Hydrogen Bonds in Cellulose and Cellulose Derivatives

3
Hydrogen Bonds in Cellulose and Cellulose Derivatives

Tetsuo Kondo
Kyushu University, Fukuoka, Japan
I. HYDROGEN BONDS IN CELLULOSE formation of hydrogen bonds in parallel direction to a

glucopyranose ring, and to van der Waals’ interaction per-
The native biopolymer assembly has been shown to be a pendicular to the ring.
complex process involving two separate but integrated Another important point for the hydroxyl groups is
steps of polymerization and crystallization [1,2]. In the type of hydroxymethyl conformation at the C-6
particular, cellulose has shown to be assembled by a position, because the conformation of C(5)–C(6) and the
macromolecular complex of enzymes located on the cell resulting interactions including inter- and intramolecular
surface. Nature has designed an efficient system for regu- hydrogen bonds in the present cellulose structure may
lating the molecular weight, crystallinity, size, and shape of differ from that in crystallites as described in the following
the nanostructure of cellulose (called cellulose microfi- section, and it is also assumed to make up the extent of
brils). Then the microfibrils are self-assembled to form cell crystallization, as well as the final morphology of cellulose
walls maintaining tree-frame structure. In this manner, [3–5]. In the noncrystalline regions, the rotational position
cellulose molecules biosynthesized at angstrom scale as- of hydroxymethyl groups at the C-6 position may be
semble to be microfibrils at nanoscale, and the microfibrils considered as indeterminate or totally nonoriented,
assemble to be cell walls at micronscale, then they scale up whereas all of those are identical in the crystallites.
with growing (Fig. 1). Hydrogen bonds are no doubt a Therefore it was important to confirm the type of O(6)
major interaction to stabilize this hierarchical architecture rotational position with respect to the O(5) and C(4) in a
of higher plants. Therefore considering hydrogen bonds h-glucan chain, employing CP/MAS 13C NMR [6]. The
of cellulose requires in your mind a picture of the size type of hydroxymethyl conformations, gauche–trans (gt),
(angstrom, nano, or micron) of the subject that you are trans–gauche (tg), or gauche–gauche (gg) at the C-6 posi-
looking at. tions in carbohydrates is shown in Fig. 4. In the gt
First, cellulose is considered as a single molecule conformation, hydroxyl groups (OH) at the C-6 position
(primary or chemical structure): cellulose owns an ex- locate at the opposite side to OH at the neighboring C-2
tended structure with a 21 screw axis composed of the position, and thus they are supposed to form intermolec-
h-1,4 glucosidic linkages between anhydroglucose units. ular hydrogen bonds with the neighbors, whereas tg
Thus it would be natural to accept the dimer called ‘‘cello- conformation may provide intramolecular hydrogen
biose’’ as a repeating unit. The present three kinds of bonds engaged between OH groups at the C-2 and C-6
hydroxyl groups within an anhydroglucose unit exhibit positions. As for the noncrystalline states, they are con-
different polarities, which contribute to the formation of sidered as the gg conformation.
various kinds of inter- and intramolecular hydrogen bonds As described above, the difference in polarity among
among secondary OH at the C-2, secondary OH at the hydroxyl groups and hydroxymethyl conformation at the
C-3, and primary OH at the C-6 position (Fig. 2). In addi- C-6 position in relation to equatorial bonding of them to an
tion, all the hydroxyl groups are bonded to a glucopyra- anhydroglucose ring is strongly attributed to inter- and
nose ring equatorially. This causes the appearance of intramolecular hydrogen bonds of cellulose. Further, the
hydrophilic site parallel to the ring plane. On the con- hydrogen bonding patterns in cellulose are considered as
trary, the CH groups are bonded to a glocopyranose ring one of the most influential factors on the physical proper-
axially, resulting in a hydrophobic site perpendicular to ties of cellulose and its derivatives shown in Fig. 2. This
the ring as shown in Fig. 3. These effects lead to the issue will be treated later in this chapter.
Copyright 2005 by Marcel Dekker

70 Kondo
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Figure 1 Hierarchical system of cellulose self-assembly.
Of course, cellulosic fibers and materials are made of

inter- and intramolecular hydrogen bonds, and turning to
the molecular structure of cellulose, intramolecular hydro-
gen bonds are primarily to be employed as a most influen-
tial interaction to the molecule. Cellulose is supposed to
have at most two different intramolecular hydrogen bonds,
which are between the OH-3 and adjacent ring O-5V and
between the OH-6 and OH-2V when the hydroxymethyl
conformation at the C-6 position is tg (Fig. 5) [7–11]. The
intramolecular hydrogen bonds influence first on the mo-
lecular main chain stiffness. Is the main chain for each
cellulose single molecule that seems to be stiff really stiff ?
For this question, extensive studies of solution properties
and liquid crystalline properties for cellulose and cellulose
derivatives have been carried out. At the moment it is
explained that the main chain for each cellulose molecule is
not so stiff, and rather the molecule itself is a semiflexible
one in which the worm-like chain model by Heine et al. [12]
can be well applied to [13–15]. Therefore one single mole-
cule is considered relatively mobile. Only a single molecule,
however, cannot exist in normal states. The molecules are
mutually influenced and interacted with each other. There
may be two stabilizing ways for each molecule, depending
on the initial step. One is that after a single molecule
interacts with other molecules, then each molecule com-
pensates the potential energy to be stabilized. Another is
that first the potential energy for each molecule is mini-
mized and after the minimization, it starts interacting with
each other by hydrogen bonding, van der Waals’ force, and
dipole moment interaction. In any case, every single cellu-
lose molecule interacts with each other. Therefore it Figure 2 A general idea on the correlation of basic
becomes important to characterize the interaction that is characters for each hydroxyl group with physicochemical
engaged between molecules and further the relationship properties.

Hydrogen Bonds in Cellulose and Cellulose Derivatives 71
Figure 3 Hydrophilic and hydrophobic nature in cellulose chemical structure.

between the interaction and physical properties of cellulose the state such as crystals, noncrystalline and amorphous
and the derivatives in order to anticipate both the physical solids, gels, liquid crystals, and solutions.
and chemical characteristics of new cellulosic materials
[16–28]. A. Hydrogen Bonds in Cellulose Crystals
Among the interactions in cellulose, the hydrogen
bonding interaction should be most frequently observed. In this section, the object is up-scaled from a single
Fig. 2 shows a general idea on the correlation of basic molecule of cellulose up to a microfibril as a molecular
characters for each hydroxyl group with the physicochem- assembled state. As shown in Fig. 6, after the biosynthesis
ical properties. Cellulose exhibits really versatile properties of cellulose molecular chain, each single glucan chain
ranging from transformation of crystalline form to the starts associating with each other to self-assemble into a
regiochemical difference of the reactivity for the chemical microfibril at a nanoscale (3.5–4.0 nm for wood micro-
derivatization and enzymatic hydrolysis. We have to dis- fibrils). Biosynthesis is an integrated step to form crystal-
tinguish the situation for the hydrogen bonds depending on line form of cellulose as a microfibril. The process mostly
Figure 4 Schematic diagram of the hydroxymethyl conformations at the C-6 position, namely, the orientation of the C6–O6
bond, gauche–trans (gt), trans–gauche (tg), or gauche–gauche (gg) with a cellobiose unit.

72 Kondo
backbone conformation, with the two glucose residues

repeating in approximately 1.03 nm. Recently, native cel-
lulose (cellulose I) was found to be a composite of cellulose
Ia and cellulose Ih crystalline forms by Atalla and Vender-
Hart [30]. However, some of the crystalline structures such
as cellulose IV are still in question so far. Therefore we only
focus on conventional crystalline structure, cellulose I and
cellulose II. In particular, for cellulose I, we will employ
cellulose Ih, which is two-chain monoclinic [31] and is close
to the proposed models on the basis of X-ray and electron
Figure 5 Possible intramolecular hydrogen bonding forma- diffraction data as well as chain packing energetics [32,33].
tion in tg conformation of hydroxymethyl groups in cellulose. Thus we can easily understand the formation of hydrogen
bonds using the models. On the other hand, because, to
date, we cannot have pure cellulose Ia, it is still difficult to
produces highly crystalline domains, but not necessarily a explain the hydrogen bonding formation for the cellulose
perfect process to secrete a cellulose crystalline fiber. Ia crystalline form. Just recently, a revised structure and a
Therefore a cellulose fibril contains a certain amount of hydrogen bonding system in cellulose Ih [34] and cellulose
noncrystalline domains as illustrated in Fig. 6. About II [35] have been proposed. In this section, the new insight
cellulose biosynthesis, there are many books from different as well as the previous one will be compared historically.
viewpoints (see, for example, Ref. [29]). In this way, Before getting into the details, we will confirm how to take
crystalline cellulose domain is an idealistic assembly of the crystallographic axes (a, b, and c) and a certain angle, g,
cellulose molecules in the biological system. Then hydrox- between the a–b axes. Now many people use the recent
yl groups equatorially bonded to the glucose ring become crystallographic rule, namely, c axis is a molecular axis, but
closer enough among neighboring h-glucan chains to form still some researchers take b axis for the molecular chain
intermolecular hydrogen bonding. Therefore it would be axis. In fact, the number of researchers who use the recent
of more importance to understand intermolecular inter- crystallographic rule is increasing gradually. In this chap-
actions in crystalline cellulose. ter, we will follow the recent rule.
Crystalline cellulose has different crystalline forms
from cellulose I to cellulose IV, and even in alkaline 1. Hydrogen Bonds in Native Cellulose (Cellulose I)
conditions it shows so-called alkali–cellulose crystals, The crystalline nature of cellulose was revealed almost a
which still gives a question as to the manner of existence. century ago when Nishikawa and Ono recorded the first
In each form, the chains have approximately the same X-ray diffraction patterns from fiber bundles originated
Figure 6 Crystalline and noncrystalline regions of cellulose microfibrils.

