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Complex Liquid Crystal Emulsions for Biosensing

Alberto Concellón, Darryl Fong, and Timothy M. Swager*
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ABSTRACT: Herein we describe a highly responsive optical

biosensor based on dynamic complex liquid crystal (LC) emulsions.
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These emulsions are simple to prepare and consist of immiscible

chiral nematic liquid crystals (N*) and fluorocarbon oils. In this
work, we exploit the N* selective reflection to build a new sensing
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paradigm. Our detection strategy is based on changes in the LC/

water interfacial activity of boronic acid polymeric surfactants caused
by reversible interactions with IgG antibodies at the LC interface.
Such biomolecular recognition events can vary the pitch length of the
N* organization due to the presence of binaphthyl units in the
polymeric structure, which are known to be powerful chiral dopants.
We demonstrate that these interface-triggered reflection changes can
be used as an effective optical read-out for the detection of the
foodborne pathogen Salmonella.

■ INTRODUCTION
Liquid crystals (LCs) are dynamic self-assembled systems that
Herein, we demonstrate that complex N* LC emulsions can
be used to fabricate a new optical sensor scheme (Figure 1).
display a unique combination of crystalline order and liquid The emulsions are dynamically reconfigurable and have two
fluidity.1,2 The intrinsic anisotropy and facile manipulation of immiscible compartments that are composed of a N* liquid
their alignment enable features for a plethora of applications, crystal and a fluorocarbon oil. The detection strategy depends
including chemical and biological sensing, optics, and soft
robotics.3−5 Confining LCs within micrometer-sized emulsion
droplets imposes constraints on the LC orientational ordering,
resulting in several mesoscale organizations that are highly
responsive to molecular-level perturbations that occur at the
LC/water (W) interface.6,7 LC emulsions are therefore
promising for sensing technologies wherein the LC alignment
acts as an amplifier for local perturbations, resulting in optical
appearance changes.8,9 For instance, recent reports have
demonstrated that LC emulsions undergo ordering transitions
in response to the presence of proteins, lipids, bacteria, or
viruses.10−14 However, the observables in these LC emulsion-
based sensors require optical microscopies with crossed-
polarizers, which can limit their real-world utility. To simplify Figure 1. Schematic representation of the mechanism for the
the optical read-out, we aimed to incorporate chiral nematic detection of Salmonella enterica using chiral nematic (N*) complex
LCs to produce complex liquid emulsions that give color emulsions. Changes in the reflected light are produced through
changes in the interfacial activity of boronic acid polymeric surfactants
changes in response to pathogens. Chiral nematic (N*) LCs,
induced by a competitive binding/unbinding of IgG antibodies at the
also informally referred to as cholesteric LCs, are one- LC/W interface.
dimensional photonic materials that reflect light as a result of
a periodic helical molecular organization. The selective
reflection is directly related to the pitch of the helical Received: April 19, 2021
organization, which can be easily changed with external stimuli Published: June 10, 2021
(i.e., pH, temperature, chemical composition, etc.). This
property has demonstrated its utility for constructing
inexpensive optical sensors that can operate under ambient
light without need for a power source.15,16

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9177 J. Am. Chem. Soc. 2021, 143, 9177−9182
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Figure 2. Schematic representation of the preparation of multicompartment emulsions comprised of immiscible N* liquid crystals (LC) and
fluorocarbon (FC) oils in water. In the evaporation-induced phase separation method, DCM is added to create a single phase and slowly evaporates
postemulsification to produce the phase-separated complex emulsion structure.

Figure 3. (a) Schematic representations (i) and side-view microscopy images (ii) and (b) polarized-light optical microscopy images without (i) and
with (ii) crossed polarizers of N*1 complex emulsions that reconfigure in response to surfactant variations. The FC/LC/W double emulsions
shown left are produced when the continuous phase has a 0.1 wt % PVA aqueous solution. The Janus droplets in the center were created in water
solutions containing 0.1 wt % PVA and 0.01 wt % Zonyl, (9:1 v/v). The LC/FC/W double emulsions shown on the right were produced in water
solutions containing 0.1 wt % PVA and 0.01 wt % Zonyl (1:1 v/v).

