In this work, we demonstrate control of the handedness of semicrystalline modulated helical nanofilaments (HNFmods) formed by achiral bent-core liquid crystal molecules by axially chiral ...binaphthyl-based additives as guest molecules solely under spatial nanoconfinement in anodic aluminum oxide nanochannels. The molecules of the same chiral additives are expelled from the HNFmods in the bulk, and as a result thereof do not affect the handedness or helical pitch of bulk HNFmods, resulting in an HNFmod conglomerate with chirality-preserving growth within each domain. However, under confinement these axially chiral guest molecules, likely embedded in the HNFmod host, do affect the helicity of the HNFmods. The configuration of the axially chiral molecules decides the HNFmod helix handedness and their concentration, and the helix angle is related to the helical pitch of the HNFmods. In addition to local imaging data obtained by scanning electron microscopy, global studies by thin-film circular dichroism spectropolarimetry support the imaging results.
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Induction, transmission, and manipulation of chirality in molecular systems are well known, widely applied concepts. However, our understanding of how chirality of nanoscale entities can be ...controlled, measured, and transmitted to the environment is considerably lacking behind. Future discoveries of dynamic assemblies engineered from chiral nanomaterials, with a specific focus on shape and size effects, require exact methods to assess transmission and amplification of nanoscale chirality through space. Here we present a remarkably powerful chirality amplification approach by desymmetrization of plasmonic nanoparticles to nanorods. When bound to gold nanorods, a one order of magnitude lower number of chiral molecules induces a tighter helical distortion in the surrounding liquid crystal-a remarkable amplification of chirality through space. The change in helical distortion is consistent with a quantification of the change in overall chirality of the chiral ligand decorated nanomaterials differing in shape and size as calculated from a suitable pseudoscalar chirality indicator.
The effect of the molecular chirality of chiral additives on the nanostructure of the twist-bend nematic (NTB) liquid crystal phase with ambidextrous chirality and nanoscale pitch due to spontaneous ...symmetry breaking is studied. It is found that the ambidextrous nanoscale pitch of the NTB phase increases by 50% due to 3% chiral additive, and the chiral transfer among the biphenyl groups disappears in the NTB* phase. Most significantly, a twist-grain boundary (TGB) type phase is found at c > 1.5 wt% chiral additive concentrations below the usual N* phase and above the non-CD active NTB* phase. In such a TGB type phase, the adjacent blocks of pseudo-layers of the nanoscale pitch rotate across the grain boundaries.
Amplification of chirality across length scales is a key concept pertinent to many models aiming to unravel the origin of homochirality. Tactoids of lyotropic chromonic liquid crystals formed by DNA, ...dyes, and other flat ionic molecules in water in the biphasic nematic + isotropic regime turn out to be a particularly relevant system to investigate chirality transfer and amplification. Herein, we present experiments to determine the amplification of chirality by luminescent gold nanoclusters decorated with adenosine monophosphate inducing chiral nematic tactoids formed by disodium cromoglycate in water. Polarized optical microscopy investigations of the induced homochiral tactoids reveal that adenosine monophosphate shows a higher optical activity when bound to the surface of such gold nanoclusters in comparison to free adenosine monophosphate, despite a three-time lower overall concentration. Free adenosine monophosphate also induces the opposite chiral twist both in the bulk nematic phase as shown by induced thin film circular dichroism spectropolarimetry and in the tactoids in comparison to adenosine monophosphate bound to the gold nanocluster. Overall, these experiments demonstrate that lyotropic chromonic liquid crystal tactoids are powerful systems to image and quantify chirality amplification by key biological chiral molecules that would have played a role in the origin of homochirality.
