Nonequilbrium Phase Transitions and Equilibrium Textures of Charged Chiral Rods (Fd-Viruses)

You might also like

You are on page 1of 10

J ournal of Physical Science and Application 4 (1) (2014) 26-35

Nonequilbrium Phase Transitions and Equilibrium


Textures of Charged Chiral Rods (fd-Viruses)
Kyongok Kang
Institute of Complex System (ICS-3), Forschungszentrum Juelich, Germany

Received: September 04, 2013 / Accepted: September 30, 2013 / Published: J anuary 15, 2014.

Abstract: Both non-equilibrium phase transitions and equilibrium textures of interacting charged chiral rods are explored, where
thick electric double layers are present in the suspensions of charged chiral fibrous (fd) viruses at a low ionic strength. We first start
with the electric phase/state diagram, illustrating dynamic frequency responses at the concentration of isotropic-nematic (I-N)
coexistence, leading to various field-induced phases/states. As a low frequency response, two sharp transitions of chiral-nematic
phases and dynamical states are induced, while as one transition is found to a homeotropic phases that is stabilized at a
high-frequency. The characterizations of field-induced phases/states, and critical slowing down behaviors in the non-equilibrium
criticality are discussed, by means of image-time correlation, dynamic light scattering and electric birefringence. For the equilibrium
phase behaviors, depolarized optical morphology is studied with their texture dynamics, as an increase of rod concentration for a long
equilibration time (80-100 h). Structure arrest has been observed by dynamic light scattering, above a glass transition concentration.
Below the glass transition concentration, chiral-nematic textures are equilibrated at low, but above the I-N coexistence concentration.
At higher, near to the glass transition concentration, another type of the equilibrium is reached as domain textures (of the helical
domains) . Whether there will be a thermodynamic access of the density in orientational domains in these equilibrated textures in the
interaction of charged chiral rods would be an interesting issue.

Key words: Electric-field induced phase transitions, equilibrium orientation textures, charged chiral rods, disorder-order transition,
lyotropic systems, image-time correlation, electric birefringence, dynamic light scattering.

Nomenclature
I: Transmitted intensity
t: Time
Greek Letters
v : Electric field frequency
t : Characteristic time constant
I: Decay rate
1. Introduction


The suspensions of charged fibrous chiral virus (fd)
are presented, here, for both non-equilibrium phase
transitions and the equilibrium state. It has been
known that fd-virus is a chiral DNA stand of the

Corresponding author: Kyongok Kang, Ph.D., research
field: soft condensed matter physics. E-mail:
k.kang@fz-juelich.de.
structure and the dynamics are studied in the single
molecular studies [1-5]. The bare length and diameter
of fd-virus is about 880 nm and 6.7 nm,
respectively [5]. Since the system is highly anisotropic,
the orientation order increases with an increase of
concentration. Depending on the ionic strength and the
concentration of particles, several interesting liquid
crystalline orders are observed in the equilibrium
phase behaviors, at higher ionic strengths [6-9]. At a
low ionic strength, relatively thick electric double
layers are present due to the dissociation of fd-coat
proteins that are on the surface of fd-virus [10-13].
Then the system exhibits a good model system for
charged colloidal rods. The physical dimension of
fd-virus is dependent on the ionic strength, such that
the effective diameter increases with lowering an ionic
strength. The analytic concentration of
DAVID PUBLISHING
D
Nonequilbrium Phase Transitions and Equilibrium Textures of Charged Chiral Rods (fd-Viruses)

