This article was downloaded by: [Northwestern University]

On: 27 December 2014, At: 05:10

Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer House,
37-41 Mortimer Street, London W1T 3JH, UK

Liquid Crystals
Publication details, including instructions for authors and subscription information:
http://www.tandfonline.com/loi/tlct20

New insights into the transitional behaviour of

methyl-6-O-(n-dodecanoyl)-α-D-glucopyranoside using
variable temperature FTIR spectroscopy and X-ray
diffraction
a b c c a
A.G. Cook , A. Martinez-Felipe , N.J. Brooks , J.M. Seddon & C.T. Imrie
a
Department of Chemistry, School of Natural and Computing Sciences, University of
Aberdeen, Aberdeen AB24 3UE, Scotland, UK
b
Institute of Materials Technology, Universitat Politècnica de València, 46022 Valencia,
Spain
c
Department of Chemistry, Imperial College of Science, Technology and Medicine, London
SW7 2AY, UK
Published online: 01 Nov 2013.

To cite this article: A.G. Cook, A. Martinez-Felipe, N.J. Brooks, J.M. Seddon & C.T. Imrie (2013) New insights into the
transitional behaviour of methyl-6-O-(n-dodecanoyl)-α-D-glucopyranoside using variable temperature FTIR spectroscopy and
X-ray diffraction, Liquid Crystals, 40:12, 1817-1827, DOI: 10.1080/02678292.2013.854556

To link to this article: http://dx.doi.org/10.1080/02678292.2013.854556

PLEASE SCROLL DOWN FOR ARTICLE

Taylor & Francis makes every effort to ensure the accuracy of all the information (the “Content”) contained
in the publications on our platform. However, Taylor & Francis, our agents, and our licensors make no
representations or warranties whatsoever as to the accuracy, completeness, or suitability for any purpose of the
Content. Any opinions and views expressed in this publication are the opinions and views of the authors, and
are not the views of or endorsed by Taylor & Francis. The accuracy of the Content should not be relied upon and
should be independently verified with primary sources of information. Taylor and Francis shall not be liable for
any losses, actions, claims, proceedings, demands, costs, expenses, damages, and other liabilities whatsoever
or howsoever caused arising directly or indirectly in connection with, in relation to or arising out of the use of
the Content.

This article may be used for research, teaching, and private study purposes. Any substantial or systematic
reproduction, redistribution, reselling, loan, sub-licensing, systematic supply, or distribution in any
form to anyone is expressly forbidden. Terms & Conditions of access and use can be found at http://
www.tandfonline.com/page/terms-and-conditions
 Liquid Crystals, 2013
Vol. 40, No. 12, 1817–1827, http://dx.doi.org/10.1080/02678292.2013.854556

INVITED ARTICLE
New insights into the transitional behaviour of methyl-6-O-(n-dodecanoyl)-α-D-glucopyranoside
using variable temperature FTIR spectroscopy and X-ray diffraction
A.G. Cooka, A. Martinez-Felipeb, N.J. Brooksc, J.M. Seddonc and C.T. Imriea*
a
Department of Chemistry, School of Natural and Computing Sciences, University of Aberdeen, Aberdeen AB24 3UE, Scotland,
UK; bInstitute of Materials Technology, Universitat Politècnica de València, 46022 Valencia, Spain; cDepartment of Chemistry,
Imperial College of Science, Technology and Medicine, London SW7 2AY, UK

The liquid crystalline behaviour of methyl-6-O-(n-dodecanoyl)-α-D-glucopyranoside, 1, has been characterised

using X-ray diffraction and variable temperature Fourier transform infrared (FTIR spectroscopy). 1 exhibits a
monotropic interdigitated smectic A phase consisting of bilayers in which the alkyl chains are overlapped. The
crystal–isotropic transition is accompanied by a pronounced decrease in the strength of the hydrogen bonding
Downloaded by [Northwestern University] at 05:10 27 December 2014

network involving the sugar groups resulting in a marked change in the environment of the alkyl chains. The
isotropic phase consists of disordered smectic-like domains stabilised via hydrogen bonding between the sugar
groups. At the transition to the smectic A phase, a subtle change in hydrogen bonding is observed which is
manifested by a change in the temperature dependence of the OH stretching peak position in the FTIR spectrum.
On crystallisation, the strong hydrogen bonding network is re-established accompanied by a change in the
conformational distribution of the alkyl chains. A model is proposed in which a combination of hydrogen
bonding (enthalpic effects) and conformational arrangements (entropic effects) promotes initially the formation
of smectic-like domains in the isotropic phase and subsequently stabilises the smectic A phase by inhibiting the
microphase separation leading to the crystal phase.
Keywords: carbohydrate liquid crystal; smectic A phase; variable temperature FTIR; hydrogen bonding

1. Introduction external stimuli such as UV light or mechanical forces.

Carbohydrate-based liquid crystals have attracted
increasing attention in recent years and not only because
of their important role in a range of biological processes
and considerable application potential in emerging bio-
technologies [1–4] but also, more fundamentally, as they
provide a demanding challenge to our understanding of
self-assembly in condensed systems. [2,3,5,6] The mole-
cular architecture of a carbohydrate-based mesogen typi-
cally consists of a hydrophilic (polar) head group
attached to one or more lipophilic (nonpolar) chains. [2]
This amphiphilic character promotes the formation of
microphase-separated hydrophilic and hydrophobic
phases, and consequently these materials have a great
tendency to self-assemble and exhibit lyotropic liquid
crystalline behaviour. [7] The hydrophilic domains are
widely believed to be stabilised via hydrogen bonding
between the hydroxyl groups and the hydrophobic
domains by van der Waals interactions between the
alkyl chains. [2] Carbohydrate-based liquid crystals can
also exhibit thermotropic mesophases. [8–10] Their excit-
ing application potential includes their use as hydrogels or
electrolytes whose physical properties can be tuned by
[11–15]
It is clear that the successful design of new liquid
crystal carbohydrates now requires an improved under-
standing of the empirical relationships between molecular
structure and aggregation behaviour. With that aim,
recently, we studied the transitional behaviour of a series
of monosaccharides, the methyl-6-O-(n-acyl)-α-D-gluco-
pyranosides, as a function of the alkyl chain length, n. [16]
At sufficiently high values of n, the compounds exhibit
thermotropic liquid crystallinity, specifically, a monotro-
pic smectic A phase seen on cooling from the isotropic
phase, and which can be supercooled by ca 30ºC prior to
crystallising. On increasing the alkyl chain length further,
liquid crystallinity is extinguished and this has been attrib-
uted to back folding of the alkyl chains which disrupts the
packing of the molecules. [16] We now investigate in
greater detail the role of the different intermolecular inter-
actions in determining the phase behaviour of the dodecyl
member of this homologous series, namely, methyl-6-O-
(n-dodecanoyl)-α-D-glucopyranoside, 1, shown in
Scheme 1. [16] Specifically, we have characterised the
phase structures shown by 1 using X-ray diffraction,

