65

Missal Blue: Anthocyanins in Nature and Art

Maria Joo Melo
Abstract Anthocyanins are the water-soluble colorants, ubiquitous in flowers and fruits, which are
responsible for their impressive red and blue colours. This paper discusses some of the old recipes
used to produce a blue colour, such as missal blue, from the cornflower (Centaurea cyanus L.). The
capture of a blue from a flower or berry is not an easy task, due not only to the complexity of the
natural supramolecular structure of the colorant, but also to the various structural transformations
that it undergoes in aqueous solutions driven by pH changes. Therefore a correct recipe can be an
important piece of evidence testifying to the use of these colorants in the past. Our present knowledge
of the molecular properties of anthocyanins places us in a good position to analyse these old recipes.
Introduction
The colours of flowers and fruits have attracted
the attention of humankind throughout history:
flowers as a fundamental source of artistic
inspiration and beauty and fruits as an impor-
tant part of the human diet. Anthocyanins are
the ubiquitous water-soluble colorants found
in flowers and fruits that are responsible for
their impressive red and blue colours (Plate 13,
Fig. 1).
1
Several references on the use of these
compounds as pigments in decoration, namely,
as substitutes for inorganic pigments when
these are not available, or in ancient illustra-
tions to give special lighting effects, have been
reported. Descriptions of this type of use range
from the Roman empire, by the famous architect
Vitruvius,
2
to the paintings of the Maya civilisa-
tion.
3
Their use as watercolours was frequently
described in treatises or recipe books on illumi-
nation such as the Strasbourg (or Strassburg)
manuscript,
4
an early Portuguese work on
manuscript illumination, The book on how one
makes colours of all shades, and the Italian De
arte illuminandi.
5
Anthocyanins could be used
to produce clothlets (pezzuole) as described by
Cennino Cennini in the 15th century.
6
Due to the pioneering work of Richard
Willsttter,
7
who received the Nobel Prize for
Chemistry in 1915 for his research into plant
Figure 1 The basic chemical structure of anthocy-
anins: a hydroxyl group is present in positions 4 and
7, and a sugar in position 3 (monoglycosides) or 3
and 5 (diglycosides).
66
DYES IN HISTORY AND ARCHAEOLOGY, VOL. 21, 2008
pigments, much information has been accumu-
lated regarding the role played by anthocyanins
and the colours they produce.
8
Isolation of the
most common anthocyanins has shown that
they follow a general pattern, summarised in
Scheme 1 for cyanidin 3,5-diglucoside.
9
The red
flavylium cation (AH
+
) is the dominant species
in very acidic solutions, but with increasing pH
a series of more or less reversible chemical reac-
tions take place: (i) proton transfer leading to
the blue quinoidal base (A); (ii) hydration of the
flavylium cation, giving rise to the colourless
hemiacetal (B), (iii) a tautomerisation reaction
responsible for ring opening, to give the pale
yellow cis-chalcone form (C
cis
), and finally, (iv)
cis-trans isomerisation to form the pale yellow
trans-chalcone (C
trans
).
A useful way to illustrate the pH domain of
the red and blue colours is to represent the pH
dependence of the mole fraction distribution
of the species (Plate 14a), when the system has
reached the thermodynamic equilibrium. In this
illustration, the key parameter is pK
ap
, defined as
the pH value for which the mole fraction distri-
bution of the red flavylium cation is reduced by
one half,
10
and as a consequence colour is also
reduced by one half.
Anthocyanins in nature
Anthocyanins are located inside vacuoles, where
the pH can assume a large range of values,
depending on the plant species.
11
However,
as can be visualised in the band at the top of
Plate 14a, the colouring power of cyanidin 3,5-
diglucoside is very low, even for the most favour-
able pH values that can appear in the vacuoles of
Scheme 1 Equilibria in aqueous solution for cyanin: AH
+
flavylium cation; A quinoidal base; B hemiacetal;
C
cis
cis chalcone; C
trans
trans chalcone.