27
Tris/HCl-buffer of 0.16 mM (of pH value of 6.8) is
used, here, corresponding to the Debye length of 27
nm [11, 14]. Suspensions of various fd-concentrations
are prepared from a concentrated stock sample of 22
mg/ml that is dialyzed against a Tris/HCl buffer. The
concentrated stock is then diluted with the buffer that
is osmotically balanced with the suspensions.
Typically, for low buffer concentrations, the
contribution to the actual ionic strength from the
dissolved carbon dioxide in air cannot be neglected. A
detailed analysis of the effect of dissolved carbon
dioxide on both ionic strength and pH can be found in
the Appendix D in Ref. [14]. The isotropic-nematic
(I-N) coexistence concentration for the above ionic
strength is then obtained as 1.5-3.4 mg/ml [11], which
is far crowded compared to an overlap concentration
(of 0.0076 mg/ml). Also the glass transition
concentration is found, independently, as 11.7 mg/ml,
at far above the I-N two-phase coexistence
concentration [15, 16].
Here, in this paper, the non-equilibrium phase
transitions are presented in the electric-field induced
phases/states, where the concentration is chosen as the
isotropic-nematic coexistence (of 2.0 mg/ml). Several
phase/ states are induced in an AC electric field, as the
dynamical frequency response is revealed in the
system. For the equilibrium state, in the absence of the
external electric field, higher concentrations (below
the glass transition concentration) are used to explore
the equilibration of the orientation textures for
different waiting times. When the concentration is far
above I-N coexistence, glass transition is found as the
initial caging via structural arrest, where it has shown
clearly the propagation of a mechanical flow in
microscopic particle dynamics, as well as the freezing
of texture dynamics [15, 16].
However, at the concentration below the glass
transition, different orientation textures are
equilibrated, as an increase of the concentration,
disregard of the same equilibrium time (about 80-100
hours). The concentration-dependent orientation
textures are then interesting subjects to discuss in the
equilibrated bulk elasticity and two dynamical modes
(of fast and slow) that are observed in the microscope
particle dynamics in dynamic light scattering. On the
contrary, near the glass transition concentration has
shown that the elasticity is diminished, due to a partial
freezing of the elasticity in thermal fluctuations [16].
It is the particular aim of this paper to discuss the
relation between non-equilibrium phase transitions
and the equilibrium state, such that how the twist
elasticity can play a delicate role to orientational
ordering by either an external field or the waiting time.
Furthermore, the common feature of chiral-nematic
phases, observed in the system of many interacting
charged chiral fibrous viruses (fd) is beneficiary to
access in experiments for exploring both features on
out-of-equilibrium and equilibrium states.
The paper is consists of the brief description of
experimental setups for both non-equilibrium and the
equilibrium state in Section 2. Overview of the
experimental results on non-equilibrium phase
transitions are listed as optical pitch variance,
electric-field induced criticality via image-time
correlation spectroscopy, microscopic particle
dynamics and electric birefringence in Subsection
3.1-3.4, respectively. Also the equilibrium texture
dynamics are discussed by means of both image-time
correlation spectroscopy and dynamic light scattering
in Subsection 3.5.
2. Experiments
The overview of experimental setups are presented
to explore both non-equilibrium and equilibrium state
in Fig. 1: Non-equilibrium phase transitions are
obtained with an in-situ electric-cell, in the middle (as
labeled 1), together with the characterization of
dynamic light scattering (as 2), image-time correlation
functions (as 3), and the electric birefringence (as 4) in
Fig. 1a. The brief scheme of an experimental setup
for the equilibrium texture dynamics is shown in
Fig. 1b.
Nonequilbrium Phase Transitions and Equilibrium Textures of Charged Chiral Rods (fd-Viruses)

28
4
2
3
1
(a)
(b)

Fig. 1 Overview of the experimental setup: (a) In-situ
electric cell -1, small angle vertical dynamic light scattering
-2, image-time microscopy -3, and electric birefringence-4,
and (b) Equilibrium texture dynamics setup.