from various plants [36]. Since then, in addition to X-ray, 2: : : O6V, to give an even more rigid four-ring layer config-
many powerful tools have appeared for investigating cel- uration. In these structures there is an intermolecular
lulose crystalline structures such as electron diffraction and hydrogen bond, OH-6: : :O3 (Fig. 7C), linking the layers
microscope, FT-IR, Raman spectroscopy, and 13C CP/ laterally, but no bonding between layers. In other words,
MAS NMR. The development of high-resolution 13C there is no intermolecular hydrogen bonding along the
solid-state NMR techniques in the 1980s has brought a (110) and (110) planes, but there is only one along the (200)
new dimension to determining the crystal structure of plane as shown in Fig. 7A. Investigating hydrogen bonds in
cellulose. In fact, 13C CP/MAS NMR of highly crystalline cellulose using IR was first performed by Marrinan and
cellulose samples such as Valonia showed the presence of Mann [44,49], and then Liang and Marchessault [46,47]
two crystalline allomorphs (cellulose Ia and Ih) in cellulose proceeded to assign the whole area of OH stretching
I. However, FT-IR is still one of the best tools to study frequencies in IR spectra for celluloses I and II. They used
hydrogen bonding formation with consideration of the polarized IR measurements for oriented films having cel-
two-chain unit cell models (21 axis) [37]. In particular, lulose I or cellulose II crystalline structures and assigned
not only FT-IR but also advanced FT-IR technique in some typical maxima for the OH regions of the IR spectra
combination with suitable attachments could provide us on the basis of the difference between the parallel and the
with further information on cellulose supermolecular perpendicular bands. Now let us take a look at Table 1
structure. Many reports using IR analyses have appeared [46,48,50–52] and you would find that two intramolecular
to date. Fengel analyzed the hydroxyl absorption bands by hydrogen bonds and an intermolecular hydrogen bond
deconvoluted FT-IR spectra of celluloses [38–40]. Michell have already been assigned. Some experimental assign-
used the second-derivative mode in order to improve the ments correspond to the calculated wavenumbers [48].
FT-IR resolution [41–43]. The assignments for the hydrox- In the 1980s, the crystalline dimorphism of native
yl frequencies had been established from the late 1950s to celluloses was found [30,53], and the two phases, cellulose
the early 1960s on the basis of the modified Meyer–Misch Ia and Ih, have been considered to differ in their hydrogen
model [44–47]. In addition, the O–H stretching frequencies bonding rather than in the conformation on the basis of
due to intra- and intermolecular hydrogen bonds in cellu- Raman [51] and FT-IR [31,43] spectral data. According to
lose I were calculated [48]. Table 1 lists these reported Sugiyama et al. [52], a characteristic hydroxyl absorption
band-assignments for native cellulose. To make an easy band due to Ia crystalline phase is 3240 cm 1, whereas a
understanding of the hydrogen-bonding network, we will band at 3270 cm 1 is due to Ih crystalline phase. There are
use the ab and bc projection of the unit cell for cellulose I a number of literatures reporting on the IR data of native
(21 screw) originally proposed by Gardner and Blackwell cellulose [40–46,49,52,54]. Most of these studies give more
[32] as shown in Fig. 7. This permits the formation of two or less complete lists of IR band assignments on the
intramolecular hydrogen bonds, OH-3: : :O5V and OH- hydrogen bonding system. Most of these earlier IR studies,
Table 1 IR Assignments for OH Regions Reported in Native Cellulose
Interpretation
(Liang et al. 1959:L) Calculated
Frequency (Ivanova et al. 1989:I) Interpretation by Raman wavenumbers
(cm 1) (Sugiyama et al. 1991:S) (Wiley et al. 1987) (Tashiro et al. 1991)
3230–3310 I: O(6)H–O(3)
Inter H-bond
3231 Cellulose Ia (?)
appeared in Valonia
3240 S: Cellulose Ia
3270 S: Cellulose Ih
3305 L: OH Inter H-bond
3309 OH Inter H-bond
3340–3375 L&I: O(3)H–O(5)
intra H-bond
3372 OH Intra H-bond
inter–O(3)H–O(5)
3405 L: OH Inter H-bond
3410–3460 I: O(2)–O(6)
Intra H-bond
O(2)–O(6)–inter
3429 Cellulose Ih (?)
appeared in Ramie

74 Kondo
Figure 7 Proposed structure of cellulose I before the discovery of native cellulose allomorphs, Ia and Ih, in 1983 by Atalla and
VanderHart [29]. (A) ab projection (looking along the chain axis); (B) bc projection; (C) hydrogen-bonding network in the sheet
parallel to the bc plane. This figure is modified on the basis of the Gardner and Blackwell model [31].
however, were made before the discovery of the two crys- requires data of pure Ia and Ih fibers. Recently, the revised
talline phase system of cellulose. Thus a number of the data have been proposed using synchrotron and neutron
earlier band assignments should be reevaluated in light of diffraction for oriented fibrous samples from tunicate
the two-phase system. Recently, Maréchal and Chanzy [55] cellulose microcrystals [34]. The study proposed not only
have reported the revised assignments of the IR bands in the revised Ih crystalline structure, but also the tg confor-
cellulose Ih from hydrothermally treated Valonia micro- mation of hydroxymethyl groups and the hydrogen bond-
fibrils. Their assignments are illustrated in Fig. 8. Accord- ing fashion. The hydrogen bonding scheme is represented
ing to them, hydroxymethyl moieties were found adopting schematically in Fig. 9: There is no hint of intersheet O–H–
three conformations (a dominant one and two minor ones) O hydrogen bonds in cellulose Ih, indicating that the
allowing the formation of different hydrogen bonding on cellulose sheets are held only by hydrophobic interactions
adjacent chains. Most probably, the primary hydroxyl and weak C–H–O bonds. Within the sheet, the intramo-
groups (OH) that accept a hydrogen bond from the adja- lecular O3–O5 hydrogen bonds were well defined, whereas
cent OH at the C-2 position were not the ones adopting the those corresponding O2–O6 hydrogen bonds were indi-
dominant conformation. However, there are still some cated in a variety of the fashion.
questions remaining as OH bands due to different modes
overlap with each other, causing difficulties in interpreta-
tion even in crystalline structures. 2. Hydrogen Bonds in Cellulose II
The crystal and molecular structure of cellulose I need Native cellulose can be easily transformed into cellulose II
to be revised also in light of this dimorphism. This revision after an alkaline treatment at more than 18 wt.% and

Figure 8 Assignment of IR bands of cellulose Ih, with stretching bands drawn as two-headed arrows and bending bands of
alcoholic groups as single-headed arrows. Assignments of bending bands to a particular alcohol group are tentative and may be
the object of permutations between the three types of alcohols. Three conformations of hydroxymethyl groups at the C-6 position
are displayed labeled I, II, and III. Conformations of II and III are deduced from conformation I by rotation of them around the
C5–C6 bond. Conformation I represents at least 2/3 of the total conformations, conformation II (tg) less than 10%. Hydrogen
bonds are supposed to be established by these primary alcohols on O atoms of other chains. For commodity hydroxyl groups at
the C-2 position establishing weak hydrogen bonds is drawn with free OH groups [55].
subsequent washing thoroughly with distilled water. For hydrogen bond OH-2: : :OH-2V to the next chain along the
cellulose II crystalline structure, some models have been long ab diagonal. This bond is shown in Fig. 10E and is
proposed and they have defined the crystals as consisting of indicated by the dashed lines in Fig. 10A. This extra
two antiparallel and crystallographically independent intermolecular bonding is a major difference between
chains. The proposed structure has a monoclinic cell where cellulose II and native cellulose and probably goes a long
the chains are aligned on the 21 screw axes. Both chains way to explain the higher stability of the regenerated form
have equivalent backbone conformation but differ in the [58]. Table 2 lists the experimental IR assignments [47] and
conformation of hydroxymethyl groups proposed by two
groups, Kolpak and Blackwell [56] and Stipanovic and
Sarko [57]. Their antiparallel model for cellulose II is
shown in Fig. 10. The ab projection shows that the chains
have approximately the same orientation about their axes
and are stacked along the short ab diagonal (Fig. 10B).
These stacks will be stabilized by hydrophobic (van der
Waals) forces, more so than between the sheet in native
cellulose. The relative stagger of the chains is 0.216c, again
close to the quarter-stagger position. The refinement has
led to different conformations of the –CH2OH groups on
the center and corner chains. Adjacent center chains along
the a axis are shown in Fig. 10C. The –CH2OH groups are
oriented like those in native cellulose, so as to allow the
formation of a second intramolecular hydrogen bond OH-
2V: : :OH-6 and an intermolecular hydrogen bond OH-
6: : : OH-3 along the a axis. The sheet of corner chains is Figure 9 Schematic representation of the hydrogen bonds
shown in Fig. 10D. Here the –CH2OH group is swung in the origin (top) and center (bottom) sheets of cellulose Ih.
round so that it forms an OH-6: : :OH-2 intermolecular Hydrogen bonds are represented by dotted lines. Only the
hydrogen bond. Intramolecular bonding for OH-2 is now oxygen atoms involved in hydrogen bonding have been
not possible, and this group forms another intermolecular labeled for clarity. (From Ref. 34.)

76 Kondo
Figure 10 Structure of cellulose II proposed by Kolpak and Blackwell [56]. (A) ac projection; (B) ab projection (- - - hydrogen
bonds between center and corner chains); (C) hydrogen-bonding of the center chains; (D) hydrogen-bonding of the corner chains;
(E) hydrogen-bonding between corner and center chains. This figure is modified on the basis of their model.

Table 2 IR Assignments for OH Regions Reported in B. Hydrogen Bonds in Regioselectively

Cellulose II Substituted Cellulose Derivatives in Solid-State
Noncrystalline Films
Frequency Calculated
(cm 1) wavenumbers 1. Characterization Using FT-IR and Solid-State
(Tashiro (Marchessault CP/MAS 13C NMR Spectra
et al. 1991) Interpretation et al. 1960)
The formation of hydrogen bonds in cellulosics is consid-
3175 OH stretching ered as one of the most influential factors on the physical
(Corner chain)
3350 ?
3435 (center chain)
3447 OH stretching
(corner chain)
calculated wavenumbers [48] for cellulose II. The model for

the crystalline structure indicated the formation of intra-
and intermolecular hydrogen bonds for cellulose II. In this
model, hydroxymethyl moieties are near gt conformation
for the glycosyl residues located at the origin of the cell as
opposed to tg conformation for those at the center chain.
The model of cellulose II has been further investigated
using h-cellotetraose hemihydrate and methyl h-cellotrio-
side monohydrate 0.25 ethanolate [59–62]. Their molecular
configuration was also similar to that of the cellulose II
model except in two main respects: all hydroxymethyl
groups are in gt conformation and the sugar pucker was
different for the two chains. In addition, the proposed
hydrogen bonding schemes using oligosaccharides were
significantly different from the previous ones.
Recently, Langan et al. have reexamined the structure
of cellulose II using a neutron fiber diffraction analysis [35].
In crystalline fibers of cellulose II, a 3-D network of
hydrogen bonds exists. This new model as shown in
Fig. 11 indicates a new substantially different hydrogen
bonding network from previous proposals. In Fig. 11,
intermolecular hydrogen bonds are O2-D-O6 in sheets
containing only origin molecules and O6-D-O2 in sheets
containing only center molecules. In the sheets containing
both center and origin molecules there are O6-D-O6 and
O2-D-O2 intermolecular hydrogen bonds. The former has
minor components involving O5 and O3 as acceptors.
Intramolecular hydrogen bonds are O3-D-O5 in each
molecule with a minor component involving O6 as accep-
tor. However, you would notice that there are still difficul-
ties in the interpretation of reactivity, properties of
cellulose in various forms, and transformation process of
cellulose from one to the other as well as even crystalline Figure 11 A schematic representation of hydrogen bonds
structures, as OH groups with different modes overlap with on cellulose II proposed by Langan et al. [35]. Only atoms
each other. involved in hydrogen bonds are represented by dotted lines.

