Cellulose 10: 201–212, 2003.

© 2003 Kluwer Academic Publishers. Printed in the Netherlands.

201

Empirical polarity parameters of celluloses and related materials

S. Spange1,3 , K. Fischer1 , S. Prause1 & T. Heinze2

1 Department of Polymer Chemistry, Institute of Chemistry, University of Technology Chemnitz, Straße der
Nationen 62, D-09107 Chemnitz, Germany
2 Institute of Organic and Macromolecular Chemistry, University of Jena, D-07743 Jena, Germany
3 Author for correspondence

Received 23 October 2002; accepted in revised form 3 February 2003

Key words: Cellulose, Kamlet–Taft parameters, LSE relationships, Polysaccharides, Solvatochromism, Surface
polarity

Abstract
Kamlet–Taft’s α (hydrogen-bond donating (HBD) ability), β (hydrogen-bond accepting (HBA) ability), and π ∗
(dipolarity/polarizability) parameters of native cellulose batches, carboxymethyl celluloses (CMCs), cellulose to-
sylates (CTs), and other derivatives with different degree of substitution (DS), chitine, amylose, amylopectine, and
cellobiose are presented. Fe(phen)2(CN)2 [cis-dicyano-bis-(1,10)-phenanthroline-iron(II), (1)], Michler’s ketone
[bis-4,4 -(N,N-dimethylamino)benzophenone, (2)], 4-aminobenzophenone (3), coumarine 153 (4), and Reichardt’s
dye (5) were used as solvatochromic surface polarity indicators. The UV/Vis reflectance spectra of the five surface
polarity indicators 1, 2, 3, 4, and 5, adsorbed on the samples from the organic solvents, were measured and the
absorption maxima were used to calculate the α, β, π ∗ , and ET (30) values of the polysaccharides surface. α, β, and
π ∗ depending on degree of crystallinity of the cellulose samples have been determined. α depends on both amount
and strength of accessible acidic surface groups on the cellulose surface. It is significantly larger for crystalline
sections than for amorphous parts. The π ∗ scale is suitable for the classification of different cellulose batches,
because it seems to be independent of inhomogeneities of the cellulose surface. The α-values of CMCs and CTs
significantly decrease with increasing DS inasmuch the number of cellulosic-OH groups (Cell-OH) decreases. A
slight increase of π ∗ with DS is observed for CTs.