2.1 In-Situ Electric-Cell
A homemade optically transparent electrical cell is
used to facilitate imaging through a microscope (in a
red circle in Fig. 1a), birefringence measurements, and
dynamic light scattering experiments. Commercially
available custom-designed ITO coated float glass
(from Przisions Glas und Optik GmbH) is used. A
sinusoidally varying electric potential is then applied
to the electrodes. The two glass slides are held apart
by an insulating rectangular PTFE teflon ring
film-spacer (Armbrecht and Matthes GmbH, AR5038
and AR5038GP), within which the sample is
contained.
The detailed descriptions of instrumentation can be
found in Ref. [17]. For the equilibrium texture
dynamics, a brief scheme of experimental setup is
shown in Fig. 1b, where the beam shutter (before
CCD camera, 5) is particularly incorporated with the
automated image-time data flow. In the image-time
correlation spectroscopy, the optimization of field of
view and time binning is required to get a reasonable
correlation function and an appropriate statistical
background in the image-time correlation
functions [17, 18].
2.2 Image-Time Correlation Spectroscopy
To perform the image-time correlation spectroscopy,
the time-lapsed images are collected. For an
electric-field included dynamical states, the in-situ
electric cell is loaded on to the inverted optical
microscope (Carl Zeiss, Axiovert 40CFL model). The
direction of the incident light is always along the
external electric field, i.e., normal to the two ITO
substrates. In order to probe local orientational order,
two crossed polarizers are used, together with
differential interference contrast (DIC) to enhance the
optical contrast (PlasDIC (LD A-Plan 40x) from Carl
Zeiss, Axiovert 40CFL). Transmitted light images are
collected with a CCD camera (AxioCam Color
A12-312). Since the dimensions of morphologies are
of the order of tens of microns, we have chosen a
low-magnification 10X objective lens (NA 0.30 EC
Plan-Neofluar) to probe a relatively large field of view
while the electric field is applied. TheAXIOVISION REL.
4.6 software (from Carl Zeiss) for image data
acquisition (black/white images up to 16 bit and color
images up to 3 by 16 bit).
For the study of an equilibrium state texture
dynamics, a commercially available round Hellma
glass cuvette (of diameter of 20 mm and thickness of
1 mm) is used to load the sample. The cuvette is
placed between crossed polarizers to visualize the
birefringent orientation textures, together with a
telescopic lens. Slow time-lapsed images are recorded
with the synchronized beam shutter to calculate the
image-time correlation functions.
2.3 Small Angle Vertical Dynamic Light Scattering
For an incident laser beam, a 35 mW He-Ne (J DS
Uniphase 1145P, 633 nm wavelength) is used as
perpendicular to the electric cell and along the
Nonequilbrium Phase Transitions and Equilibrium Textures of Charged Chiral Rods (fd-Viruses)

29
external electric field direction. Two mirrors are used
to align the incident beam onto a vertical stage. A
rotation stage (NanoRotator, Melles Griot) is used as a
goniometer, which is controlled by the software
stepper motor controller (APT, Melles Griot,
17BSC002).
For the vertical alignment of an optical path, two
pinholes and a photon detector are mounted on an
optical rail. The scattered light is then collected
though an optical fiber that is connected to an
avalanche photo diode (APD) detector.
ALV-5000/EPP multiple tau digital real time
correlator (ALV-GmbH) is used for computing the
photon correlation functions.
An essential element of the vertical small angle
(5-10) DLS is the achromatic lens (a focal length of
75 mm) in the detection side, to probe the sample in
the bulk scattering volume, i.e., away from the surface
of the substrates. The sample-mount is also situated on
a 45 vertically adjustable micrometer stage to
optimize the sample height. Both VV- and VH-mode
of dynamic light scattering are possible. In particular,
at very small angles (less than the scattering angle of
20), the scattering geometry is as the wavevector of a
perpendicular to the sample substrates is probed.
2.4 Electric Birefringence
The alignment of particle orientations are employed
by the electric birefringence setup: A laser beam
passes through a Glan-Thompson polarizer, which is
oriented at 45 with respect to the direction that is
perpendicular to the plane, where the entire optical
train can be rotated. A QWP (quarter-wave-plate) is
positioned, with one of its optical axes parallel to that
of the polarizer. Then the transmitted intensity is
measured as the orientation of a Glan-Thompson
analyzer. BSC002 dual channel APT stepper motor
controller (Melles Griot) is connected to a micro
stepping stage, in a parallel operation with the
Hamamatsu photosensor tube (H7468-20). The
photosensor module is incorporated with a
photomultiplier (PMT) to convert into a 12-bit digital
data for the data transfer to a PC by RS-232 interface.
In this way the transmitted intensity can be collected
of 0.28 at a time step (of ~0.36 s).
3. Experimental Results
3.1 Electric-Field-Induced Phase/State Diagram
Electric-field induced phase/state diagram is
presented with the depolarized optical morphology, as
the applied electric field amplitude and the frequency
in Fig. 2, for the concentration of 2.0 mg/ml, which is
the I-N coexistence concentration. The solid lines are
shown as the sharp phase transitions, and dashed ones
for the gradual change.
The depolarized optical morphology of the given
concentration (in the absence of field) is shown in the
bottom right image of Fig. 2, where the large blurry
nematic domain is in the isotropic background. As an
increase of field amplitude at a low frequency,
chiral-nematic phases (at the blue transition line) and
dynamical states (at the red transition line) are induced,
while as the homeotropic, H-phase is induced at high
frequency.
The brief summary of field-induced phase
transitions is follows: At low frequency by increasing
the field amplitude, two sharp transitions of entering