*Corresponding author. Email: c.t.imrie@abdn.ac.uk

Present addresses for Martinez-Felipe: Departamento de Química Orgánica, Facultad de Ciencias, Instituto de Ciencia de Materiales
de Aragón (ICMA), Universidad de Zaragoza-CSIC, Pedro Cerbuna, Zaragoza 50009, Spain and Centro de Tecnologias Físicas,
Unidad Asociada ICMM/CSIC-UPV, Universitat Politècnica de València Av, Los Naranjos s/n, Valencia 46022, Spain.

© 2013 Taylor & Francis

 1818 A.G. Cook et al.
H
HO
HO
C(17) C(15)
C(18) C(16) C(14)
Scheme 1. Chemical structure of 1, methyl-6-O-dodecanoyl-α-D-glucopyranoside, and the numbering scheme used to refer to
the atoms in the molecule.
Downloaded by [Northwestern University] at 05:10 27 December 2014
and attempted to correlate these with the different chemi-
cal environments of the functional groups deduced using
temperature-dependent Fourier transform infrared
(FTIR) spectroscopy. [17] It is important to note that
the monotropic character of 1 [16] allows us to study
both the crystal-isotropic and isotropic-smectic A transi-
tions for the same compound, and to probe the differences
in the change in molecular interactions occurring at these
transitions which would be impossible to achieve for an
enantiotropic material.
2. Materials and experimental
Scheme 1 shows the chemical structure of 1 and defines
the numbering scheme used to refer to the atoms within
the molecule. The synthesis of methyl-6-O-dodeca-
noyl-α-D-glucopyranoside, 1, and the characterisation
of its thermal behaviour have been described in detail
elsewhere. [16] X-ray diffraction measurements were
carried out using a custom-built beamline based on a
Bede Microsource system, with a Photonic Science
CCD detector. The sample, in a 1.5 mm thin-wall
glass capillary, was mounted in a brass holder with
mylar windows in the X-ray sample chamber and
heated into the isotropic phase at 74.7°C. After mea-
suring the diffraction pattern, the sample was cooled in
0.5°C steps to 62.8°C, at each temperature waiting 15
seconds, taking a 15-second exposure, waiting a further
15 seconds, then taking a second 15-second exposure.
The temperature fluctuation was ± 0.2°C. As the sam-
ple remained in the smectic A phase after 10 minutes,
the temperature was further lowered in 1°C steps to
57.7°C. The images were analysed using AXcess soft-
ware developed in-house, [18] and calibrated with sil-
ver behenate (d = 58.38 Å).
The IR spectra as a function of temperature were
obtained using a Nicolet Nexus FTIR bench attached
(CH2)10CH3
O
O
H C(MeO)
H H
OH C(1) O(1)
H OMe
O(5)
O(2)
C(6) C(2)
C(7)
C(13) C(11) C(9) C(3)
O(6) O(3)
C(12) C(10) C(8) C(5)
C(4)
O(7) O(4)
to a Continuum FTIR microscope equipped with a
Linkam FTIR 600 heating stage and a TMS 93 con-
trol unit. The sample was sandwiched between a gold-
coated microscope slide and a 3 mm thick KBr disc,
and a thin film of the sample was obtained by heating
it into the isotropic phase. The FTIR spectra were
obtained on subsequent heating and cooling scans in
the 18–93ºC temperature range, with scan rates of
±3ºC/min. The spectra were collected over 64 scans
with a resolution of 4 cm−1, in the 4000 to 400 cm−1
range, and the samples were run in duplicate and the
average was taken. The spectra were recorded in a
trans-reflectance mode, i.e., the IR beam passed
through the sample was reflected by the gold surface
back through the sample, and then detected. [19]
3. Results and discussion
3.1. Phase behaviour of 1
Methyl-6-O-(n-dodecanoyl)-α-D-glucopyranoside, 1,
exhibits a monotropic smectic A phase. The crystal–
isotropic transition temperature (TCrI) is 73ºC while
the smectic A–isotropic transition temperature
(TSmAI) is 65ºC. Both temperatures were measured
on heating using differential scanning calorimetry.
[16] Thus to measure TSmAI, the isotropic phase was
cooled to ca 50ºC to obtain the smectic A phase and
immediately heated to above 70ºC. On cooling the
sample in the DSC, the smectic A phase crystallised at
about 30ºC.
For the X-ray diffraction measurements, a
crystalline sample of 1 was heated through its melting
point of 73°C. The isotropic phase at 74.7°C shows a
relatively sharp, yet diffuse small-angle peak
(FWHM = 0.012 Å−1) centred at a spacing of 27.2
Å, and a very broad wide-angle peak centred at a
spacing of 4.65 Å, see Figure 1. The presence of a
 Liquid Crystals 1819

