Chromonic mesophases
Chromonic mesophases
Chromonic mesophases
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Current Opinion in Colloid and Interface Science 8 (2004) 480–490<br />
<strong>Chromonic</strong> <strong>mesophases</strong><br />
John Lydon<br />
University of Leeds, The School of Biochemistry and Molecular Biology, Leeds LS2 9JT, UK<br />
Abstract<br />
Over the last 10 years, there has been a growing acceptance of the concept of chromonic phases and a wider recognition that<br />
they form a well-defined family of lyotropic liquid crystalline phases, with a package of properties distinct in almost every aspect,<br />
from those of conventional amphiphiles. New chromonogenic compounds have appeared and new technological uses for chromonic<br />
systems are being actively explored. Recent promising investigations include the synthesis of a chromonic dye, C.I. Direct Blue<br />
67, which has an N phase of high order parameter and which can be dried down to give well-oriented films of solid. When dried<br />
down on a ‘command surface’ of photoaligned substrate this can produce a highly patterned film. The use of chromonic phases<br />
in the construction of compensating plates for improving the viewing characteristics of twisted nematic displays has been explored.<br />
Although this technology may not be suitable for commercially exploitation in its present form, the success of the devices is<br />
significant. It is suggested that current studies of the way in which the temperature range of thermotropic discotic <strong>mesophases</strong> is<br />
enhanced in 1:1 CPI mixtures may well lead to improved formulations for chromonic dyes. It is predicted that the marriage of<br />
chromonic phase technology with current biochemical analytical techniques will give rise to a new generation of medical<br />
diagnostic tests.<br />
2004 Elsevier Ltd. All rights reserved.<br />
1. Introduction<br />
About two decades ago it was becoming clear that<br />
there is an extensive and well-defined family of lyotropic<br />
mesogens with properties distinct from those of conventional<br />
amphiphiles. This family consists of various<br />
drugs, dyes, nucleic acids, antibiotics, carcinogens and<br />
anticancer agents. In almost every respect the properties<br />
are different to those of ordinary lyotropic mesogens of<br />
the soapydeterergentyphosphilipid type. The molecules<br />
have aromatic rather than aliphatic structures. They are<br />
rigid rather than flexible and planar disc-like or planklike,<br />
rather than rod-like. The hydrophilic solublising<br />
groups are disposed around the periphery of the molecules<br />
rather than at one end. The molecules aggregate<br />
in solution, not into micelles, but into columns. They<br />
have distinctive optical textures (involving characteristic<br />
types of paramorphosis). Thermodynamic measurements<br />
indicate that the driving force for the aggregation is<br />
enthalpic rather than entropic. Their phase diagrams<br />
tend to be of the peritectic rather than eutectic type.<br />
They do not show cmc’s or Krafft points. These are the<br />
chromonic <strong>mesophases</strong><br />
E-mail address: j.e.lydon@leeds.ac.uk (J. Lydon).<br />
This review is intended to be read as an update of<br />
●●<br />
two previous papers. The first w1 x, in The Handbook<br />
of Liquid Crystals, gives details of the prehistory of<br />
chromonic phases, the patterns of molecular aggregation<br />
in N an M phases and NyM phase diagrams and includes<br />
a description and analysis of characteristic optical textures.<br />
The second w2 x, in this journal 5 years ago,<br />
●●<br />
described the newer brickwall and chimney types of<br />
aggregation encountered in some chromonic dyeywater<br />
systems and discussed the extension of the Israelachvili<br />
approach from lyotropic amphiphile systems to chromonics<br />
(Figs. 1 and 2).<br />
The recent developments discussed in this review fall<br />
into three categories. The first concerns the use of an<br />
optical alignment technique to produce detailed patterns<br />
of alignment in dried down films of dyes. The second<br />
concerns the experimental use of chromonic phases in<br />
compensating plates to improve the performance of the<br />
standard twisted nematic display devices. The third<br />
concerns CPI mixtures—a theme of current interest in<br />
thermotropic discotic systems, which I predict will<br />
become of importance in the future technological exploitation<br />
of chromonic systems.<br />
1359-0294/04/$ - see front matter 2004 Elsevier Ltd. All rights reserved.<br />