67
MISSAL BLUE: ANTHOCYANINS IN NATURE AND ART
certain plants. There is no doubt that cyanidin
3,5-diglucoside, for example, at a pH of about
3.1, does not exhibit any substantial colouring
power, neither red nor blue. At this pH value
neither the blue quinoidal base nor the red
flavylium cation are thermodynamically stable
species, and therefore the system will naturally
evolve to the colourless species, the hemiacetal
and the chalcones. For the most common natural
anthocyanins, the major species, at neutral pH,
is the colourless hemiacetal.
This is the reason why, when extracting an
anthocyanin at neutral pH the colour disap-
pears. This reaction can be reversible, if the
only process taking place is proton transfer. In
this case the anthocyanin will behave as an acid-
base indicator and colour can be restored by
changing the pH.
For the formation of a blue colour some
interaction between the blue quinoidal base and
other compounds is required (Plate 14b). This
phenomenon is called co-pigmentation and can
involve other flavonoid compounds and compl-
exation with metals.
12
The mole fraction distri-
bution of the several cyanidin 3,5-diglucoside
forms obtained upon complexation can be simu-
lated for a simplified model system, consisting
of a single 1:1 equilibrium with association
constant K
cp
involving the species A and the
co-pigment.
13
The results are shown in Plate
14b, and indicate that a blue colour can now be
obtained at moderately acidic pH values.
Colour in nature, as far as anthocyanins are
concerned, depends also on the substitution
pattern of the benzopyrilium ring (Fig. 2). Most
of the anthocyanins present in flowers and fruits
have a sugar substitution in position 3 (monoglu-
cosides) (Fig. 3). A sugar can also be present in
position 5 (di-glucosides) or sometimes in posi-
tion 7. The ring B can also be substituted with
hydroxyl or methoxy groups.
Luteolinidin is a prehistoric anthocyanin
colorant, more precisely a 3-deoxyanthocya-
nidin, present in mosses and ferns (Fig. 2).
Luteolinidin gives wonderful sunset colours,
ranging from yellow to violet, without forget-
Figure 2 Molecular structures, common name and
max
of absorption in
aqueous acidic solutions for four anthocyanidins.
68
DYES IN HISTORY AND ARCHAEOLOGY, VOL. 21, 2008
ting the splendid orange colours almost as
beautiful as a Turner sunset (Plate 13) but no
red and no blue. As can be observed there is
no substitution in position 3. With a hydroxyl
(OH) group in this position, the wavelength at
maximum absorption (
max
) will increase by
about 25 nm in the visible region, and more
importantly, the possibility of creating a red
flavylium and a blue quinoidal base will also
increase. On the other hand, with a hydroxyl
group in this position the quinoidal base will
decompose. However, if this OH group is not
free for example, if a glucosyl bond is formed
the base will not degrade. The presence of
this sugar causes a reduction in
max
of 510
nm in the visible region, but with no particular
consequences for the observed colour; the net
result is still very positive: + 25 nm (OH substi-
tution) 5 nm (OGl substitution) = + 20 nm
in the visible region; and, more importantly, the
quinoidal base can be blue! Another sugar in
position 5 has almost no influence on
max
(Fig.
3), but can reduce the pH domain of the red
colour (that is, of AH
+
).
14
With these compounds and depending on
the strategy used, nature is able to construct the
exuberant red displayed by poppies, the delicate
blue of a cornflower, and also all the imperial
purples that lie in-between. Many examples of
the strategies used by nature to obtain colour in
plants are based on the formation of a supramo-
lecular structure, through molecular recogni-
tion and self-assembling of the components in
solution.
15
In effect, many of the structures that
have been found to be responsible for the blue
colour are supramolecular complexes shaped by
metallic cations and anthocyanins (compare the
values for cyanidin and its glycosides in Table 1
and the spectra in Fig. 4). The presence of other
flavonoids is also necessary for the build-up of
the blue.
