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Importance of polyelectrolyte modification for

rectifying the ionic current in conically shaped
Cite this: Phys. Chem. Chem. Phys.,
2017, 19, 5351 nanochannels†
Jyh-Ping Hsu,ab Hou-Hsueh Wu,a Chih-Yuan Lina and Shiojenn Tseng*c

Received 10th November 2016,
Accepted 15th January 2017
DOI: 10.1039/c6cp07693a
rsc.li/pccp
Due to their specific geometry, conical nanochannels/nanopores are capable of exhibiting several
interesting electrokinetic phenomena including, for example, ion concentration polarization (ICP) and
ion current rectification (ICR). Extending previous analyses, we consider two types of nanochannels: only
the inner surface of a nanochannel is functionalized by a polyelectrolyte (PE) layer in a type I
nanochannel, and both its outer and inner surfaces are functionalized in a type II nanochannel. The
influences of the thickness of a double layer and that of the PE layer on ICR are examined through
numerical simulation. We show that the ICP of a type I nanochannel is more significant than that of the
corresponding type II nanochannel. The behavior of the rectification factor of the former as the bulk salt
concentration varies also differs significantly from that of the latter. In particular, the rectification factor
of a type I nanochannel at a low bulk salt concentration shows an inversion.

1. Introduction phenomena including, for example, ion concentration polar-

Due to its capability of mimicking ion channels in living
organisms, the ionic transport in artificial nanochannels/nano-
pores has drawn the attention of researchers in various
fields.1–3 Recent advances in nanochannel/nanopore fabrication
technology also make relevant applications versatile. These
include, for example, sensing of biomolecules and ions,4–12 ionic
gates,13–15 energy conversion,16–18 and water desalination.19
Fu et al.4 showed that nanopipettes can be used in DNA sequencing
through monitoring the ionic current shift. Ali et al.5 studied the
binding capability of calcium ions by a conical nanopore coated
with poly acid chains. Umehara et al.6 proposed the use of
various materials and methods for nanopipettes based bio-
sensing. German et al.8 and Lan et al.9 investigated the trans-
location of nanoparticles in a glass nanopore. Vogel et al.10
estimated the size of a nanoparticle by its translocation in a
polymeric conical nanopore.
As the size of a nanochannel is down to the order of the
Debye length (or the thickness of an electric double layer, EDL),
the overlapping of EDLs yields distinctive electrokinetic
a
Department of Chemical Engineering, National Taiwan University, Taipei, 10617,
Taiwan
b
Department of Chemical Engineering, National Taiwan University of Science and
Technology, Taipei, 10607, Taiwan
c
Department of Mathematics, Tamkang University, New Taipei City, 25137,
Taiwan. E-mail: topology@mail.tku.edu.tw; Fax: +886-2-26209916;
Tel: +886-2-26215656 ext. 2508
† Electronic supplementary information (ESI) available. See DOI: 10.1039/c6cp07693a
ization (ICP),20,21 ion selectivity,22,23 and ionic current rectifica-
tion (ICR).24–27 ICR is the phenomenon that a nanochannel/
nanopore shows a diode-like current–voltage behavior, or the
preference for ionic current in a certain direction when an
electric potential bias is applied. In biological science, ICR is
observed in ion channels such as those of K+ and Na+.28–30 For
charged nanochannels, ICR might arise from, for instance,
asymmetric pore geometry,26,31–34 the imposed salt gradient,22,35–37
and bipolar surface properties.38–41
Polyelectrolyte (PE) is often used to modify the surface of
inorganic13,36,42,43 and organic nanochannels,14,44,45 providing
them a versatile characteristic and, therefore, an ICR nature.44,46
Zhang et al.,13 for example, found that a glass conical nanopore
modified by poly[2-(dimethylamino)ethyl methacrylate], a smart
homopolymer capable of undergoing conformational transitions
stimulated by pH and temperature, exhibits ICR behavior.
Umehara et al.42 showed that after coating with poly-L-lysine a
quartz nanopipette is capable of amplifying ionic current and
giving a rectification direction opposite to that of an uncoated
nanopipette. In a study of the ICR of a glass nanopipette coated
with PEI, Deng et al.36 found that its rectification factor has a
local maximum as the bulk salt concentration varies, regardless
of whether a salt gradient is applied. The coating of materials
on a nanopore also provides a way for estimating the pKa of
the coating materials through the experimentally measured
pH–ionic current relationship. Liu et al.,43 for instance, estimated
the pKa of polyethyleneimines (PEIs) by coating them on a glass
nanopipette.