on a dynamic variation of the N* pitch in response to the helical twisting power (HTP) of a chiral dopant is related to its
presence of micro-organisms. This pitch variation is achieved ability to twist the nematic phase and is defined as HTP = 1/
using chiral polymer surfactants with boronic acid function- (P × C), where C is the concentration of the chiral dopant and
alities. Boronic acids are widely used recognition elements that P is the helical pitch. The wavelength of the selective reflection
reversibly bind N-glycans present in the fragment-crystallizable (λ) is defined as λ = n × P × cosθ, where n is the average
(Fc) region of IgG antibodies. Hence, the combination of the refractive index of the LC and θ is the incidence angle of the
polymer and the antibody produces a new functional light. Visible light is selectively reflected by N* phases when
macromolecular surfactant complex. We anticipated that the their pitch length is in the same regime as visible light. In this
antibody’s interaction with the target bacteria would produce work, we chose E7 as the nematic LC matrix, and (S)-4-cyano-
optical changes as a result of the modulation of the chiral 4′-(2-methylbutyl)biphenyl (CB15, HTP ≈ 7.1 μm−1) as the
polymer at the LC/water interface. We demonstrate that these chiral dopant. We prepared two chiral nematic mixtures with
changes produce optically readable and triggered reflectance different compositions of CB15 in E7, namely 1 wt % (N*1)
changes that can be used as an effective optical read-out for the and 32 wt % (N*32). The higher concentration gave a
detection of Salmonella enterica serovar Typhimurium. reflection band of the N* LC that was centered in the red

■ RESULTS AND DISCUSSION

We previously reported dynamically reconfigurable multi-
region (P = 0.44 μm, λ = 720 nm), which is useful for
investigating the emulsion’s optical properties. The lower
concentration produced a helical periodicity in the micrometer
compartment emulsions consisting of immiscible nematic LCs range (P = 14.0 μm), which can be imaged by optical
and fluorocarbon oils (FC) dispersed in water.17 The nematic microscopy.
phase is the least-ordered LC phase wherein molecules only The performance of our complex LC emulsions relies on a
exhibit orientational order. Adding a chiral compound fine control of the LC orientation, which can be accomplished
(dopant) induces the helical twisting of the mesophase by incorporating appropriately designed LC surfactants.
director, leading to a N* LC phase. The main advantage of Specifically, photonic effects in N* LC droplets are enhanced
doped N* LCs is the facility with which their pitch can be when the helical twist axis has a radial helical orientation
modulated by changing the chiral dopant concentration. The wherein the LC molecules are parallel to the droplet aqueous
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Figure 4. (a) Schematic representations (i) and side-view microscopy images (ii) and (b) reflection-mode (i) and transmission-mode with crossed
polarizers (ii) optical microscopy images of N*32 complex emulsions that reconfigure in response to surfactant variations. The FC/LC/W double
emulsions shown on the left are produced when the continuous phase has a 0.1 wt % PVA aqueous solution. The Janus droplets, in the center, are
in water with 0.1 wt % PVA and 0.01 wt % Zonyl (9:1 v/v). LC/FC/W double emulsions shown on the right were created in a water solution of 0.1
wt % PVA and 0.01 wt % Zonyl (1:1 v/v). (c) A schematic representation of the cross-communication mechanism. (d) The reflection-mode optical
microscopy images of Janus N*32 droplets (i), wherein focusing on a single droplet shows that light is transferred to neighboring droplets. Isolated
droplets (ii) do not display the radial lines that come from cross optical communication. Higher-intensity communication lines are observed from
droplets that are closer together (iii).

