crystals

Review
Chiral, Topological, and Knotted Colloids in Liquid Crystals
Ye Yuan 1, * and Ivan I. Smalyukh 1,2,3,4, *

1 International Institute for Sustainability with Knotted Chiral Meta Matter (WPI-SKCM2),
Hiroshima University, Higashi-Hiroshima, Hiroshima 739-8526, Japan
2 Department of Physics, University of Colorado, Boulder, CO 80309, USA
3 Department of Electrical, Computer and Energy Engineering, Materials Science and Engineering Program and
Soft Materials Research Center, University of Colorado, Boulder, CO 80309, USA
4 Renewable and Sustainable Energy Institute, National Renewable Energy Laboratory and
University of Colorado, Boulder, CO 80309, USA
* Correspondence: yeyuan@hiroshima-u.ac.jp (Y.Y.); ivan.smalyukh@colorado.edu (I.I.S.)

Abstract: The geometric shape, symmetry, and topology of colloidal particles often allow for control-
ling colloidal phase behavior and physical properties of these soft matter systems. In liquid crystalline
dispersions, colloidal particles with low symmetry and nontrivial topology of surface confinement
are of particular interest, including surfaces shaped as handlebodies, spirals, knots, multi-component
links, and so on. These types of colloidal surfaces induce topologically nontrivial three-dimensional
director field configurations and topological defects. Director switching by electric fields, laser
tweezing of defects, and local photo-thermal melting of the liquid crystal host medium promote
transformations among many stable and metastable particle-induced director configurations that can
be revealed by means of direct label-free three-dimensional nonlinear optical imaging. The interplay
between topologies of colloidal surfaces, director fields, and defects is found to show a number of
unexpected features, such as knotting and linking of line defects, often uniquely arising from the non-
polar nature of the nematic director field. This review article highlights fascinating examples of new
physical behavior arising from the interplay of nematic molecular order and both chiral symmetry
and topology of colloidal inclusions within the nematic host. Furthermore, the article concludes with
a brief discussion of how these findings may lay the groundwork for new types of topology-dictated
self-assembly in soft condensed matter leading to novel mesostructured composite materials, as well
as for experimental insights into the pure-math aspects of low-dimensional topology.

Citation: Yuan, Y.; Smalyukh, I.I. Keywords: liquid crystal; colloids; topology; chirality
Chiral, Topological, and Knotted
Colloids in Liquid Crystals. Crystals
2024, 14, 885. https://doi.org/
10.3390/cryst14100885 1. Introduction
Academic Editor: Samo Kralj Liquid crystals (LCs) are characterized by the long-range orientational order of con-
stituting mesogens with anisotropic shapes, with the simplest form being a nematic LC
Received: 23 August 2024
Revised: 3 October 2024
consisting of rodlike molecules [1–3] (Figure 1a). Despite the crystal-like anisotropic prop-
Accepted: 8 October 2024
erties stemming from the orientational ordering, the weak intermolecular interactions
Published: 11 October 2024 between LC mesogens still allow for uninhibited translational motions of the building
blocks and thus liquid-like flow, earning the name “liquid crystal” of the medium that
combines properties of crystals and liquids. Different from isotropic fluids such as water,
LCs feature large anisotropic dielectric and optical properties as a result of the molecular
Copyright: © 2024 by the authors. orientation field. The combination of such anisotropy and the facile responsiveness to ex-
Licensee MDPI, Basel, Switzerland. ternal stimuli enables far-reaching technological applications, notably the flat-panel liquid
This article is an open access article crystal displays. Such properties of LCs also provide a unique anisotropic environment for
distributed under the terms and
colloidal particles, giving rise to rich phenomena not observed in conventional isotropic
conditions of the Creative Commons
solvents, opening avenues for addressing fundamental physics questions as well as explor-
Attribution (CC BY) license (https://
ing pre-designed development of novel functional materials [4–8]. Of particular interest is
creativecommons.org/licenses/by/
how the geometric shape, symmetry, and topology of colloidal particles interact with the
4.0/).

Crystals 2024, 14, 885. https://doi.org/10.3390/cryst14100885 https://www.mdpi.com/journal/crystals