Introduction et al. (2000) investigated the interaction of unsaturated

Surface properties of native celluloses and their tech-
nical derivatives are of importance to understand their
solubility, miscibility with other polymers, and chem-
ical reactivity in heterogeneously occurring derivati-
zation reactions (McCormick et al. 1985; Klemm
et al. 1998; Spange et al. 1998). In this context the
term polarity of polymers has often been used in a
broader sense. In the past time period from 1997 till
now, several papers have appeared dealing with the
acid/base and polarity properties of native celluloses.
Inverse gas chromatography (Tshabala 1997; Papirer
et al. 2000), FTIR spectroscopy (Ilharco et al. 1997),
and fluorescence measurements (Moorthy et al. 1998;
Yamamoto et al. 1998) have been applied. Papirer
hydrocarbon probes, acidic probes, H-bond-forming
solutes, and other probes with cellulose by means of
inverse gas chromatography. A multiple correlation
has been established between Gutmann’s donor and
acceptor number (Gutmann 1978) of the solutes which
are adsorbed on various cellulose batches and the spe-
cific interaction-free energies. This showed that the
acid/base interactions are favoured as compared to dis-
persion forces (Papirer et al. 2000). Dispersion forces
mainly contribute to the dipolarity/polarizability of a
surface.
In this minireview we will describe a specific em-
pirical concept in order to determine the ‘surface
polarity’ of celluloses and related materials. Because
of the complexity in the field, it is necessary to
202
discuss briefly the term polarity in view of physical
and chemical aspects. Originally, this term was asso-
ciated solely with the dielectric properties of solvents
(Liptay 1969). The lack of comprehensive theoretical
expressions for the calculation of environment effects
and the inadequacy of defining polarity in a broader
sense in terms of simple physical characteristics led
to the introduction of empirical parameters of solvent
polarity (Reichardt 1988; Nigam and Rutan 2001).
Empirical solvent polarity scales based on spectro-
scopic measurements usually employ changes in the
UV/Vis absorption (solvatochromism) or the fluores-
cence spectrum (fluorochromism, Hamm effect) of a
solvatochromic probe molecule which serves as an
observer at the molecular level (Reichardt 1994).
However, there is still a strong demand to create
a well-defined measure to characterize the polarity of
different kinds of polymers. For solvents and their
chemistry the IUPAC recommended the following
definition of the term polarity (extract): all possible,
nonspecific and specific intermolecular interactions
between solute ions or molecules and solvent mo-
lecules, excluding such interactions leading to definite
chemical alterations (Müller 1994). In principle, this
definition seems also applicable to polymers, because
related effects are active for each part of a macro-
molecular segment. Thus, application of empirical
polarity parameters and acid–base concepts derived
for solution processes to surface phenomena has been
recommended by several authors (Park and Carr 1989;
Rutan et al. 1989; Jensen 1991; Brune et al. 1997;
Spange et al. 2000a, b). For this purpose, the Kamlet–
Taft linear solvation energy (LSE) relationship (Taft
and Kamlet 1979; Kamlet et al. 1983) and use of
UV/Vis probes have been established as shown by sev-
eral authors (Spange et al. 1992a, b, 1996, 1998, 1999,
2000a, b; Rutan and Harris 1993; Macquarrie 1999;
Nagimis and Rutan 2002).
The well-accepted empirical Kamlet–Taft polarity
parameters α, β, and π ∗ of solid materials can be
determined by means of solvatochromic probes (for
an explanation see below). The simplified Kamlet–
Taft equation applied to solvatochromic UV/Vis shifts
(XY Z = υ̃max, Probe ) (Marcus 1993; Reichardt 1994;
Novaki and El Seoud 1996) is given in Equation 1.
XY Z = (XY Z)o + aα + bβ + s(π ∗ + dδ) (1)
(XY Z)o is the value for the solvents reference sys-
tem, for example, a nonpolar solvent or the gas
phase, α is the HBD (hydrogen-bond donating) abil-
ity, β is the HBA (hydrogen-bond accepting) ability,
and π ∗ the dipolarity/polarizability of the solvents.
δ is a polarizability correction term that is 1.0 for
aromatic solvents, 0.5 for polyhalogenated solvents,
and zero for aliphatic solvents. a, b, s, and d are
solvent-independent correlation coefficients.
Desired are such solvatochromic probes, each of
them solely responding only to one of the Kamlet–
Taft parameters of Equation 1. This requires for the
respective indicator s = b = 0 for α, a = s = 0
for β, and a = b = 0 for π ∗ albeit HBD and
HBA groups are present. Unfortunately, such solvato-
chromic probes are still not widespreadly available for
highly polar materials. The search for those probes is
a challenge (Spange et al. 2003). Therefore, at least
a pair of probes is required which shows a significant
dependence of υ̃max, Probe with two of the parameters
(Marcus 1992; Spange and Keutel 1992; Spange et al.
2000b) in order to determine these two parameters in
Equation 1 (Spange et al. 2000a, b). We will later
come back to this problem.
The objective of this minireview is the presen-
tation and discussion of α, β, π ∗ , and ET (30) of
various native celluloses varying in crystallinity and
source, functionalized celluloses with different degree
of substitution (DS), and other polysaccharides such
as chitine, amylopectine, and amylose. Furthermore,
how does substitution affect the HBD and HBA ability
in relation to dipolarity/polarizability of the materi-
als and can this be measured using solvatochromic
indicators as the probes.
Results and discussion
General aspects of the solvatochromic method
applied to celluloses
Using solvatochromic probe dyes has several advant-
ages: the measurements require very low concen-
trations of the probe molecules, are simple, and
reproducible. Because of the high sensitivity of this
method in detecting gradual changes in polarity and
acidity, the interpretation of the result should be
handled with care, because acidic impurities or water
can induce a stronger effect on the UV/Vis band of a
probe than the environment of interest.
D -(+)-cellobiose [4-O-β- D -(+)-glucopyranosyl- D -
(+)-glucose] is the lowest repeating molecular unit
of cellulose. A practicable classification of α, β,
and π ∗ parameters for this moiety is demonstrated
in Scheme 1. The sizes of solvatochromic probe mo-
lecules are of similar magnitude as the cellobiose unit.
 203

dimethylamino)benzophenone] (2), 4-aminobenzo-

phenone (3) and coumarine 153 (4) (Scheme 2)
have been found suitable for the determination of
the surface polarity parameters α, β, and π ∗ of
polysaccharides.
The mathematical procedure for the determination
of α, β, or π ∗ using pairs of the solvatochromic probes
1, 2, and 3 has been reported (Spange and Keutel 1992;
Fischer and Spange 2000; Spange et al. 2000a, b)
(Equations 2–4)

α = 0.086 υ̃max (2) × 10−3 + 0.486 υ̃max (1)