doi:10.1016/j.cocis.2004.01.006
J. Lydon / Current Opinion in Colloid and Interface Science 8 (2004) 480–490<br />
481<br />
Fig. 1. The Structures of <strong>Chromonic</strong> N and M Phases. <strong>Chromonic</strong> mesogens can be regarded as being insoluble in one dimension. They tend to<br />
aggregate face-to-face, producing a variety of stacked structures. The classic chromonic phases are the nematic, N phase and the hexagonal, M<br />
phase. In both of these, the molecules are stacked in columns. In the N phase, these lie in a nematic array (i.e. the columns are more or less<br />
parallel, but there is no positional order and there is no orientational order of the columns about their long axes). In the M phase, the columns<br />
lie on a lattice with statistical hexagonal symmetry and have long-range order. Other chromonic structures have been identified by Tiddy et al.<br />
and Harrison et al. where the molecules are aggregated into brickwork patterns or cylindrical chimneys w2,18,19x.<br />
2. Outline of chromonic phase structure and<br />
properties<br />
The name chromonic was derived from the bischromone<br />
structure of the widely marketed anti-asthmatic<br />
known in the UK as INTAL and in the US as<br />
Chromolyn w3–10x—by no means the first mesogen of<br />
this type to be reported—but one of the most extensively<br />
studied. It was considered (by its creator at least) to be<br />
a particularly good name because of the fortuitous<br />
combination of connotations of the word, with both<br />
colour (with reference to dyestuffs) and with chromosomes<br />
(with reference to nucleic acids).<br />
<strong>Chromonic</strong> <strong>mesophases</strong> are the lyotropic counterparts<br />
of the discotic <strong>mesophases</strong>-and there are some parallels<br />
in their history. In both cases, the definition of the<br />
concept came far later than one would have expected.<br />
The so-called ‘carbonaceous phases’ had been known<br />
and characterised by the coking industry for decades<br />
and there were predictions of ‘negative nematic’ liquid<br />
crystalline phases years before Chandrasekhar’s classic<br />
work. Similarly, references to the aggregation of dye<br />
molecules, stacking like piles of pennies or packs of<br />
cards were scattered in the dye chemistry literature for<br />
almost a century. Terms such as H- and J-aggregates<br />
were widely used in the industry—but there was scarcely<br />
ever a mention of liquid crystalline properties.<br />
In many aspects, chromonic systems are closer to<br />
thermotropic systems than to conventional amphiphiles.<br />
In both cases, the driving force causing liquid crystalline<br />
phase formation is the face-to-face aggregation of molecules<br />
forming columns—and the geometrical aspects<br />
of the packing of these columns are more or less the<br />
same in the two cases—the difference being that in one<br />
case the columns lie in a sea of alkyl chains and in the<br />
other, they lie in a sea of water. I had expected that by<br />
now, chromonic counterparts of all of the thermotropic<br />
discotic phases would have been found. Bearing in mind<br />
the extensive literature of the dye industry concerning<br />
tilted stacks of dye molecules (J-aggregates), I find it<br />
surprising that there are, as yet, no well-authenticated<br />
tilted chromonic systems.<br />
In general, there is a strong tendency for chromonic<br />
molecules to aggregate into columns, even in very dilute<br />
solution—just as conventional lyotropic mesogens form<br />
micelles before a mesophase is formed w11,12x.<br />
Although there may be a threshold concentration before<br />
significant aggregation begins to occur, there is no<br />
specific optimum column length and, therefore no analogue<br />
of the critical micelle concentration (cmc) of<br />
Fig. 2. A snapshot plan view of the chromonic M phase. The array<br />
shown in this sketch has orthorhombic symmetry – but the rotational<br />
disorder of the columns between the three possible orientations (as<br />
indicated for the central column) leads to the phase having overall<br />
hexagonal symmetry. The hexagonal lattice spacing is approximately<br />
half the length of the molecule plus half the width of the molecule<br />
plus the thickness of the interlying water w1,4,10,29x. For the dye<br />
molecule shown in Fig. 3, this is approximately 24 A. ˚
482 J. Lydon / Current Opinion in Colloid and Interface Science 8 (2004) 480–490<br />
conventional amphiphiles. The term ‘isodesmic’ (first<br />