1500 4000

3000
1000
Intensity

Intensity
2000

500
1000

0
0
0.0 0.1 0.2 0.3
0.0 0.1 0.2 0.3
–1
s/Å s / Å–1

Figure 1. X-ray pattern of the isotropic phase exhibited by Figure 3. X-ray pattern of the smectic A phase exhibited by
1 at 74.7ºC. 1 at 58.5ºC.
Downloaded by [Northwestern University] at 05:10 27 December 2014

strong and relatively sharp low-angle peak implies that
there are residual disordered smectic-like domains sur-
viving within the isotropic phase. These are presum-
ably stabilised by hydrogen bonding between the sugar
head groups and we will discuss this issue later. Upon
cooling, a transition to a smectic A phase occurred at
64.7°C, and is marked by an abrupt sharpening of the
small-angle peak into a single, first-order Bragg peak
(FWHM = 0.004 Å−1) at a layer spacing of 28.7 Å,
see Figure 2. There is the merest hint of a second-order
Bragg peak, see Figure 3, and this fact, together with
the absence of any higher-order peaks, implies that the
electron density along the layer normal is close to
sinusoidal, as is commonly observed with smectic A
phases. The wide-angle peak remains very diffuse and
centred at the same spacing as for the isotropic phase,
proving this to be a fluid mesophase. We can rule out
the possibility of a smectic C phase both from the
optical texture, and from the fact that fluid hydrocar-
bon chains are unable to sustain a cooperative tilt.
Since the smectic A phase is monotropic, it is meta-
stable and can spontaneously transform to the more
stable crystal phase, via a nucleation and growth
mechanism, at any temperature upon cooling below
TCrI. For the X-ray sample studied, crystallisation
occurred at 57.7°C, and was complete within a few
seconds. The crystal phase exhibits sharp first- and
second-order Bragg peaks (FWHM = 0.004 Å−1) in
the low-angle region, with a layer spacing of 27.8 Å,
see Figure 4. The wide-angle region contains a number
of sharp peaks, confirming the crystallinity of this
phase.
The crystal structure of 1 has been reported pre-
viously [20] and consists of bilayers composed of
either the sugar head groups or interdigitated alkyl
chains. The interface between these sub-layers was
taken to be the plane within the layer containing the
C8 atoms (for the numbering scheme, see Scheme 1).
The sugar moieties are disordered within the crystal
structure while the ester and alkyl chain fragments are

60

1500

65
1000
T/°C

Intensity

70
500

75 0
0.1 0.2 0.3 0.0 0.1 0.2 0.3
s / Å–1 s / Å–1

Figure 2. (colour online) Temperature cooling scan of the Figure 4. X-ray pattern of the crystal phase exhibited by 1
small-angle diffraction pattern exhibited by 1. at 57.7ºC.
 1820 A.G. Cook et al.

ordered with adjacent alkyl planes lying perpendicu- Log (1/R)

CH st.
lar to each other. The c lattice parameter is 28.443 Å 3
C = O st.
which is in good agreement with the layer spacing of OH st.
2.5
27.8 Å reported here for the crystal phase. Hydrogen (a)
bonding involving the hydroxyl groups on the sugar 2
moieties within the hydrophilic sub-layer was consid-
1.5
ered to be the driving force stabilising the crystal
structure. [20] If we now return to the molecular 1
arrangement within the smectic A phase, then we
0.5
have seen that the smectic periodicity is 28.7 Å. The
estimated molecular length of 1 is 22.3 Å such that 0
the ratio of the smectic periodicity to molecular 3600 3200 2800 2400 2000 1600
length, d/l, is 1.3, implying that the smectic phase Wavenumber (cm–1)
must have an interdigitated structure in which the Log (1/R) C–O st. + δ
alkyl chains overlap considerably. Figure 5 shows a 3 (b)
sketch of the molecular organisation within the phase C(6), C(7) Pyranoside Ring
Downloaded by [Northwestern University] at 05:10 27 December 2014

2.5
consistent with this d/l value and is similar to that CH2 δ
CC st.
commonly observed for carbohydrate-based liquid 2 COH δ
crystals. [21,22]
C(5)O(5)C(1)
1.5
CH2 ρ

3.2. FTIR spectrum of 1 in the crystal phase 1

The 3700–1600 cm−1 and 1600–700 cm−1 regions of the 0.5

FTIR spectrum of 1 obtained for a crystalline sample
at 18ºC are shown in Figures 6(a) and 6(b), respec-
tively. The broad band between 3600–3000 cm−1 is
highly characteristic of stretching (st.) vibration
modes of OH bonds (Figure 6(a)). The band is centred
at lower wavenumbers than that characteristic of free
OH groups (sharp band expected at ν ≥ 3500 cm−1),
indicating extensive hydrogen bonding in the crystal
phase. [23–25] This is consistent with the crystal struc-
ture described earlier, in which the OH groups are
closely packed, and the suggestion that hydrogen
bonding stabilises the crystal phase. [20] The 3000–
2700 cm−1 region contains several strong bands asso-
ciated with C–H stretching. The peaks observed at
2854 and 2845 cm−1 may be assigned to the C–H
stretching mode of the carbon atoms neighbouring
ester, C(6), and ether, C(1) and oxygen atoms. [24,26]
28.7 Å
22.3 Å
Figure 5. (colour online) Schematic representation of the
local molecular arrangement of 1 found in the smectic A
phase.
0
1500 1300 1100 900 700
Wavenumber (cm–1)
Figure 6. The (a) 3700–1600 cm−1 and (b) 1600–700 cm−1
regions of the FTIR spectrum of 1 obtained in the crystal
state (T = 18ºC). The numbering scheme for the atoms is
shown in Scheme 1.
The stretching vibration of the ester carbonyl bond,
C=O st., is associated with at least two strong bands
located at 1724 and 1735 cm−1, which may be assigned
to carbonyl groups more, or less, strongly involved in
hydrogen bonding, respectively.
At lower frequencies, see Figure 6(b), the peaks
around 1470 cm−1 are associated with the C–H δ
mode (scissoring vibrations of the alkyl chain C–H)
while the band at 1417 cm−1 may arise from bending
of the C(6)–H bonds, shifting to lower frequencies by
the proximity of the O(6) atom. The 1400–1200 cm−1
region contains several overlapping bands associated
with the deformation of C–H bonds and C–C stretch-
ing, i.e., dominated by contributions arising from the
aliphatic segment of the molecule. A number of peaks
can be seen between 1320 and 1220 cm−1 and these
are assigned to bending deformations of the C–H
bonds adjacent to OH groups (C(2–4)), oxygen
atoms (C(1), C(5), C(6)) or carbonyl groups (C(8)).
Several strong IR contributions characteristic of
monosaccharides are observed in the complex region
below 1200 cm−1, including C–O and C–C stretching
 Liquid Crystals 1821