× 10−3 − 10.260, (2)
Scheme 1. Possible classification of α, β, and π ∗ with respect to
functional groups of a cellobiose moiety.
π ∗ = −0.297 υ̃max (2) × 10−3
− 0.229 υ̃max (1) × 10−3 + 12.800, (3)
The simplified view in Scheme 1 explains that α
and β correspond to different HBD and HBA atoms,
respectively, of cellulosic hydroxyl groups (Cell-OH), β = 9.645 − 0.353 υ̃max (3) × 10−3 (cm−1 )
whereas π ∗ represents a nonspecific quantity. The
occurrence of structurally different acidic groups com- + 0.041 υ̃max (2) × 10−3 (cm−1 ). (4)
pared to Cell-OH in native cellulose is well estab-
Because coumarine 153 adsorbs well on celluloses,
lished. Carboxyl groups and other acidic impurities
its suitability to observe dipolarity/polarizability has
give rise to peculiarities, because they do also interact
been investigated. Then, π ∗ -values can be calculated
with the polar probes. It is assumed that the strongest
by Equation 5; n is the number of solvents considered,
acidic sites preferentially interact at low dye concen-
r is the correlation coefficient, and sd is the standard
trations, but the energies are average energies of all
deviation:
the sites to which a base co-ordinates. This average
energy is a measure of the acid strength or polarity
υ̃max (4) = 25.63 − 0.91 α − 1.92 π ∗ ,
strength of the strongest site only if just the strongest
site interacts. n = 22, r = 0.94, sd = 0.3,
F < 0.0001. (5)
Choice of the solvatochromic probes
Acceptor numbers according to Gutmann (1976) can
While polar solvatochromic dyes such as differently be calculated using υ̃max (1) values (Soukup and
substituted pyridinium N-phenolate betaines of the Schmid 1985). A significant correlation of υ̃max (1)
famous Reichardt dye type do particularly well ad- and α results (Equation 6) since HBD solvents are
sorb on various solid materials like silica and other exclusively considered.
solid acid catalysts from organic solvents (Macquarrie
et al. 1999; Spange and Reuter 1999; Spange et al. υ̃max (1) = 16.09 + 2.06 α, n = 15,
2000a, b), their adsorption on cellulose batches often r = 0.92, sd = 0.32, F < 0.0001. (6)
lacks. Therefore, several other solvatochromic probes
established for solids have been checked for celluloses Equation 6 is suitable to determine α-values of poly-
to decide best pairs for evaluating α, β, and π ∗ . Pre- saccharides using solely 1 as probe. Application of
liminary results concerning the suitability of genuine Equation 6 requires that residual Cell-OH are one
solvatochromic probes for investigating the polarity more present.
of cellulose and related materials are summarized in Reichardt’s ET (30) [2,6-diphenyl-4-(2,4,6-
Table 1. triphenyl-1-pyridinium-1-yl)phenolate] (5) and
Fe(phen)2(CN)2 [cis-dicyano-bis(1,10)-phenan- [Cu(tmen)(acac)]+ ClO− 4 (6) have been success-
throline-iron(II)] (1), Michler’s ketone [4,4 -bis(N,N- fully used for specific cellulose batches like never
204
Table 1. Genuine solvatochromic probes checked for investigating the surface polarity of celluloses (see also Scheme 2).

Probe Adsorption on cellulose Remark

1 Fe(phen)2 (CN)2 Excellent α sensitive

2 Michler’s ketone Good α and π ∗ sensitive
3 4-Aminobenzophenone Good π ∗ and β, or α sensitive
4 Coumarine 153 Excellent π ∗ and α sensitive
5 Reichardt’s ET (30) dye Mediocre, poor α and π ∗ sensitive
6 Cu[tmen(acac)]+ ClO4 − Mediocre, poor β sensitive
7 Aminobenzodifuranone Poor π ∗ and β, or α sensitive
8 Brooker’s merocyanine dye Good Solely pH sensitive
9 Lipophilic ET (30) dyes Very poor π ∗ and α sensitive
10 MK(OH)2 a Excellent π ∗ , α, and β sensitive
a (N,N-dimethylaminophenyl)[bis-N ,N -(2-hydroxyethyl)aminophenyl] ketone.

