-Notur .
General Principles of the Geometry
wlssenscnanen
The Structure
of the Blue Starch-
Iodine Complex
Wolfram Saenger*
Institut ffir Kristallographie
der Freien Universitfit, D-IO00 Berlin
In the classical blue starch-iodine complex,
linear amylose is screwed into a left-handed
helix with 6 glucoses per 8 * pitch. The 5
wide central cavity of this helix accommo-
dates polyiodide which consists of 15 units
modulated as I2"I~- o r I 2 " I - . I 2. The I . . . I
distances between these units are shorter than
van der Waals and therefore charge delocal-
ization can occur along the chain which ex-
plains the deep color effects. In contrast to
earlier hypotheses, I... O charge transfer con-
tact to amylose oxygens is not possible.
* Dedicated to Professor Friedrich Cramer on the occa-
sion of his 60. birthday
Naturwissenschaften 71, 31-36 (1984) 9 Springer-Verlag 1984
of the Starch-Iodine Complex
The starch-iodine reaction known to every chemist
from elementary courses in qualitative and quanti-
tative analysis was discovered by Colin and
Claubry in 1814 [1]. Despite the numerous investi-
gations that have been carried out in order to ex-
plain the nature of the chromophore absorbing at
620 nm which gives the starch-iodine complex or
"iodine's blue" the characteristic deep blue color
[2-4], many controversies still existed which could
be settled to some extent in recent years.
Starch itself contains two components, the
branched amylopectin and the unbranched, linear
amylose consisting exclusively of e(1-4)-linked
glucoses. Only the latter produces the blue complex
with iodine which, therefore, is more adequately
described as amylose-iodine. In this complex, amy-
lose forms a helical structure of 8.0 A pitch with
an outer diameter of 13.0A, a 5 ~ wide central
cavity and 6 glucoses per turn [5-8]. The cavity
provides enough space to accommodate iodine
atoms. They line up to produce a linear polyiodide
chain with an average I-I separation of 3.1 ~, a
characteristic distance also observed in other io-
dine complexes which are deeply colored due to
the presence of polyiodide chains [9, 10]. Later,
more detailed X-ray studies and model calculations
indicated that the helix forming amylose-iodine
called V-amylose (V = Verkleisterung) is probably
left-handed and stabilized by interglucose hydro-
gen bonds [11, 12].
What is the cause of the deep blue color of the
amylose-iodine complex? The 3.1 A inter-iodine
distance is indicated in X-ray patterns by diffuse
lines suggesting statistical disorder within the po-
lyiodide chain, thus yielding only an average dis-
tance. Consequently we know neither individual
I - I separations nor do we have an idea about
the actual structure of the iodine units since the
I - I distances in molecular I2, 2.67 A and in ionic
I~, 2.90A, are considerably shorter whereas the
van der Waals I . . . I distance of 4.3 A is much lon-
ger than 3.1 A. Therefore some special type of I - I
bonding was assumed and early attempts to ex-
plain the color on the basis of the electron-gas
theory suggested that 14 equidistantly spaced io-
dine atoms at 3.1 A separation would produce the
observed absorption spectrum with maximum at
620 nm [13]. In addition, spectroscopic data fa-
vored charge-transfer interactions between amy-
lose glycosyl and hydroxyl oxygen atoms and io-
dine [2-4].
All the evidence combined gave some explanation
31
of the problem, yet there was no direct description
of the factual structure of the polyiodide chain and
of the surrounding helical amylose which acts as
stabilizing matrix. Since no single crystals suitable
for detailed X-ray analysis are available with amy-
lose-iodine, a way out of the dilemma is only pro-
vided by model compounds which, in combination
with studies on amylose-iodine, have recently shed
some new light on the configuration of the polyio-
dide chains.
Model Systems to Study the Structure
of Polyiodide Chains
The best models for amylose are its cyclic degrada-
tion products called cyclodextrins. They are ob-
tained enzymatically [15, 16] and can be regarded
as single turns of the amylose helix collapsed into
a circle (Fig. 1). Cyclodextrins consist of six, seven
or eight glucoses per annulus and are designated
with the prefix 0r fl or y. The smallest member,
c~-cyclodextrin (0r represents a direct analog
of V-amylose, if overall dimensions are considered.
In fact, if the cyclodextrins are cocrystallized with
metal iodide/iodine, only ~-CD produces crystals
in shades ranging from deep blue to black which
exhibit metallic luster whereas the larger fl- and
y-CD yield only brown or red, transparent crystals.
0-6
0-5
0-4
0-3 O- 2
% /o(6).
H/i e
I/.
0~4)~C|4) M 0(4')
~(~"" ",/C,,)----
C131~C12)
I
tl
I ide)2.HI3, caffeine.HI3.H20 [18] and (trimesic
O(2)H
Fig. 1. Chemical structure of fl-cyclodextrin (e oxygen atoms,
| hydroxyl groups). The insert shows the atomic numbering
scheme
32
The analogy of 0r crystals with
amylose-iodine was recognized on the basis of ab-
sorption spectra [16], and diffuse X-ray diffraction
lines indicated linear polyiodide chains with aver-
age I - I separation of 3.1 A [17]. Linear or almost
linear chains of polyiodide are also found with
other matrices formed by organic molecules such
as benzamide, tetra(n-butyl)-ammonium ion and
trimesic acid [18, 19].
//-CD forms only one type of structure with metal
iodide/iodine whereas cr produces four crystal
structures depending on the kind of metal ion used
[20]. So far, detailed X-ray analyses are available
for (fl-CD)2"KIT'9H20 [21], (cr 2.
8H20 and (0r [22] (Fig. 2).
In all these complexes, cyclodextrin molecules are
in head-to-head arrangement to form dimers and
these dimers are stacked to produce long cylinders,
reminiscent of the amylose helix in overall struc-
ture (Fig. 2). In fl-CD, the 6.2 ~ wide channel with-
in the cylinder is filled by zigzagged I~ or 12 9I 3 9I2,
with 12 and I~- units nearly vertical to each other
forming a Z-like structure. The situation is very
different in the channels of about 5.2 ~ diameter
provided by 0r (Fig. 2). Here, the polyiodide
has to straighten out in order to fit into the given
matrix. It forms near-linear chains of alternating
units (I2. I~-), in the Li + complex and exactly linear
chains (I~) n or (I2.I-.I2) n in the Cd 2+ complex,
with average I . . . I distances of 3.14 and 3.09A,
respectively. Each of the ~-CD dimers accommo-
dates five iodines of which the central one is disor-
dered twofold. Between the units, the I... I separa-
tions of 3.3 to 4.0,~ are much shorter compared
with the 4.3 A van der Waals distance. On the other
hand, the inter-unit I - I separations in the range
2.83 to 3.17~ are wider than observed in unper-
turbed 12 and I;-, suggesting considerable charge
delocalization along the polyiodide chains and
bonding through 5px orbitals which could also be
rationalized by quantum chemical methods [24,
251.
Other complexes have been investigated with linear
polyiodide chains embedded in organic matrices
such as tetra(n-butyl)-ammonium.I~, (benzam-
acid. H20)10.HI 5 [19]. In the first two, almost lin-
ear single and double chains made up of I{ are
present, with inter-unit distances ranging from 3.82
to 4.00~. In caffeine.HI3.H20, the polyiodide
chain is best described as (I 2 9I - ) , , with the iodide
ion disordered 0 . 6 8 ' apart in two pos!tions so that
I 2 . . . I - distances are 3.13 and 3.81A. The most
interesting of these complexes is (trimesic acid"
H20) 1o" HI 5 with linear polyiodide chain. I - I dis-