The significance of nanoparticle shape in chirality transfer to a surrounding nematic liquid crystal reporter medium

This perspective reports on recent progress toward the development of an approach to a priori predict - both chirality "strength" and efficacy of chirality transfer from a chiral nanoshape solute to an achiral nematic environment

Synthesis of Distinct Iron Oxide Nanomaterial Shapes Using Lyotropic Liquid Crystal Solvents

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

Chirality amplification by desymmetrization of chiral ligand-capped nanoparticles to nanorods quantified in soft condensed matter

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

Molecular conformation of bent-core molecules affected by chiral side chains dictates polymorphism and chirality in organic nano- and microfilaments

https://kent-islandora.s3.us-east-2.amazonaws.com/node/14391/83901-thumbnail.jpgThe 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 [1-5] 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. References: [1] L. Li, M. Salamonczyk, A. Jakli, T. Hegmann, Small 2016, 12, 3944. [2] L. Li, M. Salamonczyk, S. Shadpour, C. Zhu, A. Jakli, T. Hegmann, Nat Commun 2018, 9, 714. [3] S. Shadpour, A. Nemati, N. J. Boyd, L. Li, M. E. Prévôt, S. L. Wakerlin, J. P. Vanegas, M. Salamończyk, E. Hegmann, C. Zhu, M. R. Wilson, A. I. Jákli, T. Hegmann, Materials Horizons 2019, 6, 959. [4] S. Shadpour, A. Nemati, J. Liu, T. Hegmann, ACS Appl Mater Interfaces 2020, 12, 13456. [5] S. Shadpour, A. Nemati, M. Salamonczyk, M. E. Prevot, J. Liu, N. J. Boyd, M. R. Wilson, C. Zhu, E. Hegmann, A. I. Jakli, T. Hegmann, Small 2020, 16, e1905591.</p

Missing Link between Helical Nano‐ and Microfilaments in B4 Phase Bent‐Core Liquid Crystals, and Deciphering which Chiral Center Controls the Filament Handedness

The range of possible morphologies for bent‐core B4 phase liquid crystals has recently expanded from helical nanofilaments (HNFs) and modulated HNFs to dual modulated HNFs, helical microfilaments, and heliconical‐layered nanocylinders. These new morphologies are observed when one or both aliphatic side chains contain a chiral center. Here, the following questions are addressed: which of these two chiral centers controls the handedness (helicity) and which morphology of the nanofilaments is formed by bent‐core liquid crystals with tris‐biphenyl diester core flanked by two chiral 2‐octyloxy side chains? The combined results reveal that the longer arm of these nonsymmetric bent‐core liquid crystals controls the handedness of the resulting dual modulated HNFs. These derivatives with opposite configuration of the two chiral side chains now feature twice as large dimensions compared to the homochiral derivatives with identical configuration. These results are supported by density functional theory calculations and stochastic dynamic atomistic simulations, which reveal that the relative difference between the para‐ and meta‐sides of the described series of compounds drives the variation in morphology. Finally, X‐ray diffraction, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and atomic force microscopy (AFM) data also uncover the new morphology for B4 phases featuring p2/m symmetry within the filaments and less pronounced crystalline character

Heliconical-layered nanocylinders (HLNCs) –hierarchical self-assembly in a unique B4 phase liquid crystal morphology

A unique morphology for bent-core liquid crystals forming the B4 phase has been found for a class of tris-biphenyl bent-core liquid crystal molecules with a single chiral side chain in the longer para-side of the molecule. Unlike the parent molecules with two chiral side chains or a chiral side chain in the shorter meta-side, which form helical nano- or microfilament B4 phases, the two derivatives described here form heliconical-layered nanocylinders composed of up to 10 coaxial heliconical layers, which can split or merge, braid, and self-assemble into a variety of modes including feather- or herringbone-type structures, concentric rings, or hollow nest-like superstructures. These multi-level hierarchical self-assembled structures, rivaling muscle fibers, display blue structural color and show immense structural and morphological complexity

Indication of a twist-grain-boundary-twist-bend phase of flexible core bent-shape chiral dimers.

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 &gt; 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