Organic chiral nano- and microfilaments: types, formation, and template applications.

Organic chiral nanofilaments are part of an important class of nanoscale chiral materials that has recently been receiving significant attention largely due to their potential use in applications such as optics, photonics, metameterials, and potentially a range of medical as well as sensing applications. This review will focus on key examples of the formation of such nano- and micro-filaments based on carbon nanofibers, polymers, synthetic oligo- and polypeptides, self-assembled organic molecules, and one prominent class of liquid crystals. The most critical aspects discussed here are the underlying driving forces for chiral filament formation, potentially answering why specific sizes and shapes are formed, what molecular design strategies are working equally well or rather differently among these materials classes, and what uses and applications are driving research in this fascinating field of materials science.

Controlling the Structure and Morphology of Organic Nanofilaments Using External Stimuli.

In our continuing pursuit to generate, understand, and control the morphology of organic nanofilaments formed by molecules with a bent molecular shape, we here report on two bent-core molecules specifically designed to permit a phase or morphology change upon exposure to an applied electric field or irradiation with UV light. To trigger a response to an applied electric field, conformationally rigid chiral (S,S)-2,3-difluorooctyloxy side chains were introduced, and to cause a response to UV light, an azobenzene core was incorporated into one of the arms of the rigid bent core. The phase behavior as well as structure and morphology of the formed phases and nanofilaments were analyzed using differential scanning calorimetry, cross-polarized optical microscopy, circular dichroism spectropolarimetry, scanning and transmission electron microscopy, UV-vis spectrophotometry, as well as X-ray diffraction experiments. Both bent-core molecules were characterized by the coexistence of two nanoscale morphologies, specifically helical nanofilaments (HNFs) and layered nanocylinders, prior to exposure to an external stimulus and independent of the cooling rate from the isotropic liquid. The application of an electric field triggers the disappearance of crystalline nanofilaments and instead leads to the formation of a tilted smectic liquid crystal phase for the material featuring chiral difluorinated side chains, whereas irradiation with UV light results in the disappearance of the nanocylinders and the sole formation of HNFs for the azobenzene-containing material. Combined results of this experimental study reveal that in addition to controlling the rate of cooling, applied electric fields and UV irradiation can be used to expand the toolkit for structural and morphological control of suitably designed bent-core molecule-based structures at the nanoscale.

Macromolecular Engineering and Additive Manufacturing of Polyisobutylene-Based Thermoplastic Elastomers. II. The Poly(styrene-b-isobutylene-b-styrene)/Poly(phenylene oxide) System.

This series of publications describes research rendering soft polyisobutylene (PIB)-based thermoplastic elastomers 3D printable by blending with rigid chemically compatible thermoplastics. The molecular structure, morphology, physical properties, and 3D printability of such blends have been systematically investigated. The authors' first report was concerned with the rendering of soft poly(styrene-b-isobutylene-b-styrene) (SIBS) 3D printable by blending with rigid polystyrene (PS). Here they report the macromolecular engineering of SIBS/polyphenylene oxide (PPO) blends for 3D printing. PPO, a rigid high-performance thermoplastic, is compatible with the hard PS block in SIBS; however, neither PPO nor SIBS can be directly 3D printed. The microphase-separated structures and physical properties of SIBS/PPO blends are systematically tuned by controlling blending ratios and molecular weights. Suitable composition ranges and desirable properties of SIBS/PPO blends for 3D printing are optimized. The morphology and properties of SIBS/PPO blends are characterized by an ensemble of techniques, including atomic force microscopy, small-angle X-ray scattering, and thermal and mechanical properties testing. The elucidation of processing-structure-property relationship of SIBS/PPO blends is essential for 3D printing and advanced manufacturing of high-performance polymer systems.

Chirality Transfer from an Innately Chiral Nanocrystal Core to a Nematic Liquid Crystal 2: Lyotropic Chromonic Liquid Crystals.

The importance of and the difference between molecular versus structural core chirality of substances that form nanomaterials, and their ability to transmit and amplify their chirality to and within a surrounding condensed medium is yet to be exactly understood. Here we demonstrate that neat as well as disodium cromoglycate (DSCG) surface-modified cellulose nanocrystals (CNCs) with both molecular and morphological core chirality can induce homochirality in racemic nematic lyotropic chromonic liquid crystal (rac-N-LCLC) tactoids. In comparison to the parent chiral organic building blocks, D-glucose, endowed only with molecular chirality, both CNCs showed a superior chirality transfer ability. Here, particularly the structurally compatible DSCG-modified CNCs prove to be highly effective since the surface DSCG moieties can insert into the DSCG stacks that constitute the racemic tactoids. Overall, this presents a highly efficient pathway for chiral induction in an aqueous medium and thus for understanding the origins of biological homochirality in a suitable experimental system.