Scheme 2. Solvatochromic probes used for this work.

dried samples (Spange et al. 1992a, 1998). The measured in the relevant environment (Reichardt
original ET (30) solvent polarity parameter is 1991):
defined as the molar transition energy of the in-
tramolecular CT (charge transfer) absorption band ET (30)(kcal mol−1 ) = 2.859 × 10−3
of the dye 5 given in kcal mol−1 (Equation 7) υ̃max (5)(cm−1 ). (7)

β can be determined using υ̃max (6) (Migron and
Marcus 1991):
β = 6.716 − 0.358 υ̃max (6). (8)
Unfortunately, 5 and 6 cannot widespreadly be used,
because native cellulose samples do rarely adsorb
these probes. When the two phenyl rings of the phe-
nolate moiety of 5 are omitted, then an improved
adsorption on celluloses takes place (Bigos 2000).
However, the well-established empirical ET (30)
solvent polarity parameter can be calculated by an
LSE relationship using the independently available
Kamlet–Taft parameters α and π ∗ (Marcus 1993)
(Equation 9).
ET (30) = 31.2 + 15.2 α + 11.5 π ∗
n = 155, r = 0.98, sd = 1.1. (9)
If ET (30) is not directly available by Equation 7,
apparent values can be calculated via Equation 9. Fur-
thermore, Equation 9 demonstrates that ET (30) values
contain contributions of both the hydrogen-bond acid-
ity (60%) and the dipolarity/polarizability (40%) of
the solvents.
The application of Equation 9 requires that the
coefficients a and s from Equation 1 are independent
of the environment. This presumption seems not al-
ways accomplished for solid materials, as discussed
for functionalized silicas (Spange and Reuter 1999)
and solid acid catalysts (Spange et al. 2000b). The
probes 7, 8, and 9 have been found unsuitable for a
general application to polysaccharides.
Correlation analyses of all υ̃max -values
with each other
Source and purification of the solvatochromic indi-
cators and cellulose samples as well as procedures
for preparing dye-loaded polysaccharide samples and
UV/Vis measurements are reported in detail in re-
cent references (Fischer and Spange 2000; Fischer
et al. 2002). More than 170 UV/Vis absorption data
for correlation analyses have been taken from these
recent references and unpublished results (Fischer
2002).
As discussed in Table 1, indicators 2 and 3 can
interact manifold with structurally complex surfaces.
1 interacts preferentially via the cyano groups on HBD
surface groups (Corio et al. 1999) and, therefore,
serves as an α indicator. If significant correlations
between the measured υ̃max data of 1, 2, and 3 with
each other exist, the respective indicator pair observes
205
quite the same property of a surface. Such results
would be in particular detrimental to the concept for
separation of α, β, or π ∗ from different υ̃max -values
derived from different indicators.
The correlation of υ̃max (1) with υ̃max (2), includ-
ing all measured UV/Vis data from recent references
(Fischer et al. 2001, 2002), gives similar results as ob-
served for well-behaved solvents (Spange and Keutel
1992). Therefore, it is justified to make use of υ̃max (1)
and υ̃max (2) for determining reliable α and π ∗ -values.
If 3 observes HBD sites among HBA sites on the sur-
face, then a significant correlation between υ̃max (1)
and υ̃max (3) results as observed for polypeptide sur-
faces (Spange et al. 2001). Such a dependence has
only been observed for the CTs (Fischer et al. 2002).
Thus, β-values for CTs cannot be determined using
probe 3.
The problem with determining reliable π ∗ -values
demonstrates the correlation analyses of υ̃max (2) with
υ̃max (4) for solvents (Equation 10), celluloses, and
cellulose derivates studied.
υ̃max (4) = 5.81 + 0.65 υ̃max (2),
n = 20, r = 0.95, sd = 0.28. (10)
Both probes are preferentially sensitive to π∗ and less
to α: s/a = 1.22 for 2 and s/a = 2.11 for 4. A
trend correlation between υ̃max (2) and υ̃max (4) exists
for most (about 75%) of the polysaccharides which
fit well in the solvent correlation, as indicated by the
cloud of points in Figure 1.
However, both probes measure the relevant scale
of surface polarity. For all polysaccharide samples
studied, 2 differentiates the scale of polarity of cel-
luloses more sensitive than 4. Hence, we have 2
considered as the probe for the discussion, because
of its established applicability for silicas and related
macromolecules. For specific problems the use of the
π ∗ sensitive probe 4 is additionally helpful (Fischer
et al. 2002).
Polarity parameters of cellulose samples
Empirical polarity parameters α, β, π ∗ , and ET (30)
of various celluloses are compiled in Table 2. As
mentioned, native cellulose fibres do rarely adsorb
Reichardt’s dye nor its substituted derivatives from
1,2-dichloroethane or cyclohexane solution (Fischer
and Spange 2000). Regenerated celluloses (Spange
et al. 1998) and cellulose membranes (Bigos 2000)
do it in special cases. Then, ET (30) values for cel-
lulose are directly measurable. They range between
206

Figure 1. Correlation of υ̃max (4) with υ̃max (2) for solvents (straight line according to Equation 10), celluloses (
), cellulose derivatives (),
and chitine (∗).