16
In vivo, the metal centre organises a
hydrophobic core, where the sugars are directed
to the outside, interfacing with the more polar,
aqueous media. Several examples of intermo-
lecular, intramolecular or self association co-
Figure 3
max
in aqueous solution at pH = 1 for pelargonidin, pelargonidin-3-glucoside and
pelargonidin-3,5-diglucoside.
250 300 350 400 450 500 550 600 650
wavelength (nm)
0.7
0.525
0.35
0.175
0
a
b
s
o
r
b
a
n
c
e
Figure 4 UV-visible spectra in aqueous solutions at
pH = 1 for cyanidin (), cyanidin-3,5-diglucoside
(- -) and for a 1:1 complex between cyanidin-3,5-
diglucoside and Al
3+
(-
.
-).
Table 1 Absorption max ima (
max
)
for cyanidin, cyanidin-3-glucoside and
cyanidin-3,5-diglucoside in aqueous
solutions at pH = 1.

max
AH
+
Cy-3,5-OGl 508 nm
Cy-3-OGl 509 nm
cyanidin 515 nm
69
MISSAL BLUE: ANTHOCYANINS IN NATURE AND ART
pigmentation have been reported,
17
in particular
the fascinating structures unveiled by Goto and
Kondo (1991) and Kondo et al. (1992).
18
Anthocyanins in art
Blue clothlets and missal blue
As reported in the introduction, there are several
references dating from antiquity to the use of
watercolours for painting, particularly for illu-
minations. These watercolours could be used as
described by Cennino Cennini.
19
For a saffron yellow watercolour, a carote-
noid, the procedure is rather easy: the colour
is extracted in warm water,
20
then a piece of
cloth is dyed with this solution and allowed to
dry in the dark. The operation is repeated until
a saturated cloth is obtained (that is to say, it has
taken up enough of the colorant). Finally, a gum
arabic coating is applied. The colour is then kept
in a wooden box, carefully protected from light
and humidity (the cloths were thoroughly dried
first). For use as a watercolour, a little piece
is cut into a convenient receptacle (mussel or
scallop shell, or horn), some gum arabic is added
and the colour is ready to be applied.
Extracting and capturing an anthocyanin blue
is not as easy, because the supramolecular struc-
ture must be conserved, otherwise the colour
is lost. For the cornflower (Centaurea cyanus
L.), this implies that the concentration of the
supramolecular elements must be maintained,
and also that pH must be controlled. This is
the case for all the recipes described in the
Strasbourg Manuscript (see the Appendix).
21
The structure of the self-assembled supramo-
lecular pigment from the blue cornflower
was elucidated by Kondo et al.(1994);
22
the
supramolecular components are succinylcy-
anin (Sucy, a cyanidin chromophore with a
sugar in position 3), malonylflavone (Mafl, a
flavone with a sugar in position 3) and magne-
sium and iron(III) ions, the exact composition
being (Sucy
6
Mafl
6
Fe
3+
Mg
2+
). These authors
proposed that the supramolecular complex
should be similar to that of commelinin (Fig.
5). The metal centre organises the geometry of
the complex, which is held together by weak
hydrophobic interactions, as the - stacking
of the aromatic rings and hydrogen through the
sugar moieties.
23
The anthocyanin molecules
bond to the metal through the two OH groups
present in ring B (catechol unit). The inner parts
of the molecule are hydrophobic and the surface
of the supramolecule is hydrophilic. This not
only enables the formation of a blue complex,
but also can protect against water attack in the
2 position and consequent formation of the
hemiacetal.
For cornflower blue as well as for commelin
the blue colour is only stable in concentrated
solutions. When diluted the solution quickly
becomes colourless due to decomposition of
the supramolecular complex.