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A room temperature reduction-hydrolysis of Fe(III) precursors such as FeCl₃ or Fe(acac)₃ in various lyotropic liquid crystal phases (lamellar, hexagonal columnar, or micellar) formed by a range of ...ionic or neutral surfactants in H₂O is shown to be an effective and mild approach for the preparation of iron oxide (IO) nanomaterials with several morphologies (shapes and dimensions), such as extended thin nanosheets with lateral dimensions of several hundred nanometers as well as smaller nanoflakes and nanodiscs in the tens of nanometers size regime. We will discuss the role of the used surfactants and lyotropic liquid crystal phases as well as the shape and size differences depending upon when and how the resulting nanomaterials were isolated from the reaction mixture. The presented synthetic methodology using lyotropic liquid crystal solvents should be widely applicable to several other transition metal oxides for which the described reduction-hydrolysis reaction sequence is a suitable pathway to obtain nanoscale particles.
The creation and transmission of chirality in molecular systems is a well-known, widely applied notion. Our understanding of how the chirality of nanomaterials can be controlled, measured, ...transmitted through space, and applied is less well understood. Dynamic assemblies for chiral sensing or metamaterials engineered from chiral nanomaterials require exact methods to determine transmission and amplification of nanomaterial chirality through space. We report the synthesis of a series of gold nanorods (GNRs) with a constant aspect ratio of ∼4.3 capped with C 2-symmetric, axially chiral binaphthyl thiols, preparation of dispersions in the nematic liquid crystal 5CB, measurements of the helical pitch, and the determination of the helical twisting power as well as the average distance between the chiral nanomaterial additives. By comparison to the neat organic chiral derivatives, we demonstrate how the amplification of chirality facilitated by GNRs decorated with chiral molecules can be used to clearly distinguish the chiral induction strength of a homologous series of binaphthyl derivatives, differing only in the length of the nontethered aliphatic chain, in the induced chiral nematic liquid crystal phase. Considering systematic errors in sample preparation and optical measurements, these chiral molecules would otherwise be deemed identical with respect to chiral induction. Notably, we find some of the highest ever-reported values of the helical twisting power. We further support our experimentally derived arguments of a more comprehensive understanding of chirality transfer by calculations of a suitable pseudoscalar chirality indicator.
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Nematic liquid crystals of achiral molecules or racemic mixtures of chiral ones form flat films when suspended in submillimeter size grids and submerged under water. Recently, it has been shown ...(Popov et al., 2017) that films of nematic liquid crystals doped with chiral molecules adopt biconvex lens shapes underwater. The curved shape together with degenerate planar anchoring leads to a radial variation of the optical axis along the plane of the film, providing a Pancharatnam–Berry-type phase lens that modifies geometric optical imaging. Here, we describe nematic liquid crystal microlenses formed by the addition of chiral nanoparticles. It is found that the helical twisting power of the nanoparticles, the key factor to form the lens, is about 400 μm–1, greater than that of the strongest molecular chiral dopants. We demonstrate imaging capabilities and measure the shape as well as the focal length of the chiral nanoparticle-doped liquid crystal lens. We show that measuring the shape of the lens allows one to calculate the helical pitch of the chiral nematic liquid crystal and thus determine the helical twisting power of the chiral ligand-capped nanoparticles. Such measurements require the use of only nanograms of chiral nanoparticles, which is 3 orders of magnitude less than that required by conventional techniques. Since NPs are sensitive to external stimuli such as light and electric and magnetic fields, the use of chiral NPs may allow the achievement of tunable optical properties for such microlens arrays.