Fig. 2 The electric field induced phase/state diagram and
their depolarized optical morphology.
Nonequilbrium Phase Transitions and Equilibrium Textures of Charged Chiral Rods (fd-Viruses)

30
chiral-nematic phases (as N
*
, N
D
*
) and dynamical
states (as D
s
, D
F
) are found. However at higher
frequency, the only one phase transition is found (as N
H).
Depending on the frequency, dynamical responses
are then shown in Fig. 2, such as the electrode
polarization (at very low frequency range, below
60-100 Hz), the critical frequency (at pink region,
around 400-800 Hz), and the electro-osmotic flow (at
higher frequency range, above ~1 kHz) [11].
Field-induced critical point is then explored in terms
of the divergence of time and domain size in
melting/forming of small nematic domains in
dynamical states [19]. Also the field-induced
phase/states are unique in the sense that they exist
independently with different pathways to reach.
Detailed characterization of each phase/states and the
transition lines are presented in Ref. [11].
The dynamics of melting and forming of nematic
domains in the dynamical states is analyzed by
image-time correlation spectroscopy. There is a
discontinuity found at the N
D
*
D
s
transition line
that is due to the 2nd sharp transition of the
microstructural ordering, companied by the
disappearing of the chiral-nematic texture and entering
the small nematic domains in dynamical states,
measured, independently by dynamic light
scattering [11]. Furthermore, much critically slowing
down microscopic dynamics is found at near the
transition line. High-frequency stabilized hometropic,
H-phase has itself shown for two dynamical modes (of
fast and slow mode) [20]. This is also agreed with
dynamic light scattering results of the equilibrium
state at low, but upper binodal concentrations, where
the chiral-nematic textures are equilibrated.
3.2 Optical Pitch Variance at Electric-Field-Induced
Chiral-Nematic Phases
Above the threshold field amplitude, at a low
frequency, chiral-nematic phase is induced. Further
increasing of field amplitude (see the blue arrow in
Fig. 2), the optical pitch variance decreases
systematically as an increase of field amplitude, which
is indicated in Fig. 3. The Fourier transforms of
morphologies have also shown in the increase of
magnitude of wavenumber, disregard of the slight
orientations of short-ranged ordering. The optical
t -pitch is shown to diverge at the N N
*
transition
line as an increase of the field amplitude. The pitch
saturates at higher field amplitude, where the
N
D
*
-phase is induced (as 10 m).
Note that chiral-nematic phase is induced at
threshold field amplitude, with much broadness of the
pitch variance that has shown, and followed by the
decrease of pitch as an increase of field amplitude.
Also the apparent true pitch is indicted as a solid
line where the largest value of the pitch, since only the
projection of chiral pitch can be measured in
depolarized morphology. However, at higher
frequency, for a given field amplitude, the optical
pitch seems to diverge again, as
*
N -phase is
approached. This suggests that the range of the
electrostatic interactions is sensitive with the salt
concentration and the external field strength.
3.3 Field-induced Criticality in Dynamical States
Several transition lines of field-induced phases and