Crystals 2024, 14, 885 2 of 16

LC molecular orientation field to enrich this behavior, leading to unusual topological field
distributions, colloidal interactions, and self-assembly processes.
Colloids are mixtures where particles of 1 nm to 10 µm are stably suspended in a
solvent [9–11]. Particles of this size range are susceptible to Brownian motions which ensure
the equilibrium suspension of colloidal systems, and are also responsible to other unique
colloidal behaviors including light scattering, depletion interaction, capillary assembly, etc.
Common everyday objects including milk, fog, and clay are all colloids in nature, while
artificial colloidal systems have found applications in cosmetics, energy harvesting, smart
materials, etc., as well as in understanding fundamental science questions ranging from
mechanisms of phase transitions to emergent properties of self-assembled materials [9–14].
When introduced to a LC medium, colloidal particles force the surrounding LC molecules to
reorient in order to accommodate the volume occupied and interfacial boundary conditions
imposed by the foreign objects. Such accommodation manifests as the redistribution of
the LC orientation field including both continuous deformations and singular defects,
which can spatially propagate far beyond the physical extent of the colloidal particle.
The equilibrium state of the LC colloidal system is determined by the configuration that
minimizes the total energy cost associated with the field distortions, which also leads to
long-range colloidal interactions mediated by the LC anisotropic elasticity. With the ability
to define how the LC orientation field is disturbed, the size, shape, and surface properties
of colloidal inclusions become important contributing factors determining the equilibrium
states and dynamic processes of the composite LC colloidal systems.
Early studies of LC colloids were usually carried out on highly symmetric particles of
trivial topological characteristics, such as spheres, rods, or discs [15,16]. The technological
advancement in colloidal fabrication [4,5,17,18] and microscopic imaging [19] in recent
years has allowed researchers to obtain colloidal particles of much more complex morpho-
logical characteristics, as well as resolve fine details on LC field distributions induced by
these particles. Examples of fabrication techniques include two-photon photopolymer-
ization (2PP) and new chemical synthesis protocols to obtain chiral or knotted colloidal
particles in nano and micrometer size ranges and made of a large range of constituent mate-
rials ranging from polymerizable resin to noble metals, which are reviewed elsewhere [18].
Imaging and optical manipulation techniques include three-photon excitation fluorescence
polarizing microscopy (3PEF-PM) and holographic laser tweezer. Concurrently, devel-
opments in computational modeling have enabled accurate simulations of complex LC
colloidal systems, providing insights into the underlying physics and guiding experimental
design [4,5,20].
In this review, the authors intend to provide a concise account of nematic LC colloids
containing particles of complex geometries such as chiral, topological, knotted, and linked
features. These types of colloidal particles impart their symmetry-breaking and topologi-
cally nontrivial geometries into the LC orientation field in the forms of chirality-dictated
interactions, topological constraints on singular defects, as well as knotted field configu-
rations, which is of both fundamental science and application significance. The review
is structured as follows: after these introductory statements and remarks, the following
section will lay out the physical underpinnings of colloidal particles in LCs, overviewing
the relevant theories of LC elastic energy and topological defects, which will be followed
by three main sections discussing colloidal particles of various symmetry and topology
characteristics; in the last section, we discuss further the context and implication of LC
colloids and potential future directions of development for this field.
Crystals
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FOR PEER REVIEW 3 of 16
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Colloidsin
Figure1.1.Colloids
Figure inliquid
liquidcrystals
crystals(LCs).
(LCs).(a)
(a)Microscopic
Microscopicstructure
structureofofaanematic
nematicLCLCwith
withrod-like
rod-like
mesogens, i.e., pentylcyanobiphenyl (5CB). The micrograph (right image) shows
mesogens, i.e., pentylcyanobiphenyl (5CB). The micrograph (right image) shows the texture of a 5CB the texture of a
droplet observed
5CB droplet underunder
observed a microscope with crossed
a microscope polarizers,
with crossed polarization
polarizers, direction
polarization marked
direction with
marked
white doubledouble
with white arrows. Inset shows
arrows. the chemical
Inset shows structure
the chemical of 5CBof
structure molecules and their
5CB molecules andcollective align-
their collective
ment within
alignment a small
within volume.
a small (b) Topological
volume. defects
(b) Topological in LCs
defects in LCsof of
different
differentwinding
windingnumbers;
numbers;green
green
rods
rods represent LC molecules. (c,d) Homeotropic and planar surface anchoring whereLC
represent LC molecules. (c,d) Homeotropic and planar surface anchoring where LCmolecules
molecules
align perpendicular and parallel to the surface of colloidal inclusions. Orange dots and dashes rep-
align perpendicular and parallel to the surface of colloidal inclusions. Orange dots and dashes
resent surface functioning agents such as polymer grafting that impose the anchoring direction. (e,f)
represent surface functioning agents such as polymer grafting that impose the anchoring direction.
Micrograhs showing microspheres with homeotropic surface anchoring inducing “hedgehog” point
defectMicrograhs
(e,f) and “Saturn showing
ring” linemicrospheres
defect; white with homeotropic
double surfacethe
arrows indicate anchoring inducing “hedgehog”
crossed polarizers. (g) Micro-
graphs showing microsphere with planar surface anchoring inducing “boojum” crossed
point defect and “Saturn ring” line defect; white double arrows indicate the surface polarizers.
defects at
(g) polar
the Micrographs
points ofshowing microsphere
the sphere. with planarschematics
(h–j) Corresponding surface anchoring inducing
illustrating “boojum”
LC director surface
field config-
urations around the colloidal spheres. The black dots and line represent the hedgehog defect, field
defects at the polar points of the sphere. (h–j) Corresponding schematics illustrating LC director the
Saturn ring loop,
configurations and the
around surface
the boojums,
colloidal spheres.respectively. Schematics
The black dots and lineare not drawn
represent the to scale. The
hedgehog far-
defect,
field director
the Saturn is shown
ring by the
loop, and the double
surfacearrow marked
boojums, with n0. Adapted
respectively. Schematics from
areRef.
not [21].
drawn to scale. The
far-field director is shown by the double arrow marked with n0 . Adapted from Ref. [21].
2. Basics of Physical Behavior of Colloidal Particles in LCs
The LC
2. Basics molecular
of Physical orderingofcan
Behavior be described
Colloidal Particles using the so-called director field n(r)
in LCs
representing
The LC the local average
molecular orderingof thecanmolecular
be described alignment,
using thewhich can vary
so-called as a function
director field n(r)
of
representing the local average of the molecular alignment, which can vary astoa afunction
coordinates r on scales much larger than molecular dimensions. In contrast vector
field, the constraint n(r) = −n(r) is imposed to comply with the non-polar
of coordinates r on scales much larger than molecular dimensions. In contrast to a vector nature of the LC
molecular orientations [1]. In the undisturbed state, molecules of a nematic
field, the constraint n(r) = −n(r) is imposed to comply with the non-polar nature of the LC can orient
along the sameorientations
LC molecular direction with [1]. the helpundisturbed
In the of proper surface confinement,
state, molecules of atypically
nematic setting
LC can
surface boundary
orient along conditions
the same corresponding
direction to aof
with the help uniform
properdistribution of the director
surface confinement, n(r)
typically
=setting
n0, which alsoboundary
surface corresponds to thecorresponding
conditions energy-minimizing state ofdistribution
to a uniform a uniaxial ofnematic LC.
the director
Deviating from such a “ground state” uniform alignment via producing
n(r) = n0 , which also corresponds to the energy-minimizing state of a uniaxial nematic LC.spatial gradients
of the director
Deviating fromissuch
energetically
a “groundcostly, which can
state” uniform be quantitatively
alignment via producingdescribed
spatialusing the
gradients
Frank-Oseen
of the director freeisenergy densitycostly,
energetically functional
which𝑓e can[1]:be quantitatively described using the
1 Frank-Oseen
1 free energy density
1 functional f e [1]:
𝑓e = 𝐾11 (𝛁 ⋅ 𝒏)2 + 𝐾22 (𝒏 ⋅ 𝛁 × 𝒏)2 + 𝐾33 (𝒏 × 𝛁 × 𝒏)2 − 𝐾24 𝛁 ∙ [𝒏(𝛁 ∙ 𝒏) + 𝒏 × (𝛁 × 𝒏)], (1)
2 2 2
Crystals 2024, 14, 885 4 of 16

1 1 1
fe = K (∇ · n)2 + K (n · ∇ × n)2 + K (n × ∇ × n)2 − K24 ∇·[n(∇·n) + n × (∇ × n)], (1)
2 11 2 22 2 33
where K11 , K22 , K33 , and K24 are the so-called elastic constants characterizing the energetic
costs of splay, twist, bend and saddle-splay director deformations. The typical value of
elastic constants is a few pN, for example for cyanopentylbiphenyl (5CB), a very common
LC that is in the nematic phase at room temperature (Figure 1a). In colloidal systems, where
the characteristic length scale of colloidal inclusions can be L ~ 1 µm, the ratio between
the elastic and the thermal energy is KL/kB T ~ 103 (K ~ 1–10 pN is a representative elastic
constant of LCs, kB is the Boltzmann constant and T = 300 K is the room temperature).
Therefore, the elastic energy is sufficient to overcome thermal fluctuations and lead to
elasticity-mediated colloidal interactions and self-assembled structures in LCs.
Another form of energetic cost is related to the surface of the colloidal particles.
Boundary conditions imposed by grafted polymer or other functional groups can also
define a preferred direction (often called “easy axis”) for the LC molecules to align to,
which can be normal, tangential, or sometimes conical to the surface [15,16,21]. The two
most common cases are homoetropic (normal) and planar (tangential) surface anchoring
(Figure 1c,d). The free energy density functional characterizing the energy cost of the
director deviation from the easy axes takes the Rapini-Papoular form [1]:

1
f s = − W (n·e)2 (2)
2
where e is a unit vector along the easy axis and W is the surface anchoring strength with
a typical value in the range 10−6 –10−4 J/m2 ; integrating this free energy density over
the area of LC interfaces with particles or confining substrates gives the overall energy
cost of LC-surface interaction. A parameter called “extrapolation length” can be defined
as ξ e = K/W, yielding typical values in the range ~ 10−2 –1 µm. When particle’s size is
much smaller than ξ e , it cannot disturb the director field significantly enough and thus
the bulk elastic energy contribution can be ignored; conversely, in the opposite regime
where the boundary conditions defined by the easy axis orientation at the interface can be
assumed infinitely strong, the energy cost of inserting the particle into the LC consists of
only that from elastic deformations and singular defects around the particle. Overall, in the
most general case, the equilibrium distribution of the director field around the colloidal
inclusions are determined by minimizing the total free energy of the system, which includes
integrating over the bulk volume of the system V and the enclosing surface S for the bulk
and surface energies, respectively:
Z Z
Ftotal = f e dV + f s dS. (3)
V S

