Molecular Design and Alignment for Ambipolar SCLC Mobility in Self-Assembled Columnar Discogens.

The future of next-generation electronics relies on low-cost organic semiconductors that are tailored to simultaneously provide all requisite optoelectronic properties, focusing greatly on ambipolar charge-transport and solution processability. In this regard, room-temperature discotic liquid crystals (DLCs) are potential candidates, where quasi-1D self-assembly affords a charge-transport channel along their columnar axis. This work shows a molecular design strategy by utilizing anthraquinone as the primary motif, surrounded by ester functionalized tri-alkoxy phenyl units to develop room-temperature DLCs (1.

Enhancing Hole Transport and Autonomous Healing Properties of Supramolecular Columns in Unsymmetrical Discotics.

Designing smart autonomous healing soft materials is crucial to attaining cost-efficiency and optimal performance in organic semiconductors. In this context, we design an unsymmetrical thiophene-fused phenazine (TFP)-based discotic liquid crystal (DLC) with the goal of creating an active organic semiconductor that encompasses favorable attributes, such as polarizability, mobility, and processability. Aligned with our objective, we successfully synthesized two unsymmetrical TFP core-based DLCs by linking alkyl chains of variable lengths at the periphery through a coupling reaction.

Observation of ferroelectric behaviour in non-symmetrical cholesterol-based bent-shaped dimers.

Non-symmetrical cholesterol-based dimers have emerged as crucial materials in the field of liquid crystal research, owing to their remarkable ability to stabilize various exotic mesophases, including the blue phases (BPIII, BPII, BPI), cholesteric nematic (N*) phase, smectic blue phase (SmBP), twist grain boundary (TGB) phase, smectic A/smectic A* (SmA/SmA*) phase, and smectic C/smectic C* (SmC/SmC*) phase. These mesophases have garnered considerable attention due to their diverse applications in spatial light modulation, chiro-optical devices, optical switching, thermochromic materials, and more. In this study, we present the synthesis and comprehensive characterization of a series of non-symmetrical cholesterol-based bent-shaped dimers (1/12, 1/14, 1/16) in which the cholesterol unit is intricately linked to an aromatic mesogenic core through a flexible spacer.

Temperature-Induced Nanoarchitectonics of Monolayer Self-Assembly of Heterocoronene-Based Discotic Liquid Crystals.

Enhancing molecular self-assembly at the monolayer level offers significant potential for various applications. For monolayers made of π-conjugated discotic liquid crystal (DLC) molecule nanowires, achieving precise separation and alignment of these nanowires has been a long-standing challenge. This research explores an approach using the manipulation of subphase temperature and surface pressure within a Langmuir trough to control molecular nanowire separation.

Stimuli-Responsive Control over Self-Assembled Nanostructures in Sequence-Specific Functional Block Copolymers.

The precise sequence of a protein's primary structure is essential in determining its folding pathways. To emulate the complexity of these biomolecules, functional block copolymers consisting of segmented triblocks with distinct functionalities positioned in a sequence-specific manner are designed to control the polymer chain compaction. Triblock polymers and and random diblock copolymer consist of a hydrophilic poly(ethylene oxide) (PEO) block and a hydrophobic block with coumarin () and ferrocene () moieties that are grafted in a sequence-specific or random manner onto the hydrophilic block.

Label-free liquid crystal-based optical detection of norfloxacin using an aptamer recognition probe in soil and lake water.

Norfloxacin (NOX), a broad spectrum fluoroquinolone (FQ) antibiotic, is commonly detected in environmental residues, potentially contributing to biological drug resistance. In this paper, an aptamer recognition probe has been used to develop a label-free liquid crystal-based biosensor for simple and robust optical detection of NOX in aqueous solutions. Stimuli-receptive liquid crystals (LCs) have been employed to report aptamer-target binding events at the LC-aqueous interface.

Arylazo-3,5-diphenylpyrazole Derivatives: Molecular Probes Exhibiting Reversible Light-induced Phase Transitions for Energy Storage and Direct Photolithographic Patterning.

We report azopyrazole photoswitches decorated with variable N-alkyl and alkoxy chains (for hydrophobic interactions) and phenyl substituents on the pyrazoles (enabling π-π stacking), showing efficient bidirectional photoswitching and reversible light-induced phase transition (LIPT). Extensive spectroscopic, microscopic, and diffraction studies and computations confirmed the manifestation of molecular-level interactions and photoisomerization into macroscopic changes leading to the LIPT phenomena. Using differential scanning calorimetric (DSC) studies, the energetics associated with those accompanying processes were estimated.