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Several attempts have been made for analyzing the ionic
transport in nanopores and nanochannels.47–51 For example,
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Siwy et al.48 investigated the influence of the surface charge of a
conical nanopore on its ICR behavior. The influences of bulk
salt concentration, grafting density, and PE thickness on the
electrokinetic ion and fluid transports in two types of nanopores
obtained by different ways of modifications were examined by
Yeh et al.21 If the bulk salt concentration is low, Yeh et al.20
observed an appreciable ICP near the cathode end of a PE
modified nanopore, and near the anode end if that concen-
tration is sufficiently high and the applied electric field is
relatively weak. In addition, the counterion-rich CP in a PE
modified nanopore is more significant than that in the corres-
ponding solid state nanopore, in general. Yeh et al.22 showed
that for a nanopore of constant surface charge, both ionic
transport and ion selectivity can be tuned by applying simulta-
neously a voltage bias and a salt gradient across the nanopore.
For instance, a reversed ion selectivity can be achieved by
adjusting the levels of these two factors. Recently, several
groups52,53 have concluded that the ICR behavior in a conical
nanochannel can be influenced significantly by the electro-
osmotic flow inside it.
In this study, we analyze the ICR in a PE-modified conical
nanochannel, focusing on the influence of how a nanochannel
is modified. A complete set of electrokinetic equations com-
prising Poisson–Nernst–Planck (PNP) equations for ionic trans-
port and electric field, and modified Stokes–Brinkman
equations for flow field is solved. The behaviors of the system
considered under various conditions are simulated by varying
the applied voltage, bulk salt concentration, and the thickness
of the PE layer.
2. Theory
The system under consideration comprises a nanochannel of
tip radius RT, base radius RB, and length LN connecting two
Fig. 1 Conical nanochannel modified by a PE layer: (a) only its interior is coated with a negatively charged PE layer; (b) both its interior and exterior are
coated with a PE layer. (c) Variation of the conductance of a charged nanochannel, G = I/Vapp, with the bulk salt concentration C0. Solid curve: analytic
result at a constant surface charge,56 discrete symbols: present result.
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identical, large, cylindrical reservoirs. Referring to Fig. 1, we
consider two types of conical nanochannels: only the interior of
a nanochannel is coated with a PE layer in a type I nanochannel,
and both its interior and exterior are coated with a PE layer in a
type II nanochannel. The PE layer is homogeneously structured
and ion-penetrable, having dissociable functional groups and
thickness RS. The dissociation of these functional groups makes
the PE layer negatively charged with a fixed charge density,
rfix = eZNfsPE/RS, where e, Z, N, f, and sPE are the elementary
charge, the valance of the dissociated functional groups, the
number of dissociable functional groups per PE chain, the
dissociation fraction, and the site density of the PE chain,
respectively. The nanochannel and the two reservoirs are filled
with an aqueous KCl solution. Cylindrical coordinates (r, y, z)
are used with the origin at the nanochannel center.
Let f, u, Nj, and p be the electrical potential, the fluid
velocity, the flux of the j th ionic species, and the hydrodynamic
pressure, respectively. Assuming steady state, the present problem
can be described by the following verified continuum-based
model:21
re þ irfix
r2 f ¼  ; i ¼ 0; 1 (1)
e
 
zj Fcj
r  Nj ¼ r  cj u  Dj rcj  Dj rf ¼ 0 (2)
RT
ru = 0 (3)
Zr2u  rp  rerf  igu = 0 (4)
P
2
re ¼ zj ecj is the space charge density of mobile ions with
j¼1
zj , cj, and Dj being the valence, the concentration, and the
diffusivity of the j th ionic species ( j = 1, cations, 2, anions),
respectively. e, F, R, and T are the fluid permittivity, Faraday
constant, gas constant, and the absolute temperature, respec-
tively. The region index i is 0 (1) outside (inside) the PE layer.
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Z and g are the fluid viscosity and the friction coefficient of the
PE layer, respectively.54 u = uer + wez, where er and ez are the
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unit vectors in the r- and z-directions, respectively.
