Electric-field modulation of component exchange in constitutional dynamic liquid crystals

Article abstract of DOI:10.1002/anie.200600430

(Figure Presented) Playing the field: Application of an electric field to the thermodynamic equilibria of constitutionally dynamic sets of imines and amines that contain an imine with liquid-crystalline properties and a negative dielectric anisotropy leads to the amplification of the constituent that couples most strongly to the electric field, namely the liquid crystal (LC, see example). The field can thus induce a liquid to nematic phase transition.

Full text of DOI:10.1002/anie.200600430

Angewandte
Chemie
Dynamic Combinatorial Chemistry
DOI: 10.1002/anie.200600430
Electric-Field Modulation of Component
Exchange in Constitutional Dynamic Liquid
Crystals**
Nicolas Giuseppone and Jean-Marie Lehn*
Dynamic combinatorial chemistry (DCC) forms the covalent
domain of constitutional dynamic chemistry (CDC)[1,2] which
covers reversible constitutional reorganization on both the
molecular (covalent) and supramolecular (noncovalent)
levels.It gives access to all possible combinations of the
available components, which are connected through rever-
sible covalent bonds.It thus generates constitutional dynamic
libraries (CDLs) that, at thermodynamic equilibrium, display
all the constituents or leave some of them virtual, depending
on the conditions.[1a] Such systems can be driven either by
internal organization (self-recognition) or by external inter-
action (species binding).As a result, the equilibrium may shift
to the over-expression of selected products through an
adaptative process.To date, the discrimination between the
constituents of dynamic libraries has centered on the utiliza-
tion of target recognition as a driving force, in particular as a
result of applications in drug discovery.[3] In the course of our
[*] Dr. N. Giuseppone, Prof. Dr. J.-M. Lehn
Institut de Science et d’IngØnierie SupramolØculaires
8 AllØe Gaspard-Monge, BP 70028, 67083 Strasbourg (France)
Fax: (+33)390-245-140
E-mail: lehn@isis.u-strasbg.fr
[**] We thank Dr. Jean-Louis Schmitt for checking the experimental
results. We are grateful to Dr. Daniel Guillon, Dr. Jacques MalthÞte,
and Dr. Jacques Prost for their constructive remarks on the
manuscript.
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investigations toward the design of adaptative chemical
systems that respond to a wide array of environmental
parameters, we have become interested in the potential
offered by the possibility to drive constituent reorganization
and amplification/selection by component exchange, by
external physical (temperature,[4a] phase transition[5]), or
chemical (protons,[4] metal ions[4b,c,6]) triggers.Changes in
the composition of the members of a constitutional dynamic
library (CDL) represent an adaptation of the dynamic system
in response to the perturbation.Such effects are of special
interest in terms of developing dynamic materials that
respond to environmental effectors.[7,8]
To extend the range of physical external triggers for
inducing selection processes, we have explored the possibility
of using an electric field to influence the thermodynamic
equilibrium in a mixture of constitutionally interrelated
compounds.To this end, the development of dynamic liquid
crystals (LCs) appeared particularly well-suited for three
main reasons: 1) the wide use of LCs as materials, in
particular for display technology;[9] 2) the potential existence
of various LC phases—such as nematic, smectic, etc.—
depending on the constitution of the mixtures and molecular
structure of the components;[10] and 3) the well-known
behavior of LCs to become macroscopically oriented and
stabilized in either electric[11] or magnetic fields.[12]
We herein describe the perturbations imposed by an
electric field on mixtures of imines and amines containing an
LC-type imine with a negative dielectric anisotropy, namely
MBBA (1) or EBBA (5, Scheme 1).Two distinct phenomena
have been observed that are linked to the transitions between
isotropic and nematic phases.The first one consists of the
expulsion from the LC, upon application of an electric field,
of compounds that do not participate in the formation of a
nematic phase; the second is based on a direct effect of the
electric field on the thermody-
Figure 1. Representation of the evolution of the phase-transition tem-
perature (TN/I) of MBBA (1) as a function of increasing amounts of
various additives. Phase-transition temperatures were determined by
using variable temperature UV/Vis spectroscopy as the average of the
transitions recorded in the heating/cooling cycles of 10 mm thickness
films (l=400 nm and VDT =18C/min). NMR spectroscopic observa-
tion was used to ensure that equilibrium was reached.
close to room temperature.This differential behavior sug-
gested that it was the generation of recombinant imines that
led to marked changes in the value of TI/N
.