interface.18−20 The complex emulsion droplets have an internal In contrast, the short pitch of the N*32 Janus emulsions
interface, and we used CB-diRF as the surfactant, which prevents the observation of the helical organization by optical
stabilizes the LC/FC interface and provides a parallel (planar) microscopy. Nonetheless, reflection-mode bright-field images
alignment of the LC molecules. The planar alignment of the showed different colored patterns, confirming a periodic
mesogens at the LC/W interface was achieved using CB- internal structure (Figure 4). Specifically, N*32 Janus droplets
diTEG and poly(vinyl alcohol) (PVA). LC complex droplets showed a bright central spot together with radial lines that
were prepared using an evaporation-induced phase separation connected these central spots. The central reflection originates
method (Figure 2). Specifically, droplets were produced by the from the normal reflection of the N* arrangement, whereas the
emulsification of a 1:1:3 volume ratio of N*/HFE7200/ less-intense radial reflections are attributed to photonic
dichloromethane into a 0.1 wt % aqueous solution of PVA. interdroplet cross-communication.20 These photonic patterns
After the complete evaporation of dichloromethane (DCM), evidence the formation of an uniform radial helical structure
fluorocarbon-in-LC-in-water (FC/LC/W) double emulsions within N*32 Janus droplets. The cross-communication
were obtained. The morphology of these complex LC mechanism is shown in Figure 4c. When the incident light
emulsions can be dynamically triggered in response to changes hits at an angle of 45° (blue lines in Figure 4c), it is reflected at
in the aqueous surfactant mass balance.17,21 Thus, the addition an angle of 45° to the adjacent droplet and then reflected again
of an aqueous solution of Zonyl (a nonionic fluorosurfactant) by this droplet at an angle of 45° (depicted by the orange
transforms the droplet morphology to either a Janus arrows in Figure 4c). To corroborate this cross-communication
configuration or a LC-in-fluorocarbon-in-water (LC/FC/W) mechanism, we closed the illuminated area in our reflection
double emulsion (Figure 3). microscope; nonilluminated droplets did not show the central
To gain insight into the internal structure of these chiral reflection spot and only showed the radial reflections coming
nematic double emulsions, we initially investigated N*1 from the neighboring illuminated droplet (Figure 4d(i)).
emulsions since they have a helical pitch in the micrometer Moreover, we isolated one and three droplets to study their
range that can be readily visualized by optical microscopy. reflection patterns. The isolated single droplet did not show
Periodic dark and bright concentric rings were observed in any lateral communication and only showed the central
N*1 Janus droplets. This suggests a radial disposition of the reflection (Figure 4d(ii)). However, the cross-communication
N* helixes that originates from the equator of the droplet. This interactions between adjacent droplets can be readily visualized
radial helical structure produces a pattern of equidistant in the group of three droplets. We also noticed that the
concentric rings whose inter-ring periodicity corresponds to P/ intensity of the cross-communication process depends on the
2 (Figure 3).22 In the case of FC/LC/W and LC/FC/W distance between the droplets, disappearing with large
double emulsions, they also exhibited helical structures with interdroplet distances (Figure 4d(iii)). FC/LC/W and LC/
concentric rings due to the radial disposition of the N* layers. FC/W double emulsion droplets also exhibited radial helical
In addition, a radial defect line was observed in LC/FC/W structures. The uniform radial disposition of the N* helixes in
droplets, suggesting that all N* layers follow a group of circles LC/F/W double emulsions was confirmed by the presence of a
that pass through the same point (Frank−Pryce model).23 central defect in the LC compartment. In addition, FC/LC/W
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double emulsions exhibited a colored pattern by reflectance of the polymeric surfactants as the large IgG molecules (≈150
microscopy, which was generated by photonic cross- kDa) provide an additional hydrophilic character.32 We
communication between adjacent droplets similarly to those hypothesized that our bioconjugated surfactants would be
of previously reported water-in-oil-in-water N* shells (Figure mainly located at the LC/W interface due to their higher
4b).24,25 Nonetheless, LC/FC/W did not exhibit any colored interfacial activity, and their ability to affect the helical
pattern due to a total internal reflection across the LC/FC structure of the N* LC would thus be much lower. In
interface that confined all light within the fully encapsulated contrast, a powerful chiral dopant activity was expected for
LC compartment (Figure 4b).26 nonbioconjugated block copolymer surfactants as a result of
Having optimized the preparation of N* complex emulsions, their lower tendency to assemble at the LC/W interface.
we targeted their use as biosensors wherein a change of the Because of the high HTP of the binaphthyl side-chains (an
pitch may produce a change in the reflection wavelength. This HTP value of 122 μm−1 was calculated for P1, see the
pitch variation can be achieved by adsorbing the analyte at the Supporting Information), minuscule changes in the interfacial