When multiple particles are present, however, they can move relative to each other to
minimize the total energy, which effectively determine the elasticity-mediated colloidal in-
teraction patterns in LCs. Under the one-constant approximation where all elastic constants
are equal in value, the director field with small perturbations far away from the colloidal
particles n = (nx , ny , 1) follows the Laplace-like equation [22]:

∆nµ = 0 (µ = x, y) (4)

obtained by minimizing the Frank-Oseen free energy. Like that in electromagnetic theories,
this equation can be solved using multipole expansion expressed in terms of spherical
harmonics, and the colloidal interactions mediated by the LC elasticity can thus be inter-
preted in the multipole paradigm [22–25]. However, it is worth mentioning that in the
regime when colloidal particles are too close to each other, such that the small-perturbation
approximation may no longer hold true, contributions from higher-order multipoles and
Crystals 2024, 14, 885 5 of 16

nonlinear field effects may appear, which goes beyond the multipole expansion analysis.
While the first experimental demonstrations of elastic interactions resembling that between
electrostatic multipoles were made in 1997 when Poulin et al. discovered dipole–dipole-like
interactions between water droplets with homeotropic anchoring in a nematic LC [15],
Brochard and de Gennes in 1970 had considered such electrostatic analogy theoretically [22].
Thus far, elastic multipoles of zeroth till fourth order (monopole to hexadecapole) have
been experimentally demonstrated using various type of LC colloidal systems [15,21,26,27]
(Figure 1d), paving the way for establishing LC colloidal systems with structures and
emergent behaviors mimicking that of atomic systems [28].
In addition to continuous deformations, singularities where the local director cannot
be well-defined may also be induced by colloidal inclusions [3]. These singularities can
exist in the bulk as defect points (also called hedgehogs) and defect lines (disclinations),
as well as on the surface of the colloidal particles, where the surface point singularities
are called boojums. In fact, the name “nematic” originated from the Greek word meaning
thread, refers to the thread-like disclination lines observed in a nematic LC (Figure 1a). The
defects can be classified by computing the winding number in 2D for surface boojums and
cross section of disclinations, or topological charge in 3D for hedgehogs and compact closed
loops of disclinations [29,30]. The winding number s counts the number of times as the
director rotates by 2π following a loop circumnavigating the defect core once (Figure 1b);
the sign indicates whether the rotation direction of the director is the same or opposite
to that of the circumnavigation. Similarly, the topological hedgehog charge m counts the
number of times the unit sphere is wrapped by the director on a surface enclosing the
defect core [30]:
1
Z
m= (n·∂1 n × ∂2 n) dx1 dx2 . (5)
4π S
Several examples of singular defects with winding number of ±1/2 and ±1 are
illustrated in Figure 1b. In addition to representing the director distribution of surface
boojums, they also serve as the cross-sectional schematic of disclination lines, with the
defect core extending out of the viewing plane.
The topology of colloidal particles imposes constraints on the generation of singular
defects. Following the Gauss-Bonnet theorem and assuming uniform far-field director
n(|r| >> L) = n0 , one finds that the total topological charge induced by a colloidal particle
compensates that due to its boundary conditions and is equal to half of particle surface’s
Euler characteristic [31]
∑i mi = ±χ/2. (6)
The Euler characteristic χ is a topological invariant that can be computed, for example,
based on the number of vertices, edges, and faces of the surface, denoted by V, E, and
F, respectively
χ = V − E + F. (7)
For surface boojums in cases of tangential degenerate surface boundary conditions, the
mathematical theorems impose the requirement on the total winding number of surface
defects [32]:
∑i si = χ. (8)
However, it is important to note that the topological constraints alone cannot determine
the exact distribution of topological defects. The constraint limits the net topological
charge or winding number, while it is the minimization of the total free energy that
determines the director field deformation and defect distribution that satisfy this topological
constraint. For example, the elastic energy per unit length of a disclination line scales
with the winding number as ∝ s2 [3], indicating that disclinations of higher strength
involve significant field distortions and, thus, are energetically unfavorable, tending to
split into lower-winding-number ones. For colloidal spheres with a homoetropic surface
anchoring, either a hedgehog defect or a disclination loop named “Saturn ring” can be
found accompanying the particle (Figure 1e,f,h,i). While both configurations satisfy the
Crystals 2024, 14, 885 6 of 16

constraint in Equation (6) since spherical surfaces have an Euler characteristic of 2, the
Saturn ring is the energetically preferred one when the sphere is small, i.e., <1 µm [29]. In
contrast, the constraint in Equation (8) is fulfilled by two +1 surface boojums at both poles
for a colloidal sphere with planar surface anchoring (Figure 1g,j). More discussions on the
interplay between topological defects and colloidal particles of non-trivial topology are in
Section 4.
In addition to the literature referenced above, interested readers can refer to other
in-depth reviews and textbooks [3–5].

3. Chiral Colloids
Chirality manifests itself in many different scales, ranging from subatomic elementary
particles to molecular enantiomers with opposite optical activity and to biological and even
cosmological objects [33]. Chiral colloidal particles suspended in a LC may transfer the
broken symmetry manifestations into the surrounding medium, for example, in the form
of low-symmetry director field distributions both in the close vicinity of the particle and
in the far field, leading to topological defect distributions and novel colloidal interactions
mediated by the LC elasticity. This is in direct contrast to colloidal spheres in nematic
LCs inducing director distortions resembling symmetric distributions corresponding to
dipoles, quadruples, or higher-order multipoles [5,16]. Martinez et al. used 2PP-based 3D
microprinting to fabricate custom-designed chiral microparticles bound to substrates in LC
cells (Figure 2a,b) [34]. Nonlinear optical imaging reveals that these surface-attached parti-
cles impose a twist on the LC director field that propagates across the cell and generates
low-symmetry director distortions. A colloidal sphere inducing elastic dipole moments is
found to be attracted to the surface-bound particles following monopole–dipole interaction
scaling (Figure 2c). By engaging surface structures with chiral features, this finding pro-
vides a new way to control LC molecular alignment and the ensuing elastic interactions,
demonstrating possibilities of directing the self-assembly of colloidal particles through
engineered surfaces.
The fundamental role of particle chirality on colloidal behaviors is further revealed
with free-standing colloidal structures with chiral symmetry. Yuan et al. fabricated col-
loidal springs and helices of both handedness and re-suspended them in a nematic LC
(Figure 2d–i) [35]. Despite their complex shape, these chiral structures are topologically
equivalent to spheres, with an Euler characteristic χ = 2. Given their planar surface an-
choring, the winding numbers of the surface boojums should sum up to two following
Equation (8). For the colloidal springs, two stable (corresponding to the lowest energy
states) and metastable (local energy minima) orientations are observed experimentally,
with their helical axes tilting slightly away from being perfectly orthogonal and parallel to
n0 , respectively (Figure 2d,e). In the stable state, the topological constraint is satisfied by
two s = 1 boojums located at the edges of the spring’s two end faces, while the metastable
state has additional pairs of self-compensating boojums at positions where the surface nor-
mals are parallel to n0 . Additionally, dipole-like pair interactions arise due to the director
field deformations with chiral symmetry induced by the microsprings: the interaction is
dependent on the angle that the center-to-center separation vector makes with n0 and the
interaction potential scales as d−3 , as expected for dipole–dipole interactions (Figure 2h,i).
The interesting observation is that the equivalent dipole direction depends on the relative
handedness: same-handed microsprings interact as if they possess the same direction of
dipolar moments, while the interaction direction flips when one of the springs changes its
handedness (Figure 2f,g). These experimental observations are further supported by the
numerical modeling based on the minimization of the Landau-de Gennes free energy. The
shape anisotropy of such colloidal particles also brings in anisotropic diffusive behavior
coupled with the LC director field [36]. Overall, both reports demonstrate how chirality
can be used as an important parameter to control and engineer the colloidal interactions in
LCs. The findings bridge the microscopic chirality of individual particles with mesoscale
self-assemblies of colloidal structures, which may enable novel optical, photonic, and other
Crystals 2024, 14, x FOR PEER REVIEW 7 of 16

