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Shape-Enhanced Open-Channel Hydrodynamic Chromatography

Valentina Biagioni, Stefano Cerbelli, and Gert Desmet*

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ABSTRACT: Hydrodynamic chromatography (HDC) is a well-established

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analytical separation method for the size separation of nano- and microparticles
and large molecular weight solutes such as synthetic polymers and proteins. We
report on a theoretical study showing that the separation resolution of open-
tubular HDC can be significantly enhanced by changing the cross-sectional shape
of the separation channel. By enforcing Brenner’s macro-transport approach, we
provide theoretical/numerical evidence showing how the shape of the cross section
influences quantitatively both the selectivity and the axial dispersion of the
suspended particles in HDC. The separation performance of square-, triangle-, and
star-shaped channel cross sections is compared to that of a cylindrical capillary
over three decades of the particle Péclet number in terms of the minimal
separation length and time to obtain the unit resolution of a two-particle mixture.
Enhancement factors up to 400% are found in the case of triangular shapes, with
the best performing case being the 70.6° angle, which can be obtained by KOH etching of bulk silicon.

1. INTRODUCTION and Guttmann theory.10,11 Their work culminated in the

Hydrodynamic chromatography (HDC) is a chromatographic conduction of HDC separations in flat rectangular micro-
separation technique suitable for the size-based separation of channels (1 μm deep and 1000 μm wide), envisioning to
colloidal matter, both macromolecular and particulate.1,2 It combine the increased size selectivity of the very shallow
differs from other modes of chromatography in the sense that channel depth with the increased detection sensitivity
it does not rely on a stationary phase but makes use of the emanating from the large channel width.7,12 More recently,
difference in migration velocity experienced by different-sized the HDC principle has also been applied in perfectly ordered
micro-pillar array columns, showing the separation of 20 and
solutes in the parabolic velocity field that is established in
40 nm particles in 90 s in a 4 cm long channel filled with 1.5
pressure-driven flows through channels or the interstitial pores
mm pillars.13,14 It has also been shown that the HDC effect can
in packed beds. This difference in particle migration velocity
play a role in the Taylor Dispersion Analysis of large MW
becomes appreciable when the size of the solutes becomes
solutes, such as proteins.15
significant with respect to the cross-sectional diameter. It is
In the present contribution, we report on a theoretical
caused by the fact that the center of mass of larger particles is
exploration of the effect of the cross-sectional shape on the
more effectively excluded from the low-velocity regions near
resolution of open-tubular HDC. It can be hypothesized that
the wall. Hence, bigger particles assume a larger average
an alteration of the cross-sectional shape will change the shape
velocity than smaller ones, whose centers of mass can come
of the parabolic velocity profile and hence the selectivity of the
closer to the enveloping walls and hence sample more of the
separation process. Selectivity improvements have, for
low velocities. This effect has, for the first time, been observed
example, been demonstrated for channels with a triangular
by Pedersen while studying the separation of proteins in
cross section.5 At the same time, any deviation from a circular
packed glass sphere beds and has subsequently been
cross section can also be expected to worsen the axial
theoretically explained by DiMarzio and Guttmann.3−5 Their
dispersion. In the literature, the question of whether there are
theoretical work was complemented by Brenner and Gaydos,
cross-sectional shapes whose gain in selectivity can overcome
who also included the effect of the hydrodynamic interactions
with the wall and the slip velocity.6,7 Experimentally, the
technique was fully developed in the 1970s by the seminal Received: June 28, 2022
work of Small and coworkers at the Dow Chemical Company Accepted: November 2, 2022
on the size separation of polymers as well as colloidal silica Published: November 12, 2022
mixtures on packed bed columns.8,9 In the 1980s and 1990s,
Tijssen and coworkers applied the HDC principle in open
tubular channels, showing good agreement with the DiMarzo