78 Kondo
cellulose can be useful in controlling the formation of

hydrogen bonds without causing a resultant change in
the glucose ring conformation. Thus the regioselectively
methylated celluloses have been proven to be satisfactory
model compounds for cellulose.
In continuation, the formation of hydrogen bonds in
the regioselectively substituted cellulose derivatives was
characterized by FT-IR and solid-state CP/MAS 13C
NMR spectra of the film samples [67]. Fig. 13 shows OH
frequencies for film samples of typical regioselectively
substituted cellulose ethers, namely, 2,3-di-O- and 6-O-
methylcellulose (23MC and 6MC), compared with that of
pure cellulose. They were all predominantly noncrystalline
films with ca. 5-Am thickness prepared by casting from their
dimethyl acetoamide (DMAc) solutions for methylated
derivatives and the DMAc-LiCl cellulose solution for pure
cellulose, respectively. Therefore we do not have to take
into account specifically oriented intermolecular hydrogen
bonds, differently from the crystalline samples. Thus we

Figure 12 The chemical structures of regioselectively sub- have only to consider the following hydrogen bonds for the
stituted cellulose derivatives prepared in Ref. [67]. above amorphous film samples: isotropic intermolecular
hydrogen bonds and two different intramolecular hydro-
gen bonds, which are between the OH-3 and adjacent ring
O-5V and between the OH-6 and OH-2V (Fig. 14A). Look-
properties of not only cellulose itself but also its derivatives. ing at the spectra in Fig. 13 under these assumptions, we
The previous section explained the possible formation of will find that they exhibited characteristic band shapes in
hydrogen bonds in native cellulose and cellulose II crystal- the OH stretching vibration regions. The shape of the 6-O-
line structures. As for cellulose derivatives, they show either methylcellulose (6MC) having two OH groups in a unit is
crystalline structure or noncrystalline structure, depending rather symmetric and sharp, compared with that of 2,3-di-
on the degree of substitution (DS) and the structural O-methylcellulose (23MC), which has one OH group per
regularity or the distribution pattern of substituted units anhydroglucose unit. Generally, increasing the number of
along the molecular chain. For cellulose derivatives we can
use NMR spectroscopy to observe hydrogen-bonding
engagements [63]. In this case, we can mostly use solution
NMR as solid-state NMR still has a problem on the
resolution for signal splitting. However, most of the inves-
tigations on hydrogen bonding formation in cellulose as a
polymer have difficulties in interpreting the chemical shift
for the same reason as those studies using IR spectroscopy.
Therefore we had better simplify the formation of hydro-
gen bonds to be more easily analyzed if possible. How can
we do this? Kondo and Gray developed the methods for
synthesizing regioselectively substituted cellulose ethers,
2,3-di-O-, 6-O-, and tri-O-substituted cellulose derivatives
[64–67] as shown in Fig. 12. As the hydroxyl groups should
form controlled intra- and intermolecular hydrogen bonds
particularly in regioselectively methylated celluloses, the
cellulose derivatives are thought to be cellulose model
compounds to investigate the relationships between for-
mation of hydrogen bonds and physical properties of
cellulose, as well as the cellulose derivatives. When the
OH groups within the anhydroglucose units are blocked by
methyl groups, it remains a question whether the pyrano-
glucose ring conformation still keeps the original shape
(4C1 chair conformation) or not. To answer this question, it
has already been reported [25] that the OH groups in the
anhydroglucose units, despite being blocked by methyl Figure 13 IR spectra of noncrystalline film samples of (A)
groups, do not affect the structure of the glucose ring. In cellulose, (B) 2,3-di-O-, and (C) 6-O-methylcellulose deriva-
other words, blocking hydroxyls by methyl groups in tives in the region of OH stretching vibration.

biological structures. When the donor group is cation-like

or the acceptor group is anion-like, as in O–H+–O or O–
H–O , strong and almost symmetrical hydrogen bonds
are also observed [1]. Because in 2,3-di-O-substituted cellu-
lose free OH groups at the C-6 position are comparatively
flexible, intermolecular hydrogen bonds may be formed
favorably. The OH groups may also form intramolecular
hydrogen bonds with the ether oxygen at the adjacent C-2
position (Fig. 14B). Thus, mixture of the inter- and the
intramolecular hydrogen bonds is considered to cause
the broadening of the OH band in the IR spectra. On the
other hand, two intramolecular hydrogen bonds may
form in the 6-O-substituted cellulose derivatives as shown
in Fig. 14C. The two intramolecular hydrogen bonds (O6-
HO-2V and 3-OH-O5V) have similar type of formation,
which is between the OH group and the ether or acetal
oxygen. Therefore the sharp and symmetric IR spectra of 6-
O-substituted cellulose derivatives in Fig. 15 indicate that
the two intramolecular hydrogen bonding structures may

give a similar OH absorption band, and intermolecular
hydrogen bonding formation which broadens the OH band
may be not significant. Furthermore, the strengths of the
two hydrogen bonds may be almost equivalent, and hence
both of the intramolecular hydrogen bonds between the
OH and the ether oxygen appear at almost the same wave
number around 3465 cm 1 in OH stretching frequencies of
the IR bands.
In another experiment [68], the curve fitting procedure
Figure 14 Schematic representation of possible hydrogen was performed for the regions due to OH stretching
bonds in cellobiose units of (A) cellulose, (B) 2,3-di-O-, and vibration in the IR spectra of the noncrystalline films from
(C) 6-O-substituted cellulose derivatives. 2,3-di-O-methylcellulose (2,3-di-O-MC) and 6-O-methyl-
cellulose (6-O-MC). The results are shown in Fig. 16. The
OH bands for 2,3-di-O-MC are resolved into two Lorent-
OH groups per unit should show the diversity of OH fre- zian bands, sharper (3472 cm 1) and broad (3382 cm 1)
quencies in IR spectra, and then the absorption band ones; 6MC has one major Lorentzian OH absorption band
should become broader. In the present case, however, (3460 cm 1) and a small subband (3270 cm 1). These bands
the appearance of OH band of 6MC, which has two OH may correspond to the presence of specific inter- and
groups per unit, is contradictory. This phenomenon intramolecular hydrogen bonds involved in 2,3-di-O-MC
appeared in other relationships between 6-O- and 2,3-di- and 6-O-MC as mentioned above. Thus the bands with
O-substituted cellulose derivatives with the same substitu- peak positions at higher wavenumbers of 3460–3470 cm 1
ent [67]. It is assumed that the phenomenon is attributed for both 2,3-di-O-MC and 6-O-MC result in the assign-
mainly to the manner of formation of hydrogen bonds. ments of the following intramolecular hydrogen bonds,
Schematic representations of possible inter- and intra- because in general for cellulosic materials the intramolec-
molecular hydrogen bonds in the cellobiose unit are shown ular hydrogen bonds tend to appear at relatively higher
in Fig. 14. Cellulose may possibly have two types of wave numbers (3410–3460 cm 1 in cellulose I [50] and
intramolecular hydrogen bonds and some intermolecular 3460–3480 cm 1 in cellulose II [47,68,69]) in the IR spectra.
hydrogen bonds, depending on the phase. While the inter- There may be between OCH3 at the C-2 position and OH at
molecular hydrogen bonds are not specified, the two the C-6 position for 2,3-di-O-MC. There may be between
intramolecular hydrogen bonds are assumed to be either OH at the C-3 position and the adjacent ring oxygen and
OH-3-OV5 or OH-6-OH-2V (Fig. 14A). In the 2,3-di-O- between OH at the C-2 position and OCH3 at the C-6
substituted cellulose derivatives, the main reason for the position for 6-O-MC. It has been confirmed that such
broader OH bands due to the diversity of OH frequencies intramolecular hydrogen bonds can be formed in either
appears to be the formation of intermolecular hydrogen solid film or homogeneous solution states [69–72]. The
bonds associated with OH-6. In the case of 6-O-substituted formation of such intramolecular hydrogen bonds has also
cellulose, specific intramolecular hydrogen bonding for- been observed in a DMSO solution state of 23MC using
mation, which makes the IR band of the OH region NMR analyses with deuteration [73].
symmetric and sharper, may exist. Hydroxyl and ring ether To investigate the intramolecular hydrogen bonds,
(C-O-C) groups correspond to the hydrogen bonding the film samples were also analyzed by CP/MAS 13C
donor and acceptor, respectively, which are common in NMR [67]. Fig. 17 shows the CP/MAS spectra of (1)

80 Kondo
2,3-di-O-MC, (2) 6-O-MC, and (3) Tri-O-MC. The intro-

duction of an O-alkyl group promotes strong deshielding
of the 13C nucleus of the substituted carbinol group,
usually by ca. 9 ppm in solution NMR [74,75]. In the
spectra of cellulose ethers, this characteristic should be
reflected in the chemical shifts of carbons at C-2, C-3, and
C-6 positions bearing alkoxy substituents. Thus peak
assignment was carried out in the CP/MAS 13C NMR
spectra of the film samples using the solution-state 13C
NMR results of Parfondry and Perlin [76]. Unsubstituted
C-2, C-3, and C-5, and substituted C-6 carbon signals in
6-O-MC overlapped to some extent with each other in the
range of 77–70 ppm. Signals of the C-2, C-3, and C-6
carbons shifted to downfield (ca. 10 ppm) by methyl
substitution. In the 2,3-di-O-MC and Tri-O-MC, the C-4
carbon signals, which are assignable in cellulose, shifted
upfield by substitution of the adjacent OH groups at the
C-3 position and overlapped with the C-5 carbon signal.
Signals of C-2 and C-3 carbons in the two MCs overlapped

with each other and cannot be identified because of their
similar and strong deshielding of 13C nuclei of completely
substituted methoxy groups at both positions.
Considering a weak deshielding effect of the intramo-
lecular hydrogen bonds between the methoxy oxygen at the
C-2 position and the OH groups at the adjacent C-6
position as described later, the C-2 carbon may resonate
Figure 15 IR spectra of film samples of cellulose, 2,3-di-O-

and 6-O-substituted cellulose derivatives in the region of OH
stretching vibration. MC: O-methylcellulose; EC: O-ethyl- Figure 16 Curve fitting for OH stretching regions in 2,3-di-
cellulose; AC: O-allylcellulose; and BC: O-benzylcellulose. O-MC and 6-O-MC.