We then investigated whether an electric field would
influence the equilibria involving compounds 1, 2, 3, and 4 as
well as 5, 2, 3, and 6, respectively, where the imines 1 and 5 are
LCs, but 4 and 6 are not (Scheme 1) and should result in
changes in the TI/N value.
namic equilibria in a CDL by
the coupling of the field to the
LC-forming entity and its sub-
sequent stabilization/amplifica-
tion.
The effect of constitutional
modifications by component
Scheme 1. Component exchange between MBBA (1) or EBBA (5) and cyclopentylamine (2) leading to a
constitutional dynamic equilibrium with 4-butylaniline (3) and imines 4 or 6, respectively, modulated by
an applied electric field.
exchange on the isotropic/nem-
atic phase transition tempera-
tures (TI/N) of MBBA (1) was
investigated by following UV/
Vis spectroscopic changes upon introduction of various
The experiments were performed on thin films of 21-
(Æ5%) mm thickness between transparent indium tin oxide
(ITO) plates so that sufficiently high voltages could be
applied to the systems.Under these conditions, the maximum
voltage applied was 3.5 ” 104 VcmÀ1(Æ0.15”104 VcmÀ1)
which enabled a high resistivity (R ꢀ 6 ” 107 WcmÀ1) to be
maintained and to avoid fast degradation of the compounds as
well as heating-induced phenomena arising from the electric
current.[15] The phase transition could be observed both with
the naked eye (as a consequence of the opacity of the nematic
phase under a high electric field in the dynamic scattering
mode, DSM)[16] and by using a polarized light microscope
(Figure 2A).
amounts of several additives (Figure 1).[13]
The value of TI/N decreased linearly as a function of the
amount of additive and the slopes of the lines fall into two
sets.In one set are the additives which cannot lead to a new
imine by constitutional reorganization (triethylamine, cyclo-
pentanol, N,N-dimethylaniline) and where the addition of
15 mol% of compound results in a decrease in the TI/N value
to close to room temperature.The second set contains the
additives which can react with MBBA (1) by transimination
reactions[14] (cyclopentylamine, aniline, 2,4-dimethoxybenzyl-
amine) with formation of new imines, and where the addition
of only 3 mol% of compound is enough to give a TI/N value
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Figure 2. A) Left: Typical appearance of the ITO plates (7.25”2.5 cm) as a function of time in an experiment using MBBA (1) in the presence of
additives and under the influence of an electric field (when the applied voltage is superior to the minimum necessary for observing the changes
through the dynamic scattering mode[16]): top: liquid mixture; middle: coexistence between liquid and nematic phases; bottom: nematic phase
over the entire ITO plate. Right: Microscopy observation, using a polarized light microscope in transmission mode (”40), which shows the
expansion of the nematic phase into the liquid one under the influence of an electric field (E=0 V at the instant of the snapshot). B) Partial
400 MHz 1H NMR spectra showing the changes in chemical composition induced by the application of an electric field (E=3.5”104 VcmÀ1
(Æ5%)) at 248C for 2 h on the equilibrium described in Scheme 2 (red spectrum), compared to the control experiment without field (black line).
The molecular composi-
tion of the system described
in Scheme 1 at equilibrium
was obtained from the
1H NMR spectra of the solu-
tions of complete mixtures in
CDCl3 set between the ITO
plates, and by superimposition
of the NMR spectra of the
pure compounds.Under neat
conditions, the rate of the
transimination reaction was
slow enough (V0 = 1.84m hÀ1,
t
1/2 = 64 min; for a 1:2 ratio of
Figure 3. A) Effect of the strength of the electric field, at 22.58C after 24 h, on the equilibria described in
1:0.64 and for T= 22.78C) to
&
Scheme 1 for an initial molar ratio of MBBA:cyclopentylamine of 1:0.2Æ1.1% ( ) and for an initial molar
ratio of EBBA:cyclopentylamine of 1:0.25Æ1.1% (&)). B) Effect of the temperature, after 24 h, on the
equilibrium of the reaction described in Scheme 1 with MBBA (initial molar ratio of MBBA:2 1:0.2). D
shows the scale change for comparing the effect of electric field (A) and temperature (B) on the
equilibrium.
allow accurate measurements
by NMR spectroscopy.[17]
A
static electric field was applied
to the two dynamic mixtures
illustrated in Scheme 1 and the
evolution of the equilibrium amounts (namely, expression) of
MBBA (1) and EBBA (5) was followed as a function of field
strength (Figure 3).