© 2022 American Chemical Society https://doi.org/10.1021/acs.analchem.2c02766

15980 Anal. Chem. 2022, 94, 15980−15986
Analytical Chemistry
the inevitable increase in band broadening, leading to an
improvement of the overall resolution (combination of
resolution and dispersion), has, to the best of our knowledge,
not been considered yet.
Here, we consider conduits having an angular cross section,
that is, shapes marked by the presence of distinct corners, as
these can be expected to lead to steeper velocity gradients (see
Figure 2 for an overview of considered shapes). The present
study makes use of Brenner’s macro-transport formalism to
compute the effective velocity (via Brenner’s first order
moment) and the effective dispersion (via the second order
moment), which can be quantified by the Taylor-Aris
dispersion coefficient16−18 Previously, this theory has been
applied to study effective macrotransport in a diverse range of
fields.19−24 As this is a first exploration into the present topic,
the solutes are treated as hard, impermeable spheres, and the
hydrodynamic effects induced by the interaction of the
particles with the wall and the velocity profile (wall friction,
particle rotation, concomitant lift forces, and slip) are not
taken into account. Hence, results have been limited to the
range of dimensionless particle size λ = dp/l ≤ 0.2 (where dp is
the particle size, and l is the cross-sectional characteristic size
parameter, see Figure 2 for further details). Previous studies on
the shape optimization of micro- and nanochannels that have
been conducted in the area of analytical chemistry have mainly
been focused on minimizing the axial dispersion of point-sized
solutes.25−27 Here, the finite size of the particles is taken into
account (Figure 1).
Figure 1. Excluded-volume model for finite-sized particles. The
boundaries of the fluid dynamic domain (∂Ω) and of the particle
transport domain (∂Ωp) are depicted in blue and red lines,
respectively.
Let us consider a pressure-driven flow through an empty
microchannel of arbitrary cross-section, which is henceforth
denoted by Ω.
Owing to the prevailing laminar flow regime characterizing
microchannel flow, the pressure-driven velocity field of the
eluent only consists of its axial component, v = (u, v, w) = (0,
0, w(x, y)), where x and y ∈ Ω are the cross-sectional
(Cartesian) coordinates
2 1 P
w=
z (1)
2 2 2 2 2
where ∇⊥ = ∂ /∂x + ∂ /∂y is the cross-sectional Laplacian
operator. Equation 1 can be made dimensionless by taking the
characteristic dimension of the cross section, say l, as a
reference length, the average eluent velocity
U = w(x , y)dx dy / dx dy as a reference velocity, and the
characteristic viscous stress as the reference pressure, Pref =
μU/l, where μ is the dynamic viscosity of the fluid. By using
the same symbols as those used in eq 1 for the corresponding
dimensionless variables, the latter equation is written as
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2 P
w=
z (2)
Equation 2 is equipped with the no-slip conditions, w = 0,
on the walls, ∂Ω, of the cross section Ω.
The simplest approach to HDC modeling hinges on a one-
way coupling, overdamped regime assumption for particle
motion. Here, the eluent flow is considered unperturbed by the
presence of the particles, and the generic individual particle is
regarded as a point-sized tracer ideally located at the particle
center-of-mass. Thus, in this approach, size influences particle
dynamics only through wall−particle interactions. On the
assumption that particles are spherical and rigid and hydro-
dynamic interactions are negligible, particle motion is identical
to that of passive tracers onto an effective domain, Ωp, that
takes into account particle hindrance. The effective domain Ωp
can be constructed from Ω by excluding all the points of the
cross section closer than the particle radius to the wall along
the local normal direction. Figure 4 shows the fluid domain
and the particle transport domain for two of the shapes that are
next considered.
Let c(x, y, z, t), represent the particle number density
(henceforth referred to as PND), where c(x, y, z, t) dV yields
the fraction of the total number of particles at time t falling
within an elementary volume dV embedding a generic point (x,
y, z). Let c0(x, y, z) = c(x, y, z, t = 0) be a uniform distribution
of particles over the cross section. By the above assumptions,
the PND obeys the micro-transport equation28
c c 1 ijj 2
2
c yzz
+w = j c+ z
t z Pep jk 2
z z{ (3)
Equation 3 has been made dimensionless with respect to a
reference concentration, and with respect to the same
characteristic length, l, and velocity, U, used in eq 2. Here,
Pep = Ul/Dp is the particle Péclet number, where Dp is the bare
particle diffusivity. The numerical solution of eq 3 is
numerically challenging in view of its intrinsic multiscale
nature. Specifically, as the particle distribution becomes more
and more dispersed along the channel axis, the smallest length
scale to resolve PND gradients is still constrained by the
characteristic cross-sectional length l, which, for typical HDC
applications, is several orders of magnitude smaller than the
dispersion bandwidth. Therefore, the number of degrees of
freedom necessary to preserve accuracy of the particle
distribution swiftly becomes exceedingly large. Besides, in
chromatography applications in general, and in HDC in
particular, the information about the particle distribution
throughout the channel cross section is irrelevant, since the
signal detected at the device outlet is proportional to the total
particle number exiting the channel in a prescribed time
interval. Thus, for all practical purposes, the main piece of
information necessary to predict the separation performance is
provided by the marginal particle distribution
C(z , t ) = c(x , y , z , t )dx dy , w h e r e , b y d e fi n i t i o n ,
p
C(z,t)dz yields the fraction of particles falling in the volume
dV between the cross sections at z and z + dz at time t,
regardless of their position on the cross section. Macro-
transport theory shows that in the long-time asymptotic limit,
this marginal distribution obeys the effective transport
equation28
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Analytical Chemistry pubs.acs.org/ac Article

