Invited Paper

Nematic liquid crystal interfaces for chemical and biological detection

Darrin R. Most, Heidi J. VanTreeck, Bart A. Grinwald, Kurt A. Kupcho, Avijit Sen,
Michael D. Bonds, Karla Anhalt, Barbara A. Israel, and Bharat R. Acharya*
Platypus Technologies LLC, 5520 Nobel Dr., Madison WI 53711
*e-mail: bacharya@platypustech.com

ABSTRACT
Nematic liquid crystals (NLCs) have traditionally been used in displays and other electro-optical applications where the
orientation of NLC is manipulated by using an external electric field to display the information. In recent years, there
have been significant advances in unconventional applications of NLCs in photonics, sensors, and diagnostics. In this
paper, the application of NLCs for detection of vapor phase chemicals and biological entities is presented. When NLCs
are in contact with another medium (solid, liquid or air) the delicate interplay between the properties of medium and
NLCs determines the nature of the alignment assumed by NLCs at the interface. Interfaces functionalized with select
chemical or biological entities promote alignment of NLCs in predetermined orientations (perpendicular or parallel to
that interface) that are primarily dictated by local interactions at the interface. When these interfaces are exposed to
target analytes, the interactions at the interfaces are perturbed and the NLC films undergo orientational transitions from
perpendicular to parallel alignment, or vice versa. The orientational transition can be detected by viewing the film of
NLCs between crossed polarizers (optical signal) or by measuring the differential capacitance associated with the change
in alignment of NLCs (electrical signal). By engineering surfaces with different interfacial properties, sensors based on
this principle have been demonstrated to selectively detect a wide variety of chemical and biological analytes that have
relevance in industrial hygiene, environmental monitoring, homeland security, diagnostics, and biomedical applications.

KEY WORDS: Nematic liquid crystals, Chemical sensors, DMMP, Virus detection, Vescicular stomatitis virus,
Dielectrophoresis, Mass transport.

I. INTRODUCTION

Nematic liquid crystals (NLCs) have traditionally been used in displays and other electro-optical devices where the
orientation of NLC is manipulated by applying an external electric field to display the information [1]. In recent years,
there have been significant advances in unconventional applications of NLCs in photonics [2] and in chemical and
biological sensors [3, 4, 5]. Here we describe two diverse applications of NLCs for detection of vapor phase chemicals
and biological entities using NLC interfaces that are in contact with a solid surface. When these interfaces are exposed to
target analytes, the interactions at the interfaces are perturbed and the NLC film undergoes orientational transitions from
perpendicular to parallel alignment, or vice versa. This orientational transition can be detected by simply viewing the
film of NLCs between crossed polarizers. To showcase the breadth of the NLC-based sensing technology, we
demonstrate sensitive detection of dimethylmethylphosphonate (DMMP) vapor in the part per billion (ppb) range and
rapid detection of vesicular stomatitis virus (VSV) following a ten minute incubation.

II. DETECTION OF SIMULANT OF SARIN (i.e., DMMP)

Some NLC materials, when supported between two surfaces treated with select transition metal complexes, assume an
alignment perpendicular to the surfaces, i.e., homeotropic alignment [6]. Using surfaces functionalized with transition
metal complexes, the selective binding of organophosphonate compounds, such as di-isopropyl methylphosphonate
(DIMP), has been demonstrated using infrared spectroscopy [7]. By exploiting the sensitivity of the NLC to molecular
changes at the NLC-substrate interface, the presence of different organophosphonate vapors has been detected using

Emerging Liquid Crystal Technologies VI, edited by Liang-Chy Chien, Hiroshi Yokoyama,
Proc. of SPIE Vol. 7955, 79550L · © 2011 SPIE · CCC code: 0277-786X/11/$18 · doi: 10.1117/12.881429

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 sensor surfaces treated with different transition metal complexes [3, 8, 9]. We have further developed this approach for
quantitative detection of a number of other gases
including DMMP, a stimulant of the nerve agent sarin.