Table 2. Physical properties and chemical constitution of the cellulose samples used in this work. Empirical polarity parameters α, β, π ∗ , and
ET (30) of cellulose from literature in chronological order.

No. Reference Sample specification DPa Remark Source, trade name β α π∗ ET

(kcal mol−1 )

1 Spange et al. 1992 Bead cellulose – Dehydratedb Leipziger 0.6 0.98 0.66 51.4
(regenerated) Arznei-mittelwerk
2 Spange et al. 1992 Beech sulphite pulp – Grinded Heweten 0.6 1.27 0.41 53.0
3 Macquarrie et al. Not specified – – Aldrich Not reported 49.1
1999
4 Bigos 2000 Membrane – Dehydratedb Membrana GmbH Not reported 51.7
(regenerated)
5 Fischer 2002 Prehydrolyzed 800 Nondriedc Buckeye 0.58 1.50 0.24 56.8d
kraft-pulp V-60
6 Fischer et al. 2002 Linters 4410/30 2000 Dried Buckeye 0.08 1.33 0.29 54.7d
7 Fischer 2002 Sulphite kraft-pulp 800 Nondriedc Borregaard 0.5 1.49 0.1 55.1d
quality svs
8 Fischer 2002 Prehydrolyzed 2000 Nondriedc Buckeye 0.46 1.51 0.31 57.7d
kraft-pulp A-6
9 Fischer et al. 2002 Linters 4410/030 2000 Nondriedc Buckeye 0.26 1.33 0.29 54.7d
10 Fischer et al. 2002 Linters 4401 1470 Nondriedc Buckeye 0.13 1.48 0.30 57.1d
11 Fischer 2002 Micro-crystalline Not specified Nondried BASF 0.62 1.31 0.34 55.0d
12 Fischer 2002 Bacteria cellulose 2000 Lyophil. FMBe 0.86 0.78 0.69 52.1d
13 Fischer 2002 Bacteria cellulose 2000 Dried FMBe 0.87 0.79 0.76 53.0d
a Weight average.
b Dehydrated by a stepwise solvent exchange (water → ethanol → acetone → dichloromethane).
c As received.
d From Equation 9.
e FMB, Research Centre for Medicine technique, Bad Langensalza.

ET (30) = 49.1 (Macquarrie et al. 1999) and 58 kcal mol−1 of the ET (30) polarity scale. Experi-
ET (30) = 53 kcal mol−1 (Spange et al. 1992a, b). mentally determined ET (30) are always lower. Exper-
Calculated values cover the section between 54 and imentally determined and calculated ET (30) values,