Crystals 2024, 14, 885 7 of 16

mesoscale self-assemblies of colloidal structures, which may enable novel optical, pho-
tonic, and other functional materials. While chirality transfer from guest molecules to the
host LC medium
functional is widely
materials. While known
chiralityand technologically
transfer from guestutilized,
moleculese.g.,
to in
thecholesteric LC dis-
host LC medium
plays
is andknown
widely electro–optic devices, the fact
and technologically that e.g.,
utilized, colloidal inclusions
in cholesteric LCwith dimensions
displays three
and electro–
orders
optic of magnitude
devices, the factlarger than theinclusions
that colloidal host LC’s molecules can also
with dimensions transfer
three chiral
orders symmetry
of magnitude
breaking
larger thaninto
thethe otherwise
host achiral can
LC’s molecules nematic host is achiral
also transfer fundamentally
symmetry important finding
breaking into the
otherwise achiral technological
with a significant nematic host potential
is a fundamentally importantoffinding
from the standpoint view ofwith a significant
the self-assembly
technological potential
of mesostructured from the
functional standpoint of view of the self-assembly of mesostructured
materials.
functional materials.

Figure
Figure 2. 2. Chiral colloids in LCs. (a) Micrograph of a chiral microstructure obtained by 3D micro-
printing.
printing. (b)(b)Director
Directorfield
fielddistortions
distortionsaround
aroundsuch sucha aparticle
particlewith
with planar surface
planar anchoring
surface anchoring bound to
bound
to the
the confining
confining substrate.
substrate. TheThelineslines
in theinmiddle
the middle
layerlayer
and theandcylinders
the cylinders
show show thatdeformation
that twist twist defor-
mation
is induced is induced in thefield
in the director director
over thefieldparticle
over the particle
despite despite
uniform uniform
far-field far-field (c)
alignment. alignment. (c)
Interaction
Interaction forces vs. distance between the surface-bound chiral structure and
forces vs. distance between the surface-bound chiral structure and a free-floating colloidal sphere. a free-floating colloi-
dal sphere. The inset is a micrograph of the interacting objects and the interaction trajectory is color-
The inset is a micrograph of the interacting objects and the interaction trajectory is color-coded with
coded with time. (d,e) Director distributions around right-handed microsprings with a planar sur-
time. (d,e) Director distributions around right-handed microsprings with a planar surface anchoring
face anchoring at energy-minimized positions. The double arrows indicate the far-field director n0;
at
theenergy-minimized
color on the particlespositions. The double
represents arrows indicate
the orientation of thethe far-field
surface director
director n0 ; the to
projected color
theon the
plane
particles
orthogonal represents the scheme
to n0; color orientation of the as
is shown surface director
the inset projected
of (d). to the plane
(f,g) Snapshots orthogonal to n0 ;
of elasticity-mediated
color schemebetween
interactions is shownlike-
as the
(f)inset
and of (d). (f,g)(g)
opposite- Snapshots
handed of elasticity-mediated
microsprings, interactions
exhibiting attractionbetween
and re-
like- (f) and
pulsion, opposite- (g)
respectively, handed
over microsprings,
the time of 10–100 exhibiting
s. Scale barsattraction
are 5 μm. and(h,i)
repulsion, respectively,
Numerically over
calculated
Landau-de
the Genness. free
time of 10–100 Scale energy vs.5particle
bars are µm. (h,i) distances between
Numerically like- (h)
calculated and opposite-
Landau-de Gennes (i) handed mi-
free energy
crosprings.
vs. When particles
particle distances between arelike-
far away
(h) and from each other,
opposite- the free
(i) handed energy scales
microsprings. as d−3particles
When like thatare
of
dipole–dipole interactions. The distance between particles
− 3 d is normalized
far away from each other, the free energy scales as d like that of dipole–dipole interactions. The by the particle radius R;
the free energy FLdG is normalized by the thermal energy kBT, where kB is the Boltzmann constant
distance between particles d is normalized by the particle radius R; the free energy FLdG is normalized
and T is the room temperature. Adapted from Refs. [34,35].
by the thermal energy kB T, where kB is the Boltzmann constant and T is the room temperature.
Adapted from Refs. [34,35].
4. Topological Colloids
4. Topological
Although Colloids
not explicitly emphasized, colloidal particles of non-trivial topology, i.e.,
non-homeomorphic to spheres
Although not explicitly (square particles
emphasized, withparticles
colloidal a hole at of
thenon-trivial
center) were introduced
topology, i.e.,
into a LC as early asto2009
non-homeomorphic (Figure
spheres 3a,b)particles
(square [37]. Thesewithsquare
a holeparticles induced
at the center) werequadrupolar
introduced
deformations
into in the
a LC as early as director field,3a,b)
2009 (Figure though
[37].the central
These holeparticles
square did not play an important
induced quadrupolarrole
in determining
deformations inthe
thecolloidal
director interactions
field, thoughinthe this particular
central hole system,
did not playwhich anwas the focus
important of
role
that
in study [37].the
determining Thecolloidal
importance of particle
interactions in topology, however,
this particular system, lieswhich
in its ability
was thetofocus
control
of
that study [37]. The
the distribution importance
of induced of particle
topological topology,
defects however,
by defining liestopological
the net in its abilityinvariant
to control
of
the
the distribution of induced
defects as described in topological defectsthe
Section 2. While bycases
defining
are the net topological
simple invariant
for topologically of
trivial
the defectsparticles,
spherical as described in Section
the most common 2. While
ones in the cases are
colloidal simple Senyuk
sciences, for topologically
et al. and trivial
Liu et
spherical particles,
al. fabricated theparticles
colloidal most common ones topology,
of nontrivial in colloidal sciences, Senyuk
handlebodies et al.genus
of various and (i.e.,
Liu
et al. fabricated colloidal particles of nontrivial topology, handlebodies
number of holes) (Figure 3c,d), and demonstrated that the total charge or winding number of various genus
(i.e., number of holes)
of topological defects(Figure
induced 3c,d),
byand demonstrated
particles that thewith
is consistent totaltopological
charge or winding
surface
number of topological defects induced by particles is consistent with topological surface
characteristics of the colloidal inclusions, following the relations given by the Gausss–
Crystals 2024, 14, 885 8 of 16