To specify the boundary conditions associated with eqn (1)–(4),
we assume the following. (i) The rigid surface of the membrane
(O1) is non-slip (u = 0), ion-impenetrable (nNj = 0), and
uncharged (sw = 0), where sw and n are the surface charge
density of the membrane and the unit outward normal vector,
respectively. (ii) The electric potential, ionic concentration,
and flow field are all continuous at the PE layer–liquid inter-
face (O2). (iii) The ionic concentrations in the two reservoirs
are at their bulk salt concentration cj = C0. (iv) An electric
potential Vapp is applied on the bottom surface of the base-end
reservoir (O4), and the top surface of the tip-end reservoir (O3) is
grounded. (v) No external pressure is applied to the system.
(vi) The side boundaries of the two reservoirs (O5) are slip, free
of normal flux (nNj = 0), and free of charge (nrf = 0). (vii) The
present problem is symmetric about the axis of the conical
nanochannel.
The ionic current I is evaluated by using21
ð !
X 2
I¼ F zj Nj  ndS; (5)
S j¼1
with S being the cross sectional area of either reservoir.
For convenience, eqn (1)–(4) are rewritten in the following
scaled form:
1 layer thickness. For illustration, we assume RT = 10 nm,
r2 f ¼  ðkRT Þ2 ðz1 c1 þ z2 c2 Þ  irfix  ; i ¼ 0; 1
2
r*Nj* = r*(cj*u*  Dj*r*cj*  Dj*cj*r*f*) = 0
r*u* = 0
1
r2 u  r p  ðkRT Þ2 ðz1 c1 þ z2 c2 Þr f  iðlRT Þ2 u ¼ 0
2 4.1
(9)
The scaling factors adopted include the tip-end radius RT, the
bulk salt concentration C0, the reference potential ekBT/z1e, the
Fig. 2 Variation of the ionic current I with the applied voltage Vapp at various levels of bulk salt concentration for type I, (a), and II, (b), nanochannels.
Curves: conical nanochannel modified by PE; discrete symbols: bare conical nanochannel (i.e., free of PE layer) at sw = 0.35 e nm2. The insets highlight
the I–Vapp curve at C0 = 1 mM.
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reference pressure ekB2T2/z12e2RT2, the reference velocity
ekB2T2/z12e2RTZ, the reference charge density ekBT/z1eRT2, and
2 2
the reference diffusivity ek T /z12e2Z. The superscript * denotes
pBffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
1
a scaled variable. k ¼ ekB T=2C0 z1 e2 is the EDL thickness,
pffiffiffiffiffiffiffiffiffiffiffiffi
and lRT ¼ ga2 =Z the scaled friction coefficient. For illustra-
tion, we assume l1 = 1 nm in the subsequent discussion.20,21
The typical value of sPE ranges from 0.1 to 0.6 nm2.21,55
3. Solution procedure
The present problem is solved numerically by using COMSOL
MultiPhysics (version 4.3a, www.comsol.com) operated in a
high performance cluster. Its applicability is first examined
by solving the conductance in a charged nanochannel solved
analytically by Steinbock et al.56 As seen in Fig. 1(c), the
performance of the software adopted is satisfactory. The deviation
at low levels of C0 might arise because the ICP effect, which is
important when C0 is low, is neglected in the analytic study.
Typically, using a total number of 81 000 mesh elements is sufficient
for a type I nanochannel, and 100 000 for a type II nanochannel.
4. Results and discussion
The electrokinetic behaviors of the nanochannels considered in
this study are examined through numerical simulation by
varying the bulk salt concentration, applied voltage, and PE
(6) RB = 98 nm, LN = 1000 nm, RS = 5 nm, Z = 1, sPE = 0.35 nm2,
N = 3, and f = 1/3.40 For convenience, the size of the computational
(7) domain of a reservoir is chosen as 200 nm with equal radius
(8) and length.20,57,58 The rectification factor Rf is defined as
Rf = |I(1 V)/I(+1 V)|.