and deformation modes of the oxymethylene group.
[26] The two strong bands located at 1196 and
1141 cm−1 may be attributed to stretching vibrations
of the C(6)–O and C(7)–O bonds, respectively.
Between 1120 and 1000 cm−1, we see bands associated
with mixed stretching and bending vibrations of C–C
and C–O bonds in the glucopyranoside ring. At lower
frequencies, ca 1000–950 cm−1, contributions arising
from the oxymethylene group (deformation modes of
O(1)–C(OMe)–H and stretching vibrations of C
(OMe)–O(1)) are seen. [26] The bands present in the
950–800 cm−1 region of the spectrum may be asso-
ciated with the complex stretching vibration of the
chain of atoms O(6)–C(6)–C(5)–O(5), and their
appearance is particularly sensitive to configurational
and conformational transformations in monosacchar-
Downloaded by [Northwestern University] at 05:10 27 December 2014
3.3. Temperature dependence of the FTIR spectra of
1 on heating
The high- and low-frequency regions of the FTIR
spectra of 1 obtained on heating from 18ºC to 93ºC
are shown in Figures 7(a) and 7(b), respectively.
Several pronounced changes in the spectra are seen
around the crystal–isotropic phase transition, ca
73ºC. In particular, the OH st. band shifts to
higher frequencies and decreases in intensity, see
Figure 7(a). Thus, in Figure 8, we show the tempera-
ture dependence of the maximum of the OH st. band
peak position, and two distinct regions of behaviour
on heating are seen: below the melting point, the peak
shifts to higher frequency on increasing temperature
while in the isotropic phase appears to remain essen-
tially constant. Melting is accompanied by a jump in

ides. [26] The envelope of this region is similar to that
observed for glucopyranoside, but contains a new peak
at 855 cm−1 associated with vibrations involving the
chain of atoms C(8)–C(7)–O(6)–C(6) containing
the ester linkage. Finally the bands seen below
800 cm−1 are related to rocking deformations, ρ, of
C–H bonds. [27]
the position of the OH st. band of around 70 cm−1 to
higher wavenumbers. These changes indicate a dra-
matic reduction in the strength of hydrogen bonding
within the system. However, the breadth of the
OH band and the absence of a sharp peak above
3500 cm−1 indicate the persistence of hydrogen bond-
ing in the isotropic phase, at least to some degree.

Log (1/R)

Heating (a)

3500 3000 2500 1800 1750 1700 1650

Wavenumber (cm–1)

Log (1/R)

(b)
Heating

1500 1300 1100 900 700

Wavenumber (cm–1)

Figure 7. Temperature dependence of the (a) 4000–2600 cm−1 and (b) 1800–700 cm−1 regions of the FTIR spectra of 1
obtained on heating. Large arrows indicate the direction of heating (T = 18, 28, 38, 48, 58, 68, 78 and 88ºC). Dashed arrows
and the grey spectrum indicate the phase transition.
 1822 A.G. Cook et al.
ν max (cm–1)
3480 T = 64ºC
WTCI = –0.46 cm–1/K
3460
WTCSmA = –1.22 cm–1/K
3440
3420
3400
3380
WTCCr = 0.79 cm–1/K
3360
3340
0 20 40 60 80 100
T (°C)
Figure 8. (colour online) Temperature dependence of the
maximum of the OH stretching band on heating from the
Downloaded by [Northwestern University] at 05:10 27 December 2014
crystal phase (red diamonds) and subsequent cooling from
the isotropic phase (blue squares).
This is consistent with the view that hydrogen bond-
ing stabilises disordered smectic-like domains in the
isotropic phase as observed by X-ray diffraction, see
Figure 1.
We investigated the dynamic nature of the hydro-
gen bonding network by calculating the so-called
wavenumber-temperature-coefficient, WTC, of the
OH st. band which was defined by Wolkers et al.
[23,28] as the gradient of the plot of peak position
against temperature and has been interpreted in glasses
in terms of Angell’s strength and fragility concept.
[29,30] The regions of linear behaviour are also indi-
cated in Figure 8, and we found a WTCCr value of 0.79
cm−1 K−1 in the crystal phase. This is rather higher
than those typically measured in a sugar-based glass or
melt [28] and presumably reflects an equilibrium shift-
ing towards free OH groups with temperature.
The C=O stretching region is essentially
unchanged on heating the crystal phase, but its inten-
sity increases dramatically at the crystal–isotropic
transition, see Figure 7(a). This dramatic increase in
intensity, which is also seen for other bands, for
example, 2930 and 2850 cm−1 (see Figure 7(a)), may
be attributed to a loss of surface alignment of the
liquid crystal on entering the isotropic phase.
Specifically, the incident IR beam is polarised, at
least to some extent, on reflection at the gold surface
and so vibrations parallel to the surface will not be
detected as strongly as those perpendicular to the
surface. [31] Given the strong tendency of carbohy-
drate-based liquid crystals to align homeotropically,
the intensity of vibrations perpendicular to the mole-
cular long axis, including, for example, the C=O
stretch, will have reduced intensities. [30] The tem-
perature dependence of the carbonyl peak positions is
difficult to quantify because of the complex nature of
this region of the spectra. However, it is clear that
on melting the higher frequency band (ca. 1735 cm−1)
increases in intensity to a much greater extent than
the 1724 cm−1 component (see Figure 7), implying a
reduction in the intermolecular interactions involving
the carbonyl groups. These changes in the carbonyl
stretching region reinforce the view that the strength
of hydrogen bonding is reduced on melting the crystal
phase.
At lower wavenumbers, the 1500–1300 cm−1 region
of the FTIR spectra also shows significant variations
on heating, see Figure 7(b), revealing changes in the
hydrophobic regions of the molecule. Increasing
the temperature causes shifts to lower frequencies of
the peaks related to the methylene groups, located
principally in the alkyl chain, see, for example, the
temperature dependence of the rocking C–H band at
ca. 763 cm−1 in Figure 9. On heating the crystal phase,
the peak position shows a small linear decrease. By
comparison, on melting, a sudden shift to lower fre-
quency is seen while on heating the isotropic phase, the
peak position shows little change. These observations
reveal, at least in part, changes in the van der Waals
forces between the molecules on heating.
The region associated with the stretching/bending
vibrations of the pyranose ring also shows
noticeable changes on increasing the temperature.
For example, the peaks related with the methoxy
group (1330–1220 cm−1) remain essentially
unchanged on heating the crystal phase, while at
around the melting point rapidly decrease in intensity
and wavenumber. In the isotropic phase, a rather
smooth FTIR profile is observed for this region,
ν max (cm–1)
780
776
772
768
764
760
756
752
748
744
740
0 20 40 60 80 100
T (°C)
Figure 9. (colour online) Temperature dependence of the
characteristic IR band associated with the rocking mode of
C–H bonds on heating (red diamonds) and cooling (blue
squares).