A DMMP sensor is comprised of a microstructured gold-

coated glass substrate that is functionalized with a self-
assembled monolayer of 11-mercaptoundecanoic acid
and coated with a thin layer of aluminum perchlorate salt.
A micrometer-thick film of NLC supported on this
functionalized substrate initially assumes an alignment
perpendicular to the substrate (homeotropic alignment) as
depicted schematically in Figure 1a and the NLC film
appears dark between crossed polarizers (Figure 1c).
When the sensor is exposed to the test environment, the
DMMP molecules diffuse through the thin film of NLC
to bind to Al+3 ions on the surface. The DMMP molecules
displace the NLCs at the interface from their interaction
with the Al+3 on the surface to reorient NLC molecules
parallel to (or tilted from) the substrate (Figure 1b) and Figure 1(color): Principle of NLC-based sensors for
the NLC film appears bright between crossed polarizers detection of DMMP. (a) A surface is functionalized with
(Figure 1d). This response can be quantified by receptors that align a thin film of NLC in a prescribed
measuring the intensity of transmitted light through the orientation. (b) Upon binding of the target analytes at the
NLC film. Figure 2 shows the selective detection of 125 solid-NLC interface, the target molecules induce an
ppb DMMP relative to vapors of toxic industrial orientational transition of NLCs that can be detected by
compounds and environmental components, including monitoring the film between crossed polarizers. The sensor
humid nitrogen. This tolerance to potentially interfering appears dark in the absence (c) and bright (d) in the
compounds, especially humidity, is one attribute that presence of DMMP.
differentiates NLC-based sensors from many existing
sensors. By measuring the time required for the light transmitted through the sensor to reach a fixed intensity above the
initial value (e.g., time to reach 50% response)
we can determine the concentration of the target
160
analyte [10]. DMMP - 125ppb
Ethanol - 777ppm
Response (arb)

In order to access the effect of temperature on the Acetone - 3020ppm

performance of the sensors, the NLC-based 120 Ammonia - 100ppm

DMMP sensors were exposed to different Hydrogen Sulfide - 100ppm

Nitrogen Dioxide - 5ppm
concentrations of DMMP at various
5% Humidity
temperatures. The response time, defined as the
80 95% Humidity
time it takes for the sensor response to reach 50% Acetic Acid - 145ppm
of the full response, of identical sensors was
measured at different DMMP concentrations. The
results, as shown in Figure 3, demonstrate that 40
NLC-based sensors have minimal effect of 0 100 200 300 400 500
temperature on the response behavior at all
Exposure Time (secs)
concentrations tested. Similar effects have been
observed when the sensors were exposed to a Figure 2 (color): Selective detection of DMMP: NLC-based DMMP
range of humidity levels from 0 to 90% [11]. sensors were exposed to 125ppb DMMP and select potential
interfering compounds.

III. DETECTION OF AN ENVELOPED VIRUS

When NLCs contact interfaces decorated with lipids or lipid assemblies, the interactions of the NLCs and lipids give rise
to distinctive (e.g., homeotropic) orientations of the NLCs [12]. This exquisite sensitivity of NLCs to lipids has been

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 exploited to detect, amplify, and report the presence of biological assemblies comprised of lipid moieties such as
vesicular stomatitis virus (VSV), an enveloped virus possessing a lipid bilayer. To demonstrate the ability of NLCs to
report the presence of enveloped viruses,
clean glass substrates were coated with thin
films of polyimide (Nissan 7510). 100 o o

50% Response Time (s)

o o
50oC 40oC 24oC 5oC
Antibodies that specifically recognize
glycoproteins that are components in the
envelope of the virus or non-specific
antibodies were then physically adsorbed on
10
the polyimide coated surface by incubating a
10 l droplet of antibodies on the surface for
2 hrs at room temperature in a water
saturated environment. The antibody
functionalized surfaces were then exposed to 1
10 l of cell culture media containing 5x10 8 125 250 500 1000
plaque forming units (pfus) per ml of VSV. DMMP Concentration (ppb)
After overnight incubation at 37oC, excess
Figure 3: Effect of temperature on response of NLC-based DMMP
unbound virus was removed and the
sensors. Identical sensors (n=4) were exposed to a range of DMMP
substrates were paired with silane coated
concentrations at different temperatures.
glass slides (that provides homeotropic
alignment) forming a ~20 m thick cavity that was filled with NLC E7.

