Technological advancements in bio-recognition using liquid crystals: Techniques, applications, and performance.

The application of liquid crystal (LC) materials has undergone a modern-day renaissance from its classical use in electronics industry as display devices to new-fangled techniques for optically detecting biological and chemical analytes. This review article deals with the emergence of LC materials as invaluable material for their use as label-free sensing elements in the development of optical, electro-optical and electrochemical biosensors. The property of LC molecules to change their orientation on perturbation by any external stimuli or on interaction with bioanalytes or chemical species has been utilized by many researches for the fabrication of high sensitive LC-biosensors. In this review article we categorized LC-biosensor based on biomolecular reaction mechanism viz. enzymatic, nucleotides and immunoreaction in conjunction with operating principle at different LC interface namely LC-solid, LC-aqueous and LC-droplets. Based on bimolecular reaction mechanism, the application of LC has been delineated with recent progress made in designing of LC-interface for the detection of bio and chemical analytes of proteins, virus, bacteria, clinically relevant compounds, heavy metal ions and environmental pollutants. The review briefly describes the experimental set-ups, sensitivity, specificity, limit of detection and linear range of various viable and conspicuous LC-based biosensor platforms with associated advantages and disadvantages therein.

Hierarchical self-assembling and helical structure in focal conic domains in meniscus of ferroelectric liquid crystal.

We investigate experimentally the formation of focal conic domains of the ferroelectric phase of a liquid crystal, chiral smectic C (SmC^{*}), in the meniscus geometry. The meniscus geometry is formed in the gap between two glass plates which are placed on a common substrate. This gap is called here a physical cavity. Focal conic domains (FCDs) in the physical cavity with dimensions of micrometer scale are investigated under an optical polarizing microscope which enables us to extract the information on the helical structure formation in the constraint and gradient topological meniscus interface. The helical pitch in the FCD is observed to be shorter than in planar confined geometry. A crucial phenomenon of unwrapping and wrapping of helical structure from one FCD to another is also observed. In-plane application of an electric field on a FCD revealed the asymmetric helical unwinding process whereas an increase in temperature has shown symmetrical unwinding. The helical structure based observation is significant for understanding the ferroelectric phase in focal conic domains and their application in microlenses and optical components.

Correlation between alignment geometries and memory effect in a surface-stabilized ferroelectric liquid crystal.

Memory effect in weakly aligned surface stabilized ferroelectric liquid crystal (SSFLC) material has been investigated by electro-optical and dielectric spectroscopy in three configurations of alignment: antiparallel, 90^{∘} twisted, and unaligned planar samples. It has been observed that two types of molecular dynamics exist in antiparallel rubbed cell in which memory effect is observed for longer duration than in other samples. One dielectric relaxation process is near the surface of the electrode and a second is in the bulk of the SSFLC. Both the molecular dynamics contribute in the switching process and affect the memory phenomenon in surface stabilized geometries. However, a single dielectric process is observed in twisted geometry in which the sample is showing shorter memory effect than in antiparallel and this is compared with unaligned samples also having cell thickness less than the pitch value of FLC. In an unaligned sample, a single dielectric process is observed and the smaple does not show memory effect at all. The investigation is significant to understand the anomalies occurring in memory observations in various geometries.

Collective dielectric processes at the transition temperature of the Sm-C

An anomalous dielectric relaxation process, called the partially unwound helical mode (p-UHM), is a collective dielectric process apart from the well known Goldstone and soft mode process; it is studied in the smectic C^{*} (Sm-C^{*}) phase and at the transition temperature of the Sm-C^{*}-Sm-A^{*} phase in the ferroelectric liquid crystal (FLC) material. To avoid the surface effect, a thick cell of 40 µm thickness was prepared with highly rubbed surfaces of the ITO substrates. It has been observed that the dielectric properties in Sm-C^{*} and at the T_{c} temperature are dominated by the p-UHM process which is dependent on an applied oscillating field in the Sm-C^{*} phase. The probing ac and dc bias field dependences of all these collective dielectric processes have been reported in the Sm-C^{*} and Sm-A^{*} phases of FLC materials.

Interfacial behavior of confined mesogens at smectic-C*-water boundary.

In this paper, we have investigated the behavior of mesogens at smectic-C*-water interface confined in a liquid crystal (LC) cell with interfacial geometry. Polarized optical microscopy was used to probe the appearance of various smectic-C* domain patterns at water interface owing to the reorientation of mesogens. The undulated stripe domains observed at the air interface of smectic-C* meniscus vanished as the water entered into the smectic layers and focal conical domain patterns appeared at smectic-C*-water boundary. A spatially variable electro-optical switching of LC molecules was also observed outside the electrode area of the interfacial cell. The electrode region at the interface, as well as on the water side, was damaged upon application of an electric field of magnitude more than 150 kV/m. The change in dielectric parameters of mesogens was extensively studied at interface after evaporating the water. These studies give fundamental insights into smectic-C*-water interface and also will be helpful in fabricating better LC devices for electro-optical and sensing applications.