LC interface or dissolving it in the LC medium, producing a activity of the boronic acid surfactants is enough to alter the
physical swelling of the N* helix and a red-shift of the reflected pitch of the chiral nematic organization, which can be detected
light.27,28 The selectivity of such sensors is therefore by monitoring the normal reflection.
determined by the analyte solubility in the N* LC. However, To ensure an efficient dynamic assembly at the LC/W
most biomolecules or micro-organisms are not soluble in N* interface, we synthesized three different polymers with the
LCs; hence, different mechanisms are needed in emulsion- same LC block, molecular weights (Mn ≈ 12 kDa), and
based biosensors. To this end, we targeted the incorporation of hydrophilic/hydrophobic balance (whydrophilic ≈ 20 wt %) but
IgG antibodies in our complex N* emulsions for the selective different hydrophilic block compositions (Figure 5). Given
detection of the Salmonella bacteria, a foodborne pathogen that that we were unsure of how this structural variation in the
causes a gastrointestinal infection. hydrophilic block would affect the polymer assembly at the
Side-chain LC polymer surfactants have been widely used to LC/W interface, the surfactant ability was quantified by
trigger LC ordering transitions in response to external stimuli. pendant-drop measurements. All non-bioconjugated polymers
In these systems, changes in the polymeric assembly at the were surface active, reducing the LC/W interfacial tension
LC/W interface propagates throughout the LC, resulting in a (γLC/W) from 52.9 mN/m to 32.9 (P1), 29.0 (P2), and 16.7
change in the LC organization.29,30 In our case, to generate mN/m (P3) when 5 mg/mL of the polymer was dispersed in
changes in the pitch of the N* structure in response to the the N* LC. Pendant-drop studies also confirmed the impact of
presence of micro-organisms, we designed amphiphilic block bioconjugation on γLC/W, since the addition of anti-Salmonella
copolymers that contained LC and water-soluble blocks IgG antibodies to the continuous water phase further reduced
(Figure 5). The LC-soluble block is composed of binaphthyl the value of γLC/W to 16.3 (P1), 16.9 (P2), and 14.2 mN/m
(P3). Therefore, pendant-drop measurements revealed that
polymers position boronic acid groups at the LC/W interface,
enabling bioconjugation via boronate ester formation with the
N-glycans in the Fc region of the IgG antibodies and the
production of IgG-decorated N* LC droplets.
Our sensing scheme relies on changes in the interfacial
activity of boronic acid surfactants associated with a
competitive binding/unbinding of IgG antibodies at the LC/
W interface (Figure 6a). Therefore, we prepared complex N*
LC emulsions containing the polymeric surfactant P1, since P1
showed the biggest differences in γ LC/W values upon
bioconjugation with IgG antibodies. Janus droplets naturally
gravity align on a horizontal surface as a result of the higher
density of the fluorocarbon phase. In this natural configuration,
the normal reflection can be measured by positioning a fiber-
Figure 5. Chemical structures of boronic acid surfactants and
optical spectrophotometer connected to a white light over a
pendant-drop analysis of the bioconjugation reaction. Note that the monolayer array composed of monodisperse N* Janus
polymer/antibody complexes lower the water/N* LC interfacial emulsions (Figure 6b). Reflectance spectra of N*32 droplets
tensions. showed a main peak located at a wavelength of around 720 nm,
which originated from the normal reflection of the chiral
nematic LC (Figure 6c). A less-intense secondary peak was
motifs, which are known to provide a high HTP value,31 that also observed at around 515 nm, which was coincident with λ
were randomly copolymerized with a cyanobiphenyl meth- × cos(45°) due to the photonic cross-communication between
acrylate to favor its solubility in the nematic LC matrix the droplets. The incorporation of P1 into the LC mixture (5
(binaphthyl/cyanobiphenyl weight proportion ≈80:20). The mg/mL) resulted in N* emulsions with a main reflection band
water-soluble block has boronic acid functionalities. These around 590 nm, demonstrating the ability of P1 to alter the
multifunctional block copolymers function as cosurfactants in pitch of the N* organization. Moreover, the attachment of
the emulsification process to prepare our N* droplets. The hydrophilic IgG antibodies led to a red-shift of the main
boronic acid groups are positioned at the LC/W interface for reflection band to 670 nm as a result of a major localization of
reversible binding with anti-Salmonella Typhimirium IgG P1 at the LC/W interface.
antibodies. We previously observed that bioconjugation with The pitch variation as a function of the concentration of
IgG antibodies results in an increase of the interfacial activity heat-killed Salmonella enterica serovar Typhimurium (HKST)
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Figure 6. (a) Scheme of the detection mechanism for Salmonella using boronic acid-decorated complex N* colloids. Changes in the interfacial
activity of boronic acid surfactants are produced by the attachment of IgG antibodies at the LC/W interface and upon their removal by Salmonella
cells, resulting in a change of the pitch length. (b) Experimental setup for measuring the reflectance spectra of the emulsions. (c) Reflectance
spectra of N*32 emulsion droplets after the addition of HKST at different concentrations. (d) Correlation of the relative reflection versus the
concentration of HKST cells.