indicating a greater homogeneity of the chemical
interactions between the rings. These results presum-
ably reflect the changes of the local structure arising
from the abrupt change in hydrogen bonding, leading
to a higher disordering of the sugar groups than in the
crystal phase.
3.4. Temperature dependence of the FTIR spectra of
1 on cooling
Figure 10 shows the FTIR spectra of 1 recorded on
cooling from the isotropic phase. The OH st. band
shifts to lower wavenumbers, with an associated
WTCI value of 0.46 cm−1/K, see Figure 8, revealing
changes in the hydrophilic regions of 1. This value is
comparable to those measured in the isotropic phases
Downloaded by [Northwestern University] at 05:10 27 December 2014
of other conventional low-molar mass sugars. [23]
There is no step change in either the peak position or
intensity of the band at the isotropic–smectic A transi-
tion but we do see an increase in the associated
WTCSmA value to 1.22 cm−1/K, see Figure 8. On crys-
tallisation, the peak maximum jumps to a lower value
and shows a sudden and pronounced increase in inten-
sity, which indicates a step increase in hydrogen
Log (1/R)
3500 3000 2500
Wavenumber (cm
Log (1/R)
1500 1300
Wavenumber (cm–1)
Figure 10. Temperature dependence of the (a) 4000–2600 cm−1 and (b) 1800–600 cm−1 regions of the FTIR spectra of 1
obtained on cooling. Large arrows indicate the direction of cooling (T = 88, 78, 68, 58, 48, 38 and 28ºC). Dashed arrows and
the grey spectrum indicate the phase transition.
Liquid Crystals 1823
bonding. A similar behaviour is observed in non-meso-
genic sugars and the magnitude of the position change
of the OH st. peak appears to be linked to the size of the
crystallisation enthalpy. [32] In the crystal phase, the
spectra recorded on cooling are essentially identical to
those described in the previous section on heating.
The peak frequency of the OH st. band is some 60
cm−1 higher in the smectic A phase than in the crystal
phase, indicative of weaker hydrogen bonding. In
addition, we have seen that the WTC value recorded
on cooling the smectic A phase, 1.22 cm−1/K, is much
larger than that seen on heating the crystal phase,
0.79 cm−1/K, indicating that the hydrogen bond net-
work is more sensitive to changes in temperature in
the mesophase. This latter observation presumably
reflects that the increase in the order parameter on
cooling the smectic A phase is considerably larger
than the change in ordering on heating the crystal.
This is only the second WTC value reported for a
carbohydrate-based liquid crystal and is considerably
larger than that reported previously for a nonsym-
metric liquid crystal dimer containing a single carbo-
hydrate-based unit. [30] The physical significance of
this difference in behaviour is not yet clear.
(a)
CT100C_B
1800 1750 1700 1650
–1)
(b)
Cooling
1100 900 700
 1824 A.G. Cook et al.

Cooling the isotropic phase is also accompanied
by changes in the IR peaks related to the alkyl groups
of 1 as seen, for example, in Figure 9, which
shows the temperature dependence of the band at
ca. 752 cm−1 associated with the C-H rocking mode.
The peak position increases slightly and in a linear
fashion on cooling the isotropic and smectic A phases.
Crystallisation is then accompanied by a sudden
increase in the peak position suggesting that the
alkyl chains are now in an environment of weaker
intermolecular interactions.
The effect of temperature on the alkyl groups of 1
may be studied in further detail by analysing the
1500–1430 cm−1 region of the FTIR spectra, see
Figure 11, corresponding to the C–H in-plane (scis-
soring) vibrations. Despite the complexity of the
Downloaded by [Northwestern University] at 05:10 27 December 2014
unchanged, see Figure 11(a). On melting, we see a
dramatic decrease in intensity for the highest wave-
number contribution, a moderate but clear decrease
in intensity for the 1463 cm−1 band, and an increase
in the intensity of the lower frequency contributions.
The changes in this region of the FTIR spectra
reflect, at least to some extent, a combination of the
complex variations in the intramolecular (conforma-
tional) and intermolecular factors involving the
hydrophobic segments of 1 on heating. Specifically,
the 1472 cm−1 band can be assigned to C–H groups
preferentially found in trans conformations. [33,34]
The increase in the 1463 cm−1 contribution may
then be attributed to a dynamic exchange towards
an increased number of gauche configurations of the
alkyl chain, indicative of an increase in disorder on