13
Figure 17 CP/MAS C NMR spectra of regioselectively substituted O-methylcelluloses (MCs).
upfield to the C-3 carbon. Only the C-1 signal is easily bonding formation effects cannot be simply applied to the
assignable as it is completely separated from other signals. C-1 signals of the tri-O-substituted derivatives. Because the
The presence of an ether substituent at the C-2 position substitution of both C-2 and the adjacent C-6 hydroxyls
causes an upfield shift of the C-1 resonance relative to that can cause a mutual repulsion between the two substituents,
of the glucose residue [76]. Therefore it is assumed that the the interaction occurring among them can be of different
C-1 resonances may have an upfield shift similarly by the types such as hydrophobic linkage and hence the confor-
hydrogen bonding formation at the adjacent C-2 position. mation of the main chain should change.
Naturally, the change in the hydrogen bonding arrange- As discussed in the previous section using FT-IR, CP/
ment should be more weakly attributed to the chemical MAS 13C NMR may suggest the type of the hydroxymethyl
shift of C-1 carbon than the effect due to the substitution of conformations, gt or tg at the C-6 positions in carbohy-
the OH at the C-2 position. Kamide et al. [70] reported that drates. Horii et al. indicated [6] that the C-6 carbon reso-
the chemical shift of the C-1 carbon may appear to have an nance occurs only as a singlet near 64 ppm in the case of the
upfield value of more than 105 ppm in the case of the gt conformation, whereas a resonance band near 66 ppm
intramolecular hydrogen bond between the C-2 and C-6 will appear when the tg conformation is present within
positions (Fig. 14A and C). They also mentioned that the the crystalline structures, as shown in Fig. 18 [6]. According
C-1 chemical shift may have a field value lower than 105 to them, the chemical shifts fall into three groups of 60–
ppm in the case of the free OH at the C-2 position that did 62.6, 62.5–64.5, and 65.5–66.5 ppm, which are related to
not include the hydrogen bond between the C-2 and C-6 gg, gt, and tg conformations, respectively. In fact, the
positions. The latter case was based on the assumption that chemical shift of the C-6 for cellulose II [77–80] indicated
a seven-membered k–jelectron conjugate system is formed the gt conformation, which agrees with the recent result
in a cellobiose unit [C-4-O-C-1V-O5V-HO-3-C-3-C-4: con- from the neutron fiber diffraction analysis as described
sider the case without the intramolecular hydrogen bond above [35]. In the regioselectively methylated cellulose
between C-6 and C-2V in Fig. 14(A)]. In Table 3, the C-1 ethers shown in Fig. 17 and other experiments, the chem-
chemical shifts of 6-O-substituted cellulose derivatives ical shifts of the C-6 were 61.58 and 61.66 ppm for 2,3-di-O-
except 6-O-tritylcellulose show smaller values than 105 MC and 3-O-MC [81], respectively. These results show that
ppm, suggesting the existence of intramolecular hydrogen the conformation of the OH groups at the C-6 position for
bonds between the C-2 and C-6 position. From this result the two regioselectively methylated cellulose derivatives
and FT-IR analyses, it is indicated that in the 6-O-substi-
tuted cellulose derivatives except 6-O-tritylcellulose, two
intramolecular hydrogen bonds (O6-HO-2V and 3-OH- Table 3 Comparison of Chemical Shifts at the C-1 Positions
O5V) form predominantly and the strengths of the two of Anhydroglucose Unit in CP/MAS 13C NMR Spectra of
bonds may be almost equivalent (Fig. 14C). Various Cellulose Derivatives
The C-1 chemical shifts of 2,3-di-O-substituted cellu-
lose derivatives in Table 3 also show smaller values than Sample 6-O- 2,3,di-O- Tri-O-
105 ppm. This indicates the formation of the intramolec-
ular hydrogen bonds between O2-HO-6V (Fig. 14B) in Methyl cellulose 104.1 103.9 106.5
addition to intermolecular hydrogen bonds at the C-6 Ethyl cellulose 103.8 103.5 102.2
Propyl cellulose 102.8 104.5 102.6
position. As for tri-O-substituted cellulose ethers, the C-1
Decyl cellulose 104.2 104.4 LCa
signals appeared more upfield than those of 2,3-di-O- and
Allyl cellulose 103.1 103.9 102.5
6-O-substituted cellulose derivatives. Only tri-O-methyl- Benzyl cellulose 103.2 102.4 102.0
cellulose shifted downfield compared with other tri-O-sub- Trityl cellulose 105.5 — —
stituted cellulose derivatives. To explain these phenomena,
a
the above explanation of chemical shifts with the hydrogen LC: Liquid crystal at room temperature.

82 Kondo
number, two intramolecular hydrogen bonds expected to

be formed in 6-O-MC were maintained in 6-O-alkylcellu-
loses. Only in 6-O-decylcellulose there appeared a small
shoulder around 3600 cm 1. In the case of electron-with-
drawing substituents such as allyl and benzyl groups that
are easy to form cations (Fig. 15C and D), the hydroxyl
frequencies also appeared sharp and symmetric, although
there was a slight shoulder at around 3580 cm 1. However,
a remarkable shoulder of hydroxyl frequencies appeared at
around 3580 cm 1 in both an electron-withdrawing and
bulky trityl substituent as shown in Fig. 20. In general,
hydroxyl frequencies at 3584–3650 cm 1 are considered as
absorption band of ‘‘free’’ OH groups [54,71]. Hydroxyl
frequencies due to the intermolecular hydrogen bonds were
reported as 3305, 3350, and 3405 cm 1 by Marchessault
and Liang [46,47]. The shoulder at 3580 cm 1 in the
hydroxyl absorption band of the tritylcellulose was found
to be due to rather ‘‘free’’ hydroxyl groups. The OH bands
should be broad because of the diversity. Thus an intra-

molecular hydrogen bond and ‘‘free OH’’ appear to be
formed at the C-2 position of the tritylcellulose.
The 6-O-tritylcellulose was then multiple-methylated
to investigate the behavior of OH groups at the C-2 and C-
3 positions. The change of distribution of the methyl group
as a block of OH groups in a step is monitored in Table 4.
Figure 18 13C chemical shifts of the CH2OH carbon vs. tor- As OH groups at the C-2 position were rapidly methylated
sion angles v around the exo-cyclic C–C bonds. a: a-D-glu- in the first methylation, the DS of methyl groups at the C-3
cose; b: a-D-glucose H2O; c: h-D-glucose; d: h-D-cellobiose; position increased slowly in the step. This difference
e: a-D-lactose H2O; f: h-lactose; g: sucrose; h: a-melibiose indicates a quick break of hydrogen bond and methylation
H2O; i: h-methyl cellobioside CH3OH.
may be gg. However, the indication due to the chemical

shifts [6] was derived from mono- and oligosaccharides,
which have different hydrogen bonding engagements from
the present samples. As mentioned already, even hydrogen
bonds for celluloses I and II may be totally different from
those of 2,3-di-O-MC and 3-O-MC, judging from the OH
stretching frequencies in the IR spectra. As the relatively
large scattering of data within 2 ppm depending on the
conformation at the C-6 may be due to other additional
effects such as packing [82] and hydrogen bonding [83,84],
the chemical shifts of the C-6 for the regioselectively
methylated cellulose derivatives, which are expected to
have controlled and specific hydrogen bonds, may not
agree with the indication. In addition, the conformation
of the glucopyranose ring may be somehow changed by
the regioselective substitution by methyl groups. Further
studies will be required.
2. Influence of Substituent on the Hydrogen Bonding

Formation
Hydroxyl frequencies in the IR spectra of 6-O-alkylcellu-
loses with different lengths of alkyl chains are shown in
Fig. 19. The sharp and symmetric shape of the IR spectrum Figure 19 IR spectra of 6-O-alkylcellulose films in the
for 6-O-MC did not show a significant change with in- region of OH stretching frequencies: (a) 6-O-methylcellulose;
creasing of alkyl chain length. It suggests that irrespective (b) 6-O-ethylcellulose; (c) 6-O-propylcellulose; and (d) 6-O-
of the alkyl chain length with the range of 1 to 10 in carbon decylcellulose.

Table 4 Degree of Substitution at Individual 2,3-di-O-methyl-6-O-tritylcellulose prepared in another

Positions in 6-O-trityl- and Methylated Tritylcellu- way [64]. This indicates that ‘‘free’’ OH groups coming
lose Derivatives from the hydroxyl group at the C-2 position and scission
of intramolecular hydrogen bonds at the C-3 position were
Sample X2 X3 X6 methylated.
6-O-TC 0 0 Trityl CP/MAS 13C NMR spectra of the above samples also
MTC1 0.74 0.55 Trityl showed the same behavior of the hydroxyl groups through
MTC2 0.82 0.66 Trityl methylation (Fig. 21). Broad C-1 signal at 105.5 ppm in the
MTC3 0.84 0.73 Trityl tritylcellulose shifted to upfield peak that has three peak
tops at 105.5, 102.5, and 101.4 ppm in MTC1 (Fig. 21 (2)).
Xn: DS on the OH of Cn (n=2, 3, and 6). Each peak top at the three values is due to ‘‘free OH’’, the
intramolecular hydrogen bond, and methylation of hy-
droxyl groups at the C-2 position, respectively. The broad
of the free hydroxyl groups at the C-2 position, and a slow C-1 signal of the tritylcellulose also has a shoulder at
scission of the intramolecular hydrogen bond between C-3 around 102.5 ppm due to the intramolecular hydrogen
and O5 through three methylation steps. Namely, the first bond. Judging from the C-1 peak shape, the region around
apparent change in the IR spectrum of methylated trityl- 105.5 ppm is main and the vicinity at 102.5 ppm is relatively
cellulose is attributed to the behavior of the hydroxyl small. This indicates that the free OH is the one, rather than
group at the C-2 position. In the traces of Fig. 20, as the the OH engaged in the intramolecular hydrogen bonds at
methylation step preceded, the intensity of the absorption the C-2 position.
band at 3484 cm 1 decreased gradually and the shoulder When the methylation proceeded, the peak top at
at 3580 cm 1 got smaller and sharper. In Fig. 20, the 105.5 ppm decreased as the other two peak tops appeared
absorbance of the OH bands for the MTCs was normal- distinguishably. The peak top at 102.5 ppm decreased and
ized on the basis of the internal standard band at 1596 eventually the C-1 signal became one peak at 101.4 ppm
cm 1 due to the trityl group which was not affected by the in 2,3-di-O-methyl-6-O-tritylcellulose whose OH groups
methylation, and the peak heights between 6-O-TC (tri-
tylcellulose) and MTC1-3 were not comparable with each
other. Eventually, OH frequencies mostly disappeared and
all hydroxyl groups were almost completely methylated in
Figure 21 Change of the C-1 chemical shift of tritylcellulose

Figure 20 Change of OH stretching frequencies in IR and methylated tritylcellulose derivatives: (1) 6-O-tritylcellu-
spectra of tritylcellulose through the multiple methylation lose; (2) MTC1*; (3) MTC2*; (4) MTC3*; and (5) 2,3-di-O-
step. 6-O-TC: tritylcellulose; MTC1-3: see Table 4. methyl-6-O-tritylcellulose. *See Table 4.

84 Kondo
were almost completely blocked by methyl. This phenom-

enon also indicates that ‘‘free OH’’ at the C-2 position
is rapidly methylated and then scission of the intramolec-
ular hydrogen bonds at the C-2 position occurred and
finally all hydroxyl groups at the C-2 position were com-
pletely methylated.
3. Assignment of ‘‘Free’’ Hydroxyl Groups

in Cellulose
As described in the above section, Kondo et al. have ex-
tensively characterized intra- and intermolecular hydrogen
bonds involved in cellulose derivatives using regioselec-
tively methylated cellulose derivatives as model com-
pounds by FT-IR and CP/MAS 13C NMR analyses. It
mentioned that not only the assignments due to inter- and
intramolecular hydrogen bonds but also the IR interpre-
tation of ‘‘free’’ or non-hydrogen-bonded hydroxyl groups
should be of importance to characterize the formation

of hydrogen bonds. So far not many papers reported on
the IR interpretation of ‘‘free’’ or non-hydrogen-bonded
hydroxyl groups. Kondo attempted to assign the ‘‘free’’
hydroxyl groups in the IR absorption bands [68].
In the multiple-methylated derivatives (MTC1V-3V)
from 6-O-tritylcellulose (6TC), which have a different
distribution pattern from the above MTC1-3, the methyl
substitution behavior of hydroxyl groups at the C-2 and
C-3 positions in 6TC was monitored by FT-IR (Fig. 22)
together with the change of the DS of methyl and the Figure 22 Change of IR spectrum for the methylated 6-O-
tritylcellulose (MTC1V–3V) and 2,3-di-O-methyl-6-O-trityl-
remaining hydroxyl groups at each position for the above
cellulose (23M6TC) prepared from 6-O-tritylcellulose (6TC).
four samples determined by gas-chromatographic analyses
for the hydrozates of the polymer (Table 5). All spectra in
Fig. 22 were normalized on the basis of the internal
standard band at 1596 cm 1 due to trityl groups that are Considering that the product was very similar to these
not affected by the methylation. In the C–H stretching tri-O-substituted derivatives and that the remaining OH
regions from 2800 to 3100 cm 1, the methylation had an groups were quite small, the IR absorption bands cannot
influence obviously on each spectrum. Even in the be considered simply due to hydrogen-bonded OH groups;
23M6TC spectrum shown at the bottom of Fig. 22, the they may be due to ‘‘free’’ or non-hydrogen-bonded hy-
hydroxyl absorption band was slightly observed. This band droxyl groups. In other words, a trace amount of hydroxyl
cannot be noise because S/N ratio in this FT-IR machine groups in the original tritylcellulose remained intact during
was better than 1/15,000. The same band shape was also this methylation process, possibly because of heterogeneity
observed carefully in the other tri-O-substituted derivatives in the reaction mixtures. Thus when the film sample for
that were already prepared in previous papers [65,67]. FT-IR measurements was cast from the clear solution of
Table 5 Distribution of Methyl and Hydroxyl Groups in Regioselectively

Methylated 6-O-tritylcellulose Derivatives
DS at positions DS of OH at each position

Overall
Sample DS X2 X3 X6 OH-2 OH-3 OH-6
MTC1V 1.39 0.82 0.57 — 0.18 0.43 Xtri

MTC2V 1.67 0.91 0.76 — 0.09 0.24 Xtri
MTC3V 1.68 0.91 0.77 — 0.09 0.23 Xtri
23M6TC 1.80 0.92 0.88 — 0.08 0.12 Xtri
Overall DS equals X2+X3+X6. Each Xn was determined by a gas chromatographic
analysis. Xn is the mole fraction of glucitol derivatives substituted on the OH of Cn (n=2, 3,
and 6). DS of OH-n = 1-Xn; Xtri: degree of trityl substitution.