cells was quantified using the normal reflection of N* droplets. N* complex colloids with radial helical structures. The pitch
A rapid shift (ca. 3 h.) of the reflection band to lower length of the N* organization can be easily controlled by the
wavelengths was observed after the addition of HKST cells to amount of the chiral dopant, thereby obtaining emulsions with
IgG-decorated Janus emulsions (Figure 6c). Figure 6d shows wavelengths of reflected light. Moreover, the helical internal
the correlation of the relative reflection band and the organization provided complex reflection patterns caused by
concentration of HKST cells. The detection limit was the unique combination of the selective reflection of N* LC
calculated to be 103−104 cells/mL. In the control experiments emulsions and lateral interactions between neighboring
under the same conditions with a block copolymer droplets. In this work, we exploited these rich photonic
cosurfactant that did not have binaphthyl motifs in the LC properties to construct a new sensing paradigm. Specifically,
block (P1-achiral), the reflection band did not show any we designed boronic acid polymeric surfactants that change
change upon the addition of HKST, confirming the key role of their LC/W interfacial activity as a result of their selective
binaphthyl units in inducing changes in the helical pitch binding with IgG antibodies. Such biomolecular recognition
(Figure 6d). A second control experiment was carried out with events can vary the pitch length of the N* organization as a
a block copolymer that had N-hydroxysuccinimide groups result of the presence of binaphthyl units in the polymeric
instead of boronic acids (P1-NHS). No variation of the structure, which are known to be powerful chiral dopants.
reflection band was observed, thereby demonstrating the These dynamic interface-triggered reflection changes were
importance of the reversible interfacial reactions in our sensing used to fabricate a sensitive and quantitative detection
scheme, since P1-NHS forms covalent amide bonds with IgG approach for the foodborne pathogen Salmonella. The simple
antibodies that avoid the pathogen-induced extraction of IgG fabrication of chiral nematic emulsions and the quantitative
from interfaces (Figure 6d). Therefore, this N* emulsion optical read-out illustrates an alternative method for biological
sensor scheme illustrates an alternative and robust strategy for and chemical sensing.
detecting Salmonella, which can be used in a complex protein
matrix.26 Moreover, it is not limited to a particular pathogenic
organism and can be adapted to a wide range of analytes
■
*
ASSOCIATED CONTENT
sı Supporting Information
without the need for specialized equipment. The Supporting Information is available free of charge at