used in the study of the aggregation of nucleic acids in<br />
solution) has been applied to the steady build up of<br />
chromonic aggregates where the addition or removal of<br />
one molecule to a stack is always associated with the<br />
same increment of free energy w13,14x. This is in direct<br />
contrast with the situation for conventional amphiphile<br />
association, where the micelle represents a free energy<br />
minimum—and there is a cost to the system in having<br />
either larger or smaller units.<br />
A further fundamental distinction between conventional<br />
amphiphile and chromonic systems concerns what<br />
happens at the lower temperature limit of mesophase<br />
formation. In conventional amphilphiles, there are two<br />
micro-phase regions; the aqueous and the hydrophobic,<br />
aliphatic parts. As the temperature is lowered, the alkyl<br />
chain motion in the hydrophobic region usually freezes<br />
out, forming a gel phase. The system becomes too brittle<br />
to be able to pack into the micelles required for<br />
mesophase formation. This gives a lower temperature<br />
limit characterised by its Krafft temperature. In chromonic<br />
systems the opposite happens. Because of the<br />
absence of alkyl chains in chromonic systems (or at<br />
least the absence of significant lengths of alkyl chains),<br />
chromonic systems do not show a Krafft point and the<br />
lower temperature is limit is marked by the appearance<br />
of ice—usually a few degrees below 0 8C. Note that<br />
there is evidence that one can access monotropic chromonic<br />
phases at sub-zero temperatures by adding an<br />
antifreeze to the system w7,9x.<br />
Misciblity is a feature of liquid crystalline systems –<br />
and in general, an understanding of the rules which<br />
govern miscibility is crucial to our understanding of the<br />
factors which determine the dynamics of each type of<br />
mesophase. The chromonic analogue of miscibility is<br />
intercalation where guest molecules can be accepted<br />
randomly into chromonic stacks. Although there have<br />
been no extended systematic studies of chromonic miscibility<br />
it appears that this is as widespread as miscibility<br />
in other mesophase systems w15x.<br />
There is another related pattern of behaviour of<br />
chromonic mixtures (which is discussed in more detail<br />
below). This occurs where there is a strong preference<br />
for an ABAB alternating arrangement of the two components<br />
in every stack w47–53x. This occurs to such a<br />
pronounced extent that the alternating column must be<br />
regarded as the structural unit of the phase. Since at<br />
least some of these CPI ‘compounds’ give <strong>mesophases</strong><br />
with enhanced stability (and since the aromatic cores of<br />
the compounds in both families of mesophase are<br />
similar), it is an obvious suggestion that the search for<br />
similar effects in chromonic systems would be<br />
worthwhile.<br />
<strong>Chromonic</strong> systems can be doped with small soluble<br />
chiral compounds to give a chiral N phase (in an<br />
Fig. 3. The molecular structure of C.I. Direct Blue 67. This new dye<br />
forms a chromonic N phase of high order parameter and which can<br />
be dried down to give an aligned solid film. Matsunaga et al. w29x<br />
have shown that a highly patterned film can be produced by drying<br />
down the N phase on a photaligned command substrate as sketched<br />
in Fig. 5.<br />
analogous way to the chiral doping of thermotropic<br />
nematics). Since the twist produced is proportional to<br />
the concentration of the dopant, this property has been<br />
proposed as a practical assay for chiral compounds<br />
w7,9x. A new exploitation of the chirally-doped N phase<br />
is in compensating devices for TN cells as described<br />
below w38–40x.<br />
3. New chromonic materials<br />
The range of compounds which form chromonic<br />
phases now includes xanthoses (used as antiasthmatic<br />
drugs, azo dyes, cyanine dyes, nucleic acids (guanosine<br />
derivatives) and perylenes w16–26x.<br />
Over the last few years, reports of new chromonic<br />
<strong>mesophases</strong> have grown from a trickle to a stream.<br />
These include a report of a new metallo-mesogen and<br />
excitingly, a non-aqueous chromonic system (where the<br />
solvent is dimethyl formamide) w27,28x (Fig. 3).<br />
Significant amongst new chromonic materials is the<br />
●<br />
azo dye, C.I Direct 67 w29 x. This shows typical NyM<br />
phase behaviour promises to become a useful new<br />
chromonic compound. The chromonic phases formed by<br />