respectively, likely reflect different sections of an acid-
ity distribution on the cellulose surface. These results
show that polarity of cellulose cannot be classified in
terms of a rigid parameter.
For all native cellulose samples studied, α is
evidently larger than π ∗ . Adsorbed water signifi-
cantly modifies the polarity of both environments:
the amorphous as well as the microcrystalline part.
The residual water content amounts to 4–6% weight
(determined by thermogravimetry) depending on the
procedure of drying. Freeze dried samples show a
larger BET surface area than vacuum dried samples.
A drying process clearly levels the differences of α
between the different cellulose batches 5–10, which
shows that morphology has an effect on the surface
polarity. X-ray measurements confirmed that the cellu-
lose batches 5–11 are celluloses with the modification
I (cellulose I). The crystallite dimensions of Linters
celluloses are larger compared to the other cellulose I
batches. Besides to the samples 1, 3, and 5, the Lin-
ters celluloses show a better order (Fischer 2002). The
cellulose batches 6, 9, and 10 as well as the samples
5, 7, and 8 are similar with respect to their crystallin-
ity. But the samples 6, 9, and 10 are more crystalline
than samples 5, 7, and 8, which is shown by the in-
tensity of the corresponding reflexes (Fischer et al.
2002).
The UV/Vis band shift of dye 1 adsorbed on
the cellulose samples 5–10, respectively, apparently
shows a dependence on its concentrations. This shows
that a wide HBD strength distribution contributes to
the overall HBD acidity for those cellulose batches.
For example, the cumulative acidity α of sample 9 as
function of the concentration of 1 [1] can be expressed
by Equation 11:
log[1]
α = 0.132 (cellulose, sample 9)
100 mg
+ 0.597
[1] in mol n = 5, r = 0.998, (11)
α apparently decreases from 1.56 to 1.05 with increas-
ing [1] from 2 × 10−7 to 2 × 10−3 mol per 100 mg
cellulose.
Using the standard dye concentrations per gram
cellulose (2 × 10−5 mol per 100 mg cellulose for 1,
2 or 3), centres of stronger acidity of the cellulose
surface are preferentially observed. Therefore, α in
Table 2 often represents the most acidic part and not
an average of all HBD sites, which obviously explains
the apparently large ET (30) values.
207
The order of magnitude for α is confirmed by
zetapotential (ξ in mV) measurements (Fischer et al.
2002). Both the shift of the isoelectric point as well
as the absolute ξ value in the pH range of 5–10 cor-
respond to α. This result indicates that concentration
and strength of acidic sites on cellulose contribute to
α. Because the concentration of the most acidic sites is
very low (below 2×10−7 mol per gram cellulose), it is
not possible to decide at which surface site the probe
is located by other spectroscopic methods. It is likely
that these sites are to carboxyl groups, because large
α-values are also observed for related native cellulose
batches like banana fibres (Pothan et al. 2000). Strong
acidic sites are also responsible that 2 observes likely
a too low π ∗ term for specific batches, because pro-
tonation at the lone electron pair of the dimethylamino
group of 2 cannot be excluded. Then a hypsochromic
UV/Vis shift of 2 takes place, indicating a too low π ∗
term. This feature is not considered as Equation 3 has
been calculated (Spange and Keutel 1992).
Hence, bacteria cellulose shows reasonable π ∗ -
values compared to solvent models, because strong
acidic sites are not detectable on these samples.
Celluloses I with similar crystallinity show similar
effects in the UV/Vis absorption spectra by measur-
ing [1] as function on υ̃max (1). A negligible influ-
ence of [1] on υ̃max (1) results when celluloses are
investigated which bear smaller dimensions of the
crystallites.
β-Values of celluloses I range between 0.1 and 0.6.
The agreement between β derived from 6 and 3 is good
for samples 1, 2, 5, 7, 8, and 11, and less for the
rest. β-Values of celluloses I observed by indicator 3
and calculated by Equation 7 are reasonable compared
to β of protic solvents, that is, glycerol (β = 0.51)
or methanol (β = 0.66). The β-values complete the
interpretation of zetapotential results, because a low β
corresponds to weak proton affinity of cellulose I in
water (Fischer et al. 2002). Cellulose II shows larger
β-values which correspond to ethanol (β = 0.75) as
solvent. The influence of the concentration of 2 when
adsorbed on cellulose I on υ̃max (2) is negligible, in-
dependent of the kind of cellulose batch used. This
result indicates a homogeneous distribution of dipolar-
ity/polarizability on the cellulose I surface compared
to the acidity. Microcrystalline sections of cellulose I
exhibit apparently a relatively low π ∗ -value. The scale
of π ∗ is supported by means of pyrene fluorescence
measurements using the I1 /I3 ratio (Py). Py is defined
as the intensity ratio of the solvent-dependent emission
bands at λ = 354 nm (I1 ) and 374 nm (I3 ) of pyrene.
208
Table 3. π ∗ -values of two microcrystalline celluloses, silica, and water, calculated via pyrene emission from Equation 12, using the
independently determined α-value of 1 from Equation 6.

Material Py π∗ α υ̃max (1) × 10−3 /cm−1

Cellulose 0.81 (Yamamoto et al. 1998) 0.31 1.0a –

Cellulose 0.81 (Yamamoto et al. 1998) 0.35 1.5a –
Cellulose (no. 9 of Table 2) 1.24 (Fischer et al. 2002) 0.73 1.47 (19.13)b
Silica 1.78 (Krasnanski and Thomas 1994) 1.10 1.3 (18.78)c
Water 1.87 (Dong and Winnik 1984) 1.22 1.6 (19.4)d
a Assumed values.
b From Fischer et al. (2002).
c Spange et al. (2000).
d Spange (unpublished result).