Fig. 3 Optical pitch variance as a function of the field
amplitude.
Nonequilbrium Phase Transitions and Equilibrium Textures of Charged Chiral Rods (fd-Viruses)

31
states meet at a critical point, in Fig. 2, and mimic the
field-induced criticality in a sense that there is a
divergence of a length- and time-scale [19]. Either an
increase of field amplitude or the frequency, slow
dynamical state becomes fast, as one can see in the
phase/state diagram (Fig. 2). Here, image-time
correlation spectroscopy is used to study the
field-induced critical slowing down behaviors in
dynamical states.
To determine the non-equilibrium criticality in
field-induced dynamical states, where the image-time
correlation function is defined as Eq. (1):
2
( ) ( ) (0) (0)
( )
( ) ( )
V
I t I t I I
C t
I t I t
( (

=
(

(1)
where, (I(t)) is the average of transmitted intensity
throughout the overall pixels. Detailed optimization of
the region of view and time binning is discussed in
Refs. [17, 18]. The examples are shown in Fig. 4, for
the divergences of time- (upper) and length-scale
(lower) of melting/ forming nematic domains (size of
few tens of microns), respectively.
To extract, precisely, the field-induced criticality,
non-critical background value ought to be subtracted,
which is typically shown as the steady value (see the


Fig. 4 Field-induced criticality by an image-time
correlation spectroscopy: the divergence of time-(upper)
and length-scale (lower) of meting/forming of nematic
domains are shown, respectively.
left panels in Fig. 4). Also a critical parameter (either
in frequency or field amplitude) can be determined,
independently, by finding the inverse values of
observables (time and domain size) becomes zero for
the divergence, shown in the middle of Fig. 4. The
rightest panels have shown that field-induced
criticality in both time- and length- divergences. Then
one can finally find as:
( ) ~ 1
b
C
v
t

v
t v t
v

| |

|
\ .
(2)
where,
v
t

is the exponent of a time observable


varied by the frequency parameter. Both power law-
and logarithm-divergences have been found in time-
and length- scale, respectively [19].
Much slowing divergence is observed at the critical
frequency by lowering field amplitude, as compared to
the increase of the frequency at critical field
amplitude [19]. Also weaker divergence is present at
off-critical approach, where the field amplitude is low
and away from the critical point, the characteristic
time diverges logarithmically, while the domain size
remains finite. Recently, the microscopic origin and
semi-quantitative theory have been provided for the
dynamical states, attributed to the experimentally
found limit cycle of field-induced
dissociation/association of condensed ions [21].
3.4 Field-induced Orientation and Particle Dynamics
in Homeotropic Phase
At a relatively high frequency, homeotropically
aligned, so-called H-phase is induced in the
phase/state diagram. The electric birefringence and
dynamical light scattering are also performed to
characterize the H-phase itself [17, 22].
Field-induced orientation is found as independent
on the pathways, as shown in the left of Fig. 5, which
indicates that this is due to the influence of an
electro-osmotic flow. Also much different particle
dynamics is observed at higher frequency, H-phase, as
presented in the middle and right of Fig. 5, for
off-critical and critical path approaches, respectively.
Nonequilbrium Phase Transitions and Equilibrium Textures of Charged Chiral Rods (fd-Viruses)