A one-pot telescopic synthesis of benzo[]carbazoles and exploration of their liquid crystalline properties.

We describe a diversity-oriented one-pot telescopic synthesis of various benzo[]carbazoles with the naphthannulation of indoles as the key step, enabled by an intramolecular furan-olefin Diels-Alder reaction. This strategy is general and efficient across a wide range of substrates. We applied this method to synthesize and characterize the first benzo[]carbazole-based liquid crystalline materials, where the unique molecular design led to the formation of a rare nematic phase at room temperature.

Dynamic Microparticle Assembly at the Interface of Chemoresponsive Liquid Crystal Droplets.

The confinement of liquid crystals (LCs) in spherical microdroplets results in exotic internal configurations and topological defects in response to physical and chemical stimuli. Recent exploration into the placement of colloids on the surface of LC microdroplets has led to the design of a new class of functional materials with patterned surface properties. It is established that the placement of a colloid on a LC droplet surface can pin the topological defect at the interface, thereby restricting changes in the LC configuration.

Ultrasensitive Detection of Lipid-Induced Misfolding of the Prion Protein at the Aqueous-Liquid Crystal Interface.

The misfolding of the α-helical cellular prion protein into a self-propagating β-rich aggregated form is a key pathogenic event in fatal and transmissible neurodegenerative diseases collectively known as prion diseases. Herein, we utilize the interfacial properties of liquid crystals (LCs) to monitor the lipid-membrane-induced conformational switching of prion protein (PrP) into β-rich amyloid fibrils. The lipid-induced conformational switching resulting in aggregation occurs at the nanomolar protein concentration and is primarily mediated by electrostatic interactions between PrP and lipid headgroups.

High Electrical Conductivity and Hole Transport in an Insightfully Engineered Columnar Liquid Crystal for Solution-Processable Nanoelectronics.

Discotic liquid crystals (DLCs) are widely acknowledged as a class of organic semiconductors that can harmonize charge carrier mobility and device processability through supramolecular self-assembly. In spite of circumventing such a major challenge in fabricating low-cost charge transport layers, DLC-based hole transport layers (HTLs) have remained elusive in modern organo-electronics. In this work, a minimalistic design strategy is envisioned to effectuate a cyanovinylene-integrated pyrene-based discotic liquid crystal (PY-DLC) with a room-temperature columnar hexagonal mesophase and narrow bandgap for efficient semiconducting behavior.

Tailoring Chiral Discotic Liquid Crystals: Mesophase Engineering through Alternative Approaches and Chain Lengths.

Hydrogen (H)-bonding is crucial in constructing superstructures in chemical (such as chiral discotic liquid crystals (DLCs)) as well as in biological systems due to its specific and directional nature. In this context, we achieved the successful synthesis of two branches of heptazine-based H-bonded complexes using distinct strategies. Hpz*-Es-C , we incorporated chiral alkyl tails (Hpz-chiral) onto the central C symmetric heptazine core, connected to achiral benzoic acid derivatives (Es-C acid) through H-bonding.

Architectural Effect on Self-Assembly and Biorecognition of Randomly Grafted Linear and Branched Polymers at Liquid Crystal-Water Interfaces.

Because of simple synthetic strategies, randomly functionalized amphiphilic polymers have gained much attention. Recent studies have demonstrated that such polymers can be reorganized into different nanostructures, such as spheres, cylinders, vesicles, etc., similar to amphiphilic block copolymers.

Self-assembled discotics as molecular semiconductors.

With the advent of a new era of smart-technology, the demand for more economic optoelectronic materials that do not compromise with efficiency is gradually on the rise. Organic semiconductors provide greener alternatives to the conventional inorganic ones, but encounter the challenge of balancing charge carrier mobility with processability in devices. Discotic liquid crystals (DLCs), a class of self-assembling soft organic materials, possess the perfect degree of order and dynamics to address this challenge.

Deciphering pressure-induced nanoarchitectonics in a monolayer of heterocoronene-based discotics at air-water and air-solid interfaces.

Understanding and control of molecular alignment at the nanoscale in self-assembled supramolecular structures is a prerequisite for the subsequent exploitation of molecules in functional devices. Here, we have clarified the surface-pressure induced molecular nanoarchitectures in a monolayer of a heterocoronene-based discotic liquid crystal (DLC) at air-water and air-solid interfaces using surface manometry, real-time Brewster angle microscopy, and real-space atomic force microscopy (AFM). Chloroform-spread DLCs at a concentration of ∼108 μM exhibit floating domains at the air-water interface comprising small aggregates of edge-on stacked molecules interacting peripheral alkyl chains.