Figure 23 Curve fitting and peak assignments for OH stretching regions in 23M6TC.
the product powder, the molecules in the powder may have able. After the best curve fitting, the peak positions of the
rearranged to give ‘‘free’’ hydroxyl groups in the film. The three deconvoluted bands were 3579, 3558, and 3489 cm 1,
probability of the formation of intermolecular hydrogen respectively. The two bands (3579 and 3558 cm 1) were
bonds in this film is fairly low because neighboring hy- assigned to the free hydroxyl groups because they appeared
droxyl groups are rare; the intramolecular hydrogen bonds at higher wavenumbers than those for inter- or intramo-
can occur: between OH at the C-3 position and the adjacent lecular hydrogen-bonded hydroxyl groups in cellulose
ring oxygen, between OCH3 at the C-2 and OH at the C-6 (Tables 1 and 2). As a reference for the IR band due to
positions, and between OH at the C-2 position and OCH3 free hydroxyl groups, it is reported that the free OH in
at the C-6 position. As reported by Kondo [18], the secondary alcohol appears at 3620–3635 cm 1, whereas the
intramolecular bonds may still be maintained even in the free OH for primary alcohol shows bands at 3630–3645
homogeneous solution state. The formation of such intra- cm 1 [85]. The difference in the band positions between
molecular hydrogen bonds has also been observed in a cellulose and alcohol can be due to the regiochemical effects
DMSO solution state of 2,3-di-O-methylcellulose (23MC) in cellulose.
using NMR analyses with deuteration [81]. To assign the
IR band due to free OH groups, it is necessary to evaluate
the contribution of the intramolecularly hydrogen-bonded
OH groups. In addition, the three hydroxyl groups at each Table 6 The Results from a Curve Fitting Method Ap-
position are quite different in the sense that secondary plied to the Methylated Tritylcelluloses, MTC1–MTC3 and
hydroxyl groups at the C-2 position are influenced by the 23M6TC. Each Correlation Coefficiency (R2) is Better than
0.99
anomeric C-1 carbon, secondary hydroxyl groups at the C-
3 position are favorable to form the intramolecular hydro- Three peaktops of the deconvulated IR bands
gen bonds, and the hydroxyl groups at the C-6 position are
primary OH. Therefore the hydroxyl groups at each posi- a (cm 1) b (cm 1) c (cm 1)
tion can exhibit three different IR absorption bands.
The IR absorption bands for OH stretching regions in MTC1V 3579 3513 3480
23M6TC of Fig. 22 were deconvoluted into three bands for MTC2V 3577 3552 3486
MTC3V 3578 3559 3487
the curve fitting as shown in Fig. 23. To improve the
23M6TC 3579 3558 3489
calculation, the peaks needed to be well resolved, and the
number of peaks, the positions, and the areas were accu-
rately determined. Three was employed as the number of
peaks and the position was determined by the point at
which the second derivative of the spectrum contained OH2 OH-6 Intramolecular
peaks. All other parameters in the calculations were vari- H-Bonds

86 Kondo
To assign the three OH bands, the corresponding molecular association can be categorized in cellulose. A
deconvoluted IR bands in partially methylated tritylcellu- major consideration is that the predominant crystalline
loses as cast films, MTC1V–MTC3V, were compared with state of cellulose is included as a component in the ordered
those for 23M6TC. The results are shown in Table 6. IR state. This means that the ordered state also contains non-
absorption bands in the OH stretching region for each crystalline-ordered states. The category ‘‘ordered’’ is in
sample were also deconvoluted into three IR bands (a, b, contrast to the ‘‘nonordered’’ state which, to date, has been
and c in Fig. 23) with peak tops at around 3580, 3555 considered as ‘‘amorphous cellulose’’ for lack of a useful
(‘‘free’’ hydroxyl groups), and 3485 cm 1, respectively. The way to characterize the product. It should be noted that the
wave number of band c with a lower peak top at 3485 cm 1 amorphous state being categorized as the ‘‘nonordered’’
coincides with that calculated for intramolecular hydro- state should be distinguished from the ‘‘noncrystalline state
gen-bonded hydroxyl groups in regenerated cellulose (Ta- of cellulose. Thus in this classification it becomes crucial
ble 2) and is very close to the assignment (3470–3480 cm 1) whether the state is ‘‘ordered’’ or ‘‘nonordered.’’ The
proposed for intramolecular hydrogen-bonded hydroxyls relationship is schematically illustrated in Fig. 24 [5].
using regioselectively methylated cellulose derivatives in Historically, it has been difficult to find an appropriate
Fig. 15 [17] and Fig. 14B and C, between OH at the C-3 method to characterize noncrystalline or amorphous
position and the adjacent ring oxygen, between OCH3 at domains of cellulose. Often, wide-angle X-ray diffraction
the C-2 position and OH at the C-6 position, and between (WAXD) has been used for determining the crystalline
OH at the C-2 position and OCH3 at the C-6 position. forms and the crystallinity; however, in most cases when
Considering these results, band c in Fig. 23 may involve not WAXD provides a diffuse diffraction pattern, it is consid-
only the intramolecular hydrogen bonds at the C-3 posi- ered simply as ‘‘amorphous cellulose.’’ However, as men-
tion, but also possible intramolecular hydrogen bonds tioned above, noncrystalline state does not necessarily
between the functional groups at the C-2 and C-6 positions. indicate amorphous state. Noncrystalline state includes
Therefore some of the free hydroxyl groups at the C-2 and both liquid crystalline and nematic-ordered cellulose [5]
C-6 positions may contribute to band c, which may be the that exhibits a certain order state, whereas amorphous state
reason for the inconsistency between FT-IR results and does not own any preferred orientation. Thus we have
OH values determined by the gas chromatographic method attempted to determine the ‘‘noncrystalline regions’’ of
as shown in Table 5. noncrystalline cellulose films using FT-IR monitoring of
Bands a and b, because of the remaining free OH the deuterated hydroxyl groups [86]. We have found that
groups at either C-2 or C-6 position which were not such noncrystalline regions may comprise at least three
tritylated in 6TC (although some of them may contribute different domains. The study [86] also indicated the pres-
to intramolecular hydrogen bonds), can be assigned in the ence of ordered domains in the noncrystalline regions.
following way: The original IR bands in Fig. 23 show two As the regioselectively methylated celluloses, 23MC
peak tops at 3575 and 3485 cm 1, where bands a and c are (64), 6MC(66), and tri-O-methylcellulose (236MC)(65)
mainly indicated, and their relative intensities change had a controlled distribution of substituents and thus
depending on the samples (MTC1V-3V in Fig. 22). In hydrogen bonds, they were considered to be model com-
contrast, the relative intensity of band b does not change pounds for amorphous cellulose and hence ideal in exam-
significantly. During this multiple methylation process, the ining the relationship between polymer structure and the
OH groups at the C-2 and C-3 positions are replaced and
their FT-IR spectra are affected. On the other hand, for the
OH at the C-6 position, which was a trace amount from the
beginning, the influences are small. Thus bands a and b
with peak tops of 3580 and 3555 cm 1 are assigned to free
OH at the C-2 and C-6 positions, respectively.
Furthermore, the two peak positions of bands a and c
did not shift significantly from 23M6TC to MTC1V as
shown in Table 6. However, the peak position of band b at
3558 cm 1 changed to a lower wave number between
MTC2V (3552 cm 1) and MTC1V (3513 cm 1). This indi-
cates that intramolecular hydrogen bonding at the C-6
position starts to perturb the OH bands.
C. Hydrogen Bonds in Noncrystalline

or Amorphous Cellulose
1. Noncrystalline Cellulose and Amorphous Cellulose
Cellulose, which is a h-1,4-linked glucan homopolymer, is
normally classified according to how the h-glucan chains
associate. We expand the concept of how various states of Figure 24 Concept of glucan chain association for cellulose.

physical properties of cellulose and its derivatives in terms

of hydrogen bond formation. It is noted that pure cellulose
tends to order somehow in a certain way, so that it is
difficult to keep amorphous state in cellulose if it can be
obtained.
In the previous sections, FT-IR spectroscopy was used
to identify intra- and intermolecular hydrogen bonds in the
regioselectively synthesized 23MC and 6MC. Films of
23MC and 6MC exhibited narrow OH stretching bands
in their IR spectra because of the controlled hydrogen
bonding (Fig. 13). Morphologically, films cast from these
methylcellulose derivatives were also found to be predom-
inantly noncrystalline or rather amorphous than crystal-
line. Therefore the narrow OH absorbance bands and the
amorphous homogeneity of the sample microstructure
enabled us to clarify and classify the interchain hydrogen
bond interactions found in the samples. It is believed that a
characterization of the hydrogen bonds found in amor-
phous cellulose would be of fundamental value and, fur-