The resultant alignment of the NLC on the VSV treated surface is shown in Figure 4. The active area that was treated
with VSV-specific antibody captured VSV and the NLC molecules assumed homeotropic alignment on these surfaces;
resulting in a dark NLC film when viewed between crossed polarizers. The active area that was functionalized with
control (non-specific) antibodies was not able to capture VSV and the NLC molecules adopted planar alignment on these
surfaces; resulting in a bright NLC film when viewed between crossed
polarizers. At lower concentrations of VSV, both the surface areas
treated with specific and non-specific antibodies promoted planar
alignment. Typically, the surface density of virions required to achieve
hometropic alignment is on the order of 1 virion/100 m2 [13]. A
simple calculation suggests that the number of virions used in the
sample is significantly greater than that needed to induce homeotropic
alignment on the surface. This suggests that with the diffusion
controlled processes, the density of virions on the surface is not
sufficient to induce homeotropic alignment of NLC with VSV
concentrations lower than 5x108 pfu/ml, thereby limiting the practical Figure 4 (color): Detection of VSV using
applications of this approach. In order to improve the sensitivity and NLCs. Optical image of NLC sensors
reduce the time required for detection of VSV, dielectrophoresis was fabricated using surfaces functionalized with
used to rapidly transport virus and concentrate it on an antibody antibodies specific to VSV glycoprotein (a)
functionalized surface for detection with NLC. Dielectrophoresis is a and non-specific antibodies (b) that were
phenomenon where the dielectric particle suspended in a medium subsequently exposed to VSV. The blue lines
experiences a net force when subjected in a non-uniform AC electric are the fiduciary marks on the back of the
field. The magnitude and the direction of the force exerted on the glass substrate to identify the active area.
particle depends heavily on the dielectric properties of the particle and
the medium of suspension, the size of the particle, and the nature of the AC electric field (the distribution, amplitude, and
frequency) [14]. Dielectrophoretic manipulation of particles has been used to separate micron-sized latex particles and
for transport of biological entities such as bacteria and viruses [15, 16, 17]. We employed dielectrophoresis to accelerate
movement of VSV particles to the surface and concentrate them in a small area to increase the surface density.

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 Quadrupolar electrodes separated by a 20 m gap were prepared using conventional photolithography. The junction
between the electrodes (i.e., the active area) was
functionalized with antibodies specific to glycoproteins
on the VSV envelope or non-specific control antibodies (a) (b)
using covalent surface chemistry on the glass surface.
When the antibody functionalized-substrate is exposed
8
to a 10 l sample containing VSV at a 5x10 pfu/ml
concentration, in the presence of an AC electric
field (10Vpp, 3MHz) applied across the electrodes
for 10 mins, the virions are transported to the
active area presenting the antibodies. As shown in
Figure 5a, the active area functionalized with (c)
antibody specific to VSV and subsequently
exposed to VSV shows a positive response (dark
appearance) with brief 10 minute incubation. In
contrast, the active area treated with non-specific
antibody (i.e., a control antibody) is bright indicating a
negative response (Figure 5b). This indicates that the
electrokinetic effects and dielectrophoretic forces
associated with the non-uniform AC electric field
enhances the transport of virus particles onto the
surface. This principle also permits detection of lower 7 6 5
concentrations of VSV in an aqueous sample (Figure
5c). We note that, from an extremely small sample
volume (10 l), we can detect 2000 pfu of the virus with
a short 10 min incubation. With further optimization of Figure 5 (color): Detection of enveloped viruses using
the substrate and enrichment conditions, this limit of NLCs. Optical appearance of a NLC film (between
detection could be significantly improved to permit crossed polarizers) supported on a substrate
detection of lower concentrations of enveloped viruses. functionalized with antibody specific to VSV (a) or non-
The ability of lipids to promote homeotropic alignment specific to VSV (b) and subsequently exposed to VSV.
of NLCs at interfaces has also been shown to permit
The gold colored pads are four gold electrodes used for
detection of other lipid containing biological assemblies
in crude samples including E-coli bacteria and West application of electric field. The red circle depicts the
Nile virus in tissue homogenates of infected crows (data 20 m diameter active area. Concentration dependence
not shown). of the response (i.e., area with homeotropic alignment
normalized with respect to active area) is shown in (c).
IV. SUMMARY

Using DMMP and VSV as examples for chemical and biological targets respectively, we have demonstrated that NLC
interfaces that are decorated with (bio)chemical receptors can form the basis of a sensor platform with attractive features,
including a small footprint (< 5 mm diameter) for portability, reversible response for real-time monitoring and constant
surveillance, direct visual indication or easy integration into reporting systems (optical or electronic), ease of operation
and low manufacturing costs. This combination of attributes makes NLC sensors attractive over a range of applications
that are prohibited by the cost or complexity of other existing technologies.

V. ACKNOWLEDGEMENTS
This research was partially supported by DARPA contract # W31P4Q-04-C-R319 and NIEHS grant #R43ES16389. The
authors would like to thank Professors Nick Abbott, Department of Chemical and Biological Engineering, University of
Wisconsin-Madison and Aris Docoslis, Department of Chemical Engineering, Queens University for stimulating
discussions and suggestions.

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