Influence of the applied voltage
Fig. 2 illustrates the variation in the ionic current I with the
applied voltage Vapp at various levels of the bulk salt concen-
tration C0 for both types of nanochannels when their wall is free
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of charge (i.e., sw = 0 e nm2). For comparison, the corres-
ponding results for a bare nanochannel (without PE layer) at
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sw = 0.35 e nm2 are also presented. As expected, the higher
the C0 the larger the I. Note that the curves in Fig. 2 are non-
linear, exemplifying the ionic current preference of these
nanochannels and, therefore, their ICR nature. Fig. 2(a) reveals
that for the type I nanochannel, I(Vapp = +1 V) 4 |I(Vapp = 1 V)|
at C0 = 10 mM (red curve). However, if C0 is raised to 100 mM
(blue curve), |I(Vapp = 1 V)| 4 I(Vapp = +1 V), implying that the
ion current preference of the type I nanochannel depends on
the level of bulk salt concentration. In contrast, Fig. 2(b) indicates
that for all the levels of C0 examined, |I(Vapp = 1 V)| 4 I(Vapp = +1 V)
for the type II nanochannel, especially at higher levels of C0
(50 and 100 mM). Note that the ionic current of a PE-
functionalized nanochannel is not necessarily larger than that
of the corresponding bare pore (without PE).43 However, the
rectification factor of the former is larger than that of the latter,
in general, which is consistent with the literature results.5,13,43
4.2 Counterion enrichment inside the nanochannel
Because the PE layer coated on the nanochannel wall is
negatively charged, anions (cations) are repelled (attracted) by
the nanochannel. Fig. 3 illustrates the cross sectional averaged
ion concentration cj ( j = 1, cations, 2, anions) at various
Fig. 3 Cross sectional averaged ion concentration distribution cj in type I, (a) and (b), and type II, (c) and (d), nanochannels. Solid curves: cations; dashed
curves: anions. Shaded region: nanochannel interior.
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combinations of C0 and Vapp for the two types of nanochannels.
This figure shows that if C0 is low (1 mM and 10 mM), cations
(counterions) are significantly enriched near the nanochannel
tip region. This is because EDL overlaps significantly in that
region, thereby capable of retaining more counterions. In
Fig. 3(a) and (c), where Vapp = +1 V, the degree of enrichment
of c1 at C0 = 1 mM can be comparable to that at C0 = 10 mM.
However, if C0 is raised to 100 mM, EDL overlapping is
unimportant, so the degree of counterion enrichment is much
less significant compared to that at C0 = 1 mM.
Fig. 3(a) and (c) also reveal that at Vapp = +1 V and
C0 = 100 mM, a depletion of both counterions and coions
occurs near the nanochannel center. At C0 = 1 mM, because
EDL is thick the depletion of coions is significant in both types
of nanochannels. For both types of nanochannels at C0 = 1 mM,
the concentration of coions reaches a local minimum near the
nanochannel base end (z = 500 nm). The distribution of ions
in the type II nanochannel is similar to that in the type I
nanochannel, but a more significant coion depletion is
observed in the former. Note that the region of ion depletion
in the type II nanochannel is larger than that in the type I
nanochannel. This is because both the interior and the exterior
walls of the former are modified by PE, yielding a broader
region to repel coions.
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Fig. 3(b) and (d) indicate that at Vapp = 1 V, counterion
enrichment occurs inside the nanochannel for all the levels of C0
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examined. However, different from that at Vapp = +1 V, the degree of
counterion enrichment at C0 = 1 mM does not reach the level at
C0 = 10 mM seen in Fig. 3(a) and (c). As can be seen in Fig. 3(b) at
C0 = 1 mM coion depletion occurs in the entire interior of the type I
nanochannel, with a local minimum near its tip end (z = 500 nm).
However, at both C0 = 10 mM and 100 mM the depletion of coions
near the nanochannel tip end is less appreciable, and can even lead
to enrichment near the region inside the tip end. The depletion of
coions at C0 = 1 mM lowers the total ionic concentration and,
therefore, the corresponding ionic current differs from that at other
levels of C0. This will be discussed later in detail. Fig. 3(d) shows that
the depletion of coions in the type II nanochannel is less significant
than that in the type I nanochannel, with ion enrichment inside the
nanochannel and less depletion near its tip end.
The behavior of the ionic current in Fig. 2 can be explained
by Fig. 3. At Vapp o 0, the ion current of the type II nanochannel
is larger than that of the type I nanochannel since the former
contains a larger amount of ions. In contrast, if Vapp 4 0,
because the depletion of coions in the type II nanochannel is
more significant than that in the type I nanochannel, the ionic
current of the former is smaller than that of the latter.