Figure 2. Dimensionless velocity profile w(x,y)/U. Panels (a−c) depict circle-, square-, and star-shaped cross sections. Panels (d−g) depict
triangular shapes characterized by different values of the bottom angle α, α = 70.6, 60, 45, and 30°, respectively.

2 b-field (so termed after Brenner). The relationship between the

C C 1 C
+ Wp = eff 2 b-field and the Taylor-Aris coefficient can be expressed as
t z Pep z (4)
( b) × ( b)dx dy
where the dimensionless transport parameters, Wp and 1/Peeff p p
p =
are referred to as effective particle velocity and effective particle dx dy
Péclet number, respectively. The effective velocity is given by p (8)
the eluent velocity averaged over the effective cross section of The knowledge of the effective particle velocity and of the
the channel Taylor-Aris coefficient for any given particle size allows us to
w(x , y)dx dy predict the column length necessary to achieve the separation
p of a size-dispersed suspension. Specifically, the separation
Wp =
dx dy resolution of a mixture of particles of two different sizes, say
p (5) “1” and “2” in a channel of length L can be expressed as
where the dimensionless dispersion coefficient 1/Peeff
p is given 1 1
by28 1 W2 W1
Rs =
1 1 2 2(1 + 1Pe12)
+ 2(1 + 2Pe 2 2)
eff
= + pPep Pe1(W1)3 Pe 2(W2)3 (9)
Pep Pep (6)
By assuming that the bare particle diffusivity can be
It can be observed that the inverse effective particle Péclet estimated from the Stokes−Einstein relationship,
number coincides with the Height Equivalent of the = k bT /(3 d p ) (where kb, T, dp, and μ are the Boltzmann
Theoretical Plate (HETP), say Hp, normalized with respect
to the characteristic cross-sectional length l, that is, hp = Hp/l = constant, the absolute temperature, the particle diameter, and
1/Peeff the dynamic viscosity of the fluid, respectively), the fact that
p . The constant Γp appearing at the right hand side of eq
6 is referred to as Taylor-Aris coefficient, and its value controls both particle types are entrained in the same channel flow
the increase of the dispersion bandwidth at values of particle implies that Pe 2 = Pe1(d p2/d p1). Thus, if the effective particle
Péclet number larger than 1/ p . Therefore, geometries transport parameters are known, and eq 9 allows us to
determine the minimal length, Lmin, yielding a prescribed level
providing the lowest Taylor-Aris coefficient that are compat- of separation resolution.
ible with operating and constructive constraints are sought
after. Besides this, the macro-transport theory also provides an 2. MATERIALS AND METHODS
explicit expression for Γp in terms of the solution of the steady-
The geometries considered throughout are depicted in Figure
state (elliptic) equation28
2, which also shows the dimensionless axial velocity profile
2 w(x,y)/U obtained by solving eq 2 using a commercial finite-
b = Wp w(x , y) (7)
element software (Comsol Multiphysics 5.5) onto an
equipped with vanishing normal gradient at the boundary of unstructured mesh on the order of 105 degrees of freedom.
the effective particle transport domain, ∂b/∂n = 0 on the The dispersion data shown below were computed by solving
boundary of Ωp. The dependent variable b(x,y) is referred to as eq 7 using the same Comsol Multiphysics 5.5 software on a
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Analytical Chemistry
Figure 3. (A) Effective velocity and (B) selectivity Wp′ (definition: see text) vs the dimensionless particle radius l for different cross-sectional
shapes. (C) Corresponding plot of dimensionless residence time τ vs l. The labeling is consistent with that of Figure 2. The dashed line in panel C
represents the case of a flat-rectangular channel (infinite width). The reference case (circular channel) is colored in red.
triangular unstructured mesh corresponding to an order of 106
degrees of freedom. Specifically, the steady-state PARDISO
solver algorithm was used with the relative tolerance set to
10−5. In the case of shapes with sharp corners (triangular and
star), mesh refinement was enforced in the near-corner regions
of the domain.
We observe that, beyond the parabolic profile associated
with the circular channel, analytical expressions are also
available for the square [panel (b)] and the equilateral triangle
[panel (d)] in terms of Fourier expansion. Nevertheless, since
