Jan S. JaworskiFaculty of ChemistryFaculty of Chemistry

University of Warsaw, Poland

Frascati, 4-6 May 2010

Origin of the image on the Veil of Manoppello?

(1) the nature of pigments responsible for the image

(2) possible image formation processes .

SPECTRAL CHARACTERISTICS OF THE VEIL

Giulio FantiVolto Santo di ManoppelloRelazione Tecnica

black

25th Sept. 2001

plitu

de

red

Am

p

white

Wave length [nm]e- energy

gap

● No peaks from different chromoforesbroad band (like for organic semiconductors) light( g )

● Wave length at maximum λmax ≈ 450 ÷ 476 nmabsorption of dark blue, transmition of orange light

● Highest and lowest amplitude for black and white colors400 nm

light

amplitude more important for the colors ? 500 nm

t d b b l d f

BYSSUS THREADS Mussel: Mytilus edulis(sea silk)

secreted by a byssus gland ofmussels to fast a shell to the rock.

Pen shell (Pinna nobilis)mussel of the mediterranean

(X. Qin, J.H. Waite, 1995)

Brown color of byssus threadsis not affected by:

dil d id- diluted acids- bases- organic solvents

id t- some oxidants - temperature- UV light (254 nm, dry threads)

www.designboom.com/eng/education/byssus.html

MELANIN PIGMENTS

EUMELANIN PHEOMELANINEUMELANIN PHEOMELANIN

+

99% EuM 95% EuM 67% EuM

C.R. Borges, J.C. Roberts, D.G. Wilkins, and D.E. Rollins; Anal. Biochem., 290, 116-125, 2001.

1% PheoM 5% PheoM 33% PheoM

?Brown hair

Byssus

EUMELANIN PHEOMELANIN

Insoluble in waterBroad-band monotonic UV-vis absorptionExtremely small fluorescence

(99.9% non-radiative dissipation) –photoprotective phototoxic ?

Electrical conductivity and photoconductivity

Pheomelanin in aqueous solution

A: from hairB: syntheticElectrical conductivity and photoconductivity

(amorphous organic semiconductor,act as reversible electrical switch)

Paramagnetic properties depending on pH

B: syntheticC: + Zn2+ ions

Paramagnetic properties depending on pHComplexation of various metal ionsAbsorbs strongly water and gasesRedo properties (antio idant protection ROS)

A. Napolitano, M. De Lucia,L. Panzella, M. d’Ischia;

Redox properties (antioxidant protection, ROS)

P. Meredith, T. Sarna; Pigm. Cell Res., 19, 572-594, 2006.

Photochem. and Photobiol.;84, 593-599, 2008.

R.A. NicolausMelanins, 1968MELANIN

S C

H t l ?

STRUCTURE

Heteropolymers ?

PheomelaninPheomelanin

Chemical degradationStacked oligomers ? gives building blocs

3 4 Å

Stacked oligomers ?

3.4 Å

3.4 ÅChemical bleaching of

synthetic melaninefragmentation

J. Cheng, S.C. Moss. M.Eisners; Pigm. Cell Res., 7, 263-273, 1994.

fragmentation K.C. Littrell at el., Photochem.

Photobiol, 2003.

HPLC analysis of human hairHPLC of byssus threads (9.5 mg) andbrown hair (40 mg) after degradation 20 hours in NH3 + H2O2

MELANINMARKERS

black

20 hours in NH3 + H2O2for eumelanin

hair

brown byssus

2 3 4 5 6 7 8 9 10Time, mi

5.61

): Exp 7, 283.0/89.0 amu from Sample 19 (brazaowe z NH3 odp) of 22-04-10.wiff (Tu2 3 4 5 6 7 8 9 10

Time, min

9.055.563.19

irs): Exp 7 283 0/89 0 amu from Sample 6 (bisior z NH3 odp) of 23 04 10 wiff (Turbo Spra

redbyssus

Time, minTi iirs): Exp 7, 283.0/89.0 amu from Sample 6 (bisior z NH3 odp) of 23-04-10.wiff (Turbo Spra

4.46for pheomelaninredhair

Time, min

4.52brown byssus

2 3 4 5 6 7 8 9 10Time, mi

2 3 4 5 6 7 8 9 10Time, min

black

Pheomelanin is the main pigment in byssus threadsModified method ofA. Napolitano et al., 2006

Original byssus threads

10 μm

19 μm

38 μm

SEM Mag = 250x

μ

14±6 μm G. Fanti, 2001SEM, Mag = 250x

20 μm

Original byssus thread

20 μm

Byssus treated by 1M H2SO4 + 3% KMnO4 (200x)

200x

Heated in 1M K2CO3; after cooling + 30% H2O2500x

200x

Treated by 1M NaOH + 30% H2O2

20 μm

20 hours degradation in NH3 + H2O2 Original byssus

Heated in 1M K2CO3+ ca. 3% H2O2 500x

Heated 25 minutes in HI + 50% H3PO23 2

Heated 30 minutes in HI

CONCLUSIONS● The brown color of byssus threads originates from

the pheomelanin pigment; its marker (BTCA) wasdetected by HPLC after degradationy g

● Degradation of byssus threads (e.g., chemicaly bysome oxidants in proper media) results in changes ofthe brown color: bleaching to pale straw-color, tocolorless and to reddish

● It looks highly probable that the image on the Veil ofManoppello (at least in most parts) was formed bymodifications of pheomelanin, natural pigment of byssus

● Thus, there is an additional similarity with the imageon the Shroud of Turin, which was „created” by

id ti /d h d ti f ll l f thoxidation/dehydration processes of cellulose of thelinen

● Byssus properties are responsible for some unique properties of the Veil of Manoppello like theproperties of the Veil of Manoppello, like thetransparency after strong illumination

● Future detailed investigations on byssus properties(including color changes) are desirable and(including color changes) are desirable, and they are possible, even if the examination of theoriginal Veil of Manoppello will be not available

Acknowledgements

Dr Magdalena Biesaga

Dr Mikołaj Donten

Fr. CarminoCucinelli Thank you

for your attention

Dr Maciej MazurKasia Abramczyk