region, at least two high wavenumber bands are evi- melting. In addition, the relative increase of the lower
dent, centred at 1472 and 1463 cm−1, as well as a wavenumber contributions (~1454 cm−1) may be
broad lower wavenumber contribution (~1454 cm−1), understood in terms of a greater number of C–H
presumably consisting of a number of overlapping units being involved in stronger intermolecular inter-
bands and related to methylene groups involved in actions. On cooling, this region shows effectively no
stronger intermolecular interactions. On heating the change in intensity at the smectic A–isotropic transi-
crystal phase, this region of the spectrum is essentially tion, presumably indicating that both the dynamics
and environment of the chains undergo little change
at this transition, see Figure 11(b). This is in agree-
Log (1/R) ment with the behaviour discussed earlier for the C–H
2 T = 88°C rocking bands, see Figure 9. By comparison, on crys-
1.8 (a) tallisation, dramatic changes are seen in this region
T = 53°C
1.6
and, as would be expected, these are opposite in sense
1.4 T = 28°C
to those observed on melting.
1.2
1
0.8
0.6
3.5. Discussion of the phase behaviour of 1
0.4 The changes seen in the FTIR spectra of 1 on heating
0.2 and cooling, described in the preceding sections, pro-
0 vide new insights into the temperature dependence of
1490 1478 1466 1454 1442 1430
the intermolecular environments experienced by the
Wavenumber (cm–1) hydrophobic and hydrophilic segments of 1. In the
reported crystal structure, [35] the pyranose ring is
Log (1/R)
tilted with respect to the long axis of the alkyl chain.
T = 78°C
The alkyl chains are in all-trans conformations facil-
2 T = 48°C
1.8
itating their packing in the hydrophobic domains of
(b)
1.6 T = 28°C the crystal, except for the C(7)–O(6)–C(6)–C(5) bond
1.4 which adopts a gauche conformation allowing the
1.2 sugar head groups to pack efficiently into the hydro-
1 philic layers. This phase separated crystal structure,
0.8
0.6
typical of amphiphilic liquid crystals, is stabilised by
0.4 the strong hydrogen bonds, principally involving the
0.2 OH groups in the sugar moieties.
0 On melting, a fraction of the hydrogen bonds in
1490 1478 1466 1454 1442 1430
the polar regions of the structure is broken (probably
Wavenumber (cm–1)
the strongest, i.e., those associated with O–H st. hav-
Figure 11. (colour online) The 1500–1430 cm−1 region of ing lower frequencies), and this increased molecular
the FTIR spectrum of 1 obtained at three different tempera- freedom allows for conformational rearrangements
tures on (a) heating and (b) cooling. within the system. The geometry of the C(7)–O(6)–C