the solution of the two-dimensional Stokes equation poses no
severe numerical challenge, we used the same numerical
approach for all the shapes. All of the shapes, except for the
star-shaped geometry of panel (c), can in principle be obtained
by lithography-etching microfabrication. Specifically, the cross-
sectional geometry in panel (d) can be directly obtained by wet
KOH etching of bulk silicon.29 The star-shaped geometry can
in principle be obtained by 3d (nano)printing. One is to note
how the scaled value of the maximum axial velocity depends on
the cross-sectional shape. The highest values are those
associated with the star- and triangle-shaped geometries
depicted in panels (c,d), respectively.
3. RESULTS AND DISCUSSION
The results showed next are obtained through the finite-
element solution of the b-field eq 7 enforced onto the same
computational domain as that used to compute the axial
velocity profile.
3.1. Effective Particle Velocity and Separation
Selectivity. Panel A of Figure 3 shows the dimensionless
effective particle velocity Wp (scaled with respect to the eluent
velocity) versus the relative particle radius λ, defined with
respect to the characteristic length of the cross section (λ = dp/
(2l), where dp is the particle diameter). The different curves
refer to the shapes depicted in Figure 2 and are labeled
consistently with this figure.
Note that values beyond λ = 0.2 were not considered, as the
enforcement of the one-way coupling approximation becomes
questionable for such large particles and two-phase effects
might become important. The most common shapes, namely
the cylindrical capillary and the square duct represented by
curves (a,b), respectively, are those showing the weakest
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dependence of Wp on λ, whereas the star and the triangle shape
associated with α = 70.6° [curves (c,d), respectively] exhibit
the most sensitive dependence of the effective particle velocity
on the particle size. The remaining triangle shapes display a
behavior intermediate between these two extremes. This result
is qualitatively consistent with the axial velocity profiles
depicted in Figure 2, where the shapes (c) and (d) display
the highest values of the eluent maximum velocity when
compared to circular and squared shapes. Clearly, geometries
yielding a swift increase of Wp with Rp are sought after for
maximizing the separation efficiency. In fact, if one considers
two particle types of size λ and λ + Δλ, the difference Wp(λ +
Δλ) − Wp(λ + Δλ) controls the distance, say δpeaks, between
the peaks of the Gaussian-shaped marginal distributions C(z,t)
of each particle type, which grows linearly with time as
peaks = (Wp( + ) Wp( + ))t and ultimately deter-
mines the distance between the average residence times in the
chromatogram for a column of given length. By this
observation, an intrinsic measure of the driving force for the
separation is represented by the derivative W′p = dWp/dλ,
which can be referred to as the selectivity of the HDC
separation and is depicted in panel (B) of Figure 3. Here, the
difference between the standard channel shapes (circular and
squared) and the triangular and star-shaped cross sections can
be appreciated quantitatively. For small particle diameters of λ
< 0.12, the best performing shape is the triangular one with α =
70.6°. For larger particle radii, however, the selectivity
associated with this shape drops rapidly, and falls below that
of the star cross-sectional geometry. By contrast, the selectivity
of the star shape displays a nonmonotonic behavior and shows
an overall behavior that is relatively insensitive to the particle
size. On a practical level, this means that the separation
performance would essentially be equally effective for all
particle sizes in the range considered, which, in turn, allows us
to use HDC for a particle suspension characterized by a wide
size distribution. To verify with the existing HDC literature,
panel (C) of Figure 3 plots the dimensionless residence time τ
(=1/Wp) versus λ.1,7,11 For a cylindrical tube, it can be
rigorously shown that, for the simplified case of a hard,
nonrotating sphere considered here, τ is given by1
2 1
= (1 + 2 ) (10)
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Analytical Chemistry
This equation fits to within 99.9% with our computed result