Chiral, Magnetic, and Photosensitive Liquid Crystalline Nanocomposites Based on Multifunctional Nanoparticles and Achiral Liquid Crystals.

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.

Highly Tunable Circularly Polarized Emission of an Aggregation-Induced Emission Dye Using Helical Nano- and Microfilaments as Supramolecular Chiral Templates.

Aggregation-induced emission (AIE)-based circularly polarized luminescence (CPL) has been recognized as a promising pathway for developing chiroptical materials with high luminescence dissymmetry factors (|glum|). Here, we propose a method for the construction of a thermally tunable CPL-active system based on a supramolecular self-assembly approach that utilizes helical nano- or microfilament templates in conjunction with an AIE dye. The CPL properties of the ensuing ensembles are predominantly determined by the intrinsic geometric differences among the various filament templates such as their overall dimensions (width, height, and helical pitch) and the area fraction of the exposed aromatic segments or sublayers. The proposed mechanism is based on the collective data acquired by absorption, steady state and time-resolved fluorescence, absolute quantum yield, and CPL measurements. The highest |glum| value for the most promising dual-modulated helical nanofilament templates in the present series was further enhanced, reaching up to |glum| = 0.25 by confinement in the appropriate diameter of anodized aluminum oxide (AAO) nanochannels. It is envisioned that this methodology will afford new insights into the design of temperature-rate indicators or anti-counterfeiting tags using a combination of structural color by the nano- and microfilament templates and the AIE property of the guest dye.

Effects of shape and solute-solvent compatibility on the efficacy of chirality transfer: Nanoshapes in nematics.

Chirality, as a concept, is well understood at most length scales. However, quantitative models predicting the efficacy of the transmission of chirality across length scales are lacking. We propose here a modus operandi for a chiral nanoshape solute in an achiral nematic liquid crystal host showing that that chirality transfer may be understood by unusually simple geometric considerations. This mechanism is based on the product of a pseudoscalar chirality indicator and of a geometric shape compatibility factor based on the two-dimensional isoperimetric quotients for each nanoshape solute. The model is tested on an experimental set of precisely engineered gold nanoshapes. These libraries of calculated and in-parallel acquired experimental data among related nanoshapes pave the way for predictive calculations of chirality transfer in nanoscale, macromolecular, and biological systems, from designing chiral discriminators and enantioselective catalysts to developing chiral metamaterials and understanding nature's innate ability to transfer homochirality across length scales.

Chirality Transfer from an Innately Chiral Nanocrystal Core to a Nematic Liquid Crystal: Surface-Modified Cellulose Nanocrystals.

The vast majority of nanomaterials studied in light of their ability to transmit chirality to or amplify their chirality in a surrounding medium, constitute an achiral core with chirality solely installed at the surface by conjugation or encapsulation with optically active ligands. Here we present the inverse approach focusing on surface-modified cellulose nanocrystals (CNCs) with core chirality at both the molecular and the morphological level to quantify transmission and amplification of core chirality through space using a host nematic liquid crystal (N-LC) as reporter. We find that CNCs functionalized at the surface with achiral molecules, structurally related to the N-LC, exhibit better N-LC solubility, thereby serving as highly efficient chiral inducers. Moreover, functionalization with chiral molecules only marginally enhances the efficacy of helical distortion in the host N-LC matrix, indicating the high propensity of CNCs to transfer chirality from an inherently chiral core.

Molecular Conformation of Bent-Core Molecules Affected by Chiral Side Chains Dictates Polymorphism and Chirality in Organic Nano- and Microfilaments.

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.

Converging Microlens Array Using Nematic Liquid Crystals Doped with Chiral Nanoparticles.

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.

Directing the Handedness of Helical Nanofilaments Confined in Nanochannels Using Axially Chiral Binaphthyl Dopants.

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.

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.

Amplification of Chirality by Adenosine Monophosphate-Capped Luminescent Gold Nanoclusters in Nematic Lyotropic Chromonic Liquid Crystal Tactoids.

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.