32
Here, clearly much slowing down behaviors is shown
in path (iii) (see the pink region in the right of Fig. 5),
at critical amplitude by lowering the frequency. This
is due to the transient behaviors of sudden rise of
extended blurry regions (in polarization state), as a
dynamic frequency response near to the critical
transition, bringing the most fd-rods become to align
to the planar scheme [22].
The reason for showing different microscopic
dynamics, between off-critical and critical behavior, is
related to the interaction among particles as the
location of a critical point in phase/state diagram. Also
two dynamical modes are found by the dynamical
light scattering in H-phase, which indicates the
diffusivity of charged chiral fd-rods is shown
collectively, as either parallel or perpendicular motion
of the averaged director field [20]. For lower ionic
strength at a given same fd-concentration, thermal
fluctuation is hindered to an extent as compared to the
interaction of chiral nature of particle plays a role.
3.5 Equilibrium Orientation Texture Dynamics and
Architects of Helical Domains
In the absence of an external electric-field, and an
increase of concentration, the equilibrium orientation
textures are also studied. The glass transition exists at
far above the I-N coexistence concentration, where the
orientation texture freezes in and structural arrest
occurs in particle dynamics [15, 16]. Image-time
correlation spectroscopy is used to obtain the kinetics
of the orientation textures and to determine the
equilibrium time.
First, time-lapse depolarized optical morphology is
collected, in every 10 minute for 1 week long (168 h)
and broader field of view as 7 7 mm
2
. Typical
performance of image-time correlation functions for a
low concentration, are shown in Fig. 6a, at different
waiting times. The decay rates are obtained from the
initial slope of these correlation functions in Fig. 6a.
The time to reach the equilibrium is then obtained as
the lowest plateau value in the decay rates, which
turned out to be 80-100 h of waiting time.
At this low (but still above the I-N coexistent)
concentration of charged chiral fd-rods, the
chiral-nematic textures are equilibrated as a bulk
orientation. Interestingly, the equilibration time is
found as independent of the concentration of chiral
fd-rods, below the glass transition concentration,
however, the equilibrium orientation textures can be
as distinguishably different [15, 16]. Fig. 7 has shown
the comparative orientation textures, as an increase of

10
0
10
1
10
2
10
3
10
4
0.0
0.5
1.0
C(t)
t [ms]
n
path (ii)
10
-1
10
0
10
1
10
2
t [s]
E=3.52 V/mm
n
path (iii)
0 2 4
-1.5
-1.0
-0.5
0.0
DE [V/mm]
a D
E
n
(ii)
(iii)
(i)

Fig. 5 Orientation order (left) and microscopic dynamics
(middle and right) in field-induced homeotropic, H-phase.

5 hours 7 9
15 50 100
7 mm
1/tw [1/hours]

Fig. 6 Slow orientation texture dynamics (upper) and the
image-time correlation functions (a), and the decay rates of
texture dynamics (b).

Nonequilbrium Phase Transitions and Equilibrium Textures of Charged Chiral Rods (fd-Viruses)

33
the concentration, in both Fourier Transforms and the
real space. Here, at two lower concentrations, one is
the chiral-nematic textures (of ~100 um pitch) are
equilibrated (in 3.8 mg/ml), and the other has shown
an existence of the mechanical kink (as 4.5 mg/ml)
among the neighboring chiral-nematic textures due to
the differences on pitch length. However, at two
higher concentrations, the equilibrated orientation
textures are consisted of much smaller length scale,
helical domains (of pitch 10 um), which have shown
no secondary FT peaks. Furthermore discussion on
this subject will be reported separately.
Thus, for the intermediate concentration, after the
existence of a mechanical kink, the chiral-nematic
texture becomes unstable, and qualitatively different
orientation textures are equilibrated. As once can see
in Fig. 7, two higher concentrations are even
equilibrated as different length scale textures, where
the zooming view of the 1 mm
2
, shown in the bottom
of Fig. 7. It has clearly shown the helical domains of
different helical axes. This strongly suggests that the
existing helical domains are then responsible for the
slow dynamics of equilibrium states, below the glass
transition concentration. This is also a good agreement
with on the dynamic light scattering results [15, 16]. An
example is shown in Fig. 8, where the time-averaged
intensity autocorrelation function are shown for a
fd-concentration of 3.64 mg/ml for different waiting
times (of up to ~113 h), with the duration time (of 3 h)
and 3 independent measurements for each time
correlation function. For the non-ergodic
ensemble-averaged intensity correlation functions, the
sampling of different scattering volumes, are discussed
separately in Ref. [16].
Thus, the suspension of charged chiral fibrous virus
(fd) is used as a good lyotropic model system for
studying the electric-field-induced phase/state
transitions, field-induced criticality, and slowing down
behaviors in the equilibrium phase behaviors. It is
found as a common feature of the orientation order
in the polarization, between the electric-field induced
[fd] = 3.8 mg/ml 4.5 mg/ml 7.3 mg/ml 11.1 mg/ml

