Sumyra Sidiq

New perylene-based non-conventional discotic liquid crystals

The synthesis, optical properties and thermal behaviour of three novel non-conventional 3,4,9,10-tetrasubstituted perylene-based discotic oligomers are reported for the first time consisting of a perylene core attached to which are four 4-cyanobiphenyl, triphenylene and cholesteryl units via flexible alkyl spacers. All the oligomers self-assemble into a mesophase and exhibit excellent fluorescence emission properties making them suitable for various opto-electronic applications.

Applications of liquid crystals in biosensing and organic light-emitting devices: future aspects

ABSTRACT This article summarises recent advances made in our laboratory towards the development of new technological applications, such as biosensors and organic light-emitting diodes (OLEDs) based on liquid crystals (LCs) other than LC displays. The study of biomolecular interaction using LC material relies on the specific interaction between the LC and the biomolecule of interest at interfaces that permit the biomolecular events to be amplified into easily measured signals for various sensing applications. In the first part, we emphases recent studies in the design and modulation of LC-based interfaces based on robust colloidal LC gels for biological amplification, qualitative and quantitative understanding of important biomolecular interactions at LC–aqueous interfaces for diagnostic and laboratory applications and design of LC droplets that hold promise to act as a marker for cells and cell-based interactions. In the second part, we described design of organic materials for application in OLEDs on various discotic monomers, dimers and oligomers. These molecules have the ability to transport charges, holes and electrons. In addition, because of the high conductivity and π–π stacking, they are considered as the advanced materials for practical applications. The technological advances in our laboratory using discotic LCs will be briefly presented in this article. GRAPHICAL ABSTRACT

Colloid-in-Liquid Crystal Gels that Respond to Biomolecular Interactions

This paper advances the design of stimuli-responsive materials based on colloidal particles dispersed in liquid crystals (LCs). Specifically, thin films of colloid-in-liquid crystal (CLC) gels undergo easily visualized ordering transitions in response to reversible and irreversible (enzymatic) biomolecular interactions occurring at the aqueous interfaces of the gels. In particular, LC ordering transitions can propagate across the entire thickness of the gels. However, confinement of the LC to small domains with lateral sizes of ∼10 μm does change the nature of the anchoring transitions, as compared to films of pure LC, due to the effects of confinement on the elastic energy stored in the LC. The effects of confinement are also observed to cause the response of individual domains of the LC within the CLC gel to vary significantly from one to another, indicating that manipulation of LC domain size and shape can provide the basis of a general and facile method to tune the response of these LC-based physical gels to interfacial phenomena. Overall, the results presented in this paper establish that CLC gels offer a promising approach to the preparation of self-supporting, LC-based stimuli-responsive materials.

pH-Driven Ordering Transitions in Liquid Crystal Induced by Conformational Changes of Cardiolipin.

We report an investigation of interfacial phenomena occurring at aqueous-liquid crystal (LC) interfaces that triggers an orientational ordering transition of the LC in the presence of cardiolipin (CL) by varying pH, salt concentration and valence. In particular, the effects of three different conformational isomeric forms of the CL are observed to cause the response of the LC ordering to vary significantly from one to another at those interfaces. An ordering transition of the LC was observed when the CL is mostly in undissociated (at pH 2) and/or in bicyclic (at pH 4) conformation in which LC shows changes in the optical appearance from bright to dark. By contrast, no change in the optical appearance of the LC was observed when the pH of the system increases to 8 or higher in which the CL mostly exists in the open conformation. Fluorescence microscopy measurements further suggest that pH-dependent conformational forms of the CL have different ability to self-assemble (thus different packing efficiency) at aqueous-LC interfaces leading to dissimilar orientational behavior of the LC. Specifically, we found that change in headgroup-headgroup repulsion of the central phosphatidyl groups of the CL plays a key role in tuning the lipid packing efficiency and thus responses to interfacial phenomena. Orientational ordering transition of the LC was also observed as a function of increasing the ionic strength (buffer capacity) and strongly influenced in the presence of mono and divalent cations. Langmuir-Blodgett (LB) and polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS) measurements provide further insight in modulation of the lipid packing efficiency and alkyl chain conformation of the CL at different pH and ionic conditions. Overall, the results presented in this paper establish that LCs offer a promising approach to differentiate different conformations (label free detection) of the CL through ordering transition of the LC at aqueous-LC interfaces.

A new pathway for the formation of radial nematic droplets within a lipid-laden aqueous-liquid crystal interface

A new pathway for the formation of liquid crystal (LC) droplets with radial LC ordering in the presence of surfactants and lipids is reported. This study also shows that the response of these droplets due to the interactions between an enzyme and the topological defects in the LC may be exploited in applications such as sensing.