■ CONCLUSIONS
We have developed complex liquid emulsions that consist of
https://pubs.acs.org/doi/10.1021/jacs.1c04115.
Materials, characterization techniques, experimental
procedures, synthesis, and characterization (PDF)

■
immiscible chiral nematic (N*) liquid crystals (LC) and
fluorocarbon oils (FC). The morphologies of these LC
emulsions can be dynamically changed by varying the mass AUTHOR INFORMATION
balance of the aqueous surfactants. Moreover, the incorpo- Corresponding Author
ration of appropriately designed LC surfactants, which control Timothy M. Swager − Department of Chemistry,
the LC orientation at the interfaces, enables the preparation of Massachusetts Institute of Technology, Cambridge,
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J. Am. Chem. Soc. 2021, 143, 9177−9182
Journal of the American Chemical Society pubs.acs.org/JACS Article

Massachusetts 02139, United States; orcid.org/0000- (15) Schenning, A. P. H. J.; Crawford, G. P.; Broer, D. J. Liquid
0002-3577-0510; Email: [email protected] Crystal Sensors; CRC Press: Boca Raton, FL, 2018; p xiv.
(16) Mulder, D. J.; Schenning, A. P. H. J.; Bastiaansen, C. W. M.
Authors Chiral-nematic liquid crystals as one dimensional photonic materials
Alberto Concellón − Department of Chemistry, Massachusetts in optical sensors. J. Mater. Chem. C 2014, 2 (33), 6695−6705.
Institute of Technology, Cambridge, Massachusetts 02139, (17) Concellón, A.; Zentner, C. A.; Swager, T. M. Dynamic
Complex Liquid Crystal Emulsions. J. Am. Chem. Soc. 2019, 141 (45),
United States; orcid.org/0000-0002-8932-9085
18246−18255.
Darryl Fong − Department of Chemistry, Massachusetts (18) Schwartz, M.; Lenzini, G.; Geng, Y.; Rønne, P. B.; Ryan, P. Y.
Institute of Technology, Cambridge, Massachusetts 02139, A.; Lagerwall, J. P. F. Cholesteric Liquid Crystal Shells as Enabling
United States; orcid.org/0000-0002-0231-683X Material for Information-Rich Design and Architecture. Adv. Mater.
Complete contact information is available at: 2018, 30 (30), 1707382.
https://pubs.acs.org/10.1021/jacs.1c04115 (19) Park, S.; Lee, S. S.; Kim, S.-H. Photonic Multishells Composed
of Cholesteric Liquid Crystals Designed by Controlled Phase
Separation in Emulsion Drops. Adv. Mater. 2020, 32 (30), 2002166.
Notes (20) Fan, J.; Li, Y.; Bisoyi, H. K.; Zola, R. S.; Yang, D.-k.; Bunning,
The authors declare no competing financial interest. T. J.; Weitz, D. A.; Li, Q. Light-Directing Omnidirectional Circularly

■ ACKNOWLEDGMENTS
This work was supported by the Vannevar Bush Faculty
Polarized Reflection from Liquid-Crystal Droplets. Angew. Chem., Int.
Ed. 2015, 54 (7), 2160−2164.
(21) Zarzar, L. D.; Sresht, V.; Sletten, E. M.; Kalow, J. A.;
Blankschtein, D.; Swager, T. M. Dynamically reconfigurable complex
Fellowship (Grant N000141812878). D.F. is grateful for an emulsions via tunable interfacial tensions. Nature 2015, 518 (7540),
NSERC Postdoctoral Fellowship from the Government of 520−524.
Canada. (22) Cipparrone, G.; Mazzulla, A.; Pane, A.; Hernandez, R. J.;