for the cylindrical tube case, thus validating the presently
proposed procedure. The fact that the (λ,τ)-curves for the
other considered shapes are flatter than the one for the circular
tube reconfirms the superior selectivity of the angular shapes
already clear from panels (A) and (B). For the sake of
comparison, we also added (dashed line) the selectivity of a
flat-rectangular channel.12 As can be noted, this has the worst
selectivity of all possible shapes. This is due to the blunt shape
of its velocity field parabola.
3.2. Taylor-Aris Coefficient and Scaled HETP. This
much is established for the effective particle velocity, and the
resolution of HDC separation also depends on the dispersion
bandwidth, as is evident from eq 9. We, therefore, next focus
on how the relationship between the Taylor-Aris coefficient,
Γp, and the relative particle size depends on the cross-sectional
shape. Figure 4A shows the results for the different geometries
considered obtained from the expression in eq 8.
Figure 4. (A) Taylor-Aris coefficient Γ vs dimensionless particle
radius for different channel geometries. (B) Evolution of dimension-
less plate height hp with Pep for λ = 0.2. Curve labeling is consistent
with Figure 1. The reference case (circular channel) is colored in red.
In this case, the performance of the different shapes does not
follow the same ordering as that observed for the selectivity.
The best-performing shapes (i.e., those associated with lowest
values of Γ) are the triangles (d) and (e), whereas the
remaining wedge-shaped triangles and the squared cross
section yield the highest Γp-value and therefore the largest
dispersion. All the shapes share the same decreasing tendency
of the Taylor-Aris coefficient with the increasing particle size.
To link the Γp coefficients to the general dispersion behavior,
panel B of Figure 4 translates the Γp values into a plot of the
dimensionless plate height hp versus Pep for the case of a
particle of dimensionless diameter λ = 0.2. The monotonically
decreasing trend of Γp with the particle size, which has been
observed in a variety of channel flows, can be explained based
on the following argument. From eq 8, the dispersion-
enhancing effect caused by the axial flow is given by the
average value of the squared gradient of the b-field, which is
obtained as the solution of eq 7. In this latter equation, the
magnitude of ∇b is related to the range of values attained by
the source term Wp − w(x,y) appearing at the right-hand side
of the equation, which ranges from the largest (positive) value
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attained at the boundary of the effective transport domain to
the (negative) minimum value attained at the point of the core
channel region, where the eluent velocity reaches its maximum
value. In general, the larger the range of values of Wp − w(x,y),
the higher the average magnitude of ∇b. When the particle size
increases, the maximum value decreases in view of the fact that
the boundary of the effective transport domain for the particle
moves away from the channel walls, whereas the minimum
value remains fixed. As a result, the range of values on the
right-hand side of eq 7 decreases as the particle size increases,
as does the magnitude of the gradient of the b-field. More
interesting is the structure of the integrand function ∇b × ∇b
(which could be regarded as the local source of axial
dispersion) for a fixed particle size when the shape of the
channel cross section is varied. Figure 5 shows the spatial
Figure 5. (∇⊥b) × (∇⊥b) for different channel cross sections. Same
panel labeling as in Figure 2.
contour of this function for the different geometries of a
particle of dimensionless radius Rp = 0.05. The white areas in
the contour depict the excluded volume that is inaccessible to
the center of the particle. The highest values of the gradient
magnitude are reached in the wedge-shaped triangle (g) (note
that the legend scale is different for the different shapes). By
taking the circular capillary as a benchmark to understand the
localization behavior of the gradient of the b-field, where ∇b
only possesses the radial component, one observes the
seemingly counter-intuitive phenomenon that the areas
contributing the most to axial dispersion are those where the
right-hand side of eq 7 is close to zero (i.e., where the axial
