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Rodolfo Alessandro Nicolaus. Chemist born August 1, 1920 in Naples off Mustair parents. Pupil of M. Bakunin (Naples), T.Reichstein (Basle), L. Panizzi  ( Rome ).Professor of Organic Chemistry at Naples,  Basle, Rome Universities. Member of Accademia Pontaniana,of Accademia di Scienze Fisiche e Matematiche della Società Nazionale di Scienze Lettere ed Arti in Napoli,Golden Medal of Accademia delle Scienze detta dei XL, Golden Medal De Luca della Società Chimica Italiana, Honorary Member of Pigment Cell Society and Italian Chemical Society.

### Research  on Archaebacteria from Campi Flegrei-volcanos started at the Laboratorio per la Chimica e Fisica delle Molecole di Interesse Biologico (Arco Felice CNR, Rome,  1968-1975)  . bnicolaus@icmib.na.cnr.it  

### Centrospermae pigments were discovered, isolated,synthetized ( Piattelli M.,Minale L.Nicolaus R.A. (1965) mario.piattelli@poste.it   rnicolaus@tightrope.it at the Organic Chemistry Institute of Naples University.The structure of indicaxanthin (Opuntia ficus-indica),Vulgaxanthin (Beta vulgaris L.), Portulacaxanthin (Portulaca grandi flora), Miraxanthin (Mirabilis jalapa), Phyllocactin (Phyllo cactus hybridus Hort.), Betacyanins (Phyllocactus hybridus.Celosia cristata,Iresine herbstii), Amarantin (Amarantus tricolor) was elucidated.

 ### The beginn of marine products chemistry (Minale L. Fattorusso E.  1970 ). occurs in the same period.  fattoru@unina.it

### Following earlier research (1949-1975) papers on chemistry and physics of black particles were published (1995-2005 ).

### Chemistry of eumelanin started at the Institute of Organic Chemistry Naples University.Degradation products of eumelanin were isolated for the first time. (Panizzi L. Nicolaus R.A.,1959 )

### Melanosome was isolated for the first time (Hearing V.J. 1970 )

 ###  5-S-Cysteinyldopa, the precursor of pheomelanins was  discovered, isolated, synthetized  ( Nicolaus R.A.  1966. ).Structure  of the Pigment of red hair was elucidated.. The chromophores of Pheomelanins and Pheochromes were synthetized ( Kaul B.L.,Prota G. 1974).The importance of Cysdopas in Biology ( Rorsman H. 1970)

### The acetylene-black radical-polarone-system is present in  eumelanin ( Nicolaus R.A. 2001 ).

### Quinones hydrate of eumelanin to explain the content of oxygen (Nicolaus 2001).

### Melanins are particles (Chedekel M.S. 1992)

### Graphite,fullerene or elicoidal cage of eumelanin ( Bolognese A.2002 ). bologne@unina.it

 

 

 

 

Melanin chemical study should be carried out on samples of pure granules

 

.Melanin appear to be instrumental for various brain functions, for the ear to hear, for the eyes to see. No blue or green colours would be seen in animal and plant kingdom without melanin .No blue or green eyes to admire.  If you don’t believe it, remove the melanin from those organs and observe what happens………………

The chemical study of melanins have given poor results until now because of using   of  raw material in chemical and physical analyses and scarce knowledge of  solid state by chemists and biologists. The discovery of the particle may change our strategy in the study of structure and function of melanins.

 Melanin is necessary for brain, ear, eyes, skin to function.  It would not be possible to see  blue or green colours  in animal or plant kingdom without melanin. No blue or green eyes to admire……

If you don’t believe it imagine to remove the melanin from the biological tissue  and observe what happens. 

 

                                                                                        

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Melanin studies:  (1995-2005 )   

 

 

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 Black pigments  are amorphous semicoductors  mostly after doping.Threshold switching was observed   (http://www.organicsemiconductors.com/  ). Black materials are generally amorphous semiconductors but the conducting and superconducting fulvalenes ( EDOEDTTTF, EDOMDTTTF, EDOVDTTTF, MDTTTF )  complex salts are known to form beautiful black crystals.

  ‘’ Colour ’’  depends not only on the gap (expressed in eV ) of the semiconductor model  but also by particle structure ( morphology)  or doping of yellow or red material which could explain why the methyl ether is not  black anymore.

Blue or green pigments don’t exist in animal or plant kingdom.

Melanin is  responsible for blue , green or yellow colours in  animal  and plant kingdoms.  

 

The black material is classified as BCM  (Black Cell Material) and BSM (Black Synthetic Matter ).