aqueous solutions of this dye were investigated by means<br />
of temperature-controlled X-ray diffraction, polarised<br />
light microscopy and UV–visible spectroscopy. The dye<br />
molecules form columnar aggregates, even at low concentrations.<br />
The structural study gave results very similar<br />
to those of earlier work on the INTALywater system<br />
w5,6,10x. As one would expect, the stacking repeat was<br />
3.4 A ˚ (and was found to be independent of concentration<br />
and temperature). The diameter of the column was<br />
found to be comparable with the length of the molecule—suggesting<br />
that the column is a unimolecular<br />
stack. One interesting feature of this investigation was<br />
the observation that the addition of a small amount of<br />
anionic surfactant (0.01% by wt.) was found to enhance<br />
the stability of the nematic phase (at the expense of the
J. Lydon / Current Opinion in Colloid and Interface Science 8 (2004) 480–490<br />
483<br />
Fig. 4. The production of an aligned dye coated polymer film using<br />
a ‘command plate’ produced by the Weigert effect. A spin-coated film<br />
of the azo compound is photaligned with a beam of plane polarised<br />
light to produce a ‘command plate’.<br />
M phase). Clearly at this concentration there is no<br />
suggestion of the added amphiphile having a direct<br />
structural effect on the mesophase such as coating the<br />
columns. The effect must be more subtle. Perhaps in<br />
some way it stabilises column ends or simply alters the<br />
chemical potential of the counter ions.<br />
Over the last 10 years, a photoalignment approach<br />
has been developed which appears to have the potential<br />
for achieving this w30–37x. This technique utilises the<br />
Weigert effect. This is the sensitivity of some photohemical<br />
reactions to the orientation of the plane of polarised<br />
light striking the molecule. Reactions for which the<br />
Weigert effect has been observed include photobleaching,<br />
photodimerization and photoisomerism. In the photoalignment<br />
of photoisomerisable molecules the final<br />
state of the sample has the molecular director aligned<br />
normal to the electric vector of the incident light (Figs.<br />
4 and 5).<br />
Azobenzene has been a favourite compound for producing<br />
aligned films using the Weigert effect. Unfortunately,<br />
it is only weakly absorbing in the visible<br />
wavelengths range and it is, therefore by no means<br />
ideal. There is a way round this problem, however. It<br />
has been found that a film of phoaligned azobenzene<br />
molecules is able to epitaxially align liquid crystalline<br />
phases. The photoaligned substrate can, therefore be<br />
used as a ‘command surface’, which is in turn able to<br />
direct the alignment if the mesophase. Photoinduced<br />
alignment of this kind was first demonstrated with<br />
thermotropic <strong>mesophases</strong> (using films of azodoped polymer,<br />
polymers with azobenzene side groups or polymers<br />
with cinnamic acid side groups). However, it also works<br />
for lyotropic phases and can be used to align the<br />
chromonic N phase.<br />
●<br />
In their recent paper, Matsunga et al. w30 x describe<br />
the production of a patterned film of dye using this<br />
approach. They used a striped template command surface<br />
prepared from the photoinduced alignment of a<br />
polyamide with azo side-groups. The chromonic N phase<br />
of the dye, C.I. Direct Blue 67 is aligned by this surface<br />
and then dried down to give a patterned film. They<br />
4. The production of patterned dye films<br />
In the production of optical elements such as polarisers,<br />
retarders and optical compensators, it is necessary<br />
for us to be able to control the alignment of birefringent<br />
material embedded in (or deposited on) a film. A variety<br />
of manufacturing processes have been tried, including<br />
classical mechanical methods such as stretching the<br />
film, shearing, rubbing the surface and newer approaches<br />
such as electric field poling. The disadvantage of all of<br />
these approaches is that they are only able to produce<br />
surface films with same alignment over the entire area<br />
of film being treated. What would be much more<br />
desirable is a technique which could align small areas<br />
of film in different orientations, ultimately giving us the<br />
ability to align individual pixels in any required<br />
orientation.<br />
Fig. 5. The epitaxial alignment of a chromonic N phase by a photoaligned<br />
command plate. (redrawn from Ref. w30x).