The very first step in the recipes used to obtain
a blue clothlet from cornflower is to break only
the petals, crush them in a mortar and wring the
colour through a straining cloth (the process is
shown schematically in Plate 15).
24
In this case,
the first requirement for the stabilisation of the
supramolecular structure is observed; that is to
say, by squeezing the flower juice the concen-
tration of the supramolecular components is
maintained and therefore they will be in the
stoichiometric ratio necessary to self-assemble.
The pH of the cornflower juice is about 4.7; this
value must also be maintained around pH = 5
0.5, to profit from all the blue colour. This
is precisely what is recommended as the second
step: take a settit of sal-ammoniac and put it in
Figure 5 Schematic representation of the blue
supramolecular complex involving anthocyanins.
The 2 metals (black spheres) form 2 planes under
a ternary axes; a top view of one of this planes is
represented on the left. Each metal coordinates three
anthocyanin chromophores (striped); three flavones
(light grey) are intercalated with the anthocyanins,
filling the void spaces.
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DYES IN HISTORY AND ARCHAEOLOGY, VOL. 21, 2008
the coloured juice and it will dissolve at once.
The sal-ammoniac is our modern ammonium
chloride (NH
4
Cl), which, used as described, will
buffer the pH of the solution to a value around
5: perfect for the blue colour!
The next day the procedure is repeated, but the
sal-ammoniac is substituted by alum (aluminium
potassium sulfate, AlK(SO
4
)
2
12H
2
O) and some
gum arabic is also added to the juice; the gum
arabic will form a protective coating and will also
be the binding medium. The presence of alum
shifts the pH of the medium to lower values and
also to a more violet shade. This violet shade
can be due to the lower pH value, but also to
substitution of the natural coordinated metal
ions, Fe
3+
or Mg
2+
, by Al
3+
.
Finally, it is also worth mentioning that it is
stated that the blue obtained with these recipes
is a good and durable colour, quoting for missal
blue: it is a good and valuable colour.
25
Dyeing parchment
In the Book on how one makes colours of all
shades,
26
Abrao B. Judah Ibn Hayyim uses the
term cor de mora; in Portuguese we still have
the verb morar, which means to give the colour
of a blackberry, as the Portuguese common name
for blackberry is amora. Dyeing with anthocy-
anins follows the same general concept as dyeing
with anthraquinones such as alizarin, or flavo-
noids such as quercetin. Dyeing is accomplished
through the very densely charged aluminium
ion, Al
3+
that will bond to the fibre as well as
to the colorant. In cyanidin, as in the case of
quercetin, the bonding is performed through the
ortho-dihydroxy groups located in ring B, the
catechol unit.
In blackberry, as in raspberry, the basic
chromophore is cyanidin exhibiting 3-substi-
tuted sugars;
27
surprisingly, the anthocyanin
concentration in blackberry is roughly half that
present in raspberry. The strong blue, almost
black, colour of blackberry, when compared
with the charming raspberry red, is an indi-
cation that the capture of colour in these two
berries has followed different strategies. In the
raspberry, colour is due to the colorant power
of the single anthocyanin, which is present in
large concentration;
28
for blackberry, a more
complex structure must be involved.
The colours obtained when dyeing parch-
ment can range from a reddish-violet to a bluish-
violet or bluish-grey colour, depending on the
berry, but also, as expected, on the pH and on
the Al
3+
concentration (Plate 16).
Conclusion
Anthocyanins are the water-soluble colorants
responsible for the marvellous diversity of red,
purple and blue colours found in flowers and
fruits. The exuberant red displayed by poppies
and the delicate blue that tints a cornflower
have a common chemical origin: the cyanidin
chromophore.
The use of anthocyanins as pigments was
already reported by Vitruvius. These molecules
were used in manuscript illuminations as water-
colours, where their light effects and softness
were irreplaceable.