Bonnet and Poincare–Hopf index theorems [31,32]. For the surface of a particle, its Euler
characteristic is related to the genus g by χ = 2 − 2g, where genus g can be intuitively
understood as the number of holes of the surface. Thus, the topological constraint in
Equations (6) and (8) becomes [31]

∑i mi = ±(1 − g), (9)

and [32]
∑i si = 2 − 2g. (10)
The relations were experimentally confirmed while g was varied from 1 to 5, cor-
responding to handlebodies with 1 to 5 holes. For a g = 1 handlebody particle with
homeotropic surface anchoring, the most commonly observed orientation is the particle
plane being perpendicular to n0 to minimize the free energy cost. Curiously, although no
defects are topologically required to form as Equation (9) is 0 when g = 1, the constraint is
satisfied by a pair of self-compensating disclination loop or an exterior disclination loop
and a hedgehog defect at the particle center, totaling net zero on the sum of the topological
charge (Figure 3c,d) [31]. The same type of handlebody particle with g = 1 and planar
surface anchoring induces two pairs of opposite-sign boojums so that the net winding
number is 0 [32]. More interestingly, the topological constraints are still obeyed even when
external stimuli cause significant redistribution of the director field. This emergent behavior
shows how topological defects can nontrivially emerge while both satisfying pure math
theorems and yielding energetic minima of the LC–colloidal soft matter system. Scenarios
demonstrated in the above reports [31,32] include explorations of inter-transformations be-
tween point defects and disclination loops at the central regions of the handlebodies’ holes
when locally melting the LC, or when particles are reoriented following the application of
external field. In other words, the total charge is a conserved quantity that is dictated only
by the topological characteristic of the defect-inducing particles, i.e., the Euler characteristic
of the 2D LC–colloidal interface.
It is an important result vividly demonstrating how topological theorems result in
constraints on induced defects that are still “soft” in the sense of allowing the system to
choose defect configurations of a certain net topological charge that are also energetically
favorable. This energy-dependent selection of topology-satisfying configurations distantly
resembles other types of director field transformations driven by energy minimization,
such as the radial director configuration in a cylindrical homoetropic confinement escaping
into the third dimension [38]. Moreover, variations in morphological features of colloidal
particles can significantly diversify the type of defects and director deformations induced
and modulated by the surface topology even within the same constraint. Below, we discuss
two examples both involving g = 1 particles, where we find that the ensuing defects and
director distributions are drastically different because of differences in the details of the
particle geometry. Senyuk et al. discovered quarter-strength defect lines pinned to the sharp
edges of torus-like particles with a large cross section of the tube measuring 5 × 5 µm2
(compared to 1 × 1 µm2 of the handlebodies in Refs. [31,32]) (Figure 3e) [39]. While the
total topological charge is still consistent with Equation (9), the quarter-strength defect
lines are observed to migrate between edges of the particles by transforming into half-
integer disclinations across the surface of the particle, causing the particle to tilt in its
energy-minimizing orientation (Figure 3e–g). The disclinations can also be stretched and
repositioned using optical tweezers while conserving the total topological charge. A more
extreme case of changing geometric features while preserving topology involves fractal
particles with many defect-inducing corners and edges once introduced to a LC. Hashemi
et al. fabricated Koch star-based fractal particles from the 0th to the 3rd fractal iteration
order [40]. As particles of genus g = 1 with homeotropic surface anchoring, the total
topological charge induced should be 0 even though fractal shapes at high iteration orders
exhibit complex geometric details (Figure 3h). It is observed that this constraint is fulfilled
by pairs of oppositely charged defect points and disclinations found at the corners of the
 the total topological charge induced should be 0 even though fractal shapes at high itera-
tion orders exhibit complex geometric details (Figure 3h). It is observed that this constraint
is fulfilled by pairs of oppositely charged defect points and disclinations found at the cor-
Crystals 2024, 14, 885 9 of 16
ners of the fractal particles, with the number of defects growing exponentially following
the increased fractal order. However, when the fractal feature size is comparable to the
nematic correlation length characterizing the mesoscopic size of the nematic ordering, di-
fractal particles, with the number of defects growing exponentially following the increased
rector regions of reduced order parameters start to overlap, effectively causing local ne-
fractal order. However, when the fractal feature size is comparable to the nematic correlation
matic-to-isotropic
length characterizingphasethetransitions
mesoscopic in size
the vicinity of the fractal
of the nematic corners.
ordering, Self-similarities
director regions of
ofreduced
the nematic response such as defect distributions following the fractal stimulus
order parameters start to overlap, effectively causing local nematic-to-isotropic are ob-
served
phaseacross different
transitions fractal
in the iteration
vicinity of theorders,
fractal despite
corners.being limited by the
Self-similarities of nematic
the nematic corre-
lation length.
response This
such work distributions
as defect demonstratesfollowing
that colloidal particles
the fractal with are
stimulus fractal morphological
observed across
complexity, whileiteration
different fractal following the constraints
orders, despite being imposed
limitedbybythe
thetopological theorems,
nematic correlation exhibit
length.
emergent
This work behavior stemming
demonstrates that from theirparticles
colloidal fractal nature and may
with fractal be instrumental
morphological in prob-
complexity,
while
ing andfollowing the constraints
understanding nematicimposed by the topological
order interactions theorems,surfaces
with confining exhibit emergent
at limiting
behavior
length stemming from their fractal nature and may be instrumental in probing and
scales.
understanding nematic order interactions with confining surfaces at limiting length scales.