(6)–C(5) bond changes, resulting in a more linear
molecule, which may assist the formation of the smec-
tic-like aggregates observed in the isotropic phase, see
Figure 5.
On supercooling the isotropic phase, the smectic A
phase is formed, and this appears to be facilitated by
the higher free volume available to the hydrophilic
and hydrophobic regions in the melt. The temperature
dependence of the OH st. peak revealed both a subtle
change in the hydrophilic interactions when cooling
from the isotropic phase (see Figure 8), and also a
dynamic hydrogen bonding network in the smectic
A phase, reflected in the unusually high WTCSmA
(–1.22 cm−1/K) value. It is also interesting to note
that the isotropic–smectic A transition temperature
seen for 1 is considerably higher than the melting
Downloaded by [Northwestern University] at 05:10 27 December 2014
temperatures of either lauric acid (T ~ 40ºC) or
methyl laureate (T ~ 10ºC), [36] suggesting that the
alkyl chains are expected to be highly mobile in the
smectic phase. Thus, it is reasonable to assume that
thermal activation promotes the adoption of a greater
number of conformations by the hydrophobic frag-
ments of the molecule above melting. The existence of
this dynamic conformational equilibrium is entropi-
cally favourable and, taken together with additional
kinetic barriers impairing the formation of crystal
nuclei, may offset the unfavourable hydrophilic–
hydrophobic interactions in the interdigitated smectic
layers and inhibit crystallisation.
Finally, we need to consider the role of the carbo-
nyl group in determining the phase behaviour of 1.
The intermolecular environment experienced by the
carbonyl group appears little altered at the isotropic–
smectic transition, but undergoes considerable
changes on melting and crystallisation, see Figures 7
and 10. The ester group (C(8)–O(7)–O(6)) links the
hydrophobic and hydrophilic regions of the molecule,
and its contribution to determining phase behaviour
is twofold. On the one hand, the FTIR spectra show
that in the crystal phase, the carbonyl group is
involved in the strong hydrogen bonded network
within the hydrophilic layer, thus contributing to the
stability of the crystal phase. On the other hand, on
melting, the conformational change of the C(7)–O(6)–
C(6)–C(5) bond increases the molecular linearity and
reduces the ability of the carbonyl group to form
strong intramolecular hydrogen bonds. Instead, the
carbonyl group becomes involved in weaker intermo-
lecular hydrogen bonding which helps to stabilise the
formation of smectic-like aggregates. This view is
consistent with both the spectroscopic changes
observed in the ν ~1470 cm−1 region, see Figure 11,
and with the interdigitated smectic arrangement
found using X-ray diffraction, see Figure 5. It is also
noteworthy that the corresponding materials but
Liquid Crystals 1825
without the carbonyl link, the methyl-6-O-(n-alkyl)-
α-D-glucopyranosides, do not exhibit liquid crystal-
linity [10], providing further evidence that the carbo-
nyl groups participate in the hydrogen bonding
required for smectic phase stabilisation. From a gen-
eral molecular design viewpoint, this observation
highlights the key role of the linker group between
the polar head and the hydrophobic chains in promot-
ing thermotropic liquid crystallinity in this class of
sugar-based mesogens.
4. Conclusions
Methyl-6-O-(n-dodecanoyl)-α-D-glucopyranoside, 1,
exhibits a monotropic smectic A phase consisting of
bilayers in which the alkyl chains interdigitate. This
study of a monotropic liquid crystal has allowed us to
compare the crystal–isotropic and smectic A–isotro-
pic transitions for the same compound.
Melting is accompanied by a significant decrease
in the strength of hydrogen bonding within the hydro-
philic domains in the crystal phase of 1, although
some hydrogen bonding persists resulting in disor-
dered smectic-like domains in the isotropic phase.
On cooling the isotropic phase, a subtle change in
hydrogen bonding drives the formation of an inter-
digitated smectic phase. Crystallisation is inhibited by
a combination of enthalpic (persistence of moderate
hydrogen bonds which stabilise the lamellar order)
and entropic factors (the fluid nature of the alkyl
chains and the dynamic nature of the hydrogen
bond network). Crystallisation of the smectic A
phase is then accompanied by a sudden increase in
the strength of hydrogen bonding, leading to a micro-
phase separated crystal structure. These observations
reinforce the view that the melting point of a carbo-
hydrate-based liquid crystal is largely determined by
the strength of the hydrogen bonding network within
the crystal [37]. By comparison, the van der Waals
interactions between the alkyl chains play a rather
secondary role in the formation of the smectic phase
(a view consistent with the absence of change in the
FTIR spectra shown, for example, in Figures 9 and
11) but undergo greater change during crystallisation
and melting.
This model for the phase transition also accounts
for the unusually low values of the entropy change
observed at the isotropic–smectic A phase transition
for 1, [16] which, in fact, is more similar in magnitude
to that observed for nematic–isotropic transitions.
[38–40] This appears to be a rather general observa-
tion [5,41,42] but has not attracted significant atten-
tion. Thus, the persistence of these hydrogen bonded
aggregates in the isotropic phase reduces the changes
in the orientational and translational ordering that
 1826 A.G. Cook et al.
would normally be expected at the smectic A–isotro-
pic transition giving a smaller than expected entropy
change. A similar model has been proposed to
account for the low values of the entropy change
seen for the smectic A–isotropic transition for ionic
liquid crystals in which the aggregates are stabilised
by ionic interactions. [43]
To the best of our knowledge, this is the first
detailed study of the temperature dependence of the
FTIR spectrum of a carbohydrate-based liquid crystal
and has revealed new insights into the phase beha-
viour of this class of materials. The generality of these
observations, however, must now be tested for a wide
range of carbohydrate-based liquid crystals.
Downloaded by [Northwestern University] at 05:10 27 December 2014
Acknowledgements
The authors would like to thank the Spanish Ministry of
Science and Innovation, through the Research Project
ENE2011-28735-C02-01, and the financial support of the
Generalitat Valenciana, through the GRISOLIAP/2010/057
and APOSTD/2013/054 programs. The UPV is also thanked
for additional support through the PAID-06-11-2037
program.
Funding
JMS is pleased to acknowledge support from the EPSRC
Platform [grant number EP/G00465X].
References
[1] Goodby JW. Liquid-crystalline glycolipids: towards
understanding the roles of liquid crystals in biological
and life processes. Liq Cryst. 2006;33(11–12):
1229–1237.
[2] Goodby JW, Goertz V, Cowling SJ, Mackenzie G,
Martin P, Plusquellec D, Benvegnu T, Boullanger P,
Lafont D, Queneau Y, Chambert S, Fitremann J.
Thermotropic liquid crystalline glycolipids. Chem Soc
Rev. 2007;36(12):1971–2032.
[3] Hashim R, Sugimura A, Minamikawa H, Heidelberg
T. Nature-like synthetic alkyl branched-chain glycoli-
pids: a review on chemical structure and self-assembly
properties. Liq Cryst. 2012;39(1):1–17.
[4] Jewell SA. Living systems and liquid crystals. Liq
Cryst. 2011;38(11–12):1699–1714.
[5] van Doren HA, Smits E, Pestman JM, Engberts J,
Kellogg RM. Mesogenic sugars. From aldoses to liquid
crystals and surfactants. Chem Soc Rev. 2000;29
(3):183–199.
[6] Brooks NJ, Hamid HAA, Hashim R, Heidelberg T,
Seddon JM, Conn CE, Husseini SMM, Zahid NI,
Hussen RSD. Thermotropic and lyotropic liquid crys-
talline phases of Guerbet branched-chain ß-D-gluco-
sides. Liq Cryst. 2011;38(11–12):1725–1734.
[7] Hashim R, Mirzadeh SM, Heidelberg T, Minamikawa
H, Yoshiaki T, Sugimura A. A reevaluation of the
epimeric and anomeric relationship of glucosides and
galactosides in thermotropic liquid crystal self-assem-
blies. Carbohydr Res. 2011;346(18):2948–2956.
[8] Dorset DL, Rosenbusch JP. Solid-state properties of
anomeric 1-O-n-octyl-D-glucopyranosides. Chem Phys
Lipids. 1981;29(4):299–307.
[9] Goodby JW. Liquid-crystal phases exhibited by
some monosaccharides. Mol Cryst Liq Cryst.
1984;110(1–4):205–219.
[10] Miethchen R, Holz J, Prade H, Liptak A. Amphiphilic
and mesogenic carbohydrates. 2. Synthesis and char-
acterization of mono-O-(n-alkyl)-D-glucose deriva-
tives. Tetrahedron. 1992;48(15):3061–3068.
[11] Martinez-Felipe A. Liquid crystal polymers and iono-
mers for membrane applications. Liq Cryst. 2011;38
(11–12):1607–1626.
[12] Kaneko T, Yamaoka K, Gong JP, Osada Y. Liquid-
crystalline hydrogels. 1. Enhanced effects of incorpora-
tion of acrylic acid units on the liquid-crystalline order-
ing. Macromolecules. 2000;33(2):412–418.
[13] Clemente MJ, Fitremann J, Mauzac M, Serrano JL,
Oriol L. Synthesis and characterization of maltose-
based amphiphiles as supramolecular hydrogelators.
Langmuir. 2011;27(24):15236–15247.
[14] Clemente MJ, Romero P, Serrano JL, Fitremann J,
Oriol L. Supramolecular hydrogels based on glycoam-
phiphiles: effect of the disaccharide polar head. Chem
Mater. 2012;24(20):3847–3858.
[15] Clemente MJ, Tejedor RM, Romero P, Fitremann J,
Oriol L. Maltose-based gelators having azobenzene
as light-sensitive unit. Rsc Advances. 2012;2
(30):11419–11431.
[16] Cook AG, Wardell JL, Imrie CT. Carbohydrate liquid
crystals: synthesis and characterisation of the methyl-6-
O-(n-acyl)-α-D-glucopyranosides. Chem Phys Lipids.
2011;164(2):118–124.
[17] Martinez-Felipe A, Lu Z, Henderson PA, Picken SJ,
Norder B, Imrie CT, Ribes-Greus A. Synthesis and
characterisation of side chain liquid crystal copolymers
containing sulfonic acid groups. Polymer. 2012;53
(13):2604–2612.
[18] Seddon JM, Squires AM, Conn CE, Ces O, Heron AJ,
Mulet X, Shearman GC, Templer RH. Pressure-jump
X-ray studies of liquid crystal transitions in lipids.
Philosophical Transactions of the Royal Society a-
Mathematical Physical and Engineering Sciences.
2006;364(1847):2635-2655.
[19] Martinez-Felipe A, Imrie CT, Ribes-Greus A. Study of
structure formation in side-chain liquid crystal copolymers
by variable temperature fourier transform infrared spectro-
scopy. Ind Eng Chem Res. 2013;52(26):8714–8721.
[20] Abe Y, Harata K, Fujiwara M, Ohbu K. Molecular
arrangement and intermolecular hydrogen bonding in
crystals of methyl 6-O-acyl-D-glycopyranosides.
Langmuir. 1996;12(3):636–640.
[21] Donaldson T, Henderson PA, Achard MF, Imrie CT.
Chiral liquid crystal tetramers. J Mater Chem. 2011;21
(29):10935–10941.
[22] Bault P, Gode P, Goethals G, Goodby JW, Haley JA,
Kelly SM, Mehl GH, Ronco G, Villa P. An homolo-
gous series of 6-O-n-alkyl-α-D-galactopyranoses:
synthesis and thermotropic mesomorphic properties.
Liq Cryst. 1998;24(2):283–293.
[23] Wolkers WF, Oliver AE, Tablin F, Crowe JH. A four-
ier-transform infrared spectroscopy study of sugar
glasses. Carbohydr Res. 2004;339(6):1077–1085.