29
In common with other
pigments already in use in antiquity, such as the
anthraquinones alizarin, present in madder dye,
and kermesic and carminic acids in scale insect
dyes, anthocyanins share the ability to complex
metal ions such as Al
3+
(present in alum); an
important difference is that anthocyanins form
water-soluble supramolecular structures and the
anthraquinones insoluble lakes. The supramo-
lecular structures of anthocyanins, if obtained
in the past using the previously described
procedures, could be easier to identify than the
anthraquinone lakes,
30
not only because they
might be present in higher concentrations, but
also because they are water-soluble compounds
that can easily be extracted. A century-old missal
blue is still waiting to be discovered, to prove
that the delicate anthocyanins can defy time!
Appendix
The recipes transcribed are from the Strasbourg
(or Strassburg) Manuscript, dating from the
beginning of the 15th century; the raw mate-
71
MISSAL BLUE: ANTHOCYANINS IN NATURE AND ART
rials are flowers, namely, cornflowers, thus the
colorants obtained and used could be anthocy-
anins. In one of the recipes for a violet colour
the flowers used are not identified, but are
described as large red flowers: could these be
poppies?
31
If you want to make a bright rag colour,
proceed as follows. During the first week after
Whitsun pick a quantity of fully opened corn-
flowers these should be gathered during the
morning, that is, before midday. Break off the
flowers at the top of the stem, put them in a
clean vessel and pound them in a clean mortar
very thoroughly till they are reduced to a
mash. After this, put them in a clean straining-
cloth and wring out the juice into a glazed pan.
Then take a settit of sal-ammoniac and put
it in the coloured juice and it will dissolve at
once. After this take a well-washed piece of
material, such as a piece of fine old veiling or
of an old tablecloth and put this, cut in small
pieces, into the colour so that the rags soak
up all the coloured liquid and become neither
too wet nor too dry, but just soak up the colour
and are evenly tinted. After this one should
hang up the rags on a line in the garden, letting
them dry well in the open air.
The next day, pick the same amount of
fresh flowers as before and repeat the process
of breaking off the heads of the flowers, of
pounding them as before and of wringing the
juice through a straining-cloth into the pan.
Then take very clear gum arabic that has been
previously softened. This gum must first be
well stirred round with the finger and then
be mixed with the juice of the flowers and
stirred with a wooden stick. Then take a settit
of alum crystals ground to a fine powder and
put this into the above-mentioned juice and
stir it well until the alum has melted. Then
take the already coloured rags (which have
been drying overnight) and dip them once
again in the juice and leave them steeping in
the colour till they have soaked up enough
to dye them thoroughly. After this, hang up
the rags again in the open air and let them
dry thoroughly. Lastly, wrap them up in clean
paper and keep them in a clean wooden box
somewhere high up and well ventilated, in
order that they may not get damp.
32
This is followed by a similar recipe for a violet
rag colour using pink cornflowers, gathered at
the same time of the year, using one settit of
alum crystals; if you have a lot of flowers, ...
but you should note that if the flowers amount
to a quarter pound the correct amount of alum
would be one settit, but if the amount of petals
were less, put less alum.
When you want to make a violet rag colour
which is useful for many things, you must in
the first place, manage one morning before
midday to gather some of those beautiful
large red flowers as many as you require
you must break off only the petals or the
colour will be spoilt; when they have all been
pulled off you must crush them into a clean
stone vessel or in a mortar and wring the
colour thoroughly through a straining cloth
and collect it into a glazed earthenware
dish. Then take a piece of alum the size of
a hazelnut, ground to powder on the slab
and sprinkle it into the colour and stir well
together until the alum is quite dissolved.
Then take well-washed linen rags and soak
them in the colour so that they are thoroughly
saturated and yet not wet to drip and then
hang these rags in the open air and leave them
to dry. Now soak them again in the colour
and once again leave them hanging up to dry.