The data showed a nonlinear displacement of the
equilibrium, which shifts towards the generation of MBBA
and EBBA, respectively, as the field strength increases.That
this change (about 6%) was not a result of a variation in
temperature is indicated by the fact that heating the ITO
plates (even by tens of degrees) led to a much smaller
displacement of the equilibrium (about 2%) than that
observed with the electric field.[15,18] Several other mixtures
involving aniline, benzylamine, isopentylamine, and allyl-
amine, and even libraries containing all these amines together
led to similar observations.In all these cases an accelerated
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loss of the volatile amines by evaporation occurred (Fig-
ure 3A), which led to irreversible systems.To confirm these
findings, we studied a nondynamic system consisting of a
mixture of MBBA (1) and cyclopentanol in which component
exchange does not occur; a similar enhanced loss of cyclo-
pentanol by evaporation under the influence of the electric
field was observed.[19] The behavior of the present systems
may be related to some electrohydrodynamic effects in the
DSM that result from the coupling of the LC molecules (of
negative dielectric anisotropy) to the electric field, and that
lead to an extrusion (and subsequent evaporation) of the
foreign (volatile) substances not involved in the LC mole-
cules.[20] It could also present interesting applications, for
example, for the controlled release of molecules or for the
design of sensors.
The next step was to design a fully reversible system to
examine the direct influence of the electric field on the
equilibrium itself.A proof of principle was finally obtained
using EBBA (5) and (the nonvolatile) 2-methoxyaniline (7;
b.p. 2258C) in the process described in Scheme 2, which led
through transimination to an equilibrating reaction with 3 and
the non-LC imine 8.
1
The H NMR spectra of mixtures of EBBA (5) and 7,
chosen so as to correspond to a TI/N value close to room
temperature (molar ratio 5:7 = 79.3:20.7 Æ 1.2%) were deter-
mined in the absence and in the presence of an applied
electric field (E = 3.5 ” 104 VcmÀ1(Æ5%)) after 2 h equilibra-
tion at 248C (Figure 2B).The relative variation of the
percentage of 4-butylaniline (3) with respect to the initial
molar ratio of 5:3 (93:7) for various strengths of the electric
field is shown in Figure 4, together with kinetic data for
reaching equilibrium in the presence of the electric field and
after switching it off.
Figure 4. A) Effect of the strength of the electric field, at 248C for 2 h
on the equilibrium described in Scheme 2 (molar ratio of EBBA:7
79.3:20.7Æ1.2%); each reaction was repeated three times and the
error bars represent values between Æ10%. B) Kinetics of the variation
of the equilibrium between ITO plates under a field E=3.5”104 VcmÀ1
~
(Æ5%; ; solid line curve); kinetics of equilibration after stopping the
*
electric field and dissolution (C=3.84m in CDCl3; , dashed line
curve); and kinetics of equilibration after stopping the electric field
The spectra in Figure 2B show an increase in the amount
of 5 and 7 at equilibrium under the applied electric field, and a
concomitant decrease of 3 and 8.The increase in 7 is of
particular importance: as it is nonvolatile relative to cyclo-
and dissolution, for an initial applied field of E=3.03”104 VcmÀ1
~
(Æ5%; , dashed line curve). The values are given using the relative
variation in the percentage of amine 3 (experiments with and without
&
field ( ; solid line curve)), and corrected for the dilution effect.
field, after switching it off, the initial
position of the equilibrium was
restored after about 6 h in a CDCl3
solution at 248C.The reversibility
between the ITO plates at 248C was
a very slow process in the absence of
DSM (more than several days), while
heating the plates without field at 458C
for 4 h led to the return of the equilib-
Scheme 2. Transimination reaction between EBBA (5) and 2-methoxyaniline (7) leading to an equilibrium
with 4-butylaniline (3) and imine 8, modulated by the presence of an electric field.
pentylamine (2), loss by evaporation cannot here be the
driving force for the evolution of the system, thus the changes
observed may be ascribed to the direct effect of the electric
field on the equilibrium.Moreover, there is an exponential
correlation between the strength of the field and the
equilibrium displacement (Figure 4A).Furthermore, the
field-induced perturbation was fully reversible, as shown in
Figure 4B by the evolution of the system as a function of time
under applied electric field, compared to the control experi-
ment, and after the field had been shut off.Whereas the
equilibrium was attained in about 2 h in the presence of the
rium to its initial position.Thus, a faster interconversion over
several cycles would require acting on both parameters:
electric field and temperature.