 

BCM are classified in

 

 

Eumelanin  particles generally derived from DOPA, and widespread in the animal kingdom  ( skin, hair, eyes, brain, feathers etc. )

Neuromelanin particles generally derived from dopamine and cysteinyldopamine. Neuromelanin  from  Substantia nigra  was isolated by H.Rorsman in 1991. As reported by  M.G.Bridelli the  IR of neuromelanin has features similar to those of synthetic dopamine-melanin but different with other catecholamine-blacks

 

Pheomelanin  particles generally derived from Cysteinyldopa discovered by R.A.Nicolaus in 1967. Light brown, or reddish , free or as protein complex alkali soluble animal pigments. .Eumelanins and Pheomelanins may coexist in Nature. 

 

Pheochromes     red , yellow crystallisable compounds derived from Cysteinyldopa . The only   pigment elucidated (see formula below) is that of red hair isolated for the first time from the  New Hampshire chicken feathers by R.A.Nicolaus. (  different confusing names are trichosiderins, tricochromes, pyrrotricholes  ).Some products are common degradation products of  pheomelanins and pheochromes. Chromophores ( I,II,III,IV ) have been synthetised by Kaul B.L.and Prota G .

 

BSM has famous partners like :

Acetylene-black

Aniline-black

Pyrrole-black

Indole-black

 

In nature the black particles ( BCM = black cell matter, melanin ,  natural melanins , eumelanins etc  )  may  form from  many different precursors like decarboxycyclodopa , DHI,   serotonine, catecholamines, dihydroxytryptamines,    dopamine, adrenaline, dihydroxyquinolines or, in general from,polyphenols   The heterogeneous black material is generally formed by oxidation  of o.diphenols resulting in CO2  evolution and H2O2 formation.The carboxylic group present in many polymers of the particle are formed from the breakdown of the benzenoid part of the polymer units The elemental analysis of the black material show in general one oxygen more than the precursor.The polymer(particle) formed from oxygen-free precursors are oxygenated. This may be explained with storage of oxygen, water,  addition of water to the quinone groups, addition of water to the quinone methide structure, presence of carboxylic groups  or with a trihydroxylated-phenyalanine precursor .The precursors can  deeply change . For example pyrrole rings are present in certain melanin formed from indoles.

 Melanins  show  typical broad EPR, IR, 13C- NMR  ( an aliphatic part is always present in spectra)  spectra of amorphous state but an ordered  state appear under  the AFM  figures but results are uncertain because the raw material used. Eumelanin identification may be accomplished comparing it with a know material like  dopa-melanin, cyclodopa-melanin, DHI-melanin, DHICA-melanin, tyrosine-melanin.

 As long-awaited  the MALDI procedure  is not useful for molecular weight determination, as occurs for proteins. LASER  operates a fragmentation (explosion) of the particle. The MALDI fragments are  useful in  structural study. of melanin .

 Methylether are obtained by action of diazomethane on melanins or pyrrole-black.This could suggest the presence of  hydroxyls are present .The methyl ether of melanins are lighter in color.

 

It is frequently forgotten that sepiomelanin  ( from the ink sack of Sepia officinalis )  is the Ca Mg salt of sepiomelanic acid. The sepiomelanin  precursor and chemical structure were object of discussion during  the past fifty years.Now biologist and chemist  indicate the 5,6-dihydroxyindole ( DHI ) as precursor but the polymer analysis show more oxygen as the precursor. The samples of the  black material obtained from the ink sack are   mixture of   premelanosome,  melanosome , granules and foreign substances  which may have  different composition and physical properties.  Furthermore the black is modified  during the extractive process.

Mild oxidation or hydrolysis may produce  pyrrolic acids of different complexity derived from the  breakdown  of catechol part of the indoles units.  High proportion of degraded    units were observed in sepiomelanin samples depending on the type of preparation adopted. It is not clear that the reaction occurs also in the cell  . Generally data of   melanin elemental analysis,  physical properties like IR, EPR, 13C NMR, MALDI, conductivity, atomic force microscopy (AFM), bindig effect, storage of gas and liquids  should be considered with criticism.  

 Samples of the material formed of pure and stabilized granules are advisable in sepiomelanin study.Analysis for C,H,N,S,Cd,Ni,Fe,Cu is recommended

 

Melanins  are particles with different shape and size (  also due to different treatments used and different type of oligomers ) .Melanins are particles built up  from yellow to red oligomers ( sometimes degraded  oligomers )  of relative low and variable molecular weight Oligomers, the fundamental stones of the particle, are found to be optically active intermediates ( DHICA  tetramers ). Isomeres cis/trans have different conductivity ( pyrrole-black, acetylene-black etc. ) . Such oligomers contribute to the shape and size of the particles and other physical properties.The chemical and physical study of the fundamental structural units ( aggregates,filaments, smaller constituents, oligomeric molecules ) of the particles is of great interest for biology   and material sciences.