eluent velocity is close to its average value). This apparent
paradox can be explained by the boundary conditions of the b-
field at the boundary of the effective transport domain, where
the normal gradient of b(x,y) is forced to assume vanishing
values. Also, theoretical arguments can be brought up to show
that the gradient of the b-field must vanish at the center of the
channel, where the axial velocity reaches its maximum.
Combining this observation with the behavior of ∇b at the
boundary of the effective domain, one concludes that the
gradient of the b-field is constrained to become localized at an
intermediate value of the radial coordinate, where, incidentally,
the source term that ultimately causes the very presence of the
gradient attains vanishing values.
The situation is slightly more complex for the noncircular
shapes, where the above argument strictly holds true only
when ∇b is orthogonal to the boundary of the effective
transport domain. One notes that nonvanishing values of the
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gradient magnitude are found in all of the shapes because the the overall efficiency response is readily explained by the
tangential component of ∇b in not zero in these cases. Both behavior of the Taylor-Aris coefficient for the two shapes (see
the values and the localization patterns of the gradient of the b- Figure 4, which shows that the value of Γ associated with shape
field are sensitive to the specific geometry. Specifically, by (e) is significantly lower than that of shape (c), thus implying
comparing the data, one notes how a small variation of the that the overall efficiency of the separation is more influenced
bottom angle causes a relatively large variation of ∇b × ∇b. by the axial dispersion than by the velocity difference for these
3.3. Resolution of a Two-Particle Mixture. The data particle sizes.
discussed above are all reported in their nondimensional form, The same conclusions apply to the minimal separation time,
and selectivity and dispersion are discussed separately. In order as depicted in Figure 6B, which decreases with increasing
to clarify their impact on the resolution in a practical HDC eluent velocities until it reaches a plateau, where the positive
separation, we next consider the resolution of a two-particle effect of the reduced residence time in the column at increasing
suspension in open-channel HDC, where the characteristic eluent velocities is compensated by the efficiency-hindering
cross-sectional length is fixed to l = 1 μ and the sizes of the two effect of the increased axial dispersion associated with the
particle types “1” and “2” are assumed to be equal to dp(1) = 50 Taylor-Aris convection-dominated regime. Quantitative read-
nm and dp(2) = 100 nm. As observed in Section 2, particles of outs of the gain factors are given in Table 1, showing that gain
different sizes entrained in one and the same channel flow are
characterized by different Péclet numbers, which are in the Table 1. Performance Gain with Respect to the Cylindrical
same ratio as the particle diameters. Therefore, the dimen- Geometry for 3 Selected Eluent Velocities for the Different
sional values of the particle effective velocity and of the Shapesa
dispersion coefficient entering the expression of the separation
μm/s square star α = 70.6° α = 60° α = 45° α = 30°
resolution must be properly rescaled. The performance of the
different channel shapes is compared both in terms of the (A)
minimal length, Lmin needed to achieve unit resolution of the 101 1.05 3.18 3.36 2.8 2.2 1.7
two-particle mixture and of the corresponding separation time, 102 0.8 2.85 3.77 2.9 1.67 0.58
103 0.61 2.5 4.37 2.97 1.27 0.3
based on the slowest (smaller) particle type tmin = (1) + t (1)
(B)
, where σ(1) and t(1) are the variance and the average residence 101 1.05 3.3 3.56 2.93 2.27 1.73
time of the chromatogram of particles “1”, respectively. The 102 0.8 2.98 3.99 3.02 1.72 0.59
data reporting these quantities for the different shapes as a 103 0.616 2.62 4.64 3.12 1.32 0.32
function of the eluent velocity are shown in Figure 6. In terms a
(A) Ratio between the channel length to obtain unit resolution with
respect to that of the cylindrical capillary. (B) Ratio between the
separation time to obtain unit resolution with respect to that of the
cylindrical capillary.