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The research summarized in this dissertation investigates approaches of chirality tuning and amplification by nanoscale additives in liquid crystals. The fundamental significance of the discovered ...mechanisms is based on a combination of experimental as well as computational work on chirality of nanoscale particles and chiral induction in nematic liquid crystal phases. In this dissertation, a remarkably powerful chirality amplification approach by desymmetrization of plasmonic nanoparticles is reported. When bound to gold nanorods, a one order of magnitude lower number of chiral molecules induces a tighter helical distortion in the surrounding nematic liquid crystal phase ? a remarkable amplification of chirality through space. The change in helical distortion is consistent with a quantification of the change in overall chirality of the chiral ligand-decorated nanomaterials differing in shape (prism, rods, disks, stars), aspect ratio, and size as calculated from a suitable pseudo-scalar chirality indicator. In addition, we demonstrate how the amplification of chirality facilitated by gold nanorods decorated with axially chiral binaphthyl derivates, differing only in the length of the nontethered aliphatic chain, in the induced chiral nematic liquid crystal phase can be employed to distinguish the helical twisting power of otherwise equally potent chiral additives. The first chapter introduces the concepts related to chiral nanomaterials as well as the underlying principles of chirality transfer, especially in chiral liquid crystal phases such as the chiral nematic phase. The second and third chapter, respectively, cover the synthetic routes and characterization methods for all materials (for the cholesterol and axially chiral binaphthyl derivatives as well as the synthesis and characterization of the gold). Chapter four reports the experimental results of all chiral nanostructure compositions in liquid crystals; this chapter is devoted to the results of how the chirality of these nanoscale particles can be controlled, amplified, measured, transmitted, and reported by the liquid crystalline medium. Chapter five will introduce a phenomenological model of chiral dopants that describes the distinct effects of shape, size, aspect ratio, dispersity, and ligand shell of nanoscale additives in comparison to the experimental testing platform of a nematic liquid crystal host. Chapter six covers a device application of nanoparticles assembly and alignment effect in presence of toxic gases. Chapter seven covers a brief conclusion and future suggestion and in the final chapter this thesis reports the equations and codes for chirality quantification, and data analysis related to chapters two to five.
The coupling between molecular conformation and chirality is a cornerstone in the construction of supramolecular helical structures of small molecules across various length scales. Inspired by ...biological systems, conformational preselection and control in artificial helical molecules, polymers, and aggregates has guided various applications in optics, photonics, and chiral sorting among others, which are frequently based on an inherent chirality amplification through processes such as templating and self-assembly. The so-called B4 nano- or microfilament phase formed by some bent-shaped molecules is an exemplary case for such chirality amplification across length scales, best illustrated by the formation of distinct nano- or microscopic chiral morphologies controlled by molecular conformation. Introduction of one or more chiral centers in the aliphatic side chains led to the discovery of homochiral helical nanofilament, helical microfilament, and heliconical-layered nanocylinder morphologies. Herein, we demonstrate how a priori calculations of the molecular conformation affected by chiral side chains are used to design bent-shaped molecules that self-assemble into chiral nano- and microfilament as well as nanocylinder conglomerates despite the homochiral nature of the molecules. Furthermore, relocation of the chiral center leads to formation of helical as well as flat nanoribbons. Self-consistent data sets from polarized optical as well as scanning and transmission electron microscopy, thin-film and solution circular dichroism spectropolarimetry, and synchrotron-based X-ray diffraction experiments support the progressive and predictable change in morphology controlled by structural changes in the chiral side chains. The formation of these morphologies is discussed in light of the diminishing effects of molecular chirality as the chain length increases or as the chiral center is moved away from the core-chain juncture. The type of phase (B1-columnar or B4) and morphology of the nano- or microfilaments generated can further be controlled by sample treatment conditions such as by the cooling rate from the isotropic melt or by the presence of an organic solvent in the ensuing colloidal dispersions. We show that these nanoscale morphologies can then organize into a wealth of two- and three-dimensional shapes and structures ranging from flower blossoms to fiber mats formed by intersecting flat nanoribbons.
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Nanoparticles serving as a multifunctional and multiaddressable dopant to modify the properties of liquid crystalline matrices are developed by combining cobalt ferrite nanocrystals with organic ...ligands featuring a robust photosensitive unit and a source of chirality from the natural pool. These nanoparticles provide a stable nanocomposite when dispersed in achiral liquid crystals, giving rise to chiral supramolecular structures that can respond to UV-light illumination, and, at the same time, the formed nanocomposite possesses strong magnetic response. We report on a nanocomposite that shows three additional functionalities (chirality and responsiveness to UV light and magnetic field) upon the introduction of a single dopant into achiral liquid crystals.
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