The presence of particles in light exposed tissues suggest that they are involved in photoreactions Tetramers of DHICA ( a melanogen )brown-yellowish materials,  are found in nature like the reflecting material of the tapetum lucidum of the sea catfish.  Melanins might show  various hydration and oxidation levels.The polyacetylene radical- polarone system  is supposed to be present in all  natural (BCM) and  synthetic melanins  (BSM).

 

Some peculiar properties of black material  suggest melanin being a material of importance for living matter  :

 

( a) the morphology  state  (b)  electric and acoustic conductivity, electric switch, photoelectric conductivity  (c)   particle  binding  power for  organic and inorganic materials,   ions and  molecules . Ability of  store  liquids and gases ( meteorites,  humic acids,  cellular oxygen )  (d)   explosive fragmentation by exposure to LASER  (  formation of the fullerene C60  from graphite, depigmentation of the skin ) .

 (e)   behaviour as innovative sensor and energy generator with the capacity to grow and shrink significantly in length and volume when subjected to electric stimulation.  (f) sepiomelanin composition which change with time  in vivo and in vitro

(g) communication between tissues  and between tissues and brain.

(h)  presence of  black particle ( carbon, silicium,BSM )  in interstellar spaces

 

Some points worth of being recalled  to  the  melanin expert are the followings :

1 . Melanoma was found to be constituted  by two different melanins ( M. Bakunin 1904 )

 2 . Simple or complex pyrrole acids were isolated  among the oxidative degradation mixture   of Sepia melanin ( L.Panizzi, R.A.Nicolaus 1952 ). DHI and DHICA were obtained for the first time as degradation products ( R: A: Nicolaus, M.Piattelli 1962 ).

 3 . The precursor of pheomelanins and pheochromes  was found to be the new aminoacid 5-S-Cysteinyldopa   and related isomers ( R.A.Nicolaus 1968 ).Many degradation compounds were isolated ( R.A.Nicolaus, L.Minale,E.Fattorusso 1968-1972 )

4 . The chromophores ( dibenzothiazine and dibenzothiazinone ) of pheochromes have been synthetised.  ( B.Kaul  1974 ).

 5 Melanins are able to bind organic molecules, ions,  liquids, gases ( M.S.Blois 1965), ( H. Rorsman,  1972 )  ( N.G.Lindquist, B.Larsson ,C.Hanson, G.Agrup, E.Rosengren  and the Swedish School since 1972 ).

 6 . Melanins exhibit two separate current - voltage characteristics, the on and off. ( J.McGinness,  J.P.Proctor  1974 ) .

7 .  The neuromelanin of the human Substantia nigra was isolated  ( H.Rorsman 1991 ). 

8 . Melanins are particles (M.R.Chedekel 1992 ) .

9 . Eumelanin particles (granules covered by a membrane) are called melanosomes. Melanosomes  may be obtained in pure form.  (  V.J.Hearing  1973 ).

10 . The particles are formed by oligomers ( melanochromes ) of low molecular weight  (M.G.Peter  1996) .

11 .  Melanins and neuromelanins show the radical polarone system of acetylene black ( R.A. Nicolaus 2001 ). 

12 . All melanins have about one oxygen atom more than the precursors ( R.A.Nicolaus  2001 ).  13 . The particle may show a certain level of organization ( J.D.Simon  2001 ) .

14 . All black particles, from carbon to sepiomelanin, have similar physical properties.The melanin particle gave  X-ray examination results which may suggest not only   graphite but also  fullerene or helicoidal cages. The helicoidal system may produce a magnetic field.   ( A.Bolognese 2001 ).

 15 . The organic black matter in the interstellar clouds is supposed to regulate the ion/radical/molecule balance .  ( B.J.R.Nicolaus,R.A.Nicolaus 1999 ).

16 .  All these data and properties suggest important functions of eumelanins in Biology.( 30 )

 

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R.Nicolaus, Dr. chem.
Rampe Brancaccio 9, I-80132, Napoli.
http://www.tightrope.it/nicolaus/index.htm

rnicolaus@tightrope.it

Accademia Pontaniana, Via Mezzocannone 8, I-80134, Napoli.
e-mail:
accponta@tin.it

http://www.pontaniana.unina.it

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Other address

P.Proctor, J. McGinness    e-mail  :

drjohn@organicmetals.com

 drp@drproctor.com     http://www.organicsemiconductors.com/

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B.J.R. Nicolaus, Via Crescitelli 6, I-20052 Monza

 bruno.nicolaus@virgilio.it 

http://www.brunonic.org/ 

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A.Bolognese , Istituto Chimica Organica e Biologica,Università di Napoli

bologne@unina.it

 

Nicolaus G.,Merck Co.,Rome

gfnicolaus@virgilio.it

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Paul Meredith

meredith@physics.uq.edu.au

www.softsolid.physics.uq.edu.au

Steven L. Jacques

http://omlc.ogi.edu/spectra/melanin/index.htm

http://www.bme.ogi.edu/biomedicaloptics/

Barbara Nicolaus

bnicolaus@icmib.na.cnr.it

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 melanins  are  also  flying….