Next take some wine of a good red colour,
at least a mos and put in it oz of pure gum
arabic and let it steep in the red wine for half
a day to soften; then stir it thoroughly in the
wine and lastly soak the coloured rags in the
red wine so that it is all sopped up. Keep
turning them over in the air until they are
quite dry and then store them in a drawer to
keep them quite clean until you need them
and this is how you make a really good
violet colour.
33
On the same page,
34
instructions are given
for a lovely bright blue rag colour, according
72
DYES IN HISTORY AND ARCHAEOLOGY, VOL. 21, 2008
to the London practice, with which you can dye
yarn and which is also of use for many things
such as letters in blue and serves for a trans-
parent glaze over silver. Finally, the blue rags
must be wrapped in paper and be laid in a clean
wooden box and must be kept on some high
shelf where it smells sweet and clean and where
the colour will not be affected by mould. If the
rags are kept in this way, they will remain fresh
and lovely for as long as twenty years without
fading (wol behalten frisch und schon). In Paris
and in London this colour is called blue for
missals, but here in this country rag blue colour
and it is a good and valuable colour.
Editors note
Address for correspondence: Departamento de
Conservao e Restauro e REQUIMTE/CQFB,
Universidade Nova de Lisboa, Portugal. Paper
received 11 April 2003; revised version received
14 September 2003.
Notes and references
1. Strack, D. and Wray, V. (1994) The Flavonoids,
Advances in Research, ed. J. B. Harborne,
London, ch. 1. Anthocyanins, in nature, are gluc-
osyl compounds; when they are free from sugar
substitution, they are denominated anthocyani-
dins.
2. Picon, A. (1995) Les dix livres darchitecture de
Vitruve, Paris, Book VII, ch. XIV.
3. Colombo, L. (1995) I colori degli Antichi, Flor-
ence, pp. 1713.
4. The Strasburg Manuscript: A Medieval Painters
Handbook (1966), tr. V. and R. Borradaile, New
York (Transatlantic Arts).
5. Blondheim, D.S. (1928) An old Portuguese work
on manuscript illumination, Jewish Quarterly
Review NS, XIX, pp. 97135; Brunello, F.
(1992) De arte illuminandi, e altri trattati sulla
tecnica della miniatura medievale, Vicenza.
6. Cennini, C. (1997) Il libro dell arte, ed. F.
Brunello, Vicenza.
7. Willsttter, R. and Everest, A.E. (1913) Unter-
suchungen ber die Anthocyane. I. ber den
Farbstoff der Kornblume, Justus Liebigs Annalen
der Chemie 401, pp. 189232; Willsttter, R.
and Mallison, H. (1915) X. ber Variationen
der Bltenfarben, Justus Liebigs Annalen der
Chemie 408, pp. 14762 (this is the final paper
of a series of 10 published in the same volume,
beginning on p. 1).
8. Shibata, K., Shibata, Y. and Kasiwagi, I. (1919)
Studies on anthocyanins: color variation in
anthocyanins, Journal of the American Chem-
ical Society 41, pp. 20820; Pratt, D.D. and
Robinson, R. (1922) CLXXXVIII. A synthesis
of pyrylium salts of anthocyanidin type, Journal
of the Chemical Society, Transactions 121, pp.
157785; Robinson, R.and Robinson, G. (1932)
Developments in the chemistry of the anthocy-
anins, Nature 130, p. 21; Robinson, R. and
Robinson, G.M. (1939) The colloid chemistry
of leaf and flower pigments and the precursors
of the anthocyanins, Journal of the American
Chemical Society 61, pp. 16057.
9. Brouillard, R. and Dubois, J.E. (1977) Mecha-
nism of structural transformations of anthocy-
anins in acidic media, Journal of the American
Chemical Society 99, pp. 135964; Santos, H.,
Turner, T.L., Lima, J.C., Figueiredo, P., Pina, F.
and Maanita, A.L. (1993) Elucidation of the
multiple equilibria of malvin in aqueous solu-
tion by one- and two-dimensional NMR, Phyto-
chemistry 33, pp. 122732.