Figure
Figure3.3.Topological
Topologicalcolloids
colloidsin inLCs.
LCs. (a,b)
(a,b)AA square
square platelet withwith aa central
centralopening
openingsuspended
suspendedinin a
LC. TheThe
a LC. image
imagein (a) is taken
in (a) is takenwith fluorescence
with fluorescence confocal
confocalpolarizing
polarizing microscopy
microscopy(FCPM);
(FCPM);PFCPMPFCPM indi-
cates the polarization
indicates the polarizationdirection of the
direction of excitation light.
the excitation TheThe
light. schematic
schematicin (b) shows
in (b) shows the
thedirector
directordis-
tribution around
distribution the platelet.
around (c,d) Colloidal
the platelet. handlebodies
(c,d) Colloidal of various
handlebodies genera
of various in LCs.
genera in Panels in (c) are
LCs. Panels
micrographs obtained by overlapping fluorescence images with orthogonal
in (c) are micrographs obtained by overlapping fluorescence images with orthogonal excitation excitation polarizations
aspolarizations
indicated byasthe green by
indicated and themagenta
green and arrows;
magenta insects
arrows;below arebelow
insects cross-sectional imagesimages
are cross-sectional in the xz
plane taken along the yellow dashed lines. The schematics in (d) represent the director (black lines)
in the xz plane taken along the yellow dashed lines. The schematics in (d) represent the director
distortions and topological defects (red and purple lines; purple dots) induced by the handlebodies;
(black lines) distortions and topological defects (red and purple lines; purple dots) induced by the
the total topological charge is determined by the particle genus mc = 1 − g. (e–g) A large torus-shaped
handlebodies; the total topological charge is determined by the particle genus mc = 1 − g. (e–g) A
colloidal particle with homeotropic surface anchoring suspended in a nematic LC, inducing ½ and
large torus-shaped colloidal particle with homeotropic surface anchoring suspended in a nematic
edge-pinned ¼ defect lines. The ¼ defect lines (blue lines in the schematic (f,g)) traverses along the
LC, of
edge inducing ½ andand
the particle edge-pinned
may jump ¼ defect
between lines. The connected
edges ¼ defect linesby (blue lineslines
½ defect in the(red
schematic
lines in (f,g))
(f,g)).
traverses along the edge of the particle and may jump between edges connected
The black arrows in the micrograph in (e) indicate the location of bulk ½ defect lines; tilting of the by ½ defect lines
(red lines
particle in (f,g)). The
is indicated by theblack arrows
dashed in (rotation
line the micrograph
axis) andin (e)
redindicate
curvedthe location
arrow of bulk ½ defect
(tilt direction). Insets in
(e)lines; tilting of under
are obtained the particle
crossedis indicated
polarizers;by polarization
the dashed line (rotation
marked axis) and
by white red curved
arrows. arrow
(h) Fractal (tilt
colloidal
direction).
particles withInsets in (e) are obtained
homeotropic under crossed
surface anchoring polarizers;
in LCs. polarization
The first column ismarked
taken atbyelevated
white arrows.
temper-
(h) Fractal
atures whencolloidal particles with
the surrounding LC homeotropic
is in isotropic surface
phase;anchoring
the middle in LCs.
twoThe first column
columns is taken
are taken under
crossed polarizers
at elevated (white double
temperatures when the arrows) and crossed
surrounding polarizers
LC is in isotropicwith a retardation
phase; the middle two waveplate
columns (yel-
low
areline).
takenTheunderlastcrossed
columnpolarizers
is a computer-simulated
(white double arrows)director
andfield distribution
crossed polarizers around
with asuch particles.
retardation
Adapted
waveplate from Refs.line).
(yellow [31,37,39,40].
The last column is a computer-simulated director field distribution around
such particles. Adapted from Refs. [31,37,39,40].
 In addition to the static distributions of topological defects and direc
mations, dynamic processes involving topological colloids in LCs provide the
of exploring the out-of-equilibrium interplay between particle topology and th
Crystals 2024, 14, 885 ical feature of the director field. One cannot change the topology 10 ofofa16particle
without breaking it. However, the effective topology can be changed, for ex
smoothly opening and closing holes in a 2D surface. Exploiting the anisotropic
In addition to the static distributions of topological defects and director deformations,
formation of LCinvolving
dynamic processes elastomers upon
topological phase
colloids transitions,
in LCs Yuan et of
provide the possibility al.exploring
fabricated ri
colloidal particles and
the out-of-equilibrium discovered
interplay that when
between particle heated,
topology the
and the aspect ratio
topological ofofthe ring
feature
the director field. One cannot change the topology of a particle’s surface
and eventually, the closed holes at the center of the particles open up after the te without breaking
it. However, the effective topology can be changed, for example, by smoothly opening
isand
above
closingthe nematic–isotropic
holes phase transition
in a 2D surface. Exploiting point
the anisotropic (Figure
shape 4a) [41].
deformation Moreove
of LC
tal-like
elastomerslattices of such
upon phase LC elastomeric
transitions, Yuan et al.rings suspended
fabricated ring-shaped in the unpolymerized
colloidal particles ne
and discovered
show anisotropicthat when heated, the
collective aspect ratio of
actuations the rings
upon changes
phase and eventually,
transitions. Thetheexperim
closed holes at the center of the particles open up after the temperature is above the nematic–
ducted so far, with the director fields of elastomeric particles and unpolym
isotropic phase transition point (Figure 4a) [41]. Moreover, 2D crystal-like lattices of such
matching
LC elastomeric at the interfaces,
rings suspendeddo notunpolymerized
in the explore the induction
nematic hostand show transformation
anisotropic of
the net topological
collective actuations upon charge
phaseof the director
transitions. inside andconducted
The experiments outside so thefar,rings stays neu
with the
director fields of elastomeric particles and unpolymerized
ever, how such a change in particle topology may lead to the evolutionLC matching at the interfaces, do of t
not explore the induction and transformation of defects as the net topological charge of the
features of the director field for cases of particles made of non-LC material and
director inside and outside the rings stays neutral. However, how such a change in particle
defined
topology boundary
may lead to the conditions
evolution ofattopological
interfaces has been
features of theconsidered
director field forcomputationall
cases of
ical simulations
particles made of non-LC of such systems
material and withbywell-defined
Ravnik etboundary
al. have provided
conditions insights: for
at interfaces
has been considered computationally. Numerical simulations of such systems by Ravnik
particle with two disclination loops, shrinking of the central hole results in the
et al. have provided insights: for a toroidal particle with two disclination loops, shrinking
clination
of the centrallooping closing
hole results in theinto
innera disclination
point defect andclosing
looping eventually disappears
into a point defect and as the h
closed
eventually(Figure 4c) as[36].
disappears Weismay
the hole expect
fully closed that4c)
(Figure future
[36]. Wedevelopments in the area
may expect that future
developments
morphing in the area
colloids of shape-morphing
may allow for thecolloids
directmay allow for the of
observation direct
theobservation
interaction and
of the interaction and dynamic interplay between the topological characteristics of all
interplay
components.
between the topological characteristics of all components.

Figure 4.4.Stimuli-responsive
Figure Stimuli-responsive topological colloids. (a)
topological Ring-shaped
colloids. microparticles made
(a) Ring-shaped with liquid made
microparticles
crystal elastomers change shape upon temperature elevation over the nematic–isotropic phase
crystal elastomers change shape upon temperature elevation over the nematic–isotropic
transition point. The schematic in (a) shows the opening and closing of the central hole, effectively
sition point. The schematic in (a) shows the opening and closing of the central hole
changing the topology of the particle. (b) Alignment and polarization-dependent extinction of
changing the topology
plasmonic triangular of the
nanoframes particle.
dispersed in a(b) Alignment
nematic and polarization-dependent
LC. The schematic in (a) shows the director extinct
monic triangular
distortions caused by nanoframes dispersed
the triangular frame. in a νnematic
The normal LC.
of the plane The schematic
containing in (a)
the nanoframe has shows
distortions
the freedom to rotate in a cone shape with the far-field director n0 as the symmetry axis; P represents the nan
caused by the triangular frame. The normal ν of the plane containing
the
the freedom toofrotate
polarization in a cone
the incident light.shape with theoffar-field
(c) Contraction director
a ring-shaped n0 as
particle thehomeotropic
with symmetry axis; P
the polarization of the incident light. (c) Contraction of a ring-shaped host.
anchoring and the induced disclination loops (indicated by red lines) in a nematic LC The with h
particle
far-field director is perpendicular to the viewing plane. Adapted from Refs. [41–43].
anchoring and the induced disclination loops (indicated by red lines) in a nematic LC ho
field director is perpendicular to the viewing plane. Adapted from Refs. [41–43].