 

 

 

 

 

STUDIES

(22 link, 458 pages,19 Drawing , 172 Formulae , 109  Pictures  )

Referred to different periods of research

 Revision will be possible after the  Pigment Cell Conference, 18-23 September,Reston USA 2005

 

 

1.  Colour 70

      

  2.  Melanin 84

       

  3.  Colour 90

         

 4.  Melanin  95-97

 

 

5.  Melanins, cosmoids, fullerenes. 

 

6. On the structure of DHI-melanin      

 

7.  Speculation on the chemistry of interstellar black matter

                         

8.  The dark secret of life.

 

 

9 . Animal colours

 

10.  Perspectives in Biology and Melanin Chemistry.

 

 

11. The nature of Black,Blue, and Green colours in Animals.

                

12.  DHI-melanin and the melanin in Sepia

 

13. Italian Chemistry Founders

      People of BCM and BSM

      Curious papers, Story, Stories, Social Events

     Physical Methods Bibliography

      Criticism of literature             

      Post office

    

 

 

14.  Pheomelanin 

 

               

15.Neuromelanin

 

                  

16. Lights in the dark

 

 

 

17. Black natural conductors

           

 

18. Black Matter: Diffusion

        

 

19. The Pigment Cell and its Biogenesis

 

20. Raper's scheme

                    

 

21. The BCM story

                                

 

22.     The BCM stories

 

23. Perspectives in melanin chemistry

 

24.     The Chemical Structure of Melanin

 

 

Melanin research was started in Naples with a paper on melanoma-melanin by M.Bakunin (1904).  A paper on sepiomelanin was published by L.Panizzi  (1952).  The study  of melanins and melanogenesis started in Naples  in 1950 with two papers on chemistry  of sepiomelanin (Gazzetta Chimica Italiana 1950 and Tetrahedron 1960  ). The early efforts ( 1950-1980 ) were enabled by the continuous cooperation of  chemist and biologists of the Universities of Naples and CNR  ( Piattelli,   Scardi, Minale, Fattorusso ) ,  Aberdeen ( Thomson ), Newcastle upon Tyne  (Swan ),  Stanford ( Blois ), Manchester ( Bu ‘Lock ). In the same period pheomelanins and pheomelanogenesis  were discovered ( Nicolaus, Minale, Fattorusso,  Misuraca,  Sodano, Cimino, Prota, Piattelli,  De Stefano, Scherillo, Bolognese).The study of pheomelanins and melanins was continued by Rorsman and his pupils in Sweden,  Prota and his pupils,  D’Ischia, Pezzella, Palumbo, Napolitano, Corradini, Crescenzi    in Naples.

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List of abbreviations :

BCM   =  Black  Cell  Matter  ;  BSM  =  Black  Synthetic Matter  ; CD = Cyclodopa DP = dopachrome , DQ = dopaquinone, IQ  =  indolquinone, DHI  =  5,6-dihydroxyindole  ;  DHICA  =  5,6-dihydroxyindole-2-carboxylic acid ; Cysdopa  =  cystein-S-yl-dopa  ;  DOPA  =  3,4-dihydroxyphenylalanine  ;  MSH  =  Melanocyte Stimulating Hormone 

Key words:BCM, BSM, melanins, allomelanins, pheomelanins, eumelanins, black matter, black particles, benzene-black, indole-black, pyrrole-black, quinoline-black,  cyclodopa-melanin,  dopa-melanin, DHI-melanin, melanosome, cosmoids, graphite, fullerenes, amorphous semiconductors, charge transfer complexes, nanophysics, nanochemistry, nanobiochemistry, cosmochemistry,, electroactive polymers, Bok globules, interstellar black matter, X-rays, Mass spectrometry MALDI, , MALDI-TOF, EPR, NMR, 13C NMR, AFM , band theory, conducting polymers, semiconductors organic, organic metals, amorphous pigments,  green and blue  colours,  metal porphyrins, humic acids, PLGA, assembling factor ,tensintegrity,  threshold switching,melanin-isolation, melanin-purification , quinones hydrate, radical-polarones,  DHI, DHICA, BCM, BSM,black mammalians,  black skin, black feather,black fishes, meteorite, acoustic photo,electrical conductivity, storage of liquids, storage and transport of gases, binding of ions and molecules, brain pigment,substantia nigra,Parkinson melanosome, LASER explosion /fragmentation/degradation/depletion.    .


 

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