Highly Sensitive, Tunable Chirality Amplification through Space Visualized for Gold Nanorods Capped with Axially Chiral Binaphthyl Derivatives.

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 C2-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.

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 > 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.

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.

An unusual type of polymorphism in a liquid crystal.

Polymorphism is a remarkable concept in chemistry, materials science, computer science, and biology. Whether it is the ability of a material to exist in two or more crystal structures, a single interface connecting to two different entities, or alternative phenotypes of an organism, polymorphism determines function and properties. In materials science, polymorphism can be found in an impressively wide range of materials, including crystalline materials, minerals, metals, alloys, and polymers. Here we report on polymorphism in a liquid crystal. A bent-core liquid crystal with a single chiral side chain forms two structurally and morphologically significantly different liquid crystal phases solely depending on the cooling rate from the isotropic liquid state. On slow cooling, the thermodynamically more stable oblique columnar phase forms, and on rapid cooling, a not heretofore reported helical microfilament phase. Since structure determines function and properties, the structural color for these phases also differs.

Intermolecular G-Quadruplex Induces Hyaluronic Acid-DNA Superpolymers Causing Cancer Cell Swelling, Blebbing, and Death.

Over the past decade, nanomedicine has gained considerable attraction through its relevance, for example, in "smart" delivery, thus creating platforms for novel treatments. Here, we report a natural polymer-DNA conjugate that undergoes self-assembly in a K+-dependent fashion to form a G-quadruplex (GQ) and generate superpolymeric structures. We derivatized a thiolated conjugate of the naturally occurring glycosaminoglycan polymer hyaluronic acid (HASH) with short G-rich DNA (HASH-DNA) that can form an intermolecular noncanonical GQ structure. Gel mobility shift assay and circular dichroism measurements confirmed HASH conjugation to DNA and K+-dependent GQ formation, respectively. Transmission electron microscopy and scanning electron microscopy results indicated that the addition of K+ to the HASH-DNA conjugate led to the formation of micron-range structures, whereas control samples remained unordered and as a nebulous globular form. Confocal microscopy of a fluorescently labeled form of the superpolymer verified increased cellular uptake. The HASH-DNA conjugates showed toxicity in HeLa cells, whereas a scrambled DNA (Mut) conjugate HASH-Mut showed no cytotoxicity, presumably because of nonformation of the superpolymeric structure. To understand the mechanism of cell death and if the superpolymeric structure is responsible for it, we monitored the cell size and observed an average of 23% increase in size compared to 4.5% in control cells at 4.5 h. We believe that cellular stress is generated presumably by the intracellular assembly of this large superpolymeric nanostructure causing cell blebbing with no exit option. This approach provides a new strategy of cellular delivery of a targeted naturally occurring polymer and a novel way to induce superpolymeric structure formation that acts as a therapeutic.

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.

Oriented Gold Nanorods and Gold Nanorod Chains within Smectic Liquid Crystal Topological Defects.

We show that the use of oriented linear arrays of smectic A defects, the so-called smectic oily streaks, enables the orientation of gold nanorods (GNRs) for a large range of GNR diameters, ranging from 7 to 48 nm, and for various ligands. For the small GNRs it enables oriented end-to-end small chains of GNRs when the density is increased from around 2 GNRs/µm2 to around 6 GNRs/µm2. We have characterized the orientation of single GNRs by spectrophotometry and two-photon luminescence (TPL). A strongly anisotropic absorption of the composites and an on-off switching of GNR luminescence, both controlled by incident light polarization, are observed, revealing an orientation of the GNRs mostly parallel to the oily streaks. A more favorable trapping of GNRs by smectic dislocations with respect to ribbon-like defects is thus demonstrated. The dislocations appear to be localized at a specific localization, namely, the summit of rotating grain boundaries. Combining plasmonic absorption measurements, TPL measurements, and simulation of the plasmonic absorption, we show that the end-to-end GNR chains are both dimers and trimers, all parallel to each other, with a small gap between the coupled GNRs, on the order of 1.5 nm, thus associated with a large red-shift of 110 nm of the longitudinal plasmonic mode. A motion of the GNRs along the dislocations appears as a necessary ingredient for the formation of end-to-end GNR chains, the gap value being driven by the balance between the attracting van der Waals interactions and the steric repulsion between the GNRs and leading to interdigitation of the neighboring ligands. We thus obtain electromagnetic coupling of nanorods controlled by light polarization.