10. Pina, F. (1998) Thermodynamics and kinetics
of flavylium salts Malvin revisited, Journal
of the Chemical Society Faraday Transactions
94, pp. 210916; Pina, F., Melo, M.J., Maestri,
M., Ballardini, R. and Balzani, V. (1997) Photo-
chromism of 4'-methoxyflavylium perchlorate.
A write-lock-read-unlock-erase molecular
switching system, Journal of the American
Chemical Society 119, pp. 555661; Pina, F.,
Maestri, M. and Balzani, V. (1999) Photo-
chromic flavylium compounds as multistate/
multifunction molecular-level systems, Journal
of the Chemical Society Chemical Communica-
tions, pp. 10714.
11. Steward, R.N., Norris, K.H. and Asen, S. (1975)
Microspectrophotometric measurement of pH
and pH effect on color of petal epidermal-cells,
Phytochemistry 14, pp. 93742; Yoshida, K.,
Kondo, T., Okazaki, Y. and Katou, K. (1995)
Cause of blue petal colour, Nature 373, p.
291.
12. Shibata et al. 1919 (see note 8 above); Cai, Y.,
Lilley, T.H. and Haslam, E. (1990) Polyphenol
73
MISSAL BLUE: ANTHOCYANINS IN NATURE AND ART
anthocyanin copigmentation, Journal of the
Chemical Society Chemical Communications, p.
380; Dangles, O., Saito, N. and Brouillard, R.
(1993) Kinetic and thermodynamic control of
flavylium hydration in the pelargonidin cinnamic
acid complexation origin of the extraordi-
nary flower color diversity of Pharbitis-nil,
Journal of the American Chemical Society 115,
pp. 312532; Goto, T. and Kondo, T. (1991)
Structure and molecular stacking of anthocy-
anins flower color variation, Angewandte
Chemie International Edition 30, pp. 1733;
Kondo, T., Yoshida, K., Nakagawa, A., Kawai, T.,
Tamura, H. and Goto, T. (1992) Structural basis
of a blue-colour development in flower petals
from Commelina communis, Nature 358, pp.
51518; Pina, F. (1998) Caffeine interaction
with synthetic flavylium salts. A flash photolysis
study for the adduct involving 4,7-dihydroxyfla-
vylium, Journal of Photochemical Photobiology
A 117, pp. 519.
13. Melo, M. J., Moncada, M. and Pina, F. (2000)
On the red colour of raspberry (Rubus idaeus),
Tetrahedron Letters 41, pp. 198791.
14. Melo et al. 2000 (see note 13 above).
15. Supramolecular chemistry is a novel field of
science, with a novel terminology. As Jean-Marie
Lehn, winner of the 1987 Nobel Prize in Chem-
istry (together with D. J. Cram and C. J. Pederson),
wrote, As a novel field of science emerges, grows
and matures, it evolves basic concepts and gener-
ates novel terminology to name the concepts that
define it and to describe the objects that consti-
tute it. Such conceptualizing and naming play
a very important role, not only for shaping the
field but also by the ground they offer to crea-
tive imagination. This is the main reason for the
transcription of some important definitions: see
Lehn, J.-M. and Ball, P. (2000) The New Chem-
istry, ed. N. Hall, Cambridge, pp. 3014. The
authors present the ideas, concepts and also the
lexicon of this novel area in science, with some
wonderful analogies. Supramolecular chemistry
is also about molecular architecture or as Ball
and Lehn stated, It is as if the brick-makers have
suddenly realized that their products need not
be an end in themselves but provide a means for
them to become architects. The structures that
nature developed to capture the blue colour are
wonderful molecular architectures, where the
components self-assemble through molecular
recognition.