Finally, we investigated whether, in the absence of an
applied field, a temperature-induced phase transition would
by itself have an effect on the constitutional equilibrium
(Figure 5).
The changes in composition remained very minor com-
pared to those observed under an applied electric field, with
relative variations in the fraction of 4-butylaniline of less than
3% both inside a single phase and at the phase transitions.
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formation of the “fittest” constituent, that presenting the
strongest coupling to the field.[24] This approach may in
principle be applied 1) to more complex mixtures, in partic-
ular containing several different dynamic LC molecules, 2) to
systems involving different reversible covalent processes, as
well as 3) to supramolecular LCs or LC polymers.[8] The
phenomena discovered could also be of potential interest for
practical applications in various areas, such as the fine-tuning
of a given material or controlled release processes.
Experimental Section
General aspects: All reagents were purchased at the highest
commercial quality and used without further purification except for
EBBA (5) which was recrystallized by slow cooling from a hot
saturated solution in heptane, and for 2-methoxyaniline (7) which was
distilled two times, immediately prior to use.The phase-transition
temperatures (42.58C for MBBA and 78.58C for EBBA) agreed with
those reported in the literature. 1H NMR spectra were recorded on a
Bruker Avance 400 MHz spectrometer.To avoid the catalysis of the
transimination reaction, traces of acid in the deuterated chloroform
were removed by flash chromatography through neutral alumina
immediately prior to use.The ITO plates were purchased from
Aldrich (70–100 ohm; ref: 576352) and the electric field was applied
with a TTi EX752M multimode PSU generator.The resistivity of the
thin films was measured with a Keithley 6517A instrument.The
temperature of the samples was regulated by placing the ITO plates
on a thermostated surface, controlled by a Polystat cc2 Huber system,
and checked at the surface of the glass slides using a thermocouple
(Bead Probe Keithley 6517-TP).
Figure 5. Effect of the temperature, after two hours, on the equilibrium
described in Scheme 2 (molar ratio of EBBA:6 79.3:20.7Æ1.2%) and
under slight mechanical stirring; the error bars represent values
1
between Æ2.5%, which is close to the accuracy of the H NM R
method. The D symbol shows on the same scale the change of the
equilibrium in presence of an electric field (E=3.5”104 VcmÀ1
(Æ5%), after two hours, Figure 4).
When the same system was studied at higher temperatures,
the liquid to nematic phase transition was observed up to
558C, when the mixture starts losing its electric resistance.[21]
It is known that applying an electric field to genuine liquid
crystals with either positive[11,15b] or negative[22] dielectric
anisotropy leads only to a small change in the TI/N values
(typically ꢁ 1 K for an applied field of 2 ” 105 VcmÀ1).The
marked change in the TI/N values observed here must result
from a specific property of the present system, namely its
constitutional variation under application of an electric field.
Furthermore, when the mixture described in Scheme 2 was
studied under a field of 3.5 ” 104 VcmÀ1 (Æ 5%) for 2 h at a
5:7 ratio of 69.5:30.5 (Æ 1.3%), which does not allow a phase
transition from liquid to nematic at 248C, a comparable
change occurred in the composition at equilibrium (18% for
the relative variation of 3).This observation indicates the
coupling of EBBA (5) to the electric field even in the liquid
paranematic phase, as a result of the electric field induced
formation of cybotactic groups—small sets of locally organ-
ized molecules.