Fig. 7 Equilibrated orientation textures and ordering in
Fourier- and real-space at different concentrations of
chiral-fd rods. The helical domains at the higher
concretions are shown in depolarized morphology (field of
view is 1 mm
2
) within the equilibrated textures.

10
-4
10
-3
10
-2
10
-1
10
0
10
1
10
2
10
3
0.0
0.5
1.0
C(t)
t [s]

Fig. 8 Time-averaged intensity autocorrelation functions
of dynamic light scattering result, is shown as different
waiting time, for the fd-concentration of 3.64 mg/ml, where
the chiral-nematic textures is equilibrated.

chrial-nematic phases and the equilibrated
chiral-nematic texture as a stable state, where the
concentration is low and near to the I-N coexistence.
The microscopic dynamics measured by dynamic light
scattering has shown evident existence of two
dynamical modes, indicating the elasticity is present
in the microscopic particle dynamics, observed
chiral-nematic phases.
Nonequilbrium Phase Transitions and Equilibrium Textures of Charged Chiral Rods (fd-Viruses)

34
Based on the orientation orderings of many
interacting charged chiral fd-rods, the twist
elasticity may play a subtle role in collective
behaviors in both non-equilibrium and equilibrium
states. Particularly where the concentration is coupled
with the orientation order, the bulk elasticity can be
slightly deformed with the additional term of twist
term, as above the nematic phase, entering a
chiral-nematic phase. This can be also influenced by
the salt concentration as well. At even higher
concentrations, for the equilibrium state, other types
of the orientation textures are found, as so-called
x-pattern and domain-textures [16]. Whether these
bulk equilibrium states can be interpreted as
hierarchical chirality or not would be an interesting
discussion to be followed up. Further development of
the elasticity theory of interacting charged chiral rods
would be then left a challenging task in the near
future.
Therefore, non-equilibrium phase transitions turned
out to be somewhat beneficiary for a given I-N
coexistence concentration, to realize the potential
phases/ states that are exhibited in the system, by
adjusting the conveniently chosen external parameters,
as compared to the equilibrium phase behaviors. For
instance, when the concentration is low, as I-N
coexistence, the order-disorder transition can be
responsive to the external field, however in an
equilibrium state; the only working parameter is the
waiting time (or the sedimentation velocity) for a
given concentration. Whether there will be some kind
of thermodynamic access of charged chiral rods in
disorder-order, and continuous phase transitions via
orientation orders or not would be a fundamental
issue.
Although the relation between the non-equilibrium
and equilibrium can be a difficult question to be
answered, the critical divergences of correlation
length and relaxation times in electric-field induced
criticality and phase transitions, in our system, has
shown quite similarity of the criticality, and collective
orientation orders in the absence of the external field.
Acknowledgments
The author thanks to Dr. H. Kriegs for his
assistance on the data processing in an image-time
correlations spectroscopy, and Prof. J . K. G. Dhont for
his scientific interests on this work.
References
[1] J .J . Lipka, S.J . Opella, J .S. Wall, Visualization of
polymercurimethane-labeled fd-bacteriophage in the
scanning transmission electron microscope, Science 206
(4425) (1979) 1419-1421.
[2] T.A. Cross, S.J . Opella, NMR of fd coat protein, J ournal
of Supramolecular Structure 11 (2) (1979) 139-145.
[3] G.M. Gall, T.A. Cross, J .A. Diverdi, S. J . Opella, Protein
dynamics by solid state NMR: Aromatic rings of the coat
protein in fd bacteriophase, Proceedings of the National
Academy of Sciences 79 (1) (1982) 101-105.
[4] P. Schwind, H. Kramer, A. Kremser, U. Ramsberger, I.
Rasched, Subtilisin removes the surface layer of the
phage fd coat, European J ournal of Biochemistry 210 (2)
(1992) 431-436.
[5] J . Newman, H.L. Swinney, L.A. Day, Hydrodynamic
properties and structure of fd-virus, J ournal of Molecular
Biology 116 (3) (1977) 593-606.
[6] Z. Dogic, S. Fraden, Cholesteric phase in virus
suspensions, Langmuir 16 (2000) 7820-7824.
[7] E. Grelet, S. Fraden, What is the origin of chirality in the
cholsteric phase of virus suspensions?, Phys. Rev. Lett.
90 (2003) 198302.
[8] Z. Dogic, S. Fraden, Development of model colloidal
liquid crystals and the kinetics of the isotropic-smectic
transition, Philos. Trans. R. Soc., A 359 (2001) 997-1015.
[9] S. Fraden, Phase Transitions in Colloidal Suspensions of
Virus Particles, in Observation, Prediction and
Simulation of Phase Transitions in Complex Fluids,
Kluwer Academic Publishers, Dordrecht, 1995, Vol. 460,
NATO-ASI-Series C, p. 113.
[10] K. Kang, J .K.G. Dhont, Double-layer polarization
induced transitions in suspensions of colloidal rods, Eur.
Phys. J . E. 84 (2008) 14005.
[11] K. Kang, J .K.G. Dhont, Electric-field induced transitions
in suspensions of charged colloidal rods, Soft Matter 6
(2010) 273-286.
[12] K. Zimmermann, J . Hagedorn, C.C. Heuck, M. Hinr-
ichsen, J. Ludwig, The ionic properties of the filamentous
bacteriophage Pf1 and fd, The J ournal of Biological
Chemistry 261 (1986) 1653-1655.
Nonequilbrium Phase Transitions and Equilibrium Textures of Charged Chiral Rods (fd-Viruses)