4.3 Influence of ion concentration polarization
Fig. 4 illustrates the contours for the scaled concentration
of counterions (cations) c1* (=c1/C0) near the nanochannel tip
Fig. 4 Contours of the scaled counterion (cation) concentration (c1*) near the nanochannel tip region for the type I nanochannel, (a), (c) and (e), and the
type II nanochannel, (b), (d) and (f), at Vapp = +1 V for various values of bulk ionic concentration. Color bars: level of scaled concentration; the number
associated with m (.) denotes the maximum (minimum) value. Contours of the scaled counterion (cation) concentration (c1*) for the entire nanochannel
are placed next to those of the tip region.
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region for both types of nanochannels. As shown in Fig. S1 of
the ESI,† because the c1* near the base region of the type I
nanochannel is close to that of the type II nanochannel, only
the c1* near their tip region is discussed. Fig. 4 reveals that for
both types of nanochannels, a considerable amount of cations
is attracted by the negatively-charged PE layer, yielding signifi-
cant ion enrichment near their tip region.
Fig. 4(a) and (b) show that c1* is very large (can exceed 100 in
some region), implying that the ion concentration inside the
nanochannel is much higher than the corresponding bulk salt
concentration. This arises mainly from because EDL is very
thick under the conditions examined. In the present case
(C0 = 1 mM), the degree of ICP in both types of nanochannels
is significant.
As seen in Fig. 4(c) and (d), if C0 is raised to 10 mM, the
c1* near the nanochannel tip region is ca. 5–7 in the type I
nanochannel and 4–6 in the type II nanochannel, suggesting
that the effect of ICP in the former is more significant than that
in the latter. As illustrated in Fig. 4(e) and (f), if C0 is further
raised to 100 mM, the effect of ICP in the type I nanochannel
becomes even more apparent than that in the type II nano-
channel, where the c1* near the tip region is ca. 1.4 in the
former, and 1.2 in the latter. Note that because the EDL at
C0 = 100 mM is thin, the enrichment of counterions is not as
significant as that at C0 = 1 mM, as can be inferred from their
c1* values. We conclude that because the type I nanochannel is
capable of yielding a greater degree of ion enrichment, and
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therefore, a more significant ICP than the type II nanochannel,
and the higher the bulk salt concentration the easier to observe
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the difference between the two. Because the exterior of the type
II nanochannel is also modified by PE (capable of attracting
more counterions), the EDL near the tip region is less distorted
by the applied voltage bias, yielding a less significant ICP.
4.4 Influence of bulk salt concentration
As seen in Fig. 5, the Rf of the type I (II) nanochannel has a local
maximum of ca. 1.8 (3.5) at C0 D 200 mM (C0 D 50 mM).
Fig. 5 Variation of the rectification factor Rf with the bulk salt concen-
tration C0 for type I (black curve) and II (red curve) nanochannels. The inset
highlights the Rf for C0 ranging from 600 to 1000 mM.
Fig. 6 Contours of NC in the type I nanochannel for various combinations of C0 and Vapp. The number associated with m (.) denotes the maximum
(minimum) NC value.
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In addition, the Rf of the type I nanochannel crosses unity
at C0 D 20 mM.
It is interesting to note that the behavior of the Rf–C0 curves
in Fig. 5 is different from that reported by Momotenko et al.27
Note that their system corresponds to our type II nanochannel,
where both its interior and exterior are charged. An inversion in
Rf is observed in their study, and Rf has both a local minimum
of ca. 0.80 and a local maximum of ca. 1.05. In contrast, Rf does
not have an inversion in our case (type II nanochannel). In
addition, it shows a local maximum of ca. 3. Furthermore,
Rf inversion occurs in the type I nanochannel, and the corres-
ponding rectification effect is significant at a low level of C0.
The values of Rf reported by Momotenko et al.27 are much
closer to unity than ours, that is, the rectification effect is less
significant in their system. This might arise from because their
cone angle (30.871) is much larger than ours (51), and the
nanochannel surface is rigid in their case, but is modified by
a charged PE layer in our case.