484 J. Lydon / Current Opinion in Colloid and Interface Science 8 (2004) 480–490<br />
Fig. 6. Conventional (uncompensated) twisted nematic cells in the on<br />
and off states. There are two forms of the twisted nematic cell: normally<br />
white (NW) and normally black (NB) cells – the difference<br />
lies only in the orientation of the upper polarising layer plate.<br />
The twisted nematic (TN) device continues to dominate<br />
the flat panel liquid crystal display market. However,<br />
it is not without its shortcomings. The<br />
characteristics of an ideal device are high contrast, a<br />
wide viewing angle, good colour rendition and a completely<br />
achromatic dark state. The standard (uncompensated)<br />
TN device fails to live up to every one of these<br />
ideals. In particular, the phenomenon known as ‘greyscale<br />
inversion’ can be severe. This arises where the<br />
contrast between ‘on’ and ‘off’ areas falls to zero and<br />
is then reversed, as the viewing angle is changed.<br />
The defects of the standard TN cell can, in some<br />
measure, be corrected by the addition of a compensator.<br />
This is an optical system, which matches the optical<br />
characteristics of the sample and reduces the contrast<br />
loss as the viewing angle is increased. An ideal compensating<br />
device would ‘correct’ the optics of both the<br />
‘on’ and ‘off’ states, but this is an over-ambitious target<br />
at the present time. Current compensators are passive<br />
devices, which are designed to correct only the more<br />
critical of the two states of the device. In an uncompensated<br />
TN cell there is both leakage of light through the<br />
dark state and a decrease of intensity of the light state.<br />
However, the effects of these deficiencies are not symmetrical<br />
and the leakage of light through the dark state<br />
is the more serious. Because of this, compensators are<br />
specifically designed to improve only the dark state<br />
optics.<br />
The structures of the two variants of the standard (i.e.<br />
non-compensated) TN cell are shown in Fig. 6. In a<br />
cell in the ‘off’ state, the twisting molecular alignment<br />
rotates the plane of polarisation of the light through 908.<br />
In the ‘on’ state, the molecules are realigned to give a<br />
homeotropic state where the molecular axes lie perpendicular<br />
to the cell surface. This arrangement does not<br />
change the polarisation state of the light. There are two<br />
geometries that are used in these devices—with the two<br />
polarisers lying either parallel or perpendicular. The<br />
parallel arrangement gives a ‘normally black’ (NB)<br />
device in the absence of a field and the perpendicular<br />
arrangement gives a ‘normally white’ (NW) device.<br />
Compensators have, therefore been devised to improve<br />
the optics of the ‘off’ state of the NB device and the<br />
‘on’ state of the NW device.<br />
were able to produce a solid dye film consisting of<br />
alternating 300-mm wide rows of orthogonally aligned<br />
dye material with impressively sharp-edged resolution.<br />
5. The use of planar and twisted lyotropic chromonic<br />
liquid crystal cells as optical compensators for twisted<br />
nematic cells<br />
Fig. 7. A more accurate view of the mesophase alignment of the NW<br />
cell in the ‘on’ mode. To a first approximation, the applied field aligns<br />
the mesophase in a homeotropic pattern as sketched in Fig. 6. However,<br />
molecules near to the surfaces tend to retain a parallel alignment<br />
and the phase adopts a complex splay pattern shown.