In conclusion, we have shown that the interaction between
an electric field and LC molecules having a negative dielectric
anisotropy can lead to two different phenomena: 1) a
purification of the system by extrusion of the molecules that
do not couple to the electric field, probably through electro-
hydrodynamic processes; and 2) a direct action of the electric
field on a constitutional dynamic equilibrium involving LC
molecules formed from components connected through
reversible imine-type bonds.[23] The amplified constituent is
that which couples the strongest to the electric field (the
liquid crystal), and this amplification can consequently result
in a phase transition from liquid to nematic.The processes
described here broaden the scope of CDC by demonstrating
the influence of a particularly interesting environmental
parameter, the electric field, and illustrate the adaptation of
the dynamic mixtures to a physical effector through the
General procedure for cross-over experiments and determina-
tions of thermodynamic and kinetic data: In a typical protocol the
compounds to exchange were mixed in a closed vial.The mixture was
heated up to 608C for 5 min, then cooled down to room temperature,
and left for 2 h at that temperature.Then, 38 mL (Æ 5%) of the neat
mixture was placed between two ITO plates by using a microsyringe,
and the glass plates were gently pressed to get a thin film (21 mm,
Æ 5%) over the entire surface (18.1 cm2; see Figure 2A).The plates
were thermostated, and then connected to the cathode and the anode
of the generator; electric fields between 0 and 75 V were applied (for
an applied field of 75 V, the experimental errors will lead to a value of
3.5 ” 104 VcmÀ1 (Æ 0.15 ” 104 VcmÀ1).After a given time, the electric
field was shut off, and the whole mixture contained between the two
plates was dissolved in CDCl3 (2 mL), immediately prior to 1H NMR
measurements (within 5 minutes).The
1H NMR spectra were
recorded until stabilization of the equilibria for both the experiment
with the field as well as the thermostated control experiment (without
field but with the same initial mixture).The values for the changes in
sample composition were obtained from comparison of the spectra
for the two corresponding experiments after the same time of
equilibration in solution.
Received: February 1, 2006
Published online: June 21, 2006
Keywords: dynamic combinatorial chemistry · electrochemistry ·
.
imines · liquid crystals · phase transitions
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Poulsen, J.K.M.Sanders, Curr. Opin. Chem. Biol. 2000, 4, 270;
c) S.J.Rowan, S.J.Cantrill, G.R.L.Cousins, J.K.M.Sanders,
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Communications
[2] a) J.-M. Lehn, Proc. Natl. Acad. Sci. USA 2002, 99, 4763; b) J.-M.
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[21] The coexistence between liquid-crystalline and liquid domains is
observed between the ITO plates.
[22] S.Dhara, N.V.Madhusudana, Europhys. Lett. 2004, 67, 411.
[23] For a theoretical study of the effect of an external electric field
on bond activation reactions, see: S.Shaik, S.P.de Visser, D.
Kumar, J. Am. Chem. Soc. 2004, 126, 11746.
[3] O.Ramström, J-.M.Lehn, Nat. Rev. Drug Discovery 2001, 1, 26.
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[5] S.Nampally, J-.M.Lehn, Proc. Natl. Acad. Sci. USA 2005, 102,
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[24] We thank a referee for comments concerning the origin of the
chemical effects observed by application of the electric field.In
particular, the “coupling to the field” merely indicates that the
observed effects result from the interaction of the electric field
with the liquid-crystalline species.Such coupling may involve
several factors/mechanisms.The energy necessary to displace
the equilibrium as described in Scheme 2 and Figure 4 is
calculated to be about DDG ꢂ 80 calmolÀ1.The electric inter-
action energy with the system is too weak to explain the
observations, even if a contribution from flexoelectricity[10] is
taken into account.When the field is applied close to the phase
transition, the effect could be in the correct range, but should
change on varying the temperature, which appears not to be the
case.The heat capacity associated with the isotropic/nematic
phase transition is known to be also in the range required to shift
the equilibrium,[25] however, the lack of a temperature effect
(Figure 5) indicates that it is not a major factor.Finally,
electrohydrodynamic instabilities observed in the DSM mode
are known to be caused by ionic currents;[26] the contribution of
the field heterogeneity related to the motions of ionic particles
throughout the sample could be more than enough to displace
the equilibrium with the experimentally measured values of the
conductivity.Ionic motions and the conceivable accumulation of
charges on the electrode surfaces would lead to high local field
values, capable of sufficient interaction with the liquid crystal to
result in its amplification from the DCL.
[6] N. Giuseppone, J.-L. Schmitt, J.-M. Lehn, Angew. Chem. 2004,
116, 5010; Angew. Chem. Int. Ed. 2004, 43, 4902.