Figure 25 Wide-angle X-ray diffraction patterns for cast
thermore, that a structural study of amorphous cellulose in films: (A) cellulose, (B) 23MC, (C) 6MC, and (D) a blend of
light of hydrogen bonding might be a first step in uncover- 23MC and 6MC (1.08/1 w/w).
ing details of how molecules rearrange in going from the
liquid to the crystalline state.
So-called ‘‘amorphous cellulose’’ samples are usually
prepared by ball milling of cellulose [87,88] by deacetyla-
tion of cellulose acetate with sodium methoxide in anhy- studied, and Table 7 shows the most probable assignment
drous methanol [89], or by precipitation from nonaqueous for these bands, as well as those found in a real amorphous
solvent systems into nonaqueous regeneration media with cellulose sample. Figs. 26 and 27, respectively, show OH
the avoidance of stress [90–94]. To date, most of these and C–O stretching vibration regions resulting from the
samples have been studied by WAXD [87–95], FT-IR glucose ring skeletal vibration. In comparing the real and
spectroscopy [95], and solid-state NMR [94]. Hatakeyama the artificial spectra for the amorphous cellulose, there is
and Hatakeyama [96] have previously reported on the no significant difference in the ring stretching vibration
formation of interchain hydrogen bonds with increasing region as clearly illustrated in Fig. 27. This indicates that
temperature for amorphous regions in cellulose fibers. any absorption contributions by methyl groups may be
More recently, Kondo and Sawatari [24] have tried to precluded in the methylated samples to the ring stretching
analyze and comment on the types of hydrogen bonds vibrations. Thus the artificial spectrum mirrors the glucose
formed in amorphous cellulose. The methodology was ring structure found in real amorphous cellulose. The data
threefold: (1) to quantitatively produce an artificial IR contained in Table 7, which lists typical absorption fre-
spectrum for amorphous cellulose by using a combination quencies for the two spectra, also seem to support this
of amorphous methylcellulose model compound IR spec- hypothesis. In regard to the stretching and bending vibra-
tra; (2) to characterize the difference between the real and tions for methine and methylene groups in cellulose, the
the artificial spectra in terms of the formation of hydrogen quantitative mathematical model could not completely
bonds; and, finally, (3) to compare the result of (2) with the remove the contribution by methyl groups in the methyl-
IR spectra of propyl alcohol solutions, which can serve as ated samples to totally match the artificial spectrum for
model systems for intermolecular hydrogen bonding. This amorphous cellulose.
approach lets us draw a number of conclusions about the
hydrogen bonds formed at the C-2 and C-3 positions in the Difference Between the Real and the Artificial Spectra
anhydroglucose repeating units of amorphous cellulose. There is a marked difference in the OH stretching
For this investigation, all film materials (cellulose, 23MC, region of the real and the artificial IR spectra. The differ-
6MC) used should have a nonordered amorphous micro- ence spectrum (real artificial; Fig. 26a–b) is shown in Fig.
structure at the level of WAXD patterns as shown in 28 with the region between 3750 and 3000 cm 1 expanded
Fig. 25. to clearly show this marked difference. Considering that
Fig. 13 shows the OH frequency region of the IR the artificial spectrum was constructed assuming a linear
spectra for each amorphous homopolymer film sample contribution by the intra- and intermolecular hydrogen
investigated. By using these four spectra and by quantita- bonds at the C-6 position, the difference spectrum should
tive manipulation, the artificial spectrum could be con- thus contain peaks arising from intermolecular hydrogen
structed as illustrated in Figs. 26b and 27b. The IR bonds at the C-2 and C-3 positions and any ‘‘free’’ hy-
spectrometer software produced a list of the most promi- droxyl groups. Of course, the bands resulting from com-
nent bands in this artificial IR spectrum in the region being mon hydrogen bonds in both the real and the artificial

88 Kondo
Figure 26 IR spectra in the OH stretching vibration (3750–3000 cm 1) region: (a) real spectrum of amorphous cellulose film, (b)
artificial spectrum, and (c) spectrum for the blend sample (23MC/6MC=1.08/1 w/w).
spectra are not completely canceled out by subtraction light at 3558 and 3580 cm 1 described in a previous section
because in the two spectra the magnitude for each OH (see Assignment of ‘‘Free’’ Hyroxyl Groups in Cellulose
absorbance band is not necessarily of equal value. The under Section B) [68], which is a higher wave number than
difference spectrum can thus include, to a greater or lesser the two peaks. A shoulder around 3580 cm 1 with an ab-
extent, all the hydrogen bonds present in pure amorphous sorption of 0.06 may be due to the ‘‘free OH.’’ As all the
cellulose. However, the marked differences in the two OH groups in 23MC and 6MC are engaged in some form of
spectra cannot adequately be explained simply in terms
of unequal contributions from common hydrogen bonds:
the two positive peaks and negative valley in the difference Table 7 Comparison of Typical Absorption Frequencies
spectrum are attributed to intermolecular hydrogen bonds Between the Real and the Synthesized IR Spectra of
at the C-2 and C-3 positions as well as ‘‘free’’ OH groups. Amorphous Cellulose
The main negative and positive peaks in Fig. 28
appeared at two particular wavenumbers, 3472 and 3352 Frequency (cm 1)
Relative
cm 1. Unbonded or ‘‘free’’ OH groups absorb infrared
Realb Synthesizedc intensitya Interpretation
669 671 W OH out-of-phase

bending
899 892 M Antisymmetric
out-of-phase
ring stretching
1040 1040 S C–O stretching
1070 1075 S Skeletal vibrations
involving C–O
stretching
1108 1108 S Antisymmetric
in-phase ring
stretching
1159 1154 S Antisymmetric
bridge C–O–C
stretching
1374 1375 M CH bending
1420 1425 W CH2 symmetric
bending
2892 2903 M CH stretching
3420 3457 S OH stretching
Figure 27 IR spectra in the C–O stretching vibration (1500– a
Key: S, strong; M, medium; W, weak.
700 cm 1) region: (a) real cellulose spectrum and (b) artificial b
Real spectrum of amorphous cellulose film prepared by casting.
c
cellulose spectrum. Synthesized spectrum of amorphous cellulose.

Figure 28 Difference IR spectrum obtained by subtracting the artificial (Fig. 26b) from the real (Fig. 26a) cellulose spectrum.
hydrogen bonding, the artificial spectrum formed by com- and WAXD patterns for the amorphous cellulose gave no
bining the two contributing spectra is thought to have few support to the idea that microcrystallites were present. It is
‘‘free’’ OH groups. Therefore the almost negligible signal at therefore concluded that the amorphous cellulose must
3580 cm 1 in the difference spectrum indicates that there include, to some degree, domains formed by the intermo-
are very few ‘‘free’’ OH groups in the amorphous cellulose lecular hydrogen bonds at the C-2, C-3, and C-6 positions.
itself. A negative absorbance valley at 3472 cm 1 (assigned Kondo and Sawatari therefore proposed a model for
to intramolecular hydrogen bonds) indicates that the signal amorphous cellulose in which some amorphous domains
was overcanceled in the artificial spectrum, whereas the pos- are partly interacted by intermolecular hydrogen bonds as
itive band around 3352 cm 1 was attributed to the intermo- illustrated in Fig. 29. This is similar to a fringed micellar
lecular hydrogen bonding at the C-2, C-3, or C-6 position. structure. In a dilute and semidilute cellulosic solutions
The negative valley (3472 cm 1) in the difference spec- Buchard et al. proposed the formation of the fringed
trum appeared to reflect an excess of the intramolecular micelle to explain the rheological behavior of the cellulo-
hydrogen bonds either at the C-2 position and the OCH3 at sics as shown in Fig. 30 [97–100]. Considering the above
the C-6 position, or at the C-6 position and the OCH3 at the results, there may be correlation on the aggregation states
C-2 position, or at the C-3 position and the ring oxygen in between the solution states and amorphous states of cel-
the artificial spectrum. lulose. In other words, from a dilute solution state and a
Interestingly, as the solvent is changed for the same concentrated lyotropic liquid crystalline state to an amor-
23MC sample, the crystallinity of the film varies from sol- phous and a crystalline solid state there might be a con-
vent to solvent and the OH groups at the C-6 position may nection in terms of rearrangements through inter and
be favorably involved in an intermolecular hydrogen bond- intramolecular hydrogen bonding formation.
ing. The extent of crystallization may be dependent upon
the behavior of the primary OH group located at the C-6
position. Stated differently, the OH group at the C-6 2. Hydrogen-Bonded Domain in Amorphous Cellulose
position may be significant in determining the final mor- Currently, there is a shortage of structural information
phological make-up of cellulose. This indicates that when about the noncrystalline regions including amorphous
the C-6 hydroxyls in cellulose are, to a great extent, en- state, perhaps partly because terminology suggests and
gaged in the intermolecular hydrogen bonding, the result- impression persists that molecular chains in these regions
ing cellulose should exhibit high crystallinity. Invoking are completely without structure and partly because meth-
this hypothesis, either a random distribution of micro- odology has been limited to WAXD and CP-MAS 13C
crystallites or a series of domains arising from intermolec- NMR for measuring order in the presence of substantial
ular hydrogen bonds will result in a highly amorphous state amount of disorder. It is not uncommon for substrates that
for cellulose. To confirm the existence of these postulated are not identifiable as crystalline by a method such as X-ray
microcrystallites, small angle X-ray scanning (SAXS) in- diffraction to be labeled ‘‘amorphous’’, but the definition
tensity distributions were measured using a PSPC system. of amorphous goes beyond noncrystalline to unorganized
The SAXS pattern for the amorphous cellulose showed no and having no pattern of structure as described above
significant scattering maxima, indicating that there was [5,101]. Therefore in this section details of the noncrystal-
no lamella structure present in the cellulose. Thus SAXS line regions are particularly examined in the noncrystalline

90 Kondo
only the noncrystalline regions in the cellulose model com-

pounds are focused using the FT-IR monitoring of the
deuteration process. The main advantage of this method
is that the use of a reaction cell has enabled us to obtain
not only a change in reproducible and correct IR spectra
for noncrystalline regions in cellulose, but also the rate
constant for the deuteration reaction which is assumed to
correspond to the nature of amorphous regions [86]. Thus
it is possible to characterize the morphology of noncrys-
talline regions by analyzing the diffusion behavior of D2O
as a probe. As already described in a previous section, each
polymer, 23MC and 6MC, is considered to have different
types of inter- and intramolecular hydrogen bonds. Before
analyses, it was confirmed that the morphology (smooth or
rough) on the surface of the film does not affect the rate
constant by comparison of the surface observation by
atomic force microscopy (AFM) with the rate constants
for differently prepared two film samples with different
morphologies on the surfaces.

Fig. 31 shows the change in IR spectra for 6MC
accompanied by the deuteration process. When the deu-
teration proceeded, OH stretching vibration around 3470
Figure 29 Schematic model for amorphous cellulose. cm 1 decreased, and instead the bands at 2559 cm 1 due to
OD at the C-2 and C-3 positions appeared and then
increased. Similar behaviors were observed for the OH
and OD bands in the amorphous 23MC and cellulose.
However, the deuteration was not completed regardless of
cellulose film samples, regioselectively methylated 23MC the amorphous samples, giving intact OH groups. The
and 6MC amorphous film samples used above, as model amount of the unexchangeable OH was 14.3%, 10%, and
components of amorphous cellulose using FT-IR methods 13.3% for 6MC, 23MC, and noncrystalline (amorphous)
[86]. cellulose, respectively. These unexchangeable hydroxyl
Applications of deuteration methods to IR have so far bands may also indicate the presence of domains involving
focused on the separation of IR spectra for cellulose the intermolecular hydrogen bonds in a proposed amor-
structure into two parts of crystalline and noncrystalline phous model of Fig. 29 [24].
regions, respectively, and then only the discriminated Here the OH–OD exchange reaction can be postulated
crystalline regions have been studied [44,102,103]. Here, to obey pseudo-first-order kinetics because of the large
amount of D2O to the amount of OH in each film sam-
Figure 30 Schematic drawing to demonstrate various size

of particles visualized by changing the angular dependence of
light scattering: qRg<<1 (whole particle seen); qRg > 1
(substructures approved). (From Ref. [99]; Courtesy of
Prof. Burchard; Hermann Schtaudinger Institute, Freiburg, Figure 31 Changes of OH and OD in IR absorption bands
Germany.) for monitoring the deuteration of amorphous 6MC.