Dielectric relaxation process of a partially unwound helical structure in ferroelectric liquid crystals.

The fluctuations of unwound helical structure have been observed in deformed helix ferroelectric liquid crystal (DHFLC) and conventional FLC sample cells. The helix is partially unwound by strong anchoring on the substrates. In such sample cells, the helical decarlization lines are not observed in the texture under crossed polarized microscope. The dielectric spectroscopy is employed to observe the behavior of dielectric relaxation processes in these sample cells. A dielectric relaxation process is observed at a lower frequency than the Goldstone mode processes in DHFLC and FLC, which we call partially unwound helical mode (p-UHM). However, the p-UHM process is not observed in the sample cell in which the helical lines appear. The application of various amplitudes of probing ac voltages on this mode has shown the higher frequency shift, i.e., the larger the amplitude of ac voltage, the higher is the relaxation frequency of p-UHM. At sufficient amplitude of applied probing ac voltage, the p-UHM merges with the Goldstone mode process and is difficult to detect. However, the Goldstone mode relaxation frequency is almost independent of the cell geometry and sample configuration. The electro-optical behavior of the p-UHM has also been confirmed by electro-optical technique. The dielectric relaxation of UHM at a frequency lower than the Goldstone mode is interpreted as the fluctuation of partially unwound helix.

Scientific developments of liquid crystal-based optical memory: a review.

The memory behavior in liquid crystals (LCs), although rarely observed, has made very significant headway over the past three decades since their discovery in nematic type LCs. It has gone from a mere scientific curiosity to application in variety of commodities. The memory element formed by numerous LCs have been protected by patents, and some commercialized, and used as compensation to non-volatile memory devices, and as memory in personal computers and digital cameras. They also have the low cost, large area, high speed, and high density memory needed for advanced computers and digital electronics. Short and long duration memory behavior for industrial applications have been obtained from several LC materials, and an LC memory with interesting features and applications has been demonstrated using numerous LCs. However, considerable challenges still exist in searching for highly efficient, stable, and long-lifespan materials and methods so that the development of useful memory devices is possible. This review focuses on the scientific and technological approach of fascinating applications of LC-based memory. We address the introduction, development status, novel design and engineering principles, and parameters of LC memory. We also address how the amalgamation of LCs could bring significant change/improvement in memory effects in the emerging field of nanotechnology, and the application of LC memory as the active component for futuristic and interesting memory devices.

Probing the dynamics of geometrically confined ferroelectric mesogens at the air interface.

This article focuses on the alignment and dynamics of mesogens at the ferroelectric liquid crystal (FLC)/air interface in a confined geometry. The interface has been systematically prepared and characterised with provision for applying an electric field separately to the bulk and air interface of the FLC. Polarizing optical microscopy (POM) investigations done at the FLC/air interface have exposed the concave geometry, cell thickness dependent boundary width and phase dependent optical textures of the FLC meniscus at the interface. Dielectric spectroscopy investigations revealed the presence of an additional molecular relaxation mode at the FLC/air interface, which is attributed to the short axis rotation of homeotropically aligned mesogens at the interface. Based on the observations from the POM, dielectric spectroscopy and X-ray diffraction profiles, we schematically envisaged the molecular arrangement and dynamics of the FLC/air boundary. These studies would be helpful for innovations in liquid crystal based devices and also for many other applications, where soft surfaces, interfaces and confinement play a momentous role.

Advances in gold nanoparticle-liquid crystal composites.

We present the advancement in the research of the dispersion of gold nanoparticles (GNPs) in thermotropic calamitic liquid crystals. The formation/behavior of surface plasmon resonance (SPR) in GNPs is briefly described. The uniform dispersion of GNPs into liquid crystals along with two important aspects, i.e. tuning of GNP properties by liquid crystal and vice versa, are widely discussed. Overall, the article highlights the advances in the research into GNP-liquid crystal composites in terms of their scientific and technological aspects.

Microstructural and electrochemical impedance characterization of bio-functionalized ultrafine ZnS nanocrystals-reduced graphene oxide hybrid for immunosensor applications.