J. Lydon / Current Opinion in Colloid and Interface Science 8 (2004) 480–490<br />
485<br />
7. Compensating a normally white cell<br />
For a NW cell, the situation is more complex. In the<br />
dark ‘on’ state the director field is not perfectly homeotropic<br />
and the arrangement sketched in Fig. 6 is only<br />
an approximation to reality. In practice, the situation is<br />
more like that sketched in Fig. 7 where the molecules<br />
near to the upper and lower substrate surfaces retain a<br />
parallel alignment and, as the director field curves<br />
towards the homeotropic region in the centre, there is<br />
appreciable splay distortion. A plate compensating specifically<br />
for this splay has been developed by Fuji.<br />
In addition to the splay distortion, the optics require<br />
correction for birefringence and Lavetrovitch et al.<br />
●<br />
w40 x have explored the use of chromonic cells to<br />
compensate for the birefringence and twist. The layout<br />
of their complete device is shown in Fig. 9.<br />
Fig. 8. The design of a compensated NB cell (Lavrentrovich et al.<br />
w40x). Compensators have been added to improve the optics of the<br />
dark ‘off’ state. The twisted compensating cell is filled with a chirally<br />
doped N* phase, the compensating A-plate contains a parallel-aligned<br />
chromonic mesophase. (redrawn from Ref. w40x).<br />
6. Compensating a normally black TN cell<br />
The root cause of the optical problems of a TN cell<br />
is the large positive birefringence of the cell. One can<br />
improve the optical performance of a NB display by<br />
compensating this with a passive retarder. The compensating<br />
plate should have negative birefringence and a<br />
twisted structure that mirrors that of the cell in the ‘off’<br />
mode. An early attempt at constructing a compensator<br />
with these properties consisted of several superposed<br />
polymer films with negative birefringence. These were<br />
stacked in a twisted arranged to match the twist director<br />
twist of the cell in the ‘off’ state. More sophisticated<br />
compensators have been constructed by Laventrovitch<br />
●<br />
et al. using liquid crystalline phases w38–49 x. To<br />
counteract the positive birefringence of the nematic<br />
phase, phases with negative optical anisotropy are<br />
required. This suggests the use of thermotropic discotic<br />
and lyotropic chromonic phases—and both have been<br />
tried.<br />
The design of an experimental compensated NB TN<br />
●<br />
cell devised by Laventovitch et al. w40 x is shown in<br />
Fig. 8. Note that this employs a combination of a planar<br />
N-phase chromonic cell and a twisted N* chromonic<br />
cell to match the uncompensated optics.<br />
Fig. 9. The design for a compensated NW cell (Lavrentrovich et al.<br />
w40x). Compensators have been added to improve the optics of the<br />
dark, ‘on’ state. The Fuji plates compensate for the splay shown in<br />
Fig. 7. The compensating A-plates contain a parallel-aligned chromonic<br />
mesophase. (redrawn from Ref. w40x).