ple. The general equation, d[OH]/dt=k[OH], can be em- Table 8 Rate Constants (k) from OH to OD for Every Single
ployed. Thus the derived relationship, ln{[OH]t /[OH]0 }= Reaction in the Deuteration Processes of the Amorphous
kt, was drawn in Fig. 32 for the three amorphous Three Film Samples
samples, 23MC, 6MC, and cellulose, respectively. Each
of the three samples showed similar kinetic behaviors that Time course (hr) k (hr 1) R2
were divided by three single reactions. In other words, Reaction 1
three kinds of exchange reaction (1, 2, and 3 in Fig. 32) can 23MC 0.08–5 0.136 0.98
competitively coexist. Table 8 shows the rate constants for 6 MC 0.08–4 0.247 0.99
each reaction. The rate constant for reaction 1 was rela- Cellulose 0.08–2 0.264 1.00
Reaction 2
23 MC 6–12 0.085 0.98
6 MC 5–13 0.057 0.99
Cellulose 3–12 0.075 0.98
R: Correlation coefficient.
tively different among the three samples. On the contrary,

the rate constant for two reactions seems to be similar
among them. Of course, this is still speculative. In general,
adsorption and diffusion in crystalline polymers are con-
sidered to occur in noncrystalline or amorphous regions.
However, it is very complex because the structure for the
crystalline regions may somehow have influences on it
although the morphological effects on the surface have no
influence.
Considering that the samples exhibited noncrystalline
for the X-ray measurements, noncrystalline regions in these
cellulosics may be discriminated into three phases: (1)
deuteration is fast, corresponding to reaction 1; (2) deuter-
ation is slower, corresponding to reaction 2; and (3) almost
undeuterated, corresponding to reaction 3. Interestingly,
the second rate constants among the three samples were
very similar although the first rate constants for them
differed. This indicates that the second one may correlate
with the deuteration for the intramolecular hydrogen
bonds (Fig. 6) in noncrystalline or amorphous phases
which are common interactions among the above three
samples. Further investigation will be needed because the
type of intermolecular hydrogen bonds found at the C-2, C-
3, and C-6 hydroxyl positions participates, to some extent,
in determining the structure of amorphous cellulose [25].
D. The Relationship Between Intramolecular

Hydrogen Bonds and Certain Physical
Properties of Regioselectively Substituted
Cellulose Derivatives
To date, the author has focused on clarifying the hydrogen
bonding formation involved in cellulose molecules in var-
ious states, such as blends, gels, amorphous, and liquid
crystals [17–28,67,68,104], by using regioselectively substi-
tuted methylcelluloses such as 23MC(64) and 6MC(66) as
cellulose model compounds. These investigations were
Figure 32 The relationships between decreasing ratio of OH performed mainly by using tools such as FT-IR, DSC,
groups, ln{[OH]t/[OH]0} and time, t, during the deuteration fluorescence spectroscopy, and solid-state NMR. Interest-
process for the three amorphous samples, 23MC, 6MC, and ingly, the OH absorption band in the IR spectrum of 6MC
pure cellulose. films was sharper and more symmetric than those for

92 Kondo
23MC, which has only one OH group per anhydroglucose Table 9 Solubility of Various Methylcellulose (MC)
unit. This phenomenon was also observed for other sub-
stituents with longer alkyl, benzyl, and allyl groups. To Commercial MC
clarify this behavior, a model was proposed to explain the DS DS DS 23MC 6MC
formation of intramolecular hydrogen bonds in 6-O-sub- Solvent 0.1–1.1 1.4–2.0 2.4–2.8 DS 2.0 DS 1.0
stituted cellulose derivatives. Specifically, these cellulose
derivatives have two intramolecular hydrogen bonds, one Water D o
between the OH at the C-3 position and an adjacent ether Aq. alkali o D D D
oxygen of the glucose ring, and the second between the (pH 9.5)
ether oxygen at the substituted C-6 position and an adja- Aq. acid o o D o oD
cent OH at the C-2 position (Fig. 14). Accordingly, the (pH 5.5)
aggregation state of 6-O-substituted compounds should be Acetone o
interesting to study particularly in terms of any relation- Methanol D o
ship between the formation of the hydrogen bonds and THF o o
their direct effect on certain physical properties. Chloroform o D o
In general, the formation of inter- and intramolecular DMSO oD o oD o o
hydrogen bonds in cellulose and its derivatives is consid- DMAc oD o oD o o
ered to have a strong influence on their physical properties. o: Soluble; D: swelling; : insoluble; oD: partially soluble.
However, only a few published reports [48,105,106] have

dealt directly with the above point of view, although many
papers [107, 108] have referred indirectly to this relation-
ship between structure and physical properties. Therefore
a DS of 1.0 with other methylcelluloses having a
one 6-O-substituted cellulose ether, namely, 6-O-methyl-
corresponding DS, respectively, the solubility of both
cellulose, which has been revealed to have mainly intramo-
23MC and 6MC exhibited remarkable differences. In
lecular hydrogen bonds, was chosen and its physical
particular, 6MC, which has mainly intramolecular rather
properties including solubility, hydroxyl reactivity, and
than intermolecular hydrogen bonds, exhibited more fa-
crystallinity, which should be influenced directly by any
vorable solubility in solvents having different polarities.
intramolecular hydrogen bonds, were investigated as fol-
These results indicated that the solubility of 6MC is mostly
lows [19].
determined by the absence of interchain hydrogen bonds
Three typical properties chosen to study were the
that can obstruct swelling and solvation of the polymer.
solubility, the relative reactivity of the remaining OH
Primary OH at the C-6 position can favorably form
groups at the C-2 and C-3 positions in a repeating unit,
intermolecular hydrogen bonds [18–20,23,24], causing
and the crystallinity in order to answer the following four
poor solubility of the material to solvents. In other words,
questions: (1) Can the polymer be easily dissolved in various
the amount of free OH groups at the C-6 position may
solvents due to a lack of intermolecular hydrogen bonds?
contribute more critically to determining the solubility of
(2) Is it possible to maintain intramolecular hydrogen
the material than that of free OH groups at the C-2 or C-3
bonds after dissolution to allow the solution to have an
position. In fact, comparing 6MC with MC of DS 2.4–2.8
influence on the OH reactivity mentioned above? and (3) Is
in Table 9, primary OH-6 was fully substituted for 6MC
the solution less likely to crystallize than other ordinary
whereas for the MC with DS 2.4–2.8 unsubstituted OH-6
cellulose and cellulose derivatives because of a restriction in
was more or less remaining. Therefore it may cause the
the intermolecular hydrogen bonding which is available to
superior solubility for 6MC to the MC with 2.4–2.8
the crystallizing polymer? (4) Is there any influence of
although total DS for the latter MC is higher.
intramolecular hydrogen bonds on the determination of
the handedness of cholesteric twist sense of ethylcellulose Relative Reactivities of the Remaining OH
lyotropic mesophases? Groups at the C-2 and C-3 Positions
Concerning the difference in relative reactivity of the
Solubility hydroxyl groups (OH-2, OH-3, and OH-6, respectively) at
Table 9 lists the solubility of methylcelluloses, 23MC, the two (C-2), three (C-3), and six (C-6) positions of the
6MC, and three kinds of methylcelluloses normally pre- anhydroglucose unit, it is well known [109,110] that the
pared commercially in an aqueous system so as to have order of the relative reactivity is OH-2>OH-6>OH-3 for
different DS. In general, for cellulose derivatives, the MC prepared from alkali-cellulose in an aqueous solvent
higher the DS the higher the solubility of the derivative system. The higher reactivity of OH-2 has been postulated
to organic solvents. However, interestingly enough, 6MC to be due to its high acidity that is enhanced by its
having a lower DS showed a higher solubility than did proximity to the anomeric center, C-1 [111]. Therefore, if
23MC with a DS of 2.0. As shown in a previously an intramolecular hydrogen bond was still present at the
published paper [67,68] the FT-IR spectra for 23MC and C-2 position even in the reaction mixture, then the reac-
6MC showed this was due to the presence of interchain tivity of OH-2 should be altered, and it would probably be
hydrogen bonds at the C-6 position of 23MC. Further, reduced. Within this definition, the relative reactivity of
in comparing both 23MC with a DS of 2.0 and 6MC with the remaining hydroxyl groups (OH-2 and OH-3) in 6MC,

6TC, and 6BC was examined. As reported previously [67], exhibited noncrystalline (amorphous) patterns similar to
the two kinds of 6-substituted derivatives, 6TC and 6BC, those obtained from noncrystalline celluloses obtained
are assumed not to have any intramolecular hydrogen from the DMAc-LiCl and SO2-diethyl amine-DMSO
bonds; only 6MC has them. solutions, and further the 6MC did not show a crystal-
From the change in the DS values at the C-2 and C-3 line pattern even after heat treatment at 160jC. Thus
positions before and after the reaction, the relative reac- 6MC shows poor crystallinity irrespective of the homo-
tivity was found to be in the following order: 6TC> geneity of the structural unit along a molecular chain. In
6BC>6MC. This is apparently due to the difference in general, crystallization depends not only on the regular-
reactivity at the C-2 position. Moreover, this difference is ity of chemical structure but also on sufficient chain flex-
directly attributed to the presence of intramolecular hy- ibility for coordinated molecular motion to form nuclei.
drogen bonds at the C-2 position. As described in a The 6MC chain may be sufficiently stiff to form a high
previous section, the introduction of electron-withdrawing viscosity medium during evaporation of the solvent that
and bulky functionalities such as trityl and benzyl groups at would prevent nucleation. Therefore precipitation/crys-
the C-6 position changes the structure of the intramolecu- tallization in a dilute solution was tried. However, crys-
lar hydrogen bonds to give free OH groups at the C-2 tallized 6MC could not be obtained after this process. On
position and, in addition, the substituent effect of the more the other hand, 23MC showed different patterns depend-
bulky trityl group shows itself more in the appearance of ing on the solvents. As indicated in previous papers on
free OH-2 than in the smaller benzyl group [67]. Further, crystallization [25] and gel formation [20,26] of cellulo-
the bulkiness of the trityl groups at the C-6 position for sics, the primary OH groups at the C-6 position may be
6TC may change the conformation of the glucose back- favorably involved in interchain hydrogen bonding. The
bone to cause, to some extent, a break of the intramolecular extent of crystallization may depend on the behavior of
hydrogen bonds between the OH at the C-3 position and its the primary OH groups. Thus cellulose derivatives whose
neighboring ring oxygen (O-5). Thus, this produced free OH groups at the C-6 position are blocked like in 6MC
OH-3 for 6TC which can be more methylated than 6BC. In may prevent crystallization in the same manner as crys-
the case of 6MC, this deformation of the intramolecular tallization resulting from interchain hydrogen bonding in,
hydrogen bonds is not expected by the substitution at the say, 23MC. Stated differently, 6MC, which shows strong
C-6 position. Therefore the order of 6TC>6BC>6MC intramolecular hydrogen bonds, can perhaps possibly
above can be considered as the reverse order of preference form a crystalline state simply from van der Waals’ force
for the formation of intramolecular hydrogen bonds. In- by a minimization of the system potential energy. How-
deed, in 6MC that has strong intramolecular hydrogen ever, the poor crystallinity exhibited by 6MC described
bonds, the relative reactivity at both the C-2 and C-3 above suggests that interchain hydrogen bonds at the OH
positions exhibited almost the same values, which was groups of the C-6 position may be more advantageous
distinctly different for both 6TC and 6BC. This does not in aiding crystallization in cellulosics than van der Waals’
mean an enhanced reactivity of the OH-3 reactivity, but force. The fact that the uniform structure of 6MC in
rather a reduction in the OH-2 reactivity probably due to which every structural unit is completely and regioselec-
the formation of intramolecular hydrogen bonds at this tively substituted can engage in intramolecular hydrogen
position. Simultaneously, the hydrogen bonds at the C-2 bonds is not an advantage for crystallization, which differs
position which form between OH-2 and the ether oxygen of from other synthetic polymers such as polyolefins and
a methoxy group at the C-6 position seem to be very similar polyesters. This might be due to an induced stiffness in
to the intramolecular hydrogen bonds at the C-3 position, the main chain of 6MC, which results from the presence
between OH-3 and the glucose ring oxygen. Therefore of intramolecular hydrogen bonds.
reactivity at both the C-2 and C-3 positions shows similar Concerning precedence for the primary OH at the C-
values. In contrast, 6TC and 6BC exhibited relative reac- 6 position to the secondary OH at the C-2 and C-3
tivity in the order of OH-2>OH-3. Taking hydrogen positions in crystallization, one reason is that, as de-
bonding into account, this order is reasonable and scribed above, 23MC, which has only free primary OH
coincides with that usually exhibited in aqueous systems at the C-6 position, was easier to be crystallized than 6MC
as mentioned previously. In this study, it is noted that the and yet the crystallized 23MC did not show a melting
methylation was performed in homogeneous DMSO solu- point. This appears probably due to the strong hydrogen
tion, and therefore the hydroxyl groups in 6TC and 6BC bonding engagements in the crystallized 23MC. As for the
may be solvated to prevent further involvement of the favorableness of the interaction, Kondo et al. have al-
hydrogen bonds. In 6MC, as stated above, the relative ready reported [18,23] that in the comparison of 23MC
reactivity at the C-2 and C-3 positions indicates that the with 6MC for the blend with poly(ethylene oxide) (PEO)
intramolecular bonds were still maintained even in the which has oxygen in the polymer backbone, only primary
homogeneous solution state [19,26]. OH at the C-6 position for 23MC was engaged in
intermolecular hydrogen bonds, whereas secondary OH
at the C-2 or C-3 position for 6MC did not form the
Crystallinity interaction with PEO. Therefore it is considered that the
The X-ray diffraction patterns for 6MC films cast primary 6-OH may contribute to the crystallization more
from both DMAc and CHCl3/CH3OH(4/1 v/v) solvents than the secondary hydroxyls.