Another interesting possibility recently considered experimentally is the

material behavior under conditions when the plasmonic nanoparticles dispers
matic host have nontrivial topology. The complex geometry of triangular n
Crystals 2024, 14, 885 11 of 16

Another interesting possibility recently considered experimentally is the mesoscale

material behavior under conditions when the plasmonic nanoparticles dispersed in a
nematic host have nontrivial topology. The complex geometry of triangular nanoframes
made of gold and silver enables the generation of plasmonic effects as well as the cone-like
orientation distribution of the particles’ normal relative to the director when suspended in a
nematic LC [43]. Differently from micron-scale dielectric particles with similar topology [44],
polarization direction-dependent extinction spectra are observed upon incident light in
the visible and infrared range (Figure 4b), consistent with the symmetry prescribed by
the nanoframes’ orientation distribution in the LC. Furthermore, this guest-host system
enables the electric switching of the plasmonic extinction of the hybrid LC-nanocolloid
material reminiscent of that of pure LCs in terms of timescales and threshold voltages but
now allowing for tuning the surface plasmon resonance effects. This work complements
existing works on plasmonic LC colloids with trivial topology at the time of publishing
and may now be extended to other plasmonic particles of broken symmetry or nontrivial
topology [45].

5. Knotted and Linked Colloids

Different from our everyday experience, a knot commonly studied in topology cannot
be undone because the ends are connected to form a closed loop. The simplest form of a
mathematical knot is a ring, a.k.a., an unknot, the behavior of which as a physical object
with a tubing-like surrounding immersed in LCs is described in the previous section as
genus g = 1 particles. More complex structures, i.e., non-trivial knots, in a LC director field
induce knotted, linked, and other topologically non-trivial field configurations, allowing
for experimental insights into predictions from knot theory and into the interplay of
topologies of knotted surfaces, field deformation, and defects. Martinez et al. fabricated
colloidal trefoil and pentafoil knots of tangential and homeotropic surface anchoring and
demonstrated that a rich variety of director field and defect configurations may arise from
the minimization of the total elastic energy of the system while still following the same
topological constraints imposed by theorems from pure math (Figure 5a–e) [46]. For all
cases studied of torus knots in the paper, the Euler characteristic is χ = 0, the same as
for rings or g = 1 handlebodies, which constrains the total topological charge or winding
number to be zero. In a nematic LC, trefoil particle knots with either type of surface
anchoring tend to orient with their corresponding torus plane orthogonal to n0 in their
ground state (Figure 5a,b) where the total elastic energy is the lowest but are also found in
metastable orientations such as those with the torus plane parallel to n0 . Boojums induced
by a trefoil knot with planar anchoring are usually located at the particle’s surface where the
surface normal is parallel to n0 (Figure 5a,c). A total number of 12 boojums can be found in
such cases for trefoil-knot-shaped particles, with half of them having the winding number
of +1 and the other half −1, adding to the net total charge of zero to satisfy the topological
constraint. Similarly, a pentafoil knot with planar anchoring in the stable orientation state
will induce 20 such self-compensating defects (Figure 5d), or in other words, four times
the number of turns the knot string winding around the circular axis of the corresponding
torus. For trefoil knots with homeotropic surface anchoring, however, the particles usually
induce closed disclination loops (Figure 5e). As an example, for the case of the particle’s
torus plane perpendicular to n0 , one observes two defect loops that are both trefoil knots
tracing along the tube of the knotted trefoil-shaped particle and linked with each other and
with the particle knot, forming a three-component link of knots (inset of Figure 5e). Knotted
disclination loops can also be induced by multiple topologically simple spherical particles
in twisted LCs where complex configurations of closed disclination loops are promoted by
chiral symmetry breaking [47,48].
 gent behaviors and complexities of topological particles and director distortions even
though topological constraints for particles of Euler characteristic χ = 0 do not require the
presence of topological defects. Importantly, the disclination loops and knots would not
be even topologically stable in a polar system, so the fact that such a large variety of multi-
Crystals 2024, 14, 885 component links and knots of defects can be found demonstrates the complexity 12 ofofthe
16
interplay between topologies of surfaces and nonpolar molecular alignment fields.

Figure 5.
Figure 5. Knotted
Knotted (a–e) and linked (f–l)
(f–l) colloids
colloids in
in LCs.
LCs. (a,b) Optical
Optical micrographs
micrographs of aa trefoil
trefoil knot
knot
with planar (a) and homeotropic (b) surface anchoring suspended in LCs. Crossed
with planar (a) and homeotropic (b) surface anchoring suspended in LCs. Crossed white double white double
arrowsindicate
arrows indicatethe
thedirection
directionofofthe
the polarizer
polarizer andand
thethe analyzer
analyzer andand
the the yellow
yellow double
double arrow
arrow indi-
indicates
cates the direction of the slow axis of a 530 nm retardation plate. (c,d) Numerically simulated direc-
the direction of the slow axis of a 530 nm retardation plate. (c,d) Numerically simulated director field
tor field distributions on the surface of trefoil (c) and pentafoil (d) knots with planar surface anchor-
distributions on the surface of trefoil (c) and pentafoil (d) knots with planar surface anchoring. The
ing. The color represents the orientation of the surface director projected to the plane orthogonal to
color
n0; therepresents the orientation
color scheme is shown as of the
the inset
surfaceof director
(c). The projected to the plane
far-field director n0 is orthogonal to nto
perpendicular 0 ; the
the
color scheme is shown as the inset of (c). The far-field director n0 is perpendicular to the sample plane
as marked by the dot in a circle. (e) Schematic of defect lines (represented by green and magenta lines)
induced by and entwined with a trefoil knot of homeotropic anchoring obtained from numerical
simulation. (f) Polarizing, fluorescence, and simulated micrographs of linked colloidal rings with
tangential surface anchoring suspended in LCs. The green and red double arrows represent the
excitation polarization for fluorescence imaging. (g) Elastic interaction energy vs. deviation from
the equilibrium center-to-center separation ∆d (black symbols) and orientation ∆α (green symbols)
as defined in the inset. (h) Numerically simulated director field distributions on the surface of
a Hopf link at the position in (f). The color represents the director orientation as defined in the
inset. (i, k) Polarizing micrographs of Hopf (i) and Salomon (k) links with homeotropic surface
anchoring suspended in LCs. (j,l) corresponding simulated director field distributions and defect
field (represented by the red lines) induced by the links. The red arrow in (j) points at the location
where the disclination line jumps from one colloidal loop to the other. The double arrows marked n0
represent the far-field director. Adapted from Refs. [46,49].