486 J. Lydon / Current Opinion in Colloid and Interface Science 8 (2004) 480–490<br />
I have given prominence to the use of chromonic<br />
compensators in this review. This was not done, because<br />
I believe that devices of the kind described using the<br />
chromonic solutions are immediately feasible for largescale<br />
commercial production. The narrow temperature<br />
range of the chromonic phase used would alone make<br />
this impracticable. The importance lies in the way it<br />
stresses the versatility of this family of <strong>mesophases</strong>.<br />
8. Complementary polytopic interaction (C.P.I.) in<br />
discotic systems<br />
The so-called p–p interactions which hold chromonic<br />
molecules face to face have been discussed by Hunter<br />
et al. w41–43x and Bates and Luckhurst w44x. They argue<br />
that these interactions are in fact a combination of van<br />
der Waals forces and electrostatic interactions and that<br />
no specific properties of p systems need be invoked. In<br />
recent studies of thermotropic columnar <strong>mesophases</strong>, in<br />
the search for enhanced electronic conductors, a phenomenon<br />
has been encountered which suggests that in<br />
certain cases, two different molecules can form 1:1<br />
‘compounds’ with enhanced mesophase-forming properties<br />
w45–53x. In these cases, the structural unit is<br />
thought to be the (AB) n column. The reason why these<br />
alternating columns are ‘better’ mesogenic units than<br />
those of either of the two separate species is not<br />
immediately evident. Some form of ‘bonding’ must be<br />
occurring between the two types of molecules, which is<br />
not describable in classical chemical terms. The interaction<br />
appears to be more subtle than a simple covalent,<br />
hydrogen bonding or electrostatic effect. There is no<br />
evidence that the electronic structure of either molecule<br />
is significantly disturbed and there is no detectable<br />
charge-transfer interaction. The explanation for the complementary<br />
nature of the two types of molecule appears<br />
to lie in the sum total of a large number of atom-byatom<br />
van der Waals type interactions. The term complementary<br />
polytopic interaction (C.P.I.) has been coined.<br />
Computer modelling of the interactions between the two<br />
types of molecule in such systems has been carried out<br />
using the XED program and the results appears to<br />
confirm this view.<br />
The two component phase diagram of two compounds<br />
which interact in this fashion, recently reported by<br />
●<br />
Boden, Bushby and Lozman w53 x is shown in Fig. 10.<br />
Note that one of these compounds is mesogenic on its<br />
own, and the other, although having a similar overall<br />
structure (with a polyaryl core and a halo of alky<br />
chains) is not. The thin vertical region at the centre of<br />
the diagram represents the 1:1 C.P.I. compound. The<br />
extreme narrowness of this single phase area implies<br />
that there is a very positive interaction between the two<br />
types of molecule and that we are dealing with a system<br />
qualitatively different to one based simply on the mutual<br />
solubility of the two component. Note in particular, that<br />
the discotic columnar temperature range is enhanced in<br />
both directions, with the mesophase extending to higher<br />
and lower temperatures than those of the pure mesogenic<br />
component. The result of computer modelling the docking<br />
of an ABA unit of the column using the XED<br />
program is shown in Fig. 11.<br />
The reason for highlighting a property of thermotropic<br />
mixtures in this review is that I can see no reason why<br />
such effects should not arise in chromonic systems—<br />
especially since in some cases, the core polyaryl parts<br />
of the molecules are the same. In the past, the suggestion<br />
that it ought be possible to convert intransigent, insoluble<br />
dyes into conveniently soluble <strong>mesophases</strong> by the<br />
addition of some magic colourless agent was greeted<br />
with dismissive scepticism by the (British) dye industry.<br />
Perhaps it now looks one increment more plausible.<br />
9. The future<br />
The development of chromonic mesohase studies has<br />
not proceeded in the way I had expected. Bearing in<br />
mind the large industry concerned with the production<br />
and use of dyestuffs for printing fabric and paper and<br />
the apparently widespread occurrence of chromonic<br />
phases amongst dyes, I had expected that over the last<br />
decade there would have emerged a large literature<br />
concerned with enhancing the solubility properties (i.e.<br />
the mesophase-forming properties) of dyes, the investigation<br />
of mesophase enhancing mixtures, the fine tuning<br />
of colour by the addition of non-dye chromonic additives,<br />