Civilization combats entropy through a
network of information exchange. ... When
molecules need to get organized, they adopt
analogous strategies. This is why the key
concepts of supramolecular chemistry embrace
not just those of traditional molecular chemistry
structure and energy but also a third, infor-
mation The components of supramolecular
chemistry communicate, they form associations,
they have preferences and aversions, they follow
instructions and pass on information. Central to
these exchanges is the idea of molecular recogni-
tion, whereby one molecule is able to distinguish
another by its shape or properties Supramo-
lecular systems are groups of two or more discrete
molecules that interact in specific ways to form
an organized assembly The forces that hold
together supramolecular systems are not strong
covalent or ionic bonds, but interactions that are
weaker, commonly by an order of magnitude
in bonding energy. Hydrogen bonding, donor-
acceptor interactions, metal-ion coordination,
hydrophobic interactions these are the glues
that stick supermolecules together. This subtle
attraction means that molecules can communi-
cate without becoming locked into barren unions
Self-assembly is the spontaneous association of
several (more than two) molecular components
into a discrete, non-covalently bound aggregate
with a well-defined structure. This will gener-
ally involve more than one kinetically distinct
step. Self-assembly involves molecular-recogni-
tion processes binding events, but not mere
binding. Rather, one may say that recognition is
binding with a purpose.
16. Cai et al. 1990; Dangles et al. 1993; Goto and
Kondo 1991; Kondo et al. 1992; Pina 1998 (see
note 12 above for all).
17. Picon 1995 (see note 2 above).
18. Goto and Kondo 1991 (see note 12 above);
Kondo et al. 1992 (see note 12 above).
19. Cennini 1997 (see note 6 above), pp. 1689, ch.
CLXI.
20. Cardon, D. and du Chatelet, G. (1990) Guide
des teintures naturelles, Paris-Lausanne.
21. The Strasburg Manuscript 1966 (see note 4
above).
22. Kondo, T., Ueda, M., Tamura, H., Yoshida, K.,
Isobe, M. and Goto, T. (1994) Composition of
protocyanin, a self-assembled supramolecular
pigment from the blue cornflower, Centaurea
cyanus, Angewandte Chemie International
74
DYES IN HISTORY AND ARCHAEOLOGY, VOL. 21, 2008
Edition 33, pp. 9789; Kondo, T., Ueda, M.,
Isobe, M. and Goto, T. (1998) A new molec-
ular mechanism of blue color development with
protocyanin, a supramolecular pigment from
cornflower, Centaurea cyanus, Tetrahedron
Letters 39, pp. 830710.
23. Kondo, T., Oyama, K.-i and Yoshida, K. (2001)
Chiral molecular recognition on formation of
a metalloanthocyanin: a supramolecular metal
complex pigment from blue flowers of Salvia
patens, Angewandte Chemie International
Edition 40, pp. 8947.
24. The Strasburg Manuscript 1966 (see note 4
above).
25. The Strasburg Manuscript 1966 (see note 4
above).
26. Blondheim 1928 (see note 5 above).
27. Melo et al. 2000 (see note 13 above).
28. Melo et al. 2000 (see note 13 above).
29. Wallert, A. (1993) Natural organic color-
ants on mediaeval parchment, in J. Bridgland
(ed.), ICOM Committee for Conservation,
10th Triennial Meeting, Washington, DC, USA,
2227 August 1993: Preprints, 2 vols, Paris, pp.
51623.
30. Strack and Wray 1994 (see note 1 above); Kondo
et al. 1994 (see note 15 above); Kondo et al.
1998 (see note 15 above); Kondo et al. 2001
(see note 23 above).
31. The Strasburg Manuscript 1966 (see note 4
above), pp. 29 and 37.
32. The Strasburg Manuscript 1966 (see note 4
above), p. 29.
33. The Strasburg Manuscript 1966 (see note 4
above), p. 37.
34. The Strasburg Manuscript 1966 (see note 4
above), p. 37.