35
[13] J .K.G. Dhont, K. Kang, Electric-field induced
polarization of the layer of condensed ions on cylindrical
colloids, Eur. Phys. J . E. 34 (2011) 40.
[14] K. Kang, A. Wilk, A. Patkowski, J .K.G. Dhont, Diffusion
of spheres in isotropic and nematic networks of rods:
Electrostatic interactions and hydrodynamic screening,
J ournal of Chemical Physics 126 (21) (2007)
214501-(1-17).
[15] K. Kang, J .K.G. Dhont, Glass transition in suspensions of
charged rods: Structural arrest and texture dynamics,
Phys. Rev. Lett. 110 (2013) 015901.
[16] K. Kang, J .K.G. Dhont, Structural arrest and texture
dynamics in suspensions of charged colloidal rods, Soft
Matter 9 (2013) 4401-4411.
[17] K. Kang, Image time-correlation, dynamic light scattering
and birefringence for the study of the response of
anisometric colloids to external fields, Rev. Sci. Instrum
82 (2011) 053903.
[18] K. Kang, Mesoscopic relaxation time of dynamic image
correlation spectroscopy, J . Biomed. Sci. and Eng. 3
(2010) 625-632.
[19] K. Kang, J .K.G. Dhont, Criticality in a non- equilibrium,
driven system: Charged colloidal rods (fd- viruses) in
electric fields. The European Physical J ournal E 30 (3)
(2009) 333-340.
[20] K. Kang, Diffusivity in an electric-field-induced
homeotropic phase of charged colloidal rods, Eur. Phys.
Lett. 92 (2010) 18002.
[21] J .K.G. Dhont, K. Kang, An electric-field induced
dynamical state in dispersions of charged colloidal rods,
Soft Matter (2013). (accepted and in pressed)
[22] K. Kang, Charged fibrous viruses (fd) in external electric
field: Dynamics and orientational order, New J . of Phys.
12 (2010) 063017.

You might also like