Microwave-assisted synthesis of novel mixed tail rufigallol derivatives

Microwave-assisted syntheses of five new series of rufigallol-based mesogens are reported with branched alkyl chains at the peripheral positions. The chemical structures of these newly synthesised compounds were determined by 1H nuclear magnetic resonance (NMR), 13C NMR, infrared spectroscopy, ultraviolet spectroscopy and elemental analysis. The thermotropic liquid crystalline properties were investigated by polarising optical microscopy (POM), differential scanning calorimetry and X-ray diffractometry. Most of the derivatives were found to be liquid crystalline over a wide temperature range.

Design of bio-molecular interfaces using liquid crystals demonstrating endotoxin interactions with bacterial cell wall components

Interaction of different bacterial cell membrane components such as, peptidoglycan (PG) and lipoteichoic acid (LTA) with bacterial endotoxin (LPS) shows diverse consequences on the toxicity of Gram negative bacteria in mammalian hosts, implying the huge importance of studying this interaction for clinical understanding associated with Gram negative bacterial infections. In this advance, herein, we report a liquid crystal (LC) based simple, robust experimental design for rapid and precise recognition of the interaction of LPS with PG and LTA. The optical appearance of nematic 4-cyano-4′-pentylbiphenyl (5CB) LCs changed from dark to bright (consistent with an ordering transition of the LCs) in contact with an aqueous solution of PG and LTA on LPS–laden aqueous–LC interfaces. The ordering transition demonstrates the strong interaction between PG and LTA with LPS at these interfaces. Our experiment also revealed that the interaction of PG and LTA towards LPS is highly specific. In addition, PG and LTA shows different binding affinity towards LPS and response of the LC is found to vary significantly from one to another which is conveniently quantified by measurement of the light intensity transmitted through the LC under crossed polars. Langmuir Blodgett (LB) and polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS) measurements provide further insight on LPS laden aqueous–LC interfaces. Finally, we have also quantified the different binding affinity of PG and LTA towards LPS by measuring the optical retardance of the LC at aqueous–LC interfaces. Overall, the results presented in this paper offer a promising approach to study and quantify the interactions between different bacterial cell membrane components with LPS at aqueous–LC interfaces.

Poly(l-lysine)-Coated Liquid Crystal Droplets for Cell-Based Sensing Applications

Exploring intermolecular interactions in the presence of biomolecules that dictate director configurations of liquid crystals (LCs) enables new techniques for optically probing complex biological phenomena and realizing new classes of sensors and actuators. However, the design of a new approach by probing direct protein-LC interactions (in aqueous media) that can mimic chemico-biological interactions at the cellular level remains elusive. Here, we present a simple method to produce biocompatible LC droplets through poly(l-lysine) (PLL)-LC interactions in situ for reporting the presence of cells and monitoring the real-time interaction of cells with their environments that are mediated by topological defects in those droplets. In addition, responsive PLL droplets have been found to be useful as a template for reporting Annexin V-phosphatidylserine interactions, providing a simple measure of the harmful effect on cell health.

Detection of creatinine using surface-driven ordering transitions of liquid crystals

ABSTRACT Determining creatinine levels in blood is of great importance in the detection of high risk for renal failure. Here, we report a simple methodology for real-time monitoring of creatinine employing surface-driven ordering transitions in liquid crystals (LCs) by changing pH in presence of creatinine deiminase enzyme. It is found that when 5CB (4-Cyano-4ʹ-pentylbiphenyl) LC doped with 4ʹ-hexyl-biphenyl-4-carboxylic acid, a bright optical appearance was observed (at aqueous–LC interface) which is not disturbed in presence of creatinine, consistent with a planar/tilted orientation of the LC molecules at those interface. Interestingly, in presence of creatinine deiminase, an ordering transition was observed resulting from enzymatic reactions (giving rise to NH4+ ions) that can change the local pH values and lead to dark optical appearance of the LC. Presence of different amounts of creatinine would lead varied ordering transition that can be monitored in real time in presence of creatinine deiminase. Our approach could detect the creatinine levels as low as that of the healthy adult (~50 µM) and can be successfully applied to measure higher concentration of creatinine in real time using dynamic optical response of the LC. GRAPHICAL ABSTRACT

Lipid-induced structural turnover of water droplets to liquid crystal droplets

For the first time direct observation of structural turnover of water droplets to liquid crystal (LC) droplets with radial LC ordering was observed in presence of surfactants and lipids. Study of interactions between enzymes with the topological defects in the LC mediate the response of these droplets suggesting new principles for the design of chemical and biological sensors.