the specalist use of the alignment of <strong>mesophases</strong><br />
on prepared surfaces and with electric and magnetic<br />
fields for printed material—perhaps for high grade<br />
security printing such as banknotes, credit cards and<br />
identification. As far as I am aware, little of this has<br />
occurred. However, the production of aligned dye films<br />
has materialised (albeit requiring a command surface).<br />
In the previous review, I referred to two grails. The<br />
first was of these is the production of cheap electrically<br />
conducting organic material, the second, a viable lightharvesting<br />
device. With the development of techniques<br />
to control the alignment of chromonic phases to produce<br />
multilayer stacks of aligned phases w54x, and to produce<br />
highly-aligned films by drying down chromonic phases<br />
(enabling circuits to be produced by ink jet printer),<br />
both appear to have been brought a step closer.<br />
The use of chromonic phases as compensating plates<br />
for TN devices came as a surprise—but since an<br />
optically negative nematic phase was required, there<br />
were not a lot of alternative systems to choose from.<br />
Polymer films and discotic and chromonic mesphases<br />
are the obvious three—and all have been investigated.<br />
The major distinction between chromonic phases and<br />
thermotropic phases is of course the fact that they are
J. Lydon / Current Opinion in Colloid and Interface Science 8 (2004) 480–490<br />
487<br />
Fig. 10. The production of ABAB stacks by complementary polytopic interactions (CPI). In some mixtures of thermotropic discotic and ‘near<br />
discotic’ compounds, it appears that the 1:1 mixture gives a columnar phase with a wider temperature range (and enhanced conductivity and<br />
photoconductivity) than that of either of the two separate compounds. It is presumed that the two molecules complement each other in some way<br />
and that the enhanced stability of the mesophase is due to the enhance stability of the ABAB columns. This example of the CPI effect is for a<br />
binary system of a mesogen, hexaalyltryphenylene(HAT6) – based derivative and the non-mesogenic compound, hexakis(4-nonylphenyl)dipyrazino<br />
w2,3-f:2.3.hxquoinoxalene( PDQ9). The nematic phase of the CPI 1:1 mixture occurs as a narrow vertical band at the centre of the<br />
phase diagram. The shaded area at the bottom of this band indicates where the chromonic N phase of the CPI compound is in a glassy state.<br />
(redrawn from Ref. w53x).
488 J. Lydon / Current Opinion in Colloid and Interface Science 8 (2004) 480–490<br />
proposed). However, there are still books being produced<br />
which purport to give a broad overview of ‘soft<br />
matter’, which omit all mention of chromonics. A single<br />
large-scale commercial application of chromonics will<br />
of course change this picture overnight. The widespread<br />
technological use of chromonic systems has not yet<br />
materialised, but the continuing discovery of unique<br />
properties and versatility of these systems promises<br />
much. I would hazard the guess that wherever nanotechnology<br />
takes us, the liquid crystalline state will never<br />
be far away—and chromonic systems will have something<br />
vital to offer.<br />
Acknowledgments<br />
I am indebted to Richard Bushby, Owen Lozman and<br />
to Gordon Tiddy for their continuing encouragement.<br />
References and recommended reading<br />
● of special interest<br />
●● of outstanding interest<br />
Fig. 11. Orthogonal views of the optimum stacked columnar structure<br />
of a sequence of HAT1–PDQ1–HAT1 molecules as predicted by the<br />
XED program. The material in this figure is taken from Ref. w53x.<br />
The XED program is described in Refs. w41–43x and Vinter JC, Saunders<br />
MR: Ciba F Symp 1991, 158:249–265, Vinter JC: J Comp-Aid<br />
Mol Des 1994, 8:653–668, Vinter JC: J Comp-Aid Mol Des 1996,<br />
10:417–426.<br />
‘water based’. This should makes possible a marriage<br />
between established display technology and established<br />
biochemical techniques. I foresee the diagnostic biomedical<br />
tools of the next century operating via a combination<br />
of liquid crystal display technology and biochemical<br />
recognition.<br />
10. Conclusion<br />
The recognition of chromonic <strong>mesophases</strong> as an<br />
important and distinct class of lyotropic <strong>mesophases</strong> is<br />
still patchy. Papers are now appearing where the term is<br />
used without the authors feeling the need to define it<br />
(and to refer to the literature where the word was first<br />
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w49x<br />
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w53x<br />
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