[7] J.-M. Lehn in Supramolecular Science: Where It Is and Where It
Is Going (Eds.: R. Ungaro, E. Dalcanale), Kluwer, Dordrecht,
The Netherlands, 1999, 287.
[8] J.-M. Lehn, Polym. Int. 2002, 51, 825, and references therein.
[9] For a recent review on the use of liquid crystals for display
technology, see: P.Kirsch, M.Bremer, Angew. Chem. 2000, 112,
4384; Angew. Chem. Int. Ed. 2000, 39, 4216.
[10] P.-G. de Gennes, The Physics of Liquid Crystals Clarendon,
Oxford, 1973.
[11] a) C-.P.Fan, M.J.Stephen,
Phys. Rev. Lett. 1970, 25, 500; b) I.
Lelidis, M.Nobili, G.Durand, Phys. Rev. E 1993, 48, 3818; c) I.
Lelidis, G.Durand, Phys. Rev. E 1993, 48, 3822; d) I.Lelidis, G.
Durand, Phys. Rev. Lett. 1994, 73, 672; e) I.Lelidis, G.Durand,
Phys. Rev. Lett. 1996, 76, 1868.
[12] a) J.Tang, S.Fraden, Phys. Rev. Lett. 1993, 71, 3509; b) M.I.
ˇ
Boamfa, K.Viertler, A.Wewerka, F.Stelzer, P.C.M.Chris-
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[13] a) To improve the reliability of LC displays, some studies
addressed the influence of traces of water in mixtures of
imine-type liquid crystals.[13b] The presence of residual water
was demonstrated, as well as subsequent changes in the TI/N
values of the mixtures; however, the use of mixtures of LCs as
dynamic systems, has not been explored; b) H.Sorkin, A.
Denny, RCA Rev. 1973, 34, 308.
[25] R.Chang, F.B.Jones, J.J.Ratto, Mol. Cryst. Liq. Cryst. 1976, 33,
13 (DH(NematicÀIsotropic) = 0.10 kcalmolÀ1; T= 45.88C).
[14] The choice of transimination as the exchange reaction is of
crucial importance to avoid the presence of water (that would be
formed in amine–carbonyl condensations) in the present systems
so as to maintain high resistance to the electric current upon
application of a high voltage.For catalyzed and noncatalyzed
transimination reactions, see: N.Giuseppone, J-.L.Schmitt, E.
Schwartz, J.-M. Lehn, J. Am. Chem. Soc. 2005, 127, 5528, and
references therein.
[26] a) E.F.Carr, Mol. Cryst. Liq. Cryst. 1969, 7, 253; b) W.Helfrich,
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Phys. Part 2 1982, 21, L607; d) S.J.Tavener, T.Mullin, G.I.
Blake, K.A.Cliffe, Phys. Rev. E 2000, 63, 011708.
[15] a) Under these conditions the heating appeared negligible
(ca.1 8C measured at the surface of the ITO plates), in agree-
ment with literature results: b) W.Helfrich, Phys. Rev. Lett. 1970,
24, 201; c) A.J.Nicastro, P.H.Keys, Phys. Rev. A 1981, 30, 3156.
[16] G.H.Heilmeier, L.A.Zoanoni, L.A.Barton,
Appl. Phys. Lett.
1968, 13, 46.
[17] The rate of the reaction in a CDCl3 solution (C = 3.84m) was
found to be t1/2 = 60 min at 22.58C and t1/2 = 30 min at 308C,
which is also suitable for NMR measurements.
[18] The change in the direction of the displacement of the
equilibrium above 308C (Figure 3B, right-hand part of the
curve) was found to arise from evaporation of cyclopentylamine.
Thus, the effect of heating on the equilibrium is in the opposite
direction (left-hand part of the curve, Figure 3B) than that
caused by the field before evaporation takes over.
[19] For example, the use of a molar ratio of MBBA:cyclopentanol of
55:45 leads to an evaporation of 7.5% of the cyclopentanol
without field, and of 38.5% with a field of 3.5 ” 104 VcmÀ1, after
18 h at 238C.Moreover, if MBBA is replaced by pentaethylene
glycol (with no liquid-crystal properties and similar viscosity), no
differential evaporation was observed.
[20] The effect amounts to a sort of purification under high voltage;
for electrohydrodynamic effects in the MBBA-type nematic
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