We report a mercaptopropionic acid capped ZnS nanocrystals decorated reduced graphene oxide (RGO) hybrid film on a silane modified indium-tin-oxide glass plate, as a bioelectrode for the quantitative detection of human cardiac myoglobin (Ag-cMb). The ZnS nanocrystals were anchored over electrochemically reduced GO sheets through a cross linker, 1-pyrenemethylamine hydrochloride, by carbodiimide reaction and have been characterized by scanning electron microscopy, transmission electron microscopy and energy dispersive X-ray spectroscopy. The transmission electron microscopic characterization of the ZnS-RGO hybrid shows the uniform distribution of ultra-fine nanoparticles of ZnS in nano-sheets of GO throughout the material. The protein antibody, Ab-cMb, was covalently linked to ZnS-RGO nanocomposite hybrid for the fabrication of the bioelectrode. A detailed electrochemical immunosensing study has been carried out on the bioelectrode towards the detection of target Ag-cMb. The optimal fitted equivalent circuit model that matches the impedance response has been studied to delineate the biocompatibility, sensitivity and selectivity of the bioelectrode. The bioelectrode exhibited a linear electrochemical impedance response to Ag-cMb in a range of 10 ng to 1 µg mL(-1) in PBS (pH 7.4) with a sensitivity of 177.56 Ω cm(2) per decade. The combined synergistic effects of the high surface-to-volume ratio of ZnS(MPA) nanocrystals and conducting RGO has provided a dominant charge transfer characteristic (R(et)) at the lower frequency region of <10 Hz showing a good biocompatibility and enhanced impedance sensitivity towards target Ag-cMb. The impedance response sensitivity of the ZnS-RGO hybrid bioelectrode towards Ag-cMb has been found to be about 2.5 fold higher than that of a bare RGO modified bioelectrode.

Enzyme-modified indium tin oxide microelectrode array-based electrochemical uric acid biosensor.

We fabricated a miniaturized electrochemical uric acid biosensor with a 3-aminopropyltriethoxysilane (APTES)-modified indium tin oxide (ITO) microelectrode array (µEA). The ITO-µEA on a glass plate was immobilized with the enzyme uricase, through a cross-linker, bis[sulfosuccinimidyl]suberate (BS3). The enzyme-immobilized electrode (uricase/BS3/APTES/ITO-µEA/glass) was characterized by atomic force microscopy and electrochemical techniques. The cyclic voltammetry and impedance studies show an effective binding of uricase at the µEA surface. The amperometric response of the modified electrode was measured towards uric acid concentration in aqueous solution (pH 7.4), under microfluidic channel made of polydimethylsiloxane. The µEA biosensor shows a linear response over a concentration range of 0.058 to 0.71 mM with a sensitivity of 46.26 µA mM-1 cm-2. A response time of 40 s reaching a 95% steady-state current value was obtained. The biosensor retains about 85% of enzyme activity for about 6 weeks. The biosensor using µEA instead of a large single band of electrode allows the entire core of the channel to be probed though keeping an improved sensitivity with a small volume of sample and reagents.

Electrochemical impedance spectroscopy characterization of mercaptopropionic acid capped ZnS nanocrystal based bioelectrode for the detection of the cardiac biomarker--myoglobin.

3-Mercaptopropionic acid (MPA) capped ZnS nanocrystals (ZnS(MPA)) are covalently attached to a self assembled monolayer (SAM) of 3-aminopropyltriethoxysilane (APTES) on an indium-tin-oxide (ITO) coated glass plate. The protein antibody, anti-myoglobin (Ab-Mb), is covalently linked to free carboxyl groups present on ZnS(MPA) nanocrystals via carbodiimide coupling reaction to form a bioelectrode (Ab-Mb(BSA)/ZnS(MPA)/APTES/ITO-glass). This bioelectrode has been characterized using atomic force microscopy (AFM), contact angle measurements, cyclic voltammetry and electrochemical impedance spectroscopy (EIS). The optimal equivalent circuit model that matches the impedimetric responses of the bioelectrode describes three distinct regions: the electrolyte solution resistance (R(s)), the double layer capacitance (C(dl)) and the specific charge transfer resistance (R(et)). The EIS measurements revealed that the R(et) increases considerably with no significant change in C(dl) after immunoreaction with protein specific antigen myoglobin, Ag-Mb, so that the prepared bioelectrode can be used for the detection of Ag-Mb. The bioelectrode exhibits an electrochemical impedance response to Ag-Mb, in a linear range from 10ng to 1µgmL(-1) phosphate buffer solution (pH 7.4) with a R(et) sensitivity of 117.36Ωcm(2) per decade.

Optical memory effect in a deformed helix ferroelectric liquid crystal.

Optical memory in a deformed-helix ferroelectric liquid crystal is proposed by deforming the helix under the application of a square-voltage pulse of known magnitude and frequency. This effect is based on the electromechanical effect of helix deformation due to the electric field. When the interaction between the electric field and the dipole is sufficiently strong, all of the dipoles align along the electric field. In such a situation the interlayer dipole-dipole interaction is strong enough to balance the elastic deformation energy. When the electric field is switched off, the molecules remain in a static, balanced state owing to the dipole-dipole interaction and hence the memory effect.