■
Bartolino, R. Chiral Self-Assembled Solid Microspheres: A Novel
REFERENCES Multifunctional Microphotonic Device. Adv. Mater. 2011, 23 (48),
5773−5778.
(1) Kim, Y.-K.; Noh, J.; Nayani, K.; Abbott, N. L. Soft matter from (23) Bouligand, Y.; Livolant, F. The organization of cholesteric
liquid crystals. Soft Matter 2019, 15 (35), 6913−6929. spherulites. J. Phys. (Paris) 1984, 45 (12), 1899−1923.
(2) van der Asdonk, P.; Kouwer, P. H. J. Liquid crystal templating as (24) Geng, Y.; Noh, J.; Drevensek-Olenik, I.; Rupp, R.; Lenzini, G.;
an approach to spatially and temporally organise soft matter. Chem. Lagerwall, J. P. F. High-fidelity spherical cholesteric liquid crystal
Soc. Rev. 2017, 46 (19), 5935−5949. Bragg reflectors generating unclonable patterns for secure authenti-
(3) Pilz da Cunha, M.; Debije, M. G.; Schenning, A. P. H. J. cation. Sci. Rep. 2016, 6 (1), 26840.
Bioinspired light-driven soft robots based on liquid crystal polymers. (25) Geng, Y.; Jang, J.-H.; Noh, K.-G.; Noh, J.; Lagerwall, J. P. F.;
Chem. Soc. Rev. 2020, 49 (18), 6568−6578. Park, S.-Y. Through the Spherical Looking-Glass: Asymmetry Enables
(4) Nayani, K.; Yang, Y.; Yu, H.; Jani, P.; Mavrikakis, M.; Abbott, N. Multicolored Internal Reflection in Cholesteric Liquid Crystal Shells.
Areas of opportunity related to design of chemical and biological Adv. Opt. Mater. 2018, 6 (1), 1700923.
sensors based on liquid crystals. Liq. Cryst. Today 2020, 29 (2), 24− (26) Zeininger, L.; Nagelberg, S.; Harvey, K. S.; Savagatrup, S.;
35. Herbert, M. B.; Yoshinaga, K.; Capobianco, J. A.; Kolle, M.; Swager,
(5) Kato, T.; Uchida, J.; Ichikawa, T.; Sakamoto, T. Functional T. M. Rapid Detection of Salmonella enterica via Directional
Liquid Crystals towards the Next Generation of Materials. Angew. Emission from Carbohydrate-Functionalized Dynamic Double
Chem., Int. Ed. 2018, 57 (16), 4355−4371. Emulsions. ACS Cent. Sci. 2019, 5 (5), 789−795.
(6) Miller, D. S.; Wang, X.; Abbott, N. L. Design of Functional (27) Lee, H.-G.; Munir, S.; Park, S.-Y. Cholesteric Liquid Crystal
Materials Based on Liquid Crystalline Droplets. Chem. Mater. 2014, Droplets for Biosensors. ACS Appl. Mater. Interfaces 2016, 8 (39),
26 (1), 496−506. 26407−26417.
(7) Chen, H.-Q.; Wang, X.-Y.; Bisoyi, H. K.; Chen, L.-J.; Li, Q. (28) Pschyklenk, L.; Wagner, T.; Lorenz, A.; Kaul, P. Optical Gas
Liquid Crystals in Curved Confined Geometries: Microfluidics Bring Sensing with Encapsulated Chiral-Nematic Liquid Crystals. ACS Appl.
New Capabilities for Photonic Applications and Beyond. Langmuir Polym. Mater. 2020, 2 (5), 1925−1932.
2021, 37 (13), 3789−3807. (29) Adamiak, L.; Pendery, J.; Sun, J.; Iwabata, K.; Gianneschi, N.
(8) Wang, D.; Park, S.-Y.; Kang, I.-K. Liquid crystals: emerging C.; Abbott, N. L. Design Principles for Triggerable Polymeric
materials for use in real-time detection applications. J. Mater. Chem. C Amphiphiles with Mesogenic Side Chains for Multiscale Responses
2015, 3 (35), 9038−9047. with Liquid Crystals. Macromolecules 2018, 51 (5), 1978−1985.
(9) Lowe, A. M.; Abbott, N. L. Liquid Crystalline Materials for (30) Ma, C. D.; Adamiak, L.; Miller, D. S.; Wang, X.; Gianneschi, N.
Biological Applications. Chem. Mater. 2012, 24 (5), 746−758. C.; Abbott, N. L. Liquid Crystal Interfaces Programmed with
(10) Munir, S.; Kang, I.-K.; Park, S.-Y. Polyelectrolytes function- Enzyme-Responsive Polymers and Surfactants. Small 2015, 11 (43),
alized nematic liquid crystal-based biosensors: An overview. TrAC, 5747−5751.
Trends Anal. Chem. 2016, 83, 80−94. (31) Bisoyi, H. K.; Li, Q. Light-Directing Chiral Liquid Crystal
(11) Lin, I.-H.; Miller, D. S.; Bertics, P. J.; Murphy, C. J.; de Pablo, J. Nanostructures: From 1D to 3D. Acc. Chem. Res. 2014, 47 (10),
J.; Abbott, N. L. Endotoxin-Induced Structural Transformations in 3184−3195.
Liquid Crystalline Droplets. Science 2011, 332 (6035), 1297−1300. (32) Zhang, Q.; Scigliano, A.; Biver, T.; Pucci, A.; Swager, T. M.
(12) Sivakumar, S.; Wark, K. L.; Gupta, J. K.; Abbott, N. L.; Caruso, Interfacial bioconjugation on emulsion droplet for biosensors. Bioorg.
F. Liquid Crystal Emulsions as the Basis of Biological Sensors for the Med. Chem. 2018, 26 (19), 5307−5313.
Optical Detection of Bacteria and Viruses. Adv. Funct. Mater. 2009, 19
(14), 2260−2265.
(13) Brake, J. M.; Daschner, M. K.; Luk, Y.-Y.; Abbott, N. L.
Biomolecular Interactions at Phospholipid-Decorated Surfaces of
Liquid Crystals. Science 2003, 302 (5653), 2094−2097.
(14) Aliño, V. J.; Pang, J.; Yang, K.-L. Liquid Crystal Droplets as a
Hosting and Sensing Platform for Developing Immunoassays.
Langmuir 2011, 27 (19), 11784−11789.

9182 https://doi.org/10.1021/jacs.1c04115
J. Am. Chem. Soc. 2021, 143, 9177−9182