Liquid Crystal Biosensors: A New Therapeutic Window to Point-of-Care Diagnostics.

After revolutionizing the field of electro-optic displays, liquid crystals (LCs) are emerging as functional soft materials with wide-ranging biomedical implications. Integrating smart sensor designs with label-free imaging presents exciting opportunities in diagnostics. In this Perspective, we present an elegant collage of the key findings that demonstrate the utility of LC biosensors in diagnosing a disease or infection in clinical samples, cellular microenvironments, or bodily fluids.

Solution-processable organic light-emitting diodes utilizing electroluminescent perylene tetraester-based columnar liquid crystals.

Herein, we reveal a homologous series of liquid crystals involving perylene tetraesters as the core connected to the four trialkoxyphenyl units at the periphery using the triazole moiety as the linker. A thorough analysis using differential scanning calorimetry, polarized optical microscopy, and small- and wide-angle X-ray scattering studies confirm that all the mesogens 1a-c hold a stable enantiotropic columnar mesophase. Suitable molecular orbital levels and excellent material photophysical and thermal properties encouraged the study of their electroluminescent properties.

Elucidating liquid crystal-aqueous interface for the study of cholesterol-mediated action of a β-barrel pore forming toxin.

Pore-forming toxins (PFTs) produced by pathogenic bacteria serve as prominent virulence factors with potent cell-killing activity. Most of the β-barrel PFTs form transmembrane oligomeric pores in the membrane lipid bilayer in the presence of cholesterol. The pore-formation mechanisms of the PFTs highlight well-orchestrated regulated events in the membrane environment, which involve dramatic changes in the protein structure and organization.

Tailoring liquid crystals as vehicles for encapsulation and enzyme-triggered release.

Nanoscale assemblies of amphiphiles have been vividly explored in pharmaceutical formulations as drug nanocarriers. Aqueous interfaces of liquid crystals (LCs) are known to direct the self-assembly of a range of amphiphiles. These amphiphile-decorated interfaces of LCs have evoked interest for applications as diverse as the detection of disease markers, screening of toxins, mimicking complex biomolecular interactions, and cell-based sensing.

Observation of "de Vries-like" properties in bent-core molecules.

"de Vries" liquid crystals, defined by a maximum layer shrinkage of ≤1% from the smectic A to C phase transition, are an integral component of ferroelectric liquid crystal (FLC) displays. Bona fide de Vries materials described in the literature are primarily perfluorinated, polysiloxane and polysilane-terminated rod-like (or calamitic) LCs. Herein, for the first time, we report a series of newly designed achiral unsymmetrical bent-core molecules with terminal alkoxy chains exhibiting similar properties to "de Vries" LCs.

Correction: Luminescent columnar discotics as highly efficient emitters in pure deep-blue OLEDs with an external quantum efficiency of 4.7.

Correction for 'Luminescent columnar discotics as highly efficient emitters in pure deep-blue OLEDs with an external quantum efficiency of 4.7%' by Joydip De , , 2022, DOI: 10.1039/d1sm01558c.

Luminescent columnar discotics as highly efficient emitters in pure deep-blue OLEDs with an external quantum efficiency of 4.7.

Development of materials that serve as efficient blue emitters in solution-processable OLEDs is challenging. In this study, we report three derivatives of -symmetric 1,3,5-tris(thien-2-yl)benzene-based highly luminescent room temperature columnar discotic liquid crystals (DLCs) suitable as solid-state emitters in OLED devices. When employed in solution-processed OLEDs, one of the derivatives having the highest photoluminescence quantum yield exhibited a maximum EQE of 4.

Distinct interfacial ordering of liquid crystals observed by protein-lipid interactions that enabled the label-free sensing of cytoplasmic protein at the liquid crystal-aqueous interface.

Interfaces formed between a lipid decorated liquid crystal (LC) film and an aqueous phase can mimic the bimolecular membrane where interfacially occurring biological phenomena (, lipid-protein interactions, protein adsorption) can be visually monitored by observing the surface-sensitive orientations of LCs. The ordering behavior of LCs at different phospholipid-based LC interfaces (1,2-dilauroyl--3-phosphocholine (DLPC) and lysophosphatidic acid (LPA)) were investigated to determine the sensing of an important cytoplasmic protein (juxtamembrane of epidermal growth factor receptor (JM-EGFR)). At both DLPC and LPA decorated interfaces, the LC adopts homeotropic ordering, causing a dark optical appearance under crossed polarizers.