94 Kondo
The Influence of Intramolecular Hydrogen Bonds

on Handedness in Ethylcellulose/CH2CL2
Liquid Crystalline Mesophases
In 6MC samples there was a direct correlation between
the physical properties observed and the formation of
intramolecular hydrogen bonds that can even be main-
tained in solution [19,27]. The intramolecular hydrogen
bonds were also found to have an influence on the enzy-
matic hydrolysis of 6MC [21,22].
Kondo and Gray [64] succeeded in preparing a series
of methyl- and ethyl celluloses having a systematically
controlled distribution of substituents and DS. These
polymers would appear to form an ideal set of complete
samples for determining what type of correlation exists
between the physical properties and the distribution of
substituents for alkylcellulose derivatives in terms of hy-
drogen bond formation. Thus the effect of substituent
distribution on the liquid crystalline properties of EC is
the focus in this section. The majority of cellulosic meso-

phases that have been studied to date are right-handed Figure 34 Change in DS pattern at the individual C-2, C-3,
cholesteric, but a few left-handed systems have also been and C-6 positions for series B samples prepared from a
reported [112–116]. Specifically, lyotropic ethylcellulose commercially available EC.
(EC) mesophases were observed to show both types of
handedness depending on the polymer volume fraction and
solvent [112]. Guo and Gray [115,116] reported that cho-
lesteric liquid crystalline solutions of acetylated EC in DS, the influence of intramolecular hydrogen bonds, with-
chloroform exhibited a change in handedness from a left- in the same chiral backbone, in determining the handedness
handed to a right-handed helicoidal supermolecular ar- of these lyotropic mesophases was investigated [27].
rangement with an increasing acetyl content in the EC. The Two series (A and B) of ethylcellulose samples were
twist sense of EC mesophases in chloroform and CH2Cl2 used in this experiment to cover the entire range of hy-
was also observed to change from left-handed to right- droxyl substitutions possible in EC. For this set A of sam-
handed with an increasing degree of ethyl-substitution in ples (Fig. 33), all hydroxyl groups at the C-2 and C-3
EC [117]. However, the driving force for this structural positions were almost completely ethylated and only the
reversal is still not clear. Using ethylcelluloses having a ethyl DS at the C-6 position hydroxyl was systematically
systematically controlled distribution of substituents and increased with increasing sample code number. The
hydroxyls at the C-6 position in cellulosics easily form
intermolecular hydrogen bonds, resulting in poor sample
solubility in many solvents. In this series as seen in Fig. 33,
samples 1 to 4, which had a DS at the C-6 position of less
than 0.78, did not give clear CH2Cl2 solutions even at
concentrations of 1 wt.%. A high degree of substitution
at the C-6 position was required for the polymer to dis-
solve in CH2Cl2. For series B (Fig. 34), the DS at the C-3
position was somewhat lower than that for the other posi-
tions. The C-2 and C-6 hydroxyl groups were easily and
completely ethylated to give a saturated point with a DS
of 1.0. Thus only the ethyl DS for the C-3 hydroxyls was
individually increased up to a limit of 1.0. In contrast to
series A, the C-6 position hydroxyl groups in series B were
almost completely ethylated and all samples dissolved in
CH2Cl2 at 1 wt.% to yield clear solutions.
Circular dichroism (CD) was used to determine the
handedness of the cholesteric structure by the sign of the
induced CD band that results from the selective reflection
of circularly polarized light. A positive CD band corre-
sponds to a left-handed cholesteric twist, whereas a neg-
Figure 33 Change in the degree of substitution (DS) pattern ative CD band corresponds to a right-handed twist.
at the individual C-2, C-3, and C-6 positions for series A Samples from series A, as shown in Fig. 33, showed a
samples prepared from synthesized 23EC. totally different behavior in cholesteric handedness from

that of series B samples. Series A samples that were II. CONCLUSION

prepared from 23EC have free hydroxyls only at the C-6
position. As the sample code number increases, the free In this chapter, the author has attempted to explain the
hydroxyl groups at the C-6 position are gradually replaced characterization of hydrogen bonds in various states from
by ethyl groups. As already noted, hydroxyl groups at the crystal to solution. It is clear that using regioselectively
C-6 position in cellulosics contribute favorably to the substituted cellulose derivatives some specific intramolec-
formation of intermolecular hydrogen bonds and this ular hydrogen bonds can be characterized. However, hy-
results in poor solubility of the polymer. This can be seen drogen bonds themselves are still a very difficult subject to
for samples 1 to 4 in Fig. 33, which do not dissolve clarify. Further extensive study will be desired to realize the
completely even in very dilute solution. Instead, they were correlation between the formation of hydrogen bonds and
found to swell and form gels. Samples with a DS of more their influence on the properties found in cellulosics. In
than 0.8 at the C-6 position, namely, samples 5 to 9, show addition, interchain hydrogen bonds in cellulosics/synthet-
induced CD spectra for concentrated anisotropic solutions ic polymer blends [18,23,24,104] and aggregation in gels
from 40 to 50 wt.% polymer (Fig. 33) and all are right- are dropped in this chapter. Of course, these subjects are of
handed chiral nematic liquid crystals. importance in terms of polymer–polymer interactions. The
The above results strongly suggest that the distribu- author could not find enough space to mention about it.
tion of ethyl substituents among C-2, C-3, and C-6 posi- We will wait for another review.
tions of the anhydroglucose unit in EC samples can affect
the cholesteric handedness of their anisotropic solutions.

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13
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Hydrogen Bonds in Cellulose and Cellulose Derivatives

I. HYDROGEN BONDS IN CELLULOSE formation of hydrogen bonds in parallel direction to a

Copyright 2005 by Marcel Dekker

Figure 1 Hierarchical system of cellulose self-assembly.

Of course, cellulosic ﬁbers and materials are made of

Copyright 2005 by Marcel Dekker

Figure 3 Hydrophilic and hydrophobic nature in cellulose chemical structure.

Copyright 2005 by Marcel Dekker

backbone conformation, with the two glucose residues

Figure 6 Crystalline and noncrystalline regions of cellulose microﬁbrils.

Copyright 2005 by Marcel Dekker

Table 1 IR Assignments for OH Regions Reported in Native Cellulose

Copyright 2005 by Marcel Dekker

Copyright 2005 by Marcel Dekker

Copyright 2005 by Marcel Dekker

Copyright 2005 by Marcel Dekker

Table 2 IR Assignments for OH Regions Reported in B. Hydrogen Bonds in Regioselectively

calculated wavenumbers [48] for cellulose II. The model for

Copyright 2005 by Marcel Dekker

cellulose can be useful in controlling the formation of

bonds, diﬀerently from the crystalline samples. Thus we

Copyright 2005 by Marcel Dekker

biological structures. When the donor group is cation-like

the two intramolecular hydrogen bonding structures may

Copyright 2005 by Marcel Dekker

2,3-di-O-MC, (2) 6-O-MC, and (3) Tri-O-MC. The intro-

Signals of C-2 and C-3 carbons in the two MCs overlapped

Figure 15 IR spectra of ﬁlm samples of cellulose, 2,3-di-O-

Copyright 2005 by Marcel Dekker

Copyright 2005 by Marcel Dekker

number, two intramolecular hydrogen bonds expected to

should be broad because of the diversity. Thus an intra-

may be gg. However, the indication due to the chemical

2. Inﬂuence of Substituent on the Hydrogen Bonding

Copyright 2005 by Marcel Dekker

Table 4 Degree of Substitution at Individual 2,3-di-O-methyl-6-O-tritylcellulose prepared in another

Figure 21 Change of the C-1 chemical shift of tritylcellulose

Copyright 2005 by Marcel Dekker

were almost completely blocked by methyl. This phenom-

3. Assignment of ‘‘Free’’ Hydroxyl Groups

should be of importance to characterize the formation

Table 5 Distribution of Methyl and Hydroxyl Groups in Regioselectively

DS at positions DS of OH at each position

MTC1V 1.39 0.82 0.57 — 0.18 0.43 Xtri

Copyright 2005 by Marcel Dekker

Copyright 2005 by Marcel Dekker

C. Hydrogen Bonds in Noncrystalline

Copyright 2005 by Marcel Dekker

physical properties of cellulose and its derivatives in terms

phous cellulose would be of fundamental value and, fur-

Copyright 2005 by Marcel Dekker

669 671 W OH out-of-phase

Copyright 2005 by Marcel Dekker

Copyright 2005 by Marcel Dekker

only the noncrystalline regions in the cellulose model com-

morphologies on the surfaces.

Figure 30 Schematic drawing to demonstrate various size

Copyright 2005 by Marcel Dekker

tively diﬀerent among the three samples. On the contrary,

D. The Relationship Between Intramolecular

Copyright 2005 by Marcel Dekker

However, only a few published reports [48,105,106] have

Copyright 2005 by Marcel Dekker