With increasing dipolarity/dipolarizability, π ∗ of the Table 4. α, β, π ∗ , AN, and apparent ET (30) values for CMC,
solvent Py increases (Equation 12 has been taken from dicarboxymethylcelluloses (DCMC), CT, sulfoethyl- (SEC), hy-
Dong and Winnik 1984). droxyethyl- (HEC), hydroxypropyl- (HPC), methylhydroxyethyl-
(MHEC), and methylcelluloses (MC) with different DS.
I1
= Py = 0.64 + 1.33(π ∗ − 0.24δ) − 0.25 α, Sample DS α β π∗ AN ET (30)app.
I3
(kcal mol−1 )
n = 32, r = 0.9. (12)
CMC 1 0.48 1.04 0.80 0.70 45.40 55.14
Pyrene emission spectra on cellulose are not easy to CMC 2 0.72 0.94 0.91 0.43 41.81 50.50
perform and can, therefore, not be widely applied CMC 3 1.05 0.35 0.85 0.71 34.45 44.71
(Yamamoto 1998; Fischer et al. 2002). Using the CMC 4 1.09 0.84 0.67 0.84 39.39 53.57
I1 /I3 -value of 0.8 from Yamamoto and assumed α- CMC 5 1.10 0.59 0.81 1.10 32.42 52.85
values of 1.0 and 1.5, the value of the π ∗ term (via CMC 6 1.15 0.63 0.67 0.63 32.75 48.03
Equation 12) for a microcrystalline environment of CMC 7 1.30 0.63 0.81 0.70 32.75 48.82
cellulose amounts to 0.31 and 0.35, respectively. The CMC 8 1.44 0.66 0.87 0.61 33.60 48.29
Py value of batch 9 (I1 /I3 = 1.24 from Fischer et al. CMC 9 1.58 0.69 0.84 0.57 34.44 48.28
2002) corresponds to a moderately polar environment, CMC 10 1.86 0.36 0.91 0.80 24.82 45.91
π ∗ = 0.70 ± 0.1 (see Table 3). CMC 11 1.96 0.43 0.91 0.69 26.81 45.71
The discussion shows that π ∗ of different cel- DCMC 1 0.89 0.82 0.91 0.50 38.34 49.45
lulose batches is difficult to quantify. However, an DCMC 2 1.73 0.78 0.85 0.55 37.02 49.32
independent method which shows the relevance of the CT 1 0.38 0.78 0.88 0.57 37.52 49.64
calculated π ∗ -values in relation to macroscopic prop- CT 2 0.46 0.85 0.75 0.77 39.58 52.90
CT 3 0.89 0.81 – 0.81 38.52 52.82
erties or structural features is still a challenge. Despite
this argument, we think π ∗ serves as a more sensitive CT 4 0.93 0.81 – 0.85 38.69 53.36
CT 5 1.12 0.75 – 0.82 36.77 52.05
parameter than α in order to differentiate between vari-
CT 6 1.54 0.53 – 0.96 30.44 50.39
ous native cellulose batches, because a wide surface
CT 7 1.59 0.74 – 0.87 36.42 52.43
dipolarity distribution is not observed.
CT 8 1.68 0.61 – 0.83 32.42 49.99
SEC 1 0.42 0.94 0.79 0.88 42.54 55.52
Cellulose derivatives SEC 2 0.91 0.81 0.75 1.00 38.95 55.01
HEC 1 0.73 0.64 0.31 0.74 33.17 49.46
Table 4 summarizes α, β, π ∗ and calculated ET (30) HEC 2 1.62 0.66 0.46 0.82 34.02 50.72
values of carboxymethyl celluloses (CMCs), cellulose HPC 1 0.73 0.66 0.28 0.61 33.60 48.29
tosylates (CTs), with different DS and other polar HPC 2 1.54 0.68 0.41 0.93 34.87 52.21
derivatives from the literature (Fischer et al. 2003). MHEC 1.52a 0.62 0.52 0.64 32.34 47.91
Generally, the introduction of organic function- MC 1 0.90 0.63 0.56 0.68 32.75 48.56
alities in the cellulose backbone decreases α. This MC 2 1.75 0.54 0.41 0.61 29.86 46.37
is shown by linear correlations of DS with α for a Degree of molar substitution of hydroxyethyl moieties = 2.24.
CMCs, CTs and celluloseacetates (CAs), respectively
 209
Table 5. Surface polarity parameters α, β, π ∗ , and ET (30) of polysaccharides and model compounds.

Material Source Remark α βa π∗ ET (30) (kcal mol−1 )

Glycogene Merck For biochemistry 0.78 0.60 0.61 50.1b

Amylopectine Merck From potato starch 1.37 0.69 0.26 55.0b
Amylose Merck From potato starch 0.83 0.69 0.68 51.1
Amylose Aldrich Not specified – – – 47.5c
Starch Fluka Not specified 1.39 0.88 0.29 57.7b
Cellobiose Fluka Biochemical grade ≥ 99% 1.44 0.70 0.16 54.9b
Chitine Fluka Mn ≈ 400.000 g mol−1 0.67 0.86 0.91 51.8b
Chitosaned (pH = 8) Fluka Mn ≈ 600.000 g mol−1 0.42 1.01 0.73 46.8b
a Average derived from two probe pair sets from Fischer and Spange (2001).
b From Equation 9.
c From Macquarrie et al. (1999).
d Polarity of polyelectrolytes is strongly dependent on pH.