To explain the dependence of Rf on C0, we define the
normalized conductivity NC27
c1 L1 þ c2 L2
NC ¼ ; (10)
C10 L1 þ C20 L2
where cj, Cj0, and Lj are the local concentration, the bulk
concentration, and the molar conductivity of the j th ion species
( j = 1, counterions, 2, coions), respectively.
Fig. 5 indicates that for the type I nanochannel at C0 = 1 mM,
Rf o 1, implying that I(Vapp = +1 V) 4 |I(Vapp = 1 V)|. This can
be explained by Fig. 6(a) and (b), which show that in the region
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near the nanochannel tip end NC(Vapp = +1 V) 4 NC(Vapp = 1 V).
If C0 is raised to 100 mM, Rf 4 1, that is, I(Vapp = +1 V) o
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|I(Vapp = 1 V)|. However, Fig. 6(c) and (d) reveal that in
the region near the nanochannel tip end NC(Vapp = +1 V) 4
NC(Vapp = 1 V). As can be inferred from Fig. 6(c) and (d), this is
because although NC(Vapp = +1 V) 4 NC(Vapp = 1 V) in the
region near the nanochannel tip end, NC(Vapp = +1 V) o
NC(Vapp = 1 V) in the region inside the nanochannel tip
end, implying that the ionic enrichment inside the nanochan-
nel dominates the ICR behavior.
As seen in Fig. 5, for the range of C0 considered Rf inversion
is not observed in the type II nanochannel. This can be
explained by Fig. 7(a) and (b), where the NC(Vapp = 1 V) near
the nanochannel tip region is slightly larger than NC(Vapp = +1 V),
so |I(Vapp = 1 V)| is only slightly larger than I(Vapp = +1 V), and
therefore, Rf is close to unity at C0 = 1 mM. If C0 is raised to
100 mM, Rf D 3, suggesting that |I(Vapp = 1 V)| is much larger
than I(Vapp = +1 V). Fig. 7(c) and (d) reveal that near the
nanochannel tip region NC(Vapp = 1 V) is only slightly larger
than NC(Vapp = +1 V), so |I(Vapp = 1 V)| 4 I(Vapp = +1 V).
Furthermore, Fig. 7(c) and (d) indicate that the NC inside the
nanochannel in the latter is much larger than that in the
former, which explains why |I(Vapp = 1 V)| is much larger
than I(Vapp = +1 V). We conclude that the ionic current rectifica-
tion is influenced not only by the NC in the region immediately
outside the nanochannel tip end but also by that inside.
Note that NC also measures the level of ICP. Fig. 6, for
example, shows that at C0 = 100 mM, the maximum value of NC
ranges from 1.5 to 2.2, but can be of the order of 50 at C0 = 1 mM.
Fig. 7 Contours of NC in the type II nanochannel for various combinations of C0 and Vapp. Color bars on the right denote the NC level; the number
associated with m (.) denotes the maximum (minimum) NC value.
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The significant enhancement in NC at 1 mM can be attributed to
a much thicker EDL, capable of attracting a more amount of
counterions. The increase in the counterion concentration
makes the conductivity of the liquid in the nanochannel much
larger than that in the bulk liquid, yielding a large NC.
4.5 Influence of the PE layer thickness on ionic current
The influence of the PE thickness RS on the ionic current I is
illustrated in Fig. 8. Since the PE layer is thin compared to the
nanochannel radius, its possible deformation/nonuniformity is
neglected.47,55,59 Note that as RS increases, although the charge
density of the PE layer decreases, it occupies more space in the
nanochannel interior. As seen in Fig. 8(a) at Vapp = +1 V,
I(RS = 8 nm) 4 I(RS = 6 nm) 4 I(RS = 4 nm), but |I(RS = 6 nm)| D
|I(RS = 8 nm)| 4 |I(RS = 4 nm)| at Vapp = 1 V. If Vapp 4 0, the
behavior of I for the type II nanochannel as RS varies shown
in Fig. 8(b) is the same as that in the type I nanochannel, but
that behavior is different if Vapp o 0, that is, |I(RS = 4 nm)| 4
|I(RS = 6 nm)| 4 |I(RS = 8 nm)|.
