: yorick@inwind.it
REFERENCES
[1] a) G.W. Zajac, J.M. Gallas, J. Cheng, M. Eisner, S.C. Moss, A.E. Alvarado-Swaisgood. The
fundamental unit of synthetic melanin: a verification by tunneling microscopy of X-ray scattering results,
BBA 1199, pag 271, (1994).
b) M. Olivieri, R.A. Nicolaus. Sulla DHI – melanina. Rend. Acc. Sci. Fis. Mat. Vol. LXVI, (1999).
Page 4 of 6 Cosmochemistry
1/26/02 http://www.tightrope.it/nicolaus/13.htm
http://www.tightrope.it/nicolaus/11.htm
[2] Kalyanaraman, C.C. Felix, R.C. Sealy. Photoionization and photohomolysis of melanins: an electron
spin resonance - spin trapping study. J. Am. Chem. Soc. 106 7327 (1984).
[3] S.L. Jacques, D.J. McAuliffe. The melanosome: treshold temperature for explosive vaporization and
in thermal absorption coefficient during pulsed LASER irradiation. Photochem. Photobiol. 53, 769 (1991)
[4] G.Vas, K.Vekey, G.Czira, J.Tamas, D.Favretto, P.Traldi, A.Bertazzo, C.Costa, G.Allegri.
Characterization of Melanins by Pyrolysis / Gas Chromatography / Mass Spectrometry. Rapid
Communications in Mass Spectrometry 7 870, (1993).
See also:
- G. Allegri et al. Pigment Cell Research 1, 87, (1987).
- G. Allegri et al. Biomed. Environ. Mass Spectrom. 15, 53, (1988).
- G. Allegri et al. Pigment Cell Research 3, 181, (1990).
- A. Costa et al. Pigment Cell Research 5, 122, (1992).
- K. Vekey et al. Org. Mass Spectrometry 27, 1216, (1992).
[5] Da pubblicare.
[6] B.J.R. Nicolaus, R.A. Nicolaus. Speculating on the Band colours in Nature. Atti Accademia
Pontaniana vol. XLV, pag 365-385, (1996).
[7] a) H.W. Kroto, Chem. Soc. Rev. 11 435 (1982); H.W. Kroto, Chem. Soc. Faraday Trans. 86 2465
(1990); H.W. Kroto, K. McKay, Nature Chem. 331 328 (1988)
b) T.G. Dietz, M.A. Duncan, D.E. Powers, R.E. Smalley, J. Chem. Phys. 74 6511 (1981). R.E. Smalley,
B.Y. Yakobson, Solid State Communications 107 597 (1998)
c) K.H. Homann, Angew. Chem. Int. Ed. 37 pag. 2434-2451 (1998)
[8] H.W. Kroto. Semistable molecules in the laboratory and in space. Chem. Soc. Rev. 11 435- 491
(1982)
[9] Enciclopedia delle Scienze Fisiche, Istituto della Enciclopedia Italiana fondata da Giovanni
Treccani, Vol I, pag 381, Vol III pag 629-645 (1992)
[10] Astronomia. La nascita delle stelle. Armando Curcio Editore, Vol II pag 741 (1983).
[11] D.F. Malin. Un Universo a Colori . Le Scienze 302 (1993).
[12] L.J. Allamandola, M.P. Bernstein, S.A. Sandford. Photochemical evolution of
interstellar/precometary organic material. Astrochemistry Laboratory, NASA Ames Research Center,
MS 245-6, Mountain View, CA 94035-1000, USA.
http://www.compositori.it/proceedings/bioastronomy/allaman.htm
[13] F.J. Lovas, H. Pickett. The 118 reported interstellar and circumstellar molecules. National Radio
Astronomy Observatory, USA. http://www.cv.nrao.edu/~awootten/allmols.html
[14] G.P. Gardini, A. Berlin. I polimeri conduttori. La Chimica e L’Industria. 73 764 (1991)
[15] S.W. Fox. The origins of prebiological systems. AP (1965)
[16] M.P. Bernstein, S.A. Sandford, L.J. Allamandola. Dallo spazio le molecole della vita. Le Scienze 373
(1999).
[17] M. Olivieri, R.A. Nicolaus. The Pigment of Sepia: an analytical approach. Rend. Acc. Sci. Fis. Mat.
Page 5 of 6 Cosmochemistry
1/26/02 http://www.tightrope.it/nicolaus/13.htm
Volume LXVI (1999). http://www.tightrope.it/nicolaus/12.htm
[18] D.E. Ingber. Tensegrity: the architectural basis of cellular mechanotransduction, Ann. Rev. Physiol.
59 (1997)
[19] J.Y. Wong, R. Langer, D.E. Ingber. Electrically conducting polymers can noninvasively control the
shape and growth of mammalian cells , Proc.Natl. Acad. Sci. USA 91, 3201, (1994).
[20] A. Sionkowska. Photochemical transformations in collagen in the presence of melanin.Journal of
photochemistry and photobiology A-Chemistry 124, 91, (1999).
[21] J.Borovansky, A.M. Mommaas, N.P.M. Smith, D.Eygendal, A.J. Winder, B.J.Vermeer, S.Pavel.
Melanogenesis in transfected fibroblasts induces lysosomal activation Arch. Derm. Res. 289, 145,
(1997).
[22] J. Wilczok, K. Stepien, A.Dzierzega-Lecznar, A. Zajded, A. Wilczok, Model neuromelanins as
antioxidative agents during lipid peroxidation. INABIS 98.
http://www.mcmaster.ca/inabis98/kostrzewa/wilczok0432/index.html
[23] G.M. Robinson, E.J. Iwuoha, M.R. Smith. Characterisation of electrosynthetic L-DOPA- melanin
films by electrochemical and spectroelectrochemical techniques. Electrochimica Acta 43, 3489 (1998).
[24] M.G. Bridelli. Self assembly of melanin studies by laser light scattering. Biophysical Chemistry 73
227 (1998).
[25] P.R. Crippa, S. Michelini. A model for interfacial electron transfer on colloidal melanin. J.
Photochem. Photobiol. B-Biol. 50, 119, (1999).
[26] V. Horak, G. Weeks. Poly (5,6-dihydroxyindole) Melanin film electrode. Biorganic Chemistry 21 24
(1993).
[27] M.M. Jastrzebska, S. Jussila, H. Isotalo. Dielectric response and a. c. conductivity of synthetic
dopa-melanin polymer. Journal of Materials Science. 33 pag 4023, (1998).
Page 6 of 6 Cosmochemistry
1/26/02 http://www.tightrope.it/nicolaus/13.htm
BRUNO J.R.
NICOLAUS, RODOLFO A. NICOLAUS, MARCO OLIVIERI : <<SPECULATIONS ON
THE CHEMISTRY OF INTERSTELLAR BLACK MATTER>>Rend. Acc. Sc. Fis. Mat.
Napoli, LXVI (1999); FOR INQUIRIES AND REPRINTS, PLEASE ADDRESS INFO@BRUNONIC.ORG
|