Colloidal particles consisting of separate but linked components provide another

way of generating complex topological defects, such as multi-component links. When
suspended in LCs, these multi-component linked yet disconnected colloidal surfaces result
in elastic coupling of the linked component through director deformations and topological
defects that they share in their tubular surroundings. Martinez et al. fabricated Hopf and
Salomon links with the linking numbers Lk = ±1 and ±2, respectively (Figure 5f–l) [49].
The linking number is a topological invariant representing the number of times that each
individual constituting loop winds around the other. The topological constraint requires a
net zero of the total winding number or hedgehog charge given that the Euler characteristic
is χ = 0 for all colloidal links studied. For Hopf links with planar surface anchoring, the
most commonly observed director configuration contains eight boojums on the particle
surface, with the two constituting colloidal unknot laying close to each other and their
planes crossing (Figure 5f,h). The minimization of elastic energies associated with the
Crystals 2024, 14, 885 13 of 16

director distortion and topological defects holds the linked components in their equilibrium
positions despite thermal fluctuations. The elastic coupling between the constituting loops
can be characterized by tracking their positional and angular diffusion (Figure 5g) and
is found to be Hookean-like with the interaction force in the pN range. For Hopf links
with homeotropic surface anchoring, the elastic coupling manifests itself in configurations
where the induced singular defect lines jump from one component to the other, serving as
an elastic string holding the two components together (Figure 5i,j). In the more complex
cases of Salomon links, twice as many surface boojums tend to be induced compared with
their Hopf counterparts, while pairs of individual disclination loops can be seen following
each of the linked components with homeotropic surface anchoring (Figure 5k,l). However,
many metastable particle orientations and director field configurations can be observed
for linked particles of any given linking number and surface anchoring. A non-exhaustive
survey presented in Ref. [49] shows that colloidal linked rings and accompanying singular
defect loops can form many topologically distinct multi-component systems even with the
same number of unknots and linking numbers.
The colloidal systems of links and knots in LCs described above exemplify the emer-
gent behaviors and complexities of topological particles and director distortions even
though topological constraints for particles of Euler characteristic χ = 0 do not require
the presence of topological defects. Importantly, the disclination loops and knots would
not be even topologically stable in a polar system, so the fact that such a large variety of
multi-component links and knots of defects can be found demonstrates the complexity of
the interplay between topologies of surfaces and nonpolar molecular alignment fields.

6. Conclusions and Future Perspectives

A central topic in colloidal science is to investigate the emergent behavior of consti-
tuting colloidal particles as they interact and self-assemble. They are ideal candidates for
modeling the interaction and dynamics of atomic matter, such as self-assembly, crystalliza-
tion, phase transition, etc., and even envisioning artificial forms of matter and metamaterials
that go well beyond the complexity of natural systems [50–53]. Compared to the isotropic
colloidal spheres and solvents commonly used in colloidal crystals, LC colloids provide
new forms of long-range and anisotropic interactions mediated by the LC elasticity through
director field deformation [5]. The examples described in this review have shown that
varying the morphological characteristics of constituting particles such as symmetry and
topology leads to a diversity of director configurations and colloidal behaviors. These
colloidal “big atoms” with features of chiral symmetry, nontrivial topology, as well as
knotted and linked components may readily contribute to the development of colloidal
superstructures and exceed the diversity of atomic lattices. In addition, solitonic structures
in cholesteric LCs involving topological defects and knotted and linked director configura-
tions can also serve as building blocks of colloidal matter [6]. Although this review focused
on nematic colloidal systems, other types of LC phases with additional partial positional
degrees of ordering and chiral superstructures, such as cholesteric, columnar, and smectic
LCs, may provide further symmetry-breaking director distributions and solvent-mediated
interactions for LC colloids. These more complex LC field configurations add to the tool-
box accessible for exploring fundamental mathematical and physical questions as well as
developing novel functional materials with emergent properties and practical utility.
Historically, Lord Kelvin considered a model of atoms where different chemical el-
ements in the periodic table would correspond to different knotted vortices [6]. Even
though this model turned out to be incorrect, curiously, within the “colloidal atom”
paradigm involving nematic colloids and vortices shaped as knots, researchers can now
create modern-day analogs of Kelvin’s topologically protected particles, thus opening
doors to self-assembly of mesostructured materials with topology- and chirality-based
design principles.
Future directions to be pursued as essential for the field of LC colloids may include
the (i) large-scale self-assembly of low-symmetry and complex-topology colloidal particles;
Crystals 2024, 14, 885 14 of 16

(ii) design and demonstration of out-of-equilibrium processes including stimuli-responsive

dynamic rotational and translational behavior and the ensuing collective and emergent
dynamic patterns [44,54]; (iii) design of colloidal composite materials of novel viscoelastic,
electromagnetic, photonic, etc., properties; and (iv) use of ensuing novel composite materi-
als to control transmission and directional scattering of light, as needed for applications
in smart windows, displays, and electro–optic devices should be explored [55]. Like how
knotted disclination lines guide the formation of crystal-lattice-like structures of colloidal
spheres in chiral LCs [4,6], colloidal knots or other chiral and topological particles as well
as LC solitonic structures may assemble into organization patterns not accessible to their
atomic counterparts. Such novel assemblies may open possibilities to chiral, topological,
and knotted colloidal metamatter with pre-designed physical properties.
The topology- and geometry-guided colloidal self-assembly approach combines soft
and hard materials at the mesoscale in order to develop solids and fluids that exhibit
emergent physical behavior not encountered in conventional material systems, with the
inverse design and pre-engineering capabilities. Future research will need to focus on un-
derstanding and the control of material behavior arising from highly controlled mesoscale
interpenetration of ordered solid and liquid crystalline building blocks, with the composites
exhibiting solid, liquid, or mesophase behaviors controlled by weak stimuli. The design
and realization of desired physical properties in these composites can be based on the
following strategies: (1) templating the mesoscale organization of quantum and plasmonic
nanoparticles by mesoporous structures enabled by lyotropic liquid crystals to harness
quantum mechanical and plasmon–exciton interactions; (2) coupling between topological
structures of continuous and singular field configurations in the solid and soft matter
mesoscale subsystems; (3) discovery of low-symmetry fluids in hybrid molecular-colloidal
systems enriched by exploiting particle’s geometric shapes, surface charging and chirality;
and (4) emergent effects in magnetic, colloidal, and topological solitonic spin ice systems
arising in soft-hard matter systems. Electrical realignment of the LC component of the
composites may in the future allow for the rearrangement and reorientation of anisotropic
nanoparticles, leading to unprecedented control over self-assembled nanostructures and
to dramatic changes in the material emergent behavior and properties. The LC colloidal
research transcends traditional disciplinary boundaries of physics, topology, chemistry,
engineering, and materials science and will advance our knowledge of mechanisms of
the nanoscale self-organization phenomena of importance to achieving many scientific
and technological goals of renewable energy research. Since our abilities to harvest, store,
efficiently use, and convert energy among different forms are highly dependent on avail-
able materials and their properties, this research may lead to cheaper and more efficient
renewable energy technologies, a new breed of energy-efficient information displays and
electro–optic consumer devices, as well as a fertile ground for new basic science, with
transformative impacts.

Author Contributions: Writing—original draft preparation, Y.Y.; writing—review and editing, Y.Y.
and I.I.S. All authors have read and agreed to the published version of the manuscript.
Funding: Y.Y. acknowledges the financial support from the Japan Society for the Promotion of Science
(JSPS KAKENHI grant number JP24K23088) when writing the manuscript. I.I.S. acknowledges the
financial support of the fundamental research on colloids (the U.S. Department of Energy, Office
of Basic Energy Sciences, Division of Materials Sciences and Engineering, under Award ER46921,
contract DE-SC0019293 with the University of Colorado in Boulder).
Acknowledgments: I.I.S. acknowledges the hospitality of the International Institute for Sustainability
with Knotted Chiral Meta Matter (WPI-SKCM2 ) in Japan while on a sabbatical stay, as well as the
hospitality of the Kavli Institute for Theoretical Physics in Santa Barbara while participating in the
“Nanoparticle Assemblies” KITP program, when he was partially working on this review.
Conflicts of Interest: The authors declare no conflict of interest.
Crystals 2024, 14, 885 15 of 16

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