factors on the order of 3−4.5 can be obtained with respect to

the cylindrical channel. The figures also show the separation
time in the KOH-etched shape is almost one order of
magnitude smaller than that of the cylindrical capillary and
more than one order of magnitude smaller with respect to that
of the squared channel.

Figure 6. Plots of (A) minimum channel length required to achieve
unit resolution vs eluent velocity U and (B) corresponding separation
time vs U. The characteristic length of the cross section is set to l = 1
μm, and the diameter of particles “1” and “2” is set to to dp(1) = 50 nm
and dp(2) = 100 nm, respectively. The reference case (circular
channel) is colored in red.
of the required separation length (Figure 6A), the square
channel and the wedge-shaped triangle with α = 30° perform
less well than the reference case, that is, the cylindrical
capillary. The best performing shapes are the triangular (α =
70.6 and α = 60°) cross sections [curves (d) and (e),
respectively]. It is worth highlighting how, for the particle sizes
considered (corresponding to dimensionless particle radii R(1) p leads to an increase in dispersion. Using Brenner’s macro-
= 0.025and R(2) p = 0.05), the average selectivity of the star-
shaped channel (c) is higher than that of the equilateral
triangle (e), as can be gathered from the data depicted in
Figure 3; therefore, based only on this parameter, one would
expect the star-shaped channel to be more efficient. Besides,
15985
4. CONCLUSIONS
Performing HDC separations in channels with an angular cross
section can significantly increase the separation resolution and
speed compared to the customarily considered cylindrical
capillary. This improvement is owed to the presence of the
corners, which promote the formation of regions of low
velocity, where the smaller particles are arrested with respect to
the mean velocity. At the same time, the velocity in the central
region is, for a given average fluid velocity, higher in the shapes
with sharp corners than in the circular capillaries to
compensate for their larger fraction of low velocity regions.
Both effects combined lead to a larger spread in average
velocity between larger and smaller particles, thus enhancing
the separation selectivity. On the other hand, the presence of
the corners and its concomitant effect on the velocity gradients
transport theory, it could be shown that the best overall
compromise between selectivity and dispersion is found in the
triangular shapes, with α = 60° and especially α = 70.6°, which
can be obtained by KOH etching of bulk silicon, being the best
performing. The latter has the potential to increase the
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separation speed by a factor of 4.64 compared to the (28) Edwards, D.; Brenner, H.Macrotransport Processes; Butterworth-
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■ AUTHOR INFORMATION
Corresponding Author
Gert Desmet − Department of Chemical Engineering, Vrije
Universiteit Brussel, B-1050 Brussels, Belgium; orcid.org/
0000-0001-8781-7184; Email: gert.desmet@vub.be
Authors
Valentina Biagioni − Dipartimento di Ingegneria Chimica
Materiali Ambiente, Sapienza Università di Roma, 00184
Roma, Italy
Stefano Cerbelli − Dipartimento di Ingegneria Chimica
Materiali Ambiente, Sapienza Università di Roma, 00184
Roma, Italy; orcid.org/0000-0003-3906-6595
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.analchem.2c02766

Notes
The authors declare no competing financial interest.

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