(Spange, unpublished results, data are taken in partic-
ular from Spange et al. 1992a, b) (Equations 13–15):
DSCMC = 2.20 − 1.462 α,
n = 11, r = 0.733, sd = 0.321,
DSCT = 3.64 − 3.489 α,
n = 8, r = 0.763, sd = 0.351,
DSCA = 5.02 − 3.898 α,
n = 6, r = 0.981, sd = 0.233.
The satisfactory correlation coefficients are due to
asymptotic plots from DS > 2.5 and DS < 0.5. If the
introduced substituent bears also a HBD group like the
former Cell-OH, an average α of all HBD groups is
observed.
π ∗ and β of cellulose derivatives are seldom lin-
early correlated with structural variations, because of
the manifold influences of residual Cell-OH groups,
novel organic functionalities, and the varying amount
of adsorbed water traces on υ̃max, Probe . However,
for CTs, an increase of π ∗ with increasing tosylate
functionalization has been observed (Equation 16):
DSCT = −1.695 + 3.419 π ∗,
n = 8, r = 0.763, sd = 0.351.
This effect is explained by an increase of the polariz-
ability due to the introduced aromatic moiety.
Other polysaccharides and model compounds
Empirical polarity parameters are summarized in
Table 5.
Branched polysaccharides (glycogene, starch,
amylopectine) show larger α-values than the non-
branched amylose. We think that similar co-operative
effects as for cellulose are responsible for the larger α-
values of these materials. The α-value of 1.44 for the
cellobiose crystals surface clearly supports the scale of
(13) α for the crystalline sections of cellulose.
Dipolarity/polarizability of polysaccharides in-
creases in the following order: amylopectine <
(14) glycogene < amylose < chitine. The significant in-
crease of π ∗ from amylopectine to chitine is reason-
able, because the substitution of the –OH group in the
(15) 2-position of the anhydroglucose unit with the highly
dipolar –NH–CO–CH3 moiety significantly improves
the polarizability of this polysaccharide.
Also, the scale of α and β for these materials
is reasonable and relates well to the solvents model
reference set.
Conclusions
Classification of ET (30) polarity of polysaccharides in
relation to synthetic polymers and solid acids shows
the final diagram (Scheme 3).
Because the crystallinity and water content of cel-
(16) lulose are associated properties, the surface polarity
of native cellulose batches cannot be parameterized
in terms of a rigid parameter like for solvents or
specific silicas. In the framework of the empirical
ET (30) solvent polarity scale, polarities of celluloses
cover a wide section of 49–57 kcal mol−1 relating to
1-pentanol [ET (30) = 49.1 kcal mol−1 ] and formam-
ide [ET (30) = 56.6 kcal mol−1 ] as solvents. However,
specific cellulose sites even approach the polarity level
of silica and alumina.
210
Scheme 3. Classification of celluloses and other polysaccharides in the framework of Reichardt’s empirical ET (30) solvent polarity scale.
The values of the α term of cellulose I show a
wide distribution depending on both water content and
crystallinity. Amorphous sections show low α, and
crystalline parts large α-values of the cellulose I sur-
face. Both the strength and the concentration of HBD
surface groups contribute to α. Therefore, α is a spe-
cific parameter which can be significantly changed
depending on pre-treatment of the cellulose and basic-
ity of the probe used, because of manifold acid–base
interactions. However, the π ∗ term can serve as a
suitable parameter for classifying the surface polar-
ity of different native cellulose batches. Therefore,
the solvatochromic method is suitable in detecting
small differences in the surface properties for various
cellulose batches like a fingerprint.
Cellulose derivatives and related polysaccharides
can be characterized in the same sense and classi-
fied in the framework of a polarity scale for solid
materials.
It has been well established that cellulose I surfaces
possess sections of different polarity. Now, it is ne-
cessary to observe them locally by means of UV/Vis
microscopy. This feature requires another technique
for measurements. But the results of this minireview
have shown that use of solvatochromic probes which
response sensitively to crystallites and amorphous sec-
tions seems suitable in combination with the UV/Vis
technique for this purpose.
Acknowledgements
Financial support for this study was provided as part of
the focus research program (Schwerpunktprogramm)
on ‘Cellulose and cellulose derivatives – molecular
and supramolecular structural design’ by the Deutsche
Forschungsgemeinschaft (DFG) [described in the ed-
itorial commentary of Prof G. Wenz in Cellulose
10-1]. We also gratefully acknowledge the Fonds der
Chemischen Industrie, Frankfurt (Main) for financial
support. We thank Dr C. Bellmann, Dresden, Dr J.
Adams, Clausthal-Zellerfeld, Dr H. Leipner, and Dr
S. Fischer, Freiberg, for scientific co-operation as
well as Prof S. Seeger, Zürich, for generously sup-
porting the stay of Kristin Fischer in Regensburg,
as well as the Wolf Walsrode AG, Prof Schmauder,
Bad Langensalza, and Prof Reichardt, Marburg, for
chemicals.
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