[24] Babkov LM, Korolevich MV, Moiseikina EA.
Hydrogen bonding, IR spectrum, and the structure of
methyl-ß-D-glucopyranoside. J Struct Chem. 2012;53
(1):55–62.
[25] Vinogradov S, Linnell R. Hydrogen Bonding, 272 p.
New York (NY): Van Nost Reinhold; 1971.
[26] Korolevich FV, Zhbankova MR, Piottukh-Peletskii
VN, Zhbankov RG. Interpretation of the IR spectrum
of methyl-ß-D-glucopyranoside based on the theoreti-
cal calculation of frequencies and intensities of normal
vibrations. J Struct Chem. 2007;48(5):821–830.
[27] Lin-Vien D, Colthup N, Fateley W, Grasselli J, edi-
tors. The handbook of infrared and Raman character-
istic frequencies of organic molecules. Boston (MA):
Academic Press; 1991.
[28] Wolkers WF, Oldenhof H, Alberda M, Hoekstra FA.
A Fourier transform infrared microspectroscopy study
of sugar glasses: application to anhydrobiotic higher
plant cells. Biochim Biophys Acta-General Subjects.
Downloaded by [Northwestern University] at 05:10 27 December 2014
1998;1379(1):83–96.
[29] Angell CA, Imrie CT, Ingram MD. From simple elec-
trolyte solutions through polymer electrolytes to super-
ionic rubbers: Some fundamental considerations.
Polym Int. 1998;47(1):9–15.
[30] Cook AG, Wardell JL, Brooks NJ, Seddon JM,
Martinez-Felipe A, Imrie CT. Non-symmetric liquid
crystal dimer containing a carbohydrate-based moiety.
Carbohydr Res. 2012;360:78–83.
[31] Coats AM, Hukins DWL, Imrie CT, Aspden RM.
Polarization artefacts of an FTIR microscope and the
consequences for intensity measurements on anisotro-
pic materials. J Microscopy-Oxford. 2003;211:63–66.
[32] Ottenhof MA, MacNaughtan W, Farhat IA. FTIR
study of state and phase transitions of low moisture
sucrose and lactose. Carbohydr Res. 2003;338
(21):2195–2202.
[33] Cook AG, Inkster RT, Martinez-Felipe A, Ribes-
Greus A, Hamley IW, Imrie CT. Synthesis and phase
behaviour of a homologous series of polymethacrylate-
based side-chain liquid crystal polymers. Eur Polym J.
2012;48(4):821–829.
Liquid Crystals 1827
[34] Zhu X-Q, Liu J-H, Liu Y-X, Chen E-Q. Molecular
packing and phase transitions of side-chain liquid crys-
talline polymethacrylates based on p-methoxyazoben-
zene. Polymer. 2008;49(13–14):3103–3110.
[35] Abe Y, Harata K, Fujiwara M, Ohbu K. Crystal-
structures of methyl 6-O-n-alkanoyl-ß-D-glucopyrano-
sides. Carbohydr Res. 1995;269(1):43–51.
[36] Lide D, editor. CRC handbook of chemistry and phy-
sics. 86th ed. Boca Raton (FL): CRC Press; 2005.
[37] van Doren HA, van Dergeest R, Deruijter CF, Kellogg
RM, Wynberg H. The scope and limitations of liquid-
crystalline behavior in monosaccharide amphiphiles –
comparison of the thermal-behavior of several homolo-
gous series of D-glucose derived compounds with an
amino-linked alkyl chain. Liq Cryst. 1990;8(1):109–121.
[38] Imrie CT, Taylor L. The preparation and properties of
low molar mass liquid-crystals possessing lateral alkyl
chains. Liq Cryst. 1989;6(1):1–10.
[39] Imrie CT, Karasz FE, Attard GS. Comparison of the
mesogenic properties of monomeric, dimeric, and side-
chain polymeric liquid-crystals. Macromolecules.
1993;26(3):545–550.
[40] Henderson PA, Niemeyer O, Imrie CT. Methylene-
linked liquid crystal dimers. Liq Cryst. 2001;28
(3):463–472.
[41] Letellier P, Ewing DF, Goodby JW, Haley J, Kelly
SM, MacKenzie G. The effect of hydrogen bonding,
molecular shape, dipole moments, and chain length on
the mesomorphism of some D-glucose and D-glucosa-
mine derivatives. Liq Cryst. 1997;22(5):609–620.
[42] Ewing DF, Glew M, Goodby JW, Haley JA, Kelly
SM, Komanschek BU, Letellier P, Mackenzie G,
Mehl GH. N-acyl-ß-D-glycopyranosylamines contain-
ing 1,4-disubstituted cyclohexyl and phenyl rings:
mesomorphism and molecular structure relationships.
J Mater Chem. 1998;8(4):871–880.
[43] De Roche J, Gordon CM, Imrie CT, Ingram MD,
Kennedy AR, Lo Celso F, Triolo A. Application of
complementary experimental techniques to characteri-
zation of the phase behavior of C(16)mim PF6 and C
(14)mim PF6. Chem Mater. 2003;15(16):3089–3097.