Fig. 9(a) shows the axial variation in the cross sectional
averaged normalized conductivity, NC, of the type I nanochannel
at Vapp = +1 V. Here, NC is seen to have a local maximum near its
tip, which arises from ion enrichment. For each level of RS, ion
depletion occurs inside the nanochannel, causing a decrease in
NC. Note that the NC at RS = 8 nm (4 nm) is larger (smaller) than
that at other values of RS, implying a larger (smaller) ionic current
in the former case. As can be seen in Fig. 9(c), the behavior of
NC in the type II nanochannel is similar to that in the type I
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Fig. 8 Variation of the ionic current I with the applied voltage Vapp at various values of the PE layer thickness RS for types I, (a), and II, (b), nanochannel at
C0 = 100 mM. The inset of (a) highlights the I–Vapp curves for Vapp ranging from 1 to 0.7 V.

Fig. 9 Axial variation of the cross sectional averaged normalized conductivity NC in type I, (a) and (b), and II, (c) and (d), nanochannels. Shaded region:
nanochannel interior. (e): Contours of NC near the tip region of the type I nanochannel at Vapp = 1 V; top-down: RS = 4, 6, and 8 nm.

nanochannel, so at Vapp = +1 V, I(RS = 8 nm) 4 I(RS = 6 nm) 4
I(RS = 4 nm) in both types of nanochannels.
Fig. 9(b) reveals that for the type I nanochannel at Vapp = 1 V,
NC(RS = 8 nm) is slightly smaller than NC(RS = 4 nm)
and NC(RS = 6 nm), and NC(RS = 4 nm) is comparable to
NC(RS = 6 nm), suggesting that |I(RS = 6 nm)| D |I(RS = 4 nm)| 4
|I(RS = 8 nm)|. However, according to Fig. 9(e), the depletion of
ions near the nanochannel tip end at RS = 4 nm is the most
significant, so I(RS = 4 nm) is the smallest at Vapp = 1 V.
The results shown in Fig. 9(e) also imply that the depletion of ions
near the nanochannel tip at RS = 8 nm is the least significant. Since
NC(RS = 8 nm) is only slightly smaller than NC(RS = 6 nm) and the
depletion of ions near the nanochannel tip end at RS = 8 nm is the
least significant, it can be inferred that I(RS = 8 nm) is close
to I(RS = 6 nm) at Vapp = 1 V. Therefore, |I(RS = 6 nm)| D
|I(RS = 8 nm)| 4 |I(RS = 4 nm)|. As seen in Fig. 9(d), the NC at
RS = 4 nm (RS = 8 nm) is larger (smaller) than that at other values
of RS, implying that I(RS = 4 nm) 4 I(RS = 6 nm) 4 I(RS = 8 nm).

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5. Conclusions
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The ionic current rectification (ICR) behavior of a conical
nanochannel is examined focusing on how it is functionalized
by a polyelectrolyte (PE) layer. Two types of nanochannels are
examined: only the interior of a nanochannel is functionalized
by a PE layer in a type I nanochannel, and both its interior and
exterior are functionalized in a type II nanochannel. We show
that the difference in the functionalization of a nanochannel
yields different degrees of ion enrichment and depletion, so the
corresponding electrokinetic behaviors are different signifi-
cantly. For instance, as the bulk salt concentration varies, the
type I nanochannel changes its preference for ionic current,
and at the same applied voltage, the ionic current in the type II
nanochannel is larger than that in the type I nanochannel.
At the same level of applied voltage, the distributions of
counterions in the two types of nanochannels are similar, but
the degree of coion depletion is different. If the bulk salt
concentration is low, a significant ion concentration polariza-
tion (ICP) occurs in both types of nanochannels with compar-
able degree, and if that concentration is high, the degree of ICP
in the type I nanochannel is more significant than that in the
type II nanochannel. The ICR behaviors of the two types of
nanochannels are also different. In the type I nanochannel, an
inversion of the rectification factor (Rf) occurs at low bulk salt
concentrations, but Rf has a local maximum and no Rf inversion
in the type II nanochannel. The behavior of ionic current and Rf
can be explained by conductivity, and that of ionic current as
the PE layer thickness varies by the cross sectional averaged
conductivity. We conclude that regulating the ICR behavior of a
conical nanochannel can be achieved by modifying its surface
appropriately. The results gathered provide useful information
for both designing a diode-like device and mimicking the ion
channel of living organisms.
Acknowledgements
This work was sponsored by the Ministry of Science and
Technology, Republic of China.
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